开关型捕收剂强化微细粒氧化铜矿浮选机理研究

  随着铜矿资源的快速开发利用，品位高、易回收的硫化铜矿资源逐年减少，矿相更为复杂的原生和次生氧化铜矿已成为弥补铜资源短缺的重要来源。细磨技术的引入和环境长期风化不可避免导致大量微细粒氧化铜矿的产生。微细粒氧化铜矿由于粒径小、质量小、比表面积大、亲水性强等问题导致其难以有效回收。目前，浮选是回收微细粒氧化铜矿最有效、经济和环保的方法。然而浮选微细粒氧化铜矿存在药剂消耗大和选择性差的问题，普遍精矿回收率和品位偏低。应对此挑战，本论文通过研究新型开关型捕收剂诱导疏水性团聚来增大微细粒氧化铜矿物表观粒径，降低微细粒氧化铜(CuO)浮选药剂用量、提高回收率，实现微细粒CuO和SiO₂的有效分离。

   该研究采用接触角测试、浮选实验以及聚焦光束反射测试（FBRM）探索研究常用氧化矿捕收剂，筛选出能使微细CuO颗粒疏水性团聚的长碳链十二烷基硫酸钠（SDS）和油酸（OA），初步探讨捕收剂对微细粒氧化铜矿疏水性团聚的机理和浮选行为，揭示疏水长碳链结构对疏水性团聚的重要性。随后并以SDS捕收剂为例，详细探索SDS对微细粒CuO疏水性团聚和浮选的关系，应用扩展胶体相互作用力（EDLVO）理论计算揭示疏水力在微细粒CuO颗粒疏水性团聚中的关键作用。研究表明，在一定pH范围内具有疏水长碳链结构的SDS和OA均能使微细粒CuO团聚，显著增大CuO表观粒径，从而提高微细粒CuO浮选回收率。采用全内反射荧光显微镜（TIRFM）观察到疏水的团聚体中和表面存在气核，由此提出气核桥连疏水性颗粒强化微细粒CuO疏水性团聚假说，并通过设计实验证实。

   探索实验表明捕收剂SDS虽能有效回收微细粒CuO，但药剂消耗大。为了降低浮选捕收剂用量，本研究采用质子化三乙烯四胺（TETA）和SDS阴离子之间的离子配对开发了伪双子型捕收剂T-SDS，其结构和界面活性具有pH可控性。浮选实验表明，T-SDS在酸性条件下（pH为5）形成伪双子型结构，能显著降低捕收剂用量，比单分子捕收剂SDS，药剂用量减少近两个数量级的条件下CuO回收率仍高达95%以上。但在pH为9时，T-SDS的伪双子型结构打开，SDS和TETA单独在溶液中存在，表面活性降低。基于此研究的启发，通过质子化TETA和去质子化OA之间的极性基静电作用，开发了具有伪双子型结构的pH响应开关型捕收剂T-OA。与T-SDS不同的是，在强碱性条件下，OA去质子化形成的OA^-与质子化的TETA通过静电作用形成伪双子型结构的T-OA，该分子具有极强的捕收性能，可显著降低捕收剂用量并大幅提高微细粒CuO浮选回收率。在酸性及弱碱性条件下，油酸质子化导致T-OA解组装主要以油酸分子和TETA离子形式在溶液中存在，TETA能有效络合脉石表面和矿浆中的铜离子，大幅降低铜离子对SiO₂的活化，从而抑制脉石矿物的上浮，提高精矿中铜的品位。因此，在浮选流程中，粗选调节矿浆pH至10，利用T-OA的强捕收能力，提高CuO的浮选回收率，随后在精选时调节矿浆pH至5使T-OA解组装，利用TETA的去活化功能和OA的化学吸附捕收特性提高选择性，实现微细粒CuO与SiO₂的有效分离，提高精矿铜品位。并采用浮选配位场理论以及吸附能计算解析新型捕收剂T-OA对CuO的强捕收性能及开关性能，为新型捕收剂的开发提供新方法和新思路。

   本研究提出的伪双子型捕收剂T-SDS和开关型捕收剂T-OA不仅为微细粒氧化矿新型捕收剂的开发设计和应用提供了新思路，而且可以通过间隔基和疏水配位分子的设计拓宽开关型伪双子捕收剂在各类矿物浮选中的应用。本论文提出了开关型捕收剂的概念，实现了浮选流程中捕收剂捕收性能和选择性能的开关可控性，提高了矿物整体浮选的性能。

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