典型氧化铜铅锌矿物浮选的表面硫化研究进展

doi:10.16085/j.issn.1000-6613.2017-2557

摘要/Abstract

摘要： 近年来随着硫化矿石资源的枯竭，氧化矿石资源的开发利用越来越受到关注。工业上普遍使用硫化浮选来回收氧化铜铅锌矿物资源，硫化是该工艺的关键环节。本文简述了5种典型的氧化矿物，分析了硫化的作用，重点综述了氧化矿物表面硫化机理及其影响因素的研究进展。指出氧化矿物的硫化过程包括化学吸附和化学反应两个阶段，硫离子在矿物表面吸附后，与氧化矿物反应生成金属硫化物层进而活化浮选；矿浆pH与温度、硫化时间、硫化剂用量及其添加方式、金属离子和矿物自身特征等多种因素能显著影响氧化矿物的硫化反应，且各因素之间可能存在交互影响；通过添加某些药剂可以强化氧化矿物的表面硫化，能提高硫化反应的速率与程度，或增大硫化产物的机械强度。分析认为目前表面硫化的一些影响因素及强化硫化的机制仍不清楚，应通过多学科交叉、原位表征技术和计算机模拟等手段加强研究，从而更好地指导生产；同时利用3种手段也是浮选研究的发展方向和必然要求。

关键词: 氧化铜/氧化铅/氧化锌, 浮选, 硫化, 表面, 化学反应, 化学吸附, 强化硫化

Abstract: With the exhaust of sulphide ores, development and utilization of oxide ores have been received increasing attention in recent years. Sulfidization flotation is an extensively used method to recover copper/lead/zinc oxide minerals, and sulfidization is a key part of this methodology. In this review, five oxidized minerals bearing copper, lead or zinc were introduced. Roles on oxidized minerals flotation of sulfidation were dissected. The surface sulfidization mechanism of oxide minerals and its influenced factors were presented. Two stages are involved in the sulphidizing process:chemical adsorption and chemical reaction. After adsorption on the particle surface, the sulfide ions might react with oxide minerals to form a metal sulfide coating, which activate minerals flotation. The sulphidizing reactions are affected by pH and slurry temperature, sulphidizing reactions time, sulphidizing agent dosage and its addition form, metal ions and minerals characteristic, etc. There may be interaction among the factors. Surface sulfidization can be enhanced with some reagents which can improve the rate and limit of sulphidizing reactions, or mechanical strength of reaction products. The results suggested that some influence factors and mechanism of enhanced sulfidization are unclear. In order to guide practice better, further studies on them are needed based on multidiscipline approaches, in-situ measuring technique and computer simulation which are also the research directions and inevitable requirement for flotation.

Key words: copper/lead/zinc oxide, flotation, sulfidization, surface, chemical reaction, chemical adsorption, enhanced sulfidization

中图分类号:

TD952
TD923

宋凯伟, 李佳磊, 蔡锦鹏, 刘思言, 曹阳, 苏超, 刘殿文. 典型氧化铜铅锌矿物浮选的表面硫化研究进展[J]. 化工进展, 2018, 37(09): 3618-3628.

SONG Kaiwei, LI Jialei, CAI Jinpeng, LIU Siyan, CAO Yang, SU Chao, LIU Dianwen. A review on surface sulfidization of typical copper/lead/zinc oxide minerals flotation[J]. Chemical Industry and Engineering Progress, 2018, 37(09): 3618-3628.

参考文献

[1] 周娟, 廖亚龙, 李冰洁, 等. 多金属复杂硫化铜矿中有价金属的分离研究现状与进展[J]. 化工进展, 2015, 34(1):252-257. ZHOU J, LIAO Y L, LI B J, et al. Valuable metals extraction from complex multi-metal copper sulfide ore[J]. Chemical Industry and Engineering Progress, 2015, 34(1):252-257.
[2] 李夕兵, 周健, 王少锋, 等. 深部固体资源开采评述与探索[J]. 中国有色金属学报, 2017, 27(6); 1236-1262. LI X B, ZHOU J, WANG S F, et al. Review and practice of deep mining for solid mineral resources[J]. The Chinese Journal of Nonferrous Metals, 2017, 27(6):1236-1262.
[3] 饶兵, 戴惠新, 高利坤. 烟尘中微细粒氧化铅回收研究现状及进展[J].化工进展, 2016, 35(s1):285-293. RAO B, DAI H X, GAO L K. Progress of recovery micro-fine lead oxide from smelting dust[J]. Chemical Industry and Engineering Progress, 2016, 35(s1):285-293.
[4] 丰奇成.白铅矿氯离子强化硫化浮选试验及机理研究[D].昆明:昆明理工大学, 2016. FENG Q C. Enhanced sulfidation flotation of cerussite using chloride ion[D]. Kunming:Kunming University of Science and Technology, 2016.
[5] 毛莹博. 铵-胺盐强化硫化孔雀石浮选理论与试验研究[D]. 昆明:昆明理工大学, 2016. MAO Y B. Enhanced sulfidation flotation of malachite using ammonium-amine salt[D]. Kunming:Kunming University of Science and Technology, 2016.
[6] 周乐光. 矿石学基础[M]. 3版. 北京:冶金工业出版社, 2012. ZHOU L G. The fundament of the ore mineralogy[M]. 3rd ed. Beijing:Metallurgical Industry Press, 2012.
[7] 张琳, 方建军, 赵敏捷,等. 硅孔雀石活化浮选研究进展[J]. 矿产综合利用, 2017(3):17-21. ZHANG L, FANG J J, ZHAO M J, et al. Research and application progress of activation of floating chrysocolla[J]. Multipurpose Utilization of Mineral Resources, 2017(3):17-21.
[8] LONG X, CHEN Y, CHEN J H,, et al. The effect of water molecules on the thiol collector interaction on the galena (PbS) and sphalerite (ZnS) surfaces:a DFT study[J]. Applied Surface Science, 2016, 389:103-111.
[9] PRADIP P, RAI B. Molecular modeling and rational design of flotation reagents[J]. International Journal of Mineral Processing, 2003, 72(1/2/3/4):95-110.
[10] 张亚辉.浮选药剂与矿物界面作用的镜像对称规则[J]. 有色金属(选矿部分), 2016(4):87-93. ZHANG Y H. Mirror symmetry rule for the interaction between flotation reagentsand mineral interfaces[J]. Nonferrous Metals (Mineral Processing Section), 2016(4):87-93.
[11] 许鹏云, 李晶, 陈洲, 等. 红外光谱分析技术在浮选过程中的应用研究进展[J].光谱学与光谱分析, 2017, 37(8):2389-2396. XU Pengyun, LI Jing, CHEN Zhou, et al. Progresses in applications of infrared spectral analysis technology to flotation process[J]. Spectroscopy and Spectral Analysis, 2017, 37(8):2389-2396.
[12] 石道民, 杨敖. 氧化铅锌矿的浮选[M]. 昆明:云南科技出版社, 1996. SHI D M, YANG A. Flotation of oxidized lead and zinc ores[M]. Kunming:Yunnan Science and Technology Press, 1996.
[13] 张辉, 刘士阳, 张国英. 化学吸附的量子力学绘景[M]. 北京:科学出版社, 2004. ZHANG H, LI S Y, ZHANG G Y. Quantum-Mchanics picture of chemical adsorption[M]. Beijing:Science Press, 2004.
[14] CAPPELLEN P V, CHARLET L, STUMM W, et al. A surface complexation model of the carbonate mineral-aqueous solution interface[J]. Geochimica Et Cosmochimica Acta, 1993, 57(15):3505-3518.
[15] 李加智. 超细粒α-PbO、ZnO的表面硫化络合研究[D]. 济南:济南大学, 2011. LI J Z. The research of surface complexion with α-PbO and ZnO fine particle[D]. Jinan:University of Jinan, 2011.
[16] 梁冬云, 张志雄.白铅矿、菱锌矿晶体化学性质与硫化行为[J].材料研究与应用, 1992(2):83-88. LIANG D Y, ZHANG Z X. Crystal chemical character and sulfidation of cerussite and smithsonite[J]. Materials Research and Application, 1992(2):83-88.
[17] 邱廷省, 丁声强, 张宝红, 等. 硫化钠在浮选中的应用技术现状[J]. 有色金属科学与工程, 2012(6):39-43. QIU T S, DING S Q, ZHANG B H, et al. Application situation of sodium sulfide in the flotation[J]. Nonferrous Metals Science and Engineering, 2012(6):39-43.
[18] 黄礼煌.金属硫化矿物低碱介质浮选[M].北京:冶金工业出版社, 2015. HUANG L H. Flotation of metal sulphide ores in low alkaline medium[M]. Beijing:Metallurgical Industry Press, 2015.
[19] 丁治英, 敬珊珊, 陈启元.含锌矿物的微观结构与反应活性[J].中国科技论文, 2015(18):2178-2181. DING Z Y, JING S S, CHEN Q Y. Microstructures and reaction activity of zinc-bearing minerals[J]. China Scencepaper, 2015(18):2178-2181.
[20] 李明晓.基于循环经济的低品位难处理氧化锌矿选冶联合新工艺研究[D].昆明:昆明理工大学, 2011. LI M X. Study on joint new technology of mineral processing and metallurgy for low-grade and intractable oxide zinc ores based on cyclic economy[D]. Kunming:Kunming University of Science and Technology, 2011.
[21] 赵涌泉.氧化铜矿的处理[M].北京:冶金工业出版社, 1982. ZHAO Q Y. Processing of oxidized copper ores[M]. Beijing:Metallurgical Industry Press, 1982.
[22] 戈保梁, 张文彬.硅孔雀石的活化浮选[J].云南冶金, 1995(4):15-19. GE B L, ZHANG W B. Activation flotation of Chrysocolla[J]. Yunnan Metallurgy, 1995(4):15-19.
[23] 李存兄. 低品位氧化锌矿元素硫水热硫化应用基础研究[D]. 昆明:昆明理工大学, 2012. LI C X. Applied fundamental research on hydrothermal-sulfidation and flotation of zinc oxide ore with elemental sulfur[D]. Kunming:Kunming University of Science and Technology, 2012.
[24] 胡岳华, 邱冠周, 袁诚, 等. 孔雀石/菱锌矿浮选溶液化学研究[J].有色金属, 1996(2):40-44. HU Y H, QIU G Z, YUAN C, et al. Solution chemistry studies on flotation of malachite and smithsonite[J]. Nonferrous Metals, 1996(2):40-44.
[25] FUERSTENAU M C, OLIVAS S A, HERRERA-URBINA R, et al. The surface characteristics and flotation behavior of anglesite and cerussite[J]. International Journal of Mineral Processing, 1987, 20(1/2):73-85.
[26] 刘诚. 典型氧化铜矿孔雀石的硫化浮选研究与应用[D]. 赣州:江西理工大学, 2012. LIU C. Application and study on sulfidation flotation of typical oxidized copper ores:malachite[D]. Ganzhou:Jiangxi University of Science and Technology, 2012.
[27] 徐晓军.氧化矿有机螯合剂活化浮选理论[M]. 昆明:云南科学技术出版社, 2000. XU X J. The theory of oxidized mineral flotation using organic chelating agent as activators[M]. Kunming:Yunnan Science and Technology Press, 2000.
[28] 陈晔, 陈建华, 吴伯增, 等.氢氧根与硫氢根协同效应对胺法浮选异极矿的影响[J].金属矿山, 2009, V39(3):65-68. CHEN Y, CHEN J H, WU B Z, et al. Effect of synergism between hydroxyl radical and sulfhydryl radical on the amine flotation of hemimorphite[J]. Metal Mine, 2009, V39(3):65-68.
[29] 邱显扬, 李松平, 邓海波, 等.菱锌矿加温硫化浮选动力学研究[J].有色金属(选矿部分), 2007(1):24-26. QIU X Y, LI S P, DENG H B, et al. Study of heating surface sulfurized flotation dynamics of smithsonite[J]. Nonferrous Metals (Mineral Processing Section), 2007(1):24-26.
[30] 沈同喜.氧化铅矿硫化浮选强化技术研究[D].赣州:江西理工大学, 2013. SHEN T X. Enhanced sulfidation flotation of oxidized lead ores[D]. Ganzhou:Jiangxi University of Science and Technology, 2013.
[31] 魏宗武, 陈晔.黄药体系中白铅矿的浮选行为研究[J].江西有色金属, 2008, 22(1):19-21. WEI Z W, CHEN Y. On flotation performance of cerusite in xanthate system[J]. Jiangxi Nonferrous Metals, 2008, 22(1):19-21.
[32] 申培伦. 孔雀石硫化浮选过程中磷酸乙二胺作用机理探讨[D].昆明:昆明理工大学, 2016. SHEN P L. The role of ethylenediamine phosphate on sulfidation flotation for malachite[D]. Kunming:Kunming University of Science and Technology, 2016.
[33] 吴丹丹. 铵盐对菱锌矿强化硫化浮选理论研究[D]. 昆明:昆明理工大学, 2015. WU D D. Enhanced sulfidation flotation of smithsonite using ammonium salt[D]. Kunming:Kunming University of Science and Technology, 2015.
[34] PARK K, PARK S, CHOI J, et al. Influence of excess sulfide ions on the malachite-bubble interaction in the presence of thiol-collector[J]. Separation and Purification Technology, 2016, 168:1-7.
[35] 刘殿文, 尚旭, 张文彬, 等.氧化铜矿物抗抑制作用的表面形貌研究[J].金属矿山, 2009, V39(3):59-60. LIU D W, SHAN X, ZHANG W B, et al. Surface morphology of copper oxide minerals in relation with anti-depression function[J]. Metal Mine, 2009, V39(3):59-60.
[36] 李佳磊, 宋凯伟, 刘殿文, 等. 闪锌矿浮选的活化与去活化研究进展[J]. 过程工程学报, 2018, 18(1):11-19. LI Jialei, SONG Kaiwei, LIU Dianwen, et al. Research progress on activation and deactivation of sphalerite flotation[J]. Chin. J. Process Eng., 2018, 18(1):11-19.
[37] 邓荣东. 氧化锌矿矿浆中离子存在行为及吸附机理研究[D]. 昆明:昆明理工大学, 2015. DENG R D. Existence form and adsorption mechanism of ions in oxidized zinc ores slurry[D]. Kuming:Kunming University of Science and Technology, 2015.
[38] DENG Rongdong, HU Yuan, KU Jianggang, et al. Adsorption of Fe(Ⅲ) on smithsonite surfaces and implications for flotation[J]. Colloids and Surfaces A, 2017, 533:308-315.
[39] 张国范, 蒋世鹏, 冯其明, 等.溶液体系中含锌矿物表面硫化研究[J]. 中南大学学报(自然科学版), 2017, 48(4):851-859. ZHANG G F, JIANG S P, FENG Q M, et al. Surface sulfidization of zinc minerals in solution system[J] Journal of Central South University(Science and Technology), 2017, 48(4):851-859.
[40] 高志勇. 三种含钙矿物晶体各向异性与浮选行为关系的基础研究[D]. 长沙:中南大学, 2013. GAO Z Y. Investigation on the relationship between anisotropic crystal surface characteristic and flotation behaviors of three calcium-bearing minerals[D]. Changsha:Central South University, 2013.
[41] 刘殿文. 孔雀石硫化机理探讨与氧化铜矿石浮选新技术研究[D]. 昆明:昆明理工大学, 2007. LIU D W. A study on mechanisms of malachite sulfidization and novel flotation technologies[D]. Kunming:Kunming University of Science and Technology, 2007.
[42] FENG Q C, ZHAO W J, WEN S M, et al. Copper sulfide species formed on malachite surfaces in relation to flotation[J]. Journal of Industrial & Engineering Chemistry, 2017, 48:125-132.
[43] ZHOU R, CHANDER S. Kinetics of sulfidization of malachite in hydrosulfide and tetrasulfide solutions[J]. International Journal of Mineral Processing, 1993, 37(3):257-272.
[44] 刘殿文, 张文彬, 文书明.氧化铜矿浮选技术[M].北京:冶金工业出版社, 2009. LIU D W, ZHANG W B, WEN S M, et al. Flotation technology of oxidized copper ores[M]. Beijing:Metallurgical Industry Press, 2009.
[45] 毕克俊, 魏志聪, 蒋太国, 等, 氧化铜矿石浮选活化剂的研究进展[J]. 矿产保护与利用, 2015(5):74-78. BI K J, WEI Z C, JIANG T G, et al. Research progress on flotation activators of copper oxide ore[J]. Conservation and Utilization of Mineral Resources, 2015(5):74-78.
[46] 徐晓军, 刘邦瑞. 三乙醇胺对微细粒孔雀石的活化作用特性及机理研究[J]. 有色金属, 1993, 45(1):30-35. XU X J, LIU B R. Mechanism of fine malachite flotation by activation with triethanolamine[J]. Nonferrous Metals, 1993, 45(1):30-35.
[47] 张文彬. 乙二胺磷酸盐作用机理初探[J]. 有色金属(选矿部分), 1980(5):46-48. ZHANG W B. The mechanism of ethylenediamine phosphate on malachite flotation[J]. Nonferrous Metals (Mineral Processing Section), 1980(5):46-48.
[48] WU D D, MA W H, WEN S M, et al. Contribution of ammonium ions to sulfidation-flotation of smithsonite[J]. Journal of the Taiwan Institute of Chemical Engineers, 2017, 78:20-26.
[49] FENG Q C, WEN S M, ZHAO W J, et al. Contribution of chloride ions to the sulfidization flotation of cerussite[J].Minerals Engineering, 2015, 83:128-135.
[50] WU D D, MA W H, WEN S M, et al. Enhancing the sulfidation of smithsonite by superficial dissolution with a novel complexing agent[J]. Minerals Engineering, 2017, 114:1-7.
[51] WU D D, MA W H, MAO Y B, et al. Enhanced sulfidation xanthate flotation of malachite using ammonium ions as activator[J]. Scientific Reports, 2017. DOI:10.1038/S41598-017-02136-x.