JP3544834B2 - Mixed waste treatment equipment - Google Patents

Description

このように表１から、実験例１〜１６の処理により、回路基板に含まれる鉛がほぼ完全に（例えば実験例１では、処理後の鉛の含有濃度が ０．００４％であり、除去率は９９．９％）除去されることがわかった。また実験例１において、銅の回収部で回収されるＣｕリッチ粉を定量して銅の回収率を調べたところ、回路基板に含まれる銅の約８５ｗｔ％を回収することができた。
【００７８】
実験例１７
まず、この実験例に用いる装置のハンダの分離除去槽について説明する。
【００７９】
この装置では、図１２に示すように、ハンダの分離除去槽５９が、振動発生器７４が付設されたチェーンコンベアー７５と、キャリアガスである空気７６と酸化性ガスであるオゾン７７との混合ガスの噴射口７８、および余分のガスの排出口７９とを備えており、２つ開閉扉を設けたバッチ式入り口部８０から搬入された廃回路基板６３が、チェーンコンベアー７５に吊り下げられて移動してゆき、移動過程で、空気とオゾンとの混合ガスの吹き付けおよび振動により、金属（銅）に対する濡れ性が低下したハンダが振り落とされ、落下したハンダが、ハンダ回収槽８１に回収されるようになっている。なお、このようなハンダの分離除去部を除いてその他の部分は、図１１に示す装置と同様に構成されている。
【００８０】
次いで、この装置を用いて、実験例１〜１６と同じ廃回路基板を、 ２３０℃の温度に加熱処理した。ハンダの分離除去槽５９から排出される回路基板を取り出して鉛の含有率（濃度）を調べたところ、２００ｐｐｍ（０．０２ｗｔ％）であり、鉛の除去率は９９．５％であった。また、銅の回収部で得られるＣｕリッチ粉を定量して銅の回収率を調べたところ、回路基板に含まれる銅の約８５ｗｔ％を回収することができた。実験例１８
回路基板上のハンダを電気化学的に分離除去し銅等を回収する方法について説明する。
【００８１】
この方法では、まず前処理工程で、廃回路基板からネジ止めコネクター類や実装された半導体部品を分解分離した後、図１３に示すように、ハンダ溶解銅回収工程において、この廃回路基板８２を、銅イオンを含有する電解液８３例えば硝酸銅水溶液中に浸漬し、ブラシ型電極８４を用いて電解を行ない、回路基板８２に付着したハンダを溶解するとともに、白金等の電極８５に銅イオンを析出させて回収する。次いで、中間処理工程において、ハンダが分離除去された回路基板に対して、破砕、粉砕、研磨等の処理を行なう。この工程は、例えば多層板において、銅が表面に十分に露出してしない場合などに有効である。
【００８２】
次いで、銅溶解ハンダ回収工程において、図１４に示すように、中間処理が施された回路基板８２を、ハンダ溶解液８６例えば硝酸鉛および硝酸スズの水溶液中に浸漬して電気分解を行ない、回路基板上の銅を溶解するとともに、白金等の電極８５に鉛およびスズイオンを析出させて回収する。なお、ハンダ溶解銅回収および銅溶解ハンダ回収工程では、回路基板との良好な接続のために、や導電性シートが使用される。最後に後処理工程において、処理後の基板樹脂および／またはガラス繊維を回収する。こうして回収された基板樹脂やガラス繊維は、金属成分が高い効率で除去されており、極めて付加価値が高い。
【００８３】
なお、ハンダ溶解銅回収工程において、電気回路に発生する電力は、蓄電池に回収することができ、これを安定化電源を通して電圧を調整した後、銅溶解ハンダ回収工程において、電気分解の補助電源として利用することができる。
【００８４】
次に、この方法を用いて、廃回路基板の処理を行なった。
【００８５】
すなわち、コネクター類や実装部品を分離した廃回路基板に白金製ブラシ形状の電極を接触させて、 ０．５モル／ｌの硝酸銅水溶液中に浸漬し、さらに同じ電解液中に白金板電極を浸漬した。この時点での基板からのハンダの溶解は遅いが、白金板電極とブラシ状電極とを電気的に接続すると、これらを正極、負極とする起電力が生じ、白金板電極上に銅が析出し始めるとともにハンダの溶解が加速された。電気回路中に発生した起電力は約０．４７Ｖ であり、銅の析出はハンダが全て溶出するまで続いた。白金板電極上に析出した銅を回収したところ、純度９９％以上の高純度銅が得られた。
【００８６】
次いで、銅が析出した白金板電極を新しい白金板電極に取替え、電気回路中に安定化電源を設置した。安定化電源を接続し電圧を与えたところ、電気分解により白金板電極上に鉛が析出し始めるとともに、ブラシ型電極に接触した廃回路基板上の銅が溶解し始めた。さらに電気分解を継続すると、スズが白金板電極上に析出した。白金板電極上に析出した鉛およびスズを回収して重量を測定したところ、廃基回路板上に付着していたハンダの９９％以上が回収されたことがわかった。
【００８７】
実施例６
次に、前処理工程でハンダが分離除去された回路基板の廃棄物に対して、図７に示す装置により、有機溶剤としてエチレンジアミンを用いて溶剤処理を行ない、樹脂溶解液を得た。得られた溶解液から成分をテトラヒドロフランを使用して抽出し、ゲルパーミエイションカラムにより精製し、平均分子量 ７００の樹脂由来の成分を回収した。この回収成分を凝集剤として用い、サンプルとしてアジピン酸ナトリウムの ５ｗｔ％液を処理したところ、アジピン酸ナトリウムは凝集沈殿して ０．５％以下の濃度にすることができ、凝集剤として有用であることが確認できた。また、溶剤処理後、樹脂溶解液から分離された基板からは、高品質のガラス繊維等の無機成分を容易に分離回収することができた。
【００８８】
実施例７〜２４
表２に示す樹脂廃棄物（充填剤等の無機物を含有する。）を、同表に示す粒径に粉砕した後、エチレンジアミン（ＥＤ）、イミダゾール（Ｉ）、ピリジン（Ｐ）、ジメチルホルムアミド（ＤＭＦ）、ジメチルスルホキシル（ＤＭＳ）、Ｎ−メチル −２−ピロリドン（ＮＭＰ）、１，３−ジメチルイミダゾリジノン（１，３−ＤＭＩ）、１，４−ジメチルイミダゾリジノン（１，４−ＤＭＩ）、１，５−ジメチルイミダゾリジノン（１，５−ＤＭＩ）、１，６−ジメチルイミダゾリジノン（１，６−ＤＭＩ）の各有機溶剤と混合し、樹脂分を溶解した。溶解は、表２に示す温度に加熱し、回転羽根で撹拌しながら行なった。次いで、樹脂溶解液から沈殿法により残渣を分離除去した後、残渣が分離された樹脂溶解液から蒸留により溶剤を分離し、樹脂由来の有機成分を回収した。
【００８９】
こうして回収された有機成分に、表２に示す架橋剤を加えて硬化させたところ、それぞれ成形体が得られ、再利用することができた。また、樹脂溶解液から分離された残渣は、表２に示す新たに成形された樹脂に混合することができ、充填剤としての再利用が十分に可能であった。
【００９０】
【表２】

実施例２５
前処理工程でハンダが除去され実装部品が取り外された後の廃回路基板に対して、超臨界状態の水等を用いて回路基板を構成する熱硬化性樹脂を溶解し、金属銅等を回収した。
【００９１】
まず、樹脂溶解装置について説明する。
【００９２】
この装置は、図１５に示すように、回路基板の粉砕装置８７と、基板砕成物と水とを混合したスラリーを昇圧して輪送する混合物輪送ポンプ８８と、水を昇圧して輪送・供給する水ポンプ８９と、酸化剤を昇圧して輪送・供給する酸化剤ポンプ９０と、水と酸化剤との混合物を加熱昇温する熱交換器９１と、この混合物とスラリー状の被処理物とを収容して反応させるヒータ付き反応管９２および冷却器９３と、背圧弁９４とを備えている。なお、装置各部は、ステンレス鋼、チタン、ハステロイ、インコネルのような、耐熱および耐圧性を有し高い耐腐食性を有する材料により構成することが望ましい。
【００９３】
この装置において、基板投入口から供給された回路基板は、粉砕装置８７により粉砕される。粉砕装置としては、例えば粗砕機であるシュレッダーや咀砕機や旋動破砕機、中間粉砕機であるカッターミルやロール粉砕機やコーン粉砕機やハンマーミル、微粉砕機であるボールミルや振動ボールミルなどが挙げられる。基板砕成物は、直ちに水と混合されてスラリー状の混合物となり、混合物輪送ポンプ８８により昇圧、輪送される。
【００９４】
他方、水ポンプ８９により昇圧され輪送された水に、酸化剤ポンプ９０により昇圧され輪送された空気、酸素または過酸化水素等の酸化剤が混合される。そして、熱交換器９１を経て昇温された後、混合体輪送ポンプ８８により輪送されたスラリー状の混合物と合流し、次いでヒータ付き反応管９２に入る。この反応管９２内部の圧力は、ポンプと背圧弁９４とにより制御されるようになっている。ヒータ付き反応管９２内で、水の臨界点である３７４．２℃、２２．１Ｍｐａ以上の温度および圧力に加熱・加圧されることで、流体中の樹脂成分が迅速に分解し溶解される。反応管を出た混合物は、熱交換器９１により冷却され、続いて冷却器９３によりさらに冷却された後、背圧弁９４を通過して減圧され、出口で回収される。
【００９５】
このような装置を用いて、ハンダ溶融と表面研磨により実装部品とハンダをそれぞれ除去した回路基板を、該回路基板に含まれる樹脂の完全酸化に必要な量の２倍の過酸化水素水を酸化剤として用いて溶解処理した。粉砕装置８７としては、旋動破砕機とロール粉砕機と振動ボールミルとを組み合わせたものを用い、平均粒径３００μｍまで微粉砕した。ヒータ付き反応管９２での処理温度および圧力は、入口部分において、３８０℃、２４Ｍｐａとし、反応管中における滞留時間は３０分に調節した。処理後の混合物をろ過し、銅とガラス繊維を回収した。ろ過後の溶液中の全有機炭素を測定したところ、濃度は１５ｐｐｍ以下であった。また、濾過前の混合物中のダイオキシン類を分析したところ、検出限界以下であった。
【００９６】
実施例２６
図１５に示す装置を用い、実施例２５と同様に前処理を行なった回路基板を溶解処理した。粉砕装置８７としては、旋動破砕機とロール破砕機とを組み合わせたものを用い、ヒータ付き反応管９２での処理温度および圧力は、 ３００℃、 １０Ｍｐａとした。処理後の混合物から固形分を分離し電気炉で乾燥させたところ、ガラス繊維は脆性化していなかった。実施例２４と同様にボールミルによりガラス繊維分を粉砕し、同じ篩で分別して篩上残留成分の組成を分析したところ、銅純度は８１％であった。
【００９７】
実施例２７
ハンダ溶融と表面研磨により実装部品とハンダとをそれぞれ除去した回路基板から、２４．５ｍｍ四方を切り出したものを、内容積 １２２ｃｃの圧力容器と電気炉から構成された回分式の装置を用いて溶解処理した。被処理片と３８．４ｃｃの水とを圧力容器に投入し、密閉して ３８０℃、２４Ｍｐａ の反応条件で ２時間処理した。処理後の基板片を観察したところ、各層はピンセットで容易に剥離することができ、銅箔とガラス繊維とを手で選別することができ、かつガラス繊維は脆性化していた。
【００９８】
比較例
図１５に示す装置を用い、実施例２５と同様に前処理を行なった回路基板を溶解処理した。粉砕装置８７としては、旋動破砕機とロール破砕機とを組み合わせたものを用い、ヒータ付き反応管９２での処理温度および圧力は、 １５０℃、０．５Ｍｐａとした。処理後の混合物から固形分を分離し電気炉で乾燥させた後、実施例２４と同様にボールミルによりガラス繊維分を粉砕し、同じ篩で分別して篩上残留成分の組成を分析したところ、銅純度は４４％であった。
【００９９】
実施例２８
前処理工程でハンダが除去され実装部品が取り外された後の廃回路基板に対して、超臨界状態の水等を用いて回路基板を構成する熱硬化性樹脂を溶解し、金属銅等を回収した。
【０１００】
まず、樹脂溶解装置について説明する。
【０１０１】
この装置は、図１６に示すように、基板砕成物と水とを混合した混合体を溜め置く供給槽９５と、開閉バルブＡ９６と、高圧容器Ａ９７と、開閉バルブＢ９８と、水を昇圧して輪送・洪給する高圧ポンプＡ９９と、同じく水を昇圧して輪送・供給する高圧ポンプＢ１００と、水を加熱昇温する熱交換器１０１と、水と混合体とを収容して反応させるヒータ付き反応管１０２と、冷却器１０３と、分離器１０４と、背圧弁１０５と、高圧容器Ｂ１０６と、開閉バルブＣ１０７と、開閉バルブＤ１０８と、開閉バルブＥ１０９および水ボンプ１１０を備えている。なお、装置各部は、ステンレス鋼、チタン、ハステロイ、インコネルのような、耐熱、耐圧性を有し高い耐腐嚢性を有する材料により構成することが望ましい。
この装置において、供給槽９５に溜め置かれている基板砕成物と水との混合体のうち、比重が水より大である基板砕成物が、開閉バルブＡ９６と開閉バルブＢ９８の開閉により、重力沈降によって高圧ポンプＡ９９の吐出側の配管に流れ込む。高圧容器Ａ９７中には常時水が満たされている。開閉バルブＡ９６が開の場合は開閉バルブＢ９８を閉とすることにより供給槽９５内部を特に加圧すること無しに基板砕成物を高圧容器Ａ９７に沈降させ、その後開閉バルブＡ９６を閉に、開閉バルブＢ９８を開とすることによって、高圧容器Ａ９７は瞬時に高圧ボンプＡ９９吐出側と同じ高圧条件下におかれ、基板破成物は沈降して吐出側の配管中に流れ込む。この手順を繰り返し行うことによって、基板砕成物を問欠的に高圧の場に注入できるのであるが、この方法によれば、高圧ポンプで直接、基板砕成物を輪送する場合とは異なり、ポンプの摩耗および閉塞が生じず、なおかつポンプを通過させるために基板砕成物を微粉砕する必要もなくなる。
【０１０２】
他方、高圧ポンプＢ１００により昇圧された水は、熱交換器１０１を経て昇温された後、別系統の基板砕成物と水からなる流れと合流し、次いでヒータ付き反応管１０２に入る。この反応管１０２内部の圧力は、ポンプと背圧弁１０５とにより制御されるようになっている。ヒータ付き反応管１０２内で、水の臨界点である３７４．２℃、２２．１Ｍｐａ以上の温度および圧力に加熱・加圧されることで、流体中の樹脂成分が迅速に分解し溶解される。反応管を出た混合物は、熱交換器１０１により冷却され、続いて冷却器１０３によりさらに冷却される。
【０１０３】
その後、被処理物は分離器１０４に入る。そして、分離器１０４以降では、前述のバルブの開閉による基板砕成物の高圧場への注入方法と同じ原理によって、主に被処理物中の固形分が、開閉バルブＣ１０７、高圧容器Ｂ１０６、開閉バルブＤ１０８を通じて系外に排出される。その際、開閉バルブＣ１０７の開放操作時には、水ポンプ１１０によってあらかじめ高圧容器Ｂ１０６内を水で満たしておくようにし、高温・高圧の流体ではなく、圧縮性の殆どない低温・高圧の流体から抜き出しを行うことによって、系における圧力の変動を最小限に押さえることが可能になり、処理システム全体の作動が確実になる。なお、抜き出し時において、開閉バルブＣ１０７の種類によっては、このバルブ取付部分の管路に固形分が存在する時点でバルブの閉止操作を行うと、バルブが正常に動作しない、あるいはバルブが故障する可能性があるため、開閉バルブＣ１０７の直前の管路、あるいは分離器１０４の直前の管路に、固形分の流れを検知する装置、例えば超音波流量計を設置し、このバルブ取付部分の管路に固形分が存在しない時点でバルブを閉止することが望ましい。前述したように、基板砕成物は間欠的に注入されるので、管路中には固形分が存在しない液体のみの部分が存在し、よってこの様な操作が可能になる。この固形分検知装置は、他の三つの開閉バルブ、すなわち開閉バルブＡ９６、開閉バルブＢ９８、開閉パルブＤ１０８の直前にも設置することが可能である。
【０１０４】
一方、液状の有機分を含む流れは、分離器１０４の上方出口に設置されたフィルタを通った後、背圧弁１０５を通過して減圧され出口で回収される。フィルタの存在によって、背圧弁１０５を通過する流れには固形分は含有されておらず、よってここでの閉塞や、背圧弁の摩耗が生じる恐れはない。液状の有機分は、一部分は開閉バルブＣ１０７を通って排出されうるが、開閉バルブＣ１０７または開閉バルブＤ１０８のどちらかが必ず閉止状態にあるので、大部分は背圧弁１０５の側の配管中に輪送され、ここを通って系外に排出される。排出された液状の有機分から有機分を回収する方法としては、例えは膜分離や蒸留、あるいはこれらの組合せを用いることも可能であるし、有機分を回収した後の水を再び高圧ポンプＡ９９あるいは高圧ポンプＢ１００の吸込側に還流することも可能である。
このような装置を用いて、ハンダ溶融と表面研磨により実装部品とハンダをそれぞれ除去した回路基板を溶解処理した。旋動破砕機とカッターミルを組み合わせた粉砕装置を用いて回路基板を粉砕し、粉砕物を篩分けして粒径１ｍｍ以上２ｍｍ以下のものを被処理物とした。被処理物の重量組成比率は、銅３１％、ガラス繊維４１％、エポキシ樹脂２８％である。ヒータ付き反応管１０２での処理温度および圧力は、３８０℃、２４Ｍｐａとし、反応管中における滞留時間は１時間に調節した。処理後の混合物をろ過し、ろ紙上に残留した固体を乾燥させた後、それをプラスチック容器に封入して、振とう器で毎分２００回の速さで上下に１０分間振とうして、超臨界処理により脆性化していたガラス繊維分を細かく粒状に粉末化した。内容物を６００μｍ径の篩で分別し、篩上に残留した固形物中の銅純度を分桁したところ、銅純度は９０％であった。また、ろ過した水溶液中の有機分を分析したところ、有価物である、フェノール、クレゾールおよびイソプロピルフェノ一ルを主成分として確認した。さらに、これらの回収物の被処理基板中の樹脂分に対する重量比率は、それぞれ２０．１％、４．３％および３．７％であった。また、その他の水溶性有機分として、アセトンも確認された。
【０１０５】
実施例２９
図１６に示した処理装置により、ハンダ溶融により実装部品のみを除去した回路基板を溶解処理した。旋動破砕機とカッターミルとを組み合わせた粉砕装置を用いて回路基板を粉砕し、粉砕物を篩分けして粒径１ｍｍ以上２ｍｍ以下のものを被処理物とした。被処理物の重量組成比率は、銅３０％、ガラス繊維３８％、エポキシ樹脂２７％、ハンダ５％である。処理条件は実施例２８と同じである。処理後の混合物をろ過し、ろ過した溶液中の鉛イオン、錫イオン、銅イオンを分析したところ、検出限界以下であった。
【０１０６】
実施例３０
図１６の装置を用い、実施例２８と同様に前処理、粉砕・篩分け操作を行った回路基板を溶解処理した。ヒータ付き反応管１０２での処理温度および圧力は、３００℃、１０Ｍｐａとし、反応管中における滞留時問は１時間に調節した。処理後の混合物をろ過し、ろ紙上に残留した固体を乾燥させた後、実施例２８と同様に１０分間振とうした。内容物を同じ篩で分別し、篩上に残留した固形物中の銅純度を分析したところ、銅純度は３３％であった。また、ろ過した溶液中の有機分を分析したところ、有価物であるフェノールを主成分として確認した。被処理基板中の樹脂分に対するフェノールの重量比率は９．２％であった。
【０１０７】
比較例
図１６の装置を用い、実施例２８と同様に前処理、粉砕・篩分け操作を行った回路基板を溶解処理した。ヒータ付き反応管１０２での処理温度および圧力は、１５０℃、０．５Ｍｐａとし、反応管中における滞留時間は１時間に調節した。処理後の混合物をろ過し、ろ紙上に残留した固体を乾燥させた後、実施例２８と同様に１０分間振とうした。内容物を同じ篩で分別し、篩上に残留した固形物中の銅純度を分析したところ、銅純度は３１％であった。なお、ろ過した溶液中の有機分を分析したところ、有機分は検出されなかった。
【０１０８】
実施例３１
前処理工程で実装部品が取り外された廃回路基板に対して、超臨界状態の硝酸水溶液を用いて回路基板を構成する熱硬化性樹脂を溶解し、金属鉛等を回収した。 まず、樹脂溶解装置について説明する。
【０１０９】
この装置は、図１７に示すように、基板砕成物と水とを混合したスラリーを貯蔵する廃棄物タンク１１１と、水タンク１１２と、酸素、空気または過酸化水素等の酸化剤タンク１１３と、硝酸タンク１１４と、高圧ポンプ１１５〜１１８と、熱交換器１１９と、ヒータ付き反応管１２０と、分離装置Ａ１２１と、分離装置Ｂ１２２と、冷却器１２３および背圧弁１２４を備えている。なお、装置各部は、ステンレス鋼、チタン、ハステロイ、インロネルのような、耐熱、耐圧性を有し高い耐腐食性を有する材料により構成することが望ましい。
【０１１０】
それぞれのタンクからは高圧ポンプ１１５〜１１８によって各流体が昇圧され輸迭された後に任意の比率で混合され、銅とハンダは硝酸の働きでいったんは溶解する。この混合物は、熱交換器１１９を経て昇温された後、ヒータ付き反応管１２０に入る。この反応管１２０内部の圧力は、ポンプと背圧弁１２４とにより制御されるようになっている。ヒータ付き反応管１２０内で、水の臨界点である３７４．２℃、２２．１Ｍｐａ以上の温度および圧力に加熱・加圧されることで、流体中の樹脂成分が迅速に分解し溶解される。もちろん、タンク１１４からの硝酸は酸性酸化剤ではあるが、タンク１１３からの酸化剤投入によって、生じうる酸化力の不足を補っている。同時に、溶解していた（錫はいったん硝酸に侵された後に酸化錫として不溶化している可能性があるが）金属のうち、少なくとも鉛と錫は、超臨界状態における水熱反応により酸化物微粒子となって析出する。
【０１１１】
分離装置Ａ１２１においては、粉砕されたガラス繊維が補集されるが、ここには存在しうる金属酸化物の粒径より粗く、ガラス繊維の粒径より細かいフィルタを使用する。また、フィルタは２つ以上のものが並列に配置されており、その内の１つを使用するのであるが、モニタリングによりフィルタの状態を検知して、流路およびフィルタの切り替えを行うことにより、ガラス繊維の補集による目詰まりを防止している。次に、分離装置Ｂ１２２においては、分離装置Ａ１２１よりも目の細かいフィルターを用いて、析出した金属酸化物微粒子が補集されるが、分離装置Ａ１２１と同様の目詰まり防止機構が装備されている。なお、金属酸化物の分離装置は複数個を直列に並べて設置することも可能であり、その場合は、水熱反応により酸化物が析出する温度や、金属酸化物の高温・高圧水への溶解度が金属種によって異なることを利用し、各分離装置における温度を制御することによって金属酸化物を分別して回収することができる。
【０１１２】
その後、混合物は熱交換器１１９により冷却され、続いて冷却器１２３によりさらに冷却された後、背圧弁１２４を通過して減圧され、出口で回収される。
【０１１３】
このような装置を用いて、ハンダ溶融により実装部品のみを除去した回路基板を溶解処理した。硝酸として５Ｎ濃度の硝酸を、酸化剤として３１％濃度の過酸化水素水を用いた。ヒータ付き反応管１２０での処理温度および圧力は、５００℃、３０Ｍｐａとし、反応管中における滞留時間は３０分に調節した。その結果、分離装置Ａ１２１によるガラス繊維の回収率は９６．２％、分離装置Ｂ１２２による鉛および錫の回収率はともに９９．９％以上であった。
【０１１４】
実施例３２
無機のフィラーが充填された樹脂廃棄物２．１ｇを、内容積１２２ｃｃの圧力容器と電気炉から構成された回分式の装置を用いて溶解処理した。被処理物の組成は、酸無水物硬化型エポキシ樹脂３２％、無機フィラ−６８％である。被処理物と３８．４ｃｃの水とを圧力容器に投入し、密閉して３８０℃、２４Ｍｐａの反応条件で１時間処理した。処理後の観察では無機フィラーのみが認められた。また、回収した被処理物のうち、固形物中の有機分の含有率は７．２％であった。さらに、溶液中の有機分を分析したところ、有価物であるフェノ一ル、３−フェノキシ−１，２−プロパンジオールを主成分として確認した。被処理物中の樹脂分に対する重量比率は、それぞれ、８．０％および１１．７％であった。また、他の液状の有機分として、アセトンも確認された。
【０１１５】
実施例３３
ベレット状のＡＢＳ樹脂０．３７ｇを、内容積１１７ｃｃの圧力容器および電気炉から構成された回分式の装置を用いて溶解処理した。被処理物と、２９．７ｃｃの水と、３１％過酸化本素水７．２ｃｃとを圧力容器に投入し、密閉して３８０℃、２４Ｍｐａの反応条件で１時間にわたり酸化処理した。処理後の状態を目視にて観察したところ、ペレットは存在しておらず、水中に溶解または懸濁した状態で存在していた。次に、処理後の気相中に存在するシアン化水素の濃度を分析したところ、ＡＢＳ中のシアノ基が全てシアン化水素に転換した場合のシアン化水素発生量を１００とすると存在量は０．０１５未満であった。また、液相中の全シアン濃度を分析したところ、０．００２５ｐｐｍ未満であった。
【０１１６】
実施例３４
ペレット状のＡＢＳ樹脂０．３７ｇを、内容積１１７ｃｃの圧力容器および電気炉から構成された回分式の装置を用いて処理した。被処理物と３６．９ｃｃとを圧力容器に投入し、圧力容器内の雰囲気をアルゴンにて置換後、密閉して３８０℃、２４Ｍｐａの反応条件で１時間処理した。そして、処理後の状態を目視観察したところ、ペレットは存在しておらず、水中に溶解または懸濁した状態で存在していた。次に、処理後の気相中に存在するシアン化水素の濃度を分析したところ、ＡＢＳ中のシアノ基が全てシアン化水素に転換した場合のシアン化水素発生量を１００とすると存在量は０．０１５未満であった。また、液相中の全シアン濃度を分析したところ、０．００２５ｐｐｍ未満であった。さらに、液相中の有機分を同定したところ、有価物であるアクリルアミド、アクリル酸およびスチレン等が確認された。
【０１１７】
実施例３５
ハンダ溶融と表面研磨により実装部品とハンダをそれぞれ除去した回路基板から２６．６ｍｍ四方を切り出したものを、内容積１２２ｃｃの圧力容器と電気炉から構成された回分式の装置を用いて溶解処理した。すなわち、被処理片と３３．２ｃｃのメタノ一ルとを圧力容器に投入し、密閉して２４２℃、８．２Ｍｐａの反応条件で２時間処理した。処理後の基板片を観察したところ、各層はピンセットで容易に剥離することができ、銅箔とガラス繊維とを手で選別することができた。
【０１１８】
実施例３６
ハンダ溶融と表面研磨により実装部品とハンダをそれぞれ除去した回路基板から、２４．２ｍｍ四方を切り出したものを、内容積１２２ｃｃの圧力容器と電気炉から構成された回分式の装置を用いて溶解処理した。すなわち、被処理片と３３．７ｃｃのエタノ一ルとを圧力容器に投入し、密閉して２４６℃、６．５Ｍｐａの反応条件で２時間処理した。処理後の基板片を観察したところ、各層はピンセットで容易に剥離することができ、銅箔とガラス繊維とを手で選別することができた。
【０１１９】
実施例３７
図１８の装置を用い、実施例３６と同様に前処理、粉砕・篩分け操作を行った回路基板を溶解処理した。なお、処理条件は、実施例３６と同じであるが、高圧ポンプ１２９で供給する水に、基板中に含まれる樹脂の１３．５％にあたる重量比の水酸化ナトリウムを溶解して添加した。そして、処理後の混合物中のダイオキシン類を分析したところ、検出限界以下であった。
【０１２０】
実施例３８
図１８の装置を用い、実施例３６と同様に前処理、粉砕・篩分け操作を行った回路基板を溶解処理した。なお、処理条件は、実施例３６と同じであるが、高圧ポンプ１２９で供給する水に、基板中に含まれる樹脂の１２．５％にあたる重量比の水酸化カルシウムを溶解して添加した。そして、処理後の混合物中のダイオキシン類を分析したところ、検出限界以下であった。
【０１２１】
さらに、本発明に係る他の実施形態について図面を用いて説明する。
【０１２２】
図１８は、本発明に係る処理装置を概賂的に示した図である。
【０１２３】
図１８に示す処理装置は、熱硬化性樹脂製品を取り込んで粉砕を行う粉砕機１８１と、処理液を所定温度に加熱して粉砕機１８１から排出された粉砕物とを接触させる溶解槽１８２と、溶解槽内の内容物を撹拌するために撹拌機１８３と、溶解槽１８２内の内容物の槽外への排出量を調整する弁１８４と、溶解槽１８２内の内容物を弁１８４が開いているときに送りだすポンプ１８５と、ポンプ１８５内で圧送された内容物を取り込み遠心力により内容物内の粉体と液体とを分離する分離器１８６と、分離器１８６から出た液体を圧送するためのポンプ１８８と、ポンプ１８８によって圧送された液体を取り込み遠心力により粉末と液体とを分離する分離器１８７と、分離器１８７から排出された液体を薄く塗り付け、加熱を行うベルトコンベヤ１９０と、ベルトコンベヤ１９０に付着した付着物を削り落とす爪１９１と、ベルトコンベヤ１９０と爪１９１とを取り囲むケース１８９と、ケース１８９内の圧力を減圧する減圧装置１９３と、減圧装置１９３とケース１８９とを結ぶ配管に設けられ通過ガスを冷却し凝集物を回収する回収容器１９２と、分離器１８６と１８７から出た粉体を取り込み洗浄液と混合する洗浄槽１９４と、洗浄槽１９４内の内容物の排出量を調整する弁１９５と、洗浄槽１９４内の内容物を弁１９５が開いているときに内容物を圧送するためのポンプ１９６と、ポンプ１９６から圧送された内容物を取り込み遠心力により粉末と液体とを分離する分離器１９７と、分離器から出た粉末を洗浄槽１９４または次の行程に送るか切り替えることのできる切り替え器１９８と、切り替え器１９８を通り洗浄槽１９４に粉末すためのポンプ１９９と、切り替え器１９８を通った粉末を塗り付け加熱を行うベルトコンベヤ２０２と、ベルトコンベヤ２０２に付着した付着物を削り落とす爪２０３と、ベルトコンベヤ２０２と爪２０３を取り囲むケース２０１と、ケース２０１内の圧力を減圧する減圧装置２０５と、減圧装置２０５とケース２０１とを結ぶ配管に設けられ通過ガスを冷却し凝集物を回収する回収容器２０４と、回収容器１９２と２０４内の液体を溜めるタンク２０６と、タンク２０６内の液体を圧送するためのポンプ２０７と、ポンプ２０７を通りタンク２０６から排出された液体の輪送先を切り替える切り替え器２０８と、タンク２０６からポンプ２０７を通り送られてきた液体を加熱する加熱器２１０と、分離器１９７で分離された液体を溜めるタンク２００と、タンク２００内の液体を加熱器２１０に送るポンプ２０９とを備えている。
【０１２４】
ここで、粉砕機１８１は、剪断力，圧縮力および衝撃力などを用いて粉砕を行なうように構成されている。また、粉砕後、分離された金属を比重差、形状差または電気特性差等を利用して取り除くとより好ましい。溶解槽１８２は、加熱器２１０から液体、粉砕機１８１から粉砕物をそれぞれ取り入れて、それぞれを接触混合する装置として使われる。溶解槽１８２の加熱温度は、目的とする温度に一定に保たれるように制御されることがより好ましく、加熱方法は電気、バーナーおよび高周波等が挙げられる。また、電熱面における温度を均一化するために、加熱された高沸点流体を利用して内容物に伝熱するとより好ましい。また、ケース１８９は、減圧下でベルトコンベヤ１９０の上に塗られた液体を加熱する効果を有しており、ガス化した液体はトラップ１９２により回収される。ベルトコンベヤ上に残ったものは、爪１９１で取り除かれケース１８９内に溜められる。なお、適当な時期に、分離器１８７とケース１８９との間に設けられた弁２１１を閉じ、減圧装置１９３の運転を止めてから、ケース１８９内のベルトコンベヤから爪１９１で取り除かれた回収物は取り出される。
【０１２５】
さらに、洗浄槽１９４は弁１９５を閉じた状態で分離器１９７から送られてくる固形物と、タンク２０６から送られてくる液体とを撹拌混合させる機能を備えている。また、ケース２０１は、減圧下でベルトコンベヤ２０２の上に塗られた液体を加熱する効果を有しており、ガス化した液体はトラップ２０４に回収される。なお、ベルトコンベヤ上に残ったものは、爪２０３で取り除かれ、ケース２０１内に溜められる。そして、適当な時期に、分離器１９７とケース２０１との間に設けられた切り替え器１９８を閉じ，減圧装置２０５の運転を止めてからケース２０１内のベルトコンベヤから爪２０３で取り除かれた回収物は取り出される。なお、分離器１８６、分離器１８７、洗浄槽１９４、分離器１９７およびタンク２００は、それぞれ加熱や保温ができるように構成するとより好ましい。さらに、処理装置に配設された各配管や装置類は、断熱材等で保温されていることが好ましいが、一部の配管や装置類を保温するようにしてもよい。
【０１２６】
実施例３９
図１８に示した処理装置により、磁気浮上鉄道推進コイルの絶縁材料に用いられている樹脂と同等の組成であるエポキシ樹脂廃棄物から、該樹脂由来の有機成分を分離回収し再生樹脂原料とした。すなわち、エポキシ樹脂廃棄物を平均粒径１ｍｍまで粉砕してエチレンジアミンに浸漬し、１１７℃、大気圧下で１時間攪拌することにより試料中の有機成分は溶解させることにより、充填材である無機成分だけが不溶のまま懸濁した溶液が得られた。そして、遠心分離により溶液から無機成分を分離回収して再生充填材とした。一方、上澄液は、蒸留により溶剤のみを蒸発させ、樹脂由来の有機成分を分離回収して再生樹脂原料とした。
【０１２７】
次に、再生充填材の含有成分および表面状態について分析を行った。すなわち、再生充填材よりアセトンを用いて室温で有機成分を抽出した。次に、ろ過により不溶な充填材成分を除去して抽出液のアセトンを蒸留することにより抽出物を濃縮して抽出成分を得た。ここで、抽出成分について重量スペクトル、赤外吸収スペクトルおよび核磁気共鳴スペクトルを測定したところ、該抽出成分にはアミン類が含まれていることがわかった。
【０１２８】
次いで、再生充填材を用いて新たなエポキシ樹脂硬化物を調製した。はじめに、ビスフェノ一ルＡ型のエポキシ樹脂（油化シェルエボキシ社製、商品名エピコート８２８）１００重量部に対して、メチルテトラヒドロ無水フタル酸（日立化成社製、商品名ＨＮ−５５００）８０重量部、再生シリカ充填材５００重量部を８０℃で２時間にわたり混合した。なお、混合において、充填材と樹脂との密着性を高めるための界面活性剤あるいはカップリング剤は使用しなかった。その後、ベンジルジメチルアミン０．２重量部を加え、さらに１５分間減圧下で加熱混合してエポキシ樹脂組成物を製造した。そして、混合後、成形前の状態の樹脂の粘度を測定したところ４．０Ｐａ・ｓであった。また、成形後の硬化物の曲げ強度を測定したところ、１５ｋｇｆ／ｍｍ^２であった。
【０１２９】
さらに、硬化物を任意の位置で切断した断面を研磨し、走査型電干顕微鏡を用いて樹脂硬化物中の充填材の分散の様子を観察したところ、充填材に凝集したまま硬化した部分はなく、特に、粒径の小さい３μｍ以下の充填材がきれいに分散されていることが確認された。また、未使用の充填材は、破砕状の不定形状の充填材であるが、再生充填材には鋭利な角がなくなっていた。これは、既に製造工程における剪断力が十分にかかる状態での混合を複数回にわたり経てきたために、充填材の粒子同士が擦れ合い鋭利な角が削れて丸みを帯びたものと考えられる。そして、充填材が球状に近くなることにより嵩高さが低下し、充填材混合樹脂の粘度を下げる効果があったと推測される。
【０１３０】
実施例４０〜実施例７５
条件を変更した以外は実施例３９と同様の工程にて処理を行い、処理速度および回収された回収物を評価した結果を表３〜表５に示す。また、実施例において回収された再生充填剤または再生原料樹脂を用いて得られた混合樹脂および硬化物の特性を表６に示す。なお、表３〜表６には、各条件とともに、実施例に対して比較を行った結果も示している。
【０１３１】
【表３】

【表４】

【表５】

【表６】

ただし、溶剤の略号は次の通りである。
【０１３２】
ＥＤＡ：エチレンジアミン
ＤＢＵ：１，８−ジアザビシクロ［５，４，０］−７−ウンデセン
２Ｅ４ＭＺ−ＣＮ：１−（２−シアノエチル）−２−エチル−４−メチルイミダゾール
ＴＭＡＨ：テトラメチルアンモニウムヒドロキシド
ＤＴＧ：ジオルソトリルフアニジン
ＬＡ：ラウリルアミン
ＤＢＡ：ジベンジルアミン
ＮＭＭ：Ｎ−メチルモルホリン
ＮＡ：β−ニトロアニリン
ＤＰＡ：ジフェニルアミン
ＴＣＥ：１，１，１−トリクロロエタン
処理速度の評価は次の基準で示した。
【０１３３】
◎：５時間以内の処理ですべて溶解するもの
○：５時間以上の処理ですべて溶解するもの
△：一部に残留する有機成分があるもの
×：ほとんど溶解しないもの
回収物の評価は次の基準で示した。
【０１３４】
◎：回収した樹脂成分に熱分解および酸化が起きず組成分析において副反応による分解物を含んでいないもの
○：回収した樹脂成分にわずかに褐色の着色がみられるが、組成分析においては副反応による分解物が３％以下の極微量で無視しうるもの
△：回収した樹脂が褐色に変色し、分解不純物が３％以上含まれているもの
×：回収した樹脂の有機成分の熱分解・酸化等がおき、黒化したもの
表３〜表６から明らかなように、各実施例によれば、比較例と比べて同等以上の特性を示すことが理解される。
【０１３５】
実施例７６
実施例３９と同様にして、５〜２０ｃｍのサイズに切断されたガス絶緑スイッチギア用スペーサの樹脂廃棄物を処理した。なお、該廃製品切断品は、導体のアルミニウムおよびネジ部品等の金属片が含まれている。また、処理にあたっては、溶剤として、１，８−ジアザビシクロ［５、４，０］−７−ウンデセンを用い、処理温度を１４０℃とした。さらに、処理槽において、溶解した樹脂から順次溶解成分が回収されるため未溶解の部分の滞留時間は自動的に適正化された。その結果、投入物の大きさに関係なく樹脂は全て溶解し回収することができた。また、含まれていた金属片については、処理槽において付着していた樹脂成分が全て溶解除去されたことから処理後容易に回収することができた。
【０１３６】
比較例
実施例７６と同じ処理物を１ｃｍ程度までさらに粉砕した後、同溶剤および同温度で押出機を用いて処理を試みた。しかし、押出機は溶融していない樹脂や金属片による抵抗が大きく、容易に目詰まりを起こして停止してしまうことから、処理することは不可能であった。
【０１３７】
実施例７７
ろ過あるいは沈降分離工程を設けずに、直接蒸留により溶剤を除去した以外は、実施例３９と同様にして真空遮断器用絶緑樹脂を処理した。このとき、回収物は、樹脂由来の流動性を持った有機成分と無機充填材とが混合した状態で回収され、該回収物は常温で固体で、加熱により流動化する熱可塑性を示した。また、該回収物を使用して再び硬化させた再生樹脂は、既に十分に混合および分散された充填材が含まれているため、新たに樹脂を調製する際の混合が容易で、凝集などによる混合不良を起こすことはなかった。
【０１３８】
実施例７８
樹脂の有機成分を全て溶解せずに、粉砕物の表層から一部を溶解し、充填材と樹脂有機成分が混合硬化されたままの状態で再び再生品として回収した以外は、実施例３９と同様にして破砕物の処理を行った。本実施例においては、粉砕物の表層を溶剤で溶解処理していることから、粉砕物は新しい樹脂との密着性に非常に優れており、高強度の樹脂再生品を製造することができた。
【０１３９】
実施例７９
本実施例では、回収した樹脂有機成分を分離精製し、高分子量の成分と低分子量の成分とに分離し、それぞれ単独で再利用した例である。
【０１４０】
実施例３９と同様にして溶解処理、ろ過により無機充填材を分離して得られた有機成分について、テトラヒドロフラン（ＴＨＦ）溶剤による抽出洗浄を行った。ＴＨＦ不溶分をジメチルホルムアミド溶剤に溶解しゲルパ−ミエイションクロマトグラフィにより分子量を測定したところ、平均分子量約１０万の高分子量の成分であった。また、高分子量の回収物の赤外吸収スペクトルからは、ビスフェノ−ルＡの骨格を有する主鎖に水酸基を有するポリエーテルポリオールが回収されたことがわかった。このとき、高分子量の回収物は、低分子量の物質が除去されているため、無色、無臭で強度があり、このまま単独で再生熱可塑性樹脂、例えば、射出成形等の成形体として、あるいは粒状、繊維状および膜状に成形して使用することが可能であった。
【０１４１】
一方、ＴＨＦ抽出成分は蒸留により溶剤が除去され、回収された回収物は、重量スペクトルおよび赤外吸収スペクトルの測定により主に分子量２０００以下のアミン化合物であることが判明した。なお、ＪＩＳ法（Ｋ ７２３７）に従って測定したアミン価は３６０であった。次に、該回収物を硬化剤としてビスフェノ−ルＡ型エポキシ樹脂と混合し７０℃て加熱するとにより、アミン硬化型エポキシ硬化物を得ることができ、該低分子量の回収物は、接着剤あるいは塗科等として使用可能であることが確認された。
【０１４２】
さらに、該低分子量の回収物を金属キレ一卜剤として適用した。すなわち、銅を２ｗｔ％含有する廃液に該低分子量の回収物を適量混合し、室温で１時間攪拌したところ徐々に沈殿が生じたのでこれを静置し、十分に沈降させた後に上澄液を分離した。そして、上澄液の銅含有量を測定したところ、５０ｐｐｍ以下であった。
【０１４３】
比較例
磁気浮上鉄道推進コイルの絶縁材料に用いられている樹脂と同等の組成であるエポキシ樹脂廃棄物を平均粒径１ｍｍまで粉砕した。さらに、該粉砕物を微粉砕し篩により１００μｍの篩目を通過した粉末をそのまま再生充填材として新たなエポキシ樹脂硬化物を調製した。すなわち、ビスフェノ−ルＡ型のエポキシ樹脂（油化シェルエポキシ社製、商品名エピコ−ト８２８）１００重量部、再生シリカからなる充填材５００重量部を８０℃で２時間混合した。なお、混合において、充填材と樹脂との密着性を高めるための界面活性剤あるいはカップリング剤は使用しなかった。その後、ベンジルジメチルアミン０．２重量部を加え、さらに１５分間減圧下で加熱混合してエポキシ樹脂組成物を製造した。そして、混合後成形前の状態の樹脂の粘度を測定したところ、１２Ｐａ・ｓと高粘度であった。これは、微粉枠時に粉末が凝集を起こすことにより崇高さが増加し混合粘度が上がったと推測される。さらに、該エポキシ樹脂組成物を成形し、硬化物の曲げ強度を測定したところ、１０ｋｇｆ／ｍｍ^２だった。この理由として、新たに添加した樹脂に対し再生充填材の表面のぬれ性が十分でなく、充填材の表面から破壊を起こしやすいからと考えられる。次に、該硬化物を任意の位置で切断した断面を研磨し、走査型電子顕微鏡を用いて樹脂硬化物中の充填材の分散の様子を観察したところ充填材の分散性に偏りが見られた。特に、粒径の小さな３μｍ以下の充填材は複数の粒子が連なっており、分散性が悪いことが確認された。さらに、凝集した微粉末の近接部位には、減圧下で脱気しきれなかったボイドの残りが観察され、強度の低下につながったものと推測された。
【０１４４】
比較例
本比較例は、充填材も未使用のバ−ジン材料を用いて樹脂を製造した例である。すなわち、ビスフェノールＡ型のエポキシ樹脂（油化シェルエポキシ社製、商品名エピコート８２８）１００重量部に対し、メチルテトラヒドロ無水フタル酸（日立化成社製、商品名ＨＮ−５５００）８０重量部、バージンシリカ充填材５００重量部を８０℃にて２時間にわたり混合した。なお、混合に際し、充填材と樹脂との密着性を高めるための界面活性剤あるいはカップリング剤は使用しなかった。その後、ベンジルジメチルアミン０．２重量部を加え、さらに、１５分間加熱混合してエポキシ樹脂組成物を製造した。なお、混合後、成形前の状態の樹脂の粘度を測定したところ、１０Ｐａ・ｓと高粘度であった。この理由としては、微粉砕時に粉末が凝集を起こすことにより嵩高さが増加し粘度が上がったものと推測される。また、成形後、硬化物の曲げ強度を測定したところ、サンプルによりばらつきが存在するものの平均８ｋｇｆ／ｍｍ^２であった。この理由としては、再生充填材の表面のぬれ性が十分ではなく、該充填材の表面から破壊を起こしやすいことが考えられる。
【０１４５】
実施例８０
本実施例は、樹脂製品を製造する工程で用いられ、酸無水物硬化型エポキシ樹脂組成物の混合に用いた混合器の洗浄作業を実施した例である。
【０１４６】
はじめに、エポキシ樹脂（油化シェルエポキシ社製、商品名エピコート８２８）、メチルテトラヒドロ無水フタル酸（日立化成社製、商品名ＨＮ−５５００）、平均粒径１０μｍのシリカの粉末およびベンジルジメチルジアミンを、８０℃において混合し、これを排出する動作を繰り返し１０回行った後の混合器を、エチレンジアミンを用いて洗浄した。なお、洗浄前の混合槽の壁面には硬化した樹脂が層となって強固に付着し、さらに未硬化の樹脂がこれを覆っている状態であった。特に、硬化して混合槽に付着した樹脂層は、厚い部分で約３ｍｍあった。はじめに、混合槽内をエチレンジアミンで満たし、１１７℃で１時間攪拌洗浄した後、排出口から洗浄後の溶剤を回収した。洗浄後、混合槽内に付着する未硬化の樹脂および硬化した樹脂はともに全く存在しなかった。
【０１４７】
次に、樹脂を含み回収された溶液から、沈降分離によって、無機充填材であるシリカのみを分離回収した。なお、該シリカは、エチレジアミンによりさらに洗浄した後乾燥し回収充填材とした。また、充填材を除いた上澄の溶液は、１００℃以下の温度で減圧蒸留することにより、溶剤であるエチレジアミンを回収するとともに蒸留残渣として樹脂を得た。このとき回収されたエチレジアミンには劣化はなく、再使用に際してなんら問題なかった。
【０１４８】
実施例８１
実施例８０と同様にして、不飽和ポリエステル樹脂の混合に用いた混合器の混合槽を洗浄した。不飽和ポリエステルは、無水フタル酸、無水フマル酸およびプロピレングリコ−ルを混合した後、スチレンモノマーを混合して架橋させた。本実施例においては、溶剤として、２−メチルイミダゾールを用いて混合器の混合槽の内壁面に付着した硬化樹脂を洗浄することにより、付着硬化樹脂は除去された。そして、このとき回収された２−メチルイミダゾールには劣化はなく、再使用に際してなんら問題なかった。
【０１４９】
比較例
エポキシ樹脂（油化シェルエポキシ社製、商品名エピコート８２８）、メチルテトラヒドロ無水フタル酸（日立化成社製、商品名ＨＮ−５５００）、平均粒径１０μｍのシリカの粉末およびベンジルジメチルアミンを８０℃において混合および排出し、これを繰り返して１０回行った後の混合器を、エチレンジアミンを用いて洗浄した。なお、洗浄前の混合槽の壁面には硬化した樹脂が層となって強固に付着し、さらに未硬化の樹脂がこれを覆っている状態であった。特に、硬化して混合槽の内壁に付着した樹脂層は厚い部分で約３ｍｍあった。はじめに、混合槽内を１，１，１−トリクロロエタンで満たし、１１７℃で１時間攪拌洗浄した後、排出口から洗浄後の溶剤を回収した。このとき、洗浄後の混合槽内に付着していた未硬化の樹脂はほぼ除去されていたが、硬化した樹脂は溶解せずに残留していた。また、硬化した樹脂層の厚さは約３ｍｍと全く変化なかった。
【０１５０】
実施例８２
本実施例は、樹脂製品の分析を実施した例である。
【０１５１】
フェノール硬化型エポキシ樹脂により封止され、製品通電検査により不良品とされた半導体チップを、溶剤としてイミダゾールを用いて１６０℃で２時間溶解処理することにより、フェノール硬化型エポキシ樹脂が除去され、半導体チッブの回路が露出した。そして、該チップを乾燥した後、走査型電子顕微鏡により回路の配線を観察することにより、配線の短絡個所を発見することができた。
【０１５２】
実施例８３
組成の不明な樹脂製品の一部を試料として用意し、溶剤としてトリエチルアミン／エタノ−ルを４：６（重量比）の割合で混合した溶液を用い、８０℃にて１０時間にわたり攪拌して樹脂製品の樹脂を加熱溶解した。そして、蒸留により溶剤を除去後、乾燥して得られた固体について赤外分光スペクトルを測定した。一方、標準サンプルとして、全く同じ温度、時間、圧力および溶剤の条件の下で溶解処理することにより得られた、酸無水物硬化型エポキシ樹脂、アミン硬化型エポキシ樹脂、フェノール硬化型エポキシ樹脂および不飽和ポリエステル樹脂のサンプルの赤外分光スペクトルを測定しておいた。そして、上記試料のスペクトルを標準サンプルのスペクトルと比較することにより、上記試料は、酸無水物硬化型エポキシ樹脂の標準サンプルともっとも類似していることが確認された。さらに詳しく分析するため、上記試料を溶解処理したサンプルをテトラヒドロフランに溶解し、ゲルパーミエイションクロマトグラフィおよび重量スペクトルを測定したところ、ジカルボン酸エステルとしてメチルテトラヒドロフタル酸モノメチルエステルが主成分として含まれていることがわかった。さらに、標準サンプルとして、メチルテトラヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、無水ピロメリット酸および無水メチルナジック酸を硬化剤として硬化させたエポキシ樹脂のサンプルの赤外分光スペクトルを測定しておき、該データと比較することにより、硬化剤としてメチルテトラヒドロ無水フタル酸を用いていることが確認された。また、上記試料を溶解処理したサンプルを、ジメチルホルムアミドに溶解し、ゲルパーミエイションクロマトグラフィにより分子量の分布を測定した。一方、標準サンプルとしてエポキシ等量がそれぞれ１９０、２５０、３００、４７０および９５０のビスフェノ一ルＡ型のエポキシ樹脂をメチルテトラヒドロ無水フタル酸を硬化剤として硬化させたサンプルを用意し、同様の処理によって得られた溶解処理サンプルの分子量の分布を同様にして測定したところ、原料であるビスフェノ一ルＡ型のエポキシ樹脂のエポキシ等量が増加するにしたがって、溶解処理サンプルの分子量分布も高分子量側にシフトすることがわかった。そして、標準サンプルの最大ピークの重量平均分子量とエポキシ等量との関係を表す検量線および分子量の分布チャートから、上記試料は、エポキシ等量約１９５およびエポキシ等量約３３０のビスフェノ一ルＡ型のエポキシ樹脂の２種類を原料として使用していることが判明した。また、標準サンプルの溶解処理により残渣粉末として残留した無機充填材について、比重分離により異なる組成の充填材を分離し、それぞれＸ線光電子分光装置（ＸＰＳ）による元素分析、走査型電子顕微鏡観察および光散乱法による粒度分布の測定をしたところ、充填材として平均粒径１０μｍの球状のアルミナが４０重量部、平均粒径２０μｍの破砕状の溶融シリカが６０重量部含まれていることが確認された。
【０１５３】
比較例
フェノール硬化型エポキシ樹脂により封止され、製品通電検査により不良品とされた半導体チップを、塩酸を用い１００℃で２時間にわたり溶解処理することにより、フェノール硬化型エポキシ樹脂が除去され、半導体チップの回路が露出した。該チップを乾燥した後、走査型電子顕微鏡により回路配線を観察したが、半導体のアルミ配線が、封止樹脂を溶解する酸処理によって一部溶解損傷を受けており、不良個所の特定が困難であった。
【０１５４】
また、組成の不明な樹脂製品の一部を試料として用意し、濃塩酸を用いて８０℃で１０時間にわたり攪拌して加熱溶解した。次に、溶解したサンプルを乾燥し、得られた回収物について赤外吸収スペクトル、ゲルパーミエイションクロマトグラフィおよび重量スペクトルを測定し、同様の処理により得られた標準サンプルと比較したが、いずれも樹脂の分解が激しく、原料の特徴を特定することは不可能であったことから、樹脂製品を構成する樹脂の原料を特定することはできなかった。また、残渣として残った無機充填材の粉末について、比重分離、Ｘ線光電子分光装置（ＸＰＳ）による元素分析、走査型電子顕微鏡観察および光散乱法による粒度分布の測定を試みたが、酸により無機の充填材は表面が溶解しており、また、溶解した無機成分が充填材の表面に再吸着することにより不純物が多く、シリカとアルミナ成分との分離は困難で、充填材組成、粒度分布および形状を正しく分析することができなかった。
【０１５５】
以上から、上記処理方法により使用済み製品を原料として製造された無機充填材は、混合されていた廃製品を原料とし、溶剤で樹脂の成分のみを完全溶解しながら回収しているため、粉末としての凝集がなく分散性に優れていることが確認された。また、こうして得られた充填材は、溶剤、特に、有機アルカリ溶剤での処理により充填剤の表面電荷の除去あるいは界面が改質されることにより、固／液界面の表面自由エネルギーが減少して有機物である樹脂成分に対するぬれ性が増加し、新しく充填材混合樹脂を製造するにあたって、充填材の粉末が凝集せずに分散性に優れ、混合が容易になる。さらに、高充填した場合でも粘度の増加を抑えられるため、成形のための作業性を保ったまま、従来と比べ充填率を上げることが可能になる。また、樹脂成分に対するぬれ性が高く、充填材と樹脂との密着性が高いため、界面活性剤やカップリング剤の添加がなくても、空気等の泡の残留によるボイドがなく脱泡処理が容易になる。高充填が可能であり、かつ樹脂と充填材との密着性が高く分散性がよいことから、上記充填材を混合して硬化させた樹脂は、硬化物としての特性、例えば、強度、難燃性および耐電圧等の特性が向上する。
【０１５６】
実施例８４
前処理工程で実装部品が取り外され、ハンダが除去された後の廃回路基板に対し、超臨界状態の水等を用いて回路基板を構成する熱硬化性樹脂を溶解し、金属銅等を回収した。
【０１５７】
はじめに、処理装置について説明する。
【０１５８】
この装置は、図１９に示すように、基板砕成物と水とを混合した混合体を溜め置く供給槽 １２５と、開閉バルブＡ１２６ と、高圧容器Ａ１２７ と、開閉バルブＢ１２６ と、水を昇圧して輸送・供給する高圧ポンプ１２９ と、水と混合体とを収容して反応させる反応槽１３０ と、冷却器１３１ と、背圧弁１３２ と、高温および高圧に耐えうる開閉バルブＣ１３３ と、反応槽１３０ を加熱するヒータ１３４ と、高圧容器Ｂ１３５ と、開閉バルブＤ１３６ と、開閉バルブＥ１３７ と、水ポンプ１３８ と、圧力調整バルブＡ１３９ および圧力調整バルブＢ１４０ を備えている。なお、装置の各部分は、ステンレス鋼、チタン、ハステロイおよびインコネル等の耐熱および耐圧性を有し、高い耐腐食性を有する材料により構成されることが望ましい。
【０１５９】
また、該処理装置において、供給槽１２５ に溜め置かれている基板砕成物と水との混合体のうち、比重が水より大である基板砕成物が、開閉バルブＡ１２６ と開閉バルブＢ１２８ の開閉により、重力沈降によって反応槽１３０ に流れ込む。さらに、高圧容器Ａ１２７ の中には常時水が満たされている。そして、開閉バルブＡ１２６ が開の場合には、開閉バルブＢ１２８ を閉とすることによって供給槽１２５ の内部を特に加圧することなく基板砕成物を高圧容器Ａ１２７ に沈降させ、その後、開閉バルブΑ１２６ を閉に、また開閉バルブＢ１２８ を開とすることによって、水が満たされている高圧容器Ａ１２７ は瞬時に高圧ポンプ１２９ 吐出側と同じ高圧条件下におかれ、基板際成物は沈降して反応槽１３０ に流れ込む。この工程を繰り返し行うことによって、基板砕成物を間欠的に高圧の場に注入できるのであるが、該方法によれば、高圧ポンプで直接、基板砕成物を輸送する場合とは異なり、ポンプの摩耗および閉塞が生じず、なおかつポンプを通過させるために基板砕成物を微粉砕する必要もなくなる。また、上記注入操作の際、開閉バルブＣ１３３ は閉止しており、反応槽１３０ 内部の圧力は、連続的に稼動する高圧ポンプ１２９ と背圧弁１３２ とにより一定値に制御されるようになっている。また、注入後は開閉バルブＢ１２８ および開閉バルブＣ１３３ ともに閉止状態にあり、基板砕成物は反応槽１３０ 内で、水の臨界点である３７４．２ ℃、２２．１Ｍｐａ以上の温度および圧力に加熱および加圧されて、流体中の樹脂成分が迅速に分解し溶解されるが、撹拌器等により溶液の均一化を図ることによって溶解速度はより高まる。分解した有機分を含む流れは反応槽１３０ 出口に設置されたフィルタを通った後、冷却器１３１ により冷却され、さらに背圧弁１３２ を通過して減圧されて出口で回収される。なお、フィルタの存在によって、背圧弁１３２ を通過する流れには固形分は含有されておらず、よってここでの閉塞や背圧弁の摩耗が生じる恐れはない。また、排出された流れから有機分を回収する方法としては、例えば、膜分離、蒸留および冷却されたトラップ、あるいはこれらの組合せを用いることも可能であるし、有機分を回収した後の水を再び高圧ポンプ１２９ の吸込側に還流することも可能である。
【０１６０】
一方、主に銅からなる固形分は反応槽１３０ の底に沈殿しているが、該固形分は、所定の時間経過した後に、前述のバルブの開閉による基板砕成物の高圧場への注入方法と同じ原理によって、開閉バルブＣ１３３ 、高圧容器Ｂ１３５ 、開閉バルブＤ１３６ を通じて系外に排出される。その際、開閉バルブＣ１３３ の開放操作時には、水ポンプ１３８ によってあらかじめ高圧容器Ｂ１３５ 内を水で満たしておくことによって、反応槽１３０ における圧力の変動を最小限に押さえることが可能になり、処理装置全体の作動が確実になる。また、圧力調整バルブＡ１３９ および圧力調整バルブＢ１４０ は、水ポンプ１３８ による注水時と、開閉バルブＤ１３６ の開放操作の際に、高圧容器Ｂ１３５ 内の圧力を制御するのに用いられる。なお、これら一連の操作を通じて高圧ポンプ１２９ は常に稼動し続けており、液体は背圧弁１３２ を連続的に通過する一方、固形分は前述したように、鉛直方向に間欠的に注入および排出される。また、前述の作動方式により、反応槽１３０ 内の圧力変動は最小限に抑えられる。
【０１６１】
上記処理装置を用いて、ハンダ溶融と表面研磨により、実装部品およびハンダをそれぞれ除去した回路基板を溶解処理した。旋動破砕機とカッターミルとを組み合わせた粉砕装置を用いて回路基板を粉砕し、粉砕物を篩分けして粒径２ｍｍ以上４ｍｍ以下のものを被処理物とした。被処理物の重量組成比率は、銅３４％、ガラス繊維３９％およびエポキシ樹脂２７％である。また、反応槽１３０ での処理温度および圧力は、３８０ ℃、２４Ｍｐａとし、反応槽中における滞留時間は１時間に調節した。処理後の混合物を濾過し、濾紙上に残留した固体を乾燥させた後、乾燥物をプラスチック容器に封入し、振とう器で毎分２００ 回の速さで上下に１０分間振とうして、超臨界処理により脆性化していたガラス繊維分を細かく粒状に粉末化した。そして、上記封入物を６００ μｍ径の篩で分別し、篩上に残留した固形物中の銅純度を分析したところ、銅純度は９６％であった。また、濾過した溶液中の有機分を分折したところ、有価物であるフェノール、クレゾールおよびイソプロピルフェノールを主成分として確認した。さらに、これら有機物の被処理基板中の樹脂分に対する重量比率は、それぞれ１７．１％、 ５．８％および ５．２％であった。なお、その他の液状の有機分として、アセトンも確認された。
【０１６２】
【発明の効果】
以上の記載から明らかなように、本第１の発明の方法および装置によれば、発泡ウレタン樹脂のような有機ハロゲン化物含有発泡樹脂を含む混合廃棄物の処理において、シリコーンオイルのような液状の熱媒体中で所定の温度に加熱することで、発泡樹脂を軟化あるいは流動化させると同時に含まれる有機ハロゲン化物のガスを排出させることができ、軟化あるいは流動化した樹脂成分や基板等に付着したハンダ等の低融点金属を分離回収することができる。
【０１６３】
また、本第２の発明の方法および装置によれば、廃回路基板等の樹脂を含む物体を溶剤または溶剤蒸気で処理して樹脂を溶解することにより、物体を構成する樹脂や金属の有価物を高い効率で分離回収することができる。また、処理の際の環境への負荷の増大を抑えることができる。
【図面の簡単な説明】
【図１】本第１の発明の混合廃棄物の処理装置および処理方法の一実施例を概略的に示す図。
【図２】本第１の発明に使用する混合廃棄物の処理装置の別の実施例を概略的に示す図。
【図３】本第１の発明に使用する混合廃棄物の処理装置の別の実施例を概略的に示す図。
【図４】本第１の発明に使用する混合廃棄物の処理装置の別の実施例を概略的に示す図。
【図５】本第１の発明に使用する混合廃棄物の処理装置の別の実施例を概略的に示す図。
【図６】本第２の発明により廃回路基板を溶剤処理する方法の実施例を示すフロー図。
【図７】図６のフローにより溶剤処理を行なうための装置の概略を示す図。
【図８】回路基板を溶剤処理する前処理として、実装部品を除去する装置の一例を概略的に示す図。
【図９】回路基板を溶剤処理する前処理として、粉体吹き付けによりハンダを除去する装置の一例を概略的に示す図。
【図１０】溶剤処理の後処理として、基板から、ハンダ、実装部品、銅箔、樹脂、ガラス繊維等を分離回収する装置の一例を概略的に示す図。
【図１１】溶剤処理を行なう前処理として、回路基板上のハンダを分離除去し銅を回収する装置の実施例を概略的に示す図。
【図１２】溶剤処理の前処理として、回路基板上のハンダを分離除去し銅を回収する装置の別の実施例を示す図。
【図１３】回路基板上のハンダを電気化学的に分離除去する方法において、ハンダ溶解銅回収工程を示す図。
【図１４】回路基板上のハンダを電気化学的に分離除去する方法において、銅溶解ハンダ回収工程を示す図。
【図１５】超臨界状態の水等を用いて回路基板を構成する樹脂を溶解する装置の実施例を示す図。
【図１６】超臨界状態の水等を用いて物体を構成する樹脂を溶解し、金属等を回収する装置の実施例を示す図。
【図１７】超臨界状態の硝酸水溶液等を用いて物体を構成する樹脂を溶解し、金属等を回収する装置の実施例を示す図。
【図１８】本発明に係る処理装置を概賂的に示した図。
【図１９】本発明に係る処理装置を概賂的に示した図。
【符号の説明】
１……熱媒体 ２……封入機 ３………加熱反応槽
４……熱媒体供給循環機 ６……引き抜き機 ７………固形物排出弁
８……溶融金属排出弁 １１……ヒーター
１２……軟化あるいは流動化したウレタン樹脂成分 １３……溶融金属
１５……スクリーン １６……比重分離槽 １７……ガス吸着槽
２１……円筒管型ヒーター ２２……撹拌機 ２３……循環予熱部
２４……回転式破砕機 ２７……溶剤処理槽
２８………溶剤蒸留回収槽 ２９……凝縮器 ３０……溶剤タンク
３２、３９、６３……廃回路基板 ３４……分析装置
３５……濾過処理装置 ３７……添加剤タンク
４３……スクレイパーブレード ４７……サンドブラスト処理槽
４９……アルミナ、シリカ等の無機粉末 ５１、５４……噴射ポンプ
５３……ハンマー ５５……サイクロン ５７……重量回収成分（銅）
５８……回路基板投入部 ５９……ハンダの分離除去槽
６０、９５……破砕機 ６１……銅回収部 ６５……分離液
６７………ハンダダンク ７０……気流遠心型比重分離装置
７１……静電分離装置
７２……Ｃｕリッチ粉 ７７……空気とオゾンとの混合ガス噴射口
８１……ハンダ回収槽 ８３……銅イオンを含有する電解液
８４……ブラシ型電極 ８５……白金等の電極 ８７……粉砕装置
８８……混合物輸送ポンプ ９１……熱交換器
９２……ヒータ付き反応管 ９５……供給槽 ９６……開閉バルブＡ
９７……高圧容器Ａ ９８……開閉バルブＢ ９９……高圧ポンプＡ
１００……高圧ポンプＢ １０１……熱交換器 １０２……反応管
１０３……冷却器 １０４……分離器 １０５……背圧弁
１０６……高圧容器Ｂ １０７……開閉バルブＣ
１０８……開閉バルブＤ １０９……開閉バルブＥ １１０……水ポンプ
１１１……廃棄物タンク １１２……水タンク １１３……酸化剤タンク
１１５〜１１８……高圧ポンプ １１９……熱交換器
１２０……ヒータ付き反応管 １２１……分離装置Ａ
１２２……分離装置Ｂ １２３……冷却器 １２４……背圧弁
１２５……供給槽 １２６……開閉バルブ １２７……高圧容器Ａ
１２８……開閉バルブＢ １２９……高圧ポンプ
１３０……反応槽 １３１……冷却器 １３２……背圧弁
１３３……開閉バルブＣ １３４……ヒ−タ
１３５……高圧容器Ｂ １３６……開閉バルブＤ
１３７……開閉バルブＥ １３８……水ポンプ
１３９……圧力調整バルブＡ １４０……圧力調整バルブＢ
１８１……粉砕機 １８２……溶解槽 １８３……撹拌機
１８４……弁１８４ １８５……ポンプ １８５ 分離器……１８６
１８７……分離器１８６ １８８……ポンプ １８９……ケース
１９０……ベルトコンベヤ １９１……爪 １９２……回収容器
１９３……減圧装置１９３ １９４……洗浄槽
１９５……弁 １９６……ポンプ １９７……分離器１９７
１９８……切り替え器 １９９……ポンプ ２００……タンク
２０１……爪 ２０２……ベルトコンベヤ
２０３……爪 ２０４……回収容器 ２０５……減圧装置
２０６……タンク ２０７……ポンプ
２０８……切り替え器 ２０９……ポンプ ２１０……加熱器[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method and an apparatus for treating a mixed waste containing an organic halide-containing foamed resin, a circuit board, and the like, and separating and recovering a useful component.
[0002]
[Prior art]
In recent years, it has become difficult to secure land for landfill disposal of waste, particularly in the vicinity of urban areas. Therefore, disposal of general waste or industrial waste is an urgent issue to be dealt with. Against this background, the Waste Disposal and Public Cleansing Law (Law on the Treatment and Cleaning of Waste) has been amended to include three items of refrigerators, air conditioners, televisions with a capacity of 250 l or more, Is specified.
[0003]
Of these, refrigerators, like the other three items, are composite products composed of various types of metals and plastics (synthetic resins), which make disposal not only difficult, but also ozone depleting substances. Urethane foam resin containing a halogenated hydrocarbon (CFC) as a foaming agent is widely used as a heat insulating material. Since a method of collecting and detoxifying CFCs has not been established yet, there is a possibility that CFCs may be released to the environment over time when the urethane foam resin is landfilled.
[0004]
As a conventional method of treating a urethane foam resin containing chlorofluorocarbon, a method of reducing the volume by compression after pulverizing by pulverization or crushing, and a method of recycling a chemical raw material by adding a chemical have been attempted. .
[0005]
[Problems to be solved by the invention]
However, each of these methods is a method of treating a urethane foam resin as a single material, and a technique of treating a foamed resin in a mixed system containing a metal or another resin has not been put to practical use.
[0006]
Almost all high-performance electrical and electronic devices, including home appliances, contain a large number of circuit boards, but various types of materials such as metals, inorganic substances, and resins are used for circuit boards. However, it has made disposal and recycling difficult.
In other words, circuit boards contain valuable metals such as copper foil, as well as harmful substances such as lead as solders and flame retardants. There is a demand for the development of recycling technology that separates and collects. The most common method of recovering valuable resources from waste circuit boards is a method of removing organic substances such as substrate resin by roasting and recovering metals in a blast furnace. However, this method has problems from the viewpoints of environmental protection and recovery of valuable components with high added value.For example, from a high-temperature furnace, harmful substances contained in waste, for example, evaporation of lead compounds, which are low-melting metals, can be prevented. There is concern that dioxin and the like may be generated due to incomplete combustion.
[0007]
Further, as a processing method with a small burden on the environment, methods of separating crushed and crushed waste circuit boards by specific gravity sorting, electrostatic sorting or eddy current sorting have been proposed, but these methods have limitations in separation efficiency. However, there is a problem that the recovery rate of valuable resources is low.
[0008]
Further, as a method for dissolving a thermosetting resin with a solvent, there is a known example such as hydrolysis of a thermoplastic resin bumper having a thermosetting resin coating film. However, in these methods, the treatment is performed by a pressure type extruder such as an extruder while melting the thermoplastic resin. For this reason, the thermosetting resin can be applied when it is thin and easily deformed and extruded like a coating film, but it is applicable to a thermosetting resin, particularly a high-strength and non-thermoplastic resin containing a filler. In order to treat waste mixed with metals, ceramics and the like, it is difficult to treat with such an extruder. There is also an apparatus using a batch-type reaction vessel such as an autoclave, which has been proposed as a method for recovering reinforcing material from composite plastics. There is a drawback that the processing is wasteful because the time must be reset, and continuous processing while removing and separating the dissolved components has been desired. On the other hand, in many resin products, an inorganic material such as a filler is added to improve resin characteristics. In particular, in order to improve properties such as strength, withstand voltage and flame retardancy, it is desired to increase the filling rate of the inorganic filler as much as possible. On the other hand, high filling increases the viscosity of the resin before molding. If the filling rate is too high, fluidity is lost and molding becomes impossible. For this reason, technical development has been carried out on how to increase the filling without increasing the resin viscosity. By the way, fine particles tend to agglomerate with each other, so that even at the same filling ratio, the viscosity becomes higher than when large particles of powder are mixed, making it difficult to perform high filling. In addition, since it is difficult to uniformly disperse, a decrease in strength due to defects such as voids and a decrease in withstand voltage characteristics are caused. For this reason, in order to highly fill the fine powder, it was necessary to perform strong mixing with shearing force for a long time. In addition, in order to enhance the wettability between the filler and the resin and increase the adhesion, it is essential to add a surfactant or a coupling agent.
[0009]
The present invention has been made in view of these points, and separates and recovers useful components as resources from a mixed waste of resin and metal containing an organic halide foamable resin.EquipmentThe purpose is to provide.
[0011]
[Means for Solving the Problems]
The mixed waste treatment apparatus of the present invention includes an encapsulation machine for encapsulating the mixed waste containing the organic halide-containing foamed resin in a liquid heat medium, and a mixing machine immersed in the heat medium supplied from the encapsulation machine. A heating reaction tank for heating waste, a heating medium supply circulator for forming a circulating flow while supplying a heating medium into the heating reaction tank, and a drawing machine for drawing a resin component floating in an upper layer of the heating medium And a solid material discharging means for discharging solid matter from a lower part of the heating reaction tank, and a molten metal discharging means for discharging molten metal from the lower part of the heating reaction tank.
[0014]
DepartureThe liquid heating medium to be used is not particularly limited as long as it is a high-boiling liquid that does not react with the mixed waste containing the resin or metal to be treated, but the use of silicone oil is particularly desirable. Further, the heating temperature is set to 300 ° C. or lower, and particularly desirably 250 ° C. or lower.
[0015]
The present inventionThen, mixed waste of resin and metal, including organic halide-containing foamed resin such as foamed urethane resin used for insulation of home appliances, etc., is first roughly crushed to an appropriate size, By uniformly heating to a predetermined temperature (300 ° C or lower) in a liquid heat medium such as silicone oil, the foamed resin is softened or fluidized, and at the same time, the organic halide contained in the foamed resin is reduced. Gas is released. At this time, the other components in the mixed waste are melted, denatured, and the like by heating, and each component is separated in the heat medium due to a difference in specific gravity with respect to the medium, and each is recovered. Each component separated and recovered in this way is of high purity with very little contamination of the decomposed product of the heat medium and can be reused as a raw material or the like..
[0017]
The treatment method and treatment device of the present invention can be applied to mixed waste containing various resins. In particular, it is effective for mixed waste containing an inorganic filler or an inorganic structure. The resin can be applied irrespective of the type of the thermoplastic resin or the thermosetting resin, but is particularly effective for the thermosetting resin. These include, for example, acid anhydride cured epoxy resins, amine cured epoxy resins, phenol cured epoxy resins, polyurethane resins, polyurethane foams, urea resins, melamine resins, phenolic resins, alkyd resins, polyimide resins, unsaturated polyester resins and crosslinked. It is a resin product using a synthetic resin such as a polyethylene resin. In addition, wood-based composite materials in which wood materials are impregnated with these resins, chemically modified wood-based plastics in which wood materials are chemically modified by thermal decomposition or chemical decomposition and then liquefied and then cured alone or by adding a resin monomer again It is also effective for resin products that use natural products such as natural products. The inorganic material that can be recovered according to the present invention is contained in the mixed waste as a filler, a structure, a pigment, a viscosity modifier, a catalyst, a magnetic substance, and the like. As these materials, for example, glass, silica, alumina, magnesia, beryllia, zirconia, titanium dioxide, potassium titanate, iron oxide, calcium carbonate, oxides such as barium sulfate, aluminum nitride, nitrides such as silicon nitride, Carbon black, graphite, carbides such as silicon carbide, hydroxides such as aluminum hydroxide, earth such as mica, kaolin, clay, talc, sand and gravel, metals such as iron powder, stainless steel powder, magnetite, and ferrosilicon. Examples thereof include powders, granules, short fibers, fibers, whiskers, flakes, plates and capsules. In addition, even if the substance to be filled is wood material such as wood powder, paper powder, silicon resin, resin having high solvent resistance such as fluororesin, or organic material such as surface-modified organic substance-containing microcapsules, When the solubility in a solvent is sufficiently different from that of the resin matrix, the present invention can be applied.
[0018]
Products using these resin materials include superconducting coils such as magnetic levitation railway propulsion coils or levitation coils, vacuum circuit breakers, switch gears such as gas-green switchgear, T-type bushings, composite insulator tubes, resin mold motors, Insulating resin, sealing resin and cover materials used in products such as high-voltage rotating machines, motors for vehicles, capacitors, impregnating transformers, current transformers, transformers, printed circuit boards, semiconductors, power distribution control devices, electric wires, etc. No.
[0019]
Further, the present invention is intended to wash and remove resin waste that remains and adheres to a manufacturing apparatus or tools used for manufacturing a product containing a resin, for example, a mixing apparatus, a transport apparatus, a molding apparatus, a molding mold, and the like. It is also possible to apply it for the purpose of regenerating the collected material. In addition, the present invention can dissolve and remove the organic components without denaturing the metal or inorganic substance contained in the product in any form or composition, so that the present invention is applied to the decomposition of the product firmly sealed with the resin, or further to the analysis. be able to. In addition, the dissolved resin component is also a complex chemical decomposition such as oxidative decomposition by acids, and a plurality of decomposition reactions do not proceed at the same time. The composition and the state of the chemical bond sufficiently reflect the original resin material, and can be applied to the analysis of organic components of the resin material. In the analysis of the recovered material, various physical properties such as shape, particle size, composition of constituent elements, chemical bond, molecular weight, melting point and boiling point can be analyzed by a known method.
[0038]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments of the present invention will be described with reference to the drawings.
[0039]
FIG. 1 is a diagram schematically showing an embodiment of the mixed waste treatment apparatus of the first invention.
[0040]
In the processing apparatus of the embodiment, an encapsulating machine 2 for encapsulating mixed waste in silicone oil as a heat medium 1 and a mixed waste supplied from the encapsulating machine 2 are heated while being immersed in the heat medium 1. A heating reaction tank 3, a heating medium supply circulator 4 for forming a circulation flow in the heating reaction tank 3 while supplying the heating medium 1 to the heating reaction tank 3, and melting of a resin floating in an upper layer of the heating medium 1 A drawing machine 6 for drawing out components through a drawing-out opening 5, a solids discharge valve 7 for discharging solids from the lower part of the heating and melting tank 3, and a molten metal discharge valve for discharging molten metal from the lower part of the heating and melting tank 3 8 is provided.
[0041]
The processing of mixed waste by this processing apparatus is performed as described below.
[0042]
That is, first, the mixed waste containing urethane foam resin, coated electric wires, circuit boards to which solder is attached, and the like used for the heat insulating material of a refrigerator or the like are roughly crushed into about 10 cm square, and the heating medium 1 at room temperature is stored. Into the sealing machine 2. The sealing machine 2 is provided with a piston-type press-fitting machine 9 and a movable slit 10, respectively, and the mixed waste can be sent into the heating reaction tank 3 by the press-fitting by the press-fitting machine 9 and the opening and closing of the slit 10. I can do it.
[0043]
On the other hand, in the heating reaction tank 3, silicone oil as the heating medium 1 is stored to a predetermined position in advance, and the heating medium 1 is heated to a predetermined temperature of 300 ° C. or less by a heater 11 arranged around the outer wall of the tank. Is uniformly heated to the temperature. When the mixed waste is supplied from the encapsulating machine 2 into the heating medium 1 and controlled to maintain a predetermined temperature, the urethane foam resin starts to soften or fluidize, and the gas such as the foaming agent contained in the foam resin becomes Released. Then, the softened or fluidized urethane resin component 12 stays in the upper layer of the silicone oil as the heat medium 1.
[0044]
Further, a metal having a low melting point, such as solder, is melted, and since the specific gravity of the molten metal 13 is greater than that of the heat medium 1, the molten metal 13 sinks and deposits at the lower portion of the heating reaction tank 3. The molten metal 13 that has settled and deposited is discharged from the molten metal discharge valve 8. Heating is performed while controlling the temperature at which the urethane foam resin is kept in a softened or fluidized state, and is retained in the heating reaction tank 3. At this time, in order to enhance the effect of heating by the heating medium 1, To generate a gentle circulation flow in the heat medium 1 using
[0045]
In addition, a resin-metal (metal wire or metal piece) composite having a large specific gravity, such as an electric wire, is provided with an inclined screen 15 provided at a lower portion in the heating reaction tank 3 while maintaining the state of the solids 14 in the heating reaction tank 3. It is gently descended and discharged from the solid discharge valve 7. At this time, the circulating flow of the heat medium 1 is sent from the lower part of the heating reaction tank 3 by the heat medium supply circulator 4, so that the solid matter 14 can be prevented from sticking to the screen 15. When the solid matter 14 discharged in this way is rapidly cooled, the surface of the resin coating deteriorates and becomes easily peeled off. Therefore, the solid resin 14 is rapidly cooled, the deteriorated resin coating is peeled off, and the resin part and the metal part are separated and collected. Can be. Further, it is also possible to separate and collect by specific gravity in the specific gravity separation tank 16.
[0046]
Further, the collected resin solids can be pulverized to, for example, 5 mm or less, mixed with resin or fibrous dust collected from other waste routes, and burned in a furnace. Then, by using the energy (combustion heat) of the combustion furnace to heat the heat medium 1, more effective use of the energy can be achieved.
[0047]
The gas such as the foaming agent released from the foamed resin is guided from the gas outlet at the upper portion of the heating reaction vessel 3 to the gas adsorption vessel 17, where the gas is detoxified. The main components of the gas are CFCs discharged from the urethane foam resin and hydrogen chloride generated from the vinyl chloride resin that is the covering material for the electric wires. After the hydrogen chloride is removed by washing with water, the CFCs are decomposed in the CFC decomposition process. It is processed. There are various methods for decomposing CFCs, such as a catalytic decomposition method, a combustion method, a plasma decomposition method, and a supercritical decomposition method.
[0048]
After the gas release is sufficiently generated, the heating medium 1 is further supplied into the heating reaction tank 3 to raise the liquid level, so that the softened or fluidized resin 12 is located at the center of the upper layer of the heating medium 1. It is pulled out from a certain outlet 5. Since the resin recovered in the resin recovery tank 18 has very little mixing of the decomposition product of the heat medium 1, it can be reused as a resin material for molding or the like.
[0049]
Next, another embodiment of the apparatus and method for treating mixed waste of the present invention will be described.
[0050]
In the processing apparatus shown in FIG. 2, two types of heat media 1 having different specific gravities, for example, silicone oil, are accommodated in a heating reaction tank 3 so as to form upper and lower two layers. Of the heat medium 1a are stored. That is, the heating medium 1b having a higher specific gravity is first put into the heating reaction tank 3 up to a height of 40% from the bottom, and the heating medium 1a having a lower specific gravity is housed thereon to a height of 70% from the bottom. The heating medium 1b having a large specific gravity is heated to a temperature of 200 ° C., and the heating medium 1a having a small specific gravity is heated to a temperature of 250 ° C. by a heater 11 attached to the outer wall of the heating reaction tank 3.
[0051]
The processing of mixed waste by this processing apparatus is performed as described below.
[0052]
First, mixed waste including foamed urethane resin, coated electric wires, circuit boards to which solder is attached, and the like are roughly crushed and then passed through an encapsulating machine 2 in which a heating medium 1a at room temperature is stored. It is sent into the heat medium 1a having a specific gravity. Then, in the heating medium 1a controlled to be heated to a temperature of 250 ° C., the urethane foam resin starts to soften or fluidize, and a gas such as a foaming agent contained in the foam resin is released. Then, the softened or fluidized urethane resin component 12 stays in the upper layer of the heat medium 1a having a small specific gravity.
On the other hand, low melting point metal such as solder contained in the mixed waste is heated and melted, and has a higher specific gravity than the large specific gravity heat medium 1b heated and maintained at 200 ° C. accumulate. The molten metal 13 is discharged from the molten metal discharge valve 8. Moreover, since the specific gravity differs between the solid matter 14 such as a resin-coated metal wire or a metal piece such as an electric wire and a thermoplastic resin containing no metal, by appropriately adjusting the specific gravity of the two types of heat medium 1, The ability to separate resin and metal can be improved. That is, the melt 19 of the thermoplastic resin having a specific gravity slightly lower than that of the heat medium 1b stored in the lower portion in the heating reaction tank 3 is composed of the heat medium 1b having a large specific gravity and the heat medium having a lower specific gravity in the upper layer. Since it floats up to the interface with 1a, it can be pulled out of the tank from the side outlet 20 provided at the height of the interface, and separated and collected. In addition, the solid matter 14 that does not melt, such as a resin-coated metal wire or a metal piece such as an electric wire, slowly descends on a screen 15 provided in the lower part in the tank, and is discharged from the solid matter discharge valve 7.
[0053]
Further, another embodiment of the processing apparatus of the present invention will be described.
[0054]
In the processing apparatus shown in FIG. 3, a cylindrical tube heater 21 is provided inside the heating reaction tank 3, and the heating medium 1 accommodated in the heating reaction tank 3 is uniformly heated, and the heating effect on the mixed waste is obtained. The stirrer 22 is provided so as to increase the temperature, and the stirring blades rotate along the outer peripheral surface of the heater 21. Further, a part of the circulation route of the heating medium 1 is arranged on the outer periphery of the sealing machine 2, and the mixed waste supplied from the sealing machine 2 into the heating reaction tank 3 is preheated by the circulation preheating section 23. Has become.
[0055]
In the processing apparatus shown in FIG. 4, a cylindrical tube heater 21 is provided inside the heating reaction tank 3, and a rotary crusher 24 is disposed at a connection port of the sealing machine 2 to the heating reaction tank 3. The mixed waste sent from the encapsulating machine 2 is crushed by the crushing machine 24 into a size of about 3 cm square, and then supplied into the heating reaction tank 3.
Further, in the processing apparatus shown in FIG. 5, the heating reaction tank 3 has an inclined tube shape, and a stirrer 22 is provided in the inclined tube type reaction tank 3.
[0056]
3 to 5, the mixed waste containing the attached metal such as solder, the resin-coated electric wire, the urethane foam resin, and the like can be liquidized in the heating reaction tank 3 in the same manner as in the above-described embodiment. By immersing in a heat medium 1 and heating to a controlled temperature, the foamed resin or the like is liquefied or fluidized, and a gas such as a foaming agent contained in the foamed resin is released and collected. The resin such as the wire covering material is degraded and peeled off, and the low melting point metal such as solder can be recovered without dissolving in the heat medium 1. In addition, the resin and metal thus separated and recovered can be reused, and furthermore, by burning the separated and recovered resin and heating the heat medium, resources can be effectively used in terms of thermal energy. .
[0057]
Next, an embodiment of the second invention will be described.
[0058]
FIG. 6 shows a flow of a method for treating a resin-mixed waste, for example, a waste circuit board with a solvent, according to the second invention.
[0059]
As shown in the figure, this method comprises a pretreatment step, a solvent treatment step of immersing the pretreated resin mixed waste in a solvent, swelling softening or dissolving the resin constituting the substrate, and a resin treatment after the solvent treatment. A separation and recovery step for recovering valuable resources from the mixed waste, a post-processing step for further recovering valuable resources, an analysis step for analyzing the components of the solvent after the processing, and a solvent after the processing according to the analysis result. And a solvent regeneration step of regenerating the solvent.
[0060]
In the resin mixed waste, after the parts and members that can be separated in the pretreatment step are separated and collected, the resin is swollen, softened or dissolved by the solvent in the solvent treatment step. By performing the pretreatment, a layer or a member that hinders the solvent treatment is removed and recovered in advance, so that the solvent treatment is easy and the contamination of impurities during the solvent treatment can be prevented. Resin mixed waste that has passed through the solvent treatment process is in a state where the binder resin swells and softens or dissolves, making it extremely easy to disassemble and separate each component. Then, by passing through a post-treatment step, valuable resources are more completely separated and collected. In the separation and recovery step, valuable resources are separated and recovered from the used solvent.
[0061]
Since the recovered product obtained from the separation and recovery step is separated and recovered through a treatment with a solvent, it has been subjected to high-efficiency separation or selective decomposition, and is a valuable material with particularly high added value. Among the members to be recovered, for example, the resin-derived recovery components used for the substrate include resins, oligomers, and monomers that can be melt-reformed, and a component such as a suitable hardener is added as it is. Alternatively, it is mixed with another resin, melt-reformed, and used as a cured resin. Further, it is also possible to extract and purify only useful components from the decomposition products, and reuse them as useful reagents such as chelating agents, precipitants, flocculants, and surfactants. Furthermore, the inorganic components such as glass fibers used for the substrate are not degraded because the deposits such as resin are separated and removed under mild conditions by a solvent treatment without going through a treatment such as roasting. Furthermore, since there is no adhesion of carbon, tar, and the like, it can be reused as a high-value-added valuable material, for example, as an inorganic filler for a resin, in a composite material, or by melting and remolding alone.
[0062]
In the analysis step, the state of deterioration of the solvent from which the valuables have been separated and recovered in this manner is appropriately grasped, and it is checked whether or not the solvent retains the function as the solvent. Then, in accordance with the analysis result, in the solvent regeneration step, replenishment of reduced components and removal of unnecessary impurities are performed, and the solvent is regenerated as a solvent having a usable function, sent to the solvent treatment step, and reused. .
[0063]
FIG. 7 schematically shows an example of an apparatus for performing a solvent treatment according to such a flow.
[0064]
In this processing apparatus, a solvent distillation / recovery tank 28 is connected to a solvent processing tank 27 provided with a heating device 25 and an ultrasonic generator 26 as means for accelerating the solvent processing. These two tanks, the condenser 29 and the solvent tank 30 are connected by pipes to form a circulation path, and only the solvent is vaporized by distillation in the solvent distillation and recovery tank 28, and the solvent vapor is condensed. It is condensed again in the vessel 29, temporarily stored in the solvent tank 30, and is again supplied to the solvent processing tank 27 by the pump 31 for reuse.
[0065]
The resin mixed waste 32 put in the solvent treatment tank 27 leaves only the components insoluble in the solvent in the solvent treatment tank 27, and the eluted components move to the solvent distillation and recovery tank 28 together with the solvent. Then, by repeating extraction and dissolution with the solvent and distillation of the solvent, the eluted components are concentrated and collected in the dissolved component recovery tank 33.
[0066]
An apparatus 34 for analyzing components in the solvent is provided between the solvent vapor condenser 29 and the solvent tank 30. The type of the analyzer 34 is not particularly limited as long as the analyzer can detect the deterioration state of the function as a solvent. For example, chromatographic analyzers such as gas chromatography, liquid chromatography, gel permeation chromatography, ion chromatography, infrared spectroscopy, visible / ultraviolet spectroscopy, Raman, atomic absorption, weight and other spectral analyzers, light scattering measurement, electrical conductivity Examples of the apparatus include degree measurement and pH measurement, and these apparatuses can be used alone or in combination. These analyzers 34 can be installed adjacent to the solvent processing apparatus, and sampled samples can be analyzed each time.
[0067]
Further, a filtration device 35 is connected between the analyzer 34 and the solvent tank 30 via a flow path switching device 36, and an additive tank 37 is further provided. The required function is regenerated and given to the solvent. As the solvent regenerating apparatus, in addition to the filtering apparatus 35, an apparatus for removing impurities and adding a deterioration / reduction component such as an ion-exchange resin tower is used. Or installed in a processing apparatus.
Further, in the embodiment shown in the flow chart of FIG. 6, for example, when treating a waste circuit board, in the pretreatment step, the efficiency of the solvent treatment is increased and the diffusion of harmful substances or valuables into the solvent is prevented. For this purpose, solder, mounted semiconductor components, copper foil, solder resist and the like are separated and removed. FIG. 8 shows an apparatus for removing a mounted semiconductor component using a scraper blade for melting and scraping solder by heating. In the figure, reference numeral 38 denotes a supply hopper, 39 denotes a waste circuit board, 40 denotes a mounted semiconductor component, 41 denotes a transport roller, 42 denotes a heater, 43 denotes a scraper blade, 44 denotes a board collection box, and 45 denotes a mounted component collection box. ing. FIG. 9 shows an apparatus for removing solder by powder spraying. In the figure, reference numeral 46 denotes a solder-adhered waste circuit board, 47 denotes a sandblasting tank, 48 denotes a holding jig, 49 denotes an inorganic powder such as alumina or silica, Reference numeral 50 denotes a powder injection port, and 51 denotes an injection pump.
[0068]
Further, in the post-processing step, components such as solder, mounted semiconductor components, copper foil, resin, and glass fiber are removed from the substrate which has been treated with a solvent and is easily decomposed or separated by swelling softening or dissolving of the resin. Separated and collected. FIG. 10 shows an apparatus for separating copper and glass components by impact shearing type crushing and wind sorting by cyclones. In the figure, reference numeral 52 denotes a feeder, 53 denotes a hammer, 54 denotes an injection pump, 55 denotes a cyclone, 56 denotes a lightweight recovery component (glass component), and 57 denotes a weight recovery component (copper).
[0069]
【Example】
Hereinafter, specific examples of the present invention will be described. The embodiments described below are examples that embody the present invention, and the present invention is not limited to the embodiments.
[0070]
Example 1
Mixed waste including urethane foam resin and wire scraps used for heat insulating materials for refrigerators and board materials (circuit boards) to which solder is attached is roughly crushed into square pieces of about 10 cm square and put into a sealing machine. As a result of performing the heat treatment using the processing apparatus shown in FIG. 1, 13 kg of the softened or fluidized resin per about 50 kg of the enclosed amount by one movement of the slit 10 is removed from the drawing port 18 in the upper part of the heating reaction tank 3. And was collected. Further, when the resin-coated solid discharged from the solid discharge valve 7 at the lower portion of the heating reaction tank 3 is rapidly cooled, the surface of the resin coating deteriorates and easily peels off, and the heat treatment with the heat medium 1 is not performed. It was found that the removal of the resin coating and the separation and recovery of the metal wire were easier than those of the first embodiment. Approximately 34 kg of metal was separated and recovered from these solids, but the separated metal contained a large amount of iron, copper, aluminum, etc., and could be separated and recovered using means such as specific gravity separation. Was. Further, about 2 kg of molten solder was recovered from the molten metal discharge valve 8.
[0071]
Example 2
The same mixed waste as in Example 1 was subjected to a heat treatment using the treatment apparatus shown in FIG. As a result, 13 kg of the softened or fluidized resin was withdrawn and collected from the withdrawal port 18 in the upper portion of the heating reaction tank 3 per about 50 kg of the sealed amount by one movement of the slit 10. About 4 kg of a metal-free thermoplastic resin (melt) was taken out from the side outlet 20 provided at the height of the interface between the two types of heat mediums 1a and 1b having different specific gravities. Further, about 30 kg of metal was separated and recovered from the solid discharged from the solid discharge valve 7 below the heating reaction tank 3, and about 2 kg of molten solder was recovered from the molten metal discharge valve 8.
[0072]
Examples 3 to 5
The same mixed waste as in Example 1 was subjected to a heat treatment using the processing apparatus shown in FIGS. As a result, 13 kg of the softened or fluidized resin was withdrawn and collected from the withdrawal port 18 in the upper portion of the heating reaction tank 3 per about 50 kg of the sealed amount by one movement of the slit 10. About 34 kg of metal was separated and recovered from the solids taken out of the solids discharge valve 7 at the lower part of the heating reaction tank 3. The separated metal contains a large amount of iron, copper, aluminum and the like, and could be separated and recovered by using a means such as specific gravity separation. Further, about 2 kg of molten solder was recovered from the molten metal discharge valve 8.
[0073]
(Separation and removal of solder)
As a pretreatment for performing the solvent treatment on the waste circuit board, an experiment was conducted in which the solder on the circuit board was separated and removed, and the solder and metal (copper) were collected.
[0074]
Experimental Examples 1 to 16
First, an example of an apparatus for separating solder and recovering copper will be described.
[0075]
As shown in FIG. 11, the apparatus comprises a circuit board input section 58, a solder separation / removal tank 59, a circuit board crusher 60 after removing the solder, and a copper recovery section 61. The waste circuit board 63 put into the hopper 62 is transported by the belt conveyor 64 to the solder separation / removal tank 59 in which the melting point (183 ° C.) of the melting point (183 ° C.) of the eutectic Pb—Sn solder is higher than 190 ° C. It is immersed in the separation solution 65 heated to a temperature of 350 ° C. The separation liquid 65 is obtained by adding an additive that reduces the wettability of solder to metal (copper) to a high-boiling organic solvent such as glycerin, ethylene glycol, or n-octane. In addition, the waste circuit board 63 in the separation liquid 65 is irradiated with ultrasonic waves emitted from the ultrasonic generator 66 installed at the bottom, and the peeling of the solder from metal (copper) is promoted. It has become. The peeled solder is collected in a solder dunk 67, and the supernatant of the separation liquid 65 is collected and collected in a supernatant tank 68. Further, the circuit board 69 from which the solder has been peeled off is finely pulverized by a crusher 60 to a particle size of about 200 μm, and the obtained powder is conveyed to a copper recovery unit 61. After the powder of the glass fiber or the thermosetting resin is separated, the powder is separated into a Cu-rich powder 72 and an insulator-rich powder 73 by an electrostatic separator 71, and copper is recovered from the Cu-rich powder 72. .
[0076]
Next, a waste circuit board (4.2% by weight of solder lead, 24% by weight of copper, 30% by weight of glass fiber, 30% by weight of glass fiber, 15% by weight of epoxy resin, and other mold 26.8 wt% of resin), and a liquid obtained by adding the additives shown in Table 1 at a ratio of 1 wt% to glycerin was used as a separation liquid, and heated to 220 ° C. to separate solder and recover copper. Done. When the circuit board discharged from the solder separation and removal tank 59 was taken out and the content (concentration) of lead was examined, the results shown in Table 1 were obtained.
[0077]
[Table 1]

As described above, from Table 1, by the treatments of Experimental Examples 1 to 16, lead contained in the circuit board was almost completely (for example, in Experimental Example 1, the concentration of lead after the treatment was 0.004%, and the removal rate was 99.9%) was found to be removed. Further, in Experimental Example 1, when the Cu-rich powder recovered in the copper recovery section was quantified and the copper recovery rate was examined, approximately 85 wt% of the copper contained in the circuit board could be recovered.
[0078]
Experimental Example 17
First, the solder separation / removal tank of the apparatus used in this experimental example will be described.
[0079]
In this apparatus, as shown in FIG. 12, a separation / removal tank 59 for solder is provided with a chain conveyor 75 provided with a vibration generator 74 and a mixed gas of air 76 as a carrier gas and ozone 77 as an oxidizing gas. The waste circuit board 63 carried from the batch-type entrance part 80 provided with two opening / closing doors is suspended by the chain conveyor 75 and moves. Then, in the moving process, the solder having reduced wettability to metal (copper) is shaken off by spraying and vibration of a mixed gas of air and ozone, and the dropped solder is collected in the solder collection tank 81. It has become. Except for such a solder separation / removal section, other portions are configured in the same manner as the apparatus shown in FIG.
[0080]
Next, using this apparatus, the same waste circuit board as in Experimental Examples 1 to 16 was heat-treated at a temperature of 230 ° C. When the circuit board discharged from the solder separation and removal tank 59 was taken out and the content (concentration) of lead was examined, it was 200 ppm (0.02 wt%), and the lead removal rate was 99.5%. Further, when the Cu-rich powder obtained in the copper collecting section was quantified and the copper recovery rate was examined, approximately 85% by weight of copper contained in the circuit board could be recovered. Experimental Example 18
A method for electrochemically separating and removing solder on a circuit board to recover copper and the like will be described.
[0081]
In this method, first, screw connectors and mounted semiconductor components are disassembled and separated from the waste circuit board in a pretreatment step, and then, as shown in FIG. Immersion in an electrolytic solution 83 containing copper ions, for example, an aqueous solution of copper nitrate, performing electrolysis using a brush-type electrode 84, dissolving the solder attached to the circuit board 82, and adding copper ions to an electrode 85 such as platinum. Precipitate and collect. Next, in an intermediate processing step, processing such as crushing, crushing, and polishing is performed on the circuit board from which the solder has been separated and removed. This step is effective, for example, when the copper is not sufficiently exposed on the surface of the multilayer board.
[0082]
Next, in a copper dissolving solder recovery step, as shown in FIG. 14, the circuit board 82 subjected to the intermediate treatment is immersed in a solder dissolving liquid 86, for example, an aqueous solution of lead nitrate and tin nitrate to perform electrolysis. While dissolving the copper on the substrate, lead and tin ions are precipitated and collected on an electrode 85 such as platinum. In addition, in the solder melting copper collection and the copper melting solder collection process, a conductive sheet is used for good connection with the circuit board. Finally, in a post-processing step, the processed substrate resin and / or glass fiber is recovered. The thus-recovered substrate resin and glass fiber have extremely high added value because the metal component is removed with high efficiency.
[0083]
In addition, in the solder melting copper recovery step, the power generated in the electric circuit can be recovered in a storage battery, and after adjusting the voltage through a stabilizing power supply, in the copper melting solder recovery step, as an auxiliary power supply for electrolysis. Can be used.
[0084]
Next, the waste circuit board was processed using this method.
[0085]
That is, a platinum brush-shaped electrode is brought into contact with a waste circuit board from which connectors and mounted components are separated, immersed in a 0.5 mol / l copper nitrate aqueous solution, and furthermore, a platinum plate electrode is placed in the same electrolytic solution. Dipped. At this point, the dissolution of the solder from the substrate is slow, but when the platinum plate electrode and the brush-like electrode are electrically connected, an electromotive force is generated with these as the positive and negative electrodes, and copper is deposited on the platinum plate electrode. As it started, the melting of the solder was accelerated. The electromotive force generated in the electric circuit was about 0.47 V, and the copper deposition continued until all the solder was eluted. When the copper precipitated on the platinum plate electrode was recovered, high-purity copper having a purity of 99% or more was obtained.
[0086]
Next, the platinum plate electrode on which copper was deposited was replaced with a new platinum plate electrode, and a stabilized power supply was installed in the electric circuit. When a stabilizing power supply was connected and a voltage was applied, lead began to be deposited on the platinum plate electrode by electrolysis, and copper on the waste circuit board in contact with the brush type electrode began to dissolve. When the electrolysis was further continued, tin was deposited on the platinum plate electrode. When lead and tin deposited on the platinum plate electrode were recovered and weighed, it was found that 99% or more of the solder adhered on the waste base circuit board was recovered.
[0087]
Example 6
Next, the waste of the circuit board from which the solder was separated and removed in the pretreatment step was subjected to a solvent treatment using an apparatus shown in FIG. 7 using ethylenediamine as an organic solvent to obtain a resin solution. The components were extracted from the obtained solution using tetrahydrofuran and purified by a gel permeation column to recover components derived from a resin having an average molecular weight of 700. Using this recovered component as a flocculant and treating a 5 wt% solution of sodium adipate as a sample, sodium adipate can be coagulated and precipitated to a concentration of 0.5% or less, which is useful as a flocculant. That was confirmed. After the solvent treatment, high-quality inorganic components such as glass fibers could be easily separated and recovered from the substrate separated from the resin solution.
[0088]
Examples 7 to 24
After the resin waste (containing an inorganic substance such as a filler) shown in Table 2 was pulverized to a particle size shown in the same table, ethylenediamine (ED), imidazole (I), pyridine (P), dimethylformamide (DMF) ), Dimethylsulfoxyl (DMS), N-methyl-2-pyrrolidone (NMP), 1,3-dimethylimidazolidinone (1,3-DMI), 1,4-dimethylimidazolidinone (1,4-DMI) ), 1,5-dimethylimidazolidinone (1,5-DMI) and 1,6-dimethylimidazolidinone (1,6-DMI), respectively, to dissolve the resin component. Dissolution was performed while heating to the temperature shown in Table 2 and stirring with a rotating blade. Next, after the residue was separated and removed from the resin solution by a precipitation method, the solvent was separated by distillation from the resin solution from which the residue was separated, and an organic component derived from the resin was recovered.
[0089]
When the cross-linking agents shown in Table 2 were added to the organic components thus recovered and cured, a molded article was obtained and could be reused. In addition, the residue separated from the resin solution could be mixed with the newly formed resin shown in Table 2, and could be sufficiently reused as a filler.
[0090]
[Table 2]

Example 25
Dissolve the thermosetting resin that constitutes the circuit board using supercritical water, etc., on the waste circuit board after the solder has been removed and the mounted components have been removed in the pretreatment process, and recover metal copper etc. did.
[0091]
First, the resin melting device will be described.
[0092]
As shown in FIG. 15, this apparatus includes a circuit board crushing device 87, a mixture feed pump 88 that pressurizes and feeds a slurry obtained by mixing a substrate crushed product and water, and a pressurized water to feed a wheel. A water pump 89 for feeding / supplying, an oxidizing pump 90 for feeding / supplying the oxidizing agent at a high pressure, a heat exchanger 91 for heating and raising the temperature of the mixture of water and oxidizing agent, A reaction tube 92 with a heater for accommodating and reacting with an object to be processed, a cooler 93, and a back pressure valve 94 are provided. Each part of the apparatus is desirably made of a material having heat resistance and pressure resistance and high corrosion resistance, such as stainless steel, titanium, Hastelloy, and Inconel.
[0093]
In this apparatus, the circuit board supplied from the board input port is crushed by a crusher 87. Examples of the crusher include a shredder, a crusher, and a rotary crusher, which are coarse crushers, a cutter mill, a roll crusher, a cone crusher, and a hammer mill, which are intermediate crushers, and a ball mill and a vibrating ball mill, which are fine crushers. No. The substrate crushed product is immediately mixed with water to form a slurry-like mixture, and the mixture is pressurized and fed by the mixture feed pump 88.
[0094]
On the other hand, an oxidant such as air, oxygen, or hydrogen peroxide, which is pressurized and conveyed by the oxidant pump 90, is mixed with the water conveyed by the water pump 89 and conveyed. Then, after the temperature is increased through the heat exchanger 91, the mixture with the slurry-like mixture fed by the mixture feed pump 88 is combined, and then the reaction mixture enters the reaction tube 92 with a heater. The pressure inside the reaction tube 92 is controlled by a pump and a back pressure valve 94. The resin component in the fluid is rapidly decomposed and dissolved by being heated and pressurized in the reaction tube 92 with a heater to a temperature and pressure of 374.2 ° C. or 22.1 Mpa or more, which is a critical point of water. . The mixture exiting the reaction tube is cooled by the heat exchanger 91 and then further cooled by the cooler 93, then depressurized through the back pressure valve 94 and recovered at the outlet.
[0095]
Using such an apparatus, the circuit board from which the mounted components and the solder have been removed by solder melting and surface polishing, respectively, is oxidized with twice the amount of hydrogen peroxide solution required for complete oxidation of the resin contained in the circuit board. Dissolution treatment was performed using the composition as an agent. As the pulverizing device 87, a combination of a rotary crusher, a roll pulverizer and a vibrating ball mill was used, and pulverized to an average particle size of 300 μm. The processing temperature and pressure in the reaction tube 92 with a heater were 380 ° C. and 24 Mpa at the inlet, and the residence time in the reaction tube was adjusted to 30 minutes. The mixture after the treatment was filtered to recover copper and glass fibers. When the total organic carbon in the solution after filtration was measured, the concentration was 15 ppm or less. Further, when dioxins in the mixture before filtration were analyzed, they were below the detection limit.
[0096]
Example 26
Using the apparatus shown in FIG. 15, the circuit board subjected to the pretreatment in the same manner as in Example 25 was subjected to a dissolution treatment. As the pulverizer 87, a combination of a rotary pulverizer and a roll pulverizer was used, and the processing temperature and pressure in the reaction tube 92 with a heater were 300 ° C. and 10 Mpa. When the solid content was separated from the mixture after the treatment and dried in an electric furnace, the glass fibers were not brittle. The glass fiber content was pulverized by a ball mill in the same manner as in Example 24, separated by the same sieve, and the composition of residual components on the sieve was analyzed. As a result, the copper purity was 81%.
[0097]
Example 27
A 24.5 mm square was cut out of the circuit board from which the mounted components and solder were removed by solder melting and surface polishing, respectively, and melted using a batch-type device consisting of a 122 cc pressure vessel and an electric furnace. Processed. The to-be-processed piece and 38.4 cc of water were charged into a pressure vessel, sealed, and treated at 380 ° C. and 24 Mpa reaction conditions for 2 hours. Observation of the substrate piece after the treatment revealed that each layer could be easily peeled off with tweezers, the copper foil and the glass fiber could be separated by hand, and the glass fiber was brittle.
[0098]
Comparative example
Using the apparatus shown in FIG. 15, the circuit board subjected to the pretreatment in the same manner as in Example 25 was subjected to a dissolution treatment. As the crushing device 87, a combination of a rotary crusher and a roll crusher was used, and the processing temperature and pressure in the reaction tube 92 with a heater were set to 150 ° C. and 0.5 MPa. After the solid content was separated from the mixture after the treatment and dried in an electric furnace, the glass fiber component was pulverized by a ball mill in the same manner as in Example 24, separated by the same sieve, and analyzed for the composition of the residual components on the sieve. Purity was 44%.
[0099]
Example 28
Dissolve the thermosetting resin that constitutes the circuit board using supercritical water, etc., on the waste circuit board after the solder has been removed and the mounted components have been removed in the pretreatment process, and recover metal copper etc. did.
[0100]
First, the resin melting device will be described.
[0101]
As shown in FIG. 16, the apparatus includes a supply tank 95 for storing a mixture of substrate crushed material and water, an opening / closing valve A96, a high-pressure vessel A97, an opening / closing valve B98, and a water pressurizing device. A high-pressure pump A99 that transports and floods water, a high-pressure pump B100 that also transports and supplies water by increasing pressure, a heat exchanger 101 that heats and raises water, and a reaction that accommodates and mixes water and a mixture. The reactor includes a reaction tube with heater 102, a cooler 103, a separator 104, a back pressure valve 105, a high pressure vessel B106, an open / close valve C107, an open / close valve D108, an open / close valve E109, and a water pump 110. Each part of the apparatus is desirably made of a material having heat resistance, pressure resistance and high scab resistance, such as stainless steel, titanium, Hastelloy, and Inconel.
In this apparatus, of the mixture of the substrate crushed material and water stored in the supply tank 95, the substrate crushed material having a specific gravity greater than that of water is opened and closed by opening and closing the opening and closing valves A96 and B98. It flows into the discharge-side pipe of the high-pressure pump A99 by gravity sedimentation. The high-pressure container A97 is always filled with water. When the opening / closing valve A96 is open, the substrate crushed material is settled in the high-pressure vessel A97 without particularly pressurizing the inside of the supply tank 95 by closing the opening / closing valve B98, and then the opening / closing valve A96 is closed. By opening B98, the high-pressure container A97 is instantaneously placed under the same high-pressure condition as the high-pressure pump A99 discharge side, and the substrate debris sinks and flows into the discharge-side pipe. By repeatedly performing this procedure, the substrate crushed material can be intermittently injected into the high pressure field, but according to this method, unlike the case where the substrate crushed material is directly transported by the high pressure pump, No pump wear and blockage occurs, and there is no need to pulverize the substrate material to pass through the pump.
[0102]
On the other hand, the water pressurized by the high-pressure pump B100 is heated through the heat exchanger 101, then merges with the flow of the substrate crushed material of another system and water, and then enters the reaction tube 102 with a heater. The pressure inside the reaction tube 102 is controlled by a pump and a back pressure valve 105. The resin component in the fluid is rapidly decomposed and dissolved by being heated and pressurized to a temperature and pressure of 374.2 ° C. or 22.1 Mpa or more, which is the critical point of water, in the reaction tube 102 with a heater. . The mixture leaving the reaction tube is cooled by the heat exchanger 101 and subsequently further cooled by the cooler 103.
[0103]
Thereafter, the object enters the separator 104. Then, after the separator 104, the solid content in the object to be processed is mainly changed to the open / close valve C107, the high-pressure vessel B106, and the open / close valve by the same principle as that of the method of injecting the substrate crushed material into the high-pressure field by opening and closing the valve. It is discharged out of the system through the valve D108. At that time, at the time of the opening operation of the opening / closing valve C107, the inside of the high-pressure container B106 is filled with water in advance by the water pump 110, and the low-pressure / high-pressure fluid having almost no compressibility is extracted instead of the high-temperature / high-pressure fluid. Doing so minimizes pressure fluctuations in the system and ensures operation of the entire processing system. Depending on the type of the open / close valve C107 at the time of extraction, if the valve is closed when the solid content exists in the pipeline of the valve mounting portion, the valve may not operate normally or the valve may break down. For this reason, a device for detecting the flow of solids, for example, an ultrasonic flowmeter, is installed in the pipeline immediately before the opening / closing valve C107 or the pipeline immediately before the separator 104, and the pipeline in the valve mounting portion is installed. It is desirable to close the valve when no solids are present. As described above, since the substrate crushed product is intermittently injected, there is a liquid-only portion in which no solid content exists in the pipeline, and thus such operation becomes possible. This solid content detection device can be installed immediately before the other three open / close valves, that is, the open / close valve A96, the open / close valve B98, and the open / close valve D108.
[0104]
On the other hand, the stream containing the liquid organic component passes through a filter installed at the upper outlet of the separator 104, passes through the back pressure valve 105, is depressurized, and is recovered at the outlet. Due to the presence of the filter, the flow passing through the back pressure valve 105 contains no solids, so there is no risk of blockage here or wear of the back pressure valve. A part of the liquid organic component can be discharged through the on-off valve C107, but most of the liquid organic components are contained in the pipe on the side of the back pressure valve 105 because either the on-off valve C107 or the on-off valve D108 is always closed. It is sent and discharged out of the system. As a method of recovering the organic component from the discharged liquid organic component, for example, membrane separation, distillation, or a combination thereof can be used, and the water after recovering the organic component is again supplied to the high-pressure pump A99 or It is also possible to return to the suction side of the high-pressure pump B100.
Using such an apparatus, the circuit board from which the mounted components and the solder were removed by solder melting and surface polishing was subjected to a melting treatment. The circuit board was pulverized by using a pulverizer in which a rotary crusher and a cutter mill were combined, and the pulverized material was sieved to obtain a material having a particle size of 1 mm or more and 2 mm or less. The weight composition ratio of the object to be treated is 31% of copper, 41% of glass fiber, and 28% of epoxy resin. The processing temperature and pressure in the reaction tube with heater 102 were 380 ° C. and 24 MPa, and the residence time in the reaction tube was adjusted to 1 hour. After filtering the mixture after the treatment and drying the solid remaining on the filter paper, it is sealed in a plastic container, and shaken up and down at a speed of 200 times per minute for 10 minutes with a shaker. The glass fibers that had been embrittled by the supercritical treatment were finely powdered. The content was separated by a sieve having a diameter of 600 μm, and the purity of copper in the solid remaining on the sieve was determined by digit. As a result, the purity of copper was 90%. Further, when the organic component in the filtered aqueous solution was analyzed, it was confirmed that phenol, cresol and isopropylphenol, which are valuable materials, were the main components. Further, the weight ratio of these collected materials to the resin component in the substrate to be processed was 20.1%, 4.3% and 3.7%, respectively. Acetone was also confirmed as another water-soluble organic component.
[0105]
Example 29
Using the processing apparatus shown in FIG. 16, the circuit board from which only the mounted components were removed by solder melting was subjected to a melting process. The circuit board was pulverized by using a pulverizer in which a rotary crusher and a cutter mill were combined, and the pulverized material was sieved to obtain a material having a particle size of 1 mm or more and 2 mm or less. The weight composition ratio of the object to be processed is copper 30%, glass fiber 38%, epoxy resin 27%, and solder 5%. The processing conditions are the same as in Example 28. The mixture after the treatment was filtered, and the lead ion, tin ion, and copper ion in the filtered solution were analyzed. The results were below the detection limit.
[0106]
Example 30
Using the apparatus shown in FIG. 16, the circuit board subjected to the pretreatment, pulverization and sieving operations was subjected to a dissolution treatment in the same manner as in Example 28. The processing temperature and pressure in the reaction tube 102 with a heater were set to 300 ° C. and 10 Mpa, and the residence time in the reaction tube was adjusted to 1 hour. After the mixture after the treatment was filtered and the solid remaining on the filter paper was dried, the mixture was shaken for 10 minutes in the same manner as in Example 28. The contents were separated by the same sieve, and the copper purity in the solid matter remaining on the sieve was analyzed. As a result, the copper purity was 33%. Further, when the organic content in the filtered solution was analyzed, it was confirmed that phenol which is a valuable material was a main component. The weight ratio of phenol to the resin component in the substrate to be processed was 9.2%.
[0107]
Comparative example
Using the apparatus shown in FIG. 16, the circuit board subjected to the pretreatment, pulverization and sieving operations was subjected to a dissolution treatment in the same manner as in Example 28. The processing temperature and pressure in the reaction tube 102 with a heater were 150 ° C. and 0.5 MPa, and the residence time in the reaction tube was adjusted to 1 hour. After the mixture after the treatment was filtered and the solid remaining on the filter paper was dried, the mixture was shaken for 10 minutes in the same manner as in Example 28. The content was separated by the same sieve, and the copper purity in the solid matter remaining on the sieve was analyzed. As a result, the copper purity was 31%. When the organic component in the filtered solution was analyzed, no organic component was detected.
[0108]
Example 31
The thermosetting resin constituting the circuit board was dissolved in the waste circuit board from which the mounted components were removed in the pretreatment process using an aqueous nitric acid solution in a supercritical state, and metallic lead and the like were recovered. First, the resin melting device will be described.
[0109]
As shown in FIG. 17, the apparatus includes a waste tank 111 for storing a slurry obtained by mixing substrate crushed material and water, a water tank 112, an oxidant tank 113 for oxygen, air or hydrogen peroxide, and the like. , A nitric acid tank 114, a high-pressure pump 115-118, a heat exchanger 119, a reaction tube 120 with a heater, a separator A 121, a separator B 122, a cooler 123 and a back pressure valve 124. Each part of the apparatus is desirably made of a material having heat resistance, pressure resistance, and high corrosion resistance, such as stainless steel, titanium, Hastelloy, and Intronel.
[0110]
After the fluids are pressurized from the respective tanks by the high-pressure pumps 115 to 118 and removed, they are mixed at an arbitrary ratio, and the copper and the solder are once dissolved by the action of nitric acid. The mixture is heated through the heat exchanger 119 and then enters the reaction tube 120 with a heater. The pressure inside the reaction tube 120 is controlled by a pump and a back pressure valve 124. The resin component in the fluid is rapidly decomposed and dissolved by being heated and pressurized in the reaction tube 120 with the heater to a temperature and pressure of 374.2 ° C. or 22.1 Mpa or more, which is a critical point of water. . Of course, the nitric acid from the tank 114 is an acidic oxidant, but the supply of the oxidant from the tank 113 compensates for possible shortage of oxidizing power. At the same time, at least lead and tin among the dissolved metals (though tin may be insolubilized as tin oxide after being attacked by nitric acid), at least lead and tin are fine oxide particles by a hydrothermal reaction in a supercritical state. Precipitates.
[0111]
In the separation device A121, the crushed glass fibers are collected, and a filter that is coarser than the particle diameter of the metal oxide that may exist and smaller than the particle diameter of the glass fibers is used here. In addition, two or more filters are arranged in parallel, and one of them is used. By detecting the state of the filter by monitoring and switching the flow path and the filter, Prevents clogging due to glass fiber collection. Next, in the separation device B122, the precipitated metal oxide fine particles are collected by using a filter with a finer size than that of the separation device A121, but the same clogging prevention mechanism as that of the separation device A121 is provided. . It is also possible to install a plurality of metal oxide separation devices in series, in which case, the temperature at which the oxides are precipitated by the hydrothermal reaction, the solubility of the metal oxides in high-temperature, high-pressure water, etc. By utilizing the fact that metal oxides vary depending on the type of metal, the metal oxide can be separated and recovered by controlling the temperature in each separation device.
[0112]
Thereafter, the mixture is cooled by the heat exchanger 119 and subsequently further cooled by the cooler 123, and then the pressure is reduced through the back pressure valve 124 and collected at the outlet.
[0113]
Using such an apparatus, a circuit board from which only the mounted components were removed by solder melting was subjected to a melting process. Nitric acid having a concentration of 5N was used as nitric acid, and hydrogen peroxide having a concentration of 31% was used as an oxidizing agent. The processing temperature and pressure in the reaction tube 120 with a heater were 500 ° C. and 30 Mpa, and the residence time in the reaction tube was adjusted to 30 minutes. As a result, the recovery rate of glass fiber by the separation device A121 was 96.2%, and the recovery ratio of lead and tin by the separation device B122 was 99.9% or more.
[0114]
Example 32
2.1 g of resin waste filled with an inorganic filler was subjected to a dissolution treatment using a batch-type apparatus including a pressure vessel having an inner volume of 122 cc and an electric furnace. The composition of the object to be treated is 32% of an acid anhydride-curable epoxy resin and 68% of an inorganic filler. The object to be treated and 38.4 cc of water were charged into a pressure vessel, sealed, and treated at 380 ° C. and a reaction condition of 24 Mpa for 1 hour. In the observation after the treatment, only the inorganic filler was recognized. In addition, the content of the organic matter in the solid matter among the collected objects to be treated was 7.2%. Furthermore, when the organic component in the solution was analyzed, it was confirmed that phenol and 3-phenoxy-1,2-propanediol which are valuables were the main components. The weight ratio with respect to the resin component in the object was 8.0% and 11.7%, respectively. Acetone was also confirmed as another liquid organic component.
[0115]
Example 33
0.37 g of a beret-shaped ABS resin was subjected to a melting treatment using a batch-type apparatus composed of a pressure vessel having an internal volume of 117 cc and an electric furnace. The material to be treated, 29.7 cc of water, and 7.2 cc of 31% aqueous hydrogen peroxide were charged into a pressure vessel, sealed, and oxidized under a reaction condition of 380 ° C. and 24 Mpa for 1 hour. When the state after the treatment was visually observed, the pellet was not present, but was present in a state of being dissolved or suspended in water. Next, when the concentration of hydrogen cyanide present in the gas phase after the treatment was analyzed, the hydrogen cyanide generation amount when all the cyano groups in the ABS were converted to hydrogen cyanide was 100, and the hydrogen cyanide generation amount was less than 0.015. . Further, when the total cyanide concentration in the liquid phase was analyzed, it was less than 0.0025 ppm.
[0116]
Example 34
0.37 g of ABS resin in the form of pellets was treated using a batch-type apparatus constituted by a pressure vessel having an internal volume of 117 cc and an electric furnace. The object to be treated and 36.9 cc were charged into a pressure vessel, the atmosphere in the pressure vessel was replaced with argon, and the vessel was sealed and treated under a reaction condition of 380 ° C. and 24 Mpa for 1 hour. When the state after the treatment was visually observed, the pellet was not present, but was present in a state of being dissolved or suspended in water. Next, when the concentration of hydrogen cyanide present in the gas phase after the treatment was analyzed, the hydrogen cyanide generation amount when all the cyano groups in the ABS were converted to hydrogen cyanide was 100, and the hydrogen cyanide generation amount was less than 0.015. . Further, when the total cyanide concentration in the liquid phase was analyzed, it was less than 0.0025 ppm. Further, when the organic components in the liquid phase were identified, valuable substances such as acrylamide, acrylic acid, and styrene were confirmed.
[0117]
Example 35
A 26.6 mm square was cut out of the circuit board from which the mounted components and the solder were removed by solder melting and surface polishing, respectively, and the circuit board was subjected to melting treatment using a batch type apparatus composed of a pressure vessel having an inner volume of 122 cc and an electric furnace. . That is, the to-be-processed piece and 33.2 cc of methanol were charged into a pressure vessel, sealed, and treated at 242 ° C. and a reaction condition of 8.2 Mpa for 2 hours. Observation of the substrate piece after the treatment revealed that each layer could be easily peeled off with tweezers, and the copper foil and glass fiber could be separated by hand.
[0118]
Example 36
A 24.2 mm square is cut out of a circuit board from which a mounted component and solder have been removed by solder melting and surface polishing, respectively, and is melted using a batch-type apparatus consisting of a 122 cc internal pressure vessel and an electric furnace. did. That is, the to-be-processed piece and 33.7 cc of ethanol were charged into a pressure vessel, sealed, and treated at 246 ° C. and a reaction condition of 6.5 Mpa for 2 hours. Observation of the substrate piece after the treatment revealed that each layer could be easily peeled off with tweezers, and the copper foil and glass fiber could be separated by hand.
[0119]
Example 37
Using the apparatus shown in FIG. 18, the circuit board subjected to the pretreatment, pulverization and sieving operations as in Example 36 was subjected to dissolution processing. The processing conditions were the same as in Example 36, except that sodium hydroxide having a weight ratio of 13.5% of the resin contained in the substrate was dissolved and added to water supplied by the high-pressure pump 129. Then, when dioxins in the mixture after the treatment were analyzed, they were below the detection limit.
[0120]
Example 38
Using the apparatus shown in FIG. 18, the circuit board subjected to the pretreatment, pulverization and sieving operations as in Example 36 was subjected to dissolution processing. The processing conditions were the same as in Example 36, except that calcium hydroxide was dissolved in water supplied by the high-pressure pump 129 at a weight ratio of 12.5% of the resin contained in the substrate. Then, when dioxins in the mixture after the treatment were analyzed, they were below the detection limit.
[0121]
Further, another embodiment according to the present invention will be described with reference to the drawings.
[0122]
FIG. 18 is a diagram schematically showing a processing apparatus according to the present invention.
[0123]
The processing apparatus shown in FIG. 18 includes a pulverizer 181 for taking in and pulverizing a thermosetting resin product, and a dissolving tank 182 for heating the processing liquid to a predetermined temperature and bringing the pulverized material discharged from the pulverizer 181 into contact with the pulverizer. A stirrer 183 for stirring the contents in the dissolving tank, a valve 184 for adjusting the discharge amount of the contents in the dissolving tank 182, and a valve 184 for opening the contents in the dissolving tank 182 Pump 185, a separator 186 that takes in the contents pumped in the pump 185 and separates powder and liquid in the contents by centrifugal force, and pumps the liquid out of the separator 186. 188, a separator 187 that takes in the liquid pumped by the pump 188 and separates the powder and the liquid by centrifugal force, and a belt conveyer that applies the liquid discharged from the separator 187 thinly and heats it. Conveyor 190, a claw 191 for scraping off extraneous matter adhering to the belt conveyor 190, a case 189 surrounding the belt conveyor 190 and the claw 191; a decompression device 193 for reducing the pressure in the case 189; 189, a collecting vessel 192 for cooling passing gas and collecting aggregates, a washing tank 194 for taking in powders from the separators 186 and 187 and mixing with a washing liquid, and contents in the washing tank 194. A valve 195 for adjusting the discharge amount of the substance, a pump 196 for pumping the content in the washing tank 194 when the valve 195 is open, and a centrifugal force for taking in the content pumped from the pump 196. 197 for separating the powder and the liquid from each other, and a cutter capable of switching the powder discharged from the separator to the washing tank 194 or the next step. 199, a pump 199 for powdering the washing tank 194 through the switch 198, a belt conveyor 202 for applying and heating the powder passing through the switch 198, and shaving off the deposits attached to the belt conveyor 202. Claws 203 for dropping, a case 201 surrounding the belt conveyor 202 and the claw 203, a decompression device 205 for reducing the pressure in the case 201, and a pipe provided between the decompression device 205 and the case 201 for cooling the passing gas and aggregating the aggregates. Container 204 for collecting liquid, a tank 206 for storing the liquid in the collection containers 192 and 204, a pump 207 for pumping the liquid in the tank 206, and a transport of the liquid discharged from the tank 206 through the pump 207. A switch 208 for switching the head and a liquid which is sent from the tank 206 through the pump 207 are heated. A heater 200, a tank 200 for storing the liquid separated by the separator 197, and a pump 209 for sending the liquid in the tank 200 to the heater 210.
[0124]
Here, the crusher 181 is configured to perform crushing using a shearing force, a compressive force, an impact force, and the like. Further, after the pulverization, it is more preferable to remove the separated metal by utilizing a difference in specific gravity, a difference in shape, a difference in electrical characteristics, or the like. The dissolution tank 182 is used as a device that takes in the liquid from the heater 210 and the pulverized material from the pulverizer 181 and contacts and mixes them. The heating temperature of the melting tank 182 is more preferably controlled so as to be maintained at a target temperature, and the heating method includes electricity, a burner, and high frequency. Further, in order to make the temperature on the electric heating surface uniform, it is more preferable to transfer the heat to the contents using a heated high boiling point fluid. The case 189 has an effect of heating the liquid applied on the belt conveyor 190 under reduced pressure, and the gasified liquid is collected by the trap 192. What is left on the belt conveyor is removed by the claws 191 and stored in the case 189. At an appropriate time, the valve 211 provided between the separator 187 and the case 189 is closed to stop the operation of the pressure reducing device 193, and then the collected material removed from the belt conveyor in the case 189 by the claws 191. Is taken out.
[0125]
Further, the washing tank 194 has a function of stirring and mixing the solid sent from the separator 197 and the liquid sent from the tank 206 with the valve 195 closed. The case 201 has an effect of heating the liquid applied on the belt conveyor 202 under reduced pressure, and the gasified liquid is collected in the trap 204. Note that what remains on the belt conveyor is removed by the claws 203 and stored in the case 201. Then, at an appropriate time, the switch 198 provided between the separator 197 and the case 201 is closed, the operation of the pressure reducing device 205 is stopped, and the collected material removed by the claws 203 from the belt conveyor in the case 201 is stopped. Is taken out. Note that it is more preferable that the separator 186, the separator 187, the cleaning tank 194, the separator 197, and the tank 200 be configured so as to be capable of heating and keeping heat. Further, it is preferable that the respective pipes and devices arranged in the processing apparatus are kept warm by a heat insulating material or the like, but a part of the pipes and devices may be kept warm.
[0126]
Example 39
The processing apparatus shown in FIG. 18 separates and recovers an organic component derived from the resin from an epoxy resin waste having a composition equivalent to that of the resin used for the insulating material of the magnetic levitation railway propulsion coil to obtain a recycled resin raw material. . That is, the epoxy resin waste is pulverized to an average particle size of 1 mm, immersed in ethylenediamine, and stirred at 117 ° C. under atmospheric pressure for 1 hour to dissolve the organic component in the sample, thereby to obtain an inorganic component as a filler. A solution was obtained which was suspended only insoluble. Then, the inorganic component was separated and recovered from the solution by centrifugation to obtain a recycled filler. On the other hand, in the supernatant, only the solvent was evaporated by distillation, and an organic component derived from the resin was separated and recovered to obtain a recycled resin raw material.
[0127]
Next, the components and the surface state of the recycled filler were analyzed. That is, an organic component was extracted from the recycled filler at room temperature using acetone. Next, the insoluble filler component was removed by filtration, and the extract was concentrated by distilling acetone from the extract to obtain an extract component. Here, the weight spectrum, infrared absorption spectrum, and nuclear magnetic resonance spectrum of the extracted component were measured, and it was found that the extracted component contained amines.
[0128]
Next, a new epoxy resin cured product was prepared using the recycled filler. First, 80 parts by weight of methyltetrahydrophthalic anhydride (trade name: HN-5500, manufactured by Hitachi Chemical Co., Ltd.) per 100 parts by weight of bisphenol A type epoxy resin (trade name: Epicoat 828, manufactured by Yuka Shell Evoxy Co., Ltd.) And 500 parts by weight of the regenerated silica filler were mixed at 80 ° C. for 2 hours. In addition, in the mixing, a surfactant or a coupling agent for improving the adhesion between the filler and the resin was not used. Thereafter, 0.2 parts by weight of benzyldimethylamine was added, and the mixture was further heated and mixed under reduced pressure for 15 minutes to produce an epoxy resin composition. After the mixing, the viscosity of the resin before molding was measured and found to be 4.0 Pa · s. When the bending strength of the cured product after molding was measured, it was found to be 15 kgf / mm.²Met.
[0129]
Furthermore, the cross section of the cured product cut at an arbitrary position was polished, and the state of dispersion of the filler in the resin cured product was observed using a scanning electromicroscope. In particular, it was confirmed that the filler having a small particle size of 3 μm or less was finely dispersed. The unused filler is a crushed and irregularly shaped filler, but the recycled filler has no sharp corners. This is considered to be because the particles of the filler were rubbed against each other and sharp edges were cut off and rounded because the mixing had already been performed a plurality of times in the state where the shearing force was sufficiently applied in the manufacturing process. It is presumed that the bulkiness of the filler decreases as the filler becomes closer to a sphere, which has the effect of lowering the viscosity of the filler-mixed resin.
[0130]
Example 40 to Example 75
The treatment was performed in the same process as in Example 39 except that the conditions were changed, and the results of evaluating the treatment speed and the collected material are shown in Tables 3 to 5. Table 6 shows the properties of the mixed resin and the cured product obtained by using the recycled filler or the recycled raw material resin recovered in the examples. Tables 3 to 6 also show the results of comparison with the examples, along with the respective conditions.
[0131]
[Table 3]

[Table 4]

[Table 5]

[Table 6]

However, the abbreviations of the solvents are as follows.
[0132]
EDA: ethylenediamine
DBU: 1,8-diazabicyclo [5,4,0] -7-undecene
2E4MZ-CN: 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole
TMAH: Tetramethylammonium hydroxide
DTG: Diortho tolyl guanidine
LA: laurylamine
DBA: dibenzylamine
NMM: N-methylmorpholine
NA: β-nitroaniline
DPA: diphenylamine
TCE: 1,1,1-trichloroethane
The evaluation of the processing speed was shown by the following criteria.
[0133]
◎: All dissolved in processing within 5 hours
：: All are dissolved by treatment for 5 hours or more
△: Some organic components remain
×: hardly soluble
The evaluation of the recovered material was shown based on the following criteria.
[0134]
◎: The recovered resin component does not undergo thermal decomposition and oxidation and does not contain decomposition products due to side reactions in the composition analysis.
：: The recovered resin component is slightly brownish in color, but in the composition analysis, decomposition products due to side reactions are negligible at 3% or less.
Δ: The recovered resin turned brown and contained decomposition impurities of 3% or more.
×: Blackening of the recovered resin due to thermal decomposition and oxidation of the organic components
As is clear from Tables 3 to 6, it is understood that each of the examples shows the same or better characteristics than the comparative examples.
[0135]
Example 76
In the same manner as in Example 39, the resin waste of the spacer for gaseous green switchgear cut into a size of 5 to 20 cm was treated. The cut waste product includes metal pieces such as conductor aluminum and screw parts. In the treatment, 1,8-diazabicyclo [5,4,0] -7-undecene was used as a solvent, and the treatment temperature was 140 ° C. Furthermore, in the treatment tank, the dissolved component was sequentially recovered from the dissolved resin, so that the residence time of the undissolved portion was automatically optimized. As a result, all of the resin could be dissolved and recovered regardless of the size of the input material. Further, the contained metal pieces could be easily recovered after the treatment because all the resin components adhering in the treatment tank were dissolved and removed.
[0136]
Comparative example
After the same processed product as in Example 76 was further pulverized to about 1 cm, processing was attempted using the same solvent and the same temperature using an extruder. However, since the extruder has a large resistance due to unmelted resin or metal pieces, it easily clogs and stops, so that it was impossible to treat the extruder.
[0137]
Example 77
The absolutely green resin for a vacuum circuit breaker was treated in the same manner as in Example 39 except that the solvent was removed by direct distillation without providing a filtration or sedimentation separation step. At this time, the recovered product was recovered in a state in which an organic component having fluidity derived from a resin and an inorganic filler were mixed, and the recovered product was a solid at room temperature and exhibited thermoplasticity to be fluidized by heating. In addition, the recycled resin that has been cured again by using the recovered material already contains a sufficiently mixed and dispersed filler, so that mixing when preparing a new resin is easy, and aggregation and the like are caused. There was no mixing failure.
[0138]
Example 78
Except for dissolving all the organic components of the resin, dissolving a part of the pulverized material from the surface layer and recovering as a regenerated product in a state where the filler and the organic resin components were mixed and cured, except that they were the same as those in Example 39. The crushed material was treated in the same manner. In the present example, since the surface layer of the pulverized material was subjected to a dissolution treatment with a solvent, the pulverized material was extremely excellent in adhesion to a new resin, and a high-strength resin reclaimed product could be manufactured. .
[0139]
Example 79
In this embodiment, the collected resin organic components are separated and purified, separated into a high-molecular-weight component and a low-molecular-weight component, and reused independently.
[0140]
The organic component obtained by separating the inorganic filler by dissolution treatment and filtration in the same manner as in Example 39 was subjected to extraction washing with a tetrahydrofuran (THF) solvent. The THF-insoluble matter was dissolved in a dimethylformamide solvent, and the molecular weight was measured by gel permeation chromatography. As a result, it was a high molecular weight component having an average molecular weight of about 100,000. In addition, the infrared absorption spectrum of the recovered product of high molecular weight showed that polyether polyol having a hydroxyl group in the main chain having a skeleton of bisphenol A was recovered. At this time, the high-molecular-weight recovered product is colorless, odorless, and strong because the low-molecular-weight substance has been removed, and is used alone as it is as a recycled thermoplastic resin, for example, as a molded product such as injection molding, or granular, It could be used after being formed into a fibrous or film form.
[0141]
On the other hand, the solvent was removed from the THF extraction component by distillation, and the recovered product was found to be mainly an amine compound having a molecular weight of 2000 or less by measurement of the weight spectrum and the infrared absorption spectrum. The amine value measured according to the JIS method (K7237) was 360. Next, the recovered product is mixed with a bisphenol A-type epoxy resin as a curing agent and heated at 70 ° C. to obtain an amine-cured epoxy cured product. It was confirmed that it could be used as a painting course.
[0142]
Further, the low molecular weight recovered product was applied as a metal chelating agent. That is, an appropriate amount of the low-molecular-weight recovered material was mixed with a waste liquid containing 2% by weight of copper, and the mixture was stirred at room temperature for 1 hour. As a result, a precipitate was gradually formed. Was isolated. And when the copper content of the supernatant was measured, it was 50 ppm or less.
[0143]
Comparative example
Epoxy resin waste having the same composition as the resin used for the insulating material of the magnetic levitation railway propulsion coil was ground to an average particle size of 1 mm. Further, the pulverized product was finely pulverized, and a powder having passed through a 100 μm sieve through a sieve was used as it was as a regenerating filler to prepare a new epoxy resin cured product. That is, 100 parts by weight of a bisphenol A type epoxy resin (trade name: Epicoat 828, manufactured by Yuka Shell Epoxy) and 500 parts by weight of a filler made of recycled silica were mixed at 80 ° C. for 2 hours. In addition, in the mixing, a surfactant or a coupling agent for improving the adhesion between the filler and the resin was not used. Thereafter, 0.2 parts by weight of benzyldimethylamine was added, and the mixture was further heated and mixed under reduced pressure for 15 minutes to produce an epoxy resin composition. When the viscosity of the resin before mixing and before molding was measured, the viscosity was as high as 12 Pa · s. This is presumed to be due to agglomeration of the powder at the time of the fine powder frame, thereby increasing the sublime and increasing the mixing viscosity. Further, when the epoxy resin composition was molded and the flexural strength of the cured product was measured, it was 10 kgf / mm.²was. It is considered that the reason for this is that the wettability of the surface of the recycled filler is not sufficient for the newly added resin, and the resin is easily broken from the surface of the filler. Next, the cross section of the cured product cut at an arbitrary position is polished, and the state of dispersion of the filler in the resin cured product is observed using a scanning electron microscope. Was. In particular, it was confirmed that the filler having a small particle size of 3 μm or less has a plurality of particles connected thereto and has poor dispersibility. Further, voids that could not be degassed under reduced pressure were observed in the vicinity of the aggregated fine powder, which was presumed to have led to a decrease in strength.
[0144]
Comparative example
The present comparative example is an example in which a resin is manufactured using a virgin material in which a filler is not used. That is, with respect to 100 parts by weight of a bisphenol A type epoxy resin (trade name: Epicoat 828, manufactured by Yuka Shell Epoxy), 80 parts by weight of methyltetrahydrophthalic anhydride (trade name: HN-5500, manufactured by Hitachi Chemical Co., Ltd.) and virgin silica 500 parts by weight of the filler were mixed at 80 ° C. for 2 hours. In addition, at the time of mixing, a surfactant or a coupling agent for improving the adhesion between the filler and the resin was not used. Thereafter, 0.2 parts by weight of benzyldimethylamine was added, and the mixture was further heated and mixed for 15 minutes to produce an epoxy resin composition. After the mixing, the viscosity of the resin before molding was measured and found to be as high as 10 Pa · s. It is presumed that the reason for this is that when the powder is agglomerated during the fine pulverization, the bulk is increased and the viscosity is increased. After molding, the flexural strength of the cured product was measured.²Met. It is considered that the reason for this is that the wettability of the surface of the recycled filler is not sufficient, and the surface of the filler is likely to be broken.
[0145]
Example 80
The present embodiment is an example in which a mixer used in a process of manufacturing a resin product and in which a mixer used for mixing an acid anhydride-curable epoxy resin composition is washed.
[0146]
First, an epoxy resin (trade name: Epicoat 828, manufactured by Yuka Shell Epoxy), methyltetrahydrophthalic anhydride (trade name: HN-5500, manufactured by Hitachi Chemical Co., Ltd.), silica powder having an average particle diameter of 10 μm, and benzyldimethyldiamine were After mixing at 80 ° C. and repeating the operation of discharging the mixture ten times, the mixer was washed with ethylenediamine. In addition, the cured resin was firmly adhered as a layer to the wall surface of the mixing tank before the washing, and the uncured resin was covering this. In particular, the resin layer which was cured and adhered to the mixing tank had a thickness of about 3 mm at the thick portion. First, the inside of the mixing tank was filled with ethylenediamine, and the mixture was stirred and washed at 117 ° C. for 1 hour, and then the solvent after washing was recovered from the outlet. After washing, neither the uncured resin nor the cured resin adhered to the mixing tank.
[0147]
Next, only silica as an inorganic filler was separated and collected from the solution containing the resin and collected by sedimentation separation. The silica was further washed with ethylenediamine and then dried to obtain a recovered filler. The supernatant solution from which the filler was removed was subjected to distillation under reduced pressure at a temperature of 100 ° C. or lower, thereby recovering the solvent, ethylenediamine, and obtaining a resin as a distillation residue. The ethylenediamine recovered at this time was not deteriorated, and there was no problem at the time of reuse.
[0148]
Example 81
In the same manner as in Example 80, the mixing tank of the mixer used for mixing the unsaturated polyester resin was washed. The unsaturated polyester was crosslinked by mixing phthalic anhydride, fumaric anhydride and propylene glycol, and then mixing styrene monomer. In this example, the cured resin adhered to the inner wall surface of the mixing vessel of the mixer was washed using 2-methylimidazole as a solvent, whereby the adhered cured resin was removed. The 2-methylimidazole recovered at this time did not deteriorate, and there was no problem in reusing.
[0149]
Comparative example
Epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., Epikote 828), methyltetrahydrophthalic anhydride (manufactured by Hitachi Chemical Co., Ltd., trade name: HN-5500), silica powder having an average particle size of 10 μm, and benzyldimethylamine were treated at 80 ° C. After mixing and discharging and repeating this ten times, the mixer was washed with ethylenediamine. In addition, the cured resin was firmly adhered as a layer to the wall surface of the mixing tank before the washing, and the uncured resin was covering this. In particular, the thickness of the resin layer which was hardened and adhered to the inner wall of the mixing tank was about 3 mm in a thick portion. First, the inside of the mixing tank was filled with 1,1,1-trichloroethane, and washed with stirring at 117 ° C. for 1 hour, and then the solvent after the washing was recovered from the outlet. At this time, the uncured resin adhering to the inside of the mixing tank after the washing was almost removed, but the cured resin remained without being dissolved. Further, the thickness of the cured resin layer was about 3 mm, which was not changed at all.
[0150]
Example 82
The present embodiment is an example in which a resin product is analyzed.
[0151]
A semiconductor chip sealed with a phenol-curable epoxy resin and rejected by a product current test is subjected to a dissolving treatment at 160 ° C. for 2 hours using imidazole as a solvent, whereby the phenol-curable epoxy resin is removed. The chip's circuitry is exposed. After the chip was dried, the wiring of the circuit was observed with a scanning electron microscope to find a short-circuited portion of the wiring.
[0152]
Example 83
A part of a resin product of unknown composition was prepared as a sample, and a solution obtained by mixing triethylamine / ethanol in a ratio of 4: 6 (weight ratio) as a solvent was used. The resin of the product was heated and melted. After the solvent was removed by distillation, the solid obtained by drying was measured for its infrared spectrum. On the other hand, acid anhydride-curable epoxy resins, amine-curable epoxy resins, phenol-curable epoxy resins, and non-aqueous epoxy resins obtained by dissolution treatment under exactly the same temperature, time, pressure, and solvent conditions as standard samples. An infrared spectrum of a saturated polyester resin sample was measured. By comparing the spectrum of the sample with the spectrum of the standard sample, it was confirmed that the sample was most similar to the standard sample of the acid anhydride-curable epoxy resin. For further analysis, the sample obtained by dissolving the sample was dissolved in tetrahydrofuran, and gel permeation chromatography and weight spectrum were measured. As a dicarboxylic acid ester, methyltetrahydrophthalic acid monomethyl ester was contained as a main component. I understand. Further, as a standard sample, an infrared spectroscopy spectrum of a sample of an epoxy resin cured with methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, pyromellitic anhydride and methylnadic anhydride as a curing agent has been measured, By comparison with the data, it was confirmed that methyltetrahydrophthalic anhydride was used as the curing agent. A sample obtained by dissolving the above sample was dissolved in dimethylformamide, and the molecular weight distribution was measured by gel permeation chromatography. On the other hand, as a standard sample, a sample prepared by curing a bisphenol A type epoxy resin having epoxy equivalents of 190, 250, 300, 470 and 950 using methyltetrahydrophthalic anhydride as a curing agent was prepared. When the molecular weight distribution of the obtained dissolved sample was measured in the same manner, as the epoxy equivalent of the bisphenol A-type epoxy resin as the raw material increased, the molecular weight distribution of the dissolved sample also increased toward the high molecular weight side. It was found to shift. From the calibration curve and the molecular weight distribution chart showing the relationship between the weight average molecular weight and the epoxy equivalent of the maximum peak of the standard sample, the sample was found to be bisphenol A type having an epoxy equivalent of about 195 and an epoxy equivalent of about 330. It was found that two types of epoxy resins were used as raw materials. Further, with respect to the inorganic filler remaining as the residual powder by the dissolution treatment of the standard sample, fillers having different compositions are separated by specific gravity separation, elemental analysis by X-ray photoelectron spectroscopy (XPS), scanning electron microscope observation, and light When the particle size distribution was measured by a scattering method, it was confirmed that 40 parts by weight of spherical alumina having an average particle diameter of 10 μm and 60 parts by weight of crushed fused silica having an average particle diameter of 20 μm were contained as fillers. .
[0153]
Comparative example
A semiconductor chip sealed with a phenol-curable epoxy resin and determined to be defective by a product current test is subjected to a dissolution treatment with hydrochloric acid at 100 ° C. for 2 hours to remove the phenol-curable epoxy resin. Circuit is exposed. After the chip was dried, the circuit wiring was observed by a scanning electron microscope. However, the aluminum wiring of the semiconductor was partially dissolved and damaged by the acid treatment for dissolving the sealing resin, and it was difficult to identify a defective portion. there were.
[0154]
In addition, a part of a resin product of unknown composition was prepared as a sample, and was heated and dissolved at 80 ° C. for 10 hours using concentrated hydrochloric acid. Next, the dissolved sample was dried, and an infrared absorption spectrum, gel permeation chromatography, and a weight spectrum of the obtained recovered product were measured and compared with a standard sample obtained by the same treatment. Since the decomposition of the resin was so severe that it was not possible to specify the characteristics of the raw material, it was not possible to specify the raw material of the resin constituting the resin product. The powder of the inorganic filler remaining as a residue was subjected to specific gravity separation, elemental analysis using an X-ray photoelectron spectrometer (XPS), observation with a scanning electron microscope, and measurement of particle size distribution using a light scattering method. The filler has a dissolved surface, and the dissolved inorganic component re-adsorbs to the surface of the filler, so that there are many impurities, it is difficult to separate the silica and the alumina component, and the filler composition, particle size distribution and The shape could not be analyzed correctly.
[0155]
From the above, the inorganic filler manufactured by using the used product as a raw material by the above-mentioned processing method, the mixed waste product is used as the raw material, and only the resin component is completely dissolved and recovered with the solvent. Was confirmed to be excellent in dispersibility without aggregation. In addition, the filler thus obtained has a surface free energy at the solid / liquid interface which is reduced by removing the surface charge of the filler or modifying the interface by treatment with a solvent, particularly an organic alkali solvent. The wettability with respect to the organic resin component is increased, and when a new filler-mixed resin is produced, the filler powder does not agglomerate, has excellent dispersibility, and is easily mixed. Further, even if the filling is high, the increase in viscosity can be suppressed, so that the filling rate can be increased as compared with the conventional one while maintaining the workability for molding. In addition, since the resin has high wettability to the resin component and high adhesion between the filler and the resin, even without the addition of a surfactant or a coupling agent, there is no void due to the remaining bubbles such as air, and the defoaming treatment can be performed. It will be easier. Since the resin can be highly filled and has high adhesion between the resin and the filler and has good dispersibility, the resin obtained by mixing and curing the above filler has properties as a cured product, such as strength and flame retardancy. The characteristics such as resistance and withstand voltage are improved.
[0156]
Example 84
The thermosetting resin that constitutes the circuit board is dissolved in the waste circuit board from which the mounted components have been removed in the pretreatment process and the solder has been removed, using supercritical water, etc., and metal copper and other materials are collected. did.
[0157]
First, the processing device will be described.
[0158]
As shown in FIG. 19, this apparatus includes a supply tank 125 for storing a mixture of substrate crushed material and water, an opening / closing valve A126, a high-pressure vessel A127, an opening / closing valve B126, and pressurizing water. High pressure pump 129, reaction tank 130 for containing and reacting water and the mixture, cooler 131, back pressure valve 132, open / close valve C 133 capable of withstanding high temperature and high pressure, reaction tank 130 , A high-pressure vessel B135, an on-off valve D136, an on-off valve E137, a water pump 138, a pressure adjusting valve A139 and a pressure adjusting valve B140. Each part of the apparatus is desirably made of a material having heat resistance and pressure resistance, such as stainless steel, titanium, Hastelloy, and Inconel, and having high corrosion resistance.
[0159]
Further, in the processing apparatus, of the mixture of the substrate crushed material and the water stored in the supply tank 125, the substrate crushed material having a specific gravity larger than that of water is supplied to the open / close valve A126 and the open / close valve B128. By opening and closing, it flows into the reaction tank 130 by gravity sedimentation. Further, the high-pressure vessel A127 is always filled with water. When the opening / closing valve A126 is open, the substrate crushed material is settled in the high-pressure vessel A127 without particularly pressurizing the inside of the supply tank 125 by closing the opening / closing valve B128. By closing and opening the on-off valve B128, the high-pressure vessel A127 filled with water is instantaneously placed under the same high-pressure conditions as the discharge side of the high-pressure pump 129, and the substrate intercalates and the reaction tank is settled down. 130. By repeatedly performing this step, the substrate crushed material can be intermittently injected into a high-pressure field. However, according to this method, unlike the case where the substrate crushed material is directly transported by a high-pressure pump, a pump is used. This eliminates wear and blockage of the substrate and eliminates the need to finely pulverize the substrate to pass through the pump. In addition, at the time of the above injection operation, the opening / closing valve C133 is closed, and the pressure inside the reaction tank 130 is controlled to a constant value by the continuously operating high pressure pump 129 and the back pressure valve 132. . After the injection, both the open / close valve B128 and the open / close valve C133 are closed, and the substrate crushed material is heated in the reaction tank 130 to a temperature and pressure of 374.2 ° C., which is a critical point of water, at 22.1 MPa or more. Then, the resin component in the fluid is rapidly decomposed and dissolved by pressurization, but the dissolution rate is further increased by making the solution uniform with a stirrer or the like. The stream containing the decomposed organic component passes through a filter provided at the outlet of the reaction vessel 130, is cooled by the cooler 131, passes through the back pressure valve 132, is depressurized, and is recovered at the outlet. It should be noted that due to the presence of the filter, the flow passing through the back pressure valve 132 does not contain any solids, and thus there is no danger of blockage here and wear of the back pressure valve. As a method of recovering organic components from the discharged stream, for example, membrane separation, distillation and a cooled trap, or a combination thereof can be used, and water after recovering organic components can be used. It is also possible to return to the suction side of the high-pressure pump 129 again.
[0160]
On the other hand, the solid content mainly composed of copper has settled at the bottom of the reaction tank 130, and after a predetermined time has elapsed, the solid content is injected into the high-pressure field by opening and closing the valve. According to the same principle as that of the method, the gas is discharged out of the system through the open / close valve C133, the high-pressure vessel B135, and the open / close valve D136. At this time, at the time of opening the on-off valve C133, the pressure in the reaction tank 130 can be minimized by filling the inside of the high-pressure vessel B135 with water by the water pump 138 in advance. Operation is assured. The pressure adjustment valve A139 and the pressure adjustment valve B140 are used to control the pressure in the high-pressure vessel B135 at the time of water injection by the water pump 138 and at the time of opening the opening / closing valve D136. Note that the high-pressure pump 129 is constantly operating through these series of operations, and the liquid continuously passes through the back pressure valve 132, while the solid content is intermittently injected and discharged in the vertical direction as described above. . In addition, the pressure fluctuation in the reaction tank 130 can be minimized by the above-described operation method.
[0161]
Using the processing apparatus described above, the circuit board from which the mounted components and the solder had been removed was subjected to melting treatment by solder melting and surface polishing. The circuit board was pulverized by using a pulverizer in which a rotary crusher and a cutter mill were combined, and the pulverized material was sieved to obtain a material having a particle size of 2 mm or more and 4 mm or less. The weight composition ratio of the object to be processed is copper 34%, glass fiber 39%, and epoxy resin 27%. The processing temperature and pressure in the reaction tank 130 were 380 ° C. and 24 Mpa, and the residence time in the reaction tank was adjusted to 1 hour. After filtering the mixture after the treatment and drying the solid remaining on the filter paper, the dried matter is sealed in a plastic container, and shaken up and down at a speed of 200 times per minute for 10 minutes with a shaker. The glass fibers that had been embrittled by the supercritical treatment were finely powdered. Then, the above inclusions were separated by a sieve having a diameter of 600 μm, and the copper purity in the solid matter remaining on the sieve was analyzed. As a result, the copper purity was 96%. Further, when the organic component in the filtered solution was analyzed, it was confirmed that phenol, cresol and isopropylphenol which are valuables were the main components. Further, the weight ratio of these organic substances to the resin component in the substrate to be processed was 17.1%, 5.8%, and 5.2%, respectively. In addition, acetone was also confirmed as another liquid organic component.
[0162]
【The invention's effect】
As is apparent from the above description, according to the method and apparatus of the first invention, in the treatment of mixed waste containing an organic halide-containing foamed resin such as a urethane foamed resin, a liquid such as silicone oil is used. By heating to a predetermined temperature in a heat medium, the foamed resin is softened or fluidized, and at the same time, the contained organic halide gas can be discharged and adhered to the softened or fluidized resin component or the substrate. Low melting point metals such as solder can be separated and recovered.
[0163]
Further, according to the method and apparatus of the second aspect of the present invention, by treating a resin-containing object such as a waste circuit board with a solvent or a solvent vapor to dissolve the resin, the resin or metal valuable material constituting the object is treated. Can be separated and recovered with high efficiency. In addition, an increase in the load on the environment during processing can be suppressed.
[Brief description of the drawings]
FIG. 1 is a diagram schematically showing an embodiment of an apparatus and method for treating a mixed waste according to the first invention.
FIG. 2 is a diagram schematically showing another embodiment of the mixed waste treatment apparatus used in the first invention.
FIG. 3 is a diagram schematically showing another embodiment of the mixed waste treatment apparatus used in the first invention.
FIG. 4 is a diagram schematically showing another embodiment of the mixed waste treatment apparatus used in the first invention.
FIG. 5 is a diagram schematically showing another embodiment of the apparatus for treating mixed waste used in the first invention.
FIG. 6 is a flowchart showing an embodiment of a method for solvent-treating a waste circuit board according to the second invention.
FIG. 7 is a diagram schematically showing an apparatus for performing a solvent treatment according to the flow of FIG.
FIG. 8 is a diagram schematically illustrating an example of an apparatus for removing a mounted component as a pre-treatment for performing a solvent treatment on a circuit board.
FIG. 9 is a diagram schematically showing an example of an apparatus for removing solder by spraying powder as a pretreatment for performing a solvent treatment on a circuit board.
FIG. 10 is a view schematically showing an example of an apparatus for separating and recovering solder, mounted components, copper foil, resin, glass fiber, and the like from a substrate as a post-treatment of a solvent treatment.
FIG. 11 is a diagram schematically showing an embodiment of an apparatus for separating and removing solder on a circuit board and recovering copper as a pretreatment for performing a solvent treatment.
FIG. 12 is a view showing another embodiment of an apparatus for separating and removing solder on a circuit board and recovering copper as a pretreatment before a solvent treatment.
FIG. 13 is a view showing a solder-dissolved copper collecting step in the method of electrochemically separating and removing the solder on the circuit board.
FIG. 14 is a view showing a copper melting solder collecting step in the method of electrochemically separating and removing the solder on the circuit board.
FIG. 15 is a diagram showing an embodiment of an apparatus for dissolving a resin constituting a circuit board using water or the like in a supercritical state.
FIG. 16 is a diagram showing an embodiment of an apparatus for dissolving a resin constituting an object using water or the like in a supercritical state and recovering a metal or the like.
FIG. 17 is a diagram showing an embodiment of an apparatus for dissolving a resin constituting an object by using a nitric acid aqueous solution or the like in a supercritical state and collecting metals and the like.
FIG. 18 is a diagram schematically showing a processing apparatus according to the present invention.
FIG. 19 is a diagram schematically showing a processing apparatus according to the present invention.
[Explanation of symbols]
1. Heat medium 2. Sealing machine 3. Heating reaction tank
4 Heating medium supply and circulation machine 6 Extraction machine 7 Solid matter discharge valve
8 molten metal discharge valve 11 heater
12: softened or fluidized urethane resin component 13: molten metal
15 Screen 16 Specific gravity separation tank 17 Gas adsorption tank
21: cylindrical tube heater 22: stirrer 23: circulation preheating unit
24 Rotary crusher 27 Solvent treatment tank
28: Solvent distillation recovery tank 29: Condenser 30: Solvent tank
32, 39, 63 ... waste circuit board 34 ... analyzer
35 Filtration device 37 Additive tank
43 ... Scraper blade 47 ... Sand blast treatment tank
49 ... Inorganic powder such as alumina and silica 51, 54 ... Injection pump
53: Hammer 55: Cyclone 57: Weight recovery component (copper)
58: Circuit board input section 59: Solder separation / removal tank
60, 95 Crusher 61 Copper recovery unit 65 Separated liquid
67: Solder dunk 70: Air flow centrifugal specific gravity separator
71 ... Electrostatic separation device
72 Cu rich powder 77 Mixed gas injection port of air and ozone
81: Solder recovery tank 83: Electrolyte containing copper ions
84: brush type electrode 85: electrode of platinum etc. 87: grinding device
88: Mixture transport pump 91: Heat exchanger
92: Reaction tube with heater 95: Supply tank 96: Open / close valve A
97 high-pressure vessel A 98 open-close valve B 99 high-pressure pump A
100 high-pressure pump B 101 heat exchanger 102 reaction tube
103: Cooler 104: Separator 105: Back pressure valve
106: High pressure vessel B 107: Open / close valve C
108 open / close valve D 109 open / close valve E 110 water pump
111: Waste tank 112: Water tank 113: Oxidizer tank
115-118 high-pressure pump 119 heat exchanger
120: reaction tube with heater 121: separation device A
122: Separation device B 123: Cooler 124: Back pressure valve
125 supply tank 126 opening / closing valve 127 high-pressure vessel A
128: On-off valve B 129: High-pressure pump
130: reaction tank 131: cooler 132: back pressure valve
133 open / close valve C 134 heater
135 high-pressure vessel B 136 opening / closing valve D
137: Open / close valve E 138: Water pump
139 Pressure adjustment valve A 140 Pressure adjustment valve B
181: crusher 182: melting tank 183: stirrer
184: valve 184 185: pump 185 separator: 186
187 Separator 186 188 Pump 189 Case
190: belt conveyor 191: claw 192: collection container
193: decompression device 193 194: cleaning tank
195: Valve 196: Pump 197: Separator 197
198 ... Switch 199 ... Pump 200 ... Tank
201: Claw 202: Belt conveyor
203: claw 204: collection container 205: decompression device
206 …… Tank 207 …… Pump
208: Switcher 209: Pump 210: Heater

Claims (1)

An encapsulating machine for enclosing the mixed waste containing the organic halide-containing foamed resin in a liquid heat medium,
A heating reaction tank that heats the mixed waste immersed in the heat medium supplied from the encapsulating machine,
A heat medium supply circulator that forms a circulating flow while supplying a heat medium into the heating reaction vessel,
A drawing machine that pulls out a resin component floating in an upper layer of the heat medium,
Solid discharge means for discharging solids from the lower part of the heating reaction vessel,
A molten metal discharging device for discharging molten metal from a lower portion of the heating reaction tank.

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