Flotation of copper oxide minerals: A review

Copper oxide minerals are important copper resources, which include malachite, azurite, chrysocolla, cuprite, etc. Flotation is the most widely used method for the enrichment of copper oxide minerals in the mineral processing industry. In this paper, the surface properties of copper oxide minerals and their effects on the mineral flotation behavior are systematically summarized. The flotation methods of copper oxide minerals and the interaction mechanism with reagents are reviewed in detail. Flotation methods include direct flotation (using chelating reagents or a fatty acid as collector), sulfidization flotation (using xanthate as collector), and activation flotation (using chelating reagents, ammonium/amine salts, metal ions, and oxidant for activation). An effective way to realize efficient flotation of copper oxide minerals is to increase active sites on the surface of copper oxide minerals to enhance the interaction of collector with the mineral surface. Besides, various perspectives for further investigation on the efficient recovery of copper oxide minerals are proposed.     

Sulfidization regulation of cuprite by pre-oxidation using sodium hypochlorite as an oxidant

The direct sulfidization of cuprite is inefficient because cuprite is a copper-oxide mineral with a strong surface hydrophilicity. In this study, oxidant was used to modify cuprite surfaces to regulate the sulfidization of cuprite. Microflotation tests showed that the flotation recovery of pre-oxidized cuprite was nearly 25% higher than that of direct sulfidization flotation, which indicates that the cuprite surface activity was enhanced after pre-oxidation by Cu(I) species (weak affinity with sulfur ions) transformation to Cu(II) species (strong affinity with sulfur ions). Zeta potential, scanning electron microscopy-energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and time-of-flight secondary ion mass spectrometry results showed that pre-oxidation improved cuprite sulfidization and promoted the formation of copper-sulfide species on the cuprite surfaces. The mineral surface stability and thus, xanthate species adsorption on the cuprite surfaces were improved. The surface-adsorption measurements and infrared spectroscopy showed that a large amount of xanthate species was adsorbed onto the sulfidized cuprite surfaces after pre-oxidation, which enhanced the cuprite hydrophobicity and improved the cuprite flotation.     

Effect of deep oxidation of chalcopyrite on surface properties and flotation performance

In this study, chalcopyrite was oxidized in hydrogen peroxide (H₂O₂) solutions of different concentrations to simulate different degrees of oxidation in real ores, and the effects of H₂O₂ treatment on chalcopyrite surface properties and flotation performance were investigated by surface analysis techniques and floatation experiments, which implied the reason for the poor grade and recovery of oxidized chalcopyrite concentrate in the production process of the ore. Flotation results showed that when the concentration of H₂O₂ increased from 0% (by weight) to 5%, the flotation recovery of chalcopyrite decreased sharply. However, with increasing H₂O₂ concentration from 5% to 30%, chalcopyrite recovery improved relatively to different degrees with different collector concentrations. Analyses of X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma-atomic optical emission spectrophotometry (ICP-OES) results indicated that the pretreatment with H₂O₂ caused that hydrophilic substance formed on chalcopyrite surface with the dissolution of copper ions, and the dissolution amount of copper increased with the increase of H₂O₂ concentration. UV–visible spectrophotometer and Fourier transform infrared spectrum (FTIR) studies indicated that the pretreatment of chalcopyrite with H₂O₂ had little effect on the adsorption amount of potassium butyl xanthate (PBX) on chalcopyrite surface. However, due to the dissolution of copper ions, PBX interacted with chalcopyrite mainly as buthyl dixanthogen (BX)₂.     

在孔雀石的黄药直接浮选体系中铵离子浓度的研究

已有的研究确认了无机盐对孔雀石直接浮选所起的相转移活化作用，本试验采用氨气敏电极，测定了硫酸铵、氯化铵、硫酰铁铵等无机铵盐在孔雀石浮选过程中氨浓度变化情况。研究结果表明：无论是硫酸铵、氯化铵、还是硫酸铁铵，它们在孔雀石黄药浮选的始终，铵离子浓度保持不变，而只是在浮选过程中发生变化，参与了矿物、药剂之间的反应，从而可断定：无机铵盐在孔雀石的纯矿物浮选中，表现为一种“相转移催化剂”。     

Selective depression action of taurine in flotation separation of specularite and chlorite

Chlorite, as the most representative gangue mineral associated with specularite, of which the separation of these two minerals is difficult. This paper investigated the depression effect of taurine on specularite/chlorite separation via flotation experiments, adsorption tests, contact angle measurements, Zeta potential detection, FT-IR measurements, and XPS analyses. The results of single mineral flotation indicated that chlorite could be depressed selectively by taurine with the recovery of less than 30%, but the floatability of specularite remains high with recovery rate of 81.77% at pH 10. The artificial mixed mineral flotation results confirmed the effectiveness of taurine as a depressant. Surface adsorption, contact angle, and Zeta potential detection revealed taurine primarily adsorbs on the chlorite surface, which hampered the DDA’s subsequent adsorption and results in the chlorite’s poor floatability. The FT-IR spectra and XPS analyses provided further proof that taurine adsorbed on chlorite surface as an electron donor, and part of the electrons transferred from the sulfonic acid group of taurine to metal ions during the adsorption process. In addition, the hydrogen bond between amino-group of taurine and O ions in chlorite surface was also formed in the adsorption process. Finally, optimized adsorption configurations of taurine on chlorite surfaces were proposed.     

由龙头汪金矿硫精砂中综合回收金银铜的研究

研究探讨了从硫精矿中综合回收金银铜的途径．确定了最易实现工业化的浮选流程。在原硫精矿害Cu、Au、Ag、S分别为0．67%、5．01g／t、17．23g／t、35．17%的情况下，经氧化浮选后，可获得铜金精矿；βCu=15．59％．βAu=112g／t．βAg=210g／t，εCu=77．74%，εAu=40.72%，浮选尾矿中βs=35．42%，εs=97．31%，可作为硫精矿出售。     

酸对捕收剂在胶磷矿和白云石表面吸附的影响

浮选过程中抑制剂会使矿物表面亲水,还可能与捕收剂存在竞争吸附. 硫酸和磷酸是钙（镁）质磷矿石反浮选工艺常用的抑制剂. 通过单矿物和人工混合矿浮选试验及吸附量测定,研究了胶磷矿 - 白云石反浮选体系中,抑制剂硫酸或磷酸浓度对捕收剂 GJBW 在矿物表面吸附量的影响. 结果表明,酸浓度对矿物上浮率影响较大,但对捕收剂在胶磷矿和白云石表面吸附量影响均较小,说明该体系中抑制剂和捕收剂在矿物表面不是竞争吸附而是共同吸附,综合决定表面亲/疏水性,进而影响其上浮率. 于是建立了两者在矿物表面共同吸附的双电层模型,其中不溶油酸分子（HOl）作为主要捕收剂组分在白云石 - 水界面起主导作用使表面疏水,而胶磷矿酸溶释放出的或磷酸电离出的 H ₂ PO ₄ ^- 做为主要抑制组分在胶磷矿 - 水界面起主导作用使表面亲水.     

从会理锌矿铅锌矿石中分选铜的试验研究

为从会理锌矿含铜的铅锌硫化矿中分选铜,对会理锌矿含铜的铅锌硫化矿进行了系统的工艺矿物学研究和选矿工艺研究．工艺矿物学研究结果表明会理锌矿含铜的铅锌硫化矿中铜矿物以黄铜矿、银黝铜矿-砷黝铜矿、硫锑铜银矿、车轮矿等矿物形式存在,并以黄铜矿为主,其次为银黝铜矿-砷黝铜矿系列矿物．铜矿物嵌布特征复杂,与闪锌矿互相包裹及呈固溶体分离结构较为普遍．铜矿物嵌布粒级较均匀,多集中于＋0．08mm以上粒级中,铜矿物单体解离度相对较好．基于会理锌矿舍铜铅锌硫化矿的矿石特性,采用“铜铅混浮-铜铅分离-再浮锌”浮选工艺,在原矿含铜0．94％、铅0．92％、锌10．60％的情况下,可获得含铜17．76％、铅4．35％、锌12．87％,铜回收率62．89％的铜精矿,含铜2．99％、铅54．52％、锌10．48％,铅回收率50．34％的铅精矿,含铜0．75％、铅1．20％、锌55．86％,锌回收率88．56％的锌精矿,银在铜、铅、锌精矿中的回收率分别为50．93％、2．32％、29．51％,实现了从会理锌矿含铜铅锌硫化矿中分选铜的目标．     

辛基羟肟酸浮选行为的研究进展

羟肟酸是一类高效、低毒、选择性强的捕收剂,已被广泛应用于多种金属矿,特别是稀土矿物的浮选。其中,辛基羟肟酸（OHA）碳链长度适中,生产工艺简单且成本低,具有良好的浮选性能和起泡性能。介绍了OHA的合成方法、捕收机理、分析检测手段及其在稀土矿物、钨矿物、铁矿物、锡石、孔雀石等矿物浮选中的应用。OHA可通过络合作用与多种金属离子形成稳定的杂环螯合物,从而实现药剂在矿物表面的选择性吸附。OHA浮选pH范围较宽,pH为7左右浮选效果最佳。在抑制剂的作用下,OHA能实现稀土矿物、钨矿物等有价矿物与重晶石、萤石、石英等脉石矿物的有效分离。开发基于OHA 的组合药剂,有望获得更好的选别指标和经济效益。     

利用磷灰石实现硫化矿浮选废水回用的试验评价

出于环境的考虑，越来越多的选矿厂均利用回水以减轻废水对环境的冲击和对水资源的依赖．工业生产经验表明，回水使用量的增加会对浮选带来不利的影响，尤其是对复杂矿化矿的优先浮选．浮选选择性降低的主要原因是溶液中重金属离子对闪锌矿或黄铁矿的意外活化．本文应用微型浮选试验，吸附试验和表面测试研究了利用磷灰石来实现硫化矿浮选废水回用的可行性．试验表明，磷灰石可增强对闪锌矿的抑制而提高浮选的选择性．微型浮选和表面测试表明，磷灰石与闪锌矿竞争吸附溶液中的重金属，从而降低闪锌矿表面的重金属浓度．     

钙镁离子对云南磷矿浮选的影响及回水处理

以云南晋宁、安宁和昆阳磷矿为研究对象,在浮选过程中添加钙镁离子,通过回收率、品位的变化研究其对浮选效果的影响.试验结果表明,当加入的钙镁离子达到一定浓度后,对晋宁和安宁磷矿正浮选有不同程度的影响,而对昆阳磷矿单一反浮选影响不大.同时,晋宁和安宁磷矿正浮选尾矿水钙镁离子的测定结果表明,正浮选尾矿水中的钙镁离子浓度为45 mg/L时不足以影响正浮选过程,正浮选尾矿水可直接返回正浮选;当正反浮选废水混合回用,钙镁离子离子浓度超过100 mg/L时,需处理去除.     

Effect of butanol on flotation separation of quartz from hematite with N-dodecyl ethylenediamine

In order to investigate the effect of butanol on quartz flotation when N-dodecyl ethylenediamine(ND)was used as collector, single mineral flotation and artificial mixed mineral(hematite and quartz were mixed at a mass ratio of 3:2) separation were conducted in the laboratory. Experimental results indicated that addition of butanol could improve the collecting performance of ND on quartz and enhance the floatability of quartz. Best flotation recovery of quartz was obtained when butanol was mixed with ND at a mass ratio of 1:1. Moreover, the molecular structure of alcohols had a significant effect on mineral recovery. Best separation efficiency could be obtained when tert-butanol was added as it had the largest cross-sectional area. Zeta potential measurements indicated that alcohols could strengthen electrostatic adsorption between quartz and collector. Molecular dynamic simulations revealed that co-adsorption of alcohols along with ND had taken place on the quartz surface, and ND/tert-butyl combinations were more easily absorbed on the quartz surface.     

利用磷灰石实现硫化矿浮选废水回用的试验评价

出于环境的考虑,越来越多的选矿厂均利用回水以减轻废水对环境的冲击和对水资源的依赖.工业生产经验表明,回水使用量的增加会对浮选带来不利的影响,尤其是对复杂矿化矿的优先浮选.浮选选择性降低的主要原因是溶液中重金属离子对闪锌矿或黄铁矿的意外活化.本文应用微型浮选试验,吸附试验和表面测试研究了利用磷灰石来实现硫化矿浮选废水回用的可行性.试验表明,磷灰石可增强对闪锌矿的抑制而提高浮选的选择性.微型浮选和表面测试表明,磷灰石与闪锌矿竞争吸附溶液中的重金属, 从而降低闪锌矿表面的重金属浓度.     

Exploration of amino trimethylene phosphonic acid to eliminate the adverse effect of seawater in molybdenite flotation

In this investigation, a chelating agent of amino trimethylene phosphonic acid (ATMP) was introduced to eliminate the adverse effect of seawater in molybdenite flotation. Microflotation results presented that high flotation recovery of molybdenite was achieved in freshwater using kerosene as the collector, but it was significantly decreased in the presence of seawater when pH > 9.5. Among the main ions in seawater, magnesium and calcium ions played a more detrimental role than others. After the addition of ATMP, molybdenite floatability can restore in seawater. Zeta potential distribution and solution chemistry calculation results illustrated that the decreased molybdenite floatability was attributed to the interaction of positive Mg(OH)_2(s) (major) and CaOH⁺ (minor) components with the molybdenite surface. The magnesium/calcium ions of positive components of Mg(OH)_2(s) and CaOH⁺ interacted with the ionized species of ATMP and then produced ATMP-calcium/magnesium complex, leading to the electrostatic repulsion between molybdenite and ATMP-calcium/magnesium complex that was restoring the molybdenite flotation. Hence, the ATMP can be utilized as an appropriate reagent to improve molybdenite flotation in seawater.     

低硫低铜磁铁矿选矿工艺研究

对低硫低铜磁铁矿进行了不同选别工艺研究，采用先浮后磁和使用高选择性捕收剂可获得精矿含铁64．12％，含硫0．37％，回收率84．34％的合格铁精矿，含铜13．83％，回收率50．91％的铜精矿，含硫34．23％，回收率73．85％的硫精矿，明显提高了矿产资源利用率。     

Effect of organic depressant lignosulfonate calcium on separation of chalcopyrite from pyrite

In order to selectively separate chalcopyrite from pyrite, the effect of organic depressant lignosulfonate calcium (LSC) on the flotation separation of chalcopyrite from pyrite was investigated by flotation tests. The depression mechanism was studied by Fourier-transform-infrared (FTIR) analysis. The flotation tests of single mineral show that LSC can depress the flotation of pyrite in a certain pH range, but it has little effect on chalcopyrite flotation. Flotation separation of a mixture of chalcopyrite and pyrite can be completed to obtain a copper concentrate grade up to 24.73% with a recovery of 80.36%. IR analysis shows that LSC and butyl xanthate compete in absorption on pyrite surface, and there exists an LSC characteristic peak on pyrite surface. There is little adsorption of LSC on chalcopyrite.     

Assessment of pH-responsive nanoparticles performance on laboratory column flotation cell applying a real ore feed

Nanoparticles(NPs) can promote the column flotation process in mining industry. Nanoparticles' effects on column flotation process(copper recovery, grade and flotation rate constant) are assessed in Sarcheshmeh Copper Complex, Iran, through response surface methodology(RSM) optimization technique. The c-Al_2O_3, a-Fe_2O_3, SiO_2, and TiO_2 nanoparticles are selected for these experiments. A flotation rate constant is chosen as a response to assess the effect of nanoparticles on flotation in its kinetic sense.The process p H and nanoparticle dosage are selected as the influential parameters. Results obtained from RSM indicated that the maximum percentage of Cu recovery and grade is obtained at p H of 12 and nanoparticle dosage of 6 kg/t, through a-Fe_2O_3 and c-Al_2O_3 nanoparticles, respectively. Applying nanoparticles in particular c-Al_2O_3 and a-Fe_2O_3 increases the Cu recovery by 8–10% together with the grade by 3–6% in a significant manner. It is revealed that nanoparticles could effectively be applied in enhancing the flotation performance.     

Growth of covellite crystal onto azurite surface during sulfurization and its response to flotation behavior

In this work, the growth of copper sulfide crystal onto azurite surfaces during sulfurization and its response to flotation are investigated. Filed emission scanning electron microscopy-energy dispersive X-ray spectroscopy (FESEM) and X-ray diffraction (XRD) studies confirmed that the sulfurization of azurite is not limited to the mineral surface, but rather penetrates into the bulk to form covellite crystal (syn-CuS), creating favorable conditions for the stable adsorption of xanthate and greatly promoting the azurite flotation. Additionally, as demonstrated by X-ray photoelectron spectroscopy (XPS) and time of flight secondary ion mass spectrometry (TOF-SIMS) analyses, a redox reaction occurred during this process, and Cu(Ⅱ) onto the mineral surface was reduced to Cu(I). Correspondingly, reduced S^2- was oxidized to (S₂)^2-, (S_n)^2-, and even to deeper oxidation state S⁰, (S_xO_y)^n- and SO₄^2-. Excess sodium sulfide strengthens copper sulfide to form onto the azurite surface, and provides enough raw material for crystal copper sulfide to grow, resulting in the formation of “flake-like” covellite with a better crystallinity. However, the floatability of azurite decreased dramatically under this condition, because the generated massive colloidal copper sulfide in flotation pulp deteriorates the flotation environment, resulting in a decreased effective adsorption of collector onto azurite surfaces.     

Fabrication of Stable Superhydrophobic Cupric Hydroxide Surface with Hierarchical Structure on Copper Substrate

Cupric hydroxide films with a new hierarchical architecture consisting of beautiful nanotubes and nanoflowers were directly fabricated on copper substrate via a solution-immersion process at a constant temperature of 23?℃. Stable superhydrophobic Cu(OH)₂ surface was obtained after Cu(OH)₂ films were modified with hydrolyzed 1H, 1H, 2H, 2H-perfluorooctyltrichlorosilane (C₈H₄Cl₃F₁₃Si, FOTMS). The surface morphology and composition of the film were studied using scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS), respectively. Result shows that the surface of Cu(OH)₂ films directly grown on copper substrate was hydrophilic, whereas the modified Cu(OH)₂ films exhibited the superhydrophobicity with a water contact angle (CA) of about 160.8°, as well as a small sliding angle (SA) of about 1°. The special hierarchical structure, along with the slow surface energy leads to the high superhydrophobicity of the surface.     

重金属Cu(Ⅱ)在球黏土中的吸附特性

通过批式吸附试验,考察球黏土对Cu(Ⅱ)的吸附效果,重点分析吸附时间、吸附剂用量、pH值以及初始质量浓度的影响。结果表明,Cu(Ⅱ)在球黏土上的吸附是一个先快速而后缓慢的过程,在60 min基本达到吸附平衡,且吸附量和吸附率随球黏土用量和Cu(Ⅱ)初始质量浓度的升高而提高。pH值对球黏土的吸附量有较大的影响,当pH值为6时,球黏土的吸附量可达97.93 mg/g。球黏土对Cu(Ⅱ)的吸附符合Langmiur等温吸附模型,拟合得到的最大吸附量为202.383 mg/g,准二阶动力学模型更适合描述球黏土对Cu(Ⅱ)的吸附过程,说明控制吸附速率的主要是化学吸附。与其他常见的黏土吸附剂材料相比,球黏土对Cu(Ⅱ)具有良好的吸附性能,可以作为天然矿物吸附剂来处理含Cu(Ⅱ)废水。