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POLYCHLORINATED NAPHTHALENE (PCN) AND DIBENZOFURAN (PCDF) CONGENER PATTERNS FROM PHENOL PRECURSORS IN THERMAL PROCESS: [I] A PRIORI HYPOTHESIS OF PCN AND PCDF FORMATION PATHWAYS FROM MONOCHLOROPHENOLS
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  • Journal title : Environmental Engineering Research
  • Volume 11, Issue 4,  2006, pp.217-231
  • Publisher : Korean Society of Environmental Engineering
  • DOI : 10.4491/eer.2006.11.4.217
 Title & Authors
POLYCHLORINATED NAPHTHALENE (PCN) AND DIBENZOFURAN (PCDF) CONGENER PATTERNS FROM PHENOL PRECURSORS IN THERMAL PROCESS: [I] A PRIORI HYPOTHESIS OF PCN AND PCDF FORMATION PATHWAYS FROM MONOCHLOROPHENOLS
Ryu, Jae-Yong; Kim, Do-Hyong; Choi, Kum-Chan; Suh, Jeong-Min;
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 Abstract
The gas-phase formation of polychlorinated naphthalenes (PCNs) and dibenzofurans (PCDFs) was experimentally investigated by slow combustion of the three chlorophenols (CPs): 2-chlorophenol (2-CP), 3-chlorophenol (3-CP) and 4-chlorophenol (4-CP), in a laminar flow reactor over the range of 550 to under oxidative condition. Contrary to the a priori hypothesis, different distributions of PCN isomers were produced from each CP. To explain the distributions of polychlorinated dibenzofuran (PCDF) and PCN congeners, a pathway is proposed that builds on published mechanisms of PCDF formation from chlorinated phenols and naphthalene formation from dihydrofulvalene. This pathway involves phenoxy radical coupling at unsubstituted ortho-carbon sites followed by CO elimination to produce dichloro-9, 10-dihydrofulvalene intermediates. Naphthalene products are formed by loss of H and/or Cl atoms and rearrangement. The degree of chlorination of naphthalene and dibenzofuran products decreased as temperature increased, and, on average, the naphthalene congeners were less chlorinated than the dibenzofuran congeners. PCDF isomers were found to be weakly dependent to temperature, suggesting that phenoxy radical coupling is a low activation energy process. Different PCN isomers, on the other hand, are formed by alternative fusion routes from the same phenoxy radical coupling intermediate. PCN isomer distributions were found to be more temperature sensitive, with selectivity to particular isomers decreasing with increasing temperature.
 Keywords
Municipal waste incinerator;Thermal process;Combustion;Polychlorinated Naphthalenes;Polychlorinated Dibenzofurans;Chlorophenol;
 Language
English
 Cited by
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