Hydrodechlorination of 4-chlorophenol in water with formic acid using a Pd/activated carbon catalyst

This work reports on the feasibility of hydrodechlorination as a treatment technique for chlorophenols-bearing wastewaters using formic acid as a hydrogen source. 4-Chlorophenol (4-CPhOH) has been used as target compound and the experiments were carried out in batch and continuous mode with a commercial activated carbon-supported Pd (0.5 wt.%) catalyst. The variables studied in the batch runs were HCOOH/4-CPhOH molar ratio (10-1000), temperature (25-75 degrees C) and catalyst concentration (250-1000 mg/L). The continuous experiments were performed in a fixed bed reactor where aqueous solutions of formic acid and 4-CPhOH with molar ratios between 50 and 100 were continuously fed to the reactor, at different space-time values in the range of 10.7-42.8 kg(cat)h/mol. Reaction temperatures from 35 to 100 degrees C were tested and the pressure was fixed at 2.5bar. Conversion values above 99% for 4-CPhOH were obtained in batch experiments, but using a HCOOH/4-CPhOH molar ratio as high as 500. Moreover, most of the phenol produced was adsorbed on the catalyst. Continuous runs were performed to evaluate the efficiency of the catalyst under lower HCOOH/4-CPhOH ratios and to explore the possibility of converting phenol to more hydrogenated products. The results indicated that the HCOOH/4-CPhOH molar ratios needed were an order of magnitude lower than those required in batch runs to achieve conversions of 4-CPhOH close to 95%. Besides, phenol was not the only reaction product formed, since a more hydrogenated product such as cyclohexanone was detected in the effluent, which indicates additional hydrogenation of phenol in contrast to the behaviour observed in batch experiments. A loss of activity was observed in the continuous runs after 20-30 h on stream.