复杂难处理白钨矿浮选分离的强化及其机理研究

发布时间：2018-04-17 15:31

本文选题：白钨矿 + 方解石　；参考：《东北大学》2015年博士论文

【摘要】：白钨矿与方解石和萤石的浮选分离以及微细粒白钨矿的有效回收一直是选矿工作者研究的热点,其难点在于白钨矿与含钙脉石矿物的可浮性相近,浮选过程中不同粒度的同类矿物之间、不同种类的矿物之间存在相互干扰,这些严重影响浮选精矿的回收率和抑制剂的选择性,基于此,本文通过浮选化学计算、浮选试验和多种检测手段研究了疏水性聚团、固液界面性质以及矿物溶解对白钨矿浮选的影响,在此基础上,通过强化白钨矿疏水性团聚、消除(减弱)含钙脉石矿物对抑制剂选择性的影响、设计和合成高选择性的捕收剂等方法强化了白钨矿的浮选分离。首先,本文提出和验证了基团电负性新公式和诱导共轭指数研究浮选药剂结构性能关系的可行性,并在此基础上提出了“基团电负性-诱导共轭指数法”,研究表明,使用该方法计算浮选药剂结构性能关系所得出的结论与量子化学计算结果一致,且两种计算方法具有互补性。其次,研究了含钙矿物表面性质以及矿物浮选特性,结果表明,三种含钙矿物的动电位、表面钙离子的相对含量以及晶格阴离子的基团电负性均存在明显差异,这些是能够实现矿物分离的主要原因；捕收剂的组合使用是强化白钨矿浮选的有效方法,且白钨矿粒度影响组合药剂的最佳配比,但不影响最佳添加顺序;药剂添加顺序明显影响组合药剂的性能,并与药剂结构、pH值、药剂用量及组分配比有关；浮选试验还表明,碳酸根离子对白钨矿有活化作用,但钙离子可降低白钨矿的回收率,方解石在碳酸钠消除钙离子影响中具有重要作用,此外,方解石及其溶解的钙离子可显著降低白钨矿回收率和抑制剂的选择性。在上述研究的基础上,针对微细粒白钨矿含量容易过高的特点,通过浮选化学计算新方法、浮选试验和多种检测手段,研究了细粒白钨矿对粗粒白钨矿浮选的影响以及疏水性团聚在白钨矿浮选中的重要作用,揭示了碳酸钠对白钨矿浮选回收的强化作用。研究表明,油酸钠为捕收剂时白钨矿的可浮性与粒度呈正相关关系；疏水性作用是白钨矿颗粒发生团聚的主要原因,且颗粒粒度影响颗粒间的相互作用能、流体剪切力以及两种作用力的相对大小关系,使得细粒(-10μm)与中间粒级(10-38.5μm)白钨矿易于发生疏水性团聚,与粗粒级(38.5-125μm)白钨矿难于发生疏水性团聚,从而导致了细粒对粗粒级白钨矿回收率有不同程度的降低作用,而对中间粒级白钨矿回收率的影响较小；碳酸根离子置换白钨矿表面的钨酸根离子后,有利于促进作用能力比碳酸根/碳酸氢根强的捕收剂的吸附,而捕收剂吸附量增加后有利于促进白钨矿颗粒间的疏水性团聚,因此,碳酸钠可强化微细粒白钨矿的回收和消除(减弱)微细粒白钨矿对粗粒白钨矿浮选的影响,从而提高了白钨矿的回收率和浮选速度。针对白钨矿与方解石和萤石可浮性相近、矿物之间存在相互干扰的特点,研究了消除(减弱)含钙脉石矿物对抑制剂选择性的影响的方法,以及设计和合成了高选择性捕收剂,使白钨矿和含钙脉石矿物的分离得到了强化。研究表明,硅酸钠可有效分离白钨矿与萤石,且好于白钨矿与方解石的分离效果,若通过比较简单的浮选工艺实现白钨矿与方解石的分离还需寻找其它抑制剂；浮选试验和理论计算表明,矿物溶解是方解石降低抑制剂选择性的主要原因,但碳酸钠可抑制方解石的溶解,从而可消除(减弱)方解石对抑制剂选择性的影响；白钨矿与方解石的混合矿分离时碳酸钠可强化CMC的选择性,但碳酸钠用量过高不利于提高精矿品位,基于此,在适量碳酸钠的作用下,以CMC为抑制剂实现了白钨矿与方解石的分离,且分离效果好于硅酸钠,从而使白钨矿与方解石的分离得到了强化；通过“基团电负性-诱导共轭指数法”和量子化学计算设计并合成了十二烷基丙二酸(DCA),试验表明,以CMC为抑制剂,组合使用DCA和油酸钠可成功分离白钨矿与方解石,且效果明显好于单独使用油酸钠；DCA为捕收剂分离白钨矿与方解石时不需添加碳酸钠,因为碳酸钠会降低精矿品位,但是加入钙离子可以减弱碳酸钠对品位的影响,而且进一步强化了白钨矿与方解石的分选效果。云南麻栗坡某白钨矿矿石含W03仅为0.15-0.18%,且微细粒白钨矿含量多,根据前期的基础研究,本文使用碳酸钠调节pH值、消除含钙脉石对白钨矿浮选的影响、活化白钨矿和提高自载体浮选回收率,以及使用水玻璃抑制硅酸盐矿物,利用组合捕收剂的协同效应提高了粗精矿的品位和回收率；湖南某白钨矿矿石中含大量的含钙脉石矿物,以DCA和油酸钠的组合药剂代替731后,可明显降低钨粗精矿中的含钙脉石矿物的含量以及提高粗精矿的品位。本论文研究成果丰富了白钨矿浮选的理论体系,对微细粒白钨矿富集和白钨矿与含钙脉石矿物的分离具有参考价值。
[Abstract]:The flotation separation of scheelite and calcite and fluorite and effective recovery of fine scheelite is always the research focus in mineral processing workers, the difficulty of scheelite and calcic gangue mineral floatability between similar Their natures are much the same., minerals of different particle size in flotation process, mutual interference between different kinds of minerals, which seriously affect the rate and recovery of flotation inhibitor concentrate the selectivity, based on this, this paper through flotation chemistry calculation, flotation tests and various detection methods of hydrophobic clusters, effects of solid-liquid interface properties and mineral dissolution of Scheelite Flotation, on this basis, through strengthening the hydrophobic aggregation of scheelite, eliminate the influence (weaken) the selective inhibitor of calcic gangue mineral collector, methods of design and synthesis of high selectivity and strengthen the flotation separation of scheelite. Firstly, this paper proposed and verified in groups The feasibility of the new formula and the electronegativity index of flotation reagent induced conjugate structure performance relationship, and on the basis of the "group electronegativity - induced conjugate index method, research shows that using the method to calculate the conclusion and quantum chemistry the relationship between structure and properties of flotation reagent, the calculation results are consistent, and two kinds of calculation the method is complementary. Secondly, study the surface properties of calcium minerals and mineral flotation characteristics, the results show that the dynamic potential of three kinds of minerals containing calcium, calcium content and relative surface lattice anion group electronegativity difference, which is the main reason to achieve the separation of minerals; collector combination is an effective method to strengthen the Scheelite Flotation, and the influence of particle size of scheelite best combination agent, but does not affect the optimal adding order of reagent addition order; significantly affect the drug combination Agent performance and chemical structure, pH value, dosage and ratio; flotation tests also show that carbonate ions scheelite has activation, but calcium can reduce the rate of recovery of scheelite, calcite in sodium carbonate to eliminate the effects of calcium ion plays an important role, in addition, calcium ion and calcite dissolution can significantly reduce the selectivity of scheelite recovery and inhibitors. Based on the above research, according to the characteristics of fine scheelite content to high, a new calculation method by flotation chemistry, flotation tests and various methods, studied the influence of coarse fine scheelite Scheelite Flotation and hydrophobic aggregation plays an important role in the selection of floating scheelite that reveals the strengthening effect of sodium carbonate on Scheelite Flotation. Research shows that sodium oleate as collector, the floatability of scheelite and grain size was positively related. Department of; hydrophobic interaction is the main reason for the occurrence of agglomeration of scheelite particles, and the particle size effects of interaction between particles and fluid shear stress and relative size of the two forces, makes the fine (-10 m) and middle grade (10-38.5 m) is easy to occur scheelite hydrophobic aggregation, and coarse grain grade (38.5-125 m) on the occurrence of white tungsten mine hydrophobic aggregation, resulting in a fine to coarse scheelite recovery rate decreases in different degrees, but had little influence on the intermediate recovery of scheelite particles; carbonate ion tungstate ion replacement of scheelite surface, is conducive to the promotion of ability than the carbonate / bicarbonate strong adsorption of the collector, and the collector adsorption increased after promoting hydrophobic scheelite agglomeration of particles, therefore, sodium carbonate can enhance the recovery of fine scheelite and eliminate fine (weakened) Effect of coarse scheelite Scheelite Flotation of scheelite, so as to improve the recovery rate and speed. The flotation of scheelite and calcite and fluorite flotation characteristics of Their natures are much the same., mutual interference between minerals, the elimination of influence (weaken) method for selective inhibitors of calcium gangue minerals, as well as the design and high selective collector prepared, so that the separation of scheelite and calcareous gangue minerals has been strengthened. The results show that sodium silicate can effectively separate scheelite and fluorite, and good separation effect on Scheelite and calcite, if separated by flotation process is relatively simple to achieve scheelite and calcite has yet to find other inhibitors; flotation tests and theoretical calculations show that mineral dissolution is the main reason for reducing calcite and selective inhibitor of sodium carbonate dissolved, but inhibits calcite, which eliminates calcite (weakened) Effect of selective inhibitors; scheelite and calcite mixed ore separation of sodium carbonate can enhance the selectivity of CMC, but the amount of sodium carbonate is too high is not conducive to improve the concentrate grade, based on this, the amount of sodium carbonate under the action of CMC inhibitors to achieve the separation of scheelite and calcite, and the separation effect is better than sodium silicate thus, the separation of scheelite and calcite has been strengthened; twelve alkyl malonic acid were designed and synthesized by the group electronegativity - induced conjugate index method and quantum chemistry calculation (DCA), experiments show that with CMC inhibitor, DCA and sodium oleate can be successfully combined scheelite and calcite separation, and the effect of better than using sodium oleate as collector alone; DCA separation of scheelite and calcite without the addition of sodium carbonate, because sodium carbonate will reduce the concentrate grade, but calcium carbonate can be weakened Effect of sodium on the grade, and further strengthen the effect of separation of scheelite and calcite. Yunnan Malipo scheelite ore containing W03 is only 0.15-0.18%, and the micro fine scheelite content, according to the previous research, this paper using sodium carbonate to adjust the pH value, eliminate the influence of calcic gangue Scheelite Flotation of scheelite, activation and improve the autogenous carrier the flotation recovery rate, and the use of water glass inhibition of silicate minerals, using a combination of collecting agent synergies and improve the crude concentrate grade and recovery rate; with a large number of calcareous gangue minerals scheelite ore in Hunan, with a combination of chemical DCA and sodium oleate instead of 731, can significantly reduce the content of tungsten coarse concentrate in calcium the gangue minerals and improve the rough concentrate grade. The achievements of this thesis enrich the theory system of Scheelite Flotation, fine scheelite enrichment and scheelite ore and water The separation of calcium gangue minerals is of reference value.

【学位授予单位】：东北大学
【学位级别】：博士
【学位授予年份】：2015
【分类号】：TD923;TD954

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