Continuous catalytic hydrogenation of polyaromatic hydrocarbon compounds in hydrogen-supercritical carbon dioxide.
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 x 1 cm) containing palladium supported on gamma alumina (Pd0/gamma-Al2O3) that was terminated with a capillary restrictor. The flow rate from the reactor, approximately 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 degrees 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 degrees 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, virtuallytotally, 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 coliWP2 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.
Yuan
Tao
T
Department of Food Science and Agricultural Chemistry, MacDonald Campus of McGill University, 21111 Lakeshore Road, Ste-Anne-de-Bellevue, Quebec, Canada.
Fournier
Anick R
AR
Proudlock
Raymond
R
Marshall
William D
WD
D001419:Bacteria / Q000187:drug effects / Q000235:genetics; D002245:Carbon Dioxide / Q000737:chemistry*; D002384:Catalysis; D002849:Chromatography, Gas; D004787:Environmental Pollution / Q000517:prevention & control*; D006586:Hexanes; D006859:Hydrogen / Q000737:chemistry*; D006865:Hydrogenation; D015394:Molecular Structure; D009152:Mutagenicity Tests; D011084:Polycyclic Aromatic Hydrocarbons / Q000737:chemistry* / Q000633:toxicity; D012987:Soil / Q000032:analysis
D006586:Hexanes; D011084:Polycyclic Aromatic Hydrocarbons; D012987:Soil; D002245:Carbon Dioxide; D006859:Hydrogen