WO2020209419A1 - Apparatus for removing chlorine in pyrolysis of plastic mixture containing polyvinyl chloride, and method for removing chlorine in pyrolysis of plastic mixture containing polyvinyl chloride using same - Google Patents

Apparatus for removing chlorine in pyrolysis of plastic mixture containing polyvinyl chloride, and method for removing chlorine in pyrolysis of plastic mixture containing polyvinyl chloride using same Download PDF

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WO2020209419A1
WO2020209419A1 PCT/KR2019/004358 KR2019004358W WO2020209419A1 WO 2020209419 A1 WO2020209419 A1 WO 2020209419A1 KR 2019004358 W KR2019004358 W KR 2019004358W WO 2020209419 A1 WO2020209419 A1 WO 2020209419A1
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polyvinyl chloride
plastic mixture
chlorine
mixture containing
pyrolysis
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PCT/KR2019/004358
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French (fr)
Korean (ko)
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김주식
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서울시립대학교 산학협력단
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Priority to PCT/KR2019/004358 priority Critical patent/WO2020209419A1/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/14—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means
    • C10G9/18—Apparatus

Definitions

  • Disclosed herein are an apparatus for reducing chlorine generated during pyrolysis of a plastic mixture containing polyvinyl chloride, and a method for reducing chlorine generated during pyrolysis of a plastic mixture containing polyvinyl chloride using the same.
  • the methods of recycling waste plastics are mechanical recycling, which melts the waste plastics at around 300°C to make recycled particles in the form of pellets or granules, and as a material component necessary to manufacture other compounds from waste plastics. It is divided into the feedstock recycling method that converts. Among them, the mechanical recycling method is preferred as the final recycling method because the physical properties of the product manufactured by the process fall each time mechanical recycling is repeated. Feedstock recycling methods are largely divided into pyrolysis, gasification, hydrogenation, and solvation, and among them, pyrolysis is the most actively studied. Pyrolysis oil produced from waste plastic through pyrolysis is introduced into the petroleum refining process and used as a raw material for new chemicals or fuels.
  • pyrolysis is an eco-friendly waste plastic recycling method in which waste plastic is thermally decomposed under oxygen-free to produce oil, gas, and char, a solid product.
  • the success or failure of pyrolysis of waste plastics is directly related to the removal of chlorine or chlorine compounds.
  • Waste plastics generated in cities contain PVC (polyvinyl chloride), and chlorine compounds (HCl, etc.) generated during the pyrolysis of PVC cause corrosion of the process during pyrolysis, and the life of incineration facilities when burning pyrolysis oil containing them. It causes shortening and causes dioxins.
  • the present inventors have introduced a technology to reduce the chlorine content from pyrolysis oil through Patent Application No. 10-2017-0082051, but the pyrolysis of PVC-containing plastics is not sufficiently performed in the Auger reactor.
  • the invention was completed.
  • Patent Document 1 Korean Patent Application No. 10-2017-0082051
  • an object of the present invention is to produce a pyrolysis oil suitable for recycling of waste plastics containing PVC.
  • an object of the present invention is to minimize the content of chlorine in oil, which is a product of pyrolysis of waste plastics.
  • a continuous stirring tank reactor (CSTR); It provides an apparatus for reducing chlorine of a plastic mixture comprising polyvinyl chloride, including a fluidized bed reactor.
  • the device for reducing chlorine of a plastic mixture containing polyvinyl chloride which is an aspect of the present invention, includes a continuous stirring tank reactor, so that the residence time can be adjusted so that hydrogen chloride can be sufficiently separated from PVC, so that the PVC is mixed with the waste plastic. It is possible to obtain pyrolysis oil in which chlorine is effectively reduced.
  • FIG. 1 is a schematic diagram of a system including a chlorine reduction window of a plastic mixture comprising polyvinyl chloride according to an aspect of the present invention.
  • a and/or B means A or B, or A and B.
  • the present invention a continuous stirring tank reactor (CSTR); And it is an apparatus for reducing chlorine of a plastic mixture containing polyvinyl chloride, including a fluidized bed reactor.
  • CSTR continuous stirring tank reactor
  • the apparatus includes a continuous stirring tank reactor, so that the residence time can be adjusted, and thus hydrogen chloride can be sufficiently separated from PVC.
  • the residence time of the plastic mixture in the continuous stirring tank reactor may be about 5 to 30 minutes.
  • the device may include pyrolyzing a plastic mixture comprising polyvinyl chloride.
  • Pyrolysis may mean decomposing chemical substances contained in the pyrolysis target by heating the pyrolysis target under conditions excluding oxygen.
  • An apparatus for reducing chlorine in a plastic mixture containing polyvinyl chloride which is an aspect of the present invention, includes a continuous stirring tank reactor and a fluidized bed reactor, and a fluidized bed reactor may be located behind the continuous stirring tank reactor. At this time, between the continuous stirring tank reactor and the fluidized bed reactor, a melt hopper for temporarily storing the melted plastic mixture and a feeder for feeding the melt to the fluidized bed reactor may be positioned.
  • the apparatus when a plastic mixture containing PVC, waste plastic, or powder thereof (hereinafter referred to as plastic mixture) is introduced into the continuous stirring tank reactor, the plastic mixture, such as hydrogen chloride, is thermally decomposed in the continuous stirring tank reactor. Chlorine compounds (gas or liquid form) are separated and released to form fractions (primary pyrolysis products) such as plastic mixtures with a reduced chlorine content.
  • the apparatus may further include a pyrolysate separator connected to the continuous stirring tank reactor. The pyrolysate separator is installed at the top of the continuous stirring tank reactor, and may serve to discharge gaseous hydrogen chloride.
  • the pyrolysate separator may include, for example, a separator in which the pyrolysate introduced from the reactor collides, and a baffle that collides with the separator to induce a downward flow of the separated pyrolysate.
  • the pyrolysate separated by colliding with the separator may seat on one end of the baffle and flow to the other end, and the baffle may be inclined downward from one end to the other end.
  • the baffle includes a plurality of baffles spaced apart from each other and disposed vertically, and the baffle includes a first baffle; And a second baffle positioned below the first baffle, wherein the pyrolysate is seated on one end of the first baffle and flows to the other end of the first baffle, and the pyrolysate introduced from the other end of the first baffle is It may be seated on one end of the second baffle and flowing to the other end of the second baffle.
  • the pyrolysate separator may include a cooling unit, and in one embodiment, the cooling unit may include a water cooler.
  • the cooling part is configured by a water cooler
  • the waxes of high boiling point rising to the pyrolysate fractionator are condensed when passing through this cooling part, collide with the baffle several times and separate from the rising gaseous HCl, and fall into the continuous stirring reactor . Therefore, it is possible to increase the yield of the final product, oil.
  • the operating temperature of the thermal decomposition separator including the water cooler may be 15 to 30°C.
  • a gas curtain film may be formed between the continuous stirring tank reactor and the melt hopper by the gas introduced through the gas input unit.
  • the gas of the chlorine compound separated from the plastic mixture, etc. by the gas curtain membrane is prevented from being transferred to the fluidized bed reactor while the fractions such as the plastic mixture having the reduced chlorine content are introduced into the melt hopper and the fluidized bed reactor.
  • the gas introduced through the gas inlet is preferably an inert gas, and the inert gas may be nitrogen gas, helium gas, or argon gas.
  • the fluidized bed reactor requires a fluidized gas, and as the fluidized gas, an inert gas, a gas generated and discharged from the apparatus, in particular, a non-condensed gas discharged from the fluidized bed reactor, or a mixture thereof may be used.
  • the continuous stirring tank reactor may include a discharge unit (not shown) through which the generated product is discharged.
  • the discharge part of the continuous stirring tank reactor may be directly connected to the pyrolysate separator.
  • the pyrolysis char which is solid from the pyrolysis product discharged after undergoing the secondary pyrolysis in the fluidized bed reactor, is first collected, and the pyrolysis gas is converted into oil through cooling and condensation and collected.
  • the apparatus may further include a hot filter filled with calcium oxide, calcium hydroxide, or sodium carbonate (Na2CO3), and the high temperature filter may be located behind the fluidized bed reactor.
  • a hot filter filled with calcium oxide, calcium hydroxide, or sodium carbonate (Na2CO3) may be located behind the fluidized bed reactor.
  • Ca2CO3 sodium carbonate
  • calcium oxide reacts with hydrogen chloride to form calcium chloride, which lowers the chlorine content in pyrolysis oil.
  • the temperature of the high-temperature filter may be 400 to 700°C, and the calcium oxide and calcium hydroxide may include those in the form of granules heat-treated at 850 to 1000°C.
  • the calcium oxide and calcium hydroxide may include those in the form of granules heat-treated at 850 to 1000°C.
  • a differential pressure in the reactor may occur, and thus process operation efficiency may decrease.
  • An apparatus for reducing chlorine in a plastic mixture containing polyvinyl chloride may further include a temperature control device (not shown), wherein the temperature control device includes a temperature of each of the continuous stirring tank reactor, the fluidized bed reactor, and the high temperature filter. It is desirable to be able to change independently.
  • the temperature control device may include a temperature detection unit, a temperature control unit, and a heating unit.
  • the present invention may be a system for reducing chlorine in a plastic mixture, wherein the system is a device for reducing chlorine in a plastic mixture containing PVC, a plastic mixture supply system, a pyrolysis char separation system, an electrostatic precipitator, and a gas circulation system. (Not shown), etc. may be included.
  • the temperature of the continuous stirring tank reactor may be 250 to 350°C, preferably 250 to 300°C.
  • the PVC-containing plastic mixture pyrolyzed in the auger reactor and the pyrolysate separator may be pyrolyzed again.
  • the internal temperature of the fluidized bed reactor may be 650 to 780°C, preferably, 700 to 750°C, more preferably, 700 to 720°C.
  • the plastic mixture may include waste plastic containing PVC.
  • the plastic mixture containing the PVC is a plastic containing more than one of polyethylene terephthalate (PET), high density polyethylene (HDPE), low density polyethylene (LDPE), polystyrene (PS), and polypropylene (PP) in addition to PVC. It may mean a mixture of.
  • the content of chlorine in the oil among the products produced by the apparatus may be 10 ppm (w/w) or less.
  • the chlorine content in the oil in the products produced by the above apparatus is significantly less than the known pyrolysis oil chlorine content of 10,000 ppm.
  • the present invention is a method of reducing chlorine from a plastic mixture comprising polyvinyl chloride (PVC) using the above apparatus.
  • the method may be for reducing the content of chlorine in pyrolysis oil produced from a plastic mixture including polyvinyl chloride (PVC).
  • PVC polyvinyl chloride
  • the method comprises a first pyrolysis step of pyrolyzing a plastic mixture containing PVC in a continuous stirring tank reactor; A pyrolysate separation step of removing chlorine from pyrolysis products pyrolyzed in the continuous stirring tank reactor; A second pyrolysis step of pyrolyzing in a fluidized bed reactor; And filtering the pyrolysis vapor of the PVC plastic mixture pyrolyzed in the fluidized bed reactor in a high-temperature filter filled with calcium oxide or calcium hydroxide.
  • the first pyrolysis step may be performed at 280 ⁇ 400 °C.
  • the temperature of the pyrolysis product separator is 300 ⁇ 500 °C
  • the second pyrolysis step may be carried out at 680 ⁇ 750 °C, preferably, 700 ⁇ 750 °C, more preferably, 700 ⁇ 720 °C Can be done in

Abstract

Disclosed in the present specification are an apparatus for removing chlorine from a polyvinyl chloride (PVC)-containing plastic mixture, and a method for removing chlorine from a PVC-containing plastic mixture. According to one aspect of the present invention, the apparatus for removing chlorine from a PVC-containing plastic mixture, by including a continuous stirring tank reactor, can adjust a retention time so as to allow sufficient escape of hydrogen chloride from PVC, and thus can produce, from plastic waste, thermally cracked oil with chlorine effectively removed therefrom.

Description

폴리염화비닐을 포함하는 플라스틱 혼합물 열분해의 염소 저감 장치 및 이를 이용한 폴리염화비닐 함유 플라스틱 혼합물 열분해의 염소를 저감시키는 방법Apparatus for reducing chlorine in pyrolysis of plastic mixtures containing polyvinyl chloride and method for reducing chlorine in pyrolysis of plastic mixtures containing polyvinyl chloride using the same
본 명세서에는 폴리염화비닐을 포함하는 플라스틱 혼합물 열분해시 발생하는 염소 저감 장치 및 이를 이용한 폴리염화비닐 함유 플라스틱 혼합물 열분해시 발생하는 염소를 저감시키는 방법이 개시된다. Disclosed herein are an apparatus for reducing chlorine generated during pyrolysis of a plastic mixture containing polyvinyl chloride, and a method for reducing chlorine generated during pyrolysis of a plastic mixture containing polyvinyl chloride using the same.
우리나라에서는 매년 약 400만 톤의 폐플라스틱이 발생하고 있으나, 재활용률은 20~30%로 낮아, 많은 양이 매립이나 소각에 의하여 처리되고 있다. 그러나 폐플라스틱을 매립하는 방법은, 폐플라스틱으로부터 유해성분이 용출될 수 있으며, 단위 무게에 비하여 부피가 커 보관, 운반 및 매립이 어렵다는 문제가 있다. 또한, 소각에 의한 처리는 플라스틱 소각시 발생하는 열에너지의 일부를 에너지원으로 활용할 수 있지만, 인체 및 환경에 치명적인 유독성 가스를 배출하고, 비경제적이라는 문제점이 있다. 이에, 폐플라스틱을 재활용하는 방법에 대한 사회적 관심이 높아지고 있다. In Korea, about 4 million tons of waste plastics are produced every year, but the recycling rate is low at 20-30%, and a large amount is disposed of by landfill or incineration. However, the method of embedding waste plastic has a problem that harmful components may be eluted from the waste plastic, and storage, transportation, and embedding are difficult because the volume is larger than the unit weight. In addition, treatment by incineration can utilize part of the thermal energy generated during plastic incineration as an energy source, but there is a problem in that it discharges toxic gases that are fatal to the human body and environment, and is uneconomical. Accordingly, social interest in recycling waste plastics is increasing.
폐플라스틱을 재활용하는 방법은, 크게 300℃ 부근에서 폐플라스틱을 용융시켜 펠렛 또는 그래뉼 형태의 재생입자를 만들어 사용하는 기계적 재활용 방법(Mechanical Recycling) 과, 폐플라스틱으로부터 다른 화합물을 제조하는데 필요한 재료 성분으로 전환시키는 피드스톡 재활용 (Feedstock Recycling) 방법으로 나뉜다. 이 중 기계적 재활용 방법은, 공정에 의해 제조된 제품의 물성이 기계적 재활용이 반복될 때 마다 떨어져서, 피드스톡 재활용 방법이 최종적 재활용 방법으로 선호되고 있다. 피드스톡 재활용 방법은 크게 열분해(pyrolysis), 가스화(gasification), 수소화(hydrogenation), 및 용매화(solvolysis)로 나뉘며 그 중 가장 활발히 연구되고 있는 것은 열분해다. 열분해를 통해 폐플라스틱으로부터 제조된 열분해유는 석유 정제 공정에 투입되어 새로운 화학물질 또는 연료의 원료로 사용되게 된다.The methods of recycling waste plastics are mechanical recycling, which melts the waste plastics at around 300°C to make recycled particles in the form of pellets or granules, and as a material component necessary to manufacture other compounds from waste plastics. It is divided into the feedstock recycling method that converts. Among them, the mechanical recycling method is preferred as the final recycling method because the physical properties of the product manufactured by the process fall each time mechanical recycling is repeated. Feedstock recycling methods are largely divided into pyrolysis, gasification, hydrogenation, and solvation, and among them, pyrolysis is the most actively studied. Pyrolysis oil produced from waste plastic through pyrolysis is introduced into the petroleum refining process and used as a raw material for new chemicals or fuels.
구체적으로, 열분해는 폐플라스틱을 무산소 하에서 열적 분해하여 오일, 가스, 그리고 고형 산물인 촤(char)를 생산하는 친환경적 폐플라스틱 재활용 방법이다. 폐플라스틱의 열분해의 성패는 염소 또는 염소 화합물의 제거와 직결된다. 도시에서 발생하는 폐플라스틱에는 PVC(polyvinyl chloride)가 혼합되어 있는데, PVC 열분해시 생성되는 염소 화합물(HCl 등)은 열분해 시 공정의 부식을 초래하고, 이를 함유한 열분해유 연소시, 소각 설비의 수명 단축을 유발하며, 다이옥신 발생 원인이 된다. Specifically, pyrolysis is an eco-friendly waste plastic recycling method in which waste plastic is thermally decomposed under oxygen-free to produce oil, gas, and char, a solid product. The success or failure of pyrolysis of waste plastics is directly related to the removal of chlorine or chlorine compounds. Waste plastics generated in cities contain PVC (polyvinyl chloride), and chlorine compounds (HCl, etc.) generated during the pyrolysis of PVC cause corrosion of the process during pyrolysis, and the life of incineration facilities when burning pyrolysis oil containing them. It causes shortening and causes dioxins.
이러한 이유에서 PVC를 함유하는 폐플라스틱의 열분해시 생성되는 염소화합물을 제어하고 최종적으로 열분해유의 염소 함량을 효과적으로 저감시킬 수 있는 방법을 개발하는 것이 폐플라스틱의 열분해에 필수적이다. 그러나, 아직까지 폐플라스틱의 열분해유에서 염소를 만족할 만한 수준으로 저감한 결과를 얻은 사례는 보고된 바 없다. 국내에서 PVC를 함유하는 폐플라스틱을 열분해하여 제조된 열분해유에는 약 10,000ppm 이상의 염소가 함유되어 있는 것으로 알려져 있다. 폐플라스틱 열분해유의 실질적 활용이 가능하기 위해서는 오일 내 염소함량이 10 ppm이하이어야 하는데 실질적으로 이 값 이내의 염소 함량을 가진 열분해유 생산은 이루어지지 않고 있다 (Energy Conversion and Management 115 (2016) 308-326).For this reason, it is essential for pyrolysis of waste plastics to control chlorine compounds generated during pyrolysis of waste plastics containing PVC and to develop a method that can effectively reduce the chlorine content of pyrolysis oil. However, there have been no reports of cases in which chlorine was reduced to a satisfactory level in pyrolysis oil from waste plastics. It is known that about 10,000 ppm or more of chlorine is contained in pyrolysis oil manufactured by pyrolyzing waste plastics containing PVC in Korea. For practical use of waste plastic pyrolysis oil, the chlorine content in the oil must be 10 ppm or less, but pyrolysis oil with a chlorine content within this value has not been produced (Energy Conversion and Management 115 (2016) 308-326 ).
이에, 본 발명자는 특허출원 제 10-2017-0082051호를 통해, 열분해유로부터 염소 함량을 저감시키는 기술을 소개한 바 있으나, 오거 반응기에서 PVC 함유 플라스틱의 열분해가 충분히 이루어지지 않아, 이를 개선하고자 본 발명을 완성하였다.Accordingly, the present inventors have introduced a technology to reduce the chlorine content from pyrolysis oil through Patent Application No. 10-2017-0082051, but the pyrolysis of PVC-containing plastics is not sufficiently performed in the Auger reactor. The invention was completed.
[선행기술문헌][Prior technical literature]
(특허문헌 1) 한국특허 출원번호 제10-2017-0082051호(Patent Document 1) Korean Patent Application No. 10-2017-0082051
일 측면에서, 본 발명의 목적은 PVC를 함유하는 폐플라스틱의 재활용에 적합한 열분해유를 제조하는 것이다.In one aspect, an object of the present invention is to produce a pyrolysis oil suitable for recycling of waste plastics containing PVC.
일 측면에서, 본 발명의 목적은 폐플라스틱의 열분해 산물인 오일 중 염소의 함량을 최소화하는 것이다.In one aspect, an object of the present invention is to minimize the content of chlorine in oil, which is a product of pyrolysis of waste plastics.
상기 목적을 달성하기 위하여, 본 발명은 일 측면에서, 연속교반탱크 반응기(CSTR); 및 유동층 반응기를 포함하는, 폴리염화비닐을 포함하는 플라스틱 혼합물의 염소 저감 장치를 제공한다.In order to achieve the above object, the present invention, in one aspect, a continuous stirring tank reactor (CSTR); It provides an apparatus for reducing chlorine of a plastic mixture comprising polyvinyl chloride, including a fluidized bed reactor.
본 발명의 일 측면인 폴리염화비닐을 포함하는 플라스틱 혼합물의 염소 저감 장치는, 연속교반탱크 반응기를 포함하여 PVC로부터 염화수소가 충분히 이탈될 수 있도록 체류시간을 조절할 수 있으므로, PVC가 혼합된 폐플라스틱으로부터 염소를 효과적으로 저감시킨 열분해유를 얻을 수 있다.The device for reducing chlorine of a plastic mixture containing polyvinyl chloride, which is an aspect of the present invention, includes a continuous stirring tank reactor, so that the residence time can be adjusted so that hydrogen chloride can be sufficiently separated from PVC, so that the PVC is mixed with the waste plastic. It is possible to obtain pyrolysis oil in which chlorine is effectively reduced.
도 1은 본 발명의 일 측면에 따른 폴리염화비닐을 포함하는 플라스틱 혼합물의 염소 저감창지를 포함하는, 시스템의 개략도이다.1 is a schematic diagram of a system including a chlorine reduction window of a plastic mixture comprising polyvinyl chloride according to an aspect of the present invention.
본 연구는 (재)서울시립대학교 산학협력단의 주관 하에 대한민국 환경부 산하 한국환경산업기술원의 환경정책 기반 공공기술 개발사업의 지원에 의하여 이루어진 것으로, 연구과제명은 플라스틱 포장재의 피드스톡 리사이클링 및 재순환된 포장재 합성원료 생산(과제고유번호:1485015519)이고, 연구기간은 2018.07.01~ 2019.06.30이다.This research was conducted under the supervision of the Seoul City University Industry-Academic Cooperation Foundation and was supported by the environmental policy-based public technology development project of the Korea Environmental Industry & Technology Institute under the Ministry of Environment of the Republic of Korea. It is raw material production (task serial number: 1485015519), and the research period is from 2018.07.01 to 2019.06.30.
아래에서는 첨부한 도면을 참조하여 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 본 발명의 실시예를 상세히 설명한다. 그러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 실시예에 한정되지 않는다. 그리고 도면에서 본 발명을 명확하게 설명하기 위해서 설명과 관계없는 부분은 생략하였으며, 명세서 전체를 통하여 유사한 부분에 대해서는 유사한 도면 부호를 붙였다.Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those of ordinary skill in the art can easily implement the present invention. However, the present invention may be implemented in various different forms and is not limited to the embodiments described herein. In the drawings, parts irrelevant to the description are omitted in order to clearly describe the present invention, and similar reference numerals are assigned to similar parts throughout the specification.
본 발명의 명세서 및 청구범위에 사용된 용어 또는 단어는 통상적이거나 사전적인 의미로 한정 해석되지 아니하며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.The terms or words used in the specification and claims of the present invention are not limitedly interpreted in a conventional or dictionary meaning, and the inventor can appropriately define the concept of the term in order to describe his own invention in the best way. Based on the principle, it should be interpreted as a meaning and concept consistent with the technical idea of the present invention.
본 발명의 명세서 전체에 있어서, 어떤 부분이 어떤 구성 요소를 "포함" 한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성 요소를 제외하는 것이 아니라 다른 구성 요소를 더 포함할 수 있는 것을 의미한다.In the entire specification of the present invention, when a certain part "includes" a certain component, it means that other components may be further included rather than excluding other components unless otherwise stated. .
본 발명의 명세서 전체에 있어서, "A 및/또는 B"는, A 또는 B, 또는 A 및 B를 의미한다.In the entire specification of the present invention, "A and/or B" means A or B, or A and B.
이하, 첨부된 도면을 참조하여 본 발명을 구체적으로 설명하나, 본 발명이 이에 제한되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to the accompanying drawings, but the present invention is not limited thereto.
본 발명은 일 측면에서, 연속교반탱크 반응기(CSTR); 및 유동층 반응기를 포함하는, 폴리염화비닐을 포함하는 플라스틱 혼합물의 염소 저감 장치이다.In one aspect, the present invention, a continuous stirring tank reactor (CSTR); And it is an apparatus for reducing chlorine of a plastic mixture containing polyvinyl chloride, including a fluidized bed reactor.
일 측면에서, 상기 장치는 연속교반탱크 반응기를 포함함으로써, 체류시간을 조절할 수 있고, 이에 PVC로부터 염화수소를 충분히 이탈시킬 수 있다.In one aspect, the apparatus includes a continuous stirring tank reactor, so that the residence time can be adjusted, and thus hydrogen chloride can be sufficiently separated from PVC.
일 구현예에서, 상기 연속교반탱크 반응기에서 플라스틱 혼합물의 체류시간은 약 5분 내지 30분일 수 있다. In one embodiment, the residence time of the plastic mixture in the continuous stirring tank reactor may be about 5 to 30 minutes.
일 측면에서, 상기 장치는, 폴리염화비닐을 포함하는 플라스틱 혼합물을 열분해하는 것을 포함할 수 있다.In one aspect, the device may include pyrolyzing a plastic mixture comprising polyvinyl chloride.
열분해는 산소를 배제한 조건에서 열분해 대상을 가열하여 열분해 대상에 포함된 화학물질을 분해하는 것을 의미할 수 있다. Pyrolysis may mean decomposing chemical substances contained in the pyrolysis target by heating the pyrolysis target under conditions excluding oxygen.
본 발명의 일 측면인 폴리염화비닐을 포함하는 플라스틱 혼합물의 염소 저감 장치는, 연속교반탱크 반응기와 유동층 반응기를 포함하며, 연속교반탱크 반응기 뒤에 유동층 반응기가 위치할 수 있다. 이때, 상기 연속교반탱크 반응기와 유동층 반응기의 사이에는, 멜트 상태의 플라스틱 혼합물을 일시적으로 보관하는 멜트 호퍼(hopper)와, 멜트를 유동층 반응기로 피딩하는, 피더(feeder)가 위치할 수 있다.An apparatus for reducing chlorine in a plastic mixture containing polyvinyl chloride, which is an aspect of the present invention, includes a continuous stirring tank reactor and a fluidized bed reactor, and a fluidized bed reactor may be located behind the continuous stirring tank reactor. At this time, between the continuous stirring tank reactor and the fluidized bed reactor, a melt hopper for temporarily storing the melted plastic mixture and a feeder for feeding the melt to the fluidized bed reactor may be positioned.
본 발명의 장치 중 연속교반탱크 반응기 내부로 PVC를 함유하는 플라스틱 혼합물,폐플라스틱 또는 그 분말(이하, 플라스틱 혼합물 등이라고 함)이 투입되면, 연속교반탱크 반응기에서 열분해에 의하여 플라스틱 혼합물로부터 염화수소와 같은 염소화합물(기체 또는 액체 형태)이 분리되어 방출되어, 염소 함량이 감소된 플라스틱 혼합물 등의 분획물(1차 열분해 산물)이 형성된다. 이 때, 상기 장치는 연속교반탱크 반응기와 연결된 열분해물 분리기를 더 포함할 수 있다. 상기 열분해물 분리기는 연속교반탱크 반응기의 상부에 설치되어, 기체상태의 염화수소를 배출하는 역할을 할 수 있다. 상기 열분해물 분리기는 예컨대, 반응기로부터 유입된 열분해물이 충돌하는 세퍼레이터 및 상기 세퍼레이터와 충돌하여 분리된 열분해물의 하향 흐름을 유도하는 배플(baffle)을 포함할 수 있다. 상기 세퍼레이터와 충돌하여 분리된 열분해물은 상기 배플의 일단에 안착하여 타단으로 흐르도록, 상기 배플은 상기 일단에서 타단으로 갈수록 하향 경사진 것일 수 있다. 구체적으로, 상기 배플은 서로 이격되어 상하로 배치되는 복수 개의 배플을 포함하고, 상기 배플은 제1 배플; 및 상기 제1 배플의 하부에 위치하는 제2 배플을 포함하며, 상기 열분해물은 상기 제1 배플의 일단에 안착하여 제1 배플의 타단으로 흐르고, 상기 제1 배플의 타단으로부터 유입된 열분해물은 상기 제2 배플의 일단에 안착하여, 상기 제2 배플의 타단으로 흐르는 것일 수 있다. 상기 열분해물 분리기는 냉각부를 포함할 수 있으며, 일 구현예에서, 상기 냉각부는 워터 쿨러를 포함할 수 있다. 워터 쿨러에 의해 냉각부를 구성하면, 열분해물 분획기로 상승하는 고비등점의 왁스류들이 이 냉각부를 지날 때 응축되고, 수 차례 배플과 부딪치며 상승하는 기체상의 HCl과 분리되어 하향하여 연속교반반응기 내로 떨어지게 된다. 따라서, 최종 산물인 오일의 수율을 높일 수 있다.In the apparatus of the present invention, when a plastic mixture containing PVC, waste plastic, or powder thereof (hereinafter referred to as plastic mixture) is introduced into the continuous stirring tank reactor, the plastic mixture, such as hydrogen chloride, is thermally decomposed in the continuous stirring tank reactor. Chlorine compounds (gas or liquid form) are separated and released to form fractions (primary pyrolysis products) such as plastic mixtures with a reduced chlorine content. In this case, the apparatus may further include a pyrolysate separator connected to the continuous stirring tank reactor. The pyrolysate separator is installed at the top of the continuous stirring tank reactor, and may serve to discharge gaseous hydrogen chloride. The pyrolysate separator may include, for example, a separator in which the pyrolysate introduced from the reactor collides, and a baffle that collides with the separator to induce a downward flow of the separated pyrolysate. The pyrolysate separated by colliding with the separator may seat on one end of the baffle and flow to the other end, and the baffle may be inclined downward from one end to the other end. Specifically, the baffle includes a plurality of baffles spaced apart from each other and disposed vertically, and the baffle includes a first baffle; And a second baffle positioned below the first baffle, wherein the pyrolysate is seated on one end of the first baffle and flows to the other end of the first baffle, and the pyrolysate introduced from the other end of the first baffle is It may be seated on one end of the second baffle and flowing to the other end of the second baffle. The pyrolysate separator may include a cooling unit, and in one embodiment, the cooling unit may include a water cooler. When the cooling part is configured by a water cooler, the waxes of high boiling point rising to the pyrolysate fractionator are condensed when passing through this cooling part, collide with the baffle several times and separate from the rising gaseous HCl, and fall into the continuous stirring reactor . Therefore, it is possible to increase the yield of the final product, oil.
상기 워터 쿨러를 포함하는 열분해물 분리기의 가동 온도는 15~30℃일 수 있다.The operating temperature of the thermal decomposition separator including the water cooler may be 15 to 30°C.
일 구현예에서, 상기 연속교반탱크 반응기와 멜트 호퍼 사이에는 기체 투입부를 통해 투입된 기체에 의해 기체 커튼막이 형성될 수 있다. 이를 통해 상기 염소함량이 감소된 플라스틱 혼합물 등의 분획물이 멜트 호퍼 및 유동층 반응기로 투입되는 과정에서 상기 기체 커튼막에 의해 플라스틱 혼합물 등로부터 분리되어 나온 염소화합물의 기체가 유동층 반응기로 전달되는 것이 방지된다. 상기 기체투입부 (미도시)를 통해 투입되는 기체는 비활성기체인 것이 바람직하며, 상기 비활성 기체는 질소 기체, 헬륨 기체, 또는 아르곤 기체일 수 있다.In one embodiment, a gas curtain film may be formed between the continuous stirring tank reactor and the melt hopper by the gas introduced through the gas input unit. Through this, the gas of the chlorine compound separated from the plastic mixture, etc. by the gas curtain membrane is prevented from being transferred to the fluidized bed reactor while the fractions such as the plastic mixture having the reduced chlorine content are introduced into the melt hopper and the fluidized bed reactor. . The gas introduced through the gas inlet (not shown) is preferably an inert gas, and the inert gas may be nitrogen gas, helium gas, or argon gas.
한편, 유동층 반응기는 유동화 기체를 필요로 하는데, 상기 유동화 기체로는 비활성 기체, 상기 장치에서 생성되어 배출된 기체, 특히, 유동층 반응기에서 배출된 비응축 기체, 또는 이들의 혼합 기체가 사용될 수 있다.Meanwhile, the fluidized bed reactor requires a fluidized gas, and as the fluidized gas, an inert gas, a gas generated and discharged from the apparatus, in particular, a non-condensed gas discharged from the fluidized bed reactor, or a mixture thereof may be used.
상기 연속교반탱크 반응기는 생성된 산물이 배출되는 배출부(미도시)를 포함하는 것일 수 있다. 상기 연속교반탱크 반응기의 배출부는 상기 열분해물 분리기와 직접적으로 연결될 수 있다.The continuous stirring tank reactor may include a discharge unit (not shown) through which the generated product is discharged. The discharge part of the continuous stirring tank reactor may be directly connected to the pyrolysate separator.
한편, 상기 유동층 반응기에서 2차 열분해를 거치고 배출된 열분해 산물에서 고체인 열분해 촤는 먼저 포집되고, 열분해 기체는 냉각 및 응축 과정을 거쳐 오일로 전환되어 포집된다. On the other hand, the pyrolysis char, which is solid from the pyrolysis product discharged after undergoing the secondary pyrolysis in the fluidized bed reactor, is first collected, and the pyrolysis gas is converted into oil through cooling and condensation and collected.
또한, 상기 장치는 산화칼슘, 수산화칼슘, 또는 탄산나트륨(Na2CO3) 이 충진된 고온 필터(hot filter)기를 더 포함할 수 있으며, 상기 고온 필터기는 유동층 반응기 뒤에 위치할 수 있다. 일례로 산화칼슘은 염화수소와 반응하여 염화칼슘을 만들어 열분해유 내의 염소 함량을 저하시킨다.In addition, the apparatus may further include a hot filter filled with calcium oxide, calcium hydroxide, or sodium carbonate (Na2CO3), and the high temperature filter may be located behind the fluidized bed reactor. For example, calcium oxide reacts with hydrogen chloride to form calcium chloride, which lowers the chlorine content in pyrolysis oil.
상기 고온 필터기의 온도는 400~700℃일 수 있으며, 상기 산화칼슘 및 수산화칼슘은 850~1000℃에서 열처리된 그래뉼 형태의 것을 포함할 수 있다. 일 구현예에서, 상기 온도에서 상기 열처리된 산화칼슘 또는 수산화칼슘이 아닌 미분 산화칼슘 또는 수산화칼슘을 사용할 경우에는 반응기 내 차압이 발생하여, 공정운전 효율이 떨어질 수 있다.The temperature of the high-temperature filter may be 400 to 700°C, and the calcium oxide and calcium hydroxide may include those in the form of granules heat-treated at 850 to 1000°C. In one embodiment, in the case of using finely divided calcium oxide or calcium hydroxide other than the heat-treated calcium oxide or calcium hydroxide at the temperature, a differential pressure in the reactor may occur, and thus process operation efficiency may decrease.
폴리염화비닐을 포함하는 플라스틱 혼합물의 염소 저감을 위한 장치는 온도 조절 장치(미도시)를 더 포함할 수 있으며, 상기 온도 조절 장치는 상기 연속교반탱크 반응기, 상기 유동층 반응기 및 고온 필터기 각각의 온도를 독립적으로 변화시킬 수 있는 것이 바람직하다. 상기 온도 조절 장치는 온도 검출부, 온도 조절부, 및 가열부를 포함할 수 있다.An apparatus for reducing chlorine in a plastic mixture containing polyvinyl chloride may further include a temperature control device (not shown), wherein the temperature control device includes a temperature of each of the continuous stirring tank reactor, the fluidized bed reactor, and the high temperature filter. It is desirable to be able to change independently. The temperature control device may include a temperature detection unit, a temperature control unit, and a heating unit.
또한, 일 측면에서 본 발명은 플라스틱 혼합물의 염소 저감을 위한 시스템일 수 있고, 상기 시스템은 PVC 함유 플라스틱 혼합물의 염소 저감을 위한 장치, 플라스틱 혼합물 공급 시스템, 열분해 촤 분리 시스템, 전기집진기 및 기체 순환 시스템(미도시) 등을 포함할 수 있다.In addition, in one aspect, the present invention may be a system for reducing chlorine in a plastic mixture, wherein the system is a device for reducing chlorine in a plastic mixture containing PVC, a plastic mixture supply system, a pyrolysis char separation system, an electrostatic precipitator, and a gas circulation system. (Not shown), etc. may be included.
상기 연속교반탱크 반응기 온도는, 250~350℃일 수 있고, 바람직하게는 250~300℃일 수 있다.The temperature of the continuous stirring tank reactor may be 250 to 350°C, preferably 250 to 300°C.
또한, 상기 유동층 반응기에서는, 상기 오거 반응기 및 열분해물 분리기에서 열분해된 PVC 함유 플라스틱 혼합물이 다시 열분해될 수 있다. 상기와 같은 측면에서, 상기 유동층 반응기의 내부 온도는 650~780℃일 수 있고, 바람직하게는, 700~750℃, 더욱 바람직하게는, 700~720℃일 수 있다.In addition, in the fluidized bed reactor, the PVC-containing plastic mixture pyrolyzed in the auger reactor and the pyrolysate separator may be pyrolyzed again. In the same aspect as described above, the internal temperature of the fluidized bed reactor may be 650 to 780°C, preferably, 700 to 750°C, more preferably, 700 to 720°C.
상기 플라스틱 혼합물은 PVC를 함유하는 폐플라스틱을 포함할 수 있다. 또한, 상기 PVC를 포함하는 플라스틱 혼합물은 PVC 외에 폴리에틸렌 테레프탈레이트(PET), 고밀도 폴리에틸렌(HDPE), 저밀도 폴리에틸렌(LDPE), 폴리스티렌(PS), 및 폴리프로필렌(PP) 중 하나 이상을 더 포함하는 플라스틱의 혼합물을 의미할 수 있다.The plastic mixture may include waste plastic containing PVC. In addition, the plastic mixture containing the PVC is a plastic containing more than one of polyethylene terephthalate (PET), high density polyethylene (HDPE), low density polyethylene (LDPE), polystyrene (PS), and polypropylene (PP) in addition to PVC. It may mean a mixture of.
일 측면에서, 상기 장치에 의하여 생산된 산물 중 오일 내 염소의 함량은 10 ppm(w/w) 이하일 수 있다.In one aspect, the content of chlorine in the oil among the products produced by the apparatus may be 10 ppm (w/w) or less.
상기 장치에 의하여 생산된 산물 중 오일 내 염소 함량은, 지금까지 알려져 있는 열분해 오일 염소 함류량인 10,000 ppm 보다 현저히 적은 값이다.The chlorine content in the oil in the products produced by the above apparatus is significantly less than the known pyrolysis oil chlorine content of 10,000 ppm.
일 측면에서, 본 발명은 상기 장치를 이용한, 폴리염화비닐(PVC)을 포함하는 플라스틱 혼합물로부터 염소를 저감시키는 방법이다.In one aspect, the present invention is a method of reducing chlorine from a plastic mixture comprising polyvinyl chloride (PVC) using the above apparatus.
상기 방법은 폴리염화비닐(PVC)을 포함하는 플라스틱 혼합물로부터 생산된 열분해유에서 염소의 함량을 저감시키기 위한 것일 수 있다.The method may be for reducing the content of chlorine in pyrolysis oil produced from a plastic mixture including polyvinyl chloride (PVC).
일 측면에서, 상기 방법은, PVC를 포함하는 플라스틱 혼합물을 연속교반탱크 반응기에서 열분해시키는 제1 열분해 단계; 상기 연속교반탱크 반응기에서 열분해된 열분해물 중 염소를 제거하는 열분해물 분리 단계; 유동층 반응기에서 열분해시키는 제2 열분해 단계; 및 상기 유동층 반응기에서 열분해된 PVC 플라스틱 혼합물의 열분해 증기(pyrolysis vapor)를 산화칼슘 또는 수산화칼슘이 충진된 고온 필터기에서 여과하는 단계를 포함할 수 있다. In one aspect, the method comprises a first pyrolysis step of pyrolyzing a plastic mixture containing PVC in a continuous stirring tank reactor; A pyrolysate separation step of removing chlorine from pyrolysis products pyrolyzed in the continuous stirring tank reactor; A second pyrolysis step of pyrolyzing in a fluidized bed reactor; And filtering the pyrolysis vapor of the PVC plastic mixture pyrolyzed in the fluidized bed reactor in a high-temperature filter filled with calcium oxide or calcium hydroxide.
일 구현예에서, 상기 제1 열분해 단계는, 280~400℃에서 수행될 수 있다. 또한, 상기 열분해물 분리기의 온도는 300~500℃ 이며, 상기 제2 열분해 단계는, 680~750℃에서 수행될 수 있고, 바람직하게는, 700~750℃, 더욱 바람직하게는, 700~720℃에서 수행될 수 있다.In one embodiment, the first pyrolysis step may be performed at 280 ~ 400 °C. In addition, the temperature of the pyrolysis product separator is 300 ~ 500 ℃, the second pyrolysis step may be carried out at 680 ~ 750 ℃, preferably, 700 ~ 750 ℃, more preferably, 700 ~ 720 ℃ Can be done in
이하, 실시예 및 시험예를 들어 본 발명의 구성 및 효과를 보다 구체적으로 설명한다. 그러나 이들 실시예 및 시험예는 본 발명에 대한 이해를 돕기 위해 예시의 목적으로만 제공된 것일 뿐 본 발명의 범주 및 범위가 하기 예에 의해 제한되는 것은 아니다.Hereinafter, the configuration and effects of the present invention will be described in more detail with reference to Examples and Test Examples. However, these Examples and Test Examples are provided for illustrative purposes only to aid understanding of the present invention, and the scope and scope of the present invention are not limited by the following examples.
[부호의 설명][Explanation of code]
1: 플라스틱 혼합물의 염소 저감을 위한 시스템1: System for reducing chlorine in plastic mixtures
2: 연속교반탱크 반응기2: Continuous stirring tank reactor
3: 멜트 호퍼(melt hopper)3: melt hopper
4: 피더(feeder)4: feeder
5: 유동층 반응기(fluidized bed reactor)5: fluidized bed reactor
6: 사이클론(cyclone)6: cyclone
7: 고온 필터기(hot filer)7: hot filer
8: 칠러(chliler)8: chiller
9: 전기 집진기(electrostatic precipitator)9: electrostatic precipitator
10: 컴프레셔(compressor)10: compressor
11: 프리히터(preheater)11: preheater

Claims (11)

  1. 폴리염화비닐(PVC)을 포함하는 플라스틱 혼합물의 염소 저감 장치로서,As an apparatus for reducing chlorine in a plastic mixture containing polyvinyl chloride (PVC),
    상기 장치는,The device,
    연속교반탱크 반응기; 및 유동층 반응기를 포함하는, 폴리염화비닐을 포함하는 플라스틱 혼합물의 염소 저감 장치.Continuous stirring tank reactor; And chlorine reduction apparatus for a plastic mixture comprising polyvinyl chloride, comprising a fluidized bed reactor.
  2. 제1항에 있어서,The method of claim 1,
    상기 장치는,The device,
    폴리염화비닐을 포함하는 플라스틱 혼합물을 열분해하는, 폴리염화비닐을 포함하는 플라스틱 혼합물의 염소 저감 장치.An apparatus for reducing chlorine of a plastic mixture containing polyvinyl chloride, which thermally decomposes a plastic mixture containing polyvinyl chloride.
  3. 제1항에 있어서,The method of claim 1,
    상기 연속교반탱크 반응기 온도는, 250~350℃인, 폴리염화비닐을 포함하는 플라스틱 혼합물의 염소 저감 장치.The continuous stirring tank reactor temperature is 250 ~ 350 ℃, chlorine reduction device of the plastic mixture containing polyvinyl chloride.
  4. 제1항에 있어서,The method of claim 1,
    상기 유동층 반응기의 온도는, 650~780℃인, 폴리염화비닐을 포함하는 플라스틱 혼합물의 염소 저감 장치.The temperature of the fluidized bed reactor is 650 ~ 780 ℃, the chlorine reduction device of the plastic mixture containing polyvinyl chloride.
  5. 제1항에 있어서,The method of claim 1,
    상기 장치는, 냉각부를 포함하는 열분해물 분리기를 더 포함하는, 폴리염화비닐을 포함하는 플라스틱 혼합물의 염소 저감 장치.The device further comprises a thermal decomposition product separator including a cooling unit, a chlorine reduction device for a plastic mixture containing polyvinyl chloride.
  6. 제5항에 있어서,The method of claim 5,
    상기 열분해물 분리기의 가동 온도는 15~30℃인, 폴리염화비닐을 포함하는 플라스틱 혼합물의 염소 저감 장치.The operating temperature of the pyrolysate separator is 15 ~ 30 ℃, the chlorine reduction device of the plastic mixture containing polyvinyl chloride.
  7. 제1항에 있어서,The method of claim 1,
    상기 연속교반탱크 반응기와 유동층 반응기는, The continuous stirring tank reactor and the fluidized bed reactor,
    연속교반탱크 반응기, 및 유동층 반응기의 순으로 직렬 연결된 것을 포함하는, 폴리염화비닐을 포함하는 플라스틱 혼합물의 염소 저감 장치.An apparatus for reducing chlorine of a plastic mixture comprising polyvinyl chloride, comprising a continuous stirring tank reactor and a fluidized bed reactor connected in series in order.
  8. 제1항에 있어서,The method of claim 1,
    상기 장치는, 고온 필터기를 더 포함하는, 폴리염화비닐을 포함하는 플라스틱 혼합물의 염소 저감 장치.The device further comprises a high-temperature filter, a device for reducing chlorine of a plastic mixture comprising polyvinyl chloride.
  9. 제1항에 있어서,The method of claim 1,
    상기 플라스틱은 폐플라스틱을 포함하는, 폴리염화비닐을 포함하는 플라스틱 혼합물의 염소 저감 장치.The plastic comprises waste plastic, chlorine reduction apparatus for a plastic mixture containing polyvinyl chloride.
  10. 제1항에 있어서,The method of claim 1,
    상기 장치로부터 생산된 산물은, The product produced from the device,
    산물 중 오일 내 염소의 함량이 (10)ppm(w/w)이하인, 폴리염화비닐을 포함하는 플라스틱 혼합물의 염소 저감 장치.An apparatus for reducing chlorine in a plastic mixture containing polyvinyl chloride, wherein the content of chlorine in oil in the product is (10) ppm (w/w) or less.
  11. 제1항 내지 제10항 중 어느 한 항의 장치를 이용하여, 폴리염화비닐을 포함하는 플라스틱 혼합물로부터 염소를 저감하는 방법.A method for reducing chlorine from a plastic mixture containing polyvinyl chloride by using the apparatus of any one of claims 1 to 10.
PCT/KR2019/004358 2019-04-11 2019-04-11 Apparatus for removing chlorine in pyrolysis of plastic mixture containing polyvinyl chloride, and method for removing chlorine in pyrolysis of plastic mixture containing polyvinyl chloride using same WO2020209419A1 (en)

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