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Electrophilic Chlorination of Naphthalene in Combustion Flue Gas

Wang, Dan, Zhang, Haijun, Fan, Yun, Ren, Meihui, Cao, Rong, Chen, Jiping
Environmental science & technology 2019 v.53 no.10 pp. 5741-5749
Lewis acids, chlorinated naphthalenes, chlorination, chlorine, combustion, copper, dechlorination, ferric chloride, ferrous chloride, flue gas, iron, naphthalene, oxides
Naphthalene chlorination is an important formation mechanism of polychlorinated naphthalenes (PCNs) in combustion flue gas. In this study, a total of 21 metal chlorides and oxides were screened for their activities in the electrophilic chlorination of naphthalene. Copper(II) chloride exhibited the highest activity at 200–350 °C, followed by copper(I) chloride. Copper(II) chloride primarily acted as a strong chlorinating agent to facilitate chlorine substitution on naphthalene. Iron (II and III) chlorides were only highly active at 200–250 °C. At 250 °C, the average naphthalene chlorination efficiency over CuCl₂·2H₂O was 7.5-fold, 30.2-fold and 34.7-fold higher than those over CuCl, FeCl₃·6H₂O and FeCl₂·4H₂O, respectively. The other metal chlorides were less active. Under heated conditions, copper(II) and iron(III) chlorides were transformed to copper(I) and iron(II) chlorides via dechlorination, and then transformed to oxychlorides and oxides, thereby forming dechlorination-oxychlorination cycles of copper and iron species, respectively. The results obtained suggest that electrophilic chlorination of naphthalene in combustion flue gas is primarily driven by dechlorination-oxychlorination cycles of copper and iron species, and the reaction produces a selective chlorination pattern at 1 and 4 positions of naphthalene.