Dechlorination of 2,4-dichlorophenol in a hydrogen-based membrane palladium-film reactor: Performance, mechanisms, and model development

Abstract

We created a hydrogen-based membrane palladium-film reactor (MPfR) by depositing palladium nanoparticles (PdNPs) on hollow-fiber membranes via autocatalytic hydrogenation to form a Pd-film. The MPfR was used for hydrodechlorination (HDC) of 2,4-dichlorophenol (2,4-DCP). HDC performances and mechanisms were systematically evaluated, and a continuous-flow dechlorination model was established. Approximately 87% of the input 2,4-DCP was reduced to the end-product phenol (P), while 2-chlorophenol (2-CP) was an intermediate, but only at 2%. Selective adsorption of the 2,4-DCP onto the Pd-film and fast desorption of P facilitated efficient dechlorination. Modeling results represented well the concentrations of 2,4-DCP and its intermediates. It demonstrated three dechlorination pathways: The majority of 2,4-DCP was completely dechlorinated to P in an adsorbed state without release of monochlorphenol, some 2,4-DCP was degraded to 2-CP that was released and subsequently adsorbed and reduced to P, and a small amount was reduced to 4-CP that was released and subsequently adsorbed and reduced to P. Analysis based on Density Functional Theory suggests that the pathway of full dechlorination was dominant due to its thermodynamically favorable adsorption configuration, with both Cl atoms bonded to Pd. This study documents full dechlorination of 2,4-DCP in the MPfR and the interacting roles of adsorption and HDC.

Keywords: 2,4-dichlorophenol; Hydrodechlorination; Mathematical model; Membrane palladium-film reactor.