Heavy metal removal with Mexican clinoptilolite: multi-component ionic exchange

This paper describes the interactions of Pb(II), Cd(II), and Cr(VI) competing for ion-exchange sites in naturally occurring clinoptilolite. Dissolved Pb and Cd were effectively removed within 18 h in batch reactors, with higher removal efficiencies (> 95%) in the acidic pH range. The presence of Cr(VI), which can interact with these metals to form anionic complexes, significantly diminished the Pb and Cd removal efficiencies. A decrease in the efficiency of clinoptilolite to remove Pb was also observed in the high (> or = 10) pH range. This was attributed to the formation of anionic hydroxo-complexes with little affinity for cationic ion exchange sites. Pb outcompeted Cd for ion exchange sites in a flow-through column packed with clinoptilolite (contact time = 10 s). The preferential removal of Pb in column, but not in batch reactors, reflects that competitive retention can be affected by contact time because diffusion kinetics may influence the removal efficiency to a greater extent than equilibrium partitioning. Phenol, which was tested as a representative organic co-contaminant, slightly hindered heavy metal removal in batch reactors. This was attributed to the formation of organometallic complexes that cannot penetrate the zeolite exchange channels. Altogether, these results show that natural zeolites hold great potential to remove cationic heavy metal species from industrial wastewater. Nevertheless, process efficiency can be hindered by the presence of ligands that form complexes with reduced accessibility and/or affinity for ion exchange.