Selective Flotation of Tungsten Minerals from Calcium Minerals Using Benzohydroxamic Acid Complexes

"The similar flotability of scheelite, fluorite, and calcite resulted in the difficult separation by flotation. This work revealed the effect of water glass on the flotation of scheelite by FTIR and the wettability change of the usual cleavage plane, and proved that water glass inevitably influenced the flotation of tungsten minerals to a large extend in traditional fatty acid flotation process. A new collector, benzohydroxamic acid complexes, was found to be selective for the separation of scheelite and calcium minerals with little water glass. Hence a novel flotation process was developed for the recovery of tungsten minerals in shizhuyuan mine in China. Normal temperature flotation of tungsten minerals was developed to instead of the classical “Petrov's process” for scheelite-calcite-fluorite type ores. Compared with the traditional process, the recovery was improved by 10% and the grade of scheelite concentrate was above 55%. The disappearance or decreasing of water glass contributed to improving the recovery of tungsten and fluorite and the circulation of water and reagents.INTRODUCTIONChina is rich in tungsten resources and the proved reserves accounted for 60% of the world's reserves (Cai Gaipin et al., 2009). However the wolframite has been dried up and the scheelite resource has become the main resource of the tungsten metal. Scheelite deposits were classified to scheelite-silicate type and scheelite-calcite-fluorite type based on the associated gangue minerals. Scheelite was easy to separate from the silicate minerals. Flotation separation of scheelite from calcium minerals creates difficulties because of the existence of the same cation in the minerals and similar physicochemical characteristics such as solubility, hardness, specific gravity, PZC (point of zero charge) etc.(Arnold & Warren, 1974; Yongxin & Changgen, 1983; Ozcan & Bulutcu, 1993a; Deng et al., 2015, 2016;). The conventional collectors used in the flotation of scheelite ores are generally fatty acids or fatty acid derivatives ( Yongxin & Changgen, 1983; Oliveira & Sampaio, 1988; Sivamohan, 1988; Shi et al., 2014; Bo et al., 2015). It is difficult to separate scheelite especially from calcite with these reagents because the adsorption mechanism of these collectors occurs through chemisorption of the oleate ion onto the mineral surface (Atademir et al., 1979; Changgen and Yongxin, 1983; Hiçyìlmaz et al., 1993; Hu et al., 2011). Therefore, it is almost impossible to separate them by fatty acid flotation without using any selective depressant. Although oleoyl sarcosine was used as a selective collector in the flotation of fluorite and siliceous scheelite ores (Ozcan & Bulutcu, 1993b; Ozcan et al., 1994), this selectivity is not adequate for a low-grade calcitic scheelite ore. Unfortunately, the reagents such as organic colloids (dextrine, starch), quebracho, sodium phosphates, sodium silicate solutions containing polyvalent cations (hydrosols), etc. (Yongxin and Changgen, 1983; Schubert et al., 1990; Shi et al., 2014; Bo et al., 2015) used for calcite depression also depress scheelite to a large extent."