Continuous Catalytic Hydrogenation of Polyaromatic Hydrocarbon Compounds in Hydrogen−Supercritical Carbon Dioxide

• Published in: Environmental science & technology Vol. 41; no. 6; pp. 1983 - 1988
• Main Authors: Yuan, Tao, Fournier, Anick R, Proudlock, Raymond, Marshall, William D
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 15.03.2007
• Subjects: Bacteria; Bacteria - drug effects; Bacteria - genetics; Carbon dioxide; Carbon Dioxide - chemistry; Catalysis; Chromatography, Gas; Environmental Pollution - prevention & control; Hexanes; Hydrocarbons; Hydrogen - chemistry; Hydrogenation; Molecular Structure; Mutagenicity Tests; Mutation; Polycyclic Aromatic Hydrocarbons - chemistry; Polycyclic Aromatic Hydrocarbons - toxicity; Salmonella typhimurium; Soil - analysis
• ISSN: 0013-936X; 1520-5851
• DOI: 10.1021/es062194+

A continuous hydrogenation device was evaluated for the detoxification of selected tri-, tetra-, or pentacyclic polyaromatic hydrocarbon (PAH) compounds {anthracene, phenanthrene, chrysene, and benzo[a]pyrene (B[a]P)} by hydrogenation. A substrate stream in hexane, 0.05−1.0% (w/v), was mixed with hydrogen−carbon dioxide (H2−CO2, 5−30% v/v) and delivered to a heated reactor column (25 cm × 1 cm) containing palladium supported on gamma alumina (Pd0/γ-Al2O3) that was terminated with a capillary restrictor. The flow rate from the reactor, ∼800 mL min-1 decompressed gas, corresponded to 4 mL min-1 fluid under the operating conditions of the trials. Reaction products were recovered by passing the reactor effluent through hexane. At 90 °C, the anthracene or phenanthrene substrate was hydrogenated only partially to octahydro and dodecahydro species and contained only a minor quantity of totally hydrogenated products. For substrates with increasing numbers of fused aromatic rings, the hydrogenation efficiency was decreased further. However, at an increasing temperature (90−150 °C) and increasing mobile phase flow rate (20.68 MPa corresponding to 2100 mL min-1 decompressed gas), B[a]P and chrysene were hydrogenated, virtually totally, to their corresponding perhydro analogues (eicosahydrobenzo[a]pyrenes and octadecahydrochrysenes), respectively. That this approach might be useful for decontaminating soil extracts was supported by companion in vitro trials in which the substrate and products were assayed for mutagenic activity with five bacterial strains that are auxotrophic for histidine (Salmonella typhimurium TA98 , TA100, TA1535, and TA1537) or tryptophan (Escherichia coli WP2 uvrA), using the bacterial reverse mutation assay (modified Ames test). Generally, substantial increases in revertant colony counts were not observed with any of the strains following exposure to the hydrogenation products in the absence or presence of the 10 or 30% S9 mix, which is consistent with the loss of mutagenic activity from these hydrogenation products.