Hydrodechlorination of dichlorobiphenyls over Ni–Mo/Al 2O 3 catalysts prepared by spray-drying method

Abstract

The hydrodechlorination (HDCl) process of 2,3-, 2,4- and 2,5-dichlorobiphenyls was studied over a sulphided Ni–Mo/Al 2O 3 catalyst in a stirred autoclave at a hydrogen pressure of 3 MPa. The catalysts were prepared by spray-drying. They were characterized by N 2 adsorption, thermogravimetry and scanning electron microscopy with X-ray microanalysis. The reaction temperature of the catalytic HDCl process was varied in the range of 230–290 °C. Polychlorinated biphenyls (PCBs) free transformer oil was used as reaction medium. The HDCl degree of dichlorobiphenyl isomers was in the range of 82–93%. The efficiency in the chlorine removal was found to be related to the position of the substituted chlorine atom and decreased as follows 2,4-dichlorobiphenyl ≈ 2,5-dichlorobiphenyl > 2,3-dichlorobiphenyl. For comparison, the HDCl process of 2,3-dichlorobiphenyl (2,3-PCB) without catalyst was also studied. The chlorine removal was 85% for the catalytic HDCl of 2,3-PCB whereas non-catalytic process led only to 16% of dechlorination in the same operating conditions, i.e. at 290 °C after 120 min. Monodichlorobiphenyls were not detected in the reaction products. The data for both catalytic and non-catalytic conversion of 2,3-PCB fit to a first-order model. Kinetic constants and the activation energy of the overall HDCl reaction of 2,3-PCB to biphenyl were evaluated. Compared to non-catalytic process, a nearly threefold decrease in the activation energy was observed in the presence of Ni–Mo/Al 2O 3 catalyst prepared by spray-drying (48 kJ mol −1 vs. 124 kJ mol −1).