Dechlorination of pentachlorophenol in supercritical carbon dioxide with zero-valent palladium-magnesium bimetallic mixture.
A stream of substrate pentachlorophenol [PCP, 5 mg min(-1) in water-methanol (1 + 4, v/v)] was merged with 1.5 ml min(-1) of supercritical carbon dioxide (scCO2) and delivered to a reactor column (25 cm x 1 cm) of zero-valent palladium-magnesium mixture. The resulting dechlorinations, although very efficient, were not quantitative. For continuous operation at 400 degrees C for 6 h, phenol was the principal product, with lesser quantities of methylated products and only traces of chlorinated products (principally monochlorinated species). PCP deoxygenation was not observed and ring methylation was decreased relative to analogous reactions in hydroxylic organic solvent. With time, the reactor column slowly lost dechlorination activity. Reducing the loading of Pd0 on Mg0 from 2% to 1% (w/w) apparently did not change the course of the reaction; however, the dechlorination capacity was decreased correspondingly. None the less, over 6 h or 5 h of continued operation, the dechlorination efficiency was 0.995 for the 2% (w/w) loading of Pd0 on Mg0 and 0.984 for the 1% (w/w) loading.
Yuan
Tao
T
Department of Food Science and Agricultural Chemistry, McGill, Ste-Anne-de-Bellevue, Québec, Canada.
Marshall
William D
WD
D002245:Carbon Dioxide / Q000737:chemistry*; D002713:Chlorine / Q000737:chemistry; D004785:Environmental Pollutants / Q000032:analysis*; D004787:Environmental Pollution / Q000517:prevention & control; D008274:Magnesium / Q000737:chemistry; D010165:Palladium / Q000737:chemistry; D010416:Pentachlorophenol / Q000032:analysis* / Q000737:chemistry
D004785:Environmental Pollutants; D002245:Carbon Dioxide; D002713:Chlorine; D010165:Palladium; D010416:Pentachlorophenol; D008274:Magnesium