Specific Ion Effects in NaCl-KCI Flotation with Carboxylates

"Potash flotation is an industrially proven success of flotation of soluble salts, but its collector adsorption mechanism remains elusive. In this paper, specific ion effects in NaCl-KCl flotation with carboxylate collectors were investigated. Flotation recovery and contact angle were determined as a function of brine composition of NaCl and KCl. The experimental results have shown that wettability of KCl and flotation of the soluble salts with laurate collectors were dependent on brine ion composition. Specifically, adding Na+ to brines decreased hydrophobicity of KCl crystals and their flotation recovery. Both KCl and NaCl could be floated with laurate collectors. However, flotation of NaCl was greatly enhanced by adding K+ to brine whereas flotation of KCl was significantly suppressed by the presence of Na ions. The decrease in KCl recovery upon adding Na+ is attributed to the counter-ion binding in the pulp. The flotation recovery enhancement of NaCl in the presence of K+ is explained by two effects: 1) increasing K+ concentration leads to a better dispersion of collector colloids in the pulp and 2) K+ enhances the collector adsorption at NaCl crystal surfaces. The water affinity matching rule can explain the specific ion binding behaviors and supported by the SFG spectroscopic results.INTRODUCTIONPotassium is an important fertilizer. Its primary source comes from potash ores, which are a mixture of sylvite (KCl), halite (NaCl) and many other complex double salts such as carnallite (KCl·MgCl·6H2O), alkali nitrates such as KNO3 and NaNO3, and sulfates-langbeinite (2MgSO4·K2SO4) with water-insoluble minerals such as clay and carbonate minerals. Previously, these salts were recovered with a lengthy hot leaching method, with further crystallization of potassium salts from saturated saline solutions. Selective flotation has been preferred since 1940s. Various collector adsorption mechanisms have been proposed soon after the industrial introduction of potash flotation. These include the formation of the insoluble compound model (Halbich, 1933; Singewald, 1961), an ion exchange model (Fuerstenau and Fuerstenau, 1956), a heat of solution model (Rogers, 1957), the surface hydration model (Schubert, 1988), the surface charge model (Roman, 1966; Miller et al., 1992), the interfacial water structure model (Hancer and Miller, 2000) and the colloid adsorption model (Leja, 1983; Burdukova and Laskowski, 2009). Most of the early exercises attempting to propose a unified rule on collector adsorption mechanisms can be seen as heroic endeavors due to the consideration of a vast number of salts in the pulp including alkali halides, nitrates, and sulfates, even the practically insoluble heavy earth metals. Additionally, several types of surfactants with different polarization features and alkyl chain length have been employed. As for the recent models, due probably to the preferential application of long chain amines as collectors in industrial potash flotation, most researchers are only devoted to collectors with low polarization features like amines and sulfonates (Hancer and Miller, 2000; Du et al., 2014). Collector adsorption mechanisms are therefore proposed based largely on a neglect of carboxylates as collectors. However, carboxylates remain an important collector type in soluble salt flotation systems where both salt minerals can be floated using anionic collectors and cationic collectors. Fatty acid type collectors are still one of the widely used collectors for soluble salt flotation and also one of the first to be applied on an industrial scale for the separation of potash ore (Hernáinz et al., 2003; Titkov, 2004). Here we examine some recent models that are relevant to our study to reveal a long neglected specific ion binding effects in potash flotation."