KR100824965B1 - Apparatus for refining fuel oil including apparatus for removing chlorine - Google Patents

Apparatus for refining fuel oil including apparatus for removing chlorine Download PDF

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KR100824965B1
KR100824965B1 KR1020070043953A KR20070043953A KR100824965B1 KR 100824965 B1 KR100824965 B1 KR 100824965B1 KR 1020070043953 A KR1020070043953 A KR 1020070043953A KR 20070043953 A KR20070043953 A KR 20070043953A KR 100824965 B1 KR100824965 B1 KR 100824965B1
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fuel oil
aqueous solution
oil
basic aqueous
water
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KR1020070043953A
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Korean (ko)
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이경환
신대현
노남선
김광호
전상구
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한국에너지기술연구원
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
    • 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
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2250/00—Structural features of fuel components or fuel compositions, either in solid, liquid or gaseous state
    • C10L2250/08—Emulsion details
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/02—Combustion or pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/24—Mixing, stirring of fuel components
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
    • C10L2290/543—Distillation, fractionation or rectification for separating fractions, components or impurities during preparation or upgrading of a fuel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
    • C10L2290/547—Filtration for separating fractions, components or impurities during preparation or upgrading of a fuel

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

A fuel oil-refining apparatus is provided to remove chloride components contained in fuel oil, which is obtained by treating waste plastic or waste oil, thereby producing high-quality fuel oil without chloride components. A chemical refinement unit(60) mixes low-quality fuel oil and basic aqueous solution, wherein the low-quality fuel oil is prepared by pyrolyzing and distilling one component selected from waste plastic, waste synthetic resin, waste rubber, or waste oil. A water-oil separator(70) separates fuel oil from the mixture of the fuel oil and the basic aqueous solution. A horizontal partition wall(730) is disposed in the middle of the water-oil separator to divide an inside space of the water-oil separator into a first space(710) and a second space(720). Upper portions of the first space and the second space communicate with each other. Further, a fuel oil-refining apparatus(200) additionally contains a water-oil mixer(80) at an upper part of the chemical refinement unit.

Description

염소제거장치를 구비한 연료유정제장치{Apparatus for refining Fuel Oil Including apparatus for removing chlorine}Apparatus for refining Fuel Oil Including apparatus for removing chlorine}

도 1은 본 발명의 일실시예에 따른 연료유정제장치를 도시한 개략도1 is a schematic view showing a fuel oil refinery device according to an embodiment of the present invention;

도 2는 본 발명의 일실시예에 따른 연료유정제장치에 포함되는 염소제거장치를 도시한 단면도2 is a cross-sectional view showing a chlorine removal device included in the fuel oil refinery device according to an embodiment of the present invention.

<도면의 주요 부분에 대한 부호의 설명><Explanation of symbols for main parts of the drawings>

100 : 연료유정제장치 200 : 염소제거장치100: fuel oil refinery device 200: chlorine removal device

10 : 제1정제탱크 20 : 제2정제탱크 10: first refining tank 20: second refining tank

30 : 제3정제탱크 40 : 제4정제탱크 30: third refining tank 40: fourth refining tank

50 : 저장탱크 60 : 화학정제장치50: storage tank 60: chemical purification device

610 : 연료유 유입구 620 : 온도조절장치610: fuel oil inlet 620: temperature control device

630 : 교반기 640 : 염기성 수용액 유입구 630: stirrer 640: basic aqueous solution inlet

650 : 물-오일 혼합물 배출구650 water-oil mixture outlet

70 : 물-오일 분리기 710 : 제1공간부 70: water-oil separator 710: first space part

720 : 제2공간부 730 : 세로 격벽 720: second space portion 730: vertical bulkhead

740 : 물-오일 혼합물 유입구 750, 790 : 염기성수용액 배출구 740: water-oil mixture inlet 750, 790: basic aqueous solution outlet

760 : 염기성수용액 유출입부 770 : 펌프 760: basic aqueous solution outflow 770: pump

780 : 염소제거 연료유 배출구 780: chlorine removal fuel oil outlet

80 : 물-오일 혼합기 80: water-oil mixer

810 : 시브(sieve) 820 : 연료유 유입구 810 sieve 820 fuel oil inlet

830 : 교반기 840 : 물-오일 혼합물 배출구830 stirrer 840 water-oil mixture outlet

850 : 염기성수용액 유입구 90 : 백(bag)필터장치 850: basic aqueous solution inlet 90: bag filter device

본 발명은 연료유정제장치 및 이를 구비한 열분해 유화시스템에 있어서, 폐플라스틱, 폐합성수지, 폐고무, 폐유 등의 고분자 폐기물을 열분해한 후 증류탑에 의해 증류시켜 얻어진 연료유에 포함되어 있는 불순물 및 유해성분을 제거하는 연료유정제장치에 관한 것이다.The present invention relates to a fuel oil refiner and a pyrolysis emulsifying system having the same, including impurities and harmful components included in fuel oil obtained by thermal decomposition of polymer waste such as waste plastic, waste resin, waste rubber, waste oil, etc., by distillation by a distillation column. It relates to a fuel oil refiner to remove the.

더욱 상세하게는 상기 연료유 정제장치에 있어서 상기 연료유에 포함되어 있는 염소 성분을 제거하는 염소제거장치를 더 포함하는 연료유 정제장치에 관한 것이며,More specifically, the fuel oil refining apparatus relates to a fuel oil refining apparatus further comprising a chlorine removing device for removing chlorine components contained in the fuel oil.

더욱 상세하게는 다양한 방법으로 폐플라스틱을 열분해하여 얻어진 연료유에 포함된 염소성분을 제거하여 고급연료유를 제공하는 염소제거장치, 이를 포함하는 연료유정제장치 및 이를 구비한 열분해유화시스템을 제공하는 것이다. More specifically, the present invention provides a chlorine removal device providing a high quality fuel oil by removing chlorine contained in fuel oil obtained by pyrolyzing waste plastic by various methods, a fuel oil refiner including the same, and a pyrolysis emulsion system having the same. .

현재 다양한 용도로 사용되고 있는 탄화수소로 구성되는 플라스틱과 윤활유 등은 산업발달에 의해 배출량이 증가되어 환경오염에 지대한 영향을 끼치는 심각한 사회 문제를 야기 시키고 있다.Plastics and lubricating oils composed of hydrocarbons that are currently used for various purposes are causing serious social problems that have a huge impact on environmental pollution due to increased emissions due to industrial development.

폐플라스틱의 경우 최근에 연간 수백만 톤이 발생되고 있으며, 이는 대부분 매립과 소각에 의해 처리되지만, 점차 매립은 불가능하고 소각 또한 대기오염 등 환경적인 문제점을 발생시켜 대체 재활용 방법이 제시되고 있다. 또한 재활용의 경우도 부가가치가 있는 일부 품목에 제한되어 있으나 대부분은 경제성이 낮아 재활용에는 점차 어려움이 예상되고 있다. 그 중의 하나가 폐플라스틱을 화학처리하여 대체 연료유를 생산하는 방법이 시도되고 있다.In the case of waste plastics, millions of tons are generated annually, and most of them are disposed of by landfilling and incineration, but gradually landfilling is impossible and incineration also causes environmental problems such as air pollution. Recycling is also limited to some value-added items, but most of them are economically difficult to recycle. One of them is a method of chemically treating waste plastic to produce alternative fuel oil.

또한 폐유의 경우에는 자동차, 농기계 등에서 폐기 처분되는 폐유 발생량은 연간 백만 드럼 이상으로 막대한 양으로 일부 회수되어 재활용되지만 고부가가치 물질로 전환되지 못하고 있다. In addition, in the case of waste oil, the amount of waste oil disposed of in automobiles, agricultural machines, etc., is partially recovered and recycled in an amount of over one million drums per year, but is not converted to high value-added materials.

이러한 상황 속에서 기존 공정에서 고비점 물질에 의한 연속 운전의 어려움을 해결할 수 있고, 유해 대기 및 폐기물의 다량 발생에 의한 환경적인 문제를 최소화할 수 있는 자동화에 의한 안정적, 연속 운전이 가능한 상용 규모의 최신 열분해 유화장치에 대한 필요성이 대두되었다. Under these circumstances, it is possible to solve the difficulty of continuous operation due to high boiling point materials in the existing process, and to provide stable and continuous operation by automation that can minimize environmental problems caused by the generation of hazardous air and wastes. There is a need for a modern pyrolysis emulsifier.

본 출원인은 상기와 같은 필요성을 인식하고, 혼합 폐플라스틱 또는 폐유 그리고 이들 두 성분을 동시에 열분해에 의해 대체 연료유를 안정적, 연속적으로 대 량 생산하는 시스템을 발명하여 우리나라특허출원번호 10-2006-81825호로 출원한 바 있다.Applicant is recognizing the necessity as described above, and invented a system for stably and continuously producing a large amount of alternative fuel oil by thermal decomposition of mixed waste plastic or waste oil and these two components at the same time, Korean Patent Application No. 10-2006-81825 Has been filed.

그러나 상기 출원된 발명에서, 혼합 폐플라스틱의 열분해에 의해 생성되는 연료유가 폐플라스틱에 포함된 PVC나 브롬계 난연제를 함유하는 플라스틱물질에서 유래하는 염산이나 브롬산을 제거하지 못하여 열분해 후 생성되는 연료유의 질에 악영향을 미치게 되어 좋지 않았다. 즉, 최종 생성 연료유에는 염소 성분등의 불순물 또는 유해한 산 성분이 포함되어 있어 대체 연료유로 연소 장치에 사용할 때에 장치의 부식이나 노화등의 장애를 발생시킬 뿐만 아니라 염소 성분등이 배출되게 되어 환경을 악화시킨다. However, in the above-described invention, the fuel oil produced by pyrolysis of the mixed waste plastic does not remove hydrochloric acid or bromic acid derived from the plastic material containing PVC or bromine-based flame retardant contained in the waste plastic. It was not good to adversely affect the quality. In other words, the final fuel oil contains impurities such as chlorine or harmful acid, and when used in a combustion device as an alternative fuel oil, not only does it cause corrosion or aging of the device, but also chlorine is released. Worsen.

따라서 폐플라스틱으로부터 얻어진 연료유를 대체 연료로 안전하게 판매하기 위해서는 상기와 같이 저급 연료유를 고급화하는 정제 기술 개발이 필요하며, 특히 염소성분을 제거하는 정제 기술이 결합된 연료유정제장치의 개발이 필요한 실정이다.Therefore, in order to safely sell fuel oil obtained from waste plastics as an alternative fuel, it is necessary to develop refining technology to upgrade low-grade fuel oil as described above, and in particular, to develop a fuel oil refiner combined with refining technology to remove chlorine components. It is true.

본 발명은 상기의 문제점을 해소하기 위해 안출된 것으로, 폐플라스틱, 폐합성수지, 폐고무, 폐유 등의 고분자 폐기물을 열분해하여 수득한 연료유 중 대부분을 차지하는 저급연료유를 경제성이 있는 고품질로 정제하기 위한 연료유정제장치를 제공하는 것을 목적으로 하며, The present invention has been made to solve the above problems, to purify low-grade fuel oil, which occupies most of the fuel oil obtained by pyrolyzing polymer waste such as waste plastic, waste synthetic resin, waste rubber, waste oil, etc. at high quality with economical efficiency. To provide a fuel oil refinery device for

특히 염소성분을 효과적으로 제거하여 공해 물질 발생을 억제하고 연료유의 품질을 더욱 향상시키기 위한 연료유정제장치를 제공하는데 보다 구체적인 목적이 있다. In particular, there is a more specific object to provide a fuel oil refinery device for effectively removing the chlorine components to suppress the generation of pollutants and further improve the quality of fuel oil.

상기 과제를 달성하기 위한 본 발명의 연료유정제장치는, 폐플라스틱, 폐합성수지, 폐고무, 폐유 등의 고분자 폐기물을 열분해하고 증류탑에 의해 증류시키고, 이를 포집하여 생성한 연료유에 포함되어 있는 불순물 및 유해성분을 제거하는 연료유정제장치에 있어서, 연료유에 포함되어 있는 염소 성분을 제거하는 연료유정제장치를 더 포함하는 것을 특징으로 한다.The fuel oil refiner device of the present invention for achieving the above object, the pyrolysis of polymer waste, such as waste plastic, waste synthetic resin, waste rubber, waste oil, distilled by a distillation column, and the impurities contained in the fuel oil produced by the collection and A fuel oil refiner for removing harmful components, characterized in that it further comprises a fuel oil refiner for removing chlorine contained in the fuel oil.

상기 특히 염소성분을 제거하기 위한 연료유정제장치는 화학정제장치와 물-오일 분리기를 포함하여 구성된다.In particular, the fuel oil refiner for removing the chlorine component comprises a chemical refiner and a water-oil separator.

상기 화학정제장치는 탱크 상단의 유입구로 염산을 함유하는 연료유 및 물-오일 분리기로부터 수산화나트륨수용액 등의 염기성 수용액을 유입시켜 염산등의 산성분을 함유하는 연료유와 상기 염기성 수용액을 화학정제장치의 배부에 설치된 교반기로 혼합하여 접촉시킴으로써 연료유에 함유된 염소성분을 제거하는 것을 특징으로 한다. 또한 상기 화학정제장치는 탱크 본체 외부에 탱크의 온도를 조절하기 위한 온도조절장치를 더 구비할 수 있다. The chemical refining apparatus is a chemical oil refining apparatus containing fuel oil containing an acid component such as hydrochloric acid by introducing a basic aqueous solution such as sodium hydroxide aqueous solution from a fuel oil containing hydrochloric acid and a water-oil separator to the inlet of the tank top. It is characterized in that the chlorine component contained in the fuel oil is removed by mixing and contacting with a stirrer provided in the back of the. In addition, the chemical purification apparatus may further include a temperature controller for controlling the temperature of the tank outside the tank body.

상기 물-오일 분리기는 탱크 내부 중간에 세로 격벽이 형성되어 탱크 내부의 공간을 상부가 연통되도록 제1공간부와 제2공간부로 이등분하며, 제1공간부에는 염기성 수용액이 저장되고, 제1공간부 하단 일측에 화학정제장치에서 처리된 연료유 와 염기성용액이 혼합되어 유입되는 유입구가 형성되며, 제1공간부와 상단에서 연통이 되도록 형성된 제2공간부는 그 중간부의 일측에 염소가 제거된 연료유를 배출하는 배출구가 형성된다. The water-oil separator has a vertical partition formed in the middle of the tank so that the space inside the tank is divided into two parts into the first space portion and the second space portion, the first space portion is stored in the basic aqueous solution, the first space On the lower side of the lower portion is formed an inlet through which the fuel oil and the basic solution treated by the chemical refining apparatus are mixed, and the second space portion formed to communicate with the upper portion of the first space portion has the chlorine removed fuel at one side of the middle portion thereof. An outlet for oil discharge is formed.

상기 화학정제장치의 물-오일분리기의 제1공간부에서 접촉된 물-오일 혼합물은 제1공간부의 하부로부터 일정한 거리의 상부로 유입되어 물과 연료유의 상분리가 이루어지도록 하고, 상분리된 오일성분인 연료유는 일정 수위로 상승하면 세로격벽을 넘어 제2공간부로 이동됨으로써 물-오일 분리가 이루어지며, 물-오일 분리기의 제1공간부의 최하단에는 염기성 수용액을 배출하고 새로운 염기성 수용액을 주입할 수 있도록 염기성 수용액 유출입구가 형성되어 있다.The water-oil mixture contacted in the first space portion of the water-oil separator of the chemical refining apparatus is introduced into the upper portion of a predetermined distance from the lower portion of the first space portion so that water and fuel oil can be phase separated from each other. When the fuel oil rises to a certain level, water-oil separation is performed by moving to the second space portion beyond the vertical bulkhead. At the bottom of the first space portion of the water-oil separator, a basic aqueous solution is discharged and a new basic aqueous solution can be injected. A basic aqueous solution outlet inlet is formed.

또한 본 발명의 연료유정제장치는 상기 물-오일분리기 상부에 물-오일 혼합기를 더 구비할 수 있다.In addition, the fuel oil refiner of the present invention may further include a water-oil mixer on the water-oil separator.

상기 물-오일 혼합기는 폐플라스틱을 분해하여 생산한 염소화합물이 제거되지 않은 연료유와 물-오일분리기로부터 유입되는 염기성수용액을 상부로부터 유입시키고, 상기 물-오일혼합기의 내부 상단에 시브(sieve)가 구비되어, 물-오일혼합기로 유입되는 연료유와 염기성수용액이 접촉하여 혼합되도록 하고(시브는 밑면에 복수의 유출구가 형성되어 유입되는 연료유와 염기성수용액의 유량을 적절히 조절하여 시브내부에 일정수위로 유지되어 연료유와 염기성수용액의 접촉시간을 갖도록함), 시브를 통과한 혼합물은 상기 시브 밑부분에 형성된 교반기에 의해 교반되어 연료유와 염기성수용액을 더욱 접촉하도록, 즉 상기 혼합기의 상단의 유입구로 유입되는 염소함유 연료유 및 염기성 수용액이 시브(sieve)을 거치면서 1차 혼합된 후 하단에 구비된 교반기에 의해 2차 혼합된 후 물-오일혼합기의 하단에 구비된 배출구를 통해 화학정제장치로 공급함으로써 염소함유 연료유에 염기성 수용액을 보다 효과적으로 접촉하도록 하여 염산등의 화합물 형태로 존재하는 염소의 제거 효율을 높일 수 있다.The water-oil mixer introduces the basic oil solution from the upper portion of the fuel oil and the water-oil separator from which the chlorine compound produced by decomposing the waste plastic is removed from the top, and sieves on the inner top of the water-oil mixer. The fuel oil flowing into the water-oil mixer and the basic aqueous solution are brought into contact with each other (the sheave has a plurality of outlets formed at the bottom thereof, and the flow rate of the flowing fuel oil and the basic aqueous solution is appropriately adjusted within the sieve. To maintain the contact time between the fuel oil and the basic aqueous solution), and the mixture passed through the sieve is stirred by an agitator formed at the bottom of the sieve to further contact the fuel oil and the basic aqueous solution, that is, at the top of the mixer. The chlorine-containing fuel oil and the basic aqueous solution flowing into the inlet are first mixed while passing through a sieve and then provided at the bottom of the bridge. After the second mixing by semi-annual, it is supplied to the chemical refining device through the outlet provided at the bottom of the water-oil mixer to more efficiently contact the basic aqueous solution to the chlorine-containing fuel oil to remove the chlorine in the form of a compound such as hydrochloric acid Can increase.

염소제거장치의 화학정제장치는 상기 물-오일 혼합기 또는 폐플라스틱의 분해에 의해 생성된 연료유와 염기성수용액을 함께 유입시켜 화학정제장치의 내부에 구비한 교반기에 의해서 염산 등의 산 성분을 염기성수용액과 접촉시켜 염산을 반응시켜 물속으로 용해시켜 연료유 내의 염산 등의 염소성분을 제거하게 된다.The chemical refining device of the chlorine removal device is a basic aqueous solution of an acid component such as hydrochloric acid by a stirrer provided inside the chemical refining device by introducing the oil and the basic aqueous solution together with the fuel oil produced by the decomposition of the water-oil mixer or the waste plastic. Hydrochloric acid is reacted and dissolved in water to remove chlorine components such as hydrochloric acid in fuel oil.

화학정제장치 내의 혼합물은 충분히 교반한 후 물-오일분리기로 이송한다. 상기 물-오일 분리기는, 제1공간부에 저장된 염기성 수용액은 물-연료유의 상분리에 의해 수상의 수위가 기 설정된 수위에 도달하면 제1공간부 하단에 형성된 염기성 수용액 배출구로부터 염기성 수용액을 화학정제장치의 상단 유입구 또는 물-오일 혼합기의 상단 유입구로 공급될 수 있도록 하며, 제 1공간부에서 상분리된 연료유가 일정수위 이상일 경우 세로격벽의 상단부를 통하여 제 2공간부로 이동하고 다시 수용상과 연료유의 상분리에 의해 연료유만을 제 1정제탱크로 이송하여 정제한다.The mixture in the chemical purifier is stirred sufficiently and then transferred to a water-oil separator. In the water-oil separator, the basic aqueous solution stored in the first space part is a chemical purification device from the basic aqueous solution outlet formed at the bottom of the first space part when the water level of the aqueous phase reaches a predetermined level by phase separation of water-fuel oil. It can be supplied to the upper inlet of the water inlet or the upper inlet of the water-oil mixer, and when the fuel oil phase separated in the first space portion is above a certain level, it moves to the second space portion through the upper end of the vertical partition wall and phase separation of the receiving phase and fuel oil again. Only the fuel oil is transferred to the first purification tank for purification.

또한 본 발명에 따른 염소제거장치의 물-오일 혼합기(80)로 유입되는 염소함유 연료유는 염소제거장치로 유입되기 전에 백(bag)필터 장치(90)를 거쳐 10㎛이상의 큰 입자가 제거하는 것이 더욱 바람직하다.In addition, the chlorine-containing fuel oil introduced into the water-oil mixer 80 of the chlorine removal device according to the present invention is removed by large particles of 10 μm or more through the bag filter device 90 before being introduced into the chlorine removal device. More preferred.

본 발명의 염소제거장치에 사용되는 염기성 수용액은 연료유에 함유되어 있 는 염산과 같은 무기염소화합물과 반응이 용이한 염기성 물질을 사용하는 것이 좋으며 Ca(OH)2 수용액 또는 NaOH 수용액을 사용할 수 있으나 염소 제거효율 측면에서 NaOH 수용액이 보다 바람직하며 염기성수용액의 농도는 크게 제한 받지 않는다.The basic aqueous solution used in the chlorine removal device of the invention, it is recommended to use a basic substance which is easy to inorganic chlorine compound and a reaction such as hydrochloric acid is there is contained fuel oil available Ca (OH) 2 aqueous solution or an aqueous NaOH solution, but chlorine NaOH aqueous solution is more preferable in terms of removal efficiency, and the concentration of the basic aqueous solution is not significantly limited.

연료유에 함유될 수 있는 염소 화합물로는 대부분이 염산이며, 기타 폐플라스틱의 종류나 또는 첨가제로부터 유도되는 극히 일부의 기타 염소화합물이 포함될 수 있다. 염소화합물로서는 염소가 하나이상 치환된 지방족 또는 방향족 탄화수소류이거나, 카보닐클로라이드화합물일 수 있으나 이에 한정하는 것은 아니다. 예를 들면 유기염소화합물은 1-클로로메틸-2-메틸벤젠(1-(chloromethyl)-2-methylbenzene), 클로로시클로헥산(chlorocyclohexane), 1-클로로테트라데칸(1-chlorotetradecane), 1-클로로옥타데칸(1-chlorootadecane), 1-클로로헵탄(1-chloroheptane), 2-클로로-4-메틸펜탄(2-chloro-4-methylpentane), 시클로헥산카보닐클로라이드(cyclohexanecarbonylchloride) 등을 들 수 있다.Chlorine compounds that may be contained in fuel oils are mostly hydrochloric acid, and may include very few other chlorine compounds derived from other types of waste plastics or additives. The chlorine compound may be an aliphatic or aromatic hydrocarbon substituted with at least one chlorine, or a carbonyl chloride compound, but is not limited thereto. For example, the organic chlorine compound is 1-chloromethyl-2-methylbenzene, chlorocyclohexane, 1-chlorotetradecane, 1-chloroocta Decane (1-chlorootadecane), 1-chloroheptane (1-chloroheptane), 2-chloro-4-methylpentane (2-chloro-4-methylpentane), cyclohexanecarbonyl chloride and the like.

상기 유기염소화합물에서 염소 성분을 제거하는 것은 염기성 수용액 내 함유된 히드록시기(OH)와의 중화반응, 치환반응 또는 히드록시기에 의한 제거(elimnation) 반응에 의한 것으로 설명할 수 있다. 상기 치환반응은 히드록시기(OH)가 염소(Cl)과 치환되는 것이고, 상기 제거반응은 히드록시기(OH)에 의해 수소(H) 및 염소(Cl)가 떨어져 나와 유기염소화합물은 이중결합을 갖는 화합물로 되는 반응이이며 이 때 염산은 다시 히드록시기와 반응하여 중화되어 물 층으로 용해되어 제거되는 것으로 생각된다. 또한 연료유에 함유될 수 있는 염산(HCl)과 같은 무기염소 성분은 염기성 수용액과의 중화반응에 의해 연료유로부터 제거되게 된다.Removal of the chlorine component from the organic chlorine compound may be explained by neutralization reaction with a hydroxyl group (OH) contained in a basic aqueous solution, a substitution reaction, or an elimination reaction by a hydroxyl group. The substitution reaction is a hydroxy group (OH) is substituted with chlorine (Cl), the removal reaction is hydrogen (H) and chlorine (Cl) is released by the hydroxy group (OH) is an organic chlorine compound is a compound having a double bond It is believed that the hydrochloric acid then reacts with the hydroxyl group to be neutralized, dissolved in the water layer and removed. In addition, inorganic chlorine components such as hydrochloric acid (HCl) which may be contained in the fuel oil are removed from the fuel oil by neutralization with the basic aqueous solution.

이하 첨부한 도면을 바탕으로 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

본 발명에 따른 일 실시예로서 폐플라스틱의 열분해 유화시스템을 소개하면 이건 발명과 동일한 발명자에 의해 출원된 우리나라특허출원번호 10-2006-81825호에서 공개한 열분해 유화시스템을 들 수 있는데, 고상 폐플라스틱 및/또는 액상 폐유의 저장조로부터 용융조로 투입하여 용융한 후 열분해조에서 열분해하여, 분해된 유분은 증류탑에서 회수하여 저장조에 저장한 후, 이를 다시 불순물 및 유해성분을 제거하는 연료유정제장치를 거쳐서 정제되어 연료유로 제공된다. Introducing the pyrolysis emulsification system of the waste plastic as an embodiment according to the present invention is a pyrolysis emulsification system disclosed in Korean Patent Application No. 10-2006-81825 filed by the same inventor as the invention, solid waste plastic And / or from the storage tank of the liquid waste oil into the melting tank and melted, and then pyrolyzed in the pyrolysis tank, and the decomposed oil is recovered in a distillation column and stored in the storage tank, and then, through the fuel refiner to remove impurities and harmful components. It is refined and provided as fuel oil.

그런데 상기의 발명의 연료유정제장치는 폐플라스틱을 열분해하여 제조한 불순물이 포함된 연료유를 유입하여 봉투형상의 백(bag)필터에 큰입자를 필터링하는 제1정제단계, 이어서 필터로 미세입자를 필터링하는 제2정제단계 및 제2, 3의 필터로 초미세입자와 수분을 필터링하는 제3정제단계 및 활성탄소 등의 카본으로 구성된 제4필터를 통과시켜 유해화학성분을 필터링하는 제4정제단계 등으로 이루어져 있을 뿐, 재생 연료유를 사용하는 경우 이를 사용하는 장치 등에 부식이나 노화 등의 심각한 문제를 일으키는 염소를 발생시키는 염산을 포함한 염소화합물을 효율적으로 제거하기 위한 장치가 충분하지 않아, 기계장치등에 심각한 손실을 야기하게 되었다. However, the fuel oil refiner of the present invention includes a first purification step of filtering large particles into an envelope-shaped bag filter by introducing fuel oil containing impurities prepared by pyrolyzing waste plastic, followed by fine particles by a filter. The fourth purification step of filtering harmful chemical components through a second purification step of filtering the second filter and the third purification step of filtering the ultrafine particles and water with a filter of the second, third and a fourth filter composed of carbon such as activated carbon. In the case of using recycled fuel oil, there are not enough devices for efficiently removing chlorine compounds including hydrochloric acid, which generates chlorine, which causes serious problems such as corrosion and aging. It caused serious loss on the back.

상기의 불순물을 제거하기 위한 본 발명에 따른 연료유정제장치는 도 1에 나타낸 바와 같은 염소제거장치를 증류탑에서 회수되는 폐플라스틱에서 재생한 연료유에 포함된 염소원소를 함유하는 성분을 제거하기 위하여 연료유정제장치에 연결 한 것을 특징으로 한다. The fuel oil refinery device according to the present invention for removing the impurities is a fuel to remove the chlorine element contained in the fuel oil recycled from the waste plastic recovered from the distillation column in the chlorine removal device as shown in FIG. It is characterized in that connected to the oil refinery.

즉, 본 발명은 염소를 함유하는 화합물을 제거하기 위한 염소제거장치를 연료유정제장치와 결합한 것이다.That is, the present invention combines a chlorine removal device for removing a compound containing chlorine with a fuel oil refinery device.

본 발명의 염소제거장치를 구체적으로 나타내면 도 1과 같으며, 이를 구체적으로 설명하면 다음과 같다.The chlorine removal apparatus of the present invention is shown in detail as shown in FIG. 1, which will be described in detail below.

도 1에서 보는 바와 같이 폐플라스틱을 열분해하여 증류탑에 의해 회수한 재상연료유를 염소제거장치(200)로 도입하거나, 또는 상기 증류탑에 의해 회수한 재생연료유를 백(bag) 필터장치(90)를 거쳐 10㎛ 이상의 입자를 제거한 연료유를 염소제거장치로 도입한다. 상기 연료유는 상기와 같이 열분해 후 곧바로 도입하거나 또는 백필터장치(90) 등에 의해 고체상의 불순물을 제거한 후 도입할 수도 있으며, 필요에 의해서는 백필터, 카트리지필터 및/또는 활성탄소필터를 통과시킨 재생 연료유를 염소제거장치(200)로 도입할 수도 있다.As shown in FIG. 1, the recycled fuel oil recovered by the distillation column by pyrolyzing the waste plastic is introduced into the chlorine removal device 200, or the recycled fuel oil recovered by the distillation tower is bag filter device 90. A fuel oil from which particles of 10 µm or more are removed therethrough is introduced into the chlorine removal device. The fuel oil may be introduced immediately after pyrolysis as described above, or may be introduced after removing solid impurities from the bag filter device 90 or the like, and, if necessary, passed through a bag filter, a cartridge filter and / or an activated carbon filter. Regenerated fuel oil may be introduced into the chlorine removal apparatus 200.

본 발명의 염소제거장치(200)는 화학정제장치(60)와 물-오일분리기(70)로 구성된다.Chlorine removal device 200 of the present invention is composed of a chemical purification device 60 and a water-oil separator (70).

본 발명의 또 다른 염소제거장치(200)는 화학정제장치(60)와 물-오일분리기(70) 및 화학정제장치(60) 상부에 형성된 물-오일혼합기(80)로 구성된다.Another chlorine removal device 200 of the present invention is composed of a chemical purification device 60, a water-oil separator 70 and a water-oil mixer 80 formed on the chemical purification device (60).

본 발명에 따른 연료유에 함유된 염소화합물은 플라스틱의 종류, 그 혼합정도, 또는 첨가제 등에 따라 다양한 함량으로 존재하며, 통상적으로는 염소를 함유하는 폐플라스틱을 제거한 후 연료유를 제조하므로, 일반적인 경우의 염소화합물을 함유량은 대략 100ppm 내지 10000ppm 정도의 범위를 가지며, 염소 성분은 염산 및/ 또는 유기염소화합물이 될 수 있다.The chlorine compound contained in the fuel oil according to the present invention is present in various contents according to the type of plastic, the degree of mixing thereof, or an additive, and the fuel oil is prepared after removing the waste plastic containing chlorine. The content of the chlorine compound is in the range of about 100 ppm to about 10000 ppm, and the chlorine component may be hydrochloric acid and / or an organic chlorine compound.

도 1에 따른 본 발명은, 폐플라스틱을 열분해 한 후 회수한 연료유내에 포함되어 있는 10미크론 이상의 입자를 제거하는 백(bag) 필터 장치(90)에 의해 입자상 물질을 제거한 연료유 및 물-오일분리기(70)의 제1공간부(710)의 하부로부터 투입된 염기성수용액을 염소제거장치(200)내의 물-오일혼합기(80)의 상부로 유입시켜 혼합한 후, 화학정제장치(60)로 투입하여 교반기(630)에 의해 교반하면서 지속적으로 염소화합물을 제거하게 된다. 화학정제장치(60)에서 정제된 연료유는 물-오일분리기(70)로 유입되어 연료유와 수용을 상분리하여 연료유를 회수하여 염소가 제거된 연료유를 얻게되고, 통상의 정제단계를 진행하여 최종적으로 재생 연료유로 사용하게 된다.The present invention according to FIG. 1 is a fuel oil and water-oil from which particulate matter is removed by a bag filter device 90 for removing particles of 10 microns or more contained in fuel oil recovered after pyrolysis of waste plastic. The basic aqueous solution introduced from the lower portion of the first space portion 710 of the separator 70 is introduced into the upper portion of the water-oil mixer 80 in the chlorine removal device 200, mixed, and then introduced into the chemical purification device 60. The chlorine compound is continuously removed while stirring by the stirrer 630. The refined fuel oil in the chemical refining device 60 flows into the water-oil separator 70 to phase-separate the fuel oil and the water to recover the fuel oil, thereby obtaining a fuel oil from which chlorine is removed, and proceeding with a conventional refining step. Finally used as recycled fuel oil.

본 발명의 화학정제장치(60)는 상단부로부터 상기 물-오일 혼합기(80)로부터 유입되는 연료유 혼합물을 유입시키거나 또는 폐플라스틱의 분해에 의해 생성된 연료유와 물-오일분리기(70)의 제1공간부(710)의 저부로부터 유입되는 염기성수용액을 함께 유입시켜, 교반기에 의해서 염산 등의 산 성분을 포함하는 연료유를 염기성수용액과 접촉시켜 염소화합물을 반응시켜 물에 용해되게 함으로써 연료유 내의 염산 등의 염소성분을 제거하게 된다.The chemical refining apparatus 60 of the present invention introduces a fuel oil mixture introduced from the water-oil mixer 80 from an upper end portion of the fuel oil and water-oil separator 70 generated by decomposition of waste plastic. The basic aqueous solution flowing from the bottom of the first space portion 710 is introduced together, and the fuel oil containing an acid component such as hydrochloric acid is brought into contact with the basic aqueous solution by the stirrer to react the chlorine compound to dissolve in water. Chlorine components, such as hydrochloric acid, are removed.

본 발명의 물-오일 분리기(70)는, 염기성수용액이 일정 수위로 저장된 제1공간부(710)와 세로로 물-오일분리기를 분활하는 세로격벽(730) 및 세로격벽(730)에 의해 분리된 제2공간부(720)로 구성된다. 제1공간부(710)에는 일정수위로 염기성수용액이 저장되어 있으며, 화학정제장치(60)로부터 연료유와 수용액이 제1공간 부(710)에 유입되면, 연료유는 상승하고 수용액은 하강하여 상분리가 형성되고, 수용액의 수위가 일정수위에 도달하면 자동으로 염기성수용액은 제1공간부(710)의 하단으로부터 물-오일혼합기(80) 또는 화학정제장치(60)의 상단부로 유입되어 증류탑에서 유입되는 연료유와 접촉하여 염소를 제거하게 된다.The water-oil separator 70 of the present invention is separated by a vertical bulkhead 730 and a vertical bulkhead 730 dividing the water-oil separator vertically with the first space 710 in which the basic aqueous solution is stored at a predetermined level. The second space portion 720 is configured. The basic aqueous solution is stored in the first space portion 710 at a predetermined level. When the fuel oil and the aqueous solution flow into the first space portion 710 from the chemical purification apparatus 60, the fuel oil rises and the aqueous solution descends. Phase separation is formed, and when the water level of the aqueous solution reaches a certain level, the basic aqueous solution is automatically introduced from the bottom of the first space portion 710 into the water-oil mixer 80 or the upper end of the chemical purification device 60 in the distillation column Chlorine is removed in contact with the incoming fuel oil.

제1공간부(710)의 상부로 상승하여 상분리된 연료유는 세로격벽(730)의 높이보다 높을 경우 제2공간부(720)로 흘러들어가 하강하면서 일부 상분리되지 않은 수용액이 다시 상분리되어 수용액은 하부로 침강하고 연료유는 상부로 상승하면서 연료유를 회수하게 된다. 제1공간부에서 제2공간부로 이송될 경우 별도로 물-오일분리기의 상단부와 연결되고 하부로 뻗어 내려진 별도의 세로격벽(별도의 도시 않음)을 설치하여 제2공간부를 별도의 공간부로 형성하여 제1공간부로부터 이송되는 연료유가 제2공간부의 하부로부터 유입되게 하여 연료유는 상부로 상승하게 하고, 미량의 미분리된 수용액은 침강하도록 하는 것이 또한 좋다.When the fuel oil separated by the upper portion of the first space portion 710 is separated from the height of the vertical partition 730, the fuel oil flows into the second space portion 720 and descends while some of the non-phase separated aqueous solution is phase-separated again. It is settled to the bottom and the fuel oil is raised to the top to recover the fuel oil. When transferred from the first space portion to the second space portion, a separate vertical bulkhead (not shown) connected to the upper end of the water-oil separator and extended downward is installed to form the second space portion as a separate space portion. It is also preferable that the fuel oil conveyed from the one space portion flows in from the lower portion of the second space portion so that the fuel oil rises to the upper portion and the trace amount of the unseparated aqueous solution is settled.

또한 상기 물-오일 분리기(70)의 제2공간부는 그 중간부 또는 상부의 일측에 염소성분이 제거된 연료유를 배출하는 배출구(780)가 형성되며 저부에는 상분리된 수용액을 배출하는 염기성수용액 배출구(790)가 형성된다. In addition, the second space portion of the water-oil separator 70 has a discharge port 780 for discharging the fuel oil from which the chlorine component is removed at one side of the middle portion or the upper portion thereof, and a basic aqueous solution discharge hole for discharging the phase separated aqueous solution at the bottom portion. 790 is formed.

또한 물-오일 분리기(70)의 제1공간부(710)의 하단에는 사용된 염기성 수용액을 배출하거나 새로운 염기성 수용액을 주입할 수 있도록 염기성 수용액 유출입구(760)가 형성되어 있다.In addition, a basic aqueous solution outlet inlet 760 is formed at the bottom of the first space portion 710 of the water-oil separator 70 so as to discharge the used basic aqueous solution or inject a new basic aqueous solution.

또한 본 발명의 염소제거장치(200)는 화학정제장치(60)의 상부에 물-오일 혼합기(80)를 더 구비할 수 있다.In addition, the chlorine removal device 200 of the present invention may further include a water-oil mixer 80 on top of the chemical purification device (60).

상기 물-오일 혼합기(80)은 폐플라스틱을 분해하여 생산한 염소화합물이 제거되지 않은 연료유와 물-오일분리기(70)의 제1공간부(710)으로부터 유입되는 염기성수용액을 상부로부터 유입시키며, 상기 물-오일혼합기(80)의 내부는 상부에 시브(sieve)(810)이 구비되고, 하부에는 교반기(830)이 구비되어 있어, 2단계로 물-오일혼합기(80)로 유입되는 연료유와 염기성수용액이 접촉되어 혼합되도록 한다. 시브(810)은 밑면에 복수의 유출구가 형성되어 유입되는 연료유와 염기성수용액의 유량을 적절히 조절하여 시브에 일정수위로 유지되어 연료유와 염기성수용액의 접촉시간을 갖도록하고, 시브(810)의 하부의 유출구를 통과한 혼합물은 교반기(830)에 의해 교반되어 연료유와 염기성수용액을 더욱 접촉하도록, 즉 상기 혼합기의 상단의 유입구로 유입되는 염소함유 연료유 및 염기성 수용액이 시브(sieve)을 거치면서 1차 혼합된 후 하단에 구비된 교반기에 의해 2차 혼합된 후 물-오일혼합기의 하단에 구비된 배출구를 통해 화학정제장치(60)로 공급함으로써 염소함유 연료유에 염기성 수용액을 보다 효과적으로 접촉하도록 하여 염산등의 화합물 형태로 존재하는 염소의 제거 효율을 높일 수 있다.The water-oil mixer 80 introduces a fuel oil from which the chlorine compound produced by decomposing waste plastic and the basic aqueous solution flowing from the first space portion 710 of the water-oil separator 70 is introduced from above. The inside of the water-oil mixer 80 is provided with a sieve 810 at the upper portion and a stirrer 830 at the lower portion thereof, so that the fuel flows into the water-oil mixer 80 in two stages. Allow the oil and basic aqueous solution to contact and mix. The sieve 810 has a plurality of outlets formed at the bottom thereof to appropriately adjust the flow rate of the introduced fuel oil and the basic aqueous solution to maintain a constant water level in the sieve so as to have a contact time between the fuel oil and the basic aqueous solution. The mixture passing through the lower outlet is stirred by the stirrer 830 to further contact the fuel oil and the basic aqueous solution, that is, the chlorine-containing fuel oil and the basic aqueous solution flowing into the inlet at the top of the mixer are subjected to sieves. After the first mixing and the second mixing by a stirrer provided at the bottom and then supplied to the chemical purification device 60 through the outlet provided at the bottom of the water-oil mixer to give a basic aqueous solution to the chlorine-containing fuel oil more effectively Thus, the removal efficiency of chlorine present in the form of a compound such as hydrochloric acid can be improved.

이를 다시 설명하면, 염소함유 연료유가 물-오일 혼합기(80) 상단의 유입구로 유입됨과 동시에 염기성수용액인 예를 들면 NaOH 수용액은 물-오일 분리기(70)의 제1공간부(710)에 수용되어 있다가 하단의 배출구(750)로부터 펌프를 통해 물-오일 혼합기의 상단의 유입구로 유입된다. 유입된 연료유 및 NaOH 수용액은 시브(sieve)(810)를 통과하면서 1차 혼합되고 물-오일 혼합기 하단으로 이동하며 하단에 위치한 교반기(830)에 의해 2차 혼합된 후 배출구(840)를 통해 물-오일 혼합 물이 배출된다.In other words, the chlorine-containing fuel oil is introduced into the inlet of the upper portion of the water-oil mixer 80 and at the same time, for example, a basic aqueous solution of NaOH is contained in the first space portion 710 of the water-oil separator 70. From the outlet 750 at the bottom through the pump to the inlet at the top of the water-oil mixer. The introduced fuel oil and NaOH aqueous solution are first mixed while passing through a sieve 810 and then moved to the bottom of the water-oil mixer and secondly mixed by the stirrer 830 located at the bottom, and then through the outlet 840. The water-oil mixture is discharged.

상기 물-오일 혼합물은 화학정제장치(60)의 유입구로 유입되고 화학정제장치 내부의 교반기(630)에 의해 혼합되어 물-오일 접촉에 의해 연료유 내의 유기염소화합물의 염소 및 HCl 등의 염소성분이 NaOH 수용액과 반응하여 제거되어 물 층으로 추출된다. 이 때 반응이 원할히 이루어질 수 있도록 교반 속도, NaOH 농도, 온도 등을 조절할 수 있다.The water-oil mixture enters the inlet of the chemical refining device 60 and is mixed by the stirrer 630 inside the chemical refining device. The chlorine component, such as chlorine and HCl, of the organic chlorine compound in fuel oil by water-oil contact It is removed by reaction with an aqueous NaOH solution and extracted with a water layer. At this time, the reaction rate can be adjusted to adjust the stirring speed, NaOH concentration, temperature and so on.

이어서, 상기에서 설명하였듯이, 화학정제장치(60)에서 충분히 혼합되고 연료유와 NaOH 수용액의 반응이 이루어진 상태의 반응 혼합물인 물-오일 혼합물은 물-오일 분리기(70)로 유입하여 염기성 수용액 층과 염소성분이 제거된 연료유 층으로 상 분리가 이루어지고 위층의 연료유만을 종래의 연료유정제장치의 제1정제탱크(10)로 공급하게 된다.Subsequently, as described above, the water-oil mixture, which is a reaction mixture sufficiently mixed in the chemical purifier 60 and reacted with the fuel oil and the NaOH aqueous solution, flows into the water-oil separator 70 and the basic aqueous solution layer and Phase separation is performed to the fuel oil layer from which chlorine is removed, and only the upper fuel oil is supplied to the first purification tank 10 of the conventional fuel oil refinery device.

물-오일 분리기(70)의 일 형태에 대하여 더욱 상세히 설명하면, 탱크 내부 중간에 세로격벽(730)이 형성되어 탱크 내부의 공간을 상부가 연통되도록 제1공간부(710)와 제2공간부(720)로 이등분되어 있으며, 세로 격벽의 하부는 사선 형태로 기울어져 탱크 일측면과 접하도록 하여 탱크 하단의 염기성 수용액 저장 공간을 보다 넓게 확보할 수 있다. 제1공간부(710)에는 NaOH 수용액이 저장되고 제1공간부(710) 하단 일측에 화학정제장치에서 처리된 물-오일 혼합물이 유입되는 유입구(740)가 형성되어 있다. 상기 화학정제장치에서 처리된 물-오일 혼합물이 NaOH 수용액이 저장된 제1공간부의 유입구(740)로 유입이 되면 물-오일 혼합물의 물층과 오일층의 상분리가 이루어져 오일층이 제1공간부(710)의 NaOH 수용액층 상부에 형 성된다. 유입되는 물-오일 혼합물의 양이 증가하게 되면 오일층이 높이가 상승하고 결국에는 격벽(730)을 넘어 오일층이 제2공간부(720)로 이동하게 된다. 제2공간부(720)의 중단 일측에는 연료유 배출구(780)가 형성되어 있어 제2공간부로 이동한 염소 제거 연료유는 배출구(780)를 통해 제1정제탱크(10)로 공급하게 된다. 제2공간부(720)의 최하단에는 오일층과 함께 일부의 NaOH 수용액층이 넘어올 가능성이 있으므로 물층을 배출하기 위한 염기성 수용액 배출구(790)가 형성되어 있다.Referring to one embodiment of the water-oil separator 70 in more detail, a vertical partition 730 is formed in the middle of the tank so that the first space portion 710 and the second space portion communicate with the upper portion of the space inside the tank. It is divided into 720, and the lower portion of the vertical partition wall is inclined in an oblique form to contact with one side of the tank to secure a wider basic aqueous solution storage space at the bottom of the tank. NaOH aqueous solution is stored in the first space 710 is formed in the inlet 740 is introduced into the water-oil mixture treated in the chemical refining device on one side of the first space 710. When the water-oil mixture treated by the chemical refining apparatus is introduced into the inlet 740 of the first space portion in which the NaOH aqueous solution is stored, the water layer of the water-oil mixture is separated from the oil layer and the oil layer is formed in the first space portion 710. It is formed on top of NaOH aqueous solution layer. As the amount of the water-oil mixture introduced increases, the oil layer rises in height, and eventually the oil layer moves over the partition wall 730 to the second space portion 720. A fuel oil outlet 780 is formed at one end of the second space portion 720 so that the chlorine-removed fuel oil moved to the second space portion is supplied to the first purification tank 10 through the discharge port 780. At the lowermost end of the second space portion 720, a portion of the NaOH aqueous solution layer may pass along with the oil layer, and a basic aqueous solution outlet 790 for discharging the water layer is formed.

물-오일 분리기 탱크 제1공간부(710)에 저장된 NaOH 수용액은 제1공간부 하단에 형성된 염기성 수용액 배출구(750)로부터 NaOH 수용액을 펌프(770)에 의해 화학정제장치의 상단 유입구(640) 또는 물-오일 혼합기의 상단 유입구(850)로 주입할 수 있도록 연결되어 있다. 여러 번 사용을 하고 나서 NaOH 수용액의 농도가 달라진 경우에는 NaOH 수용액을 더 공급하거나 교체할 필요가 있는데, 물-오일 분리기 탱크 제1공간부(710)의 최하단에는 염기성 수용액 유출입구(760)가 형성되어 사용된 염기성 수용액을 배출하고 새로운 염기성 수용액을 주입할 수 있다.The NaOH aqueous solution stored in the water-oil separator tank first space 710 is pumped from the basic aqueous solution outlet 750 formed at the bottom of the first space 750 by the pump 770 to the upper inlet 640 of the chemical purifier or It is connected for injection into the top inlet 850 of the water-oil mixer. When the concentration of NaOH aqueous solution is changed after several times, it is necessary to supply or replace NaOH aqueous solution, and the basic aqueous solution outlet inlet 760 is formed at the bottom of the water-oil separator tank first space 710. The used basic aqueous solution can be discharged and fresh basic aqueous solution can be injected.

이하 실시예를 들어 본 발명을 보다 상세히 설명하나 하기 실시예에 의해서 본 발명의 범위가 한정되는 것은 아니다.The present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited by the following examples.

[실시예 1]Example 1

폐플라스틱을 열분해하여 얻어진 염소 성분의 총 함량이 1400ppm 인 임으로 제조한 저급 연료유를 동일한 함량의 2N NaOH 수용액과 함께 투입하여 400rpm으로 교반하면서 이들 혼합물을 화학정제장치에 공급하였다. The lower fuel oil prepared with the total content of chlorine component obtained by pyrolysis of waste plastic was 1400 ppm, was added together with an aqueous 2N NaOH solution of the same content and stirred at 400 rpm, and the mixture was fed to a chemical purifier.

화학정제장치의 온도는 50℃이고 2시의 채류시간의 유속으로 400rpm으로 교반 후, 이를 물-오일 분리기의 제1공간부 및 제 2공간부로 이송시켰으며, 제1공간부와 제2공간부의 채류시간은 각각 1시간으로 조절하여 염소성분을 제거한 재생연료유를 얻었다. 그 결과 얻어진 재생 염소성분이 제거된 연료유는 하기 표 1의 결과에서 보듯이 1회의 염소제거공정만으로도 염소성분을 50% 이상 감소시킬 수 있음을 알 수 있다. The temperature of the chemical refining apparatus was 50 ° C., and after stirring at 400 rpm at a flow rate of 2 o'clock, it was transferred to the first space portion and the second space portion of the water-oil separator. The holding time was adjusted to 1 hour to obtain regenerated fuel oil from which chlorine was removed. As a result, the obtained fuel oil from which the regenerated chlorine component was removed can be seen that the chlorine component can be reduced by 50% or more by only one chlorine removal process as shown in the results of Table 1 below.

[표 1]TABLE 1

Figure 112007033747904-pat00001
Figure 112007033747904-pat00001

[실시예 2]Example 2

실시예 1에 따르는 저급 연료유를 동일한 장치에서 동일한 유속으로 정제하는 경우, 염소제거장치(200)에서 정제조건을 변화시키면서 염소 제거효율에 대한 평가를 진행하였다. 이 때 변화시킨 조건을 제외하고는 실시예 1의 조건과 동일하게 진행하였다.When the lower fuel oil according to Example 1 was purified at the same flow rate in the same apparatus, the chlorine removal efficiency was evaluated in the chlorine removal apparatus 200 while changing the purification conditions. The same procedure as in Example 1 was conducted except for the changed conditions.

(1)염기성 수용액의 종류 및 농도(1) Types and concentrations of basic aqueous solutions

총염소 함량이 720ppm인 저급 연료유를 대상으로 염소제거 실험을 진행하되 염기성 수용액의 종류 및 농도를 하기 표 2와 같이 변화시켰다.Chlorine removal experiment was performed on the lower fuel oil having a total chlorine content of 720ppm, but the type and concentration of the basic aqueous solution were changed as shown in Table 2 below.

[표 2]TABLE 2

Figure 112007033747904-pat00002
Figure 112007033747904-pat00002

상기 표 1의 결과에 따르면 Ca(OH)2 수용액 및 NaOH 수용액을 모두 사용할 수 있으나 NaOH 수용액을 사용하는 경우 염소 제거 효율이 보다 높았다.According to the results of Table 1, both Ca (OH) 2 aqueous solution and NaOH aqueous solution can be used, but when NaOH aqueous solution was used, chlorine removal efficiency was higher.

(2)반응온도(2) reaction temperature

총염소 함량이 5730ppm인 연료유를 대상으로 염소제거 실험을 진행하되 반응온도를 하기 표 3과 같이 변화시켰다. The chlorine removal experiment was performed on fuel oil having a total chlorine content of 5730 ppm, but the reaction temperature was changed as shown in Table 3 below.

[표 3]TABLE 3

Figure 112007033747904-pat00003
Figure 112007033747904-pat00003

염소 제거효율은 반응 온도에 그다지 민감하지는 않으나 온도가 증가할수록 제거효율이 증가하는 현상을 보였다.The chlorine removal efficiency is not very sensitive to the reaction temperature, but the removal efficiency increases with increasing temperature.

(3)NaOH 수용액의 농도(3) Concentration of NaOH aqueous solution

총염소 함량이 5730ppm인 연료유를 대상으로 염소제거 실험을 진행하되 NaOH 농도를 하기 표 4와 같이 변화시켰다. The chlorine removal experiment was performed on the fuel oil having a total chlorine content of 5730 ppm, and the NaOH concentration was changed as shown in Table 4 below.

[표 4]TABLE 4

Figure 112007033747904-pat00004
Figure 112007033747904-pat00004

염소 제거효율은 NaOH 농도가 1N 이상에서 거의 비슷한 수준을 보였으며 1N 내지 4N 범위에서는 2N이 가장 효율이 좋았다.The chlorine removal efficiency was almost the same at NaOH concentration of 1N or more, and 2N was the most efficient in the range of 1N to 4N.

(4)화학정제장치에서의 교반시간(4) Stirring time in chemical purification equipment

총염소 함량이 1863ppm인 저급 연료유를 대상으로 염소제거 실험을 진행하되 화학정제장치에서 교반시간을 하기 표 5와 같이 변화시켰다.Chlorine removal experiment was carried out on the lower fuel oil having a total chlorine content of 1863 ppm, but the stirring time was changed as shown in Table 5 below.

[표 5]TABLE 5

Figure 112007033747904-pat00005
Figure 112007033747904-pat00005

염소 제거효율은 교반시간이 증가할수록 증가하는 경향을 나타내었다.Chlorine removal efficiency tended to increase with increasing stirring time.

(5)화학정제장치에서의 교반속도(5) Stirring speed in chemical purification equipment

총염소 함량이 2283ppm인 저급 연료유를 대상으로 염소제거 실험을 진행하되 화학정제장치에서 교반속도를 하기 표 6과 같이 변화시켰다. Chlorine removal experiment was carried out on the lower fuel oil with a total chlorine content of 2283 ppm, but the stirring speed was changed as shown in Table 6 below.

[표 6]TABLE 6

Figure 112007033747904-pat00006
Figure 112007033747904-pat00006

염소 제거효율은 교반속도가 증가할수록 비례적으로 증가하는 경향을 나타내었다.Chlorine removal efficiency tended to increase proportionally with increasing stirring speed.

(6)중화처리 횟수(6) Number of neutralization treatments

1회 중화처리하여 염소 함량이 716ppm인 연료유에 대하여 중화 횟수 즉, NaOH 수용액으로 처리하는 횟수 증가에 따른 염소제거 효율을 평가하여 그 결과를 하기 표 7에 나타내었다.The chlorine removal efficiency according to the increase in the number of neutralizations, that is, the number of treatments with an aqueous NaOH solution, was evaluated for the fuel oil having a chlorine content of 716 ppm by one neutralization treatment, and the results are shown in Table 7 below.

[표 7]TABLE 7

Figure 112007033747904-pat00007
Figure 112007033747904-pat00007

NaOH 수용액으로 처리하는 횟수를 2회로 한 경우 1회 처리한 것에 비해 매우 높은 염소 제거효율을 보였으며 처리 횟수를 증가할수록 염소 제거효율이 향상되는 경향을 보였다.In the case of two treatments with NaOH aqueous solution, the chlorine removal efficiency was significantly higher than the one treatment.

(7)NaOH 수용액량(7) NaOH aqueous solution amount

총염소 함량이 720ppm인 저급 연료유를 대상으로 염소제거 실험을 진행하되 NaOH 수용액량을 하기 표 8과 같이 변화시켰다.Chlorine removal experiment was performed on the lower fuel oil having a total chlorine content of 720ppm, but the amount of aqueous NaOH solution was changed as shown in Table 8 below.

[표 8]TABLE 8

Figure 112007033747904-pat00008
Figure 112007033747904-pat00008

NaOH 수용액량을 오일의 50%로 하는 경우가 오일의 20%보로 하는 경우에 비해 제거효율이 높게 나타났다.When the amount of aqueous NaOH solution was 50% of oil, the removal efficiency was higher than that of 20% of oil.

이상과 같은 본 발명의 연료유정제장치 환경 문제로 대두되는 PVC가 포함되는 혼합 폐플라스틱 또는 폐유를 처리한 연료유에 함유되어 있는 염소성분을 제거함으로써 염소 성분이 제거된 고품질의 연료유를 생성할 수 있는 효과를 가진다.As a fuel oil refiner of the present invention as described above, by removing the chlorine component contained in the mixed waste plastic or the waste oil treated fuel oil containing PVC, it is possible to generate high-quality fuel oil from which the chlorine component is removed. Has the effect.

한편, 상기 서술한 예는, 본 발명을 설명하고자하는 예일 뿐이다. 따라서 본 발명이 속하는 기술 분야의 통상적인 전문가가 본 상세한 설명을 참조하여 부분변경 사용한 것도 본 발명의 범위에 속하는 것은 당연한 것이다.In addition, the above-mentioned example is only an example to demonstrate this invention. Therefore, it is obvious that the ordinary skilled in the art to which the present invention pertains uses the partial change with reference to this detailed description.

Claims (16)

폐플라스틱, 폐합성수지, 폐고무 또는 폐유에서 선택되는 어느 한 성분을 열분해하고 증류하여 제조된 저급 연료유 및 염기성수용액을 교반에 의해 접촉 및 혼합하는 화학정제장치(60), 화학정제장치(60)에서 처리된 연료유와 염기성수용액의 혼합물을 수용하여 상 분리하여 연료유를 분리하는 물-오일분리기(70)를 가지고, 상기 물-오일분리기(70)는 내부 중간에 세로격벽(730)이 형성되어 분리기 내부의 공간을 상부가 연통 되도록 제1공간부(710)와 제2공간부(720)로 형성한 것을 특징으로 하는 염소제거장치(200)를 가지는 저급 연료유정제장치.Chemical refining device 60, chemical refining device 60 for contacting and mixing lower fuel oil and basic aqueous solution prepared by pyrolyzing and distilling any component selected from waste plastic, waste synthetic resin, waste rubber or waste oil by agitation. It has a water-oil separator (70) for separating the fuel oil by receiving a mixture of the fuel oil and the basic aqueous solution treated in the phase separation, the water-oil separator 70 has a vertical partition 730 is formed in the middle The lower fuel oil purification device having a chlorine removal device 200, characterized in that formed in the first space portion 710 and the second space portion 720 so as to communicate the space inside the separator. 제 1 항에 있어서,The method of claim 1, 상기 염소제거장치(200)는 화학정제장치(60) 상부에 저급연료유와 염기성수용액을 접촉하게 하는 물-오일혼합기(80)를 더 포함하는 것을 특징으로 하는 저급 연료유정제장치.The chlorine removal device 200 is a lower fuel oil purification device further comprises a water-oil mixer (80) for contacting the lower fuel oil and the basic aqueous solution on the chemical purification device (60). 제 2 항에 있어서,The method of claim 2, 상기 물-오일혼합기(80)는 그 내부에 상단부에는 시브(810)를 구비하여 저급연료유와 염기성수용액을 1차 접촉하게 하고, 하단부에는 교반기(830)를 구비하여 교반함으로써 2차 접촉하게 하는 것을 특징으로 하는 저급 연료유정제장치.The water-oil mixer 80 has a sheave 810 at the upper end thereof to make primary contact with the lower fuel oil and the basic aqueous solution, and has a stirrer 830 at the lower end thereof to make the secondary contact by stirring. Lower fuel oil refinery device, characterized in that. 제 1 항에 있어서,The method of claim 1, 상기 물-오일 분리기(70)의 제1공간부(710)의 저부에는 염기성 수용액이 저장되고, 제1공간부(710) 하단 일측에 화학정제장치(60)에서 처리된 연료유-염기성수용액 혼합물이 유입되어 상 분리된 연료유는 세로격벽(730)을 넘어 제2공간부로 이동됨으로써 연료유-염기성수용액의 상분리가 이루어지도록 하는 것을 특징으로 하는 저급 연료유 정제장치.The basic aqueous solution is stored at the bottom of the first space portion 710 of the water-oil separator 70, and the fuel oil-based aqueous solution mixture treated by the chemical refining device 60 at the lower side of the first space portion 710. The fuel oil separated by the introduced phase separation is moved to the second space portion beyond the vertical partition wall (730), so that the phase separation of the fuel oil-basic aqueous solution is made. 제 4항에 있어서,The method of claim 4, wherein 상기 제1공간부의 하단에는 물-오일혼합기(80) 또는 화학정제장치(60)로 유입되는 염기성수용액 배출구(750)가 구비되는 것을 특징으로 하는 저급 연료유 정제장치. Lower fuel oil refining device, characterized in that the lower portion of the first space is provided with a basic aqueous solution outlet (750) flowing into the water-oil mixer (80) or the chemical purification device (60). 제 5 항에 있어서,The method of claim 5, wherein 상기 제1공간부(710)의 하단에는 염기성 수용액 유출입구(760)가 형성되어 사용된 염기성 수용액을 배출하고 새로운 염기성 수용액을 주입할 수 있는 것을 특징으로 하는 저급 연료유 정제장치.The lower portion of the first space portion 710 is formed with a basic aqueous solution outlet inlet 760, the lower fuel oil refining apparatus, characterized in that it can discharge the used basic aqueous solution and inject a new basic aqueous solution. 제 1 항 내지 제 6항에서 선택되는 어느 한 항에 있어서,The method according to any one of claims 1 to 6, 상기 저급 연료유가 염소제거장치(200)에 유입되기 전에 백(bag)필터 장치(90)를 거쳐 고체상 입자가 제거하도록 하는 것을 특징으로 하는 저급 연료유 정 제장치.Lower fuel oil purification device, characterized in that to remove the solid particles through the bag (bag) filter device 90 before the lower fuel oil flows into the chlorine removal device (200). 제 7 항에 있어서,The method of claim 7, wherein 상기 염기성 수용액은 NaOH 수용액인 것을 특징으로 하는 연료유정제장치.The basic aqueous solution is a fuel oil refiner, characterized in that the NaOH aqueous solution. 폐플라스틱, 폐합성수지, 폐고무 또는 폐유에서 선택되는 어느 한 성분을 열분해하고 증류하여 제조된 저급 연료유 및 염기성수용액을 교반에 의해 접촉 및 혼합하는 화학정제장치(60), 화학정제장치(60) 상부에 형성되어 저급연료유와 염기성수용액을 미리 혼합하는 물-오일혼합기(80) 및 화학정제장치(60)에서 처리된 연료유와 염기성수용액의 혼합물을 수용하여 상 분리하여 연료유와 염기성수용액을 분리하여 연료유를 회수하는 물-오일분리기(70)를 가지는 염소제거장치(200)를 구비하는 저급 연료유 정제장치.Chemical refining device 60, chemical refining device 60 for contacting and mixing lower fuel oil and basic aqueous solution prepared by pyrolyzing and distilling any component selected from waste plastic, waste synthetic resin, waste rubber or waste oil by agitation. A mixture of fuel oil and basic aqueous solution formed in the upper portion, which is pre-mixed with the lower fuel oil and the basic aqueous solution, and the treated oil and the basic aqueous solution in the chemical refining device 60, is separated and phased into the fuel oil and the basic aqueous solution. Lower fuel oil refining apparatus having a chlorine removal device (200) having a water-oil separator (70) for separating and recovering fuel oil. 제 9항에 있어서,The method of claim 9, 상기 물-오일분리기(70)는 내부 중간에 세로격벽(730)이 형성되어 분리기 내부의 공간을 상부가 연통 되도록 제1공간부(710)와 제2공간부(720)로 형성한 것을 특징으로 하는 저급 연료유정제장치.The water-oil separator 70 has a vertical partition 730 formed in the middle of the interior, and the space inside the separator is formed by the first space portion 710 and the second space portion 720 so as to communicate with the upper portion. Low-grade fuel oil refiner. 제 10 항에 있어서,The method of claim 10, 상기 물-오일혼합기(80)는 그 내부에 상단부에는 시브(810)를 구비하여 저급 연료유와 염기성수용액을 1차 접촉하게 하고, 하단부에는 교반기(830)를 구비하여 교반함으로써 2차 접촉하게 하는 것을 특징으로 하는 저급 연료유정제장치.The water-oil mixer 80 has a sheave 810 at the upper end thereof to make primary contact with the lower fuel oil and the basic aqueous solution, and has a stirrer 830 at the lower end to make the secondary contact by stirring. Lower fuel oil refinery device, characterized in that. 제 10 항에 있어서,The method of claim 10, 상기 물-오일 분리기(70)의 제1공간부(710)의 저부에는 염기성 수용액이 저장되고, 제1공간부(710) 하단 일측에 화학정제장치(60)에서 처리된 연료유-염기성수용액 혼합물이 유입되어 상 분리된 연료유는 세로격벽(730)을 넘어 제2공간부로 이동됨으로써 연료유-염기성수용액의 상분리가 이루어지도록 하는 것을 특징으로 하는 저급 연료유 정제장치.The basic aqueous solution is stored at the bottom of the first space portion 710 of the water-oil separator 70, and the fuel oil-based aqueous solution mixture treated by the chemical refining device 60 at the lower side of the first space portion 710. The fuel oil separated by the introduced phase separation is moved to the second space portion beyond the vertical partition wall (730), so that the phase separation of the fuel oil-basic aqueous solution is made. 제 12항에 있어서,The method of claim 12, 상기 제1공간부의 하단에는 물-오일혼합기(80) 또는 화학정제장치(60)로 유입되는 염기성수용액 배출구(750)가 구비되는 것을 특징으로 하는 저급 연료유 정제장치. Lower fuel oil refining device, characterized in that the lower portion of the first space is provided with a basic aqueous solution outlet (750) flowing into the water-oil mixer (80) or the chemical purification device (60). 제 13 항에 있어서,The method of claim 13, 상기 제1공간부(710)의 하단에는 염기성 수용액 유출입구(760)가 형성되어 사용된 염기성 수용액을 배출하고 새로운 염기성 수용액을 주입할 수 있는 것을 특징으로 하는 저급 연료유 정제장치.The lower portion of the first space portion 710 is formed with a basic aqueous solution outlet inlet 760, the lower fuel oil refining apparatus, characterized in that it can discharge the used basic aqueous solution and inject a new basic aqueous solution. 제 9 항 내지 제 14항에서 선택되는 어느 한 항에 있어서,The method according to any one of claims 9 to 14, 상기 저급 연료유가 염소제거장치(200)에 유입되기 전에 백(bag)필터 장치(90)를 거쳐 고체상 입자가 제거하도록 하는 것을 특징으로 하는 저급 연료유 정제장치.Lower fuel oil refining device, characterized in that to remove the solid particles through the bag filter device (90) before the lower fuel oil flows into the chlorine removal device (200). 제 15 항에 있어서,The method of claim 15, 상기 염기성 수용액은 NaOH 수용액인 것을 특징으로 하는 연료유정제장치.The basic aqueous solution is a fuel oil refiner, characterized in that the NaOH aqueous solution.
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