基于高熵浮选理论的多组元捕收剂浮选兰坪氧化锌矿研究

Research on Multi−Component Collector Flotation of Lanping Zinc Oxide Ore Based on High−Entropy Flotation Theory

    摘要
  • 摘要: 兰坪氧化锌矿品位低、矿物组成复杂、矿石泥化严重，导致含锌矿物可浮性极差，现有浮选工艺在产业化应用方面都存在缺陷和不足。通过吸附量测试分析了硫化后的菱锌矿表面多组元捕收剂（十二胺、戊基黄药、丁铵黑药、乙硫氮和辛基羟肟酸）的吸附行为。应用高熵浮选理论公式计算了菱锌矿表面多组元捕收剂吸附后的捕收熵变。计算结果表明，当捕收体系由2×10−4 mol/L十二胺和1×10−4 mol/L戊基黄药二元体系增加为由2×10−4 mol/L十二胺、1×10−4 mol/L戊基黄药、 1×10−4 mol/L丁铵黑药、1×10−4 mol/L辛基羟肟酸组成的四元捕收剂体系时，矿物表面捕收熵由4.97 J·mol−1·K−1增加至10.35 J·mol−1·K−1。将高熵浮选理论应用于兰坪低品位难处理氧化锌矿实际矿石浮选过程中，采用先铅后锌优先浮选工艺，氧化锌浮选作业在硫化钠用量为9 kg/t，抑制剂KG−248和水玻璃用量分别为400 g/t和1000 g/t时，锌粗选使用200 g/t 的十二胺、400 g/t的戊基黄药、200 g/t的丁铵黑药、100 g/t的辛基羟肟酸四元捕收体系。在原矿含锌品位为6.97%的情况下，最终全流程开路实验获得合计锌精矿含锌品位为25.14%、锌回收率为87.96%的理想浮选指标。与单一十二胺捕收剂相比，使用四元捕收体系后浮选回收率提高12个百分点左右，同时浮选泡沫寿命显著下降，泡沫量减少，"跑槽"现象消失。该研究为实现难选氧化锌矿高效浮选回收提供了新思路，同时为该技术产业化应用奠定了基础。

     

    Abstract: Zinc oxide ore represents a significant component of zinc ore resources.The sulfidization−amine flotation method is the most extensively studied method for recovering zinc oxide ore in laboratory research. However, this method is sensitive to the slurry and suffers from persistent amine froth stability, which has prevented its large−scale industrial application to date. The flotation recovery of low−grade and difficult−to−process zinc oxide ore remains a major challenge in the mineral processing industry. The Lanping zinc oxide ore exhibited low grade, complex mineral composition, and severe ore mudification, resulting in extremely poor floatability of zinc−bearing minerals. This study systematically analyzed the adsorption behavior of multi−component collectors (dodecylamine (DDA), isoamyl potassium xanthate (KAX), ammonium dibutyl dithiophosphate (ADD), sodium diethyl dithiocarbamate (DDTC), and octyl hydroxamic acid (OHA)) on the sulfidized smithsonite through adsorption capacity tests. Applying high−entropy flotation theory, the entropy change ( \Delta S^c ) of collector adsorption on smithsonite was calculated using the derived thermodynamic formula: \Delta S^c=-R\displaystyle\sum _i=1^kx_i^clnx_i^c . The \Delta S^c increased from 4.97 J·mol−1·K−1 in a binary system (2×10−4 mol/L DDA + 1×10−4 mol/L KAX) to 10.35 J·mol−1·K−1 in a quaternary system (2×10−4 mol/L DDA + 1×10−4 mol/L KAX + 1×10−4 mol/L ADD + 1×10−4 mol/L OHA). Applying the high−entropy theory to the difficult−to−treat low−grade Lanping zinc oxide ore (Zn grade: 6.97%) via selective floatation of Pb and Zn. Under conditions of Na2S dosage (9 kg/t), depressants dosage (400 g/t KG−248 + 1000 g/t sodium silicate), and a quaternary collector system (200 g/t DDA + 400 g/t KAX + 200 g/t ADD + 100 g/t OHA), open−circuit tests yielded a mixed zinc concentrate grade of 25.14% and a zinc recovery of 87.96%. Compared with the single DDA collector system, the quaternary collector system improved the flotation recovery by approximately 12 percentage points. Moreover, the froth stability and froth amount was significantly reduced, eliminating "overflow phenomena" (i.e., uncontrolled froth spillage). This study provides a new approach for the efficient flotation of difficult−to−treat zinc oxide ores, and lays the foundation for the industrial application of this technology.

     

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