Precious metal-based Catalytic Membrane Reactors for continuous flow catalytic hydrodechlorination

This work is focused on the development of Catalytic Membrane Reactors (CMRs) comprising precious metals as active phases for a comparative assessment in continuous-flow catalytic hydrodechlorination (HDC). HDC has proved its remarkable potential for application as polishing step in drinking water treatment plants, but studies operating in continuous mode are scarce. Preliminary experiments were conducted in batch operation using Pd/Al2O3, Rh/Al2O3 and Pt/Al2O3 powder catalysts to evaluate the influence of the active phase on the removal of prochloraz (PCZ) (100 mu g L-1), a pesticide listed on the EU Watch List (2022/1307), by HDC. PCZ removal was successfully described by a pseudo-first order kinetic equation and reaction pathways were proposed. Among the catalysts tested, Pt-based suffered a significant deactivation, not warranting the elimination of this micropollutant. Pd/Al2O3 exhibited a faster removal of PCZ than Rh/Al2O3, while this catalyst resulted in further hydrogenation of the non-chlorinated reaction product. Accordingly, different CMRs were developed by decorating cylindrical inert porous alumina membranes with Pd, Rh, and a combination of Pd-Rh as active phases (similar to 1% wt.). All CMRs showed a remarkable stability along 100 h on stream, being Pd/CMR be the most effective, with a pseudo-first order rate constant value of 0.062 min(-1). An assessment of the impact of operating conditions (aqueous flow rate, PCZ initial concentration, temperature and H-2 flow rate) was conducted using the Pd/CMR, which notably remained stable for 450 h on stream. The versatility of the system was finally demonstrated in tap water, achieving a steady-state PCZ conversion close to 95 %.