微细粒级氧化锌矿物氯-氨耦合催化硫化机理研究

几十年来，氧化锌矿的回收一直没有突破硫化—胺法的范畴，而该方法却受到矿泥的严重影响。与硫化—胺法相比，硫化—黄药浮选受矿泥的影响要小得多。本项目以矿泥中的微细粒级菱锌矿为代表，通过密度泛函计算分析影响矿物表面硫化的分子轨道因素；通过溶液化学和反应平衡常数计算，研究氯氨组份、硫离子浓度对硫化过程的影响；通过高浓度硫离子硫化、氯-氨耦合催化和无机铵盐催化等方式，深入研究菱锌矿硫化体系中硫-氨-锌-碳酸根的四元耦合催化机制，建立菱锌矿表面催化硫化稳态模型；通过光电子能谱、拉曼光谱、表面电位等手段对菱锌矿硫化表面进行表征，分析与硫化锌矿物表面硫化前后的性质差异；检测高级黄药在矿物表面的吸附量和表面接触角，表征催化硫化前后矿物表面黄药吸附层的疏水性差异，通过浮选实验，研究氯-氨耦合催化的影响因素，形成微细粒级氧化锌矿物的氯-氨耦合催化硫化—黄药浮选新技术原型，并为该新技术原型的实际应用提供理论依据。

In the mineral processing industry, there is no breakthrough in the areas of sulfidization - amine method for the recovery of zinc oxide ore in decades. This method has hitherto failed to be applied in the industrial flotation of zinc oxide ore. The main reason is that, slime has seriously affected the sulfidization - amine processing, resulting in the deterioration of flotation indexes. Compared with the sulfidization - amine flotation, the influences of slime on sulfide - xanthate flotation are much smaller. In order to avoid the influences of the undesirable slime as much as possible, Innovative flotation method for the recovery of zinc oxide ore effectively is therefore studied. In the present project, microfine smithsonite, which is one of main oxidized zinc minerals in the slime is served as the raw material. Density functional approach is employed to calculate the factors during the sulfidization-treated processing of smithsonite, such as the substitution reaction energy between sulfur ion andcarbonate ion, electron transfer, density states, etc, in order to analyze the molecular orbital factors of sulfidization surface of smithsonite. Also, solution chemistry calculation, thermodynamics and reaction equilibrium constant calculations are conducted to study the effects of chlorine and ammonia and sulfur ion concentrate on the sulfidization-treated processing. Catalyzed - sulfidization mechanism of four elements coupled with "sulfur-ammonia-zinc-carbonate ion" in system of smithsonite surface is studied through sulfidization by adding high concentrate of sulfur ions, coupling catalyzed- sulfidization with sodium chloride and ammonium hydroxide addition and catalyzed-sulfidization with inorganic ammonia salt addition. Meanwhile, the steady state model of catalyzed-sulfidization on the smithsonite surface is established. X-ray photoelectron spectroscopy (XPS), raman spectroscopy (RS) and surface potential detection are employed to characterize surface properties of the sulfidization-treated smithsonite. Furthermore, the surfaces property differences of zinc sulfide mineral before and after sulfidization are analyzed. Adsorption capacity of advanced xanthate and contact angle of mineral surfaces are detected to investigate hydrophobicity differences of the smithsonite surfaces before and after catalytzed sulfidization. Finally, factors affecting the processing of chlorine-ammonia coupling catalyzed- sulfidization are investigated through laboratory flotation tests of Halimond tube and hanging trough flotator. Based on research results of the present project, the innovative prototypes named "couplying catalyzed-sulfidization of microfine zinc oxide mineral by adding chlorine and ammonia- Xanthate flotation" can be formed, moreover, the theoretical basis for practical applications of this innovative prototypes can be obtained.