Electrosynthesis of Near-Neutral Ferrate Species for Drinking Water Treatment Using a Recirculating Batch Reactor

Abstract

High oxidation state iron species of ferrates (e.g., Fe (VI), Fe (V) and Fe (IV)) are very promising oxidants and are in particular excellent candidates for water treatment applications. Their advantages include, for instance, a higher redox potential (+2.2 V vs. SHE) than the commonly used ozone oxidant (+2.07 V vs. SHE), no production of carcinogenic and harmful disinfection by-products (DBPs – produced with disinfectants such as chlorine) and decomposition into benign ferric hydroxides which form excellent coagulants. Ferrates are known to remove many different types of pollutants, including organic matter such as biofilms, algae, and coliforms, and inorganic matter such as cyanide, heavy metals, and radionuclides, and bio-contaminants like viruses and chlorine-resistant bacteria. One approach in production of ferrates is oxidation of Fe3+-containing solutions using an inert anode electrode. The oxidation reaction can be expressed by: Fe3+ + 4H2O → FeO4 2- + 8H+ + 3e- E0 = -2.2 V vs. SHE On-site production of ferrates for drinking water treatment by electrochemical means avoids a number of challenges with respect to transport and storage of chemical ferrates and also allows for direct integration of the electrochemical process with the treatment chain. In earlier papers on electrochemical ferrates, we have reported on a novel analytical method of ferrate quantification, degradation of ferrate and production of ferrates in small batch-type reactors [1-3]. Here we present a semi-batch (2 L) reactor which includes recirculation, temperature control, lower cell resistance, excellent mixing, provision for the use of ion exchange membrane, and in-situ pH control. The reactor uses boron doped diamond (BDD), Fe (III) solution and can be operated with or without an ion exchange membrane. The impact of several variables including current density (5 - 15 mA cm-2), pH (5 - 9), concentration of the dissolved iron salts on the production of ferrates temperature (15 - 30 oC) and operation with/without membrane have been studied and will be presented. Current efficiencies of as high as 90% were reached for the first 20 minutes of operation using a 30 mM of Fe (III) feed and a current density of 45 mA cm-2. The recirculating reactor results were successfully interpreted by a simple model which considered first order kinetics for Fe (VI) generation.