Jianjun Wang

Fluorite and scheelite, which are strategic calcium-bearing minerals, have similar active sites (Ca²⁺); as a result, the efficient separation of the two minerals is still one of the world’s most difficult problems in the field of flotation. In this work, N-decanoylsarcosine sodium (SDAA), a non-toxic and low-cost amino acid surfactant, was applied in the flotation separation of fluorite from scheelite for the first time. In the test, single mineral, binary mixed minerals, and actual ore experiments showed that the pre-removal of fluorite from scheelite by reverse flotation can be achieved. The results of adsorption capacity detections, zeta potential tests, and FTIR analysis showed that the negatively charged SDAA prefers to adsorb onto the positively charged fluorite surface due to the electrostatic interaction. The results of crystal chemistry and DFT calculations showed that SDAA has a stronger chemical interaction and more electron transfer numbers to the Ca atom on the fluorite surface and forms a Ca-SDAA complex. Therefore, the significant difference in the adsorption behavior of SDAA on the surfaces of two minerals provided a new insight into the separation efficiency of amino acids and possesses a great potential for industrial application in scheelite flotation.

Scheelite and calcite are usually intergrown calcium minerals that are separated via froth flotation. However, their selective separation remains difficult because of their similar surface properties. 2-phosphonobutane −1, 2, 4-tricarboxylic acid (PBTCA or H₅L) is widely used in water treatment due to its low phosphorus content and efficient anti-scaling performance. With its excellent calcium-chelating ability, PBTCA was used as a novel depressant to selectively separate scheelite from calcite in this study. The flotation results of single mineral, binary mixed minerals, and real ore showed that PBTCA could selectively depress calcite at pH 9.0 using sodium oleate as collector. The results of zeta potential measurements, solution chemistry calculation, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and density functional theory calculation indicated that the dominant form of PBTCA was L^5-. This anion had a stronger adsorption on negatively charged calcite surfaces through electrostatic interaction. Higher Ca density and stronger Ca activity on calcite promote the adsorption of L^5-. Moreover, the active O atoms in L^5- could better match with two Ca sites on calcite in the interatom distance. Thus, PBTCA provides a new option for calcite depressants and has great industrial application potential.

The flotation separation of scheelite from calcite is problematic, where sodium silicate modified by polyvalent metal ions has shown some advantages for selective depression. In this study, an Al-Na₂SiO₃ polymer was used as the depressant for the flotation separation of scheelite from calcite using a lead complex of benzohydroxamic acid (Pb-BHA) as the collector. Furthermore, a number of measurements were conducted to investigate the structure of the Al-Na₂SiO₃ polymer and its adsorption behavior with Pb-BHA complexes on the mineral surface. Flotation experiments indicated that the Al-Na₂SiO₃ polymer shows good selectivity for the flotation separation of scheelite from calcite at pH 8, where the optimum ratio of sodium silicate to aluminum sulfate was 2:1. Fourier-Transform Infrared (FTIR) and solution chemical analyses revealed that aluminum hydroxide complexes and the hydroxy moiety of silicic acid are able to self-assemble via condensation affording an Al-Na₂SiO₃ polymer, i.e., a composite aluminosilicate polymer. The zeta potential measurements and adsorption capacity measurements indicated that, upon adsorption of the Al-Na₂SiO₃ polymer and Pb-BHA complexes on the mineral surface, the Al-Na₂SiO₃ polymer had less influence on the adsorption of Pb-BHA complexes on the scheelite surface, while the opposite was true for calcite. Therefore, more Pb-BHA complexes and fewer Al-Na₂SiO₃ polymers were deposited on the scheelite surface, while fewer Pb-BHA complexes and more Al-Na₂SiO₃ polymers were adsorbed on the calcite surface. The selective separation of scheelite from calcite was attributed to the cooperative selectivity of the Pb-BHA complexes and Al-Na₂SiO₃ polymer.

Pb–BHA complexes have been shown to be selective for the separation of tungsten and cassiterite minerals from calcium minerals. These minerals could be enriched synchronously to some extent using Pb–BHA complexes flotation. However, it is difficult to further improve the quality and recovery of the scheelite, wolframite, and cassiterite concentrate due to their different behavior in flotation, such as flotation rate and sensitivities to depressants. Moreover, the super fine particles create some challenges for the cleaning flotation process. In this study, advanced gravity separators for super fine particles were introduced for the cleaning process based on the slight difference in the specific gravity of scheelite, wolframite, and cassiterite. The new process featured pre-enrichment using Pb–BHA flotation, and upgrading using gravity separation, taking into account both the similarities and differences in floatability and density of the different minerals. The grades of WO₃ and Sn in the concentrate of the new process reached to 61% and 2.89%, respectively, and the recovery of Sn was significantly improved. In addition, gravity separation is highly efficient, cost effective, and chemical-free, which is environmentally friendly. This study has proven that physical separation can be used for the purification of flotation products and provide some solutions for separation problems of complex refractory ores, which has, up until now, been rarely reported in the literature and/or applied in mineral processing.

Fluorite (CaF₂), as an important strategic mineral source, is usually separated from calcite by the common froth flotation method, but this separation is still not selective enough. The development of a selective collector and/or depressant is the key to achieving high selective separation. 1-Hydroxyethylidene-1,1-diphosphonic acid (HEDP or H₄L) is widely used as an environmentally friendly water treatment reagent due to its low cost and excellent anti-scaling performance in an aqueous solution. In this study, a novel reagent scheme was developed using HEDP as a fluorite depressant and sodium oleate (NaOL) as a calcite collector for the first time. When 3 × 10⁻⁵ mol/L of HEDP and 6 × 10⁻⁵ mol/L of NaOL were used at pH 6, the optimal selective separation for single minerals and mixed binary minerals was obtained. Zeta potential measurements indicated that HEDP possessed a stronger adsorption on fluorite than calcite, while NaOL did the opposite. This novel reagent scheme is of low cost, uses a small dosage, and is friendly to the environment, which makes it a promising reagent scheme for fluorite flotation in industrial application.