Selective Inhibition Behavior and Mechanism of Al−starch Complex on Ultrafine Calcite in Scheelite Flotation
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摘要:
微细粒方解石与白钨矿嵌布连生紧密，其体积小、质量轻、比表面积大，难以高效抑制，严重影响钨浮选指标的提升。通过合成反应、团簇模型计算及红外光谱分析，研究了铝离子与淀粉的作用产物；通过单矿物及实际矿石浮选实验，与苛化淀粉对比，揭示了Al−淀粉的选择性抑制效果；通过Zeta电位、X射线光电子能谱，剖析了Al-淀粉对微细粒方解石的选择性抑制机理。结果表明，Al3+最容易与淀粉反式分子支链O6和邻近O1原子反应，生成键长最短的O1—Al—O6结构。苛化淀粉对白钨矿和方解石均产生抑制作用，而Al−淀粉只对微细粒方解石的浮选产生抑制效果，将钨精矿WO3品位由苛化淀粉的31.44%提升至40.51%，从而实现白钨矿与方解石的浮选分离。苛化淀粉通过羟基作用于白钨矿和方解石的表面，使两矿物的表面电位产生负偏移，影响两矿物表面的Ca、O特征原子。Al−淀粉通过金属基团，选择性地与方解石表面阴离子O位点发生化学吸附而不会与白钨矿表面发生作用，从而改变细方解石的表面电荷及特征原子，产生抑制作用。
Abstract:Ultrafine calcite was closely associated with scheelite, and its small volume, light weight, and large specific surface area resulted in difficulty inhibiting, which seriously affected the improvement of tungsten flotation index. In this study, the molecular structure of Al−starch was studied by synthesis reaction, cluster model calculation, and infrared spectrum analysis. The selective inhibition effect of Al−starch was revealed by flotation experiments of single mineral and actual ore, which was also compared with the effect of caustic starch. The selective inhibition effect of Al−starch was revealed by flotation experiments of single mineral and actual ore. The selective inhibition mechanism of Al−starch on fine calcite was analyzed by Zeta potential and X−ray photoelectron spectroscopy. The results confirmed that Al3+ was most easily chelated with the O6 and O1 of the starch molecule of trans structure to form O1—Al—O6 structure with the shortest bond length. Caustic starch could inhibit both scheelite and calcite, while Al−starch could only inhibit the flotation of ultrafine calcite, and increased the grade of WO3 in tungsten concentrate from 31.44% to 40.51% and realized the flotation separation of scheelite from calcite. The caustic starch made the surface potential of scheelite and calcite shift negatively through hydroxy, and also affected the surface characteristic atoms of Ca and O. Al−starch was selectively chemisorbed on the O site of the anionic group on the surface of calcite through metal group but did not affect the surface of scheelite, which changed the surface charge and characteristic atoms of ultrafine calcite and inhibit its flotation.
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Key words:
- Al-starch /
- flotation /
- ultrafine calcite /
- scheelite /
- inhibition mechanism
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图 7 Pb−BHA捕收剂体系下细粒级白钨矿与方解石的浮选回收率（c(Pb−BHA) = 1.5×10−4 mol/L，c(松油醇) = 12.5 µL/L）
Figure 7.
图 8 不同质量比的Al−淀粉对白钨矿和方解石单矿物浮选的影响（pH = 8.5，c(淀粉) = 10 mg/L，c(Pb−BHA) = 1.5×10−4 mol/L，c(松油醇) = 12.5 µL/L）
Figure 8.
表 1 主要矿物组成及含量分析结果
Table 1. Analysis results of mian mineral composition and content
矿物 含量/% 矿物 含量/% 白钨矿 0.23 石英 9.83 黑钨矿 0.10 石榴石 28.44 锡石 0.13 长石 11.45 绿泥石 1.46 云母 7.50 萤石 17.33 其他 8.05 黄铁矿 1.76 — — 方解石 13.72 合计 100.00 
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表 2 实验所用药剂
Table 2. Reagents used in experiments
药剂名称 主要成分 等级 生产厂家 氢氧化钠（粒状） NaOH 分析纯 天津恒兴化学试剂制造有限公司 苯甲羟肟酸 C7H7NO2 分析纯 上海梯希爱化成工业发展有限公司 硝酸铅 Pb(NO3)2 分析纯 西陇化工股份有限公司 硫酸铝 Al2(SO4)3 分析纯 国药集团化学试剂有限公司 可溶性淀粉 (C6H10O5)n 分析纯 国药集团化学试剂有限公司 松油醇 C10H18O 分析纯 上海麦克林生化科技有限公司 BHA C7H7NO2 工业级 广州明特化工制药厂 硝酸铅 Pb(NO3)2 工业级 株洲选矿药剂厂 硫酸铝 Al2(SO4)3 工业级 长沙化工一厂 水玻璃 Na2O·mSiO2 工业级 长沙化工一厂
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表 3 闭路实验结果
Table 3. Result of closed−circuit experiment
实验变量 产品 产率/% WO3品位/% WO3回收率/% 不加抑制剂 钨精矿 0.60 31.44 64.81 钨尾矿 99.40 0.10 35.19 合计 100.00 0.29 100.00 加入20 g/t Al−淀粉 钨精矿 0.44 40.1 61.52 钨尾矿 99.56 0.11 38.48 合计 100.00 0.29 100.00
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表 4 不同条件下方解石和白钨矿的原子含量变化
Table 4. Atomic content of calcite and scheelite with different treatment
元素 C/% O/% Ca/% W/% Al/% 方解石 31.75 49.29 18.96 − 0 方解石+苛化淀粉 31.85 49.72 18.43 − 0 方解石+Al-淀粉 29.78 51.21 17.32 − 1.69 白钨矿 20.47 50.16 15.53 13.83 0 白钨矿+苛化淀粉 21.69 52.91 13.48 11.92 0 白钨矿+Al-淀粉 20.50 50.23 15.28 13.90 0.09
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