KR20020048350A - The catalytic composition to stimulate cracking reaction in oil process of utilizing waste synthetic resins - Google Patents
The catalytic composition to stimulate cracking reaction in oil process of utilizing waste synthetic resins Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- 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
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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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1003—Waste materials
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4087—Catalytic distillation
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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Abstract
Description
본 발명은 폐합성수지를 이용한 유화공정시 크래킹반응을 촉진시키는 촉매 조성물에 관한 것으로, 보다 상세하게는 폐비닐이나 폐플라스틱 등과 같은 폐석유화학제품을 이용하여 휘발유와 경유 등을 제조하는 유화공정시, 용해로내에 일정온도로 열을 가하여 고분자화합물인 폐수지를 저분자화합물 상태의 탄화수소류로 분해하는 크랭킹반응에 있어, 상기 크래킹반응을 더욱 더 촉진시켜 빠른 시간내에 액체와 기체로 이루어진 저분자 탄화수소류의 혼합유상태로 분해하도록 하는 촉매 조성물에 관한 것이다.The present invention relates to a catalyst composition for promoting a cracking reaction during the emulsification process using waste synthetic resin, more specifically, during the emulsification process for producing gasoline and diesel using waste petrochemical products such as waste vinyl or waste plastic, In the cranking reaction to decompose the polymer resin waste resin into low molecular weight hydrocarbons by applying heat to a certain temperature in the melting furnace, the cracking reaction is further promoted, and the mixed oil state of low molecular hydrocarbons composed of liquid and gas in a short time. It relates to a catalyst composition for decomposition into.
석유화학공업의 발달로 현대를 살아가는 인류의 일상생활에 비닐, 플라스틱등을 이용한 합성수지제품이 다양한 생활용품으로 제조되고 있는데, 이러한 합성수지제품들은 사용자들에게 주는 편리함 등의 많은 장점에도 불구하고, 소각시 유독물질의 발생, 자연상태에서의 난분해성 등으로 인해 수질오염, 토양오염, 대기오염을 일으키는 주된 원인이 되고 있어 상기의 폐합성수지에 대한 처리가 심각한 사회문제로 대두되고 있다.Synthetic resin products using vinyl, plastic, etc. are being manufactured into various household products in the daily life of human beings living in modern times due to the development of petrochemical industry.In spite of many advantages such as convenience for users, Due to the generation of toxic substances and difficult degradability in the natural state, it is the main cause of water pollution, soil pollution, air pollution, the treatment of the waste synthetic resins has emerged as a serious social problem.
상기 석유화학제품은 1869년 미국의 하이아트가 발명한 셀룰로이드로부터 시작된 이후 많은 발전을 거듭하여 페놀수지, 요소수지, 스틸렌수지, 초산비닐수지, 염화비닐수지, 폴리에틸렌, 폴리에스테르 등의 다양한 합성수지가 개발이 되고 있는데, 이러한 석유화학제품은 크게 열가소성 수지와 열경화성 수지로 분류된다.Since the petrochemical products started from the celluloid invented by Hiart in the United States in 1869, a lot of developments have been made, and various synthetic resins such as phenol resin, urea resin, styrene resin, vinyl acetate resin, vinyl chloride resin, polyethylene, and polyester have been developed. These petrochemical products are largely classified into thermoplastic resins and thermosetting resins.
상기 열가소성 수지는 가열하면 연화되어 가소성이 생기지만 원래의 고체로 돌아가는 고분자 화합물로서, 재료자체는 이미 고분자 화합물로 되어 있으나 그 구조가 일차원적인 쇄상으로 되어 있어 가열하면 쉽게 연화하고 유동성을 일으키며, 용융된 상태에서는 화학적 반응을 전혀 일으키지 않고, 단지 물리적으로 녹아 있어 이를 냉각하면 본래의 물질로 돌아가는 합성수지이다.The thermoplastic resin is softened by heating to generate plasticity but returns to the original solid. The material itself is already made of a high molecular compound, but its structure is one-dimensional chain, and when heated, it softens easily and causes fluidity. It is a synthetic resin that does not cause any chemical reactions at all, but only physically melts and cools down to its original substance.
상기 열경화성 수지는 가열하면 경화되고 일단 경화되면 아무리 가열하여도 연화되거나 용매에 녹지 않는 고분자 화합물로서, 원래 재료 자체의 분자량은 그다지 크지 않으며, 가열하면 연화하고 마침내는 유동성을 나타내나 가열을 계속하면 간단한 분자가 떨어지면서 축합이 일어나 나중에는 고분자 화합물을 형성하게 되는 합성수지인데, 그 구조는 삼차원 망상구조로 형성되어 있다.The thermosetting resin is a polymer compound that hardens when heated and does not soften or dissolve in a solvent even if it is hardened once heated. The molecular weight of the original material itself is not very large, softens when heated, and finally shows fluidity, but when heated continues, It is a synthetic resin that condenses as molecules fall and later forms high molecular compounds. The structure is formed in a three-dimensional network.
상기에서 언급한 바와 같이 합성수지제품의 사용용도가 소멸된 폐합성수지처리의 경우 심각한 환경오염의 문제가 있어 국내외 대부분의 국가에서는 재처리시설이나 공정에 대한 많은 연구가 이루어지고 있으며, 이러한 폐합성수지의 재활용방법으로는 폐합성수지 분말을 용융시킨 후 사출기를 통해 새로운 합성수지제품으로 재생하는 방법이 있는데, 이러한 단순 물리적 변환만을 통한 폐합성수지 재생은 이용성에 한계가 있다는 문제점이 있다,As mentioned above, in the case of waste synthetic resin treatment in which the use of synthetic resin products has disappeared, there is a serious environmental pollution problem. Therefore, many researches on reprocessing facilities and processes have been conducted in most countries at home and abroad. As a method, there is a method of melting waste synthetic resin powder and then recycling it to a new synthetic resin product through an injection molding machine. However, there is a problem in that waste synthetic resin recycling through only a simple physical conversion has a limitation in availability.
또 다른 재활용방법으로는 일정한 조건하에서 폐합성수지의 구성성분인 고분자 탄화수소 화합물을 분해 및 변형시켜 저분자의 탄화수소 화합물인 휘발유나 경유 등을 제조할 수 있는 화학적인 방법이 있는데, 최근에는 후자의 재활용방법에 대한 실용성이 우수하여 이에 대한 연구가 활발하게 진행되고 있다.Another recycling method is a chemical method for producing gasoline or diesel, which is a low molecular hydrocarbon compound, by decomposing and modifying a high molecular hydrocarbon compound as a component of waste synthetic resin under certain conditions. Due to its excellent practicality, research on this is being actively conducted.
따라서, 상기 화학적인 방법에 의한 폐합성수지의 재활용방법에 대한 선출원된 자료를 토대로 내용을 간단하게 종합해보면, 폐합성수지의 원료는 석유이며, 일상생활에서 에너지원으로 사용되고 있는 휘발유, 경유, 액화가스 등도 석유로부터 추출된 것인데, 상기 폐합성수지의 경우는 분자량이 큰 고분자 화합물로 되어 있으며, 그 성분은 탄소와 수소의 결합으로 이루어져 있고, 상기 휘발유, 경유 등은 분자량이 적은 고분자 화합물로 되어 있으며, 그 성분도 역시 탄소와 수소의 결합으로 이루어져 있다.Therefore, to summarize the contents on the basis of the previously filed data on the recycling method of the waste synthetic resin by the chemical method, the raw material of the waste synthetic resin is petroleum, gasoline, diesel, liquefied gas, etc. that are used as an energy source in daily life Extracted from petroleum, the waste synthetic resin is made of a high molecular weight polymer compound, the component is composed of a combination of carbon and hydrogen, the gasoline, diesel, etc. are made of a high molecular weight polymer compound, It also consists of a combination of carbon and hydrogen.
상기 양자는 분자가 모두 탄소와 수소로 이루어져 있고, 차이점은 분자량의 크기가 다른 것인데, 이에 따라 분자량의 전환에 의해 폐합성수지는 휘발유, 경유 등으로 전환될 수 있으므로 폐합성수지와 같은 분자량이 큰 고체석유를 액체화하여 크래킹하면 액체와 기체로 구성된 석유로 전환할 수 있게 된다.The two molecules are all composed of carbon and hydrogen, the difference is that the molecular weight is different, according to the conversion of the molecular weight, the waste synthetic resin can be converted to gasoline, diesel, etc. Liquefying and cracking can convert it into petroleum consisting of liquid and gas.
상기 크래킹반응은 끊는점이 높고 분자량이 큰 탄화수소를 분자량이 작은 탄화수소로 분해하는 공정으로, 열분해법, 접촉분해법, 수소화분해법으로 분류되는데, 이러한 크래킹방법의 공통된 반응을 보면, 일정한 온도에서 탄화수소 원자사이의 연결 사슬이 길면 길수록 탄소와 탄소, 탄소와 수소원자 사이의 연결사슬이 쉽게 끊어지게 되며, 탄소원자 연결사슬이 짧을수록 쉽게 끊어지게 되며, 이러한 연결사슬이 끊어지려면 더 높은 온도가 필요하게 된다.The cracking reaction is a process of decomposing a hydrocarbon having a high breaking point and a large molecular weight into a hydrocarbon having a low molecular weight. The cracking reaction is classified into a pyrolysis method, a catalytic cracking method, and a hydrocracking method. The longer the chain, the more easily the link between carbon and carbon, carbon and hydrogen atoms is broken, the shorter the carbon atom link chain is, the easier it is to break.
폐플라스틱의 경우 1,000∼10,000개의 탄소 연결사슬로 된 탄화수소이기 때문에, 용융되는 과정에서 탄소원자 연결사슬이 일정한 크기로 끊어지며 이것이 계속 반응하여 원하는 저분자 탄화수소류의 휘발유나 경유 등을 제조하려면 일정한 온도가 필요하게 된다. 즉, 탄화수소에서 탄소원자 연결사슬이 끊어지는 반응은 분해반응으로서, 이에 생성된 물질은 분자량이 비교적 작은 하나의 메탄계 탄화수소와 다른 하나의 에틸렌계 탄화수소 분자로 된다.Since waste plastics are hydrocarbons of 1,000 to 10,000 carbon linking chains, the carbon atom linking chains are broken to a certain size during the melting process, and these reactions continue to react to produce desired gasoline or diesel of low molecular hydrocarbons. It is necessary. In other words, the reaction of breaking the carbon atom linking chain in the hydrocarbon is a decomposition reaction, and the resulting material is composed of one methane-based hydrocarbon and one ethylene-based hydrocarbon molecule having a relatively low molecular weight.
열과 촉매를 이용하여 크래킹반응을 하는 접촉분해법이 열분해법에 비해 분해속도가 빠르며, 질이 좋은 옥탄값 높은 가솔린을 얻을 수 있어 최근에는 소정의 석유분해 촉매하에서 고온으로 분해, 증류시켜 저비등점 탄화수소류를 추출하고 있는데, 이러한 촉매의 종류와 그 처리시기 및 방법 등의 차이에 의해 최종 분해되는 산물의 성분별 회수율 및 그 품질에 지대한 영향을 미치게 되기 때문에 고분자 탄화수소 화합물을 가장 효율적으로 분해, 증류시켜 저분자 탄화수소 화합물로 추출할 수 있도록 하는 촉매의 필요성이 대두되고 있다.The catalytic cracking reaction using heat and catalyst is faster than the pyrolysis method, and the gasoline can be obtained with high quality octane gasoline.In recent years, low boiling point hydrocarbons can be decomposed and distilled at a high temperature under a petroleum cracking catalyst. However, due to the difference in the type of catalyst, the processing time and the method of the catalyst, the recovery rate and the quality of each component of the final decomposition products have a great effect, so that the high molecular weight hydrocarbon compound is most efficiently decomposed and distilled. There is a need for a catalyst that allows extraction with hydrocarbon compounds.
본 발명은 상기의 제약을 극복하기 위해 안출한 것으로, 용해로내의 일정온도 이하의 일반 상압하에서 폐합성수지를 크래킹반응 시킬 때, Mg3(Si4010)(OH)2+ SiC + AlO(Al2O3) + MgO + SiO2가 일정비율로 배합된 촉매 조성물를 폐합성수지 분말과 접촉시켜 분해반응을 촉진시키도록 하여 크래킹 반응속도를 향상시키고, 최종 산출되는 고부가가치의 휘발유와 경유 등의 순도와 생산량 증산을 위한 중간 혼합유를 추출할 수 있도록 하는데 목적이 있다.The present invention has been made to overcome the above limitations, Mg 3 (Si 4 0 10 ) (OH) 2 + SiC + AlO (Al 2 when cracking the waste synthetic resin under normal atmospheric pressure below a certain temperature in the furnace The catalyst composition containing O 3 ) + MgO + SiO 2 in contact with the waste synthetic resin powder is contacted with the waste synthetic resin powder to promote the decomposition reaction, thereby improving the cracking reaction rate, and the final purity and production of high value gasoline and diesel oil. The aim is to be able to extract intermediate mixed oils for transpiration.
상기의 목적을 달성하기 위하여 온도 400℃ 이하의 일반 상압하에서 열분해 공정시, 용해로내에 폐합성수지와 촉매를 1:4∼5/1000비율로 투입하되, 상기 촉매는 Mg3(Si4010)(OH)2: 40 중량%, SiC : 15 중량%, AlO(Al2O3) : 10 중량%, MgO :15 중량%, SiO2: 20 중량%로 조성되는 폐합성수지를 이용한 유화공정시 크래킹반응을 촉진시키는 촉매 조성물을 구현하고자 한 것이다.In order to achieve the above object, during the pyrolysis process under a normal atmospheric pressure of 400 ° C. or less, waste synthetic resin and a catalyst are introduced into a furnace at a ratio of 1: 4 to 5/1000, and the catalyst is Mg 3 (Si 4 0 10 ) ( OH) 2 : 40 wt%, SiC: 15 wt%, AlO (Al 2 O 3 ): 10 wt%, MgO: 15 wt%, SiO 2 : 20 wt% Cracking reaction during emulsification using waste synthetic resin It is to implement a catalyst composition to promote the.
도1은 본 발명을 이용하는 유화 제조장치의 전체 개략도1 is an overall schematic view of an oil painting apparatus using the present invention;
*도면의 주요부분에 대한 부호설명** Description of Signs of Main Parts of Drawings *
1. 원료공급장치2. 용해로Raw material supply device 2. Melting furnace
본 발명은 고분자 탄화수소 화합물인 폐합성수지를 유화장치를 통해 저분자 탄화수소 화합물인 휘발유와 경유 등의 고품질 에너지원으로 환원함에 있어, 폐합성수지인 석유화학원료의 주성분인 탄소와 수소로 조성된 고분자의 분자고리를 끊어 탄소가 주성분인 저분자의 물질로 분해시키는 크래킹공정시 열분해와 촉매분해의 복합공정으로 이루어지도록 한 것이다.In the present invention, in order to reduce waste synthetic resin, which is a high molecular hydrocarbon compound, to a high-quality energy source such as gasoline and diesel, which is a low molecular hydrocarbon compound, the molecular ring of a polymer composed of carbon and hydrogen, which are the main components of petrochemical raw materials, which are waste synthetic resins In the cracking process in which carbon is decomposed into a low-molecular substance composed mainly of carbon, it is composed of a combined process of pyrolysis and catalytic decomposition.
본 발명에 의한 촉매를 사용하여 고분자 탄화수소류의 폐합성수지를 휘발유와 경유 등의 저분자 탄화수소류로 환원시키는 유화 제조장치에서 실시되는 과정을도면을 참조하여 살펴보면, 다음과 같다.Looking at the process performed in the emulsion production apparatus for reducing the waste synthetic resin of the polymer hydrocarbons to low molecular hydrocarbons, such as gasoline and diesel, using the catalyst according to the present invention.
도1은 본 발명을 이용하는 유화 제조장치의 전체 개략도이고, 미도시부호 3은 용해로 가열버너, 4는 냉각탑, 5는 혼합유 유수분리기, 6은 냉각탱크, 7은 정제로, 8은 냉각탑, 9는 휘발유 유수분리기, 10은 경유 유수분리기, 11은 정제탱크, 12는 완제품 저장탱크, 13. 냉각탱크, 14는 버너유 탱크이다.1 is an overall schematic view of an emulsion production apparatus using the present invention, 3 is a furnace heating burner, 4 is a cooling tower, 5 is a mixed oil oil / water separator, 6 is a cooling tank, 7 is a purification, 8 is a cooling tower, 9 Is a gasoline oil separator, 10 is a diesel oil separator, 11 is a refinery tank, 12 is a finished product storage tank, 13. a cooling tank, and 14 is a burner oil tank.
첫번째 단계는 원료공급단계로서, 폐합성수지를 용해로(2)에 투입할 수 있도록 잡질을 제거한 후, 일정크기 이하로 파쇄된 폐합성수지 분말을 호퍼와 스크류로 이루어진 원료공급장치(1)를 통해 상기 용해로(2)에 연속적으로 투입할 수 있도록 한다.The first step is a raw material supply step, after removing miscellaneous matter so that the waste synthetic resin can be introduced into the melting furnace (2), the waste synthetic resin powder shredded to a predetermined size or less through the raw material supply device (1) consisting of a hopper and a screw; Allow continuous injecting in (2).
두번째 단계는 크래킹단계로서, 용해로(2) 하단에 위치한 용해로 가열버너(3)를 통해 상기 용해로(2)의 온도를 높여주어 온도가 상승함에 따라 용해로(2)내의 폐합성수지가 액체화되고, 원료 투입후 일정시점에 투입된 촉매가 열분해 반응을 촉진시켜 고분자 구조의 폐합성수지를 저분자상태의 탄화수소류로 분해하도록 하는데, 이 때 투입되는 촉매의 양은 원료의 양의 0.5∼0.9%까지 넣게 되며, 원료 자체에 고유한 휘발유와 경유성분 중에 어느 일방의 생산량을 증산하고자 할 때 적절하게 가감하면 되며, 이 때의 용해로 가열버너(3)를 통해 용해로(2)에 전달되는 온도는 400℃ 이하에서 폐합성수지내의 유분을 추출할 수 있도록 한다.The second step is a cracking step, in which the waste synthetic resin in the melting furnace 2 is liquefied as the temperature increases by raising the temperature of the melting furnace 2 through the melting furnace heating burner 3 located at the bottom of the melting furnace 2, and inputting raw materials. The catalyst introduced at a certain time promotes the pyrolysis reaction to decompose the waste synthetic resin of polymer structure into hydrocarbons of low molecular weight, and the amount of catalyst added is 0.5 to 0.9% of the amount of the raw material, In order to increase the production of one of the inherent gasoline and diesel fuel components, it is appropriate to add or subtract appropriately, and at this time, the temperature of the oil in the waste synthetic resin at 400 ° C. or lower is transmitted to the melting furnace 2 through the melting furnace burner 3. To be extracted.
세번째 단계는 용해로(2) 내에서 열분해와 촉매분해된 저분자 탄화수소류들이 용해로(2) 상단에 연결된 이송관을 통해 냉각탱크(6)에서 혼합유상태로 1차 냉각되고, 미처 액화되지 않은 가스를 최종 액화시켜 주는 2차 냉각탑(4)을 통해 혼합유 유수분리기(5)에 저장되는데, 이 때 생성된 혼합유를 즉시 버너나 보일러용으로 사용해도 된다.In the third stage, the pyrolyzed and catalyzed low molecular hydrocarbons in the furnace (2) are first cooled in a mixed oil state in the cooling tank (6) through a transfer pipe connected to the top of the furnace (2), and finally the unliquefied gas is returned. The liquefied secondary cooling tower (4) is stored in the mixed oil oil / water separator (5). The mixed oil produced at this time may be used immediately for a burner or a boiler.
네번째 단계는 혼합유 유수분리기(5)에 저장된 혼합유를 펌프를 통해 정제로(7)로 이송한 후, 정제로(7) 하단의 가열버너를 통해 370℃까지 가열하도록 한다.The fourth step is to transfer the mixed oil stored in the mixed oil oil water separator (5) to the refinery (7) through a pump, and then to heat up to 370 ℃ through a heating burner at the bottom of the refinery (7).
다섯번째 단계는 정제로(7)의 온도상승에 따라 2차 냉각탑(8)을 통한 혼합유내의 휘발유성분과 경유성분이 비등점 차이에 의해 분리되는데, 이를 210℃ 정도에서 구분하여 전자 제어변을 통해 휘발유 유수분리기(9)와 경유 유수분리기(10)로 각각 분리 생산되는데, 휘발유와 경유의 생산비율은 P.S와 폐유류, 폐윤활유의 경우 8:2, 그 외의 수지류는 5:5로 이며, 생산되는 기름의 색깔이 짙어지면, 용해로 가열버너(3)를 15분 가량 정지시켜 용해로(2)내의 온도를 250℃ 가량 내려준 상태에서 교반기에 무리가 가지 않도록 수회 왕복회전을 시켜 용해로(2)내에 생성된 잡질을 배출구를 통해 외부로 배출시킨다.In the fifth step, the gasoline components and the diesel fuel components in the mixed oil through the secondary cooling tower 8 are separated by the boiling point difference according to the temperature rise of the refinery 7, and they are separated at about 210 ° C. through an electronic control valve. The gasoline oil separator (9) and the diesel oil / oil separator (10) are separately produced. The production ratios of gasoline and diesel oil are 8: 2 for PS, waste oil, waste lubricant, and 5: 5 for other resins. When the color of the oil produced becomes dark, the melting furnace heating burner (3) is stopped for about 15 minutes, and the temperature in the melting furnace (2) is lowered by about 250 ° C. The miscellaneous material generated in the inside is discharged to the outside through the outlet.
여섯번째 단계는 최종 정제단계로서, 필터작동 등으로 잡질, 탈색, 플라스틱 냄새를 제거하여 최종적인 휘발유와 경유를 추출할 수 있도록 한다.The sixth step is the final refining step, which removes miscellaneous, discolored and plastic odors by the filter operation so that the final gasoline and diesel oil can be extracted.
본 발명에 원료로 사용되는 폐합성수지 제품은 모든 열가소성 수지 즉, P.E, P.P, P.E.T, P.S, P.V.D.C, A.B.S 등을 원료로 생산된 폐비닐, 스치로폴 등의 폐포장제, P.P, BAG, 폴리에스텔 옷감류, 각종 음료수병류, 장난감 등 헤아릴 수 없을 정도로 방대하고, 환원비율도 우수하여 열경화성 수지에 비해 바람직하다.The waste synthetic resin products used as raw materials in the present invention are all thermoplastic resins, that is, waste packaging agents such as PE, PP, PET, PS, PVDC, ABS, etc. It is enormously large, and various kinds of beverage bottles, toys, etc., and excellent in reduction ratio are preferable compared with thermosetting resin.
본 발명에 사용되는 촉매는 일정크기로 파쇄된 폐합성수지 분말을 호퍼와 스크류로 이루어진 원료공급장치(1)를 통해 용해로(2)내에 공급하고, 용해로 가열버너(3)로 상기 용해로(2)를 가열하되, 온도를 400℃ 이하를 유지할 수 있도록 하여 열분해가 이루어지도록 하며, 상기의 열분해에 의한 크래킹반응시, 본 발명에 의해 조성된 촉매를 투입하여 분해반응이 급속하게 진행되어 탄소 연결사슬이 순식간에 끊어지게 되면서 고분자의 탄화수소류가 저분자의 상태로 분해하게 되는데, 저비점 탄화수소의 생산을 증가시킬 뿐만 아니라 방향성 및 분지형 탄화수소의 함량을 증가시키고, 왁스성분을 감소시켜 고옥탄가의 양질의 휘발유를 다량으로 생산할 수 있도록 한다.The catalyst used in the present invention supplies the waste synthetic resin powder shredded to a predetermined size into the melting furnace 2 through a raw material supply device 1 consisting of a hopper and a screw, and the melting furnace 2 with a melting furnace heating burner 3. While heating, it is possible to maintain the temperature of 400 ℃ or less so that pyrolysis occurs, and in the cracking reaction by the thermal decomposition, the decomposition reaction proceeds rapidly by inputting the catalyst prepared according to the present invention, carbon connection chain is instantaneously As it breaks down, the hydrocarbons of the polymer decompose into a low molecular state, which not only increases the production of low-boiling hydrocarbons, but also increases the content of aromatic and branched hydrocarbons, and reduces the wax content, thereby producing a large amount of high-quality gasoline of high octane number. To produce.
이 때, 폐합성수지와 촉매의 비율은 1:4∼5/1000 정도를 유지하도록 하되, 제품을 제조할 당시 투입된 약품 및 오일의 정도에 따라 비율을 일정하게 조정할 수도 있으며, 상기 촉매의 성분과 배합비율을 보면, 다음과 같이 조성되어 있다.At this time, the ratio of the waste synthetic resin and the catalyst is to maintain about 1: 4 ~ 5/1000, the ratio may be constantly adjusted according to the degree of the chemicals and oils added at the time of manufacturing the product, and the composition and the composition of the catalyst Looking at the ratio, it is as follows.
Mg3(Si4010)(OH)2: 40 중량%Mg 3 (Si 4 0 10 ) (OH) 2 : 40 wt%
SiC : 15 중량%SiC: 15 wt%
AlO(Al2O3) : 10 중량%AlO (Al 2 O 3 ): 10 wt%
MgO :15 중량%MgO: 15 wt%
SiO2: 20 중량%SiO 2 : 20 wt%
본 발명에 의해 폐합성수지가 휘발유와 경유로 촉매분해되는 열분해 과정을살펴보면, 다음과 같다.Looking at the pyrolysis process in which the waste synthetic resin is catalytically decomposed into gasoline and diesel fuel according to the present invention.
상기 촉매분해를 통해 환원되는 혼합유의 성분 중 C5H12∼C12H24는 연료로 사용할 수 있는 휘발유 가스의 성분이고, C12H26∼C20H42는 경유 성분이며, 상기 휘발유 성분인 C5H12∼C12H24의 비등점의 범위는 25∼195℃이며, 상기 경유 성분인 C12H26∼C20H42의 비등점의 범위는 195∼375℃인데, 상기 혼합유 중에 비등점의 특성 차이를 이용하여 휘발유와 경유로 분류하여 생산할 수 있도록 한다.Among the components of the mixed oil reduced through the catalytic decomposition, C 5 H 12 to C 12 H 24 are components of a gasoline gas that can be used as a fuel, and C 12 H 26 to C 20 H 42 is a gas oil component, The boiling point of C 5 H 12 to C 12 H 24 is in the range of 25 to 195 ° C., and the boiling point of C 12 H 26 to C 20 H 42 , which is the light oil component, is 195 to 375 ° C. The difference in characteristics is used to produce gasoline and diesel.
본 발명에 의한 촉매를 통해 분해반응된 상기 혼합유는 분자구조상 C5H12∼C30H62의 탄화수소류의 물질로, 포화 및 불포화 탄화수소, 방향족 탄화수소와 기타 복잡한 복소환식 화합물의 혼합물을 포함하고 있는데, 원료로 사용한 폐합성수지의 종류가 다르기 때문에 실제로 석유제품의 화합물의 함량은 불균일하다고 볼 수 있지만, 상기 화합물의 기본성분이 포화 탄화수소, 불포화 탄화수소, 방향족 탄화수소 및 그 유도체이며, 이 성분들은 일반 원유보다 유분의 특성치가 우수하다.The mixed oil decomposed through the catalyst according to the present invention is a hydrocarbon material of C 5 H 12 to C 30 H 62 in molecular structure, and includes a mixture of saturated and unsaturated hydrocarbons, aromatic hydrocarbons and other complex heterocyclic compounds. Although the content of the waste synthetic resin used as a raw material is different, the content of the compound of the petroleum product is actually uneven, but the basic components of the compound are saturated hydrocarbons, unsaturated hydrocarbons, aromatic hydrocarbons and derivatives thereof. The characteristic value of oil is more excellent.
상기 혼합유 중 석유류 비등점에 따른 평균 분자량(MCP)를 살펴보면, 표1과 같다.Looking at the average molecular weight (MCP) according to the boiling point of the petroleum oil in the mixed oil, it is shown in Table 1.
상기 혼합유 제품에 따른 평균 분자량을 살펴보면, 표2와 같다.Looking at the average molecular weight according to the mixed oil product, it is shown in Table 2.
이상에서 설명한 본 발명은, 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자에 있어 본 발명의 기술적 사상을 벗어나지 않는 범위내에서 여러 가지 치환, 변형 및 변경이 가능하므로 전술한 실시례 및 첨부된 도면에 한정되는 것이 아니다.The present invention described above is capable of various substitutions, modifications, and changes without departing from the technical spirit of the present invention for those skilled in the art to which the present invention pertains. It is not limited to the drawings.
본 발명은 폐합성수지를 사용하여 열분해반응시, 저온 상압하의 상태에서 분해반응 속도를 향상시키도록 하는 일정비율로 배합된 촉매를 투입하여 폐합성수지와 접촉되게 함으로써, 상기 폐합성수지가 빠른 시간내에 분해되어 오일과 가스형태의 혼합유상태로 환원되게 하여 고품질의 옥탄값이 높은 휘발유와 경유를 추출할 수 있도록 하고, 환경오염의 주범이 되고 있는 폐합성수지를 다시 고품질의 에너지원으로 환원할 수 있어 에너지 재생 및 환경오염을 방지할 수 있는 효과가 있다.In the present invention, the waste synthetic resin is decomposed within a short time by contacting the waste synthetic resin by adding a catalyst mixed in a proportion to improve the decomposition reaction rate at a low temperature and atmospheric pressure during thermal decomposition using waste synthetic resin. It is reduced to mixed oil and gaseous state to extract gasoline and light oil with high octane value, and it is possible to reduce waste synthetic resin which is the main cause of environmental pollution to high quality energy source. It is effective to prevent environmental pollution.
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| KR20020048350A true KR20020048350A (en) | 2002-06-22 |
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| KR1020020027761A KR20020048350A (en) | 2002-05-20 | 2002-05-20 | The catalytic composition to stimulate cracking reaction in oil process of utilizing waste synthetic resins |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101385104B1 (en) * | 2011-12-31 | 2014-04-18 | 주식회사 우주테크 | Oil recycling apparatus using waste vinyl |
| KR20240040320A (en) | 2022-09-21 | 2024-03-28 | 이순걸 | Waste disposal equipment using emulsification process |
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|---|---|---|---|---|
| JPH06312137A (en) * | 1993-04-30 | 1994-11-08 | Mazda Motor Corp | Manufacture of cracking catalyst |
| JPH08253773A (en) * | 1995-03-17 | 1996-10-01 | Mitsui Eng & Shipbuild Co Ltd | Method of pyrolyzing plastic and plastic pyrolysis catalyst for use therein |
| KR100188160B1 (en) * | 1989-12-29 | 1999-06-01 | 윌리암 제랄드 딕 | Cracking catalyst having enhanced vanadium passivation and sulfur tolerance |
| KR20000036903A (en) * | 2000-03-31 | 2000-07-05 | 김태환 | Pyrolysis waste recycling method and system |
| WO2001005908A1 (en) * | 1999-07-16 | 2001-01-25 | Enercon Technologies, Inc. | A process for producing gasoline and diesel from waste plastics and/or heavy oil |
| KR100322663B1 (en) * | 2000-03-20 | 2002-02-07 | 곽호준 | Continuous Preparing Method for Gasoline, Kerosene and Diesel Using Waste Plastics and System thereof |
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2002
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100188160B1 (en) * | 1989-12-29 | 1999-06-01 | 윌리암 제랄드 딕 | Cracking catalyst having enhanced vanadium passivation and sulfur tolerance |
| JPH06312137A (en) * | 1993-04-30 | 1994-11-08 | Mazda Motor Corp | Manufacture of cracking catalyst |
| JPH08253773A (en) * | 1995-03-17 | 1996-10-01 | Mitsui Eng & Shipbuild Co Ltd | Method of pyrolyzing plastic and plastic pyrolysis catalyst for use therein |
| WO2001005908A1 (en) * | 1999-07-16 | 2001-01-25 | Enercon Technologies, Inc. | A process for producing gasoline and diesel from waste plastics and/or heavy oil |
| KR100322663B1 (en) * | 2000-03-20 | 2002-02-07 | 곽호준 | Continuous Preparing Method for Gasoline, Kerosene and Diesel Using Waste Plastics and System thereof |
| KR20000036903A (en) * | 2000-03-31 | 2000-07-05 | 김태환 | Pyrolysis waste recycling method and system |
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| Title |
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| 한국화학공학회 2001년 가을 학술대회, 구병준, 한국에너지기술연구원 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101385104B1 (en) * | 2011-12-31 | 2014-04-18 | 주식회사 우주테크 | Oil recycling apparatus using waste vinyl |
| KR20240040320A (en) | 2022-09-21 | 2024-03-28 | 이순걸 | Waste disposal equipment using emulsification process |
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