Assessment of the floatability of chalcopyrite,molybdenite and pyrite using biosolids and their main components as collectors for greening the froth flotation of copper sulphide ores

Biosolids and representative compounds of their main components – humic acids, sugars, and proteins – have been tested as possible environment-friendly collectors and frothers for the flotation of copper sulphide ores. The floatability of chalcopyrite and molybdenite – both valuable sulphide minerals present in these ores – as well as non-valuable pyrite was assessed through Hallimond tube flotation tests. Humic acids exhibit similar collector ability for chalcopyrite and molybdenite as that of a commercial collector (Aero 6697 promoter). Biosolids show more affinity for pyrite. The copper recovery (85.9%) and copper grade (6.7%) of a rougher concentrate obtained using humic acids as main collector for the flotation of a copper sulphide ore from Chile, were very similar to those of a copper concentrate produced by froth flotation under the same conditions with a xanthate type commercial collector. This new and feasible end-use of biosolids and humic acids should be new environment-friendly organic froth flotation agents for greening the concentration of copper sulphide ore. Now, further research is needed in order to scale current laboratory assays to operational mining scales to determine efficiencies to industrial scale.     

巯基捕收剂浮选细粒的某些特性

阐明了浮选不同粒级硫化物巯基捕收剂作用的研究。结果表明,当浮选细粒硫化物时,由于黑药的结构特点（有两个非极性基）,它比黄药优越。按矿粒在气泡上沿环固着的假说,探讨了使用黄药和黑药时存在不同的矿物－气泡集合体的作用机理。研究结果可用于修正选厂的药剂制度。     

Evaluating the performance of new collectors on feed to Nkana concentrator's flotation circuit

Nkana Concentrator of Zambia Consolidated Copper Mines (ZCCM) treats copper-cobalt sulphide ore using a bulk flotation and segregation flotation flowsheet to produce separate copper and cobalt concentrates.Recently, in an effort to increase mineral recovery as well as improve copper/cobalt separation, various alternative collectors have been considered as replacement for Sodium Ethyl Xanthate (SEX) which has been used for more than 30 years. Three such collectors that were evaluated are Senkol 26, a Xanthic ester, Senkol 45, a blend of alkyl dithiophosphate and Xanthates and Senkol 700, a thionocarbomate type, which were supplied by SENMIN of South Africa.In this work a series of laboratory testworks were conducted on Nkana Concentrator feed materials from four different sources namely, Mindola, Chibuluma, South Ore Body (S.O.B.) and Central shafts to compare the performance of these collectors against the existing SEX collector. Parameters considered in the evaluation were grade-recovery relationships and copper/cobalt kinetics at different collector dosages. Release analysis techniques were also employed to determine the theoretical maximum recovery of copper and cobalt for each of the collectors.It was found that the existing collector SEX showed superior flotation performance as compared to the three Senkol collectors. SEX responded better than Senkol collectors at both bulk and segregation stages of flotation. However, the Senkol collectors, particularly Senkol 45 and Senkol 700 gave very fast flotation kinetics at all dose rates during bulk flotation.Furthermore, it was shown that depression of cobalt minerals using sodium cyanide at the pH of 11.5 is not very effective with Senkol collectors, as a considerable amount of cobalt reports to the copper concentrate, which is not the case with SEX collector.     

Flotation of mixed copper oxide and sulphide minerals with xanthate and hydroxamate collectors

Sherwood Copper’s Minto Mine processes a high grade copper–gold deposit in Yukon, Canada. The ore mined is from a primary copper sulphide deposit with separate additional deposits of copper oxides. In conjunction with Ausmelt Chemicals, Minto is currently investigating options to recover copper oxide and sulphide minerals using flotation by blending their primary sulphide ore with oxide ores. The blend used in this laboratory scale investigation was 70% sulphide ore and 30% oxide ore on a weight basis. The copper sulphides present in the blend were bornite and chalcopyrite, while the oxides were malachite and minor azurite.From previous flotation investigations of mixed copper oxide and sulphide minerals using xanthate and hydroxamate collectors it was hard to distinguish the impact of the alkyl hydroxamate collector on sulphide recovery as the sulphide and oxide minerals occurred naturally together. In the case of the Minto operation the copper oxide and sulphide minerals occur in separate ore deposits and can be treated separately or blended together. This investigation has shown that using n-octyl hydroxamates (AM28 made by Ausmelt Limited) in conjunction with traditional sulphide collectors can successfully simultaneously recover copper sulphides and oxides by flotation from blended ore minerals. The copper sulphide recovery did not decrease when processing the blended ore compared to treating the sulphide ore independently. At a blend of 70% sulphide ore and 30% oxide ore, the rougher scavenger copper recovery was as high as 95.5%. The copper recovery from the blended ore using a mixture of collectors was shown to be superior to the recovery obtained using only xanthate after controlled potential sulphidisation.     

Rougher flotation of copper sulphide ore using biosolids and humic acids

In the quest of new, less hazardous, and more ambient-friendly froth flotation reagents, the use of biosolids or humic acids as both collector and frother for the concentration of copper sulphide ores was investigated. Rougher flotation tests were conducted in Denver cells on a laboratory scale, and metallurgical indicators such as copper recovery, copper concentrate grade, and concentration and enrichment ratios were compared with those obtained under similar conditions but using conventional collectors and frothers for the industrial flotation of copper sulphide ores. With a dosage of 10% (w/w) biosolids, copper recovery and grade were 26% and 0.81%, respectively. The copper recovery and grade obtained with 1.5% (w/w) salt of humic acids were 29.7% and 3.5%, respectively. A significantly higher copper recovery (65.1%) was obtained with conventional industrial collectors and frothers, but the grade was also low (3.1% Cu). With the same dosage of humic substances, humic acid show that the flotation rate constant was significantly higher (0.2 min⁻¹) than that obtained with the same dosage of biosolids (0.09 min⁻¹). These results indicate that humic acids have more affinity than biosolids for copper-containing mineral species, and also show that biosolids and humic acids could be used as both collector and frother in the sulphide mineral concentration process by froth flotation. Because the distribution of iron in the concentrate obtained with biosolids is highest, these materials seem to have more affinity for pyrite.     

捕收剂复配效应解决羊拉硫化铜矿石选择性浮选的研究

德钦羊拉硫化铜矿是一个含硫化铁矿物的硫化铜矿床。矿石中有用矿物嵌布粒度极细,其它非铜硫化物含量较多,且与黄铜矿共生密切,互相包裹,可浮性很接近,分离非常困难。根据矿石性质,研究并配制了兼顾选择性与捕收性能的混合型捕收剂,浮选试验结果表明,捕收剂YG-7可以获得较好的精矿品位与精矿回收率;而捕收剂YG-6则能保证低的尾矿品位和高的总回收率。     

组合捕收剂在矿物表面的协同效应及其浮选应用综述

捕收剂按照一定比例组合后,形成的组合捕收剂的表面活性会显著优于单一组分.重点阐述了组合捕收剂在矿物表面产生协同效应的机理,主要包括共吸附、疏水端加长、促进吸附以及改善溶液环境等.针对组合捕收剂在难选矿石(菱锌矿、白钨矿、胶磷矿、钛铁矿、锂辉石等)的浮选分离方面的应用,分类介绍了阴离子捕收剂与阳离子捕收剂组合、阴离子捕收剂与其他阴离子捕收剂组合、阴离子捕收剂与螯合捕收剂组合、阴离子捕收剂与非离子型捕收剂组合等应用情况.     

Selective flotation separation of spodumene from feldspar using new mixed anionic/cationic collectors

The selectivity in flotation separation of spodumene from other pegmatic aluminosilicates such as feldspar and mica, using a single fatty acid anionic collector, is found to be very difficult. It is attributed to the same surface Al site for interaction with fatty acid. In this study, a collector mixture of sodium oleate (NaOL) and dodecyl trimethyl ammonium chloride (DTAC) demonstrates a high selectivity for the flotation of spodumene from feldspar. The influences of important factors such as molar ratio of the mixed collectors, dosages of calcium chloride, sodium hydroxide and sodium carbonate, and pulp temperature on spodumene and feldspar flotation using the mixed collectors have been investigated through micro-flotation tests. The optimum molar ratio of NaOL and DTAC is found to be 9:1. Sodium hydroxide has to be used as a pH regulator. Without the use of depressants, no selectivity is observed as the flotation of spodumene and feldspar are activated by Ca²⁺. Sodium carbonate must be used as depressant of feldspar. A comparison of the flotation for a lithium pegmatite ore using mixed fatty acid soaps and mixed anionic/cationic collectors (NaOL/DTAC) was carried out by the batch flotation tests. The results indicated that NaOL/DTAC decrease collector consumption by two-thirds. The recovery and grade of Li₂O concentrates increase by 4.93% and 0.31%, respectively.     

Surface chemistry features in the flotation of KCl

Despite the successful industrial practice to recover KCl by flotation, the adsorption state of collectors at KCl salt surfaces is still not fully understood. In this paper, the flotation behavior of KCl and NaCl using different collectors and captive bubble contact angle measurements at KCl and NaCl crystal surfaces in their saturated solutions are reported. The influence of collector concentration and collector structure is considered. The results show that both cationic and anionic collectors produce a hydrophobic state at the structure breaking KCl salt surface, with finite contact angle values of between 30° and 60°. In contrast, the contact angle at the structure making NaCl salt surface is zero at all collector concentrations, suggesting that no collector adsorption occurs, a supposition that is supported by results from molecular dynamics simulation (MDS). Further, it appears that the presence of surface defects such as edges and corners promote the adsorption of collectors at the KCl surface, and that the flotation is achieved by bubble attachment at the edges/corners of KCl particles with the formation of aeroflocs.     

云南水源地区某氧化铜矿石选矿试验

云南水源某铜矿石铜品位为0.88%,56.6%的铜以硫化铜形式存在,43.4%的铜以氧化铜形式存在。矿石矿物组成复杂、泥化现象严重。为给该铜矿石的合理开发利用提供参考,进行了先浮选硫化铜矿物再浮选氧化铜矿物的工艺流程试验。结果表明,在磨矿细度为-200目占80%条件下,以CaO(加入磨机中)和水玻璃为抑制剂、丁黄药为捕收剂经1粗2精硫化铜浮选,硫化铜浮选尾矿经水力旋流器脱泥后,沉砂以硫化钠为活化剂、羟肟酸钠+丁黄药为捕收剂经1粗2精2扫氧化铜浮选,获得的混合铜精矿铜品位为20.13%、回收率为72.81%。氧化铜浮选前经水力旋流器脱泥减轻了矿泥在矿浆中的循环、积累现象,使精矿由四级品提高到三级品,具有较好的经济效益。     

十二烷基胺类捕收剂的取代基基因特性对其浮选性能的影响研究

为考察取代基种类和数量对十二烷基胺类阳离子捕收剂浮选性能的影响，通过浮选试验研究了含不同取代基的捕收剂对石英、赤铁矿单矿物的捕收性能，以及对石英/赤铁矿人工混合矿的分选能力。研究结果表明，甲基取代基的引入不利于阳离子捕收剂对石英和赤铁矿的捕收，随着甲基取代基数量的增加，石英和赤铁矿的浮选回收率均逐渐降低，但赤铁矿回收率降低速率更快；甲基的引入，有助于提升阳离子捕收剂的浮选选择性；随着取代基数量的增加，人工混合矿的分选效率逐渐增大。向阳离子捕收剂分子结构中引入含羟基（-OH）或胺基（-NH2）的官能团有利于其对石英的捕收，但引入含胺基的取代基以后，赤铁矿回收率也相应提高；向十二胺极性基中引入含羟基或胺基的取代基，能够提高人工混合矿分选效率，但引入含胺基的取代基后，人工混合矿分选效率增加效果不如引入含羟基取代基时明显。对试验捕收剂分子进行量子化学计算表明：随着引入甲基数量的增加，捕收剂极性基团的横截面尺寸增加，增大了药剂与矿物表面作用的空间位阻，导致药剂的捕收能力减弱，选择性增强；含胺基取代基的引入，可以增加极性基团的总电荷量，捕收剂与矿物表面的静电引力增强；引入含羟基的取代基后，能够在增强药剂与矿物表面氢键吸附作用的同时，增加药剂极性基横截面尺寸，从而在提高药剂捕收能力的同时提高了浮选选择性。在后续研究中，结合有机化学的相关知识来提取取代基的相关参数，以定量这种影响规律，从而明确取代基参数与阳离子捕收剂浮选性能之间的基因特性，可为构建一种基于取代基效应的阳离子捕收剂设计方法奠定基础。     

镧系金属-苯甲羟肟酸有机配合物对萤石和方解石的捕收性能研究

萤石、方解石等含钙矿物表面吸附位点同为钙质点, 导致脂肪酸、羟肟酸等常用氧化矿捕收剂对它们的选择性较差, 针对该问题提出利用含钙矿物阴离子的差异性来设计金属离子配合物捕收剂的思路。利用Ce-BHA配合物对萤石与方解石质量比1 GA6FA 1的人工混合矿进行一次粗选浮选试验, 最终可得萤石精矿CaF2品位78.92%、回收率74.77%, CaCO3品位11.08%、回收率24.23%, 分离效果良好。与单独使用BHA作捕收剂相比, 浮选精矿CaF2品位提高约26百分点, 回收率提高约50百分点, 表明该配合物捕收剂对萤石的选择性好。通过量子化学计算了多种镧系金属离子与苯甲羟肟酸(BHA)的作用情况及其在萤石、方解石表面的吸附行为, 结果显示最佳的配合物捕收剂组合为Ce-BHA, 与纯矿物浮选试验结果相符。     

开发冬瓜山铜矿资源选矿原则方案探讨

冬瓜山铜矿石与冬瓜山和狮子山混合铜矿石的对比试验结果表明 ,冬瓜山铜矿石可以与狮子山铜矿石混合进行处理。首先采用选择性起泡剂BC浮出以滑石和蛇纹石为主的易浮脉石 ;然后使用选择性捕收剂BJ进行铜部分优先浮选 ,使用丁基黄药 +丁基铵黑药混合捕收剂强化铜硫混选 ;混合粗精矿再磨后应用BD1 组合抑制剂进行铜硫分离 ;混选尾矿经磁选和强化浮选脱硫 ,获得合格铜精矿、硫精矿和铁精矿。所提供工艺为合理开发冬瓜山铜矿资源提供了可靠依据     

The use of canola oil as an environmentally friendly flotation collector in sulphide mineral processing

The efficiency of mineral flotation relies on the ability to selectively recover different value minerals into their respective concentrates at optimum grades and recoveries based on the differing hydrophobicities. Many of the common hydrophobizing reagents (collectors) currently used in flotation have significant occupational and environmental implications, and hence there is a quest for environmentally benign chemical additives that give similar or better performance than the more toxic conventional reagents. In this paper, we provide substantial experimental evidence that the use of edible, fatty acid-based oils (canola and palm) can foster the flotation recovery of chalcopyrite and molybdenite minerals more selectively against pyrite than the conventional collectors, sodium isopropyl, potassium amyl xanthates and diesel oil.Single and mixed chalcopyrite/pyrite minerals and plant sulphide ores’ flotation studies using canola and palm oils, in contrast with conventional collectors, are reported herein. The results indicate greater efficacy of the canola and palm oils in comparison with the conventional collectors for chalcopyrite and molybdenite recoveries and product upgrades. This is believed to be due to the edible oils’ specific interactions with iron oxides sites preferentially formed in situ on the surfaces of the chalcopyrite or molybdenite in the pulp rather than on the pyrite surfaces, causing limited recovery of the pyrite. Complementary contact angle results confirmed that more canola oil is adsorbed onto chalcopyrite surfaces than onto pyrite surfaces. For the mineral mixtures tested, the edible oil’s degree of unsaturation had a noticeable effect on its performance as a collector. A higher pyrite recovery and slightly lower chalcopyrite grade was obtained with palm oil than with canola oil. These findings suggest that the use of canola oil has a potential to add to the existing array of flotation collectors and would represent a combined opportunity for both the mining and agricultural sectors, with concomitant health, environmental and economic benefits.     

Influence of important factors on flotation of zinc oxide mineral using cationic, anionic and mixed (cationic/anionic) collectors

In this study, the influences of important factors on smithsonite flotation are investigated. Dosages of sulphidizing agent and collector, desliming prior to flotation and the use of sodium hydroxide instead of sodium carbonate as the pH regulator are essential to the effective recovery of smithsonite in cationic flotation. The appropriate temperature for flotation was found to be 30–40 °C. Sodium hexametaphosphate (SH) and sodium silicate had the greatest selectivity between smithsonite–calcite and smithsonite–quartz, respectively. The results of oleic acid flotation showed that the grade and recovery of zinc were relatively low in comparison with the sulphidization-cationic flotation method. Despite using sodium silicate and SH as depressants in oleic acid flotation, flotation was not selective. Flotation using mixed collectors (Armac C + Potassium Amyl xanthate) showed promising results. The ratio of the mixed collectors and the sequence of addition of mixed collectors were important criteria in attaining true mixed collector flotation.     

一种捕收增效剂的快速筛选方法

混合用药和复配增效剂仍然是提高氧化矿捕收剂浮选性能的主要方法。找到一种快速评价捕收增效剂增效作用效果的方法对寻找有效的捕收增效剂和优化药剂配方至关重要。以捕收剂在目的矿物表面的吸附量为出发点,并与纯矿物试验相对照,介绍了一种捕收增效剂快速筛选的方法。     

气泡、油泡和活性油质气泡在浮选中的应用和机理探讨

浮选是高效回收矿产资源应用最广泛的技术方法。气泡作为浮选载体在浮选过程中有着举足轻重的作用。以气泡-油泡-活性油质气泡为线索,对比了传统气泡与改性后油泡(气泡表层包裹一薄层油性捕收剂)、活性油质气泡(气泡表层包裹一薄层含有捕收剂的中性油)的浮选特性。通过浮选动力学分析了气泡与油泡、活性油质气泡浮选的区别,传统气泡浮选与改性后的油泡浮选均为2步反应,而活性油质气泡实现了1步浮选,大大降低了气泡与矿物颗粒间的黏附功,提高了浮选效率。从油-水界面表面活性剂解离度这个角度分析了活性油质气泡的表面性质,指出活性油质气泡的表面电性由表层中性油中添加的捕收剂和p H决定。通过DLVO理论计算了不同气泡与矿物颗粒间的相互作用能,从理论上解释了活性油质气泡浮选指标更好的原因。活性油质气泡在选矿中的成功应用表明,活性油质气泡与矿物表面的作用均强于传统气泡与矿物表面的作用,即活性油质气泡对矿物具有更强的捕收能力,相较于气泡和油泡的浮选,活性油质气泡浮选有利于提高浮选效率,降低捕收剂用量。活性油质气泡作为浮选载体从气泡这一特殊视觉为浮选行业开辟了一个崭新的研究领域。     

捕收剂与磨矿环境对铅锌矿浮选的影响

就几种常用的铅锌矿浮选捕收剂及磨矿环境对纳米比亚某复杂铅锌矿浮选的影响进行了试验研究.试验发现:捕收剂的作用效果与磨矿环境密切相关.常规的低碳钢磨机磨矿环境下,由于其强的还原性气氛及腐蚀产生的铁类氧化物在矿物表面的覆盖,严重地影响了方铅矿的可浮性;在此磨矿环境下需采用具较强捕收能力的捕收剂,如Aerophine 3418A,Aero 242等,但其浮选选择性较低.相反地,在瓷磨机的氧化性磨矿环境下,方铅矿具有良好的可浮选,可采用捕收性较弱但选择性强的捕收剂,如苯胺黑药.     

以辉锑矿为原料放电等离子烧结快速制备黝铜矿Cu12Sb4S13及反应机理

采用辉锑矿为原料成功制备出Cu12Sb4S13块体.研究以Sb2S3矿物为原料时烧结工艺对Cu12Sb4S13合成的影响.在400～440℃温度区间内均可快速合成Cu12Sb4S13块体且二次烧结能够进一步减小中间相CuSbS2和Cu3SbS3.第二相Cu3SbS4和残留相CuS随着烧结时间的延长而降低.二次烧结前进行机械化球磨处理,干磨比湿磨更容易减小残留相.初次烧结块体的断面SEM和EDS能谱分析表明内部存在Cu或Cu2S颗粒团聚现象.适当降低Cu或CuS摩尔量(化学计量比0.1 mol)能促进烧结块表面反应进行.烧结过程中,硫磺蒸汽压的导致烧结块表面成分和内部粉末的成分不同.     

四种阳离子捕收剂对赤铁矿和石英浮选行为的影响

以赤铁矿和石英为试验原料,探究了十二胺、十二烷基三甲基氯化铵、GE-609与N-十二烷基乙二胺四种阳离子捕收剂对两种矿物浮选行为的影响。结果表明,四种阳离子捕收剂对石英和赤铁矿均有一定的捕收作用,且对石英的捕收能力均强于赤铁矿;在四种捕收剂体系中,淀粉对赤铁矿均有明显的抑制作用,对于石英,淀粉除在N-十二烷基乙二胺体系中对石英一定抑制作用外,在其他三种捕收剂体系中淀粉对石英浮选影响较小。混合矿浮选试验表明,与十二胺和N-十二烷基乙二胺相比,十二烷基三甲基氯化铵和GE-609作为捕收剂时,精矿Fe品位和Fe回收率指标相对较优,与单矿物浮选结果一致。