Korean Chemical Engineering Research

The Korean Institute of Chemical Engineers (한국화학공학회)
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The Effects of Zeolite-Type Catalysts on the Pyrolysis Reaction of Raw Material Resin to Produce Fuel-Oil from Waste Vinyl

폐 농업용 비닐 수지에서 연료유 생성을 위한 원료 수지의 열분해 반응에서 제올라이트계 촉매의 영향

  • Bak, Young-Cheol (Department of Chemical & Biological Engineering/Engineering Research Institute,Gyeongsang National University) ;
  • Choi, Joo-Hong (Department of Chemical & Biological Engineering/Engineering Research Institute,Gyeongsang National University) ;
  • Cho, Tae-Ho (Department of Chemical & Biological Engineering/Engineering Research Institute,Gyeongsang National University)
  • 박영철 (경상대학교 생명화학공학과 공학연구원) ;
  • 최주홍 (경상대학교 생명화학공학과 공학연구원) ;
  • 조태호 (경상대학교 생명화학공학과 공학연구원)
  • Received : 2009.03.27
  • Accepted : 2009.05.04
  • Published : 2009.06.30
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Abstract

The effects of zeolite type catalysts addition on the thermal decomposition of low density polyethylene(LDPE) and ethylene vinyl acetate(EVA) resin have been studied in a thermal analyzer(TGA, DSC) and a small batch reactor. The zeolite type catalysts tested were natural zeolite, FCC catalyst, used FCC catalyst, and catalyst A. As the results of TGA experiments, addition of antifogging-agent decreased the pyrolysis point to $250^{\circ}C$, but addition of longevity-agent and clay reduced the pyrolysis rate in EVA resin. Addition of the zeolite type catalysts in the LDPE resin increased the pyrolysis rate in the order of catalyst A > used FCC catalyst > natural zeolite > LDPE resin. Addition of the zeolite type catalysts in the EVA resin increased the pyrolysis rate in the order of used FCC catalyst > natural zeolite > catalyst A > EVA resin. In the DSC experiments for LDPE resin, addition of zeolite type catalysts decreased the melting point and the heat of pyrolysis reaction in the order of catalyst A > used FCC catalyst > natural zeolite> LDPE resin. In the batch system experiments, the mixing of natural zeolite enhanced the yield of liquid fuel oil.

폐 농업용 비닐을 이용한 연료유 생산 공정을 위한 저밀도폴리에틸렌(LDPE)과 에틸렌비닐아세테이트(EVA) 수지에 대한 열분해 반응 실험을 하였다. 질소 분위기에서 상온에서 $650^{\circ}C$까지의 비등온 조건에서의 열분석기(열중량분석기, 시차주사열량계)와 $420^{\circ}C$의 배치형 반응기에서 무촉매 반응과 천연제올라이트, FCC 촉매, 폐 FCC 촉매, 중국 촉매(촉매 A) 등의 제올라이트계 촉매를 사용한 열분해가 행하여졌다. TGA 실험에서 무적제가 첨가된 EVA 수지는 열분해 개시 온도가 $250^{\circ}C$ 근처로 매우 낮아졌으나, 황토와 장수제 첨가는 열분해를 다소 지연시켰다. LDPE에서 제올라이트 계열 촉매는 촉매 A>폐 FCC 촉매>천연제올라이트>LDPE의 순으로 열분해 반응속도를 높이는데 유효하였다. EVA에서 제올라이트 계열 촉매 첨가 시는 폐 FCC 촉매>천연제올라이트>촉매 A>EVA 수지의 순으로 열분해 반응을 촉진시켰다. DSC 실험에서 제올라이트 계열 촉매 첨가 시 촉매 A>폐 FCC 촉매>천연제올라이트>LDPE의 순으로 융해개시 온도와 열분해열이 낮아졌다. 회분식 실험에서 천연제올라이트 첨가 시 시료 중 가장 높은 액상의 연료유 생성수율을 얻었다.

Keywords

Acknowledgement

Supported by : 산업자원부

References

  1. Park, J. J., Park, K., Park, J. W. and Kim, D. C., "Characteristics of LDPE Pyrolysis," Korean J. Chem. Eng., 19(4), 658-662(2002) https://doi.org/10.1007/BF02699313
  2. Jang, N. P., Park, J. W. and Seo, G., 'Liquid-phase Degradation of Waste Agricultural Film over Used-FCC Catalyst,' HWAHAK KONGHAK, 41(6), 694-699(2003)
  3. Seo, G., "Production Method of Catalysts for Liquid-phase Catalytic Degradation of Waste Polymer Material from Used FCC Process Catalyst and Catalytic Degradation," Korea Patent, 2003-0035638(2003)
  4. Seo, G., "Production Method of Catalysts for Liquid-phase Catalytic Degradation of Waste Polymer Material and Catalytic Degradation," Korea Patent, 2002-0046027(2002)
  5. Park, D. W., "Catalysts for Pyrolysis of Waste Plastic and Pyrolysis Method," Korea Patent, 2000-0043100(2000)
  6. Lee, K. H. and Shin, D. H., "Influence of Plastic Type and Pyrolysis of Waste Thermoplastics into Oil Recovery," J. Korea Society of Waste Management, 21(6), 646-661(2004)
  7. Kim, D. C. and Woo, J. K., 'Effect of Thermal and Catalytic Decomposition Condition on Decomposition Lapse Time and Oil Quality in Plastic Wastes into Fuel Oil,' J. of KSEE, 26(11), 1232-1237 (2004)
  8. Marcilla, A., Beltran, M. and Conesa, J. A., "Catalyst Addition in Polyethylene Pyrolysis Thermogravimetric Study," Journal of Analytical and Applied Pyrolysis, 58-59, 117-126(2001) https://doi.org/10.1016/S0165-2370(00)00162-5
  9. Marcilla, A., Gomez, A. and Menargues, S., "TGA/FTIR Study of the Evolution of the Gases Evolved in the Catalytic Pyrolysis of Ethylene-vinyl Acetate Copolymers. Comparison among Different Catalysts," Polymer Degradation and Stability, 89, 454- 460(2005) https://doi.org/10.1016/j.polymdegradstab.2005.01.024
  10. Kim, D. C., Woo, J. K. and Nho, N. S., 'Evaluation of Oil Qulity in Thermal and Catalytic Decomposition of Waste Plastics into Fuel Oil,' J. Korea Society of Waste Management, 22(8), 765-773 (2005)
  11. Sakata, Y., Uddin, M. A. and Muto, A., "Degradation of Polyethylene and Polypropylene into Fuel Oil by using Solid Acid and Non-acid Catalysts," Journal of Analytical and Applied Pyrolysis, 51, 135-155(1999) https://doi.org/10.1016/S0165-2370(99)00013-3
  12. Uddin, M. A., Koizumi, K., Murata, K. and Sakata, Y., "Thermal and Catalytic Degradation of Structually Different Types of Polyethylene into Fuel Oil," Polymer Degradation and Stability, 56, 37-44(1997) https://doi.org/10.1016/S0141-3910(96)00191-7
  13. Onu, P., Vasile, C., Ciocilten, S., Iojoju, E. and Darie, H., "Thermal and Catalytic Decomposition of Polyethylene and Polypropylene," Journal of Analytical and Applied Pyrolysis, 49, 145-153(1999) https://doi.org/10.1016/S0165-2370(98)00109-0
  14. Serrano, D. P., Aguado, J., Escola, J. M., Garagorri, E., Rodriguez, J. M., Morselli, L., Palazzi, G. and Orsi, R., "Feedstock Recycling of Agriculture Plastic Film Wasted by Catalytic Cracking," Applied Catalysis, B Environmental, 49, 257-265(2004) https://doi.org/10.1016/j.apcatb.2003.12.014
  15. Manos, G., Yusof, I. Y., Papayannakos, N. and Gangas, N. H., "Catalytic Cracking of Polyethylene over Clay Catalysts. Comparison with an Ultrastable Y Zeolite," Ind. Eng. Chem. Res., 40, 2220-2225(2001) https://doi.org/10.1021/ie001048o
  16. Bak, Y. C., Choi, J. H. and Kim, N. K., 'A Comparision Study of LDPE Pyrolysis over Resin Additives and Inorganic Compounds of Silica Alumina Type,' J. of KSEE, 28, 596-602(2006)
  17. Gobin, K. and Manos, G., "Polymer Degradation to Fuels over Microporous Catalysts as a Novel Tertiary Plastic Recycling Method," Polymer Degradation and Stability, 83, 267-279(2004) https://doi.org/10.1016/S0141-3910(03)00272-6