Aqueous-Phase Hydrodechlorination of 2,4-Dichlorophenol over Pd/Al2O3: Reaction under Controlled pH

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The aqueous-phase hydrodechlorination (HDC) of 2,4-dichlorophenol (2,4-DCP) over a Pd/Al2O3 catalyst has been studied with adjustment of the bulk solution pH either by base (NaOH and NH4OH) addition prereaction or with a continual supply of base during HDC. With a starting pH in the range 7−11.6, the solution pH can be controlled to within ±0.1 with an external supply of NaOH during HDC. A preliminary kinetic analysis suggests that 2,4-DCP HDC is predominately stepwise, yielding 2-chlorophenol (2-CP) as the partially dechlorinated product, which is further converted to phenol and ultimately to cyclohexanone. Pd/Al2O3, operating under controlled pH, delivered maximum HDC activity in the pH range 7−8, where the selectivity with respect to 2-CP was lower than that associated with pH = 11.6. In the absence of mass transport constraints, initial HDC rate as a function of 2,4-DCP concentration exhibits Langmuir−Hinshelwood mechanistic behavior involving competitive adsorption of H2 and 2,4-DCP with the surface ...