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열공정에서 페놀류로부터 Polychlorinated dibenzo-p-dioxins(PCDDs)과 Polychlorinated dibenzofurans(PCDFs)의 생성에 관한 연구[I]
A Study of Polychlorinated dibenzo-p-dioxins(PCDDs) and Polychlorinated dibenzofurans(PCDFs) Formation from Phenols in Thermal Process[I]

류재용   (대구경북연구원 환경연구팀CC0126997  ); 서정민   (국립 부산대학교 지역환경시스템UU0000613  ); 박정호   (국립 진주산업대학교 환경공학과UU0000228  );
  • 초록

    페놀류 전구물질로부터 형성된 polychlorinated dibenzo-p-dioxins(PCDDs)와 dibenzofurans(PCDFs)의 모든 동족체와 이성질체의 경향을 페놀과 19개의 염화페놀류의 분포를 이용하여 연구하였다. 실험은 $400^{\circ}C$ (particle-mediated formation)와 $600{\sim}700^{\circ}C$ (gas-phase formation)에서 각각 행하여 졌으며, 운반가스로 사용된 가스의 조성은 92%의 질소와 8%의 산소를 사용하였다. 염소기가 없는 dibenzo-p-dioxin(DD)와 dibenzofuran(DF)를 포함한 모든 종류의 PCDDs와 PCDFs의 동족체와 이성질체들이 20개의 페놀류를 혼합하여 사용한 본 실험으로부터 얻어졌다. 가스상 실험은 PCDFs가 많이 생성하였고, 입자상 실험에서는 PCDDs를 많이 생성 하였다. 가장 많이 생성된 동족체는 각각 DD와 DF였으며, 염소기의 숫자가 증가할수록, 동족체의 생성량은 감소하였다. 하지만 가스상과 입자상 실험에서 얻어진 PCDDs와 PCDFs의 동족체와 이성질체의 분포는 거의 항상 일정하였다. 고농도로 존재하는 페놀과 적은수의 염소기를 가지고 있는 염화 페놀류의 농도가 가스상과 입자상에서 발생하는 PCDDs와 PCDFs의 분포에 아주 중요한 역활을 하였다.


    Homologue and isomer patterns of polychlorinated dibenzo-p-dioxins(PCDDs) and polychlorinated dibenzofurans(PCDFs) congeners formed from phenols in the gas-phase at $600{\sim}700^{\circ}C$ and via particle-mediated reactions at $400^{\circ}C$ were studied in an isothermal flow reactor. A mixture of 20 phenols in relative concentrations found in a municipal waste incinerator(MWI) stack gas was used for this study. PCDDs and PCDFs homologue and isomer patterns obtained from the phenol. From the phenol experiments, gas-phase formation at $600{\sim}700^{\circ}C$ favors PCDFs formation whereas particle-mediated formation at $400^{\circ}C$ favors PCDDs formation. DD and DF were most abundant homologue groups, PCDDs and PCDFs homologue fraction decreased with increasing number of chlorine substituents. PCDDs and PCDFs homologue and isomer fractions were almost constant from gas-phase formation and particle-mediated formation. Unsubstituted phenol, which was present in high concentration, played a significant role in the formation of PCDD/Fs congeners under both sets of experimental conditions.


  • 주제어

    다이옥신 .   퓨란 .   염화페놀 .   동족체와 이성질체 분포.  

  • 참고문헌 (31)

    1. Altwicker, E. R., 'Relative rates of formation of polychlorinated dioxins and furans from precursors and de novo reactions,' Chemosphere, 33, 1897 - 1904( 1996) 
    2. Huang, H. and Buekens, A., 'On the mechanisms of dioxin formation in combustion processes,' Chemosphere, 31, 4099-4117(1995) 
    3. Schramm, K. W., Wehrmeier, A., Lenoir, D., Henkel-mann, B., Hahn, K., Zimmermann, R., and Kettrup, A., 'Deduction of a typical pattern for the isomers of tetrato heptachloro-dibenzo-p-dioxins and -furans formed in combustion processes,' Organohalogen Compd., 27, 196-200(1996) 
    4. Wikstrom, E. and Marklund, S., 'Secondary formation of chlorinated dibenzo-p-dioxins, dibenzofurans, biphenyls, benzenes and phenols during MSW combustion,' Environ. Sci. Technol., 34, 604-609(2000) 
    5. Hell, K., Stieglitz, L., Altwicker, E. R., Addink, R., and Will, R., 'Reactions of 2,4,6-trichlorophenol on model fly ash: Oxidation to CO and $CO_2$, condensation to PCDD/F and conversion into related compounds,' Chemosphere, 42, 697-702(2001) 
    6. Jay, K. and Stieglitz, L., 'Identification and quantification of volatile organic components in emissions of waste incineration plants,' Chemosphere, 30, 1249-1260 (1995) 
    7. Xie, Y., Xie, W., Uu, K., Dickson, L., Pan, W.-P., and Riley, J. T., 'The effect of sulfur dioxide on the formation of molecular chlorine during co-combustion of fuels,' Energy Fuels, 14, 597-602(2000) 
    8. Ryu, J.-Y. and Mulholland, J. A., 'Metal-mediated chlorinated dibenzo-p-dioxin and dibenzofuran formation from phenols,' Chemosphere, 58, 977 - 988(2005) 
    9. Tuppurainen, K., Asikainen, A., Ruokojarvi, P., and Ruuskanen, J., 'Perspectives on the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans during municipal solid waste(MSW) incineration and other combustion processes,' Ace. Chem. Res., 36, 652-658(2003) 
    10. lino, F., Imagawa, T., Takeuchi, M., and Sadakata, M., 'De novo synthesis mechanism of polychlorinated dibenzofurans from polycyclic aromatic hydracarbons and the characteristic isomers of polychlorinated naphthalenes,' Environ. Sci. Technol., 33, 1038 -1043(1999) 
    11. Dickson, L. C., Lenoir, D., and Hutzinger, O., 'Surfacecatalyzed formation of chlorinated dibenzodioxins and dibenzofurans during ncineration,' Chemosphere, 19, 277-(1989) 
    12. Tuppurainen, K., Ruokojarvi, P., Asikainen, A., Marjaleena Aatamila., and Ruuskanen, J., 'Chlorophenols as precursors of PCDD/Fs in incineration processes: correlations, PLS modeling, and reaction mechanisms,' Environ. Sci. Technol., 34, 4958 - 4962(2000) 
    13. Zimmermann, R., Blumenstock, M., Heger, H. J., Schramm, K.-W., and Kettrup, A., 'Emission of nonchlorinated and chlorinated aromatics in the flue gas of incineration plants during and after transient disturbances of combustion conditions: delayed emission effects,' Environ. Sci. Technol., 35, 1019-1030(2001) 
    14. Nakahata, D.- T. and Mulholland, J. A., 'Effect of dichlorophenol substitution pattern on furan and dioxin formation,' P. Combust. Inst., 28, 2701 - 2707(2000) 
    15. Ryu, J.-Y., Mulholland, J. A., and Chu, B., 'Chlorination of dibenzofuran and dibenzo-p-dioxin vapor by copper (II) chloride,' Chemosphere, 51, 1031-1039(2003) 
    16. Luijk, R., Akkerman, D., Slot, P., Olie, K., and Kepteijn, F., 'Mechanism of formation of polychlorinated dibenzo-z-dioxins and dibenzofurans in the catalysed combustion of carbon,' Environ. Sci. Technol., 28, 312-321(1994) 
    17. Ballschrnitter, K., Zoller, W., Buchert, H., and Class, Th., 'Correlation between substitution pattern and reaction pathway in the formation of polychlorodibenzofurans,' Fres. Z. Anal. Chem., 322, 587-(1985) 
    18. Wehrmeier, A., Lenoir, D., Schramm, K.-W., Zimmermann, R, Hahn, K., Henkelmann, B., and Kettrup, A., 'Patterns of isomers of chlorinated dibenzo-p-dioxins as tool for elucidation of thermal formation mechanism,' Chemosphere, 36, 2775 - 2801 (1998) 
    19. Ballschmitter, K., Braunmiller, I., Niemczyk, R., and Swerev, M., 'Reaction pathways for the formation of polychloro-dibenzodioxins(PCDD) and -dibenzofurans(PCDF) in combustion processes: II. Chlorobenzenes and chlorophenols as precursors in the formation of polychloro-dibenzodioxins and -dibenzofurans in flame chemistry,' Chemosphere, 17, 995-1005(1988) 
    20. Born, J. G. P., Mulder, P., and Louw, R., 'Fly ash mediated reactions of phenol and monochlorophenols: oxychlorination, deep oxidation, and condensation,' Environ. Sci. Technol., 27, 1849-1863(1993) 
    21. Addink, R., Cnubben, P. A. J. P., and Olie, K., 'Formation of polychlorinated dibenzo-p-dioxins/dibenzofumas on fly ash from precursors and carbon model compounds,' Carbon, 33, 1463 -1471(1995) 
    22. lino, F., Imagawa, T., and Gullett, B., 'Dechlorinationcontrollea polychlorinated dibenzo-furan isomer patterns from municipal waste incinerators,' Environ. Sci. Technol., 34, 3143-3147(2000) 
    23. Cains, P. W., Mccausland, L. J., Fernandes, A. R., and Dyke, P., 'Polychlorinated dibenzo-p-dioxins and dibenzofurans formation in incineration: Effects of fly ash and carbon source,' Environ. Sci. Technol., 31, 776-785 (1997) 
    24. Weber, Rand Hagenmaier, H., 'PCDD/PCDF formation in fluidized bed incineration,' Chemosphere, 38, 2643-2654(1999) 
    25. Mulholland, J. A. and Ryu, J.-Y., 'Formation of polychlorinated dibenzo-p-dioxins by $CuCl_2-catalyzed$ condensation of 2,6 chlorinated phenols,' Combust. Sci. Technol., 169, 107-126(2001) 
    26. Sidhu, S. S., Maqsud, L., Dellinger, B., and Mascolo, G., 'The homogeneous, gas-phase formation of chlorinated and brominated dibenzo-p-dioxin from 2,4,6-trichloroand 2,4,6-tribromophenols,' Combust. Flame, 100, 11-20(1995) 
    27. Ryu, J.-Y. and Mulholland, J. A., 'Dioxin and furan formation on $CuCl_2$ from chlorinated phenols with one ortho chlorine,' Proc. Combust. Inst., 29, 2455 - 2461(2002) 
    28. Altwicker, E. R. and Milligan, M. S., 'Formation of dioxins: Competing rates between chemically similar precursors and de novo reactions,' Chemosphere, 27, 301-307(1993) 
    29. Stieglitz, L. and Vogg, H., 'On formation conditions of PCDD/PCDF in fly ash from municipal waste incinerators,' Chemosphere, 16, 1917-1922(1987) 
    30. Ryu, J.-Y., Mulholland, J. A., Dunn, J. E., lino, F., and Gullett, B. K., 'Potential Role of Chlorination Pathways in PCDD/F Formation in a Municipal Waste Incinerator,' Environ. Sci. Technol., 38, 5112-5119(2004) 
    31. Dempsey, C. R. and Oppelt, E. T., 'Incineration of Hazardous Waste: A Critical Review Update,' Air & Waste, 43, 25-73(1993) 

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