JP2011184673A - Thermal decomposition method of mixed waste plastic and thermal decomposition apparatus of mixed waste plastic - Google Patents

Thermal decomposition method of mixed waste plastic and thermal decomposition apparatus of mixed waste plastic Download PDF

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JP2011184673A
JP2011184673A JP2010076147A JP2010076147A JP2011184673A JP 2011184673 A JP2011184673 A JP 2011184673A JP 2010076147 A JP2010076147 A JP 2010076147A JP 2010076147 A JP2010076147 A JP 2010076147A JP 2011184673 A JP2011184673 A JP 2011184673A
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waste plastic
mixed waste
reactor
mixed
thermal decomposition
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Araki Abe
荒喜 阿部
Kumiko Abe
久美子 阿部
Yasushi Fujikawa
康史 藤川
Hiroshi Noma
洋 野間
Isamu Takeuchi
勇 竹内
Tetsuji Kuramoto
哲次 倉本
Daigo Aihara
大悟 相原
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RAMUSA ABE KK
Ramusa Abe KK
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RAMUSA ABE KK
Ramusa Abe KK
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    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermal decomposition method in which waste plastics (hereafter referred to as "mixed waste plastics"), a mixture of a thermoplastic resin containing chlorine as a compositional component and a thermosetting resin, are mixed with alkaline powders and are subjected to thermal decomposition at relatively low temperature in a simplified brief processing step, thereby efficiently obtaining an oil component having significantly low level of chlorine and also preventing corrosion of equipment caused by hydrogen chloride, and an apparatus used for the method. <P>SOLUTION: The thermal decomposition method of mixed waste plastics has structure in which the mixed waste plastics are contacted and mixed with the alkaline powders in a reactor, are subjected to thermal decomposition and gasification while being purged with inert gas by heating until the temperature inside the reactor is 200-700°C by an induction heating apparatus using high frequency electric current, thereby obtaining the oil component having low level of chlorine and recovering the chlorine component contained in the mixed waste plastics as alkali metal salts. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

本発明は、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）、ポリスチレン（ＰＳ）、ポリエチレンテレフタレート（ＰＥＴ）、及びポリ塩化ビニル（ＰＶＣ）やポリ塩化ビニリデン（ＰＶＤＣ）等の塩素を組成成分として含有する熱可塑性樹脂、及びフェーノル樹脂、不飽和ポリエステル樹脂等の熱硬化性樹脂が混在している廃プラスチック（以後混在プラスチックとする）をアルカリ性粉末と混合して高周波電流による誘導加熱装置で前記反応器内部温度を２００℃〜７００℃の温度領域で熱分解反応させ塩素由来物質を中和する方法及びそのための装置に関する。  The present invention is a thermoplastic containing polyethylene (PE), polypropylene (PP), polystyrene (PS), polyethylene terephthalate (PET), and chlorine such as polyvinyl chloride (PVC) and polyvinylidene chloride (PVDC) as a composition component. Resin and waste plastic mixed with thermosetting resin such as phenol resin and unsaturated polyester resin (hereinafter referred to as mixed plastic) are mixed with alkaline powder, and the internal temperature of the reactor is adjusted with an induction heating device using high frequency current. The present invention relates to a method for neutralizing chlorine-derived substances by a thermal decomposition reaction in a temperature range of 200 ° C. to 700 ° C. and an apparatus therefor.

プラスチックごみは年々増加の傾向にある。最近１０年間において年率約６％の増加をしており、このような状況から、廃プラスチックの埋立て処理や焼却処理だけでなく、発生抑制やリサイクルシステムを確立して、廃棄物の減量・資源化を積極的に進めることが望まれている。  Plastic waste tends to increase year by year. In the last 10 years, the annual rate has increased by about 6%. In this situation, not only waste plastic landfilling and incineration, but also establishment of waste reduction and recycling systems to reduce waste and resources It is hoped that this will be actively promoted.

石油価格の上昇・変動が激しくなり、上記対策のひとつとして、廃プラスチックを熱分解処理し、燃料油等の石油資源として再生することが切望されている。このような廃プラスチックを熱分解する技術は１９７０年代より多々開発されているが、適正な熱分解装置は完成してない状況である。  As oil prices rise and fluctuate, one of the above countermeasures is eagerly desired to thermally decompose waste plastic and recycle it as petroleum resources such as fuel oil. Although many technologies for pyrolyzing such waste plastics have been developed since the 1970s, an appropriate pyrolysis apparatus has not been completed.

一方、ポリ塩化ビニル（ＰＶＣ）等塩素を組成成分として含有する樹脂を加熱分解して油分を得る技術として（特許文献１）には、廃プラスチックを２５０℃（塩化ビニルは７０℃）前後の温度域に加熱した押出機により脱塩素する第１工程と塩素分が除去された廃プラスチックをさらに４５０℃（塩化ビニルは１７０℃）前後の温度域に加熱して熱分解し分解ガスを発生させる第２工程からなる油化方法であって、第１工程で脱塩素され発生した塩化水素は水で捕集処理する方法である。
特開２００３−９６４６９号公報 On the other hand, as a technique for obtaining oil by thermally decomposing a resin containing chlorine as a composition component such as polyvinyl chloride (PVC) (Patent Document 1), the temperature of waste plastic is around 250 ° C. (vinyl chloride is 70 ° C.). The first step of dechlorination by an extruder heated in the zone and the waste plastic from which chlorine content has been removed are further heated to a temperature range of around 450 ° C. (vinyl chloride is 170 ° C.) to generate pyrolysis gas by pyrolysis. This is an oil conversion method comprising two steps, in which the hydrogen chloride generated by dechlorination in the first step is collected with water.
JP 2003-96469 A

しかし上記従来技術においては、以下のような課題を有していた。
（１）（特許文献１）に記載の技術では、押出機加熱シリンダベント部及び塩化ビニル処理部より発生する有害ガスを水に吸収させると、有害ガスに同伴した有機性オイルが溶解した高濃度の排水負荷をもつ塩酸水溶液が大量に発生する。このため、前記水溶液を水質汚濁防止法に適合する排水へ処理する有機性オイルの排水処理設備が必要となる。
（２）押出機、塩化ビニル処理部、オフガス処理部と、ガス発生工程が、多段にわたるので、オフガス処理装置が煩雑で複雑である。
（３）熱分解ガス化が、熱分解槽と残渣処理槽の２工程となり煩雑な構造となっている。
２工程を連通管により接続するとともに、この連通管に開閉バルブを付設するため、連通管が詰まった場合などには、洗浄やメンテナンスが大変となる。
（４）溶解工程と熱分解工程の２工程を備えるため、設備全体が大型となり設置性の低下及び汎用性の低下を招くとともに、無用な消費電力の増加によりランニングコストが大きくなるとともに、運転操作も煩雑となる。
（５）溶解工程と熱分解工程の２工程を連通管により接続するとともに、この連通管に開閉バルブを付設するため、処理工程が煩雑になるとともに、連通管が詰まった場合などには、洗浄やメンテナンスが大変となる。However, the above prior art has the following problems.
(1) In the technique described in (Patent Document 1), when the harmful gas generated from the extruder heating cylinder vent part and the vinyl chloride treatment part is absorbed in water, the high concentration in which the organic oil accompanying the harmful gas is dissolved. A large amount of hydrochloric acid solution with a large drainage load is generated. For this reason, an organic oil drainage treatment facility for treating the aqueous solution into wastewater that complies with the Water Pollution Control Law is required.
(2) Since the extruder, the vinyl chloride processing section, the off-gas processing section, and the gas generation process are multistage, the off-gas processing apparatus is complicated and complicated.
(3) Pyrolysis gasification has two steps, a pyrolysis tank and a residue treatment tank, and has a complicated structure.
Since the two processes are connected by a communication pipe, and an open / close valve is attached to the communication pipe, cleaning and maintenance become difficult when the communication pipe is clogged.
(4) Since there are two steps, a melting step and a pyrolysis step, the entire facility becomes large, resulting in a decrease in installability and a decrease in versatility, as well as an increase in unnecessary power consumption and an increase in running cost, as well as driving operations. It becomes complicated.
(5) Since the two steps of the dissolution process and the pyrolysis step are connected by a communication pipe and an open / close valve is attached to the communication pipe, the treatment process becomes complicated, and if the communication pipe is clogged, washing is performed. And maintenance becomes difficult.

本発明は上記従来の課題を解決するもので、プロセスが簡潔であり、脱塩素率が向上し、排水処理設備も必要とせず、極めて低い塩素濃度の油分を得ることができ、さらに高いエネルギー効率を実現できる混在廃プラスチックの熱分解装置を提供することを目的とする。  The present invention solves the above-mentioned conventional problems, the process is simple, the dechlorination rate is improved, the wastewater treatment equipment is not required, an oil component with a very low chlorine concentration can be obtained, and the energy efficiency is further increased. It aims at providing the thermal decomposition apparatus of the mixed waste plastic which can implement | achieve.

上記課題を解決するために本発明の混在廃プラスチックの熱分解方法及び混在廃プラスチックの熱分解装置は、以下の構成を有する。
本発明の請求項１に記載の混在廃プラスチックの熱分解方法は、反応器内で混在廃プラスチックとアルカリ性粉末を接触・混合し、不活性ガスをパージした状態で、高周波電流による誘導加熱装置で前記反応器本体に配したコイルに高周波電流を流し反応器内部温度を２００℃〜７００℃に加熱し、前記混在廃プラスチックを分解・ガス化させる構成を有している。
この構成により、以下のような作用が得られる。
（１）１つの反応器内で混在廃プラスチックとアルカリ性粉末が接触反応することにより、ポリ塩化ビニル（ＰＶＣ）等の塩素原子を含有する樹脂が混在する廃プラスチックを接触分解ガス化するに際し、複雑な脱塩素工程を必要とせず、また、脱塩素反応によって生成する塩化水素もアルカリ性粉末と反応し、反応器内で除去されるから、この発生した分解ガスを冷却凝縮すると極めて低い塩素濃度の油分を得ることができる。即ち、従来技術では、油分に数１０，０００ｐｐｍの塩素が存在したが、本発明では３００ｐｐｍ以下まで低下する。
（２）脱塩素反応によって生成する塩化水素は、反応器内でアルカリ性粉末と反応し、アルカリ性粉末の塩類として捕捉されるため、塩化水素による機器の腐食を防止できる。さらに塩化水素回収設備、排水処理設備も不要となる。In order to solve the above-described problems, the mixed waste plastic thermal decomposition method and the mixed waste plastic thermal decomposition apparatus of the present invention have the following configurations.
The thermal decomposition method for mixed waste plastic according to claim 1 of the present invention is an induction heating apparatus using high-frequency current in a state where the mixed waste plastic and alkaline powder are contacted and mixed in the reactor and purged with inert gas. A high frequency current is passed through a coil disposed in the reactor main body to heat the reactor internal temperature to 200 ° C. to 700 ° C. to decompose and gasify the mixed waste plastic.
With this configuration, the following effects can be obtained.
(1) When waste plastic containing a resin containing chlorine atoms, such as polyvinyl chloride (PVC), is mixed in a single reactor, the mixed waste plastic and alkaline powder undergo a catalytic reaction. No dechlorination process is required, and the hydrogen chloride produced by the dechlorination reaction also reacts with the alkaline powder and is removed in the reactor. Therefore, when this cracked gas is cooled and condensed, Can be obtained. That is, in the prior art, chlorine of several 10,000 ppm was present in the oil, but in the present invention, it is reduced to 300 ppm or less.
(2) Since hydrogen chloride produced by the dechlorination reaction reacts with the alkaline powder in the reactor and is captured as a salt of the alkaline powder, corrosion of equipment due to hydrogen chloride can be prevented. Furthermore, hydrogen chloride recovery equipment and wastewater treatment equipment are not required.

以上のように、本発明の混在廃プラスチックの熱分解方法及び混在廃プラスチックの熱分解装置は、以下のような顕著な効果が得られる。  As described above, the thermal decomposition method for mixed waste plastic and the thermal decomposition apparatus for mixed waste plastic according to the present invention have the following remarkable effects.

請求項１に記載の発明によれば
（１）１つの反応器内で混在廃プラスチックとアルカリ粉末が接触反応することにより、ポリ塩化ビニル（ＰＶＣ）等の塩素原子を含有する樹脂が混在する廃プラスチックを接触分解ガス化するに際し、複雑な脱塩素工程を必要とせず、また、脱塩素反応によって生成する塩化水素もアルカリ性粉末と反応し、反応器内で除去されるから、極めて低い塩素濃度の油分を得ることができる。即ち、従来技術では数１０，０００ｐｐｍの有機塩素が存在したが、本発明では３００ｐｐｍ以下まで低下する。アルカリ性粉体には、アルカリ金属、またはアルカリ土類金属の水酸化物の粉末を使用する。
（２）脱塩素反応によって生成する塩化水素は、反応器内でアルカリ性粉末と反応し、アルカリ性粉末の塩類として捕捉されるため、塩化水素による機器の腐食を防止できる。さらに塩化水素回収設備、排水処理設備も不要となる。
（３）反応器にて、分解・ガス化された極めて塩化水素濃度が低い分解ガスは、特殊な冷却装置で冷却され、塩素濃度が３００ｐｐｍ以下の油分を得ることができる。
（４）分解ガスは、極めて塩化水素濃度の低い分解ガスであるため、塩化水素による機器の腐食を防止でき、修繕費等のランニングコストが低減し、またトラブルによる停止がない長期運転が可能な装置となる。
（５）反応器内に不活性ガスが導入された雰囲気で混在廃プラスチックの分解・ガス化を行うので、反応器内が不活性ガスでパージされた状態又は酸素が希薄な状態で混在廃プラスチックが加熱されて分解されるので、ダイオキシンの発生を防止することができ環境保全性に優れる。また、酸素が希薄な状態で混在廃プラスチックが加熱されて分解されるので、油分、可燃ガスによる爆発の危険性が無い極めて安全な装置である。According to the first aspect of the present invention, (1) waste in which a resin containing chlorine atoms such as polyvinyl chloride (PVC) is mixed due to a contact reaction between mixed waste plastic and alkali powder in one reactor. No complicated dechlorination process is required for catalytic cracking and gasification of plastics, and hydrogen chloride produced by the dechlorination reaction also reacts with the alkaline powder and is removed in the reactor. Oil can be obtained. That is, in the prior art, there were several 10,000 ppm of organic chlorine, but in the present invention, it is reduced to 300 ppm or less. As the alkaline powder, hydroxide powder of alkali metal or alkaline earth metal is used.
(2) Since hydrogen chloride produced by the dechlorination reaction reacts with the alkaline powder in the reactor and is captured as a salt of the alkaline powder, corrosion of equipment due to hydrogen chloride can be prevented. Furthermore, hydrogen chloride recovery equipment and wastewater treatment equipment are not required.
(3) The cracked gas decomposed and gasified in the reactor and having a very low hydrogen chloride concentration is cooled by a special cooling device, and an oil component having a chlorine concentration of 300 ppm or less can be obtained.
(4) Since the cracked gas is a cracked gas with a very low hydrogen chloride concentration, corrosion of equipment due to hydrogen chloride can be prevented, running costs such as repair costs can be reduced, and long-term operation without trouble stoppage is possible. It becomes a device.
(5) Since the mixed waste plastic is decomposed and gasified in an atmosphere in which an inert gas is introduced into the reactor, the mixed waste plastic is purged with an inert gas or the oxygen is lean. Since it is decomposed by heating, the generation of dioxins can be prevented and the environmental conservation is excellent. Further, since the mixed waste plastic is heated and decomposed in a state where oxygen is lean, it is an extremely safe device without risk of explosion due to oil and combustible gas.

請求項２に記載の発明によれば
反応器を脱塩素率の向上に寄与する材質の金属（一例として炭素鋼がある）で製作すると、反応器内に触媒金属を存在させることなく、脱塩素率を向上させることができ極めて塩化水素濃度の低い分解ガスが発生することになり、塩化水素による機器の腐食を防止でき、修繕費等のランニングコストが低減し、またトラブルによる停止がない長期運転が可能な装置となる。According to the second aspect of the present invention, when the reactor is made of a metal material (for example, carbon steel) that contributes to the improvement of the dechlorination rate, dechlorination can be performed without the presence of a catalytic metal in the reactor. Long-term operation that can improve the rate and generate cracked gas with extremely low hydrogen chloride concentration, prevent equipment corrosion due to hydrogen chloride, reduce running costs such as repair costs, and stop due to trouble It becomes a device that can.

請求項３に記載の発明によれば
請求項１の冷却凝縮した油分の塩素濃度を請求項８の塩素濃度自動連続測定装置で測定し、混在廃プラスチックを反応槽に投入する前工程にて、廃プラスチックへのアルカリ性粉末添加量を目標とする油分塩素濃度になるように増減して混合し、最適塩素濃度の油分を提供でき、装置の連続運転に容易に対応でき混在廃プラスチック処理量が向上し、エネルギー効率の高い装置となる。According to the invention described in claim 3, the chlorine concentration of the cooled and condensed oil of claim 1 is measured by the chlorine concentration automatic continuous measuring device of claim 8, and in the previous step of introducing the mixed waste plastic into the reaction tank, The amount of alkaline powder added to waste plastic can be increased or decreased to achieve the target oil chlorine concentration, and the oil content with the optimum chlorine concentration can be provided. And an energy efficient device.

請求項３に記載の発明によれば
（１）反応器本体にコイルを配し、前記コイルに高周波電流を流し前記反応器本体を誘導加熱し、混在廃プラスチックを分解・ガス化する混在廃プラスチックの熱分解装置を提供できる。
（２）反応器本体に付設した撹拌機により混在廃プラスチックとアルカリ性粉末が撹拌接触し、混在廃プラスチックとアルカリ性粉末の脱塩素反応、分解・ガス化が迅速に高効率で進む混在廃プラスチックの熱分解装置を提供できる。According to the invention of claim 3, (1) a mixed waste plastic in which a coil is disposed in the reactor body, a high frequency current is passed through the coil to inductively heat the reactor body, and the mixed waste plastic is decomposed and gasified Can be provided.
(2) The heat of mixed waste plastics, where the mixed waste plastics and alkaline powder are stirred and contacted by the stirrer attached to the reactor body, and the dechlorination reaction, decomposition and gasification of the mixed waste plastics and alkaline powder proceed quickly and efficiently A disassembly device can be provided.

請求項４に記載の発明によれば、請求項３の効果に加え、
混在廃プラスチックの伝熱と反応を迅速に進行せしめて混在廃プラスチックを分解・ガス化して油分を得るようにしたから、熱可塑性樹脂で８０％以上、熱硬化性樹脂で４０％以上の油分回収収率を実現し、高周波電流を流す誘導加熱設定温度の調節によりワックスも生成され難く、低流動点の油分を得ることができる混在廃プラスチックの熱分解装置を提供できる。According to invention of Claim 4, in addition to the effect of Claim 3,
Because the heat transfer and reaction of the mixed waste plastics proceeded quickly to decompose and gasify the mixed waste plastics to obtain oil, 80% or more of the thermoplastic resin and 40% or more of the thermosetting resin are recovered. It is possible to provide a thermal decomposition apparatus for mixed waste plastic that realizes a yield and is less likely to produce wax by adjusting induction heating set temperature at which a high-frequency current flows, and can obtain an oil component with a low pour point.

請求項５に記載の発明によれば
（１）複数の反応器を１基の高周波による誘導加熱装置により作動させることにより、誘導加熱装置の有効利用運転、及び初期投資の低減と設備管理負荷の低減を図ることができる。
（２）又、各反応器の負荷の変動に容易に追従することが可能となり、安定して混在廃プラスチックを分解・ガス化することができる。According to the invention described in claim 5, (1) by operating a plurality of reactors by an induction heating device using a single high frequency, it is possible to effectively use the induction heating device, reduce initial investment and reduce equipment management load. Reduction can be achieved.
(2) Moreover, it becomes possible to easily follow fluctuations in the load of each reactor, and the mixed waste plastic can be decomposed and gasified stably.

請求項６に記載の発明によれば、分解ガスを冷却凝縮する熱交換器を二重管方式とし、内管に分解ガスを通し、外管に冷却冷媒を流すことにより、多管式熱交換器の管内で多発する付着・閉塞のトラブルが極めて減少し、メンテナンスも容易な冷却装置となる。  According to the invention of claim 6, the heat exchanger for cooling and condensing the cracked gas is a double pipe system, the cracked gas is passed through the inner pipe, and the cooling refrigerant is allowed to flow through the outer pipe. The trouble of adhesion and blockage frequently occurring in the pipe of the vessel is greatly reduced, and the cooling device is easy to maintain.

請求項７に記載の発明によれば
反応器内で、２００℃〜７００℃の温度領域でカルボン酸であるフタル酸類はアルカリ性粉末との中和反応によりフタル酸塩類が生成する。このフタル酸塩類はフタル酸類より、油分・水分への溶解度が高く、従来技術ではフタル酸類固形物による装置への付着・閉塞トラブルが頻繁に発生していたが、前記トラブルの発生が皆無の混在廃プラスチックの熱分解装置を提供できる。According to the seventh aspect of the present invention, phthalates that are carboxylic acids are generated in the reactor by a neutralization reaction with an alkaline powder in the temperature range of 200 ° C to 700 ° C. These phthalates have higher solubility in oils and moisture than phthalates, and in the prior art, phthalic acid solids frequently caused troubles of sticking and clogging to the device. A waste plastic thermal decomposition apparatus can be provided.

以下、本発明を実施するための最良の形態を、図面を参照しながら説明する。なお、本実施の形態においては、アルカリ性粉体として、水酸化カルシウムを用いた場合について説明する。
（第１の実施の形態）Hereinafter, the best mode for carrying out the present invention will be described with reference to the drawings. In the present embodiment, the case where calcium hydroxide is used as the alkaline powder will be described.
(First embodiment)

以下、本発明を実施例により具体的に説明する。なお、本発明はこれらの実施例に限定されるものではない。なお、実施例で使用した混在廃プラスチックは、現在は埋め立て処分されているプラスチックである。  Hereinafter, the present invention will be specifically described by way of examples. The present invention is not limited to these examples. The mixed waste plastic used in the examples is a plastic that is currently disposed of in landfills.

（実験例１）油分塩素濃度（ｗｔ％）
混在廃プラスチックの水酸化カルシウム添加比率（ｗｔ％）と油分塩素濃度（ｗｔ％）の相関
（１）ＨＣｌ＋Ｃａ（ＯＨ）２→ＣａＣｌ２＋Ｈ２Ｏ
（２）上記の反応式により、廃プラスチック中の塩素分が塩化水素（ＨＣｌ）となり、この塩化水素（ＨＣｌ）が水酸化カルシウム（Ｃａ（ＯＨ）２）と反応し、塩化カルシウム（ＣａＣｌ２）と水（Ｈ２Ｏ）を生成する。
（３）油分塩素濃度（ｗｔ％）は、生成した水（Ｈ２Ｏ）に塩化水素（ＨＣｌ）が溶解し塩酸水溶液となり、この塩酸水溶液が油分に溶解することにより強酸であれば高い油分塩素濃度（ｗｔ％）、弱酸であれば低い油分塩素濃度（ｗｔ％）を呈する。
（４）塩酸水溶液濃度の強弱は水酸化カルシウム（Ｃａ（ＯＨ）２）との反応性により決定される。
（５）（実験例１）として混在廃プラスチックの水酸化カルシウム添加比率（ｗｔ％）と油分塩素濃度（ｗｔ％）の相関を記すが、水酸化カルシウム添加比率（ｗｔ％）に油分塩素濃度（ｗｔ％）が反比例し減少している結果を示している。
（６）ここで、水酸化カルシウム添加比率（ｗｔ％）は下記の式で表す。
水酸化カルシウム添加比率（ｗｔ％）
＝（水酸化カルシウム重量／混在廃プラスチック重量）×１００(Experimental example 1) Oil chlorine concentration (wt%)
Correlation between calcium hydroxide addition ratio (wt%) and oil chlorine concentration (wt%) in mixed waste plastics (1) HCl + Ca (OH) 2 → CaCl 2 + H 2 O
(2) According to the above reaction formula, the chlorine content in the waste plastic becomes hydrogen chloride (HCl), and this hydrogen chloride (HCl) reacts with calcium hydroxide (Ca (OH) 2 ) to produce calcium chloride (CaCl 2 ). And water (H 2 O).
(3) Oil chlorine concentration (wt%) is high oil chlorine if hydrogen chloride (HCl) is dissolved in the generated water (H 2 O) to form a hydrochloric acid aqueous solution, and this hydrochloric acid aqueous solution dissolves in the oil and is a strong acid. Concentration (wt%), low oil chlorine concentration (wt%) if weak acid.
(4) The strength of the hydrochloric acid aqueous solution concentration is determined by the reactivity with calcium hydroxide (Ca (OH) 2 ).
(5) As (Experimental Example 1), the correlation between the calcium hydroxide addition ratio (wt%) and the oil chlorine concentration (wt%) of the mixed waste plastic is described, but the oil chlorine concentration (wt%) is added to the calcium hydroxide addition ratio (wt%). wt%) is inversely proportional and decreases.
(6) Here, the calcium hydroxide addition ratio (wt%) is expressed by the following formula.
Calcium hydroxide addition ratio (wt%)
= (Calcium hydroxide weight / mixed waste plastic weight) x 100

（実施例２）油分発熱量（Ｊ／ｇ）
混在廃プラスチックの水酸化カルシウム添加比率（ｗｔ％）と油分発熱量（Ｊ／ｇ）の相関
（１）水酸化カルシウム添加比率（ｗｔ％）即ち油分塩素濃度（ｗｔ％）が低下するとともに油分発熱量（Ｊ／ｇ）が上昇する。
（２）これは油分塩素濃度（ｗｔ％）が低下するとともに油分中の塩酸水溶液含有量が減少し、水分による油分発熱量（Ｊ／ｇ）の低下が減少していることを示している。(Example 2) Calorific value of oil (J / g)
Correlation between calcium hydroxide addition ratio (wt%) of mixed waste plastic and oil heat value (J / g) (1) Calcium hydroxide addition ratio (wt%), that is, oil chlorine concentration (wt%) decreases and oil heat generation The amount (J / g) increases.
(2) This indicates that the chlorine content (wt%) of the oil component decreases, the content of the hydrochloric acid aqueous solution in the oil component decreases, and the decrease in the oil heating value (J / g) due to moisture decreases.

次に、本発明に係わる混在廃プラスチックの熱分解装置の具体的な実施の形態について図面を参照して説明する。
（第２の実施の形態）
図１に、本発明の実施の形態に係わる混在廃プラスチックの熱分解装置のブロック図を示す。図２に、本発明の実施の形態に係わる混在廃プラスチックの熱分解装置（反応プロセス）概要を示す模式図を示す。Next, specific embodiments of the thermal decomposition apparatus for mixed waste plastic according to the present invention will be described with reference to the drawings.
(Second Embodiment)
FIG. 1 is a block diagram of a thermal decomposition apparatus for mixed waste plastic according to an embodiment of the present invention. In FIG. 2, the schematic diagram which shows the thermal decomposition apparatus (reaction process) outline | summary of the mixed waste plastic concerning embodiment of this invention is shown.

混在廃プラスチックとアルカリ性粉末を混合し、原料ホッパー１に貯蔵される。アルカリ性粉末の添加量は、油分の塩素濃度を連続測定し最適又は任意の塩素濃度の油分を得るように制御される。  The mixed waste plastic and alkaline powder are mixed and stored in the raw material hopper 1. The addition amount of the alkaline powder is controlled so that the chlorine concentration of the oil is continuously measured to obtain an oil having an optimum or arbitrary chlorine concentration.

原料ホッパー１より定量で切り出された混在廃プラスチックとアルカリ性粉末の混合原料は、反応器（熱分解炉）２に投入され、不活性ガスをパージした状態で、高周波電流による誘導加熱装置９でコイル１０に高周波電流を流し反応器（熱分解炉）２内部温度を２００℃〜７００℃に加熱し、混在廃プラスチックを分解・ガス化させる。  A mixed raw material of mixed waste plastic and alkaline powder cut out from the raw material hopper 1 in a fixed amount is put into a reactor (pyrolysis furnace) 2 and purged with an inert gas, and then coiled by an induction heating device 9 using high-frequency current. A high-frequency current is supplied to 10 to heat the reactor (pyrolysis furnace) 2 to 200 ° C. to 700 ° C. to decompose and gasify the mixed waste plastic.

反応器（熱分解炉）２内で混在廃プラスチックとアルカリ性粉末が接触反応することにより、塩素原子を含有する樹脂が混在する廃プラスチックを接触分解油化するに際し、脱塩素反応によって生成する塩化水素がアルカリ性粉末と反応し、アルカリ金属、アルカリ土類金属の塩類となり反応器（熱分解炉）２内で除去される。  Hydrogen chloride produced by dechlorination reaction when waste plastic mixed with resin containing chlorine atoms is converted into catalytic cracking oil by contact reaction of alkaline waste powder with mixed waste plastic in reactor (pyrolysis furnace) 2 Reacts with the alkaline powder to become a salt of alkali metal or alkaline earth metal and is removed in the reactor (pyrolysis furnace) 2.

混在廃プラスチックが分解・ガス化した熱分解ガスは、水冷式のＮｏ．１熱交換器４・Ｎｏ．２熱交換器６で冷却液化され、Ｎｏ．１油分留出槽５・Ｎｏ．２油分留出槽７に回収される。脱塩素反応によって生成する塩化水素が前記のように、反応器（熱分解炉）２内で除去されるから、極めて低い塩素濃度の油分を得ることができる。即ち、従来技術では、油分に数１０，０００ｐｐｍの塩素が存在したが、本発明では３００ｐｐｍ以下まで低下する。この油分は製油所に送り、石油製品の原料に戻すフィードストックリサイクルすることが、環境負荷低減できるとともに、真の循環型社会を構築できることになるので、最も望ましい方法である。  The pyrolysis gas that decomposes and gasifies the mixed waste plastic is water-cooled No. 1 Heat exchanger 4 2 is cooled and liquefied by the heat exchanger 6. No. 1 oil distillation tank 5 It is recovered in the two oil fraction distillation tank 7. Since hydrogen chloride generated by the dechlorination reaction is removed in the reactor (pyrolysis furnace) 2 as described above, an oil component having an extremely low chlorine concentration can be obtained. That is, in the prior art, chlorine of several 10,000 ppm was present in the oil, but in the present invention, it is reduced to 300 ppm or less. Feedstock recycling that sends this oil to a refinery and returns it to the raw material of petroleum products is the most desirable method because it can reduce environmental burden and build a true recycling society.

反応器（熱分解炉）２内にて発生した熱分解ガスには、
水冷式のＮｏ．１熱交換器４・Ｎｏ．２熱交換器６で冷却凝縮しきれなかった低沸点のガス成分が存在する。この低沸点のガス成分は、反応器（熱分解炉）２内が不活性ガスでパージされた状態で混在廃プラスチックが加熱されて分解されるので、ダイオキシンの発生を防止することができ環境保全性に優れているので、水封槽８を経由して大気に放出する。The pyrolysis gas generated in the reactor (pyrolysis furnace) 2 is
Water-cooled No. 1 Heat exchanger 4 2 There is a low boiling point gas component that could not be cooled and condensed in the heat exchanger 6. This low-boiling gas component is heated and decomposed when the mixed waste plastic is heated while the reactor (pyrolysis furnace) 2 is purged with an inert gas, thus preventing the generation of dioxins and protecting the environment. Since it is excellent in properties, it is discharged to the atmosphere via the water sealing tank 8.

残渣ピット３に回収した混在廃プラスチックの残渣には、脱塩素反応によって生成する塩化水素がアルカリ性粉末と反応したアルカリ金属、アルカリ土類金属の塩類が含まれるが、この塩類は、道路の凍結防止剤、工事現場における防塵剤としての用途があり、有効に活用できる。  Residue of mixed waste plastic collected in residue pit 3 contains alkali metal and alkaline earth metal salts in which hydrogen chloride produced by dechlorination reaction reacts with alkaline powder. It can be used effectively as a dust-proofing agent at construction sites.

本発明は、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）、ポリスチレン（ＰＳ）、ポリエチレンテレフタレート（ＰＥＴ）、及びポリ塩化ビニル（ＰＶＣ）やポリ塩化ビニリデン（ＰＶＤＣ）等塩素を組成成分として含有する熱可塑性樹脂及びフェーノル樹脂、不飽和ポリエステル樹脂等の熱硬化性樹脂が混在している廃プラスチック（以後混在プラスチックとする）をアルカリ性粉末と混合して高周波電流による誘導加熱装置で前記反応器内部温度を２００℃〜７００℃の温度領域で加熱分解反応させ塩素由来物質を中和する方法及びそのための装置に関し分解反応効率に優れ、分解し難いといわれる直鎖分子であっても低温で分解することができ分解残渣がほとんど生じることがなく、またプロセスが簡潔であり油分収率で４０〜８０％以上の高いエネルギー効率を実現でき、フタル酸類固形物による装置への付着・閉塞トラブルの発生が皆無の混在廃プラスチックの熱分解装置を提供できる。  The present invention relates to a thermoplastic resin containing chlorine as a composition component, such as polyethylene (PE), polypropylene (PP), polystyrene (PS), polyethylene terephthalate (PET), and polyvinyl chloride (PVC) and polyvinylidene chloride (PVDC). And waste plastic mixed with thermosetting resin such as phenol resin and unsaturated polyester resin (hereinafter referred to as mixed plastic) is mixed with alkaline powder and the internal temperature of the reactor is set to 200 ° C. with an induction heating device using high-frequency current. A method for neutralizing chlorine-derived substances by a thermal decomposition reaction in a temperature range of ˜700 ° C. and an apparatus therefor can decompose even a linear molecule that is said to be excellent in decomposition reaction efficiency and difficult to decompose at a low temperature. Little residue is formed, the process is simple and the oil yield is 40-8. % Or more of higher energy efficiency can be achieved, generation of adhesion and clogging trouble to the apparatus according to the phthalic acids solids can provide a thermal decomposition apparatus of none of mixed waste plastic.

本発明の最良の実施形態に係わる混在廃プラスチックの熱分解装置（反応プロセス）概要を示すシステムフロー図である。  It is a system flow figure showing an outline of a thermal decomposition apparatus (reaction process) of mixed waste plastic concerning the best embodiment of the present invention. 本発明の実施例に係わる混在廃プラスチックの熱分解装置（反応プロセス）概要を示す模式図である。  It is a schematic diagram which shows the thermal decomposition apparatus (reaction process) outline | summary of the mixed waste plastic concerning the Example of this invention. 本発明の実施例に係わる混在廃プラスチックの熱分解方法におけるシャンプーペットボトル粉砕混在廃プラスチックの水酸化カルシウム添加比率（重量％）と油分塩素濃度（重量％）の相関を示すグラフである。  It is a graph which shows the correlation of the calcium hydroxide addition ratio (weight%) and oil chlorine concentration (weight%) of the shampoo plastic bottle grinding | mixing waste plastic in the thermal decomposition method of the mixed waste plastic concerning the Example of this invention. 本発明の実施例に係わる混在廃プラスチックの熱分解方法における医療廃棄物廃プラスチックの水酸化カルシウム添加比率（重量％）と油分塩素濃度（重量％）の相関を示すグラフである。  It is a graph which shows the correlation of the calcium hydroxide addition ratio (weight%) and oil chlorine concentration (weight%) of a medical waste waste plastic in the thermal decomposition method of the mixed waste plastic concerning the Example of this invention. 本発明の実施例に係わる混在廃プラスチックの熱分解方法における（ＰＰ＋ＰＶＣ）プラスチックの水酸化カルシウム添加比率（重量％）と油分塩素濃度（重量％）の相関を示すグラフである。  It is a graph which shows the correlation of the calcium hydroxide addition ratio (weight%) of a (PP + PVC) plastic and oil chlorine concentration (weight%) in the thermal decomposition method of the mixed waste plastic concerning the Example of this invention. 本発明の実施例に係わる混在廃プラスチックの熱分解方法におけるシャンプーペットボトル粉砕混在廃プラスチックの水酸化カルシウム添加比率（重量％）と油分発熱量（Ｊ／ｇ）の相関を示すグラフである。  It is a graph which shows the correlation of the calcium hydroxide addition ratio (weight%) and the oil calorific value (J / g) of the shampoo plastic bottle pulverization mixed waste plastic in the thermal decomposition method of the mixed waste plastic concerning the Example of this invention. 本発明の実施例に係わる混在廃プラスチックの熱分解方法における医療廃棄物廃プラスチックの水酸化カルシウム添加比率（重量％）と油分発熱量（Ｊ／ｇ）の相関を示すグラフである。  It is a graph which shows the correlation of the calcium hydroxide addition ratio (weight%) and the oil calorific value (J / g) of a medical waste waste plastic in the thermal decomposition method of the mixed waste plastic concerning the Example of this invention. 本発明の実施例に係わる混在廃プラスチックの熱分解方法における（ＰＰ＋ＰＶＣ）プラスチックの水酸化カルシウム添加比率（重量％）と油分発熱量（Ｊ／ｇ）の相関を示すグラフである。  It is a graph which shows the correlation of the calcium hydroxide addition ratio (weight%) of a (PP + PVC) plastic and oil calorific value (J / g) in the thermal decomposition method of the mixed waste plastic concerning the Example of this invention.

１ 原料ホッパー（混在廃プラスチック・アルカリ粉末仕込みホッパー）
２ 反応器（熱分解炉）
３ 残渣ピット
４ Ｎｏ．１熱交換器
５ Ｎｏ．１油分留出槽
６ Ｎｏ．２熱交換器
７ Ｎｏ．２油分留出槽
８ 水封槽
９ 高周波誘導加熱装置・制御動力盤
１０ コイル
１１ 攪拌機
１２ 自動バルブ1 Raw material hopper (mixed waste plastic / alkali powder hopper)
2 Reactor (pyrolysis furnace)
3 Residual pit 4 No. 1 Heat exchanger 5 No. 1 oil fraction distillation tank 6 No. 2 heat exchanger 7 No. 2 Oil distillation tank 8 Water-sealed tank 9 High-frequency induction heating device / control power panel 10 Coil 11 Stirrer 12 Automatic valve

Claims (8)

反応器内及び前処理工程で混在廃プラスチックとアルカリ性粉体を混合し、高周波電流による誘導加熱装置で前記反応器内部温度を２００℃〜７００℃の温度領域とし、さらに反応器内を不活性ガス雰囲気下とし、前記混在廃プラスチックを分解・ガス化させ、この発生した分解ガスを冷却凝縮して油分を得ることを特徴とする混在廃プラスチック熱分解装置。  The mixed waste plastic and alkaline powder are mixed in the reactor and in the pretreatment process, the internal temperature of the reactor is set to a temperature range of 200 ° C. to 700 ° C. with an induction heating device using high-frequency current, and the inside of the reactor is further inert gas. A mixed waste plastic thermal decomposition apparatus characterized in that the mixed waste plastic is decomposed and gasified, and the generated decomposed gas is cooled and condensed to obtain an oil. 前記の反応器材質を磁性のおびやすい金属にすることにより、混在廃プラスチックに含有する塩素分の除去率を向上させることを特徴とする請求項１に記載の混在廃プラスチック熱分解装置。  2. The mixed waste plastic pyrolysis apparatus according to claim 1, wherein the reactor material is made of a metal that is easy to be magnetized to improve the removal rate of chlorine contained in the mixed waste plastic. 反応器内部温度を２００℃〜７００℃の温度領域に温度調整する加熱手段と、混在廃プラスチックとアルカリ性粉末とを混合・撹拌する撹拌手段とを有する反応器を備えていることを特徴とする請求項１に記載の混在廃プラスチック熱分解装置。  A reactor having a heating means for adjusting the temperature inside the reactor to a temperature range of 200 ° C to 700 ° C and a stirring means for mixing and stirring the mixed waste plastic and the alkaline powder is provided. Item 4. The mixed waste plastic pyrolysis apparatus according to Item 1. 混在廃プラスチック分解装置の反応器加熱手段としては、高周波電流による誘導加熱装置を採用し、精度ある加熱温度の設定により、混在廃プラスチックの分解・ガス化を向上させることを特徴とする請求項１に記載の混在廃プラスチック熱分解装置。  The reactor heating means of the mixed waste plastic decomposition apparatus employs an induction heating apparatus using a high-frequency current, and improves the decomposition and gasification of the mixed waste plastic by setting an accurate heating temperature. Mixed waste plastic pyrolysis equipment as described in. 混在廃プラスチック分解装置の反応器を、請求項４の高周波電流による誘導加熱装置による加熱方法として、複数の反応器を１基の誘導加熱装置による加熱方式とすることを特徴とする請求項１に記載の廃プラスチック熱分解装置。  The reactor of the mixed waste plastic decomposing apparatus is a heating method by the induction heating apparatus using high-frequency current according to claim 4, and the plurality of reactors is a heating system by one induction heating apparatus. The waste plastic pyrolyzer described. 混在廃プラスチックに含有するフタル酸類やプラスチックの成形加工時に添加する安定剤はアルカリ性粉末との反応により、油分・水分に溶解しやすいアルカリ金属、アルカリ土類金属の塩類となり、機器・配管の閉塞が起こりにくいことを特徴とする請求項１に記載の混在廃プラスチック熱分解装置。  Stabilizers added during molding and processing of plastics contained in mixed waste plastics react with alkaline powders to form alkali metal and alkaline earth metal salts that are easily dissolved in oil and moisture, blocking equipment and piping. The mixed waste plastic thermal decomposition apparatus according to claim 1, which hardly occurs. 冷却装置として、混在廃プラスチックの分解時に発生するフタル酸等固形物の析出、プラスチックの成形加工時に添加する安定剤の分解物によるトラブルが起こりにくい、冷却装置を有することを特徴とする請求項１に記載の混在廃プラスチック熱分解装置。  2. The cooling device according to claim 1, wherein the cooling device is less likely to cause troubles due to the precipitation of solids such as phthalic acid generated during decomposition of the mixed waste plastic and the decomposition product of the stabilizer added during molding of the plastic. Mixed waste plastic pyrolysis equipment as described in. 冷却凝縮した油分の塩素濃度を自動連続で測定し、混在廃プラスチックへのアルカリ性粉末添加量を制御し、最適又は任意の塩素濃度の油分を得ること、及びアルカリ性粉末使用量の最適化を図ることを特徴とする請求項１に記載の混在廃プラスチック熱分解装置。  Measure the chlorine concentration of the cooled and condensed oil automatically and continuously, control the amount of alkaline powder added to the mixed waste plastic, obtain the oil content of optimum or arbitrary chlorine concentration, and optimize the amount of alkaline powder used The mixed waste plastic thermal decomposition apparatus according to claim 1.
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Publication number Priority date Publication date Assignee Title
CN102703106A (en) * 2012-06-25 2012-10-03 徐效奇 Instant cracking reaction device adopting high-frequency heating and converting oil into membrane
JP2016003189A (en) * 2014-06-16 2016-01-12 株式会社オメガ Treatment method of salt impregnated with organic matter
JP2019123771A (en) * 2018-01-12 2019-07-25 三菱マテリアル株式会社 Chlorine-containing plastic treatment method
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