A refractory zinc ore, distinguished by its high magnesium content and low grade, was found to contain valuable elements, primarily zinc and cadmium, with concentrations of 1.60% and 50.60 g/t, respectively, predominantly hosted within marmatite. The principal impurities in the ore were identified as SiO₂ and MgO, with concentrations of 37.66% and 34.47%, respectively. The gangue minerals were primarily composed of serpentine, pyroxene, amphibole, and chlorite, with marmatite exhibiting a complex paragenetic relationship with these magnesium-bearing gangue minerals. To effectively mitigate the adverse effects of high serpentine content on zinc flotation performance, a series of systematic single-factor flotation condition tests were conducted. The interaction mechanism between a combined reagent of C6H8O7+(NaPO3)6 and serpentine was analyzed using infrared spectroscopy. Additionally, changes in the elemental composition and morphological characteristics on the surface of marmatite, both before and after treatment with C6H8O7+(NaPO3)6, were meticulously examined using scanning electron microscopy and energy dispersive spectroscopy(SEM-EDS). The optimal technical parameters for the roughing flotation stage were ascertained through experimental investigations. These parameters comprised a grinding fineness of 75.23% passing 0.075 mm, a C6H8O7 dosage of 600 g/t, a (NaPO3)6 dosage of 800 g/t, a CuSO4 dosage of 500 g/t, a butyl xanthate dosage of 120 g/t, and a No.2 oil dosage of 24 g/t. Utilizing a closed-circuit flotation flowsheet characterized by “one roughing, two scavenging, and two cleaning stages, with middlings sequentially returned to the preceding stage”, a final zinc concentrate was effectively produced. This concentrate exhibited an assay of 48.52% Zn, 1 400×10-6 Cd, and 1.92% MgO, with respective recoveries of 89.47% for zinc, 84.20% for cadmium, and 0.16% for magnesium oxide. Infrared spectroscopy analysis indicated that the interaction with the C6H8O7+(NaPO3)6 reagent system resulted in the emergence of two new distinct absorption peaks on the serpentine surface. The observed spectroscopic features were identified as the C=O and P=O stretching vibration peaks. Simultaneously, the Mg-O out-of-plane vibration peak exhibited a shift from its initial position at 567 cm-1 to 546 cm-1. These spectroscopic alterations suggest that the reagent combination likely adsorbs onto the serpentine surface through complexation. Further corroboration was provided by SEM-EDS analysis, which revealed that post-treatment with C6H8O7+(NaPO3)6, elements such as O, Mg, and Si were no longer detectable on the marmatite surface. Notably, the marmatite surface was predominantly devoid of adhering serpentine particles. This compelling evidence indicates that the application of C6H8O7+(NaPO3)6 effectively mitigates hetero-coagulation between serpentine and marmatite, thereby significantly enhancing the selectivity of the flotation process.
铁闪锌矿是由于铁原子取代闪锌矿中的部分锌原子形成的,这种原子取代导致铁闪锌矿的可浮性降低、分选难度提高。硫化锌矿浮选体系中常含有镁层状硅酸盐矿物,蛇纹石是其中之一;蛇纹石易过磨泥化,微细蛇纹石颗粒通过泡沫夹杂和异相凝聚等方式进入锌精矿,导致锌精矿品位降低、氧化镁含量增高(李小黎等,2021;Liu et al,2021a;李煜等,2025)。此外,在锌湿法冶炼工艺中,镁离子具有比锌离子更低的标准电极电位和更高的水解pH值,会导致浸出液中镁离子浓度逐渐升高,进而带来管道结晶和液体流动性变差等问题(李耀山,2024)。
针对蛇纹石恶化硫化矿选矿指标的问题,国内外学者在选矿降镁工艺和浮选降镁药剂2个方面进行了大量研究,选矿降镁工艺主要是阶段磨矿—选别、新型磨矿介质应用和磁罩盖降镁等方面(Li et al,2022;张婷等,2025),常用的降镁抑制剂有磷酸盐、碳酸盐、羧酸类、膦酸类、纤维素类、壳聚糖和木质素磺酸盐等(Liu et al,2021b;郑润浩等,2024;环艳等,2025)。谢海云等(2021)针对云南兰坪某锌含量3.14%、氧化镁含量16.11%的高镁锌矿,结合细磨解离和水玻璃—六偏磷酸钠组合抑制含镁矿物,在-0.045 mm粒级含量为90%的细度条件下,采用“一粗一扫三精”浮选流程,获得锌品位为52.53%、锌回收率为90.19%的锌精矿。由于原矿性质和选矿工艺的差异,加上矿物间交互作用复杂,业界尚无通用的蛇纹石抑制剂能够实现在各类矿石浮选中高效稳定地降镁除杂。
KongN, WuD D, ZuoQ,et al,2025.Mechanism of copper activation and adsorption in marmatite enhanced via dissolution of iron and zinc by ethylenediaminetetraacetic acid complexation[J].Separation Science and Technology,60(6):619-638.
[2]
LiB B, ZhangG F, LiuD Z,et al,2022.Selective alteration mechanisms of sodium tripolyphosphate towards serpentine:implications for flotation of pyrite from serpentine[J].Journal of Molecular Liquids,368:120687.
[3]
LiuD Z, ZhangG F, ChenY F,2021a.Studies on the selective flotation of pyrite from fine serpentine by using citric acid as depressant[J].Minerals Engineering,165:106742.
[4]
LiuD Z, ZhangG F, GaoY W,2021b.New perceptions into the detrimental influences of serpentine on Cu-Ni sulfide flotation through rheology studies and improved the separation by applying garnet[J].Minerals Engineering,171:107110.
[5]
MaY L, XiaoY, TongX,et al,2025.Enhancing flotation separation of marmatite and pyrrhotite via the synergistic activation of marmatite by Cu2+ and EDP[J].Minerals Engineering,232:109477.
[6]
曹锡章,宋天佑,王杏乔,2013.无机化学:下册[M].北京:高等教育出版社. Cao Xizhang,Song Tianyou,Wang Xingqiao,2013.Inorganic chemistry:volume 2[M].Beijing:Higher Education Press.
CheYuhang, ChenWei, ZhuYangge,et al,2023.Review on the research progress of regulators towards clay mineral flotation[J].Metal Mine,52(8):36-49.
[9]
董留洋,2022.白钨矿浮选中金属柠檬酸配合物对含钙脉石矿物的抑制机理研究[D].长沙:中南大学. Dong Liuyang,2022. Study on the depressive mechanism of metal citric acid complexes on calcium gangue minerals during scheelite flotation[D].Changsha:Central South University.
HuZewei, MaYuanlin, TongXiong,2025.Research progress on flotation reagents and separation techniques of marmatite[J].Industrial Minerals & Processing,54(7):54-64.
[12]
环艳,魏志聪,谢海云,等,2025.典型镁硅酸盐类脉石矿物的浮选抑制研究进展[J].有色金属(选矿部分),(1):33-47. Huan Yan,Wei Zhicong,Xie Haiyun,et al,2025.Research progress on flotation depression of typical magnesium silicate gangue minerals[J].Nonferrous Metals (Mineral Processing Section),(1):33-47.
LiXiaoli, ZhangQidong, WangLei,et al,2021.Effect mechanism of SHMP on flotation system of pentlandite and serpentine[J].Conservation and Utilization of Mineral Resources,41(2):52-57.
[15]
李耀山,2024.湿法锌冶炼镁离子去除及其资源化利用[D].北京:北京化工大学. Li Yaoshan,2024.Removal of magnesium ions in wet zinc smelting and its resource utilization[D].Beijing:Beijing University of Chemical Technology.
LiYu, LiSi, WangYuhua,et al,2025.Strengthening the flotation of coarse and fine sulfide lead ore using aerated jet flotation cell[J].Gold Science and Technology,33(2):349-359.
LiZhihang, XiongKun, ZuoKesheng,et al,2024.Effect of carboxymethyl cellulose on flotation of ascharite/serpentine and its action mechanism[J].Metal Mine,53(10):107-111.
XiaCong, ZhangZhiwei, YangJunting,et al,2025.Development trends of China’s lead-zinc resources in 2024 and prospect[J].China Mining Magazine,34(4):153-162.
XieHaiyun, LiuYanhao, TianXiaosong,et al,2021.Study on reducing magnesium and improving quality in mineral processing of high magnesium zinc ore[J].Nonferrous Metals Engineering,11(2):79-85.
XieXian, TongXiong, ZhangShengdong,et al,2020.Mechanism of ammo-nium chloride strengthen sphalerite’s activation by copper under low alkaline condition[J].Metal Mine,49(2):1-8.
[26]
薛斐嘉,顾畔,姚金,等,2024.新型调整剂BS001对水镁石和蛇纹石浮选分离的影响[J].有色金属(选矿部分),(8):131-141,160. Xue Feijia,Gu Pan,Yao Jin,et al,2024.Effect of the new regulator BS001 on flotation separation of brucite and serpentine[J].Nonferrous Metals (Mineral Processing Section),(8):131-141,160.
[27]
薛姗娜,2023.吉林高台蛇纹石玉及其风化皮的宝石矿物学特征研究[D].北京:中国地质大学(北京). Xue Shanna,2023.Study on gemological and mineralogical characteristics of serpentine jade and weathering rind in Gaotai,Jilin[D].Beijing:China University of Geosciences.
YuYang, WangDenghong, YuFeng,et al,2024.Current status in the exploration,development,and utilization of cadmium resources in China[J].China Mining Magazine,33(4):51-56.
ZhangTing, LiZhenfei, QiuTingsheng,et al,2025.Experimental study on beneficiability of a lead-zinc ore based on process mineralogy[J].Gold Science and Technology,33(5):1101-1111.
[32]
郑润浩,郑向党,丁良忠,等,2024.金川铜镍硫化矿选矿降镁药剂研究进展[J].有色金属(选矿部分),(2):90-97. Zheng Runhao,Zheng Xiangdang,Ding Liangzhong,et al,2024.Research progress of magnesium-lowering reagent for beneficiation of copper-nickel sulfide ore in Jinchuan[J].Nonferrous Metals(Mineral Processing Section),(2):90-97.