열중량 분석 기법을 통한 RDF의 열분해 특성 조사

Study on the Pyrolysis Kinetics of RDF(Refuse Derived Fuel) with Thermogravimetric Analysis

  • 김동원 (한전전력연구원 녹색성장연구소) ;
  • 이종민 (한전전력연구원 녹색성장연구소) ;
  • 김재성 (한전전력연구원 녹색성장연구소)
  • Kim, Dong-Won (Green Growth Laboratory, Korea Electric Power Research Institute, KEPCO) ;
  • Lee, Jong-Min (Green Growth Laboratory, Korea Electric Power Research Institute, KEPCO) ;
  • Kim, Jae-Sung (Green Growth Laboratory, Korea Electric Power Research Institute, KEPCO)
  • 투고 : 2009.08.21
  • 심사 : 2009.09.28
  • 발행 : 2009.12.31

초록

본 연구에서는 국내 원주에서 생산되고 있는 RDF의 열분해 특성을 조사하기 위해 열중량 분석기(TGA)를 이용하여 비등온 실험(10, 20, $30^{\circ}C/min$)을 수행하여 분석하였다. 다양한 성분의 물질을 함유한 RDF는 승온 속도에 따라 차이가 있으나, 대체로 $350{\sim}700^{\circ}C$ 사이에서 열분해 및 연소되었으며, 최대 열분해 반응속도를 나타내는 온도는 석탄의 그것에 비해 매우 빠름을 알 수 있었다. Friedman 및 Flynn-Wall-Ozawa의 방법을 이용하여 평균한 활성화에너지 값은 각각 14.44, 18.40 kcal/mol이었으며, Friedman의 방법을 통해 반응 차수는 1.219, 빈도인자 $3.02{\times}10^5(s^{-1})$의 값을 얻었다. 또한 Coats Redfern의 방법을 통해 앞서 계산한 활성화에너지 값과의 유사성을 비교하여 고체상의 연소반응 메커니즘을 판단할 경우, 개별 입자들 사이에서 하나의 핵에서 핵화되는 반응인 1차 화학 반응($F_1$)이 가장 유사한 반응 메커니즘으로 판단되었다.

Devolatilization of the Refuse Derived Fuel(RDF) which is produced at WonJu in Korea was characterized in air atmosphere with variation of heating rate(10, 20 and $30^{\circ}C/min$) in TGA. The results of TG Analysis have shown that the pyrolysis and char combustion of the RDF occurred in the range of $350{\sim}700^{\circ}C$ depending on the heating rate. Activation energy of the RDF which was determined by using Friedman and Ozawa-Flynn-Wall method was in the range of 14.44~18.40 kcal/mol. Also, reaction order(n) and pre-exponential factors(A) were 1.219 and $3.02{\times}10^5$ by using Friedman method, respectively. In order to find out the devolatilization mechanism of the RDF, twelve solid-state mechanisms defined by Coats Redfern Method were tested. The results of the Coats Redfern Method have shown that chemical reaction is the effective mechanism by comparison with the value of the activation energy which was derived from the Friedman and Flynn-Wall-Ozawa method and correlation coefficient from twelve solid-state mechanisms of Coats Redfern Method. The solid state decomposition mechanism of the RDF was found to be a decelerated $F_1$ type, random nucleation with one nucleus on the individual particle.

키워드

참고문헌

  1. KEMCO Renewable Energy Center: 2007 Renewable Energy Statistics, 3-15(2009)
  2. MOCIE Report, The Study of 10-year National Basic Plan for New & Renewable Energy Technology Development, Dissemination, 53-57(2003)
  3. New and Renewable Energy Report, Waste Energy, 13-31(2005)
  4. Choi, Y. S., 'Coal/RDF Co-combustion in the Circulation Fluidized Bed Coal Boiler,' Journal of Korea Society of Waste Management, 24(7), 598-603(2007)
  5. Kim, D. W., Lee, J. M. and Kim, J. S., 'Co-combustion of Refused Derived Fuel with Anthracites in a CFB Boiler,' 20th International Conference on FBC, 262-270(2009)
  6. Bae, D. H. and Shun, D. W., 'Development of Circulating Fludized Bed Boiler for Refused Derived Fuel,' 31th KOSCO Symposium, 71-77(2005)
  7. Sun, J. T., Huang, Y. D., Gong, G. F. and Cao, H. L., "Thermal Degradation Kinetics of Poly(methylphenysiloxane) Containing Methacryloyl Groups", Polym. Degrad. Stabil., 91, 339-346(2006) https://doi.org/10.1016/j.polymdegradstab.2005.04.037
  8. Friedman, H. L., 'Kinetics of Thermal Degradation of Char-forming Plastics from Thermogravimetry. Application to a Phenolic Plastic,' J. Polym. Sci., 6(1), 183-195(1964) https://doi.org/10.1002/polc.5070060121
  9. Ozawa, T., "A New Method of Analyzing Thermogravimetric Data," Bull. Chem. Soc. Jap., 38(11), 1881-1886(1965) https://doi.org/10.1246/bcsj.38.1881
  10. Flynn, J. H. and Wall, L. A., 'General Treatment of the Thermogravimetry of Polymers,' Journal of Research of the National Bureau of Standards-A, Physics and chemistry, 70A(6), 487-523 (1966) https://doi.org/10.6028/jres.070A.043
  11. Coats, A. W. and Redern, J. P., "Kinetics Parameters from the Thermogravimetric Data," Nature(Lond), 201, 68-69(1964) https://doi.org/10.1038/201068a0
  12. Shin, I. S., Kim, U. Y., Sung, M. S., Kang, Y., Yoon, B. T. and Choi, M. J., 'Investigation on Pyrolysis Characteristics of Waste Polystyrene Plastics(Yakult Bottles) Using TGA', Journal of Korea Society of Waste Management, 25(1), 36-42(2008)
  13. Lee, J. M., Kim, D. W. and Kim, J. S., "Reactivity Study of Combustion for Coals and Chars in Relation to Volatile Content," KJChE, 26(2), 489-495(2008) https://doi.org/10.1007/s11814-009-0083-0
  14. Yorulmaz, S. Y. and Atimtay, A. T., 'Investigation of Combustion Kinetics of Treated and Untreated Waste Wood Samples with Thermogravimetric Analysis,' Fuelsci. Technol. Int., 90, 939-946(2009) https://doi.org/10.1016/j.fuproc.2009.02.010