Experimental and Computational Insights into the Selective Adsorption Mechanism of a Novel Flotation Reagent 4-Amino-5-Mercapto-1,2,4-Triazole On Chalcopyrite Surface

"In this work, a novel compound 4-Amino-5-mercapto-1,2,4-triazole was first synthesized and its selective adsorption mechanism on the surface of chalcopyrite was comprehensively investigated using UV-vis spectra, zeta potential, Fourier Transform Infrared Spectroscopy(FTIR), X-ray Photoelectron Spectrscpy Measurements(XPS), and Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS) and first principle calculations. The experimental and computational results consistently demonstrated that AMT would chemisorb onto the chalcopyrite surface by the formation of a five-membered chelate ring. The first principle periodic calculations further indicated that AMT would prefer to adsorb onto Cu rather than Fe due to the more negative adsorption energy of AMT on Cu on the chalcopyrite (001) surface, which was further confirmed by the coordination bonding energies of AMT-Cu and AMT-Fe based on the simplified cluster models at a higher accuracy level (UB3LYP/Def2TZVP). The bench scale results indicated that the selective index improved significantly when using AMT as a potential chalcopyrite depressant in Cu-Mo flotation separation.INTRODUCTIONFroth flotation is one of the most important processes to separate valuable minerals from gangue by taking advantage of differences in the physical chemistry of their surface properties(Laitinen et al., 2014), particularly in their surface hydrophobicity. Hydrophobicity differences between valuable and gangue minerals could be regulated by adding different chemical additives (surfactants)(Kor, Korczyk, Addai-Mensah, Krasowska, & Beattie, 2014), such as collector and depressant. It could be conducted economically to selectively separate and enrich the complicated and/or poor ores, by adopting appropriate surfactants. For example, the beneficiation of molybdenite usually relies on a two-stage process to realize flotation separation of molybdenite from other unwanted sulphide ores(Wie & Fuerstenau, 1974). In the first step, a bulk molybdenite concentrate is produced by utilizing kerosene/ diesel oil and pine oil/alcohols as collector and frother, respectively. Second, sodium hydrosulphide, sodium cyanide, ammonium sulphide, or Nokes reagent are adopted as depressants in the separation stage. However, these depressants are usually toxicant and cannot meet the requirements of environmental protection. A large number of efforts have been taken to develop alternative environmentally-friendly depressants (Ansari & Pawlik, 2007; J. H. Chen, Lan, & Liao, 2013; Li et al., 2015; Yin, Sun, Hu, Zhai, & Guan, 2017; Yin, Sun, Hu, Zhang, Guan, Liu, et al., 2017; Yin et al., 2016). Although some novel and environmental-friendly depressants have been reported to achieve good performance in Cu-Mo flotation separation at a laboratory scale, there are still some challenging problems, including toxicity, high price or poor performance in practice, which severely limit their practical applications in Cu-Mo flotation separation on a commercial scale."