Catalytic hydrodehalogenation as a detoxification methodology

Abstract

Catalytic hydrodehalogenation is presented as a viable approach in the non-destructive treatment of concentrated halogenated aromatic gas streams to generate reusable raw material. Nickel loaded (from 1.5 to 20.3% w/w) silica catalysts have been used to hydrotreat a range of halogenated feedstock, where 473 K≤ T≤573 K: chlorobenzene, chlorotoluene, chlorophenol, bromobenzene, dichlorobenzene, dichlorophenol, trichlorophenol, pentachlorophenol. The long term (up to 800 h-on-stream) stability of these catalysts has been assessed where the changes in nickel particle size and morphology as a result of the prolonged catalytic step was probed by TEM; each catalyst irrespective of any loss of initial activity was fully selective in solely promoting dehalogenation. In the case of a polychlorinated feedstock, dechlorination can proceed in a stepwise manner to generate a partially dechlorinated product. Hydrodehalogenation appears to occur via an electrophilic mechanism where the presence of electron-donating substituents on the benzene ring enhances the rate of reaction. The reaction is shown to be structure sensitive over Ni/SiO 2 where the hydrodechlorination rates and ultimate yield of the parent aromatic from a polychlorinated reactant is favored by larger nickel particle sizes. A direct contact of the freshly activated catalyst with HCl or HBr gas induced an appreciable growth of the supported metal crystallites. Chlorobenzene hydrodechlorination was suppressed on a HCl or HBr treated Ni/SiO 2 which promoted instead the unexpected growth of highly ordered carbon filaments; this carbon growth is characterized by TEM and SEM. The dependence of the experimental hydrodechlorination and hydrodebromination rates on the gas phase aromatic partial pressure (in the range 0.02–0.1 atm) is adequately represented by a kinetic model involving a non-competitive adsorption of hydrogen and halogenated aromatic where the incoming aromatic reactant must displace the hydrogen halide from the catalyst surface.