Advances in depressants for flotation separation of Cu–Fe sulfide minerals at low alkalinity:A critical review

The flotation separation of Cu–Fe sulfide minerals at low alkalinity can be achieved using selective depressants.In the flotation system of Cu–Fe sulfide minerals,depressants usually preferentially interact with the pyrite surface to render the mineral surface hydrophilic and hinder the adsorption of the collector.This review summarizes the advances in depressants for the flotation separation of Cu–Fe sulfide minerals at low alkalinity.These advances include use of inorganic depressants (oxidants and sulfur–oxygen compounds),natural polysaccharides (starch,dextrin,konjac glucomannan,and galactomannan),modified polymers (carboxymethyl cellulose,polyacrylamide,lignosulfonate,and tricarboxylate sodium starch),organic acids (polyglutamic acid,sodium humate,tannic acid,pyrogallic acid,salicylic acid,and lactic acid),sodium dimethyl dithiocarbamate,and diethylenetriamine.The potential application of specific inorganic and organic depressants in the flotation separation of Cu–Fe sulfide minerals at low alkalinity is reviewed.The advances in the use of organic depressants with respect to the flotation separation of Cu–Fe sulfide minerals are comprehensively detailed.Additionally,the depression performances and mechanisms of different types of organic depressants on mineral surfaces are summarized.Finally,several perspectives on depressants vis-à-vis flotation separation of Cu–Fe sulfide minerals at low alkalinity are proposed.

Mechanistic insights into stepwise activation of malachite for enhancing surface reactivity and flotation performance

Malachite is a common copper oxide mineral that is often enriched using the sulfidization-xanthate flotation method.Currently,the direct sulfidization method cannot yield copper concentrate products.Therefore,a new sulfidization flotation process was developed to promote the efficient recovery of malachite.In this study,Cu^(2+) was used as an activator to interact with the sample surface and increase its reaction sites,thereby strengthening the mineral sulfidization process and reactivity.Compared to single copper ion activation,the flota-tion effect of malachite significantly increased after stepwise Cu^(2+) activation.Zeta potential,X-ray photoelectron spectroscopy(XPS),time-of-flight secondary ion mass spectroscopy(ToF-SIMS),scanning electron microscopy and energy dispersive spectrometry(SEM-EDS),and atomic force microscopy(AFM)analysis results indicated that the adsorption of S species was significantly enhanced on the mineral surface due to the increase in active Cu sites after Cu^(2+) stepwise activation.Meanwhile,the proportion of active Cu-S spe-cies also increased,further improving the reaction between the sample surface and subsequent collectors.Fourier-transform infrared spec-troscopy(FT-IR)and contact angle tests implied that the xanthate species were easily and stably adsorbed onto the mineral surface after Cu^(2+) stepwise activation,thereby improving the hydrophobicity of the mineral surface.Therefore,the copper sites on the malachite sur-face after Cu^(2+) stepwise activation promote the reactivity of the mineral surface and enhance sulfidization flotation of malachite.

New influence factor inducing difficulty in selective flotation separation of Cu–Zn mixed sulfide minerals

Selective flotation separation of Cu-Zn mixed sulfides has been proven to be difficult. Thus far, researchers have found no satis- factory way to separate Cu-Zn mixed sulfides by selective flotation, mainly because of the complex surface and interface interaction mecha- nisms in the flotation solution. Undesired activation occurs between copper ions and the sphalerite surfaces. In addition to recycled water and mineral dissolution, ancient fluids in the minerals are observed to be a new source of metal ions. In this study, significant amounts of ancient fluids were found to exist in Cu-Zn sulfide and gangue minerals, mostly as gas-liquid fluid inclusions. The concentration of copper ions re- leased from the ancient fluids reached 1.02 × 10-6 tool/L, whereas, in the cases of sphalerite and quartz, this concentration was 0.62 ×10-6 mol/L and 0.44 × 10-6 mol/L, respectively. As a result, the ancient fluid is a significant source of copper ions compared to mineral dissolution under the same experimental conditions, which promotes the unwanted activation of sphalerite. Therefore, the ancient fluid is considered to be a new factor that affects the selective flotation separation of Cu-Zn mixed sulfide ores.

Adsorption behavior and mechanism of copper ions in the sulfidization flotation of malachite

Malachite is one of the main minerals used for the industrial enrichment and recovery of copper oxide resources, and copper ions are unavoidable metal ions in the flotation pulp. The microflotation, contact angle, and adsorption experiments indicated that pretreatment with an appropriate concentration of copper ions could improve the malachite recovery, and the addition of excess copper ions reduced the hydrophobicity of the malachite surface. The results of zeta potential tests indicated that sodium sulfide and butyl xanthate were also adsorbed on the surface of malachite pretreated with copper ions. X-ray photoelectron spectroscopy(XPS) results indicated that —Cu—O and —Cu—OH bonds were formed on the surface of the samples. After pretreatment with an appropriate concentration of copper ions, the number of —OH groups on the mineral surface decreased, whereas the number of Cu—S groups on the mineral surface increased, which was conducive to the sulfidization of malachite. After adding a high concentration of copper ions, the —OH groups on the mineral surface increased, whereas the number of Cu—S groups decreased, which had an adverse effect on the sulfidization flotation of malachite. Time-of-flight secondary ion mass spectrometry showed that pretreatment with copper ions resulted in a thicker sulfidization layer on the mineral surface.

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.

Separation of sulfide lead-zinc-silver ore under low alkalinity condition

A complex lead-zinc-silver sulfide ore containing 2.98% Pb, 6.49% Zn and 116.32×10^-4 % Ag （mass fraction） from Yunnan Province, China, was subjected to this work. Research on mineral processing was conducted according to the properties of the lead-zinc-silver ore. Under low alkalinity condition, the lead minerals are successfully separated from the zinc minerals with new reagent YZN as zinc depressant, new reagent BPB as lead collector, CuSO4 as zinc activator and ethyl xanthate as zinc collector. The associated silver is mostly concentrated to the lead concentrate. With the process utilized in this work, a lead concentrate of 51.90% Pb with a recovery of 82.34% and a zinc concentrate of 56.96% Zn with a recovery of 81.98% are produced. The silver recovery in the lead concentrate is 80.61%. Interactions of flotation reagents with minerals were investigated, of which the results indicate that the presence of proper amount of Na2S can precipitate Pb^2＋ and has a sulfidation on oxidized lead minerals. The results also show that NazCO3 and YZN used together as combined depressants for sphalerite can signally improve the depressing effect of new reagent YZN on sphalerite.

Cascade sulfidation and separation of copper and arsenic from acidic wastewater via gas-liquid reaction

Copper and arsenic in acidic wastewater were separated by cascade sulfidation followed by replacement of arsenic in theprecipitates by copper in the solution which was realized by recycling precipitates obtained in the first stage into the initial solution.The effects of reaction time,temperature and H2S dosage on copper and arsenic removal efficiencies as well as the effects of solid-toliquidratio,time and temperature on the replacement of arsenic by copper were investigated.With20mmol/L H2S at50°C within0.5min,more than80%copper and nearly20%arsenic were precipitated.The separation efficiencies of copper and arsenic werehigher than99%by the replacement reaction between arsenic and copper ions when solid-to-liquid ratio was more than10%at20°Cwithin10min.CuS was the main phases in precipitate in which copper content was63.38%in mass fraction.

Effect of Desliming on Flotation Response of Kansanshi Mixed Copper Ore

The Kansanshi mixed copper sulfide-oxide ore contains significant proportions of fine material manifesting in a variety of processing challenges. This paper presents the work which was carried out to evaluate the efficacy of desliming in improving the flotation response of the ore. Two modes of desliming were investigated, namely;sieving and elutriation after which the deslimed material was subjected to Kansanshi standard laboratory flotation conditions. The minimum copper feed grade for the mixed copper ore was 0.5% Total Copper (TCu). The outcome of this work has shown that desliming improves the flotation response of the Kansanshi mixed copper ore. At a rougher copper concentrate grade of 8%, copper metal recoveries obtained with desliming were in excess of 70% compared to 58% achieved with baseline tests without desliming. It was further observed that desliming resulted in improved flotation rates for the sulfide minerals. For a flotation time of 3 minutes, recoveries of 69% and 74% were obtained with elutriation and sieving respectively compared to 58% recovery for baseline tests. From the same results it was also evident that, of the two modes of desliming investigated, sieving yielded better performance than elutriation.

Sulfidation roasting of zinc leaching residue with pyrite for recovery of zinc and iron

Zinc leaching residue(ZLR) contains high content of valuable metals such as zinc and iron. However, zinc and iron mainly exist in the form of zinc ferrite, which are difficult to separate and recover. This study proposed a new process involving sulfidation roasting, magnetic separation and flotation to recover zinc and iron in ZLR. Through sulfidation roasting of ZLR with pyrite, zinc and iron were converted into ZnS and Fe3 O4. The effects of pyrite dosage, roasting temperature and roasting time on the sulfidation of zinc in ZLR were investigated. The results showed that the sulfidation percentage of zinc reached 91.8% under the optimum condition. Besides, it was found that ball-milling was favorable for the separation and recovery of zinc and iron in sulfidation products. After ball-milling pretreatment, iron and zinc were enriched from sulfidation products by magnetic separation and flotation. The grade of iron in magnetic concentrates was 52.3% and the grade of zinc in flotation concentrates was 31.7%, which realized the recovery of resources.

Depressing behaviors and mechanism of disodium bis(carboxymethyl) trithiocarbonate on separation of chalcopyrite and molybdenite

This work focuses on the organic depressant,disodium bis(carboxymethyl)trithiocarbonate(DBT),as a selectivedepressant in copper?molybdenum sulfide flotation separation.Micro-flotation,Zeta potential,FTIR and XPS measurements werecarried out to investigate the selective depression mechanism of DBT on chalcopyrite.Zeta potential and FTIR measurementsrevealed that DBT had higher affinity for chalcopyrite than molybdenite and the XPS results of chalcopyrite before and aftertreatment with DBT further proved that DBT adsorbed on chalcopyrite surface.The investigation indicates that the mechanism ofDBT adsorbing on chalcopyrite is mainly physical adsorption.Locked circuit experiments were carried out and the results showedthat DBT could be considered as a cleaner option in commercial Cu?Mo flotation separation circuits.

Recovery of Zn, Pb, Fe and Si from a low-grade mining ore by sulfidation roasting-beneficiation-leaching processes

To recover Zn, Pb, Fe and Si from a low-grade mining ore in the Lanping basin, Yunnan Province, China, a novel technology using the roasting with pyrite and carbon followed by beneficiation and hydrochloric acid leaching was proposed. Firstly, several factors such as pyrite dosage, roasting temperature, carbon powder dosage, holding time and particle size affecting on the flotation performance of Zn(Pb) and magnetic separation performance of Fe were simultaneously examined and the optimum process parameters were determined. A flotation concentrate, containing 17.46% Zn and 3.93% Pb, was obtained, and the Zn and Pb recoveries were 86.04% and 69.08%, respectively. The obtained flotation tailing was concentrated by a low-intensity magnetic separator. The grade of iron increased from 5.45% to 43.45% and the recovery of iron reached 64.87%. Hydrochloric acid leaching was then carried out for the magnetic separation tailing and a raw quartz concentrate containing 81.05% SiO2 was obtained. To further interpret the sulfidation mechanism of smithsonite, surface morphology and component of the sample before and after reactions were characterized by XRD and EPMA-EDS. The aim was to achieve the comprehensive utilization of the low-grade mining ore.

云南某细粒铜钼混合精矿分离工艺优化及工业应用

云南某细粒硫化铜钼混合精矿中主要有价金属元素为铜和钼,矿石中主要矿物为黄铜矿和辉钼矿,脉石矿物主要是石英和云母,铜、钼矿物嵌布粒度较细,与脉石矿物复杂共生。针对混合精矿分离难度大、分离指标较差、药剂单耗用量大、药剂成本高的现状,结合混合精矿含钼品位的上升,在工艺矿物学研究基础上,开展了选矿试验研究。通过对原有工艺及药剂制度进行优化试验,研制了新型铜钼分离药剂D117和D118,其中D117为铜抑制剂,D118为调整剂。在原矿铜品位20.75%、钼品位0.47%的条件下,采用“抑铜浮钼”、一次粗选、四次精选、一次扫选浮选工艺,获得钼品位45.15%、铜品位1.03%、钼作业回收率85.65%的钼精矿及含钼0.069%、铜品位20.92%、铜作业回收率99.96%的铜精矿,取得了良好的实验室选别指标。将研究成果应用于工业生产后,浮选浓度由18%提升至33%,系统台效由17.4 t/h提高至25.9 t/h,钼作业回收率由66.11%提升至80.55%,年产钼金属由286 t提高至710 t。同时,D117、D118新型小分子药剂的使用取消了水玻璃的添加,并大幅降低了硫化钠用量,硫化钠粗选用量由设计之初125000 g/t降至6000 g/t,降幅达95.20%。通过药剂制度的持续优化,进一步压缩了硫化钠用量,硫化钠单耗由13.4 kg/t降至7.53 kg/t,D117单耗由6.18 kg/t降至3.98 kg/t,在药剂成本大幅度降低的前提下,实现了铜钼分离系统处理量及生产指标的双提升。

某难选高次生铜硫化铜矿石选矿试验研究及现场技术改造

通过对某高次生铜硫化铜矿矿石的工艺矿物学分析以及矿石特性的研究,确定了合适的浮选流程,并进行了不同条件的选矿试验。试验结果表明:通过使用高效捕收剂酯-305、添加适量的Na 2 S活化铜、采用中矿集中返回再磨工艺,可取得了较好的技术指标。在试验的基础上现场实施了简单的流程改造,对于含Cu 0.92%的原矿经过磨矿分级以及两次粗选浮选后、浮选粗精矿再经过两次精选,获得了Cu品位22.16%的铜精矿产品,同时Cu总回收率达到了92.72%,取得了较好的分选指标。

河南某含金银硫化铜矿选矿试验研究

对河南某含金银硫化铜矿开展了工艺矿物学和选矿试验研究。结果表明:矿石中主要有用元素铜含量为0.82%,伴生的有益组分为硫、金和银,主要有用金属矿物为黄铜矿、辉铜矿和黄铁矿,脉石矿物主要为石英。试验以新型药剂TB1021为铜硫分离捕收剂,采用混合浮选—铜硫分离工艺获得铜精矿和硫精矿,硫精矿再经摇床重选回收部分微细粒铜精矿。混合浮选采用丁基黄药和丁铵黑药组合捕收剂,总药剂用量为120 g/t,采用一粗两精三扫工艺流程;铜硫分离浮选采用新型捕收剂TB1021,采用一粗三精三扫工艺流程。最终获得铜品位为15.21%、铜回收率为80.13%,金品位为3.02 g/t、金回收率为66.51%,银品位为160.43 g/t、银回收率为41.82%的铜精矿,以及硫品位为49.13%、回收率为54.34%的硫精矿。

矿浆难免离子对铅锌硫化矿分离的影响研究进展

这是一篇矿物加工工程领域的论文。矿浆溶液中普遍存在一些难免离子,并且其中存在的难免离子对铅锌硫化矿的浮选分离有着重要影响。矿浆中难免离子主要来源于选厂用水、矿物自身溶解、活化剂或者抑制剂解离以及流体包裹体释放引入的原生离子和磨矿过程中引入的次生离子。本文对矿浆中引入的原生离子以及磨矿体系引入的次生难免离子对铅锌硫化矿浮选分离的影响进行了总结分析发现,不论是原生离子还是次生离子对铅锌硫化矿浮选行为的影响均较为明显,较多的学者针对这种现象进行了大量的研究。通过药剂调控以及改变磨矿环境等方法已经取得了较大的突破,为后续研究者提供了重要的研究思路。本文的关注点是将前人的研究成果与现场工艺紧密结合,在不影响工业经济情况下如何从源头消除难免离子,如何从现场工艺中降低难免离子对浮选指标的影响仍是未来研究的重要方向。

铜矿浮选捕收剂研究进展与展望

浮选是铜矿分离回收最经济、最主要的富集方法。捕收剂可选择性调控铜矿物表面疏水性,增加铜矿物与脉石矿物间的疏水性差异,是铜矿浮选分离技术的核心要素。论文综述了硫化铜、氧化铜、氧化-硫化铜矿浮选捕收剂的研究进展,主要涉及黄药与黄原酸酯、黑药及其衍生物、硫氮与硫氮酯、硫氨酯和硫脲及其组合浮选硫化铜的最新研究成果;唑/嗪硫酮类等螯合剂浮选硫化铜的性能与机理;羟肟酸类、唑/嗪硫酮类等螯合捕收剂浮选氧化铜矿的性能与机理;巯基-肟基双配体螯合捕收剂和唑/嗪硫酮类等螯合剂同时疏水浮选氧化和硫化铜矿物的机制。最后,展望了铜矿浮选捕收剂的未来发展方向与应用前景。

提升某高硫低铜品位铜硫矿铜浮选回收指标试验研究

安徽铜陵某铜硫矿浮选厂处理的原矿含铜0.34%,其中硫化铜占近93%,含硫31.26%,属于高硫低铜硫化矿。选厂铜回收率长期维持在82%~84%,明显低于原矿中硫化铜理论回收率。为提升该矿石中铜的回收,开展磨矿细度优化以及复合酯类捕收剂强化铜浮选的试验研究。结果表明,在磨矿细度-74μm占75%,使用复合酯类捕收剂的条件下,小型闭路试验获得铜精矿铜品位为16.43%,铜回收率达到94.07%的指标,较现场指标分别提高1个和9个百分点;通过对小试和现场产品的粒级组成深入分析,得出现场磨矿细度不足,磨矿产品粒度组成不均匀是造成铜损失在尾矿的关键原因。同时,小试结果证明使用新型复合酯类捕收剂可强化微细粒铜矿物的回收。为选厂在实际生产中提升指标提供了科学的方向和依据。

从低浓度硫钴精矿浸出液中萃取分离铜钴试验研究

研究了采用P204+磺化煤油体系从除杂后的低浓度硫钴精矿浸出液中萃取分离铜、钴,考察了萃原液pH、萃取剂浓度、萃取相比、萃取时间、反萃取剂浓度、反萃取相比等对铜钴分离效果的影响。结果表明:在萃原液pH=4、P204体积分数25%、萃取相比V_(O)/V_(A)=1/1、萃取时间3min、反萃取剂硫酸浓度0.10mol/L、反萃取相比V_(O)/V_(A)=2/1条件下,对硫钴精矿除杂后液进行两级逆流萃取、四级逆流反萃取试验,萃余液中钴质量浓度为338.80mg/L,铜质量浓度为2.96mg/L,铜萃取率为98.32%,90.03%的钴留在萃余液中,经反萃取铜钴可得到进一步分离,有利于下一步制备高纯度硫酸钴。

充填料对硫化铜矿浮选指标的影响及其消除试验研究

安徽某矿区采用胶结充填法采矿,部分充填料混入原矿样中改变浮选矿浆原始性质,造成铜硫资源选别难度系数增大。选取充填料与硫化铜原矿样作为混合样品,采用现有生产工艺流程进行选矿试验:混合样磨至≤0.074 mm占75%后磁选得到铁精矿,磁选尾矿沉降浓缩后进行混合浮选试验,混浮粗精矿再次选别得到铜精矿和硫精矿。由试验结果可知:充填料的混入能改变矿浆pH、混合矿初始铜品位和磁选尾矿铜品位,且相对于不添加充填料时浮选闭路试验结果,添加充填料时得到的最终铜精矿中Cu品位和回收率分别降低了0.39%和1.01%;硫精矿中S品位和回收率分别降低了0.75%和4.80%。消除试验表明:加入硫酸铵1000g/t或者机械搅拌30min能降低矿浆黏度、增大矿浆浊度值和恢复捕收剂在硫化铜矿表面的吸附量,从而消除充填料对硫化铜矿浮选的恶化作用,将最终铜精矿中Cu回收率由70.37%提高至70.80%以上。

云南某贫细硫化铜矿石选矿工艺优化研究

云南某低品位细粒嵌布的铜矿石铜、硫品位分别为0.161%和9.704%,有价铜矿物嵌布粒度细,铜硫分离富集难度较大。为实现该硫化铜矿石资源的高效开发利用,在选厂原选矿流程及原矿工艺矿物学研究基础上,进行了系统的磨浮试验。结果表明:矿石采用磨矿—1粗2扫铜硫混合浮选—混浮粗精矿再磨—1粗3精2扫铜硫分离浮选闭路流程处理,可获得铜品位14.69%、铜回收率63.15%的铜精矿,硫品位29.16%、硫回收率75.10%的硫精矿,试验铜精矿品位较现场提高近3个百分点,铜回收率提高15个百分点以上,显著优于现场生产指标,达到了理想的综合回收铜硫效果。研究结果可作为工艺流程优化的依据。