菱锌矿硫化浮选机理及影响因素研究进展

doi:10.16085/j.issn.1000-6613.2023-0940

摘要/Abstract

摘要：

随着锌资源开发利用的深入，低品位难选氧化锌矿成为锌的重要来源，菱锌矿作为分布最多的典型氧化锌矿，是锌的重要矿产来源。本文详细介绍了菱锌矿重要的浮选手段——表面硫化浮选，阐述了硫化浮选的作用机理，解释了菱锌矿硫化过程中化学吸附、化学反应以及详细阐述菱锌矿硫化过程中沉淀-溶解反应机理，指出硫化过程是硫化层的沉淀与氧化层脱落的动态平衡过程，成核过程为受到以溶度积为主要驱动力所发生的非均质成核，该过程不同阶段硫化速度随时间而变化。本文列举了浮选过程中矿浆pH、硫化时间、硫化温度等因素对沉淀-溶解硫化的影响方式。同时指出高效强化硫化与绿色硫化是菱锌矿硫化浮选未来研究的重中之重，通过添加药剂进行硫化的高效强化能有效减少硫化钠的用量，通过开发绿色有机硫化剂来减少硫化钠等无机硫化剂的使用，降低选矿废水的污染以及处理难度，最后点明硫化浮选在当前乃至将来都是菱锌矿有效分选的重要方法。

关键词: 菱锌矿, 浮选, 硫化机理, 硫化因素

Abstract:

The identification of low-grade refractory zinc oxide ore as a substantial zinc reservoir has emerged as a consequence of the advancement and exploitation of zinc resources. Smithsonite, as the most prevalent form of zinc oxide ore, holds considerable significance as a valuable mineral resource for zinc extraction. As a comprehensive analysis of surface sulfidation flotation, a significant flotation technique for smithsonite was presented. The mechanism of sulfidation flotation was thoroughly elucidated, including the chemisorption and chemical reaction that occured during the sulfidation process. Furthermore, the mechanism of the precipitation-dissolution reaction during sulfidation was explained in detail. It was emphasized that the sulfidation process represented a dynamic equilibrium between the precipitation of the sulfide layer and the shedding of the oxide layer. The nucleation process in this study was characterized by heterogeneous nucleation, where the solubility product serves as the primary driving force. It was observed that the rate of sulfidation exhibited temporal variations at different stages of the process. The present study provided a comprehensive analysis of the effects of pH, sulfidation time and sulfidation temperature on the process of precipitation-dissolution sulfidation in flotation. At the same time, it was emphasized that future research on zinc ore sulfidation flotation should prioritize high-efficiency enhanced sulfidation and green sulfidation. The incorporation of chemicals in the sulfidation process can significantly enhance its efficiency, leading to a reduction in the consumption of sodium sulfide. Furthermore, the development of environmentally friendly organic sulfidation agents can help to minimize the reliance on inorganic sulfidation agents like sodium sulfide. This approach aimed to mitigate the pollution and treatment challenges associated with mineral processing wastewater. It was worth noting that sulphide flotation currently played a significant role in the efficient separation of zinc ore both presently and in the foreseeable future. It was pointed out that sulfide flotation was an important method for effective separation of smithsonite at present and in the future.

Key words: smithsonite, flotation, sulfidation mechanism, sulfidation factor

中图分类号:

TD952

林翔, 焦芬, 魏茜, 张政权. 菱锌矿硫化浮选机理及影响因素研究进展[J]. 化工进展, 2024, 43(7): 4015-4031.

LIN Xiang, JIAO Fen, WEI Qian, ZHANG Zhengquan. Research progress of sulfidation flotation mechanism and influencing factors of smithsonite[J]. Chemical Industry and Engineering Progress, 2024, 43(7): 4015-4031.

图/表 14

图1 菱锌矿表面硫化化学反应[20-21]

图2 菱锌矿表面硫化化学吸附[21]

图3 矿物表面流体边界层示意图[28]

图4 菱锌矿表面硫化沉淀-溶解耦合作用[7,21,31]

图5 硫化钠溶液组分随pH变化图[32]

图6 （001）面上S2-/HS-与ZnCO3作用后S2-、Zn原子和H2O分子的态密度图[35]

图7 锌物种的变化/硫化钠作用下回收率随pH变化图[37-38]

表1 5×10-4原始Na2S·9H2O浓度下矿浆中S浓度随硫化时间的变化[40]

时间/min	硫组分剩余浓度/×10^-5mol·L^-1
1	31.5
3	22.4
6	16.6
10	14.6
15	13.2
20	12.3
30	12.1

图8 硫化时间的影响[42-44]

图9 菱锌矿在不同硫化温度下的FESEM 图[47]

图10 菱锌矿回收率随硫化钠用量变化图[31]

图11 Ca2+吸附前后菱锌矿表面两种Zn位点吸附HS-模拟图[55]（1Å=0.1nm）

图12 金属离子对菱锌矿硫化影响[61-62,67]

图13 铵改性前后菱锌矿表面脱羟基反应[72]

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