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孔雀石−脱硫石膏体系硫化焙烧产物的浮选行为与作用机制

Flotation behavior and mechanism of sulfidation-roasted products in malachite-desulfurization gypsum system

  • 摘要: 为改善孔雀石的浮选性能,以工业固废脱硫石膏为硫化剂开展硫化焙烧试验,考察焙烧温度、焙烧时间及脱硫石膏掺量对焙烧产物浮选行为的影响,并采用X射线衍射(XRD)、X射线光电子能谱(XPS)、接触角、Zeta电位及捕收剂吸附量测试,分析孔雀石硫化重构特征及焙烧产物与丁基黄药(NaBX)的界面作用。结果表明,当焙烧温度为500 ℃、焙烧时间30 min、脱硫石膏掺量为0.2时,焙烧产物的浮选回收率达到93.86 %,较原始孔雀石提高74.68百分点。XRD结果显示,升高焙烧温度可促进脱硫石膏还原转化及CuS、CaS的形成;当温度升高至550 ℃时,Cu39S28和CaO特征峰增强,表明过高温度引起铜硫化物及含钙物相进一步转化。XPS结果表明,焙烧温度由400 ℃升高至500 ℃后,焙烧产物表面Cu+相对含量由36.42 %提高至58.53 %,Cu2+相对含量由63.58 %降低至41.47 %,说明孔雀石表面还原硫化程度提高。未添加硫化剂时,焙烧产物的接触角仅为23.71°;加入脱硫石膏后,随焙烧温度由400 ℃升至500 ℃,接触角由59.03°增大至80.25°,表明脱硫石膏参与的硫化重构显著增强了矿物表面疏水性,且升温进一步促进了该过程。Zeta电位测试结果显示,NaBX作用后,500 ℃焙烧产物的电位均较400 ℃焙烧产物向负向移动,表明其表面与NaBX的作用更强。吸附量测试进一步显示,NaBX在400 ℃和500 ℃焙烧产物表面的吸附量分别为6.06×10−5 mol/g和7.60×10−5 mol/g,增幅为25.4 %。脱硫石膏经还原转化提供活性硫,促进孔雀石含氧铜物种向含铜硫化物转变,形成更多可与NaBX作用的表面铜位点,进而增强捕收剂吸附和矿物表面疏水性,提高焙烧产物的浮选性能。该方法在强化孔雀石浮选的同时,为脱硫石膏的资源化利用提供了新途径。

     

    Abstract: To improve the flotation performance of malachite, sulfidation roasting was conducted using industrial waste desulfurization gypsum as the sulfidation agent. The effects of roasting temperature, roasting time, and desulfurization gypsum dosage on the flotation behavior of the roasted samples were investigated. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), contact angle measurements, zeta potential measurements, and collector adsorption tests were used to characterize the sulfidation-induced reconstruction of malachite and the interfacial interaction between the roasted products and sodium butyl xanthate (NaBX). The results showed that under the conditions of 500 ℃, 30 min, and a desulfurization gypsum dosage of 0.2, the flotation recovery reached 93.86 %. This value was 74.68 percentage points higher than that of untreated malachite. XRD results showed that increasing the roasting temperature promoted the reduction of desulfurization gypsum and the formation of CuS and CaS. At 550 ℃, the diffraction peaks of Cu39S28 and CaO became stronger, indicating further transformation of copper sulfides and calcium-bearing phases at an excessively high temperature. XPS analysis showed that, as the roasting temperature increased from 400 ℃ to 500 ℃, the relative surface content of Cu+ increased from 36.42 % to 58.53 %, while that of Cu2+ decreased from 63.58 % to 41.47 %. These changes indicated that the degree of reduction and sulfidation of the malachite surface had increased. Without the sulfidation agent, the contact angle of the roasted sample was only 23.71°. After the addition of desulfurization gypsum, the contact angle increased from 59.03° at 400 ℃ to 80.25° at 500 ℃. This result demonstrated that sulfidation-induced reconstruction markedly enhanced surface hydrophobicity, with higher roasting temperatures further promoting this process. After NaBX treatment, the zeta potential of the sample roasted at 500 ℃ was more negative than that of the sample roasted at 400 ℃, indicating a stronger interaction with NaBX. The NaBX adsorption amounts on the samples roasted at 400 ℃ and 500 ℃ were 6.06×10−5 mol/g and 7.60×10−5 mol/g, respectively, corresponding to an increase of 25.4 %. During roasting, desulfurization gypsum was reduced to provide active sulfur. This promoted the conversion of oxygen-containing copper species into copper sulfides and generated more surface copper sites for interaction with NaBX. The enhanced collector adsorption increased surface hydrophobicity and improved the flotation performance of the roasted samples. This method not only improves the flotation performance of malachite but also offers a new approach to utilizing desulfurization gypsum.

     

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