Minerals Beneficiation - Calcium Activation in Sulfonate and Oleate Flotation of Quartz

With either sulfonate or oleate as collector, quartz responds to flotation with moderate additions of calcium only at moderately high pH, where some portion of the activator has hydrolyzed to caOH+ . Calculations of the concentrations of various ionic and precipitated species of calcium and collectors suggest that the products of [(CaOH+) (RSO3)] and [(CaOH+)(01-)] determine whether flotation is obtained under specific conditions. Ion products on the order of 10-12 were calculated for both the sulfonate and oleate systems. The activating effect of calcium ion in nonmetallic flotation systems is of considerable interest because of the normal presence of calcium in natural water. As a result, this phenomenon has received quite some attention in the past. Kraeber and Boppel1 showed that quartz could be activated by calcium above pH 10 with sulfonate as collector. The feasibility of selectively separating quartz from hematite with calcium activation at relatively high pH was demonstrated by Clemmer, Clemmons, Rampacek, Williams, and stacy.2 Cooke and Digre3 showed with a bubble pick-up method that the minimum quantity of calcium ion required as activator for complete pick-up of particles occurs at pH 11.5 for an addition of 20 mg per liter sodium oleate. They also showed that larger additions of calcium (10-fold increase per unit decrease of pH) must be added for complete bubble pick-up as the pH is reduced. Schuhmann and Prakash,4 using a vacuum flotation technique, found that quartz could be floated with moderate additions of calcium chloride and oleic acid at neutral pH, providing the metal ion was present in stoichiometric excess over the quantity needed to form the normal soap with oleic acid. They also reported that calcium will function as an activator only in basic media. More recently, Eigeles and volova5 have shown that essentially complete flotation of quartz is obtained with 6 x 10-4 mole per liter calcium chloride and 1.7 x 10-5 mole per liter sodium oleate at pH 11.6. while no flotation is obtained at about pH 10.9 and below. The importance of adsorption of activator and collector at the air-liquid interface is also demonstrated in these systems. The important role that metal ion hydrolysis assumes in quartz activation systems was also demonstrated recently.6-8 A detailed investigation of metal activation in sulfonate flotation of quartz was undertaken in one system7 and yielded a number of interesting and important observations. Quantification of the data of this system7 to the extent desired was not possible, though, because certain species could neither be ignored nor accounted for accurately. These difficulties can be circumvented when calcium is involved as activator. This detailed analysis was undertaken to obtain a more quantitative explanation of calcium and metal ion activation in quartz flotation. EXPERIMENTAL MATERIALS AND METHODS Sodium alkyl aryl sulfonate9 mol wt 450, and pure potassium oleate were used as collectors. All other reagents used were reagent grade in quality, i.e., n-amyl alcohol as frother, KOH for pH adjustment, and calcium chloride. Conductivity water, made by passing distilled water through an ion exchange column, was used in the investigation. Quartz was prepared by leaching the sized sample (48 x 150 mesh) with HC1 until no iron could be detected in the leach liquor. The experimental equipment and procedure were the same as that described previously.6,10 EXPERIMENTAL RESULTS As the presence of precipitates was noted in all of the systems to which ca++ and collector were added, experiments were undertaken to determine the solubility products of calcium sulfonate and calcium oleate using a nephelometer. With this technique, collector is titrated into a known solution, which in this case was 5 x 10-5 mole per liter CaCl2 at pH 5.5. Upon precipitation of the calcium-col lector salt, e.g., calcium oleate, light is scattered and detected