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JP4286557B2 - Oil processing equipment for waste plastic containing PET - Google Patents

Oil processing equipment for waste plastic containing PET Download PDF

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Publication number
JP4286557B2
JP4286557B2 JP2003047724A JP2003047724A JP4286557B2 JP 4286557 B2 JP4286557 B2 JP 4286557B2 JP 2003047724 A JP2003047724 A JP 2003047724A JP 2003047724 A JP2003047724 A JP 2003047724A JP 4286557 B2 JP4286557 B2 JP 4286557B2
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oil
tank
precipitation tank
overflow
circulating
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JP2004256636A (en
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省二 児玉
正信 小林
研造 福島
英人 唐澤
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ALTIS CO., LTD.
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/62Plastics recycling; Rubber recycling

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  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Description

【0001】
【発明の属する技術分野】
本発明は、PET(ポリエチレンテレフタレート)を含有する廃プラスチックの油化処理装置に関する。より詳細には、本発明は、PETを熱分解したときに生成するテレフタル酸及び安息香酸が分解油中に析出しても、配管類を閉塞させることなく、廃プラスチックを熱分解処理することが可能な廃プラスチックの油化処理装置に関する。
【0002】
【従来の技術】
省資源・無公害化の観点から、石油を原料として合成されるプラスチック廃棄物を熱分解して、得られる分解油を燃料として利用する廃プラスチックの油化方法が、従来から数多く提案されている。例えば、ポリオレフィン系及び/又はポリスチレン系廃プラスチックを熱分解槽部で熱分解して、生成する熱分解ガスを熱交換器で粗重質油成分と軽質油成分に分離し、軽質油成分を熱交換器で凝縮して軽質油を取り出す廃プラスチックの油化方法が提案されている(特許文献1)。この油化方法では、軽質油の一部を気化した後、熱分解槽部内に供給して廃プラスチックの加熱源として利用し、残りは燃料として利用される。
特許文献1に開示された油化方法は、軽質油に重質油成分が含まれ、軽質油の気化に新たな熱源が必要であり、重質油成分が固化しやすく配管が閉塞される可能性があるなどの理由から、その改良方法が提案されている(特許文献2)。
特許文献2に開示された油化方法は、熱分解ガスをエジェクタにより熱分解槽から常圧蒸留塔に供給し、蒸留塔の塔頂成分を冷却して軽質油を得ると共に、得られる軽質油の一部を蒸留塔の塔底油(重質油)と熱交換して気化させた後、更に軽質油を燃料とする加熱炉で昇温して熱分解槽内に導入することにより、廃プラスチックの加熱源として使用するものである。この油化方法では、塔底油の一部をエジェクタに圧送してその駆動液に使用し、その残りは上記加熱炉で加熱された後に重質油タンクに貯蔵される。この油化方法においても、廃プラスチックとして、ポリエチレン、ポリプロピレン、ポリポリスチレン及びポリ塩化ビニルが用いられている。
【0003】
ところで、プラスチック廃棄物は、同種のプラスチック毎に分別回収することができるならば、その後の処理に有利である。しかしながら、近年ゴミの分別回収が一般化されたとはいえ、一般家庭から廃棄されるゴミや廃棄物から同種のプラスチックに分別することは困難であり、プラスチック廃棄物には普通各種の樹脂が混在している。特に、プラスチックのラミネートを各層毎に分離することは不可能に近いのが現状である。プラスチック廃棄物としては、特許文献2に例示されたものの他に、ナイロン、PETなどがある。
廃プラスチックの中でも、ポリエチレン等の炭化水素系樹脂は、熱分解処理が比較的容易であり、重油組成に類似した炭化水素油が生成する。また、ポリ塩化ビニルまたはポリ塩化ビニリデンを含有する廃プラスチックを熱分解すると、塩素化樹脂から大量の塩化水素と塩素化炭化水素が生成するので、塩化水素による熱分解槽や配管類の腐食を防止する必要がある。塩素化炭化水素の脱塩素化方法としては、例えば気液混合相状態の熱分解生成物を酸化鉄系触媒に接触させ、塩素成分を触媒と反応させるか触媒に吸着させて分離除去する方法が知られている(特許文献3)。
一方、PETを含有する廃プラスチックの熱分解では、PETからアセトアルデヒド、エチレン等と共に、テレフタル酸及び安息香酸が副生する。テレフタル酸は300℃で昇華し、安息香酸は100℃で昇華するという特性があり、油化装置に重大な問題を引き起こす。即ち、熱分解により生成する分解ガスを上述の各温度以下に冷却して凝縮させると、昇華性芳香族カルボン酸が気体から固体に相変化して、配管や機器を閉塞させるという問題がある。具体的には、熱分解反応器の出口配管でテレフタル酸が析出し、更に油化装置内の100℃より低い温度に冷却された配管部や凝縮器に安息香酸が析出して、配管類を閉塞させるため、PET含有の廃プラスチックを熱分解して分解ガスを油化させることは困難である。
【0004】
【特許文献1】
特開平10−195452号公報
【特許文献2】
特開2001−59089公報
【特許文献3】
特開2001−123182公報
【0005】
【発明が解決しようとする課題】
このように、PETを含有する従来の廃プラスチックの熱分解では、生成するテレフタル酸及び安息香酸(昇華性芳香族カルボン酸ということもある)が配管類を閉塞するという問題があった。
そこで、本発明の目的は、上述の従来技術の問題点を解消することにあり、廃プラスチック中にPETが含まれていても、昇華性芳香族カルボン酸が配管類を閉塞させることなく、廃プラスチックの熱分解により生成する分解ガスを分解油として回収することが可能な廃プラスチックの油化処理装置を提供することにある。
【0006】
【課題を解決するための手段】
熱交換器による熱分解ガスの冷却では、生成するテレフタル酸及び安息香酸がチューブやシェルに析出して熱交換器を閉塞してしまうので、熱分解ガスをできるだけ上流側で冷却して、気相状の昇華性芳香族カルボン酸を下流側に流さないことが望ましい。そのためには、熱分解炉出口の熱分解ガスを急冷する必要がある。このような概念の下に、本発明者らは、上記問題点を解決するために鋭意検討を重ねてきたところ、析出槽内に析出された芳香族カルボン酸を含有する熱分解生成油を沈降槽にオーバーフローさせる溢流手段を設けて、芳香族カルボン酸を沈降槽内に沈積させることによって、上述の目的が達成されることを見い出して、本発明をなすに至ったものである。
即ち、本発明の廃プラスチックの油化処理装置は、PETを含有する廃プラスチックを熱分解する熱分解炉と、廃プラスチックの熱分解反応によって生成する熱分解ガス中のテレフタル酸及び安息香酸の各昇華性芳香族カルボン酸を析出させる析出槽と、熱分解ガスの油化により生じる循環油が循環ポンプの駆動により析出槽を循環する循環経路に介在する循環油槽及び循環油クーラとを備え、熱分解炉から生じる熱分解ガスを析出槽に導入する導入管が循環油槽及び循環油クーラの下流側かつ析出槽の上流側の循環経路に接続されると共に、循環油クーラで冷却された循環油と該循環油により急冷されて熱分解ガスから上記芳香族カルボン酸が析出した生成油との混合油を析出槽から沈降槽にオーバーフローさせる溢流手段を設けたことを特徴とする。
【0007】
【作用】
本発明の廃プラスチックの油化処理装置の作用は、次の通りである。
熱分解炉内でPETを含有する廃プラスチックを熱分解すると、炭化水素類等と共にテレフタル酸及び安息香酸の昇華性芳香族カルボン酸を含有する熱分解ガスが生成する。一方、本発明の油化処理装置には、析出槽、循環油槽及び循環油クーラからなる循環経路が形成されており、熱分解ガスの油化生成物である分解油が循環油として循環ポンプの駆動により循環経路を循環している。そして、熱分解ガスを析出槽に導入する導入管が循環油槽及び循環油クーラの下流側で析出槽の上流側の循環経路に接続されているので、熱分解ガスは、循環油クーラで冷却された循環油により急冷されながら循環油と共に析出槽内に導入される。
その結果、熱分解ガスの油化による生成油と循環油との混合油中に昇華性芳香族カルボン酸が結晶化して析出槽内に析出すると同時に、析出槽内の液相部は熱分解ガスの導入によりジェットバブリングの状態にある。微粒子状の芳香族カルボン酸を含有する混合油は、次いで溢流手段を介して沈降槽にオーバーフローする。そのため、溢流液が流入する周辺を除いて、沈降槽内の液相部は層流状態にあるので、芳香族カルボン酸微粒子の沈降が促進される。
本発明においては、熱分解ガスが循環油により急冷されながら循環油と一緒に析出槽内に導入されるので、熱分解ガスを析出槽に導入する導入管及び周辺の配管類に、昇華性芳香族カルボン酸が析出するようなことがない。しかも、気相状の芳香族カルボン酸は初期の段階で析出するので、析出槽の下流側配管を閉塞させるようなこともない。従って、廃プラスチックの熱分解による分解生成物を安定して分解油に変換することが可能である。
【0008】
請求項2に係る発明によれば、析出槽に接続した注入管に熱分解ガスの導入管が接続され、その接続口近傍に循環油が注入されるエジェクタ管の出口を臨ませたものであるから、エジェクタ効果により高温の熱分解ガスが速やかに析出槽内に注入される。このダイレクト・クエンチにより、芳香族カルボン酸の析出に起因する析出槽及びその上流側配管の閉塞をより確実に防止することができる。更に、上記混合油の流出口の下方に注入管の出口部が位置するので、析出槽に導入される熱分解ガスの油化が促進される。
請求項3に係る発明によれば、微粒状芳香族カルボン酸の沈降速度を沈降槽内に流入する溢流液の上昇速度より大きくしたものであるから、沈降槽内に配置された溢流堰を越えて流出する固形分(芳香族カルボン酸微粒子)を可及的に減少させることができる。
請求項4に係る発明によれば、上記溢流液の流入口と溢流堰の間の沈降槽内に仕切板を配置したものであるから、溢流液が層流状態で溢流堰をオーバーフローするため、上記芳香族カルボン酸の分離効率を向上させることができる。また、仕切板の下部に開口部が形成されているため、仕切板で仕切られた溢流液が掻き乱されることなく層流状態で下流に流れるので、上記分離効率が更に向上する。
【0009】
【発明の実施の形態】
以下、図面を参照して本発明を詳細に説明する。
図1において、符号1はバーナ2によって加熱される廃プラスチックの熱分解炉である。熱分解炉1は1基または複数の熱分解反応器1′から構成され、その数は特に限定されるものではない。廃プラスチックにはPETが含まれており、PET含有の廃プラスチックは熱分解反応器1′において310〜550℃で熱分解される。生成する熱分解ガスは、導入管3を通って析出槽4に導入される。
PETの代表的な熱分解生成物としては、テレフタル酸及び安息香酸の他に、エチレン、アセトアルデヒド、ベンゼン、安息香酸ビニル、エチレンビスベンゾエート、ジフェニル、テレフタル酸ジビニル、テレフタル酸モノビニル、テレフタル酸モノビニルモノベンゾイルオキシエチルなどがある。これらの熱分解生成物のうち、テレフタル酸は300℃で昇華し安息香酸は100℃で昇華する物質であり、高温の熱分解ガスを冷却すると、これらの芳香族カルボン酸は気体から固体に相変化を生じる。
熱分解温度が310℃未満であると、生成するテレフタル酸が導入管3内に析出して導入管3を閉塞する恐れがある。一方、熱分解温度が550℃より高くなると、コーキング物質が生成して生成油に含有されるようになるだけでなく、エネルギー効率が低下する。廃プラスチックの熱分解温度は、350〜450℃の範囲にあることが好ましい。
【0010】
本発明の油化処理装置には、析出槽4、循環油槽5及び循環油クーラ6が配管接続された循環経路7が形成されている。循環経路7内には、循環油クーラ6で40〜60℃に冷却される循環油が循環ポンプ8の駆動により循環している。一方、前記導入管3は、循環油槽5及び循環油クーラ6の下流側で析出槽4の上流側の循環経路7に接続されている。従って、熱分解ガスは循環油により急冷されながら析出槽4に導入される。
循環油としては、廃プラスチックの熱分解ガスを油化させた分解油が用いられる。通常の廃プラスチックには、ポリエチレン、ポリプロピレン等のポリオレフィンが含まれており、熱分解により流動点の高いワックスが生成するので、配管の閉塞を防止するために、循環油の温度を40℃以上に保つ必要がある。また、熱分解ガスを循環油で急冷したとき、熱分解ガス中の安息香酸を完全に析出させるためには、循環油の温度を60℃以下とすることが好ましい。40〜60℃の循環油で310〜550℃の熱分解ガスを急冷すると、熱分解ガスからの生成油と循環油の混合油の温度は50℃から100℃未満の範囲にある。循環油の循環量を低減するためには、循環油の温度は40〜50℃の範囲にあることがより好ましく、そのときの混合油の温度は50〜80℃の範囲にある。この混合油の温度を100℃未満に保つためには、生成油流量に対して循環油の流量を20倍とする必要がある。
【0011】
析出槽4内の混合油及び析出槽4から流出する循環油は、5〜200μmの微粒子状芳香族カルボン酸を含有する。これらの油は、原料の廃プラスチック中のPETの含有量、即ち熱分解ガス中のテレフタル酸及び安息香酸の含有量に応じて、縣濁液(分散液)またはスラリーとなる。析出槽4内の液相部には、油化されなかった分解ガスが導入され、液相部は激しく攪拌される。即ち、析出槽4は、液相部が分解ガスにより常にジェットバブリングされ、固形分濃度が均一な気液混合相を呈する完全混合槽として機能する。
析出槽4は溢流手段としての溢流管9を介して沈降槽10に接続され、生成油と循環油の混合油が析出槽4から沈降槽10にオーバーフローする。この際、循環油の循環量は一定であるので、熱分解ガスの油化により生成する生成油と油化されなかった低沸点の熱分解ガス成分が沈降槽10に流入する。混合油の溢流手段としては、溢流管9以外に、例えば、沈降槽10との接続口の手前に設けられる堰または水平方向に穿孔されたスリットを有する仕切板などが挙げられる。
沈降槽10に流入したオーバーフロー液(溢流液)からは、微粒子状の芳香族カルボン酸が沈降槽10の底部に沈積する。ここで、沈降槽10における溢流液の滞留時間を制御して、即ち溢流液の流速を低下させて、溢流液から沈降する芳香族カルボン酸の沈降速度を沈降槽10内の溢流液の上昇速度より大きくすることにより、溢流液から芳香族カルボン酸を分離することができる。この際、廃プラスチックの熱分解によりコーキング物質が生成しているときは、溢流液からコーキング物質も沈降するので、より清浄な生成油を最終的に回収することが可能である。
【0012】
沈降槽10は配管11を介して分離器12に接続され、溢流堰をオーバーフローさせた溢流液を分離器12に供給することが好ましい。溢流堰を設けることによって、沈降槽10の液面を所定のレベルに保持することができるだけでなく、所定の大きさの微粒子が完全に除去された上澄液が分離器12に供給される。分離器12では、前記生成油と低沸点熱分解ガス成分が分離され、塔底の液状生成油が取り出されると共に、塔頂のガス成分は燃焼処理など適宜処理した後排ガスとして大気中に放出される。得られる生成油は、例えばボイラ燃料油やディーゼル燃料油などに利用される。
本発明において、PETを1〜50重量%含有する廃プラスチックが原料として用いられる。廃プラスチックには、PETボトルやPETのラミネートなどが含まれており、完全に分別しない限りPETを通常1重量%以上含有する。PETの含有量が1重量%以上になると、配管やバルブ等への昇華性芳香族カルボン酸の堆積が問題となる。一方、PETの含有量が50重量%より多くなると、循環経路7や前記配管3,9,11等を通過する芳香族カルボン酸の流量が増大するため、大径のパイプを使用しなければならず、コスト的に不利である。のみならず、廃プラスチックを熱分解処理して回収される単位重量当たりの生成油の量が減少するので、やはりコスト的に不利である。このような理由から、本発明においては、通常5〜30重量%のPETを含有する廃プラスチックが熱分解処理される。
本発明の油化処理装置の運転は連続式またはバッチ式のいずれでもよい。バッチ式の場合は、沈降槽10以外にも、運転停止後に析出槽4及び循環油槽5の底部に沈降してくるテレフタル酸及び安息香酸を回収することが望ましい。
【0013】
次に、前述の析出槽4及び沈降槽10について、図2,3を参照して詳細に説明する。
図2に示す析出槽4において、符号4aは析出槽4の蓋体であり、蓋体4aを貫通して注入管13が析出槽4に接続されている。注入管13は上部が析出槽4の外部に延出しており、その部分に前記導入管3が接続されている。また、注入管13には循環経路7に接続したエジェクタ管14が挿通され、その出口が導入管3の接続口13a近傍に臨んでいる。そのため、循環油クーラ6で冷却された循環油が注入管13に注入されるに伴って、導入管3から310℃以上に保たれた熱分解ガスは循環油によってダイレクト・クエンチされつつ速度を増して注入管13に導入されるので、昇華性芳香族カルボン酸が上記接続口13aの周囲や注入管13に析出するようなことはない。
注入管13下端部の出口部13bは析出槽4内の液面下に位置する。析出槽4内の液相部は、前述した通り、未油化の分解ガスのジェットバブリングによる気液混合相の状態にあり、循環油及び油化した生成油の混合油中に析出した芳香族カルボン酸を均一に含有する。注入管13の出口部13bは、長手方向に複数のスリットが等間隔で形成されており、析出槽4内に注入される混合油が直接下流側の循環経路7に通り抜けないように、下端面を有底とすることが好ましい。また、注入管13の出口部13bより上方の析出槽4には前記溢流管9が接続されている。そのため、析出槽4内で新たに油化した量の生成油が、芳香族カルボン酸と共に溢流管9を通って沈降槽10にオーバーフローする。なお、符号15は液相部の温度を検出する温度計である。
【0014】
沈降槽10内には、図3に図示するように、上端部が溢流液面から突出すると共に下部にスリット状の開口部16aを有する仕切板16を配置することが好ましい。また、仕切板16の下流に、上端が仕切板16の上端よりやや低い前記溢流堰17を配置することが好ましい。下部仕切板16は、1枚に限定されるものではなく、複数枚配置することができる。仕切板16に穿設される開口部16aは、連続していても不連続であってもよい。なお、沈降槽10の底部に排出口を設けて、底面に沈積したテレフタル酸及び安息香酸を取り出すことができる。
沈降槽10内の溢流液は、仕切板の下部開口部16aを通って下流に流れ、その下流側の溢流堰17からは上澄液がオーバーフローして、沈降槽10から流出する。溢流堰17は省略してもよく、その場合、配管11との接続口を溢流液のオーバーフロー部とすることもできる。いずれにしても、溢流液は層流状態で流れるため、昇華性芳香族カルボン酸(固形分)の沈降が良好なものとなる。
以上のような沈降槽10において、その横断面積に対する単位時間当たりの溢流液の流入量の割合で表される溢流液の上昇速度よりも、上記固形分の沈降速度を大きくしているので、固形分を確実に沈降させることができる。
【0015】
【実施例】
以下に、実施例を挙げて本発明をより具体的に説明するが、本発明は実施例に限定されるものではない。
本実施例では、PET50kg、ポリエチレン150kg、ポリプロピレン150kg及びポリポリスチレン150kgからなる廃プラスチックを熱分解処理の原料として用いた。廃プラスチック中のPETの含有量は10%である。
図4において、熱分解炉1は同能力の2基の熱分解反応器1′から構成され、各々同一組成の廃プラスチックを2等分して反応器1′に投与した。その後、灯油タンク20から供給される燃料をバーナ2で燃焼して、熱分解反応器1′内の廃プラスチックを400℃で6時間加熱した。この間、廃プラスチックの熱分解ガス生成物が導入管3を通って図2に示す析出槽4に導入される。
析出槽4には、循環油クーラ6で40℃に冷却された前述の循環油が1360L/hrの流量で循環している。油化処理装置の運転開始時における循環経路7の流動性を確保するために、装置の運転開始前に、予め温水槽21から循環油槽5のジャケット部に温水を循環させて、循環油の温度を40℃に加温しておいた。また、循環油クーラ6は冷水槽22から後述の凝縮器23を通過した循環冷却水により冷却されるが、装置の運転開始初期はバイパス弁24を開成して冷却水の一部をバイパスさせることにより、循環油の流動性を確保した。
【0016】
熱分解ガス生成物は、注入管13に流入する際に循環油でダイレクト・クエンチされ、前記エジェクタ管14のエジェクタ作用により循環油と共に析出槽4に導入される。析出槽4内には熱分解ガスが油化すると同時にテレフタル酸及び安息香酸が析出し、装置の運転が定常状態に達した後には、循環油及び油化した生成油中の固形分濃度が15%のスラリーとなり、その温度は50℃である。スラリーの大半は循環油として循環経路7を循環する。残りの新たに生成したスラリーは、生成油に換算して50L/hrの流量で溢流管9から沈降槽10にオーバーフローする。
沈降槽10としては図3に示すものを使用したが、前記溢流液に相当するスラリーの固形分が沈降する底部を下方に傾斜させて、その最下部に固形分抜取管25を接続している。底部傾斜部分を除く沈降槽10のサイズは60×160×50(cm)であり、液相部の容積は400Lである。また、溢流液の滞留時間は15分であって、固形分の沈降速度は0.075mm/secであり、溢流液の上昇速度は0.022mm/secであった。
【0017】
沈降槽10の溢流堰17をオーバーフローする溢流液の上澄液は、油化されなかった分解ガスと共に配管11を介して分離器12に供給される。分離器12上には前記凝縮器23が設置され、冷水槽22を循環する冷却水により冷却される。凝縮器23では気液分離が行われ、液化した分解ガス成分は一旦下方の分離器12に貯留される。気相の分解ガス成分は、水封槽26で水溶性ガスが除去され、次いで熱分解炉1の燃焼排ガスと合流させて、燃焼処理装置27で無害化処理された後大気中に放出される。また、分離器12内の生成油は、30μm以下の微小な固形物が浮遊しており、途中フィルタ28で固形物を除去した後、生成油タンク29に貯留される。
油化処理装置の運転終了後に、沈降槽10、析出槽4及び循環油槽5の底部に結晶化したテレフタル酸及び安息香酸が沈積しているので、これらの芳香族カルボン酸を回収した。回収された芳香族カルボン酸には分解油が含まれているので、遠心分離機にかけて分解油を除去した。
【0018】
廃プラスチックの熱分解生成物の組成を下記の表1に示す。
【表1】

Figure 0004286557
前記組成の廃プラスチック500kgから、テレフタル酸及び安息香酸が32kg生成し、分解油を311.5kg回収することができた(回収率62.3%)。
【0019】
表1中のガス組成は次の通りである。
【表2】
Figure 0004286557
以上の廃プラスチックの熱分解処理を10回繰り返してみたが、油化処理装置の配管及びバルブが閉塞されることはなく、その機器内部にも昇華性芳香族カルボン酸の堆積または付着は観察されなかった。
【0020】
【発明の効果】
本発明によれば、PETを含有する廃プラスチックの熱分解ガスが循環油により急冷されつつ循環油と一緒に析出槽内に導入されるものであるから、熱分解ガスの導入管及びその周辺の配管や機器内に、PET由来のテレフタル酸及び安息香酸が析出するようなことがない。また、気相状のテレフタル酸及び安息香酸を熱分解炉に接続する析出槽内の分解油中に析出させるので、析出槽の下流側配管及びバルブを閉塞させるようなことがない。
そのため、PET含有の廃プラスチックを安定して熱分解することができ、その熱分解生成物の油状成分を例えば燃料油として回収することができる。従って、本発明の油化処理装置は、今後熱分解によるプラスチック廃棄物の処理範囲を拡大するものと期待される。
【図面の簡単な説明】
【図1】 本発明の廃プラスチックの油化処理装置の概要を説明する工程図である。
【図2】 本発明の油化処理装置におけるクエンチ部の一実施例を示す。
【図3】 本発明の油化処理装置における沈降槽の一実施例を示し、(a)はその平面図であり、(b)は縦断面図である。
【図4】 本発明の一実施例を示す油化処理装置の工程図である。
【符号の説明】
1・・・ 熱分解炉、3・・・ 導入管、4・・・ 析出槽、5・・・ 循環油槽、6・・・ 循環油クーラ、7・・・ 循環経路、8・・・ 循環ポンプ、9・・・ 溢流管(溢流手段)、10・・・ 沈降槽、13・・・ 注入管、13a・・・ 接続口、13b・・・ 出口部、14・・・ エジェクタ管、16・・・ 仕切板、16a・・・ 開口部、17・・・ 溢流堰。[0001]
BACKGROUND OF THE INVENTION
TECHNICAL FIELD The present invention relates to an oil plasticizing apparatus for waste plastic containing PET (polyethylene terephthalate). More specifically, according to the present invention, waste plastic can be pyrolyzed without clogging pipes even if terephthalic acid and benzoic acid produced when PET is pyrolyzed precipitates in the cracked oil. The present invention relates to a possible waste plastic oil processing apparatus.
[0002]
[Prior art]
From the viewpoint of resource saving and non-pollution, many methods have been proposed to make waste plastic oil by thermally decomposing plastic waste synthesized from petroleum and using the resulting cracked oil as fuel. . For example, polyolefin and / or polystyrene waste plastics are pyrolyzed in a pyrolysis tank, and the resulting pyrolysis gas is separated into crude heavy oil components and light oil components using a heat exchanger, and the light oil components are heat exchanged. There has been proposed a method of converting waste plastic into oil that is condensed in a vessel to take out light oil (Patent Document 1). In this oil conversion method, after a part of light oil is vaporized, it is supplied into the thermal decomposition tank and used as a heating source for waste plastic, and the rest is used as fuel.
The oil conversion method disclosed in Patent Document 1 includes a heavy oil component in light oil, requires a new heat source for vaporizing the light oil, and can easily solidify the heavy oil component and block the piping. An improvement method has been proposed for reasons such as the possibility (patent document 2).
In the oil conversion method disclosed in Patent Document 2, a pyrolysis gas is supplied from a pyrolysis tank to an atmospheric distillation tower by an ejector, and a light oil is obtained by cooling a tower top component of the distillation tower to obtain a light oil. After a part of the water is vaporized by heat exchange with the bottom oil (heavy oil) of the distillation tower, the temperature is raised in a heating furnace using light oil as a fuel and introduced into the pyrolysis tank. It is used as a plastic heating source. In this oil conversion method, part of the tower bottom oil is pumped to the ejector and used as the driving liquid, and the remainder is heated in the heating furnace and then stored in the heavy oil tank. Also in this oil conversion method, polyethylene, polypropylene, polypolystyrene and polyvinyl chloride are used as waste plastics.
[0003]
By the way, if plastic waste can be collected separately for each plastic of the same type, it is advantageous for subsequent processing. However, although the separation and collection of garbage has become common in recent years, it is difficult to separate the garbage and waste discarded from ordinary households into the same kind of plastic, and plastic waste usually contains various types of resins. ing. In particular, it is almost impossible to separate a plastic laminate for each layer. Examples of plastic waste include nylon and PET in addition to those exemplified in Patent Document 2.
Among waste plastics, hydrocarbon resins such as polyethylene are relatively easy to pyrolyze, and produce hydrocarbon oils similar to heavy oil compositions. In addition, when waste plastic containing polyvinyl chloride or polyvinylidene chloride is pyrolyzed, a large amount of hydrogen chloride and chlorinated hydrocarbons are produced from chlorinated resin, preventing corrosion of pyrolysis tanks and piping by hydrogen chloride. There is a need to. As a method for dechlorinating chlorinated hydrocarbons, for example, a method in which a pyrolysis product in a gas-liquid mixed phase is brought into contact with an iron oxide catalyst and a chlorine component is reacted with the catalyst or adsorbed on the catalyst to be separated and removed. Known (Patent Document 3).
On the other hand, in the thermal decomposition of waste plastic containing PET, terephthalic acid and benzoic acid are by-produced from PET together with acetaldehyde, ethylene and the like. Terephthalic acid sublimes at 300 ° C. and benzoic acid sublimes at 100 ° C., which causes serious problems in the oiling apparatus. That is, when the decomposition gas generated by thermal decomposition is cooled to the above-described temperatures or less and condensed, the sublimable aromatic carboxylic acid undergoes a phase change from a gas to a solid, causing a problem that the pipes and equipment are blocked. Specifically, terephthalic acid is deposited at the outlet piping of the pyrolysis reactor, and benzoic acid is deposited on the piping section and condenser cooled to a temperature lower than 100 ° C. In order to clog, it is difficult to pyrolyze the waste plastic containing PET to make the cracked gas oily.
[0004]
[Patent Document 1]
JP-A-10-195542 [Patent Document 2]
JP 2001-59089 A [Patent Document 3]
Japanese Patent Laid-Open No. 2001-123182
[Problems to be solved by the invention]
Thus, in the conventional thermal decomposition of waste plastics containing PET, there is a problem that the terephthalic acid and benzoic acid (sometimes referred to as sublimable aromatic carboxylic acid) to be produced block the piping.
Accordingly, an object of the present invention is to eliminate the above-mentioned problems of the prior art, and even if PET is contained in the waste plastic, the sublimable aromatic carboxylic acid does not block the piping and is discarded. An object of the present invention is to provide a waste plastic oil conversion treatment apparatus capable of recovering cracked gas generated by thermal decomposition of plastic as cracked oil.
[0006]
[Means for Solving the Problems]
In the cooling of the pyrolysis gas by the heat exchanger, the terephthalic acid and benzoic acid that are generated deposit on the tube and shell and block the heat exchanger. It is desirable not to let the sublimable aromatic carboxylic acid in the form of a downstream flow. For this purpose, it is necessary to rapidly cool the pyrolysis gas at the outlet of the pyrolysis furnace. Under such a concept, the present inventors have intensively studied in order to solve the above-described problems. As a result, the pyrolysis product oil containing the aromatic carboxylic acid precipitated in the precipitation tank is precipitated. It has been found that the above-mentioned object can be achieved by providing overflow means for overflowing the tank and depositing the aromatic carboxylic acid in the sedimentation tank, thereby achieving the present invention.
That is, the waste plastic oil treatment apparatus of the present invention includes a pyrolysis furnace for thermally decomposing waste plastic containing PET, and each of terephthalic acid and benzoic acid in a pyrolysis gas generated by a thermal decomposition reaction of the waste plastic. A precipitation tank for precipitating the sublimable aromatic carboxylic acid, and a circulating oil tank and a circulating oil cooler interposed in a circulation path in which circulating oil generated by liquefaction of the pyrolysis gas circulates in the precipitation tank by driving a circulation pump; An introduction pipe for introducing the pyrolysis gas generated from the cracking furnace into the precipitation tank is connected to the circulation path downstream of the circulation oil tank and the circulation oil cooler and upstream of the precipitation tank, and the circulating oil cooled by the circulation oil cooler and An overflow means is provided for overflowing the mixed oil with the product oil that has been rapidly cooled by the circulating oil and deposited with the aromatic carboxylic acid from the pyrolysis gas from the precipitation tank to the settling tank. And butterflies.
[0007]
[Action]
The operation of the waste plastic oiling treatment apparatus of the present invention is as follows.
When the waste plastic containing PET is pyrolyzed in a pyrolysis furnace, pyrolysis gas containing sublimable aromatic carboxylic acids of terephthalic acid and benzoic acid is generated together with hydrocarbons and the like. On the other hand, in the oil treatment apparatus of the present invention, a circulation path including a precipitation tank, a circulation oil tank, and a circulation oil cooler is formed, and the cracked oil, which is an oilification product of the pyrolysis gas, is used as the circulation oil of the circulation pump. Circulates the circulation path by driving. And, since the introduction pipe for introducing the pyrolysis gas into the precipitation tank is connected to the circulation path upstream of the precipitation tank on the downstream side of the circulation oil tank and the circulation oil cooler, the pyrolysis gas is cooled by the circulation oil cooler. While being rapidly cooled by the circulating oil, it is introduced into the precipitation tank together with the circulating oil.
As a result, the sublimable aromatic carboxylic acid crystallizes and precipitates in the precipitation tank in the mixed oil of the product oil and circulating oil resulting from the pyrolysis of the pyrolysis gas, and at the same time, the liquid phase portion in the precipitation tank contains the pyrolysis gas. Is in the state of jet bubbling. The mixed oil containing the fine-particulate aromatic carboxylic acid then overflows into the settling tank via the overflow means. For this reason, the liquid phase portion in the settling tank is in a laminar flow state except for the periphery where the overflow liquid flows in, so that the precipitation of the aromatic carboxylic acid fine particles is promoted.
In the present invention, the pyrolysis gas is introduced into the precipitation tank together with the circulating oil while being rapidly cooled by the circulation oil, so that the sublimation aromatics are introduced into the introduction pipe and the surrounding pipes for introducing the pyrolysis gas into the precipitation tank. No group carboxylic acid is precipitated. Moreover, since the gas phase aromatic carboxylic acid is precipitated at an early stage, the downstream piping of the precipitation tank is not blocked. Therefore, it is possible to stably convert the decomposition product resulting from the thermal decomposition of waste plastic into decomposition oil.
[0008]
According to the second aspect of the present invention, the pyrolysis gas introduction pipe is connected to the injection pipe connected to the precipitation tank, and the outlet of the ejector pipe through which the circulating oil is injected faces the connection port. Therefore, a high-temperature pyrolysis gas is quickly injected into the precipitation tank by the ejector effect. This direct quench can more reliably prevent clogging of the precipitation tank and its upstream piping caused by the precipitation of the aromatic carboxylic acid. Furthermore, since the outlet part of the injection pipe is located below the outlet of the mixed oil, oilification of the pyrolysis gas introduced into the precipitation tank is promoted.
According to the third aspect of the invention, since the sedimentation rate of the particulate aromatic carboxylic acid is made larger than the rising rate of the overflow liquid flowing into the sedimentation tank, the overflow weir disposed in the sedimentation tank It is possible to reduce the solid content (aromatic carboxylic acid fine particles) flowing out beyond as much as possible.
According to the invention according to claim 4, since the partition plate is disposed in the settling tank between the overflow liquid inlet and the overflow weir, the overflow weir is in a laminar flow state. Since it overflows, the separation efficiency of the aromatic carboxylic acid can be improved. Moreover, since the opening is formed in the lower part of the partition plate, the overflow liquid partitioned by the partition plate flows downstream in a laminar flow state without being disturbed, and thus the separation efficiency is further improved.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail with reference to the drawings.
In FIG. 1, reference numeral 1 denotes a waste plastic pyrolysis furnace heated by a burner 2. The pyrolysis furnace 1 is composed of one or a plurality of pyrolysis reactors 1 ', and the number thereof is not particularly limited. The waste plastic contains PET, and the PET-containing waste plastic is pyrolyzed at 310 to 550 ° C. in the pyrolysis reactor 1 ′. The generated pyrolysis gas is introduced into the precipitation tank 4 through the introduction pipe 3.
Typical thermal decomposition products of PET include terephthalic acid and benzoic acid, as well as ethylene, acetaldehyde, benzene, vinyl benzoate, ethylene bisbenzoate, diphenyl, divinyl terephthalate, monovinyl terephthalate, monovinyl terephthalate monobenzoyl Examples include oxyethyl. Among these pyrolysis products, terephthalic acid is a substance that sublimes at 300 ° C. and benzoic acid sublimes at 100 ° C. When the high-temperature pyrolysis gas is cooled, these aromatic carboxylic acids are converted from gas to solid. Make a change.
If the thermal decomposition temperature is less than 310 ° C., the terephthalic acid produced may precipitate in the introduction pipe 3 and block the introduction pipe 3. On the other hand, when the thermal decomposition temperature is higher than 550 ° C., not only the caulking substance is generated and contained in the produced oil, but also the energy efficiency is lowered. The thermal decomposition temperature of the waste plastic is preferably in the range of 350 to 450 ° C.
[0010]
In the oil treatment apparatus of the present invention, a circulation path 7 is formed in which a precipitation tank 4, a circulation oil tank 5, and a circulation oil cooler 6 are connected by piping. In the circulation path 7, the circulating oil cooled to 40 to 60 ° C. by the circulating oil cooler 6 is circulated by driving the circulation pump 8. On the other hand, the introduction pipe 3 is connected to a circulation path 7 upstream of the precipitation tank 4 on the downstream side of the circulation oil tank 5 and the circulation oil cooler 6. Accordingly, the pyrolysis gas is introduced into the precipitation tank 4 while being rapidly cooled by the circulating oil.
As the circulating oil, cracked oil obtained by converting the pyrolysis gas of waste plastic into oil is used. Ordinary waste plastics include polyolefins such as polyethylene and polypropylene, and a wax having a high pour point is generated by thermal decomposition. Therefore, in order to prevent clogging of piping, the temperature of the circulating oil is set to 40 ° C. or higher. Need to keep. In addition, when the pyrolysis gas is rapidly cooled with the circulating oil, the temperature of the circulating oil is preferably 60 ° C. or lower in order to completely precipitate benzoic acid in the pyrolysis gas. When the pyrolysis gas of 310 to 550 ° C. is rapidly cooled with the circulating oil of 40 to 60 ° C., the temperature of the mixed oil of the product oil and the circulation oil from the pyrolysis gas is in the range of 50 ° C. to less than 100 ° C. In order to reduce the circulation amount of the circulating oil, the temperature of the circulating oil is more preferably in the range of 40 to 50 ° C, and the temperature of the mixed oil at that time is in the range of 50 to 80 ° C. In order to keep the temperature of the mixed oil below 100 ° C., the flow rate of the circulating oil needs to be 20 times the generated oil flow rate.
[0011]
The mixed oil in the precipitation tank 4 and the circulating oil flowing out of the precipitation tank 4 contain 5 to 200 μm of fine particulate aromatic carboxylic acid. These oils become suspensions (dispersions) or slurries depending on the content of PET in the raw plastic waste, that is, the content of terephthalic acid and benzoic acid in the pyrolysis gas. The liquid phase portion in the precipitation tank 4 is introduced with cracked gas that has not been converted to oil, and the liquid phase portion is vigorously stirred. That is, the precipitation tank 4 functions as a complete mixing tank in which the liquid phase portion is constantly jet-bubbled by the cracked gas and presents a gas-liquid mixed phase having a uniform solid content concentration.
The precipitation tank 4 is connected to a settling tank 10 via an overflow pipe 9 as an overflow means, and the mixed oil of the product oil and the circulating oil overflows from the precipitation tank 4 to the settling tank 10. At this time, since the circulation amount of the circulating oil is constant, the product oil generated by liquefying the pyrolysis gas and the low boiling pyrolysis gas component that has not been liquefied flow into the sedimentation tank 10. As the overflowing means of the mixed oil, in addition to the overflow pipe 9, for example, a weir provided in front of the connection port with the settling tank 10 or a partition plate having a slit drilled in the horizontal direction can be used.
From the overflow liquid (overflow liquid) that has flowed into the settling tank 10, fine-particle aromatic carboxylic acid is deposited at the bottom of the settling tank 10. Here, the residence time of the overflow liquid in the sedimentation tank 10 is controlled, that is, the flow velocity of the overflow liquid is reduced, and the sedimentation speed of the aromatic carboxylic acid that settles from the overflow liquid is determined as the overflow in the sedimentation tank 10. By making it larger than the rising speed of the liquid, the aromatic carboxylic acid can be separated from the overflow liquid. At this time, when the caulking substance is generated by the thermal decomposition of the waste plastic, the caulking substance also settles from the overflow liquid, so that a cleaner product oil can be finally recovered.
[0012]
The settling tank 10 is preferably connected to a separator 12 via a pipe 11, and it is preferable to supply an overflow liquid overflowing the overflow weir to the separator 12. By providing the overflow weir, not only can the liquid level of the sedimentation tank 10 be maintained at a predetermined level, but also the supernatant from which fine particles of a predetermined size have been completely removed is supplied to the separator 12. . In the separator 12, the product oil and the low-boiling pyrolysis gas component are separated, and the liquid product oil at the bottom of the column is taken out. The gas component at the top of the column is appropriately treated, such as a combustion treatment, and then released into the atmosphere as exhaust gas. The The resulting product oil is used, for example, as boiler fuel oil or diesel fuel oil.
In the present invention, waste plastic containing 1 to 50% by weight of PET is used as a raw material. Waste plastics include PET bottles, PET laminates, and the like, and usually contains 1% by weight or more of PET unless it is completely separated. When the PET content is 1% by weight or more, the deposition of sublimable aromatic carboxylic acid on pipes, valves and the like becomes a problem. On the other hand, if the PET content exceeds 50% by weight, the flow rate of the aromatic carboxylic acid that passes through the circulation path 7 and the pipes 3, 9, 11 and the like increases, so a large-diameter pipe must be used. It is disadvantageous in terms of cost. In addition, since the amount of product oil per unit weight recovered by pyrolyzing waste plastic is reduced, it is also disadvantageous in terms of cost. For this reason, in the present invention, waste plastics usually containing 5 to 30% by weight of PET are pyrolyzed.
The operation of the oil treatment apparatus of the present invention may be either continuous or batch. In the case of a batch type, it is desirable to collect terephthalic acid and benzoic acid that settle on the bottoms of the precipitation tank 4 and the circulating oil tank 5 after the operation is stopped, in addition to the settling tank 10.
[0013]
Next, the precipitation tank 4 and the settling tank 10 will be described in detail with reference to FIGS.
In the precipitation tank 4 shown in FIG. 2, reference numeral 4 a is a lid of the precipitation tank 4, and the injection pipe 13 is connected to the precipitation tank 4 through the lid 4 a. The upper portion of the injection tube 13 extends to the outside of the precipitation tank 4, and the introduction tube 3 is connected to that portion. Further, an ejector pipe 14 connected to the circulation path 7 is inserted into the injection pipe 13, and its outlet faces the vicinity of the connection port 13 a of the introduction pipe 3. Therefore, as the circulating oil cooled by the circulating oil cooler 6 is injected into the injection pipe 13, the pyrolysis gas maintained at 310 ° C. or higher from the introduction pipe 3 increases its speed while being directly quenched by the circulating oil. Thus, the sublimable aromatic carboxylic acid is not deposited around the connection port 13a or the injection tube 13.
The outlet 13 b at the lower end of the injection tube 13 is located below the liquid level in the precipitation tank 4. As described above, the liquid phase portion in the precipitation tank 4 is in a gas-liquid mixed phase state by jet bubbling of the non-oiled cracked gas, and the aromatics precipitated in the mixed oil of the circulating oil and the oiled product oil Contains carboxylic acid uniformly. The outlet portion 13b of the injection pipe 13 has a plurality of slits formed at equal intervals in the longitudinal direction, so that the mixed oil injected into the precipitation tank 4 does not directly pass through the circulation path 7 on the downstream side. Is preferably bottomed. The overflow pipe 9 is connected to the precipitation tank 4 above the outlet portion 13b of the injection pipe 13. Therefore, the amount of product oil newly liquefied in the precipitation tank 4 overflows the settling tank 10 through the overflow pipe 9 together with the aromatic carboxylic acid. Reference numeral 15 denotes a thermometer that detects the temperature of the liquid phase part.
[0014]
In the settling tank 10, as shown in FIG. 3, it is preferable to arrange a partition plate 16 having an upper end protruding from the overflow liquid surface and a slit-like opening 16a at the lower part. In addition, it is preferable that the overflow weir 17 is arranged downstream of the partition plate 16 with its upper end being slightly lower than the upper end of the partition plate 16. The lower partition plate 16 is not limited to one, and a plurality of lower partition plates 16 can be arranged. The opening 16a drilled in the partition plate 16 may be continuous or discontinuous. In addition, the discharge port is provided in the bottom part of the sedimentation tank 10, and the terephthalic acid and benzoic acid which were deposited on the bottom face can be taken out.
The overflow liquid in the sedimentation tank 10 flows downstream through the lower opening 16a of the partition plate, the supernatant overflows from the overflow weir 17 on the downstream side, and flows out of the sedimentation tank 10. The overflow weir 17 may be omitted, and in this case, the connection port with the pipe 11 may be an overflow portion of the overflow liquid. In any case, since the overflow liquid flows in a laminar flow state, the sublimation aromatic carboxylic acid (solid content) settles well.
In the sedimentation tank 10 as described above, the sedimentation speed of the solid content is made larger than the rising speed of the overflow liquid expressed by the ratio of the inflow amount of the overflow liquid per unit time to the cross-sectional area. The solid content can be surely settled.
[0015]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the examples.
In this example, waste plastic made of 50 kg PET, 150 kg polyethylene, 150 kg polypropylene and 150 kg polypolystyrene was used as a raw material for the thermal decomposition treatment. The content of PET in the waste plastic is 10%.
In FIG. 4, the pyrolysis furnace 1 is composed of two pyrolysis reactors 1 ′ having the same capacity, and waste plastics having the same composition are divided into two equal parts and fed to the reactor 1 ′. Thereafter, the fuel supplied from the kerosene tank 20 was burned by the burner 2 and the waste plastic in the pyrolysis reactor 1 ′ was heated at 400 ° C. for 6 hours. During this time, the pyrolytic gas product of waste plastic is introduced into the precipitation tank 4 shown in FIG.
In the precipitation tank 4, the above-described circulating oil cooled to 40 ° C. by the circulating oil cooler 6 is circulated at a flow rate of 1360 L / hr. In order to ensure the fluidity of the circulation path 7 at the start of operation of the oil treatment apparatus, warm water is circulated in advance from the hot water tank 21 to the jacket of the circulating oil tank 5 before the start of operation of the apparatus, and the temperature of the circulating oil Was warmed to 40 ° C. The circulating oil cooler 6 is cooled by circulating cooling water that has passed through a condenser 23 described later from the cold water tank 22, but at the initial stage of operation of the apparatus, the bypass valve 24 is opened to bypass a part of the cooling water. As a result, the fluidity of the circulating oil was secured.
[0016]
The pyrolysis gas product is directly quenched by circulating oil when it flows into the injection pipe 13 and is introduced into the precipitation tank 4 together with the circulating oil by the ejector action of the ejector pipe 14. After the pyrolysis gas is liquefied in the precipitation tank 4, terephthalic acid and benzoic acid are precipitated, and after the operation of the apparatus reaches a steady state, the solid content concentration in the circulating oil and the liquefied product oil is 15%. % Slurry, and its temperature is 50 ° C. Most of the slurry circulates in the circulation path 7 as circulating oil. The remaining newly produced slurry overflows from the overflow pipe 9 to the settling tank 10 at a flow rate of 50 L / hr in terms of produced oil.
As the settling tank 10, the one shown in FIG. 3 was used, but the bottom portion where the solid content of the slurry corresponding to the overflow liquid settles down is inclined downward, and the solid content extraction pipe 25 is connected to the lowermost portion. Yes. The size of the sedimentation tank 10 excluding the bottom inclined portion is 60 × 160 × 50 (cm), and the volume of the liquid phase portion is 400L. Moreover, the residence time of the overflow liquid was 15 minutes, the settling speed of the solid content was 0.075 mm / sec, and the rising speed of the overflow liquid was 0.022 mm / sec.
[0017]
The supernatant liquid overflowing the overflow weir 17 of the settling tank 10 is supplied to the separator 12 through the pipe 11 together with the cracked gas that has not been converted to oil. The condenser 23 is installed on the separator 12 and is cooled by cooling water circulating in the cold water tank 22. The condenser 23 performs gas-liquid separation, and the liquefied cracked gas component is temporarily stored in the lower separator 12. The gas-phase decomposition gas component is removed from the water-soluble gas in the water-sealed tank 26, and then merged with the combustion exhaust gas of the thermal decomposition furnace 1, detoxified by the combustion processing device 27, and then released into the atmosphere. . Further, the produced oil in the separator 12 has a fine solid matter of 30 μm or less floating therein, and after the solid matter is removed by the filter 28, it is stored in the produced oil tank 29.
Since the terephthalic acid and benzoic acid crystallized at the bottoms of the settling tank 10, the precipitation tank 4 and the circulating oil tank 5 were deposited after the operation of the oil treatment apparatus, these aromatic carboxylic acids were recovered. Since the recovered aromatic carboxylic acid contains cracked oil, it was centrifuged to remove the cracked oil.
[0018]
The composition of the waste plastic thermal decomposition product is shown in Table 1 below.
[Table 1]
Figure 0004286557
From 500 kg of waste plastic having the above composition, 32 kg of terephthalic acid and benzoic acid were produced, and 311.5 kg of cracked oil could be recovered (recovery rate: 62.3%).
[0019]
The gas composition in Table 1 is as follows.
[Table 2]
Figure 0004286557
The above pyrolysis treatment of waste plastic was repeated 10 times, but the piping and valves of the oil treatment apparatus were not blocked, and deposition or adhesion of sublimable aromatic carboxylic acid was observed inside the equipment. There wasn't.
[0020]
【The invention's effect】
According to the present invention, the pyrolysis gas of waste plastic containing PET is introduced into the precipitation tank together with the circulating oil while being rapidly cooled by the circulating oil. There is no precipitation of PET-derived terephthalic acid and benzoic acid in the piping and equipment. Moreover, since vapor-phase terephthalic acid and benzoic acid are deposited in the cracked oil in the precipitation tank connected to the thermal decomposition furnace, the downstream piping and valves of the precipitation tank are not blocked.
Therefore, the waste plastic containing PET can be thermally decomposed stably, and the oily component of the thermal decomposition product can be recovered as, for example, fuel oil. Therefore, the oil treatment apparatus of the present invention is expected to expand the processing range of plastic waste by pyrolysis in the future.
[Brief description of the drawings]
BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a process diagram for explaining the outline of a waste plastic oil treatment apparatus according to the present invention.
FIG. 2 shows an embodiment of a quench unit in the oil treatment apparatus of the present invention.
FIGS. 3A and 3B show an embodiment of a sedimentation tank in the oil treatment apparatus of the present invention, FIG. 3A is a plan view thereof, and FIG.
FIG. 4 is a process diagram of an oil treatment apparatus showing an embodiment of the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 ... Pyrolysis furnace, 3 ... Introducing pipe, 4 ... Deposition tank, 5 ... Circulating oil tank, 6 ... Circulating oil cooler, 7 ... Circulating path, 8 ... Circulating pump , 9 ... Overflow pipe (overflow means), 10 ... Settling tank, 13 ... Injection pipe, 13a ... Connection port, 13b ... Outlet part, 14 ... Ejector pipe, 16 ... Partition plate, 16a ... Opening, 17 ... Overflow weir.

Claims (4)

PETを含有する廃プラスチックを熱分解する熱分解炉と、廃プラスチックの熱分解反応によって生成する熱分解ガス中のテレフタル酸及び安息香酸の各昇華性芳香族カルボン酸を析出させる析出槽と、熱分解ガスの油化により生じる循環油が循環ポンプの駆動により析出槽を循環する循環経路に介在する循環油槽及び循環油クーラとを備え、熱分解炉から生じる熱分解ガスを析出槽に導入する導入管が循環油槽及び循環油クーラの下流側かつ析出槽の上流側の循環経路に接続されると共に、循環油クーラで冷却された循環油と該循環油により急冷されて熱分解ガスから上記芳香族カルボン酸が析出した生成油との混合油を析出槽から沈降槽にオーバーフローさせる溢流手段を設けたことを特徴とする廃プラスチックの油化処理装置。A pyrolysis furnace for thermally decomposing waste plastic containing PET, a precipitation tank for precipitating each sublimable aromatic carboxylic acid of terephthalic acid and benzoic acid in a pyrolysis gas produced by a thermal decomposition reaction of the waste plastic, and a heat A circulating oil tank and a circulating oil cooler interposed in a circulation path through which circulating oil generated by cracking gas oilification circulates in the precipitation tank by driving a circulation pump is introduced to introduce the pyrolysis gas generated from the pyrolysis furnace into the precipitation tank The pipe is connected to the circulation path downstream of the circulating oil tank and the circulating oil cooler and upstream of the precipitation tank, and the aromatic oil is cooled from the circulating oil cooled by the circulating oil cooler and rapidly cooled by the circulating oil, and is converted from the pyrolysis gas. An oil plasticizing apparatus for waste plastic, comprising overflow means for overflowing a mixed oil with a product oil in which carboxylic acid is precipitated from a precipitation tank to a settling tank. 熱分解ガス及び循環油が導入される注入管を前記析出槽に接続し、析出槽の外部に延出する注入管に前記導入管が接続され、その接続口近傍に循環経路の一部をなすエジェクタ管の出口を臨ませると共に、沈降槽への前記混合油の流出口の下方に注入管の出口部が位置することを特徴とする請求項1記載の油化処理装置。An injection pipe into which pyrolysis gas and circulating oil is introduced is connected to the precipitation tank, and the introduction pipe is connected to an injection pipe extending to the outside of the precipitation tank, and forms a part of the circulation path in the vicinity of the connection port. 2. The oil processing apparatus according to claim 1, wherein an outlet of the injection pipe is positioned below the outlet of the mixed oil to the settling tank while the outlet of the ejector pipe faces. 前記析出槽から流入する溢流液がオーバーフローする溢流堰を沈降槽内に配置して、溢流液中の前記芳香族カルボン酸の沈降速度を沈降槽内の溢流液の上昇速度より大きくしたことを特徴とする請求項1又は2記載の油化処理装置。An overflow weir in which the overflow liquid flowing from the precipitation tank overflows is disposed in the settling tank, and the sedimentation rate of the aromatic carboxylic acid in the overflow liquid is larger than the rising speed of the overflow liquid in the sedimentation tank. The oil processing apparatus of Claim 1 or 2 characterized by the above-mentioned. 前記析出槽から流入する溢流液がオーバーフローする溢流堰を沈降槽内に配置し、上端部が溢流液面から突出し下部に開口部を有する少なくとも1枚の仕切板が、溢流液の流入口と溢流堰の間の沈降槽内に配置されていることを特徴とする請求項1又は2記載の油化処理装置。An overflow weir in which the overflow liquid flowing in from the precipitation tank overflows is disposed in the sedimentation tank, and at least one partition plate having an upper end projecting from the overflow liquid surface and having an opening in the lower portion is provided for the overflow liquid. 3. The oil processing apparatus according to claim 1, wherein the oil processing apparatus is disposed in a sedimentation tank between an inlet and an overflow weir.
JP2003047724A 2003-02-25 2003-02-25 Oil processing equipment for waste plastic containing PET Expired - Fee Related JP4286557B2 (en)

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