Chemical Modelling Of The Fe2(SO4)3–FeSO4–H2SO4–H2O System

"The chemistry of electrolyte systems containing iron remains generally poorly understood despite their prevalence in many natural and industrial processes, particularly in hydrometallurgy. These systems are typically challenging to study and model due to their affinity for complex formation and precipitation even at low pH. Recent developments in the hydrometallurgical processing of nickel laterites at Anglo American have called for a deeper understanding of the fundamental chemistry of the Fe2(SO4)3–FeSO4–H2SO4–H2O system. This paper details the development of an internally consistent, Pitzer ion-interaction model of this system, with explicit recognition of important contact ion pairs (CIPs). The primary application of this model is a thermodynamic framework for the interpretation of kinetic processes occurring during iron(III) reduction with SO2. Adopting a rigorous thermodynamic basis for the system chemistry facilitates the formulation of simple rate expressions that are capable of inherently capturing complex effects. While the iron(III) reduction case study remains the focus of this work, the developments have more universal applications and the thermodynamic speciation model can be extended into other systems containing acidic ferric sulfate.INTRODUCTIONIron is present in nearly all hydrometallurgical refining circuits typically as both a necessary and unwanted impurity and needs to be removed and disposed in a safe and efficient manner. This is generally performed by precipitation to form a range of solids such as hematite, goethite or jarosite. Numerous studies in the open literature have focussed on the removal of iron from refractory gold sulfide ore (Berezowsky & Weir, 1989; Berezowsky et al., 1991) and zinc pressure leaching (Buban, 1999; Ismael, 2003), and PGM matte sulfide circuits (Dutrizac & Monhemius, 1986). Moreover, since ferric iron is a strong oxidizing agent, it has been used extensively as a leaching agent for sulfide minerals (Dreisinger, 2006). Given the outlook of challenging economic conditions, declining ore grades and increasing levels of impurities, effective iron management is going to become increasingly critical to all hydrometallurgical processes.Against this background, and considering the widespread importance of acidic iron sulfate systems throughout natural and industrial processes, it is unexpected that the knowledge of the fundamental solution chemistry of these systems contains such significant gaps, particularly at the conditions typically found in hydrometallurgical applications. Existing literature describing the measurement and modelling of solution speciation in these systems have highlighted their significant chemical complexity (Magini & Caminiti, 1977; Magini, 1979; Lee & Tavlarides, 1985; Stipp, 1990; Papangelakis et al., 1994; Gil et al., 1995; Majzlan & Myneni, 2005; Kormanyos et al., 2008; Yue et al., 2014). Partially responsible for the lack of quantitative speciation measurements is the strong tendency of ferric to hydrolyse at even low pH (Flynn, 1984), complicating the laboratory study of such systems. Moreover, the large number of aqueous species that may co-exist simultaneously makes the study of individual species and the modelling of the numerous interactions between these species extremely difficult (Dry & Bryson, 1988; Stipp, 1990; Majzlan & Myeni, 2005; Kobylin et al., 2007)."