JP3972792B2 - Method and apparatus for treating organic halogen compounds - Google Patents

Description

【００５３】
反応物質の溶媒中での拡散係数は、溶媒および溶質の物性値で決まるため、使用物質が同一であれば、拡散係数は一定であり、拡散時間ｔは流路幅Ｄｄの二乗に比例する。
【００５４】
図２１に流路幅Ｄｄと流路幅５００μｍ(０.５mm）時の拡散時間を基準にした拡散時間の比の関係を示す。
【００５５】
流路幅を大きくするにしたがって拡散時間も長くなり、流路幅５mm（５０００μｍ）時には０.５mm の約１００倍の拡散時間を要する。すなわち流路内を流れる流体の流速が一定の条件では反応を終了させるのに、流路長さが１００倍必要ということを意味する。
【００５６】
流路幅０.５mm で反応を完了するのに必要な流路長さを仮に５０mmとすると流路幅５mmでは１００倍の５０００mm（５ｍ）の長さが必要となる。
【００５７】
逆に０.５mm より小さい場合は短い流路長さでよい。
【００５８】
このように流路幅Ｄｄを広くし、流路閉塞を回避しようとすると、リアクタで所望の反応を終えるのに滞留時間が長時間必要となる。図３に示す基板３０の大きさは１００mm×４０mm程度の大きさであり、合流流路３１を５ｍ形成するのは現実的でなく、流路幅５mmで５ｍの流路長さを形成するにはさらに広い面積の基板が必要となり、製造コストも増大し、広い設置スペースも必要となる。
【００５９】
よって、流路幅Ｄｄの最大幅を２.０mm とすれば合流流路３１の必要長さは
８００mm程度となり現実的な流路長さとなる。特に省スペース化，製造コストなど考慮しない場合はさらに広い流路幅としても所望の脱ハロゲン率を満足する流路長さを確保したリアクタの流路構造とすれば良い。
【００６０】
流路幅Ｄｄを一定とすれば数１から拡散時間ｔは一定であり、反応時間も一定であることから処理量を増大するには流路幅一定で、流路断面積を増大する、すなわち流路深さを増大し、アスペクト比（縦横比）を大きくするのが有効である。
【００６１】
図２２に流路内での流速一定の条件で、合流流路３１のアスペクト比Ｌ／Ｄｄとリアクタでの摩擦損失比（アスペクト比１（正方形）の流路での摩擦損失を基準）との関係を示す。アスペクト比の増大に伴い等価直径も増大するため、摩擦損失も減少するが、アスペクト比２０以上では減少幅が少なく、摩擦損失の低減効果が小さい。そこで、合流流路３１の最大流路深さＬとしては、摩擦損失の低減効果が期待できるアスペクト比２０に相当する流路深さが好ましい。アスペクト比の増大分に伴う圧損低減効果を期待しない場合は、さらに流路深さを増大し、処理量を増大することも可能である。
【００６２】
よって、本発明でのリアクタの最大流路深さは、最大流路幅２０００μｍの
２０倍にあたる４００００μｍ、最小流路深さは最小流路幅と同じ１００μｍとなり、流路深さは１００〜４００００μｍの範囲が好ましい。
【００６３】
ところで反応は合流点３９から出口までの流路部が反応流路となる。本形態では脱ハロゲン化反応に対して十分な反応時間を確保するために基板３０を何往復もする合流流路３１長さとなっているが、所望の脱ハロゲン反応率（所望の反応後のＰＣＢ濃度）を達成できる流路長さ、すなわち脱塩素化反応を完了する滞留時間を確保できる合流流路３１の流路長さとしていれば図５に示すように、図３のように４回折りの蛇行流路よりさらに短い２回折りの蛇行流路としてもなんら問題ない。流路長さが短い場合は、リアクタ部の圧力損失の低減となり、ポンプ吐出圧の低減，低圧下での反応が可能になるなどのメリットがある。
【００６４】
図３〜図５では流体ＢすなわちＰＣＢ混合液が分岐する流れとなっているが、流体Ａ，流体Ｂを入れ替えて供給しても反応にはなんら影響はなく同じ効果が得られる。
【００６５】
図６に図４の流路構造を有する基板３０を多層に積層した積層体型リアクタ
１９を示す。図７は図６のＡ−Ａ断面を示す。流路を形成した基板３０と隔離板４０が交互に拡散接合などによる接合手段で積層され、合流流路３１の数を増し、単位時間あたりの処理量を増大するものである。
【００６６】
隔離板４０は、図８に示す様に、基板３０と同位置に導入孔３０ａ，３０ｂ，出口孔３２が板を貫通して設けてある。ただし底板４０ａは貫通しない孔または孔自体が不要である。
【００６７】
ここで、基板３０に構成した流路は基板３０を貫通しており、隔離板４０が基板３０の上下に配置され流路を形成している。
【００６８】
積層体型リアクタ１９の上面には入口流体継手１９ａ，出口流体継手１９ｂが接続されており、流体Ａ，Ｂは入口流体継手１９ａからそれぞれ流入し、導入孔３０ａ，３０ｂが流路３１と連通して、各流路に流体が流れている。
【００６９】
特に導入孔３０ａ，３０ｂおよび出口孔３２は、合流流路３１の流路より大きな流路断面積を有する流路とし、合流流路３１での流動抵抗より小さくすることで、各層の合流流路３１に均等に流量が配分される。
【００７０】
図６の積層体の場合、合流流路３１が１０流路形成される。すなわち同一時間で図３に示す１流路構造のリアクタに比べて１０倍の処理が可能となり、１流路では微量な処理量でも、多層に積層し流路数を増大することで大量処理が可能となる。
【００７１】
本図では基板３０が５枚であるが、積層枚数は５枚に限定されるものではない。
【００７２】
図９は図６の積層体型リアクタ１９の別の実施形態で、出口流体継手１９ｂが底面に配置されている。図１０は、図９のＡ−Ａ断面を示す。
【００７３】
出口流体継手１９ａをリアクタ１９の底面に設けたため、流体が重力に逆らうことなく排出されるため、鉱油より密度の大きいＮａ粒子が出口孔３２で滞留しにくくなり、図６のリアクタに比べて目詰まりしにくというメリットがある。
【００７４】
図１１は図６の積層体型リアクタ１９のさらに別の実施形態で、入口流体継手１９ａが前面に、また、出口流体継手１９ｂが背面に配置されている。図１２は、図１１のＡ−Ａ断面を示す。入口および出口流体継手１９ａ，１９ｂをそれぞれ前面と、背面に設けたためリアクタの側面４面全てに他の積層リアクタを近接して配置でき、図６，図９の積層体型リアクタ１９を並列接続する場合に比べて、省スペース化となるメリットがある。
【００７５】
次に本実施形態で使用する反応薬剤であるＮａ分散体，ＩＰＡ電気絶縁油の使用量，濃度等について説明する。
【００７６】
Ｎａ分散体のＮａ粒子は流路３１内で凝集し、流路閉塞することから、Ｎａ粒子径，分散体中のＮａ濃度は、流路閉塞および反応の両面から決定する必要がある。
【００７７】
Ｎａ分散体は、反応物質であるＮａの表面積を大きくして反応を速めるためにも粒子径は小さくし、多くの粒子を分散しておくことが好ましく、Ｎａの平均粒径は２０μｍ以下が好ましく、さらには１０μｍ以下が好ましい。さらにＮａ分散体中のＮａ濃度を高めることで反応を促進することができるがリアクタ部の合流流路３１が狭い場合はＮａ粒子が凝集して流路が閉塞する。
【００７８】
流路幅Ｄｄが１００μｍ〜２０００μｍの場合、反応部へ送液するＮａ分散体中のＮａ濃度は重量比で３０％以下が好ましい。しかしＮａが低濃度では反応が遅くなり、高濃度では流路が目詰まりし易いことから、さらにはＮａ濃度は重量比で１０％以上２０％以下が好ましい。
【００７９】
反応後の反応生成物による流路閉塞を防止するため、水素供与体であるＩＰＡを添加し、反応生成物同士の重合を抑制するが、これらＰＣＢを脱塩素化処理するのに必要な薬剤の添加量は少ないほど処理コストが低減する。
【００８０】
ＰＣＢの塩素（Ｃｌ）原子数に対して水素供与体であるＩＰＡ、およびＮａの使用量は理論量近傍であることが望ましく、過度のＩＰＡ，Ｎａの供給はＰＣＢの脱ハロゲン化処理においてはコスト高となる。
【００８１】
ＰＣＢを脱塩素化して脱塩素化後の反応生成物同士の重合を防止するためにはＰＣＢが脱塩素後に水素が置換すればよい。すなわち、ＰＣＢに結合している塩素（Ｃｌ）原子１個に対して水素原子１個が必要となる。
【００８２】
よって塩素原子１モルに対して水素原子１モルを放出するＩＰＡ添加量が理論量であり最低必要量となる。
【００８３】
ＩＰＡは、官能基であるヒドロキシル基（ＯＨ基）が１分子に１個存在する１価アルコールであり、Ｎａ原子１個とＯＨ基１個が反応しアルコキシドを生成し、同時に水素原子１個を放出する。よってＩＰＡ１モルとＮａ１モルで水素原子１モルが発生することから、ＩＰＡ／Ｃｌのモル比１の場合が理論量となる。
【００８４】
よってＩＰＡ／Ｃｌモル比１で理論上、重合抑制が可能であるがより確実に水素を供与して重合を防止するため理論量となる１倍以上のモル比を添加すれば良い。さらにはＩＰＡ使用量の抑制は処理コストの低減になることから理論量に対して１〜２倍モル比の添加量とするのが好ましい。
【００８５】
ＩＰＡではＯＨ基が１個であるが、ＯＨ基が２個以上ある多価アルコール、例えばエチレングリコール（ＯＨ基２個）ではエチレングリコール１分子で、水素原子２個を放出するため、エチレングリコールを水素供与体に選定した場合は、添加量はＩＰＡに比べて１／２のモル比で済む。このように多価アルコールを水素供与体に選定した場合、添加量が少なくて済み、廃液量が低減するというメリットもある。
【００８６】
このように反応後の生成物同士の重合を抑制する水素供与体の添加量は、有機ハロゲン化合物に含まれる塩素のモル量に対して、添加する水素供与体１分子に含まれるＯＨ基の存在数の逆数のモル比以上となる。つまり、１分子中にＯＨ基を１個含む１価アルコールでは水素供与体／Ｃｌモル比＝１，１分子中にＯＨ基を２個含む２価アルコールでは水素供与体／Ｃｌモル比＝１／２，１分子中に
ＯＨ基を３個含む３価アルコールでは水素供与体／Ｃｌモル比＝１／３となる。
【００８７】
上記の水素供与体としてはＮａと反応して容易に水素を発生するアルコール，フェノール類，カルボン酸，水があげられ、特に常温で液体でＮａとの反応も適度なアルコールが望ましい。このようなアルコールとしてはメタノール，エタノール，変成アルコール，１−プロパノール，イソプロピルアルコール，ブタノール，ペンタノール，ヘキサノール，イソアミルアルコール，エチレングリコール，シクロヘキサノール，プロピレングリコール，ベンジルアルコール，グリセリンが好ましい。特にＮａとの反応性，溶媒との親和性等を考慮するとイソプロピルアルコールが最も望ましい。
【００８８】
上記水素供与体は単独で用いても、２種類以上を混合しても、さらには溶媒との親和性を高めるために界面活性剤を添加してもよい。
【００８９】
このようにＩＰＡはＮａと反応し水素を発生することからＩＰＡの添加量に伴いＮａも消費される。
【００９０】
よってＰＣＢの脱塩素に必要なＮａ量、すなわちＮａ／Ｃｌモル比は、ＩＰＡ／Ｃｌモル比より多く必要となる。
【００９１】
ところでＮａによる脱塩素反応は、Ｎａ原子１個に塩素(Ｃｌ)原子１個が反応しＮａＣｌとなる。よって、ＩＰＡ添加量がＩＰＡ／Ｃｌモル比１の場合、脱塩素に必要なＮａ理論量は、Ｎａ／Ｃｌモル比２となる。よってＩＰＡ／Ｃｌモル比１以上、かつＮａ／Ｃｌモル比２以上の条件となるようにＮａ分散体とＰＣＢ混合液をリアクタに供給すればよい。
【００９２】
ＩＰＡ，Ｎａ使用量は処理コストの観点から重合が抑制できる理論量近傍での少量使用が望ましく、ＩＰＡ／Ｃｌモル比は１〜１０、Ｎａ／Ｃｌモル比は２〜２０が好ましく、さらには、ＩＰＡ／Ｃｌモル比１〜２、Ｎａ／Ｃｌモル比は２〜５が好ましい。
【００９３】
Ｎａ／Ｃｌモル比は、ＩＰＡと反応するＮａ消費量を考慮してＮａ／Ｃｌ比を決定すればよく、ＩＰＡ／Ｃｌモル比１の場合は、Ｎａ／Ｃｌモル比は２以上必要であり、ＩＰＡ／Ｃｌモル比が２の場合はＮａ／Ｃｌモル比は３以上必要である。つまり、Ｎａ／Ｃｌモル比が、添加する水素供与体中のＯＨ基／Ｃｌモル比より１以上多いモル比となるようにアルカリ分散体をリアクタに供給すればよい。
【００９４】
本実施の形態では、アルカリ分散体中を分散しているアルカリ金属にＮａ（ナトリウム）を選定しているが、これに限らずカリウム，リチウムまたはこれらの化合物であってもよい。
【００９５】
一方、リサイクル可能な溶媒についても使用量が少ないほうが低コスト，後処理槽の小型化などで省スペース化のメリットがあるが、溶媒である電気絶縁油量が少ないと、反応液に占める反応固体生成物量の割合が大きくなり流路閉塞の恐れ、また反応熱による流体の温度上昇の観点からも、極端に少なくできない。
ＰＣＢ混合液とＮａ分散体両液の全量（合計流量）に占めるＰＣＢ（有機ハロゲン化合物量）量（流量）は、重量比で３０％以下とするのが好ましい。
【００９６】
上記の溶媒としては、Ｎａ分散体に使用する溶媒とＰＣＢと混合する溶媒とは同一物質もしくは親和性の良いものが好ましく、特に灯油，鉱油，電気絶縁油，トランスオイル，パラフィンなどが好ましい。特に高沸点で、流動性も良い電気絶縁油，鉱油，トランスオイルが好ましい。
【００９７】
上記溶媒は単独で用いても、２種類以上を混合しても、さらには有機ハロゲン化合物および水素供与体との親和性を高めるために界面活性剤を添加してもよい。
【００９８】
本発明によれば外部からリアクタへ熱を供給することなくアルカリ金属による脱ハロゲンの反応速度を促進する効果が得られると同時に、水素供与体からの水素放出により反応生成物の重合などによる流路閉塞を防止でき、アルカリ分散体を用いて連続処理する脱ハロゲン化処理が可能となる。
【００９９】
さらに、水素供与体とＮａとの反応熱を利用することで、従来のようにＰＣＢ混合液，Ｎａ分散体を加温し反応を促進する必要がなく、従来の処理方法より投入エネルギが少なく、省エネとなる。
【０１００】
特に冬季には、外気温の低下により供給流体の粘性が高くなることから流体を加温したりする場合もあるが、従来より低い温度の昇温で済み、省エネとなるメリットは変わらない。
【０１０１】
また、リアクタでの脱ハロゲン反応時も流体の温度が高温とならなければ、脱塩素反応中もリアクタ部を冷却する必要がなく、温度制御も不要で、煩雑な温度制御も不要となり、従来より省エネ，省スペース，低コストで脱ハロゲン化が可能となる。
【０１０２】
さらに、少量のＰＣＢ処理の場合、リアクタおよび付帯設備もさらに小型で済むことから、処理装置を運搬し、保管している高圧コンデンサなどから直接PCBを抜き取り、保管現場で処理することも可能である。保管現場での処理は、PCBを処理施設まで運搬する必要がなく、ＰＣＢ運搬時の事故などによる環境への
ＰＣＢ拡散のリスクが低減されるというメリットがある。
【０１０３】
このように、有機ハロゲン化合物と少なくとも１種類の水素供与体を混合した混合液、またはさらに前記混合液に少なくとも１種類の溶媒を混合した混合液と、アルカリ金属が分散したアルカリ金属分散体とが合流する微細流路を有した合流流路を形成したリアクタに連続供給することで、流路閉塞することなく脱ハロゲン化が可能となる。
【０１０４】
特にリアクタ内の合流流路が所望の分解率を得るために必要な流路長さ以上を有していることでより確実に有機ハロゲン化合物の脱ハロゲン化が可能となる。
【０１０５】
また、リアクタを多層に積層した積層体型リアクタとし、流路数を増大することで、大量処理が実現できる。
【０１０６】
図１３〜図１６により本発明に係る有機ハロゲン化合物を脱ハロゲン化処理する処理装置の第２の実施の形態を説明する。図１３は脱ハロゲン化する処理システムの概略フロー図を、図１４は図１３のフローを具体的なハード構成にした実施の形態を、図１５，図１６は基板上に形成したリアクタの流路構成を示している。
【０１０７】
図１３に本実施の形態での概略フロー図を示す。図１３に示すようにリアクタ１９は、反応に加えてＰＣＢ，ＩＰＡ，電気絶縁油の予混合の機能を備えており、図１の予混合５をリアクタ内で行う点に特徴がある。さらに、図中には脱ハロゲン後の後処理工程も記載している。
【０１０８】
有機ハロゲン化合物２である流体Ｂ１，溶媒３である流体Ｂ２，水素供与体４である流体Ｂ３の各流体はリアクタ６へ供給され、リアクタ６で予混合されアルカリ金属分散体１である流体Ａとリアクタ内で合流し脱ハロゲン反応を行う。
【０１０９】
リアクタ６で脱塩素反応し、リアクタ６から排出された反応済液Ｃは被処理物質である有機ハロゲン化合物の脱ハロゲン化処理を確認後、過剰に供給したアルカリ金属分散体１のアルカリ金属を処理する過剰アルカリ金属処理７とアルカリ性溶液を中和する中和８からなる後処理を受けて液体Ｄとなり、排ガス９，廃液１０（廃油，廃水等）に分離され適切に処分またはリサイクルされる。
【０１１０】
廃液の油と水の分離には密度差による静置分離や遠心分離，分離膜などを用いることができる。
【０１１１】
図１３中のフローには後処理の工程も含まれているが、図１のように脱ハロゲン処理のみの場合、これら後処理は必要なく、また後処理方法もこれらに限定されるものではない。
【０１１２】
図１４に図１３のフローを具体的なハード構成にした第２の実施の形態を示している。積層型リアクタ１９内でＰＣＢ１４，鉱油１５，ＩＰＡ１６の各流体の予混合を行うため、その各流体がポンプ（図示せず）で直接積層型リアクタ１９に供給される。よって図２に示す予混合槽１７，攪拌機１８，ポンプ(図示せず)などが不要となり、さらに省スペース，省エネ化となるメリットがある。
【０１１３】
積層型リアクタ１９で脱塩素化反応を受けて、積層型リアクタ１９から排出した反応済液Ｃは後処理槽２０に入り、そこで過剰供給されたＮａの過剰アルカリ金属処理７とアルカリ性溶液を中和する中和８からなる後処理をうける。
【０１１４】
その後処理後の廃液は廃油，廃水，反応生成物であるＮａＣｌ，ＰＣＢが脱塩素したビフェニルなどに分離され、処分またはリサイクルされる。過剰供給したＮａの過剰アルカリ金属処理７には具体的には水２３を後処理槽２０内に供給し、Ｎａと水を反応させ、活性なＮａをより不活性な苛性ソーダ（ＮａＯＨ）などに処理する。また中和８の処理には中和剤２４となる塩酸，炭酸ガスなどを供給しアルカリ性溶液およびアルカリ物質を中和処理する。後処理およびリアクタ
１９の反応で発生したガスは後処理槽２０から活性炭フィルター２１を介してブロア２２で吸引して排気する。
【０１１５】
Ｎａ分散体の場合、活性なＮａは鉱油などの溶媒中に分散しており、直接空気と接触しないため空気中でも反応しないが、安全上、Ｎａ分散体容器１１，後処理槽２０は不活性ガス雰囲気下とすることが好ましい。不活性ガスとしては窒素（Ｎ₂ ），アルゴンなどが用いられる。
【０１１６】
図１５，図１６に図１４の積層体型リアクタ１９の構成部材である基板３０上に形成した流路構成を示している。
【０１１７】
基板３０にはＰＣＢ１４，鉱油１５，ＩＰＡ１６を予混合するための導入孔
３３，３４,３５および各導入孔３３，３４,３５に接続された３本の流路と、その３本の流路が一箇所で合流する合流個所で接続された蛇行経路の予混合流路
３６とが形成され、その予混合流路３６は斜め直線状の２本の流路ｂに接続され、各流路ｂは流路ａに合流点３９で接続されている。その他の基板の構成は図３の場合と同じである。この場合、導入孔３３にＰＣＢ１４が導入され、そのPCB１４がリアクタ１９の基板に形成された第４の流路１４ａを通り、導入孔３５にＩＰＡ１６が導入され、そのＩＰＡ１６がリアクタ１９の基板に形成された第５の流路１６ａを通り、導入孔３４に鉱油１５が導入され、その鉱油１５がリアクタ１９の基板に形成された３本の内の残り一本の流路１５ａを通り、ＰＣＢ１４とＩＰＡ１６と鉱油１５とは予混合流路３６との接続部で合流し混合し始める。
【０１１８】
特に、図１６の基板の場合には、その予混合流路３６は途中で分岐して各流路ａに各合流部３９で接続されている。その基板のその他の構成は図４と同じである。
【０１１９】
このような基板を用いた場合には、予混合流路３６内でＰＣＢ１４，鉱油１５，ＩＰＡ１６が十分混合されて、その混合液は合流部３９へ導かれ、流路ａからのＮａ分散体と合流流路３１内で混合しながら反応し合いついには出口孔３２から連続的に排出される。予混合流路３６はＰＣＢ１４，鉱油１５，ＩＰＡ１６が十分混合するのに十分必要な流路長さとなるように蛇行させてあるが、図１５，図１６の流路形状に限定されるものではない。
【０１２０】
本実施の形態によれば、ＰＣＢ１４，鉱油１５，ＩＰＡ１６の混合をリアクタ１９内の流路で行うので、リアクタ外で混合するのに比べて混合混合槽１７，攪拌機１８，ポンプ（図示せず）が不要となり、さらに省スペース，省エネとなるメリットがある。
【０１２１】
図１７〜図２０により本発明に係る有機ハロゲン化合物を脱ハロゲン化処理する処理装置の第３の実施の形態を説明する。図１７は脱ハロゲン化する処理システムの概略フロー図を、図１８は図１７のフローを具体的なハード構成にした実施の形態を、図１９，図２０は積層体型リアクタ１９の基板３０上に形成した流路構成を示している。
【０１２２】
図１７に本実施の形態での概略フロー図を示す。図１７に示すようにリアクタ６は、予混合，反応に加えて後処理の機能を備えており、図１３の後処理である過剰アルカリ金属処理７，中和８をリアクタで行う点に特徴がある。それ以外は図１３のフロー図と同じである。この過剰アルカリ金属処理７は、リアクタ内のナトリウムを水と反応させて、活性なナトリウムを活性がより弱いカセイソーダ（ＮａＯＨ）にするもので、ナトリウムを含む流体の不活性化処理に相当する。中和８の処理は、カセイソーダ（ＮａＯＨ）が強アルカリの性質を有するので、過剰アルカリ金属処理７を施した流体に中和剤として塩酸などの酸を加えて中性化するアルカリ性溶液やアルカリ物質の中和処理である。
【０１２３】
図１８に図１７のフローを具体的なハード構成にした実施の形態を示している。本実施の形態では過剰アルカリ金属処理７や中和８の処理で用いられる水や中和剤が直接積層体型リアクタ１９に供給され、そのリアクタ内で後処理が行われる。リアクタ１９から排出された流体は後処理が完了しており、リアクタ１９から排出した流体は、気液分離器２５で気体と液体に分離される。リアクタ１９内で後処理を行うことから図１４に示す後処理槽２０および後処理槽２０内で処理液の攪拌を行う攪拌機が不要となる。他の構成は図１４と同じである。
【０１２４】
図１７，図１８には過剰アルカリ金属処理７，中和８の処理をリアクタで行っている処理フローおよびハード構成となっているが、過剰アルカリ金属処理７のみをリアクタ６で実施することも可能である。この場合は図１４に示すような後処理槽２０が必要となるが、攪拌時間が短縮でき、第１の実施の形態より省エネルギーでＰＣＢを処理できるメリットがある。
【０１２５】
図１９，図２０に図１８の積層型リアクタ１９の構成部材である基板３０上に形成した流路構成を示している。基板３０にはＰＣＢ１４,鉱油１５,ＩＰＡ１６を基板内に導入するための導入孔３３，３４，３５と、その導入孔３３，３４，３５に接続された３本の流路と、その３本の流路が合流する部位には蛇行経路状の予混合流路３６の一端が接続され、その予混合流路３６の他端は斜め直線状の２本の流路ｂが接続され、各流路ｂは流路ａに合流点３９で接続されている。
【０１２６】
その合流部３９には合流流路３１が接続されている。その合流流路３１の下流側には、合流流路と連続して反応流路３７ａが、反応流路３７ａに連続して反応流路３７ｂが接続され、反応流路３７ａの下流側端部は出口孔３２が接続されている。
【０１２７】
基板３０には水の導入孔３７と中和剤の導入孔３８が設けられ、導入孔３７が反応流路３７ｂに、導入孔３８が反応流路３７ｂと接続されている。概ね導入孔３７と導入孔３８との間の流路を反応流路３７ａと、概ね導入孔３８と出口孔
３２との間の流路を反応流路３７ｂと称している。これらの反応流路３７ａと反応流路３７ｂとは第６の流路として基板に蛇行経路にして形成されている。
【０１２８】
各導入孔３３，３４，３５に導入されたＰＣＢ１４，鉱油１５，ＩＰＡ１６は予混合流路３６で混合しあってＰＣＢ混合液の液体Ｂとなり合流部３９に向かう。一方、各流路ａに導入孔３０ａから導入されたＮａ分散体は流体Ａとして合流部３９に向かう。両流体Ａ，Ｂは合流部３９で合流して混合しあい、且つ、反応しあってＰＣＢ１４が脱塩化処理を受け、合流後の混合液体が反応生成物を反応済液Ｃとして反応流路３７ａに流れる。反応流路３７ａでは、反応済液Ｃ内の
Ｎａが導入孔３７から導入された水と反応してＮａＯＨに生成され、ＮａＯＨを含む反応済液Ｃは反応流路３８ａに入り、導入孔３８から導入された塩酸で中和されて後処理済液Ｄとして積層型リアクタ１９から出口孔３２を通じて排ガスとともに連続的に排出される。他の構成は図１５，図１６と同じである。
【０１２９】
反応流路３７ａ，３８ａは後処理での反応に必要な流路長さであれば図１９，図２０の流路形状に限定されるものではない。
【０１３０】
本実施の形態によれば、後処理槽２０，攪拌機（図示せず）が不要となり、第２の実施の形態よりさらに省スペース，省エネとなるメリットがある。
【０１３１】
いずれの実施例でも、アルカリ金属粒子および反応生成物で流路が閉塞することなく、しかもリアクタ部をヒータなどで外部から熱を供給し加温することなく、有機ハロゲン化合物を効率よく脱ハロゲン化することができる。
【０１３２】
また、いずれの実施例でも、リアクタにアルカリ金属分散体と有機ハロゲン化合物と水素供与体と溶媒とを連続的に供給して、連続的に有機ハロゲン化合物の脱塩素処理を行い、連続的にリアクタから脱塩化処理した液体を排出できる。そのため、リアクタが有する反応効率のよさを十分に享受できる。
【０１３３】
以下、アルカリ金属分散体を用いて有機ハロゲン化合物の脱塩素処理を行った試験例と、その試験との比較のために行った比較例とを紹介する。
【０１３４】
試験例は以下のとおりである。即ち、金属ナトリウム（Ｎａ）１０ｇを鉱油
９０ｇに分散させた分散体（Ｎａ濃度１０ｗｔ％，平均粒子径約１０μｍ）５０ｇを攪拌しながら容器内に収容し、一方、溶媒となる鉱油３８ｇと有機ハロゲン化合物である１，２，４−トリクロロベンゼン（ＴＣＢ）２ｇと水素供与体となるイソプロピルアルコール（ＩＰＡ）４ｇを十分に攪拌し混和した。ＴＣＢはベンゼン環に塩素が３個付いた構造をしており、ＴＣＢ１モルにつき塩素（Ｃｌ）は３モル存在する。溶媒量に対して有機ハロゲン化合物量は約５％、ＩＰＡは、ＩＰＡ／Ｃｌモル比が約２となる量を添加した。両液体，反応部共にヒータで加熱することなく室温の条件下で、両液を定量ポンプでリアクタへ送液した。ナトリウム分散剤は、Ｎａ／Ｃｌモル比が約５となる流量でリアクタに送液した。
【０１３５】
反応試験には図３に示す流路構成のリアクタを用いた。リアクタの流路幅は
５００μｍ、流路深さは５００μｍであり、合流部から出口までの流路長さは、約３５０mmである。合流部の流量は約１ｍｌ／min 、合流流路の滞留時間は約５ｓである。リアクタはワイヤカットで流路構造を加工した５００μｍ厚さのステンレス板の上下に同じくステンレス板で拡散接合によりステンレス板同士を接合し、反応流路１本を形成した。
【０１３６】
この試験例によれば、反応生成物により流路閉塞することなく、また、ＩＰＡとＮａの反応熱により脱ハロゲン反応が促進され、リアクタ部を加温することなく、反応前に約２００００ppmであったＴＣＢ濃度は反応後に検出限界値（0.05ppm）以下となり、ほぼ完全に脱塩素することができた。
【０１３７】
比較例は以下のとおりである。即ち、金属ナトリウム（Ｎａ）２０ｇを鉱油
８０ｇに分散させた分散体（Ｎａ濃度２０ｗｔ％，平均粒子径約１０μｍ）５０ｇを攪拌しながら容器内に収容し、一方、溶媒となる鉱油２８.５ｇ と有機ハロゲン化合物である１，２，４−トリクロロベンゼン(ＴＣＢ）１.５ｇを十分攪拌して混和し、ＴＣＢ濃度５％の混合液とした。
【０１３８】
ナトリウム分散剤およびＴＣＢ混合液は、Ｎａ／Ｃｌモル比が約１５となる流量でリアクタに送液した。
【０１３９】
反応試験にはガラス製のリアクタを用いた。リアクタの流路幅は５００μｍ、流路深さは５００μｍであり、合流部から出口までの流路長さは、約６０mmである。リアクタは、オーブン内に収納し、約１３０℃にリアクタ全体を加温した。合流部の流量は約１ｍｌ／min 、合流流路の滞留時間は約１ｓである。
【０１４０】
この比較例によれば、水素供与体であるＩＰＡを添加せず、リアクタを加温することで、反応前に約２００００ppmであったＴＣＢ濃度は反応後に検出限界値（０.０５ppm）以下となり、ほぼ完全に脱塩素することができた。しかし、反応生成物の重合などによって、試験開始から数分後にリアクタの流路が閉塞し、流体を供給することができなくなった。
【０１４１】
【発明の効果】
以上説明したように本発明によれば、アルカリ金属粒子および反応生成物でリアクタの微細流路が閉塞することなく、有機ハロゲン化合物を脱ハロゲン化することができる。
【図面の簡単な説明】
【図１】本発明の第１実施形態の処理フロー図。
【図２】本発明の第１実施形態のハード構成図。
【図３】本発明の第１実施形態でのリアクタの流路構成図。
【図４】本発明の第１実施形態で採用できる他のリアクタの流路構成図。
【図５】本発明の第１実施形態で採用できる更に他のリアクタの流路構成図。
【図６】積層体型リアクタの斜視図。
【図７】図６のＡ−Ａ断面図。
【図８】積層体型リアクタを構成する隔離板の平面図。
【図９】他の積層体型リアクタの斜視図。
【図１０】図１０のＡ−Ａ断面図。
【図１１】更に他の積層体型リアクタの斜視図。
【図１２】図１２のＡ−Ａ断面図。
【図１３】本発明の第２実施形態の処理フロー図。
【図１４】本発明の第２実施形態のハード構成図。
【図１５】本発明の第２実施形態でのリアクタの流路構成図。
【図１６】本発明の第２実施形態で採用できる他のリアクタの流路構成図。
【図１７】本発明の第３実施形態での処理フロー図。
【図１８】本発明の第３実施形態のハード構成図。
【図１９】本発明の第３実施形態でのリアクタの流路構成図。
【図２０】本発明の第３実施形態で採用できる他の流路構成図。
【図２１】拡散時間と流路幅Ｄｄの関係を示すグラフ図。
【図２２】リアクタ内摩擦損失とアスペクト比の関係を示すグラフ図。
【符号の説明】
１…アルカリ金属分散体、２…有機ハロゲン化合物、３…溶媒、４…水素供与体、６…リアクタ、７…過剰アルカリ金属処理、８…中和。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a treatment method and a treatment apparatus for dehalogenating an organic halogen compound such as polychlorinated biphenyl (hereinafter referred to as PCB), which is an environmental pollutant, with an alkali dispersion.
[0002]
[Prior art]
As a method for treating a contaminated oil containing an organic halogen compound such as PCB and PCB, a sodium dispersion in which alkali metal, particularly solid metal sodium is finely dispersed in a solvent such as electrical insulating oil, With active sodium
A method is known in which chlorine atoms in PCB are reacted in a reaction tank to form sodium chloride (NaCl), and PCB is dechlorinated and rendered harmless (see, for example, Patent Document 1).
[0003]
In recent years, a technique using a reactor that performs a chemical reaction with high efficiency in a microchannel (fine channel) has attracted attention. By narrowing the reaction channel width, the diffusion distance of the reactant is shortened, and the reaction is promptly performed by molecular diffusion without using mechanical stirring or the like.
[0004]
A technique is known in which an organic compound in a developing waste liquid is decomposed by exposing it to water at a temperature and pressure in a subcritical to supercritical region using the reactor (see, for example, Patent Document 2).
[0005]
[Patent Document 1]
JP-A-49-82570
[Patent Document 2]
JP 2002-113475 A
[0006]
[Problems to be solved by the invention]
Since the dehalogenation reaction is an exothermic reaction, in order to suppress the temperature rise due to the heat of reaction, conventionally, a PCB or an alkali metal sodium dispersion was dropped into the reaction vessel and reacted for a long time while stirring with a stirrer to remove the halogen. Processing is in progress. In order to promote the reaction, the reaction vessel is heated from the outside with a heater or the like, or the heat of reaction is removed, so that electric insulation oil is added or the reaction vessel is cooled to control the reaction temperature to a predetermined level. .
[0007]
Therefore, the configuration of the temperature control device becomes large and temperature control is difficult. On the other hand, when decomposing an organic compound using a reactor having a microchannel, it is necessary to create a temperature and pressure atmosphere in the subcritical to supercritical region, which increases the amount of energy input.
[0008]
For example, in a method of decomposing an organic compound in a developing waste liquid in a fine flow path of 1 mm or less using supercritical water (25 MPa, 650 ° C. or higher), solids due to the reaction are not generated due to high temperature and high pressure (reaction zone temperature). Therefore, even if the flow path is fine, blockage of the flow path does not occur.
[0009]
However, when PCB is dechlorinated with Na dispersion, Na particles and solids due to polymerization of the product are present in the microchannel (microchannel) of the reactor. Also, the problem of blocking the flow path arises.
[0010]
Accordingly, an object of the present invention is to dehalogenate an organic halogen compound with an alkali metal dispersion without clogging the flow path of the reactor.
[0011]
[Means for Solving the Problems]
A method for achieving the object of the present invention comprises an alkali metal dispersion and an organic halogen compound and Reacts with alkali metal dispersions to donate hydrogen Formed on the reactor substrate with a hydrogen donor Fine Introduced into the flow path Fine The organic halide is dehalogenated in the flow path.
[0012]
An apparatus for achieving the object of the present invention is a first apparatus for guiding an alkali metal dispersion. Fine Flow path, organic halogen compounds and Reacts with alkali metal dispersions to donate hydrogen 2nd leading hydrogen donor Fine Flow path, first Fine Flow path and second Fine A third portion in which the alkali metal dispersion, the organic halogen compound, and the hydrogen donor are introduced in communication with a flow path; Fine A reactor having a flow path, and the first Fine Connected to the channel and the first Fine A first supply means for supplying an alkali metal dispersion to the flow path; Fine Connected to the channel and the second Fine And a second supply means for supplying the organic halogen compound and the hydrogen donor to the flow path.
[0013]
In the present invention, the third reactor Fine Polymerization between reaction products in the flow path is suppressed by hydrogen based on a hydrogen donor, and dehalogenation treatment can be performed by reaction between an organic halogen compound and an alkali metal without blocking the fine flow path of the reactor. .
[0014]
The more specific means is preferably the first Fine Channel and second Fine A flow path and the first Fine Flow path and second Fine The third communicated with the flow path Fine Said first of the reactor comprising a flow path Fine Supplying the alkali metal dispersion to the flow path; Fine In the channel, the organic halogen compound and Reacts with alkali metal dispersions to donate hydrogen Supplying a hydrogen donor; Fine Flow path and second Fine The third from the flow path Fine The alkali metal dispersion, the organohalogen compound, and the hydrogen donor are introduced into the flow path to introduce the third Fine A method for treating an organic halogen compound, characterized in that a dehalogenation treatment of the organic halide is performed in a flow path, can be proposed as a second means.
[0018]
Furthermore, the second hand In steps In the third Fine A method for treating an organic halogen compound is characterized in that at least one of an alkali metal deactivation treatment and a neutralization treatment is performed on a fluid containing a reaction product produced in a flow path. 3 It can be proposed as a means.
[0020]
Furthermore, the first that leads the alkali metal dispersion Fine Flow path, organic halogen compounds and Reacts with alkali metal dispersions to donate hydrogen 2nd leading hydrogen donor Fine Flow path, first Fine Flow path and second Fine A third is introduced into the flow path to introduce the alkali metal dispersion, the organic halogen compound and the hydrogen donor. Fine A reactor having a flow path, and the first Fine Connected to the channel and the first Fine A first supply means for supplying an alkali metal dispersion to the flow path; Fine Connected to the channel and the second Fine And a second supply means for supplying the organic halogen compound and the hydrogen donor to the flow path. 4 It can be proposed as a means.
[0021]
Furthermore, the first that leads the alkali metal dispersion Fine Flow path, organic halogen compounds and Reacts with alkali metal dispersions to donate hydrogen 2nd leading hydrogen donor Fine Flow path and first Fine Flow path and second Fine A third is introduced into the flow path to introduce the alkali metal dispersion, the organic halogen compound, and the hydrogen donor. Fine A reactor having a flow path; and the first Fine Connected to the channel and the first Fine A first supply means for supplying an alkali metal dispersion to the flow path; a mixing means for mixing the organic halogen compound and the hydrogen donor outside the reactor; and a fluid mixed by the mixing means in the second Fine And a second supply means for supplying to the flow path. 5 It can be proposed as a means.
[0026]
In addition, 4th means or 5th means The organic halogen compound processing apparatus includes a processing apparatus that performs at least one of alkali metal deactivation processing and neutralization processing on the fluid that has flowed out of the reactor. 6 It can be proposed as a means.
[0027]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail. A first embodiment of a processing apparatus for dehalogenating an organic halogen compound according to the present invention will be described with reference to FIGS. 1 is a schematic flow diagram of a dehalogenation processing system, FIG. 2 is an embodiment in which the flow of FIG. 1 is made into a specific hardware configuration, and FIGS. 3 to 5 are flow channel configurations of a reactor formed on a substrate. FIGS. 6 to 12 show the structure of a multilayer reactor that enables the mass processing by laminating the substrates in multiple layers.
[0028]
First, the processing flow of FIG. 1 will be described. A fluid mixture in which fluid A, which is an alkali metal dispersion 1, fluid B1, which is an organic halogen compound 2, fluid B2, which is a solvent 3, and fluid B3, which is a hydrogen donor 4, are sufficiently mixed by means of premixing 5. A fluid B is continuously supplied to the reactor 6 having a fine flow path.
[0029]
Each fluid continuously supplied undergoes a chemical reaction in the reactor 6, a halogen atom bonded to the organic halogen compound reacts with an alkali metal to dehalogenate, and a reacted liquid C containing a reactive organism is discharged from the reactor 6. Discharged.
[0030]
The supply flow rates of the fluids A and B are controlled so that the reacted liquid C has a desired dehalogenation rate (desired organohalogen compound concentration), and predetermined reaction conditions and reaction time in the reactor (in the reactor (Residence time). In particular, in the case of detoxification treatment by dechlorination of PCB, the PCB concentration in the treated oil after the reaction should be 0.5 mg / kg (0.5 ppm) or less.
[0031]
The organic halogen compound which is an object of the present invention is a compound in which a halogen atom is bonded to carbon, for example, a liquid compound represented by PCB (polychlorinated biphenyl) or PCB mixed oil in which the halogen atom is a chlorine atom. Etc.
[0032]
FIG. 2 shows an embodiment in which the flow of FIG. 1 has a specific hardware configuration. In particular, the apparatus performs a detoxification process by dehalogenation of PCB. In the case where the flow of FIG. 1 has a specific hardware configuration, the reactor 6 is replaced with a laminated reactor 19 from the viewpoint of processing in large quantities in a specific implementation. Also in each of the following embodiments, the reactor 6 is replaced with a laminated reactor 19 when the flow is made to have a specific hardware configuration.
[0033]
Metal alkali (hereinafter referred to as Na) is used as the alkali metal, and an Na dispersion in which Na is dispersed in an electrical insulating oil or the like is used as the alkali metal dispersion. The Na dispersion is stored in a Na dispersion container 11, and Na particles are uniformly dispersed by a stirrer 12 provided in the Na dispersion container 11. The Na dispersion is supplied to the laminated reactor 19 as a liquid A through a pipe and a distribution header by a pump 41. This is connected to the laminated reactor 19 as the first supply means. In this first supply means, it is preferable to install a filter or the like in the upstream portion of the multilayer reactor 19 in order to prevent the channel of the multilayer reactor 19 from being blocked by coarse Na particles.
[0034]
In the case of Na dispersion, active Na is dispersed in a solvent such as mineral oil and does not react directly with air because it does not come into direct contact with air. However, for safety, the Na dispersion vessel 11 should be in an inert gas atmosphere. Therefore, the inert gas cylinder 13 is connected to supply the inert gas to the Na dispersion vessel 11. The inert gas is nitrogen (N ₂ ), Argon or the like is used.
[0035]
In the figure, the Na dispersion is directly supplied from the Na dispersion container 11 to the laminated reactor 19, but it may be further diluted with a solvent such as an electric insulating oil for the concentration adjustment.
[0036]
On the other hand, PCB, which is an organic halogen compound, electrical insulating oil, which is a solvent, and isopropyl alcohol, which is a hydrogen donor (hereinafter referred to as IPA), are housed in the respective dedicated containers 14, 15, 16 and are premixed. A predetermined amount is injected into the mixing tank 17 from the dedicated containers 14, 15, 16 through the respective pipes 42 to 44 to the mixing tank 17, and is stirred by the stirrer 18 in the mixing tank 17 to be a PCB mixed solution. The Thus, the PCB mixed liquid prepared by premixing by the mixing means by the mixing tank 17 and the stirrer 18 is supplied as liquid B to the laminated reactor 19 through the piping by the pump 45. Such a second supply means is connected to the laminate type reactor 19. IPA supplies a necessary amount based on the total chlorine number of PCB and the mixed organic halogen compound in order to suppress polymerization between reaction products after the dechlorination reaction.
[0037]
In the present embodiment, the mixing tank 17 is provided with a stirrer 18, and a PCB mixed liquid in which PCB, electrical insulating oil, and IPA are sufficiently mixed is supplied from the mixing tank 17 to the laminated reactor 19 by the pump 45. However, when the mixing is performed quickly in the pipe of the second supply means without using the stirrer 18 or the like, the stirrer 18 and the mixing tank
17. The pump 45 may be unnecessary.
[0038]
The PCB in the figure may be 100% concentration, or a PCB mixed solution mixed with an organic halogen compound such as trichlorobenzene, electrical insulating oil or the like. Also,
The main purpose of the electrical insulating oil mixed with the PCB is to reduce the viscosity of the PCB. When the viscosity of the PCB mixed solution is reduced by mixing only the PCB and IPA, it is not necessary to mix the electrical insulating oil. Only a mixed liquid of IPA and PCB is a laminated reactor
19 may be fed.
[0039]
In order to cope with a desired processing amount, a multilayer reactor described later is connected in parallel to realize a large amount of processing. When the amount of processing is small, a single stacked reactor may be used without being connected in parallel, or a single reactor configured on a substrate may be used. In this case, a very compact processing system is constructed.
[0040]
Both liquids continuously supplied to the laminate type reactor 19 are joined (reacted) in a joining channel that is a fine channel formed in the reactor 19 to dehalogenate the PCB. Then discharged. The PCB concentration of the reaction liquid after discharge is
If it is 0.5 mg / kg or less, it can be discarded or recycled after appropriate treatment as industrial waste.
[0041]
If the PCB concentration in the treated oil after discharge exceeds 0.5 mg / kg, dechlorination is performed again without discharging to the environment.
[0042]
FIG. 3 shows a flow path configuration formed on the substrate 30 which is a component of the multilayer reactor 19 of FIG. The material of the substrate 30 can withstand the discharge pressure of the pump and reaction heat,
Any material that does not corrode to Na dispersion, PCB mixed solution, or the like may be used, but stainless steel, hastelloy steel, titanium steel, glass, ceramics and the like are preferable.
[0043]
The flow path is formed in the substrate 30 by wire cutting, electrical discharge machining, machining such as an end mill, etching, etc., and one flow path a into which the fluid A flows and the other flow path b into which the fluid B flows are formed. Introducing holes 30a and 30b are respectively formed. The flow paths through which the fluids A and B flow are merged at a merge point 39, and the merged flow path 31 is formed on the substrate 30 up to the flow path outlet 32 with a flow path width of Dd. As shown in the flowchart of FIG. 1, in this embodiment, the reactor 19 performs only the dehalogenation reaction, and therefore, it is sufficient if the reactor 19 includes the merging channel 31 that merges and reacts the fluids A and B. The length of the flow path 31 is a residence time for achieving a desired dehalogenation, that is, a flow path length required to obtain a desired PCV decomposition rate in the merge flow path 31 Just do it.
[0044]
Such a substrate 30 is laminated on the bottom plate with a separator interposed therebetween, and the uppermost substrate 30 is covered with a plate so that the upper part of each flow path is closed, but the flow path outlet 32 and the introduction are provided. The holes 30a and 30b are opened to the outside as connection ports with the outside. In the reactor 19 having such laminated substrates, the respective plates are fixed integrally. The introduction hole 30a is connected to the first supply means, the introduction hole 30b is connected to the second supply means, and the flow path outlet 32 is connected to a facility for collecting the reaction solution containing the reaction product. A system that inactivates or neutralizes sodium with respect to the reaction solution containing the reaction product may be connected to the flow path outlet 32.
[0045]
The fluid A entering the introduction channel 30a from the first supply means and flowing into the flow path a and the fluid B entering the introduction hole 30b and entered the flow path b from the second supply means merge at the junction 39. The reaction begins. In the reaction, IPA and Na, which are hydrogen donors, react to produce alkoxide and release hydrogen. The reaction heat in this reaction raises the temperature of the fluid in the merge channel 31 and promotes the dechlorination reaction, which is a reaction of chlorine (Cl) bonded to Na and PCB. The heat of reaction due to this dechlorination reaction The temperature further rises and the dechlorination reaction is promoted.
[0046]
During the residence time in the merging channel 31 from the merging point 39 to the channel outlet 32, the reactants sufficiently diffuse and react in the merging channel 31, and the PCB is dechlorinated and simultaneously IPA and Na react. The hydrogen generated in this way quickly substitutes for chlorine in the PCB to become biphenyl. As a result, the merged flow path 31 of the reactor is not blocked by polymerization of the reaction products, and the dechlorination reaction is continued, and the liquid C containing the reaction product is continuously discharged from the flow path outlet.
32 can be discharged out of the stacked reactor 19.
[0047]
The flow path structure shown in FIG. 4 is obtained by forming the flow path structure of FIG. 3 in parallel with the substrate 30, and the merge flow path 31 is formed on the substrate 30. In addition, the amount of PCB processing can theoretically be doubled. Further, the flow path b is branched from one flow path and connected to each flow path a so that the liquids A and B can join at each joining point 39. In addition, each merge channel 31 from each merge point 39 to the outlet hole 32 is gathered together just before the outlet hole 32 so that the reaction liquid from each merge channel 31 can be merged. Thus, only one inlet hole 30b for the fluid B communicating with the flow path b and one outlet hole 32 communicating with each merging flow path 31 are required, and there is an advantage that the substrate 30 becomes compact. PCBs may be dechlorinated using such a substrate.
[0048]
In the uppermost plate of the reactor 19 in FIG.
An inlet fluid coupling 19a communicating with 30b and an outlet fluid coupling 19b communicating with the outlet hole 32 are attached. A pipe of the first supply means is connected to the inlet fluid joint 19a communicating with the introduction hole 30a and the fluid A is supplied, and a pipe of the second supply means is connected to the inlet fluid joint 19a communicating with the introduction hole 30b. Then, the fluid B is supplied, and the outlet fluid coupling 19b is connected to a pipe for guiding the liquid discharged from the merging channel 31 to the outside of the stacked reactor 19, so that each channel of each substrate 30 is used in parallel. . In this way, the complexity of connecting the piping of each supply means for each substrate 30 is eliminated.
[0049]
By the way, the flow path width Dd of the merge flow path 31 needs to prevent the Na particles from easily clogging. The Na particle size is preferably finer from the viewpoint of reaction, and the average particle size is 20 μm or less, more preferably 10 μm or less. In reality, there are Na particles having a particle size distribution and larger than the average particle size. Therefore, the channel width Dd is preferably 100 μm or more, which is 10 times the average particle size that allows the maximum particle size to pass through the channel without any problem.
[0050]
By the way, in the dechlorination treatment of PCB which is a toxic substance, treatment under low temperature and low pressure is desirable from the viewpoint of preventing diffusion at the time of an accident in the treatment process. When the channel width Dd is reduced, the pressure loss increases, the pressure of the processing system increases, and the channel width Dd is preferably wider from the viewpoint of channel blockage.
[0051]
By the way, the molecular diffusion time in the flow channel is generally expressed by the following equation, and the shorter the diffusion time, the shorter the reaction time.
[0052]
[Expression 1]

[0053]
Since the diffusion coefficient of the reactant in the solvent is determined by the physical properties of the solvent and the solute, the diffusion coefficient is constant if the substances used are the same, and the diffusion time t is proportional to the square of the channel width Dd.
[0054]
FIG. 21 shows the relationship between the diffusion time ratio based on the diffusion time when the flow channel width Dd is 500 μm (0.5 mm).
[0055]
As the channel width is increased, the diffusion time becomes longer. When the channel width is 5 mm (5000 μm), the diffusion time is about 100 times that of 0.5 mm. In other words, it means that the flow path length needs to be 100 times to finish the reaction under the condition that the flow velocity of the fluid flowing in the flow path is constant.
[0056]
If the channel length required to complete the reaction with a channel width of 0.5 mm is 50 mm, a length of 5000 mm (5 m), which is 100 times greater, is required for a channel width of 5 mm.
[0057]
On the other hand, if it is smaller than 0.5 mm, a short flow path length is sufficient.
[0058]
Thus, if the flow path width Dd is widened to avoid blockage of the flow path, a long residence time is required to complete a desired reaction in the reactor. The size of the substrate 30 shown in FIG. 3 is about 100 mm × 40 mm, and it is not practical to form the merge flow path 31 of 5 m, and a flow path length of 5 m is formed with a flow path width of 5 mm. Requires a substrate with a larger area, increases the manufacturing cost, and requires a large installation space.
[0059]
Therefore, if the maximum width of the channel width Dd is 2.0 mm, the required length of the merge channel 31 is
It becomes about 800 mm and becomes a realistic flow path length. In particular, when space saving, manufacturing cost, etc. are not taken into consideration, the flow path structure of the reactor that ensures a flow path length satisfying a desired dehalogenation rate even with a wider flow path width may be used.
[0060]
If the flow path width Dd is constant, the diffusion time t is constant from Equation 1, and the reaction time is also constant. Therefore, in order to increase the throughput, the flow path width is constant and the flow path cross-sectional area is increased. It is effective to increase the aspect ratio (aspect ratio) by increasing the channel depth.
[0061]
FIG. 22 shows that the aspect ratio L / Dd of the merging channel 31 and the friction loss ratio in the reactor (based on the friction loss in the channel having an aspect ratio of 1 (square)) under the condition that the flow velocity in the channel is constant. Show the relationship. As the aspect ratio increases, the equivalent diameter also increases, so the friction loss also decreases. However, when the aspect ratio is 20 or more, the reduction width is small and the effect of reducing the friction loss is small. Therefore, the maximum flow path depth L of the merge flow path 31 is preferably a flow path depth corresponding to an aspect ratio of 20 that can be expected to reduce friction loss. In the case where the effect of reducing the pressure loss due to the increase in the aspect ratio is not expected, the flow path depth can be further increased to increase the processing amount.
[0062]
Therefore, the maximum channel depth of the reactor in the present invention is a maximum channel width of 2000 μm.
40000 μm which is 20 times, the minimum flow path depth is 100 μm which is the same as the minimum flow path width, and the flow path depth is preferably in the range of 100 to 40000 μm.
[0063]
By the way, in the reaction, the flow path portion from the junction 39 to the outlet becomes the reaction flow path. In this embodiment, the length of the merging flow path 31 that reciprocates the substrate 30 in order to secure a sufficient reaction time for the dehalogenation reaction is set, but a desired dehalogenation reaction rate (PCB after a desired reaction) is obtained. Concentration), that is, the length of the merged flow channel 31 that can secure the residence time for completing the dechlorination reaction, as shown in FIG. There is no problem even if the meandering flow path is two times shorter than the meandering flow path. When the flow path length is short, there is a merit that the pressure loss of the reactor section is reduced, the pump discharge pressure is reduced, and the reaction can be performed under a low pressure.
[0064]
3 to 5, the flow of the fluid B, that is, the PCB mixed solution, is branched. However, even if the fluid A and the fluid B are supplied by being exchanged, the reaction is not affected and the same effect can be obtained.
[0065]
6 is a multilayer reactor in which the substrates 30 having the flow channel structure of FIG.
19 is shown. FIG. 7 shows an AA cross section of FIG. The substrate 30 and the separator plate 40 on which the flow paths are formed are alternately laminated by a bonding means such as diffusion bonding, thereby increasing the number of merge flow paths 31 and increasing the processing amount per unit time.
[0066]
As shown in FIG. 8, the separator plate 40 is provided with introduction holes 30 a and 30 b and an outlet hole 32 through the plate at the same position as the substrate 30. However, the bottom plate 40a does not need a hole that does not penetrate or the hole itself.
[0067]
Here, the flow path formed in the substrate 30 penetrates the substrate 30, and the separators 40 are arranged above and below the substrate 30 to form a flow path.
[0068]
An inlet fluid coupling 19 a and an outlet fluid coupling 19 b are connected to the upper surface of the multilayer reactor 19. The fluids A and B flow from the inlet fluid coupling 19 a, and the introduction holes 30 a and 30 b communicate with the flow path 31. The fluid flows through each flow path.
[0069]
In particular, the introduction holes 30a and 30b and the outlet hole 32 are channels having a larger channel cross-sectional area than the channel of the merging channel 31 and are made smaller than the flow resistance in the merging channel 31 so that the merging channel of each layer The flow rate is evenly distributed to 31.
[0070]
In the case of the laminated body of FIG. 6, 10 flow paths 31 are formed. In other words, 10 times as many treatments can be performed in the same time as the reactor with the single flow path structure shown in FIG. It becomes possible.
[0071]
Although the number of the substrates 30 is five in this figure, the number of stacked layers is not limited to five.
[0072]
FIG. 9 is another embodiment of the stacked reactor 19 of FIG. 6, and an outlet fluid coupling 19b is disposed on the bottom surface. FIG. 10 shows an AA cross section of FIG.
[0073]
Since the outlet fluid coupling 19a is provided on the bottom surface of the reactor 19, the fluid is discharged without resisting gravity, so that Na particles having a density higher than that of mineral oil are less likely to stay in the outlet hole 32. There is a merit that it is hard to clog.
[0074]
FIG. 11 shows still another embodiment of the stacked reactor 19 of FIG. 6, in which an inlet fluid coupling 19a is disposed on the front surface and an outlet fluid coupling 19b is disposed on the rear surface. FIG. 12 shows an AA cross section of FIG. When the inlet and outlet fluid couplings 19a and 19b are provided on the front and back surfaces, respectively, the other stacked reactors can be arranged close to all four side surfaces of the reactor, and the stacked reactor 19 shown in FIGS. 6 and 9 is connected in parallel. There is an advantage of saving space compared to.
[0075]
Next, the usage amount, concentration, and the like of the Na dispersion, the IPA electrical insulating oil, which are reactive agents used in the present embodiment, will be described.
[0076]
Since the Na particles of the Na dispersion aggregate in the flow path 31 and block the flow path, the Na particle diameter and the Na concentration in the dispersion must be determined from both the flow path blockage and the reaction.
[0077]
In order to increase the surface area of Na, which is a reactant, and to accelerate the reaction, the Na dispersion is preferably made to have a small particle size and a large number of particles dispersed therein. The average particle size of Na is preferably 20 μm or less. Further, it is preferably 10 μm or less. Further, the reaction can be promoted by increasing the Na concentration in the Na dispersion, but when the confluence channel 31 of the reactor section is narrow, Na particles aggregate and the channel is blocked.
[0078]
When the channel width Dd is 100 μm to 2000 μm, the Na concentration in the Na dispersion to be fed to the reaction section is preferably 30% or less by weight. However, the reaction is slow when the Na concentration is low, and the flow path is likely to be clogged when the Na concentration is high. Further, the Na concentration is preferably 10% or more and 20% or less by weight.
[0079]
In order to prevent the clogging of the flow path by the reaction product after the reaction, IPA as a hydrogen donor is added to suppress the polymerization of the reaction products, but the chemicals necessary for dechlorinating these PCBs The processing cost decreases as the amount added decreases.
[0080]
It is desirable that the amount of IPA and Na used as hydrogen donors is close to the theoretical amount with respect to the number of chlorine (Cl) atoms of PCB, and excessive supply of IPA and Na is a cost in the dehalogenation treatment of PCB. Become high.
[0081]
In order to dechlorinate PCB and prevent polymerization between reaction products after dechlorination, hydrogen may be substituted after PCB is dechlorinated. That is, one hydrogen atom is required for one chlorine (Cl) atom bonded to the PCB.
[0082]
Therefore, the amount of IPA added that releases 1 mole of hydrogen atoms per mole of chlorine atoms is the theoretical amount and the minimum required amount.
[0083]
IPA is a monohydric alcohol in which one hydroxyl group (OH group), which is a functional group, is present in one molecule. One Na atom and one OH group react to produce an alkoxide, and at the same time, one hydrogen atom. discharge. Therefore, since 1 mol of hydrogen atoms is generated by 1 mol of IPA and 1 mol of Na, the case where the molar ratio of IPA / Cl is 1 is the theoretical amount.
[0084]
Therefore, the IPA / Cl molar ratio of 1 can theoretically suppress polymerization, but in order to prevent hydrogenation more reliably by supplying hydrogen, it is sufficient to add a molar ratio of 1 time or more which is a theoretical amount. Furthermore, since suppression of the amount of IPA used reduces the processing cost, it is preferable to set the addition amount in a molar ratio of 1 to 2 times the theoretical amount.
[0085]
IPA has one OH group, but polyhydric alcohols having two or more OH groups, such as ethylene glycol (two OH groups), release two hydrogen atoms with one molecule of ethylene glycol. When a hydrogen donor is selected, the addition amount may be a 1/2 molar ratio compared to IPA. Thus, when a polyhydric alcohol is selected as a hydrogen donor, the addition amount is small, and there is an advantage that the amount of waste liquid is reduced.
[0086]
Thus, the addition amount of the hydrogen donor that suppresses the polymerization between the products after the reaction is the presence of OH groups contained in one molecule of the hydrogen donor to be added with respect to the molar amount of chlorine contained in the organic halogen compound. More than the molar ratio of the reciprocal of the number. That is, for a monohydric alcohol containing one OH group in one molecule, hydrogen donor / Cl molar ratio = 1, for a dihydric alcohol containing two OH groups in one molecule, hydrogen donor / Cl molar ratio = 1 / In two or one molecule
For a trihydric alcohol containing three OH groups, the hydrogen donor / Cl molar ratio = 1/3.
[0087]
Examples of the hydrogen donor include alcohols, phenols, carboxylic acids, and water that readily generate hydrogen by reacting with Na. Particularly, alcohols that are liquid at room temperature and have an appropriate reaction with Na are desirable. As such alcohol, methanol, ethanol, modified alcohol, 1-propanol, isopropyl alcohol, butanol, pentanol, hexanol, isoamyl alcohol, ethylene glycol, cyclohexanol, propylene glycol, benzyl alcohol, and glycerin are preferable. In particular, isopropyl alcohol is most preferable in consideration of reactivity with Na, affinity with a solvent, and the like.
[0088]
The hydrogen donor may be used alone, or two or more types may be mixed, or a surfactant may be added to increase the affinity with the solvent.
[0089]
Thus, since IPA reacts with Na to generate hydrogen, Na is also consumed with the amount of IPA added.
[0090]
Therefore, the amount of Na necessary for PCB dechlorination, that is, the Na / Cl molar ratio, is required to be larger than the IPA / Cl molar ratio.
[0091]
By the way, in the dechlorination reaction with Na, one Na atom reacts with one chlorine (Cl) atom to become NaCl. Therefore, when the IPA addition amount is IPA / Cl molar ratio 1, the theoretical amount of Na necessary for dechlorination is Na / Cl molar ratio 2. Therefore, the Na dispersion and the PCB mixed solution may be supplied to the reactor so that the IPA / Cl molar ratio is 1 or more and the Na / Cl molar ratio is 2 or more.
[0092]
The amount of IPA and Na used is preferably a small amount in the vicinity of the theoretical amount that can suppress polymerization from the viewpoint of processing cost, the IPA / Cl molar ratio is preferably 1 to 10, and the Na / Cl molar ratio is preferably 2 to 20, The IPA / Cl molar ratio is preferably 1-2, and the Na / Cl molar ratio is preferably 2-5.
[0093]
The Na / Cl molar ratio may be determined in consideration of the amount of Na consumed reacting with IPA, and in the case of IPA / Cl molar ratio 1, Na / Cl molar ratio needs to be 2 or more, When the IPA / Cl molar ratio is 2, the Na / Cl molar ratio needs to be 3 or more. That is, the alkaline dispersion may be supplied to the reactor so that the Na / Cl molar ratio is one or more higher than the OH group / Cl molar ratio in the hydrogen donor to be added.
[0094]
In the present embodiment, Na (sodium) is selected as the alkali metal dispersed in the alkali dispersion, but not limited to this, potassium, lithium, or a compound thereof may be used.
[0095]
On the other hand, using less recyclable solvent has lower cost and space savings due to downsizing of the post-treatment tank, etc. However, if the amount of electrical insulating oil as the solvent is small, the reaction solid occupies the reaction liquid. The ratio of the product amount becomes large, and there is a risk of blockage of the flow path, and it cannot be extremely reduced from the viewpoint of the temperature rise of the fluid due to reaction heat.
The amount (flow rate) of PCB (organohalogen compound) in the total amount (total flow rate) of both the PCB mixed solution and Na dispersion is preferably 30% or less.
[0096]
As the above solvent, the solvent used for the Na dispersion and the solvent mixed with PCB are preferably the same substance or those having good affinity, and kerosene, mineral oil, electrical insulating oil, trans oil, paraffin and the like are particularly preferable. Particularly preferred are electrical insulating oils, mineral oils and transformer oils having a high boiling point and good fluidity.
[0097]
The above solvents may be used alone, or two or more kinds may be mixed, or a surfactant may be added to enhance the affinity with the organic halogen compound and the hydrogen donor.
[0098]
According to the present invention, the effect of accelerating the reaction rate of dehalogenation by alkali metal without supplying heat to the reactor from the outside can be obtained, and at the same time, the flow path by polymerization of the reaction product by releasing hydrogen from the hydrogen donor. Clogging can be prevented, and dehalogenation treatment can be continuously performed using an alkali dispersion.
[0099]
Furthermore, by utilizing the heat of reaction between the hydrogen donor and Na, it is not necessary to promote the reaction by heating the PCB mixed solution and Na dispersion as in the prior art, and the input energy is less than that of the conventional treatment method, It becomes energy saving.
[0100]
Especially in winter, the viscosity of the supplied fluid increases due to a decrease in the outside air temperature, so the fluid may be heated. However, the temperature can be raised at a lower temperature than before, and the merit of energy saving remains the same.
[0101]
Also, if the temperature of the fluid does not become high even during the dehalogenation reaction in the reactor, there is no need to cool the reactor part during the dechlorination reaction, no temperature control is required, and no complicated temperature control is required. Dehalogenation is possible with energy saving, space saving and low cost.
[0102]
Furthermore, in the case of a small amount of PCB processing, since the reactor and incidental equipment can be further reduced in size, it is also possible to transport the processing equipment, extract the PCB directly from the stored high-voltage capacitor, etc., and process it at the storage site. . Processing at the storage site does not require the PCB to be transported to the processing facility.
There is an advantage that the risk of PCB diffusion is reduced.
[0103]
Thus, a mixed solution in which an organic halogen compound and at least one hydrogen donor are mixed, or a mixed solution in which at least one solvent is mixed in the mixed solution, and an alkali metal dispersion in which an alkali metal is dispersed are provided. By continuously supplying a reactor having a confluence channel having a confluent fine channel, dehalogenation is possible without blocking the channel.
[0104]
In particular, the halogenated organic halogen compound can be more reliably dehalogenated because the combined flow path in the reactor has a length longer than the flow path necessary for obtaining a desired decomposition rate.
[0105]
In addition, a mass reactor can be realized by using a multilayer reactor in which the reactors are stacked in multiple layers and increasing the number of flow paths.
[0106]
A second embodiment of a processing apparatus for dehalogenating an organic halogen compound according to the present invention will be described with reference to FIGS. FIG. 13 is a schematic flow diagram of a dehalogenation processing system, FIG. 14 is an embodiment in which the flow of FIG. 13 is made into a specific hardware configuration, and FIGS. 15 and 16 are flow paths of a reactor formed on a substrate. The configuration is shown.
[0107]
FIG. 13 shows a schematic flow diagram in the present embodiment. As shown in FIG. 13, the reactor 19 has a premixing function of PCB, IPA, and electric insulating oil in addition to the reaction, and is characterized in that the premixing 5 of FIG. 1 is performed in the reactor. Furthermore, the figure also shows a post-treatment step after dehalogenation.
[0108]
The fluid B1, which is the organic halogen compound 2, the fluid B2, which is the solvent 3, and the fluid B3, which is the hydrogen donor 4, are supplied to the reactor 6, and are premixed in the reactor 6 with the fluid A which is the alkali metal dispersion 1. The dehalogenation reaction is performed by joining in the reactor.
[0109]
The reaction liquid C discharged from the reactor 6 after the dechlorination reaction in the reactor 6 confirms the dehalogenation treatment of the organohalogen compound as the material to be treated, and then treats the alkali metal of the alkali metal dispersion 1 supplied in excess. After being subjected to a post-treatment comprising an excess alkali metal treatment 7 and neutralization 8 to neutralize the alkaline solution, it becomes liquid D, separated into exhaust gas 9 and waste liquid 10 (waste oil, waste water, etc.) and appropriately disposed or recycled.
[0110]
For separation of waste oil and water, stationary separation due to density difference, centrifugation, separation membrane, etc. can be used.
[0111]
The flow in FIG. 13 includes post-processing steps. However, in the case of only dehalogenation processing as shown in FIG. 1, these post-processing are not necessary, and the post-processing method is not limited to these. .
[0112]
FIG. 14 shows a second embodiment in which the flow of FIG. 13 has a specific hardware configuration. In order to perform premixing of each fluid of PCB 14, mineral oil 15, and IPA 16 in the laminated reactor 19, each fluid is directly supplied to the laminated reactor 19 by a pump (not shown). Therefore, the premixing tank 17, the stirrer 18, the pump (not shown) and the like shown in FIG. 2 are not necessary, and there is a merit of saving space and energy.
[0113]
The reacted liquid C discharged from the stacked reactor 19 after receiving the dechlorination reaction in the stacked reactor 19 enters the post-treatment tank 20, where the excess alkali metal treatment 7 of the excessively supplied Na and the alkaline solution are neutralized. A post-treatment consisting of neutralization 8 is performed.
[0114]
Thereafter, the waste liquid after treatment is separated into waste oil, waste water, reaction product NaCl, PCB, dechlorinated biphenyl, etc., and disposed or recycled. Specifically, the excessive alkali metal treatment 7 of the excessively supplied Na is supplied with water 23 into the post-treatment tank 20, reacting Na with water, and treating the active Na into a more inert caustic soda (NaOH) or the like. To do. Further, for the treatment of the neutralization 8, hydrochloric acid, carbon dioxide gas or the like serving as the neutralizing agent 24 is supplied to neutralize the alkaline solution and the alkaline substance. Aftertreatment and reactor
The gas generated by the reaction 19 is sucked and exhausted from the post-treatment tank 20 through the activated carbon filter 21 by the blower 22.
[0115]
In the case of a Na dispersion, active Na is dispersed in a solvent such as mineral oil and does not react directly with air because it does not come into direct contact with air. However, for safety, the Na dispersion container 11 and the post-treatment tank 20 are inert gases. An atmosphere is preferable. Nitrogen (N ₂ ), Argon or the like is used.
[0116]
FIG. 15 and FIG. 16 show a flow path configuration formed on the substrate 30 which is a constituent member of the multilayer reactor 19 of FIG.
[0117]
An introduction hole for premixing PCB 14, mineral oil 15, and IPA 16 in the substrate 30
33, 34, 35 and three flow paths connected to each of the introduction holes 33, 34, 35, and a meandering path premixed flow path connected at a junction where the three flow paths merge at one place
36, and the premixing flow path 36 is connected to two slanting straight flow paths b, and each flow path b is connected to the flow path a at a junction 39. Other configurations of the substrate are the same as those in FIG. In this case, the PCB 14 is introduced into the introduction hole 33, the PCB 14 passes through the fourth flow path 14 a formed in the substrate of the reactor 19, the IPA 16 is introduced into the introduction hole 35, and the IPA 16 is formed on the substrate of the reactor 19. The mineral oil 15 is introduced into the introduction hole 34 through the fifth flow path 16a, and the mineral oil 15 passes through the remaining one of the three flow paths 15a formed on the substrate of the reactor 19, and the PCB 14 The IPA 16 and the mineral oil 15 join together at the connecting portion with the premixing flow path 36 and start mixing.
[0118]
In particular, in the case of the substrate of FIG. 16, the premixing flow path 36 is branched in the middle and connected to each flow path a at each joining portion 39. The other structure of the substrate is the same as FIG.
[0119]
When such a substrate is used, PCB 14, mineral oil 15, and IPA 16 are sufficiently mixed in the premixing channel 36, and the mixed solution is guided to the junction 39, and the Na dispersion from the channel a They react while mixing in the confluence channel 31 and are continuously discharged from the outlet hole 32. The premixing flow path 36 is meandered so as to have a flow path length sufficient for sufficiently mixing the PCB 14, mineral oil 15, and IPA 16, but is not limited to the flow path shapes of FIGS. 15 and 16. .
[0120]
According to the present embodiment, since the PCB 14, the mineral oil 15, and the IPA 16 are mixed in the flow path in the reactor 19, the mixing and mixing tank 17, the stirrer 18, and the pump (not shown) are compared with the mixing outside the reactor. Has the advantage of saving space and saving energy.
[0121]
A third embodiment of a processing apparatus for dehalogenating an organic halogen compound according to the present invention will be described with reference to FIGS. FIG. 17 is a schematic flow diagram of a processing system for dehalogenation, FIG. 18 is an embodiment in which the flow of FIG. 17 is made into a specific hardware configuration, and FIGS. 19 and 20 are on the substrate 30 of the stacked reactor 19. The formed channel configuration is shown.
[0122]
FIG. 17 shows a schematic flow chart in the present embodiment. As shown in FIG. 17, the reactor 6 has a post-treatment function in addition to premixing and reaction, and is characterized in that the excess alkali metal treatment 7 and neutralization 8 that are post-treatments of FIG. 13 are performed in the reactor. is there. The rest is the same as the flowchart of FIG. This excess alkali metal treatment 7 reacts sodium in the reactor with water to turn active sodium into less caustic soda (NaOH), and corresponds to an inactivation treatment of a fluid containing sodium. In the treatment of neutralization 8, caustic soda (NaOH) has a strong alkali property, so an alkaline solution or an alkaline substance neutralized by adding an acid such as hydrochloric acid as a neutralizing agent to a fluid subjected to excess alkali metal treatment 7. Is neutralization treatment.
[0123]
FIG. 18 shows an embodiment in which the flow of FIG. 17 has a specific hardware configuration. In the present embodiment, water and a neutralizing agent used in the treatment of the excess alkali metal treatment 7 and the neutralization 8 are directly supplied to the laminate type reactor 19, and the post-treatment is performed in the reactor. The fluid discharged from the reactor 19 has been post-processed, and the fluid discharged from the reactor 19 is separated into gas and liquid by the gas-liquid separator 25. Since the post-processing is performed in the reactor 19, the post-processing tank 20 and the stirrer for stirring the processing liquid in the post-processing tank 20 shown in FIG. Other configurations are the same as those in FIG.
[0124]
17 and 18 show a processing flow and a hardware configuration in which the excessive alkali metal treatment 7 and neutralization 8 are performed in the reactor, but only the excessive alkali metal treatment 7 can be performed in the reactor 6. It is. In this case, a post-treatment tank 20 as shown in FIG. 14 is necessary, but the stirring time can be shortened, and there is an advantage that PCB can be treated with energy saving as compared with the first embodiment.
[0125]
FIGS. 19 and 20 show a flow path configuration formed on the substrate 30 which is a component of the stacked reactor 19 of FIG. The substrate 30 is provided with introduction holes 33, 34, 35 for introducing the PCB 14, mineral oil 15, and IPA 16 into the substrate, three flow paths connected to the introduction holes 33, 34, 35, and the three One end of a meandering path-shaped premixing flow path 36 is connected to a portion where the flow paths merge, and the other end of the premixing flow path 36 is connected to two slanted straight flow paths b. b is connected to the flow path a at a junction 39.
[0126]
A merge channel 31 is connected to the merge section 39. On the downstream side of the merging channel 31, a reaction channel 37a is connected continuously to the merging channel, and a reaction channel 37b is connected to the reaction channel 37a. The downstream end of the reaction channel 37a is An outlet hole 32 is connected.
[0127]
The substrate 30 is provided with a water introduction hole 37 and a neutralizing agent introduction hole 38, and the introduction hole 37 is connected to the reaction flow path 37 b and the introduction hole 38 is connected to the reaction flow path 37 b. Generally, the flow path between the introduction hole 37 and the introduction hole 38 is a reaction flow path 37a, and the introduction hole 38 and the exit hole are generally provided.
The flow path between them is called a reaction flow path 37b. These reaction flow path 37a and reaction flow path 37b are formed as meander paths on the substrate as a sixth flow path.
[0128]
The PCB 14, the mineral oil 15, and the IPA 16 introduced into each of the introduction holes 33, 34, and 35 are mixed in the premixing flow path 36 to become the liquid B of the PCB mixed solution and go to the junction 39. On the other hand, the Na dispersion introduced into each flow path a from the introduction hole 30 a goes to the junction 39 as the fluid A. Both fluids A and B join and mix at the junction 39 and react with each other, and the PCB 14 is subjected to dechlorination treatment. The mixed liquid after the joining enters the reaction channel 37a with the reaction product as the reacted liquid C. Flowing. In the reaction channel 37a,
Na reacts with the water introduced from the introduction hole 37 and is produced into NaOH, and the reacted liquid C containing NaOH enters the reaction flow path 38a and is neutralized with hydrochloric acid introduced from the introduction hole 38 and post-treated. The liquid D is continuously discharged from the stacked reactor 19 through the outlet hole 32 together with the exhaust gas. Other configurations are the same as those in FIGS. 15 and 16.
[0129]
The reaction flow paths 37a and 38a are not limited to the flow path shapes shown in FIGS. 19 and 20 as long as the flow paths are necessary for the post-treatment reaction.
[0130]
According to the present embodiment, the post-treatment tank 20 and the stirrer (not shown) are not required, and there is a merit that further space saving and energy saving can be achieved compared to the second embodiment.
[0131]
In any embodiment, the organic halogen compound can be efficiently dehalogenated without clogging the flow path with alkali metal particles and reaction products, and without heating the reactor section with a heater or the like from outside. can do.
[0132]
In any of the examples, the alkali metal dispersion, the organic halogen compound, the hydrogen donor, and the solvent are continuously supplied to the reactor to continuously dechlorinate the organic halogen compound. The dechlorinated liquid can be discharged from Therefore, the reaction efficiency of the reactor can be fully enjoyed.
[0133]
Hereinafter, a test example in which an organic halogen compound is dechlorinated using an alkali metal dispersion and a comparative example for comparison with the test will be introduced.
[0134]
Test examples are as follows. That is, 10g of metallic sodium (Na)
50 g of a dispersion (Na concentration: 10 wt%, average particle size: about 10 μm) dispersed in 90 g was placed in a container while stirring, while 38 g of mineral oil as a solvent and 1,2,4-trimethyl as an organic halogen compound. 2 g of chlorobenzene (TCB) and 4 g of isopropyl alcohol (IPA) as a hydrogen donor were sufficiently stirred and mixed. TCB has a structure in which three chlorine atoms are attached to the benzene ring, and three moles of chlorine (Cl) are present per mole of TCB. The amount of the organic halogen compound was about 5% with respect to the amount of the solvent, and IPA was added in such an amount that the IPA / Cl molar ratio was about 2. Both liquids and the reaction part were fed to the reactor with a metering pump under the condition of room temperature without being heated by a heater. The sodium dispersant was fed to the reactor at a flow rate such that the Na / Cl molar ratio was about 5.
[0135]
For the reaction test, a reactor having a flow path configuration shown in FIG. 3 was used. The reactor channel width is
The channel length is 500 μm, the channel depth is 500 μm, and the channel length from the junction to the outlet is about 350 mm. The flow rate at the junction is about 1 ml / min, and the residence time of the junction channel is about 5 s. In the reactor, a stainless steel plate having a thickness of 500 μm, which was processed with a wire cut, was joined to the top and bottom of the stainless steel plate by diffusion bonding using the same stainless steel plate to form one reaction channel.
[0136]
According to this test example, the dehalogenation reaction was promoted by the reaction product without clogging the flow path and by the reaction heat of IPA and Na, and the reactor portion was about 20000 ppm before the reaction without heating. The TCB concentration was below the detection limit (0.05 ppm) after the reaction, and almost complete dechlorination was possible.
[0137]
The comparative examples are as follows. That is, 20g of metallic sodium (Na)
50 g of a dispersion (Na concentration: 20 wt%, average particle size: about 10 μm) dispersed in 80 g was placed in a container while stirring, while 28.5 g of mineral oil serving as a solvent and 1,2,4 being an organic halogen compound. -1.5 g of trichlorobenzene (TCB) was sufficiently stirred and mixed to prepare a mixed solution having a TCB concentration of 5%.
[0138]
The sodium dispersant and the TCB mixture were sent to the reactor at a flow rate such that the Na / Cl molar ratio was about 15.
[0139]
A glass reactor was used for the reaction test. The flow path width of the reactor is 500 μm, the flow path depth is 500 μm, and the flow path length from the junction to the outlet is about 60 mm. The reactor was housed in an oven and the entire reactor was heated to about 130 ° C. The flow rate at the junction is about 1 ml / min, and the residence time of the junction channel is about 1 s.
[0140]
According to this comparative example, by heating the reactor without adding the hydrogen donor IPA, the TCB concentration, which was about 20000 ppm before the reaction, becomes the detection limit value (0.05 ppm) or less after the reaction, Almost complete dechlorination was possible. However, due to polymerization of the reaction product, the reactor flow path was blocked several minutes after the start of the test, and fluid could not be supplied.
[0141]
【The invention's effect】
As described above, according to the present invention, alkali metal particles and reaction products can be used for the reactor. Fine The organic halogen compound can be dehalogenated without blocking the channel.
[Brief description of the drawings]
FIG. 1 is a process flow diagram of a first embodiment of the present invention.
FIG. 2 is a hardware configuration diagram of the first embodiment of the present invention.
FIG. 3 is a flow path configuration diagram of a reactor in the first embodiment of the present invention.
FIG. 4 is a flow path configuration diagram of another reactor that can be employed in the first embodiment of the present invention.
FIG. 5 is a flow path configuration diagram of still another reactor that can be employed in the first embodiment of the present invention.
FIG. 6 is a perspective view of a laminate type reactor.
7 is a cross-sectional view taken along line AA in FIG.
FIG. 8 is a plan view of a separator constituting the laminated reactor.
FIG. 9 is a perspective view of another laminated reactor.
10 is a cross-sectional view taken along the line AA in FIG.
FIG. 11 is a perspective view of still another stacked reactor.
12 is a cross-sectional view taken along the line AA in FIG.
FIG. 13 is a processing flowchart of the second embodiment of the present invention.
FIG. 14 is a hardware configuration diagram of a second embodiment of the present invention.
FIG. 15 is a flow path configuration diagram of a reactor in a second embodiment of the present invention.
FIG. 16 is a flow path configuration diagram of another reactor that can be employed in the second embodiment of the present invention.
FIG. 17 is a processing flow diagram according to the third embodiment of the present invention.
FIG. 18 is a hardware configuration diagram of a third embodiment of the present invention.
FIG. 19 is a flow path configuration diagram of a reactor in a third embodiment of the present invention.
FIG. 20 is another flow path configuration diagram that can be employed in the third embodiment of the present invention.
FIG. 21 is a graph showing the relationship between the diffusion time and the channel width Dd.
FIG. 22 is a graph showing the relationship between in-reactor friction loss and aspect ratio.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 ... Alkali metal dispersion, 2 ... Organohalogen compound, 3 ... Solvent, 4 ... Hydrogen donor, 6 ... Reactor, 7 ... Excess alkali metal treatment, 8 ... Neutralization.

Claims (6)

A hydrogen donor that reacts with the alkali metal dispersion, the organic halogen compound, and the alkali metal dispersion to donate hydrogen is introduced into a fine channel formed on a substrate of the reactor, and the organic halogen is introduced in the fine channel. A method for treating an organic halogen compound, comprising performing a dehalogenation treatment of a compound. A first micro flow path and the second fine flow path, the said first fine flow path of the reactor having a third fine flow path that is contacted with the first micro flow path and the second micro flow path Supplying an alkali metal dispersion,
Supplying a hydrogen donor that reacts with the organic halogen compound and the alkali metal dispersion to donate hydrogen to the second fine channel;
Wherein in said third micro flow channel by introducing the alkali metal dispersion and the organic halogen compound and the hydrogen donor from the first micro flow path and the second micro-flow path to the third microchannel A method for treating an organic halogen compound, comprising performing a dehalogenation treatment of an organic halide. 3. The organic material according to claim 2, wherein at least one of an alkali metal deactivation process and a neutralization process is performed on the fluid containing the reaction product generated in the third fine channel. Halogen compound treatment method. A first fine channel for guiding the alkali metal dispersion; a second fine channel for guiding a hydrogen donor that reacts with the organic halogen compound and the alkali metal dispersion to donate hydrogen; the first fine channel and the second a reactor and a third fine flow path in which the alkali metal dispersion in communication with the fine flow path, wherein the organic halogen compound and hydrogen donor is introduced,
A first supply means for supplying the alkali metal dispersion to said first micro flow path is connected to the first micro flow path,
And second supply means for supplying said organohalogen compound to the second micro flow path and the hydrogen donor is connected to the second micro-flow path,
An organic halogen compound processing apparatus comprising: First micro flow path for guiding the alkali metal dispersion, organic halogen compounds and alkali metal dispersion and react with a second fine flow path for guiding the hydrogen donor to donate a hydrogen, and the first fine flow path and the second a reactor having a third fine flow path in which the alkali metal dispersion in communication with the fine flow path, wherein the organic halogen compound and the hydrogen donor is introduced,
A first supply means for supplying the alkali metal dispersion to said first micro flow path is connected to the first micro flow path,
Mixing means for mixing the organic halogen compound and the hydrogen donor outside the reactor;
Second supply means for supplying the fluid mixed by the mixing means to the second fine channel;
An organic halogen compound processing apparatus comprising: 6. The processing apparatus according to claim 4 or 5 , wherein the processing apparatus performs at least one of an alkali metal deactivation process and a neutralization process on the fluid that has flowed out of the reactor through the third fine channel. Organic halogen compound processing equipment.

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