Discussion - Flotation Of Boron Minerals - Celik, M. S., et al

Discussion by M.R. Yalamanchili and J.D. Miller The authors, M. S. Celik et al., should be recognized for their efforts to describe the flotation behavior of boron minerals. In the case of borax and other soluble salt minerals, analysis of the flotation chemistry has been difficult because of the high ionic strengths associated with these soluble salt systems. However, considerable progress has been made in this area, and recently a surface charge/collector colloid adsorption model was proposed by Miller and his coworkers to explain the collector adsorption phenomena observed in soluble salt flotation systems (Milleret al, 1992; Yalamanchili et al., 1993; Miller and Yalamanchili, 1994; Yalamanchili and Miller, 1994a: Yalamanchili and Miller, 1994b). In this work, the sign of the surface charge of alkali halides in their saturated brines was established on the basis of nonequilibrium electrophoretic mobility measurements by laser-Doppler electrophoresis (Miller et al., 1992). Generally, these results are what would be expected from the simplified lattice-ionhydration theory. This electrokinetic information coupled with the stability and prevalence of collector colloids in such soluble salt flotation systems indicates that the selective flotation of alkali halides is due to the adsorption of oppositely charged collector colloids by heterocoagulation. Experimental flotation/bubble attachment results for 21 different alkali halides (Yalamanchili et al., 1993; Yalamanchili and Miller, I994b) confirmed that the flotation response of soluble salt minerals with weak electrolyte collectors can best be explained by the adsorption of oppositely charged collector colloids rather than by the adsorption collector ions and/or neutral molecular dipoles as originally suggested by many researchers (Fuerstenau and Fuerstenau, 1957; Schubert, 1967; Roman et al., 1968). In addition, the flotation of certain alkali oxyanions (Pizarro et al., 1993) and double salts such as schoenite and kainite can be explained by the same collector colloid adsorption mechanism (Miller and Yalamanchili, 1994). The borax flotation results reported by Celik et al. need to be examined in terms of the above mentioned surface charge/ collector colloid adsorption model. Unfortunately, the authors seem to be unaware of this recent work that nicely describes soluble salt flotation with weak electrolyte type collectors such as amines and carboxylates. In view of our past work, the flotation characteristics of borax were of particular interest, and, in this regard, the results of dodecyl amine flotation of borax reported by Celik et al. have been examined in further detail in the light of experimental results from our laboratory. In our research, a vacuum flotation technique was used to study the flotation response of borax (Na2B407.10H20), which has a solubility of 39 g/L at 25 °C) with dodecyl amine hydrochloride as collector. These chemicals were purchased from Eastman Kodak and used as received. Saturated solutions of borax at desired pH values were prepared by continuously stirring the salt solutions over a period of about 10 hrs. It should be mentioned that the conditioning time to achieve equilibrium is an important variable and can significantly change the flotation response of some soluble salts (Yalamanchili et al., 1993). Collector was added to the saturated borax solutions containing about one gram of 100x 150 mesh borax particles, and conditioning was done for about 20 minutes prior to flotation. The borax flotation recoveries from saturated brine are presented in Fig. 1 as a function of collector addition at the natural pH of 9.3, as reported both by Celik et al. and as measured in our laboratory. In addition, the region of precipitation for the dodecyl amine hydroborate is included in Fig. 1. It can be seen in Fig. 1 that the flotation response curves are separated by about one order of magnitude in R12NH3CI collector addition. The flotation results of Celik et al. show that the maximum borax recoveries can be obtained below the solubility limit of the dodecyl amine hydroborate collector. However, in our experiments borax flotation seems to occur only after the precipitation of the dodecyl amine hydroborate collector as might be expected from the collector colloid adsorption model (Yalamanchili et al., 1993) if borax were negatively charged. Further analysis by nonequilibrium and equilibrium electrophoretic mobility measurements for borax indicates that borax is negatively charged at the natural pH of 9.3, as discussed below. The reliability of the nonequilibrium electrophoretic measurements has been demonstrated previously for alkali halides and alkali oxyanions (Miller et al., 1992; Miller and Yalamanchili, 1994). The equilibrium and nonequlibrium electrophoretic measurements for borax were found to be consistent and are presented in Table 1. These results provide clear evidence that borax carries a negative surface charge in its saturated brine (pH 9.3), and the sign of the surface charge of borax reverses and becomes positive if the pH is reduced to 8.6. The equilibrium between borax and its saturated brine can be described by the following reaction: [2Na2B407.1OH2O-4Na++B407=+HB4O7 +OH+19H20] It appears that the oxyanions of the borax lattice provide