Catalytic hydrodechlorination of polychlorinated biphenyls (PCBs) in the presence of transformer oil was carried out in a batch mode to detoxify PCBs and to recycle the treated oil. Various metal supported catalysts, including 0.98 wt% Pt, 0.79 wt% Pd and 12.8 wt% Ni on gamma -alumina (gamma -Al(2)O(3)) support, and 57.6 wt% Ni on silicon oxide-aluminum oxide (SiO(2)-Al(2)O(3)) support were used for the hydrodechlorination. Metal particle size of the Pt catalyst was 2.0 nm and metal particle sizes of the Pd and Ni catalysts were in the range of 6.4-6.9 nm. Various supercritical fluids, supercritical carbon dioxide (scCO(2)), supercritical propane (scPropane), supercritical dimethyl ether (scDME) and supercritical isobutane (scIsobutane) were used as reaction media. PCBs conversion, dechlorination degree of PCBs, was measured using gas chromatograph (GC) with an electron capture detector (ECD). The hydrodechorination degree increased in the order Ni > Pd > Pt, possibly due to higher metal loading and larger metal size of the Ni catalysts. At temperatures below 175 degrees C, scCO(2) was effective as the reaction media for the catalytic hydrodechlorination of PCBs in the presence of the transformer oil. However, PCBs conversion decreased significantly when the hydrodechlorination was carried out in a homogeneous phase with using scPropane, scDME or scIsobutane as a reaction medium. This was attributed to dilution effect of the supercritical fluids. Molecular weights of the transformer oils before and after the catalytic hydrodechlorination were analyzed using high-performance size exclusion chromatography (HPSEC). The molecular weight of the treated oil with 100 % PCBs conversion did not change after the catalytic hydrodechlorination at 200 degrees C. This process has proven to be effective to detoxify PCBs containing transformer oil and to recycle the treated oil.
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