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摘要:
我国钨矿资源丰富,储量居世界首位,但随着钨矿资源的不断开发,导致大量钨尾矿的产生。钨尾矿是钨矿选矿过程中产生的固体废弃物,其中还有大量有价元素和重金属,长期堆存不仅浪费资源,占用大量土地资源,还可能对环境造成污染。分析了我国钨尾矿资源的现状及特点,论述了钨尾矿堆积对环境的影响,详细综述了钨尾矿综合利用的现状,主要包括有价组分的回收与材料制备等。在有价组分回收方面,通过物理选矿和化学浸出等技术手段,可以有效提取回收W、Mo、Bi、Rb、Cu等有价金属和石英、萤石等非金属矿物;在制备材料方面,钨尾矿可用于制造水泥、微晶玻璃、多孔陶瓷和地质聚合物等。最后指出了钨尾矿综合利用研究存在的问题和发展方向,旨在为钨尾矿的回收利用提供参考。
Abstract:Our country is rich in tungsten resources, the reserves rank first in the world, but with the continuous exploitation of tungsten resources, a large number of tungsten tailings are produced. Tungsten tailings are solid wastes produced in the process of tungsten ore beneficiation, which retain a large number of valuable elements and heavy metals. Long−term storage not only wastes resources, occupies a large amount of land resources, but also may cause environmental pollution. The current situation and characteristics of tungsten tailings resources in China are analyzed, the impact of tungsten tailings accumulation on the environment is discussed, and the current situation of comprehensive utilization of tungsten tailings is reviewed in detail, including recovery of valuable components and overall utilization of tungsten tailings. In terms of recovery of valuable components, valuable metals such as tungsten, molybdenum, bismuth, rubidium, copper and non−metallic minerals such as quartz and fluorite can be effectively extracted through physical mineral processing and chemical leaching. In terms of the overall utilization of tungsten tailings, tungsten tailings are used in the manufacture of cement, glass−ceramics, porous ceramics and geopolymers. The problems and development direction of comprehensive utilization of tungsten tailings are pointed out in order to provide reference for the recovery and utilization of tungsten tailings.
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Key words:
- tungsten tailings /
- comprehensive utilization /
- glass ceramics /
- building material
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[1] SHIV B, HASINTHA W, ACHALI I, et al. Tungsten contamination, behavior and remediation in complex environmental settings[J]. Environment International, 2023, 181: 108276. doi: 10.1016/j.envint.2023.108276
[2] ZHAO W, SUNW, HANH S, et al. Flotation chemistry of scheelite and its practice: A comprehensive review[J]. Minerals Engineering, 2023, 204: 108404. doi: 10.1016/j.mineng.2023.108404
[3] SURYA K D, NAGESH CHRVS, SREENIVAS T, et al. A treatise on occurrence, beneficiation and plant practices of tungsten−bearing ores[J]. Powder Technology, 2023, 429: 118938.
[4] WANG X, QIN W Q, JIAO F, et al. Review of tungsten resource reserves, tungsten concentrate production and tungsten beneficiation technology in China[J]. Transactions of Nonferrous Metals Society of China, 2022, 32(7): 2318−2338.
[5] 闵世珍, 温小毛, 徐敬吟. 钨尾矿再回收利用研究进展[J]. 世界有色金属, 2022(4): 164−166. doi: 10.3969/j.issn.1002-5065.2022.04.052
MIN S Z, WEN X M, XU J Y. Research progress of tungsten tailings reutilization[J]. World Nonferrous Metals, 2022(4): 164−166. doi: 10.3969/j.issn.1002-5065.2022.04.052
[6] 兰志强, 蓝卓越, 张镜翠. 钨尾矿资源综合利用研究进展[J]. 中国钨业, 2016, 31(2): 37−42. doi: 10.3969/j.issn.1009-0622.2016.02.008
LAN Z Q, LAN Z Y, ZHANG J C. Research progress on the comprehensive utilization of tungsten tailings[J]. China Tungsten Industry, 2016, 31(2): 37−42. doi: 10.3969/j.issn.1009-0622.2016.02.008
[7] 肖俊杰, 匡敬忠, 于明明, 等. 钨尾矿综合利用的研究进展[J]. 矿产综合利用, 2023(5): 120−126. doi: 10.3969/j.issn.1000-6532.2023.05.021
XIAO J J, KUANG J Z, YU M M, et al. Research progress on comprehensive utilization of tungsten tailings[J]. Multipurpose Utilization of Mineral Resources, 2023(5): 120−126. doi: 10.3969/j.issn.1000-6532.2023.05.021
[8] 李军, 龙冰. 钨矿资源开发利用现状和清洁生产技术探讨[J]. 中国钨业, 2023, 38(4): 1−6.
LI J, LONG B. The development and utilization of tungsten resource and its clean production technology[J]. China Tungsten Industry, 2023, 38(4): 1−6.
[9] 余良晖, 史登峰, 郑丽琼. 我国钨矿尾矿资源调查分析[J]. 中国金属通报, 2010(37): 18−19.
XU L H, SHI D F, ZHENG L Q. Investigation and analysis of tungsten tailings resources in China[J]. China Metal Bulletin, 2010(37): 18−19.
[10] 张绍彦. 含钙矿物与石英浮选体系中矿物的交互影响研究[D]. 赣州: 江西理工大学, 2022.
ZHANG S Y. Research on the reciprocal influences between calcium−containing ores and quartz in flotation[D]. Ganzhou: Jiangxi University of Science and Technology, 2022.
[11] 黄小年, 罗喜成, 于静, 等. 江西省钨矿资源特征及成矿规律探讨[J]. 世界有色金属, 2019(15): 78−79. doi: 10.3969/j.issn.1002-5065.2019.15.046
HUANG X N, LUO X C, YU J, et al. Discussion on characteristics of tungsten resources and metallogenic regularity in Jiangxi Province[J]. World Nonferrous Metals, 2019(15): 78−79. doi: 10.3969/j.issn.1002-5065.2019.15.046
[12] 黄军, 陈军, 黄成伟, 等. 江西赣州某钨尾矿综合回收利用工艺研究[J/OL]. 矿产综合利用, 1−13[2024−07−25]. http://kns.cnki.net/kcms/detail/51.1251.td.20231012.1513.006.html.
HUANG J, CHEN J, HUANG C W, et al. Research on the comprehensive recovery and utilization technology of a tungsten tailings in Ganzhou, Jiangxi Province[J/OL]. Multipurpose Utilization of Mineral Resources, 1−13[2024−07−25]. http://kns.cnki.net/kcms/detail/51.1251.td.20231012.1513.006.html.
[13] 陈雅, 胡明川, 韦权锋, 等. 江西香炉山钨尾矿中萤石综合回收技术的研究[J]. 有色金属(选矿部分), 2018(5): 64−71.
CHEN Y, HU M C, WEI Q F, et al. Research on comprehensive recovery technology of fluorite from a tungsten tailings in the xianglushan Jiangxi[J]. Nonferrous Metals(Mineral Processing Section), 2018(5): 64−71.
[14] TANG HH, LIU B J, WANG G, et al. Occurrence state and distribution characteristics of tungsten in Dabaoshan tungsten−bearing goethite[J]. Transactions of Nonferrous Metals Society of China, 2024, 34(4): 1263−1274.
[15] 赖长荣, 胡晔昕, 舒如霜, 等. 选钨尾砂回收有价金属研究现状综述[J]. 中国资源综合利用, 2022, 40(4): 118−123+151. doi: 10.3969/j.issn.1008-9500.2022.04.035
LAI C R, HU Y X, SHU R S, et al. Review of research status of recovery of valuable metals from tungsten beneficiation tailings[J]. China Resources Comprehensive Utilization, 2022, 40(4): 118−123+151. doi: 10.3969/j.issn.1008-9500.2022.04.035
[16] WAGH D N. , SANGITA D K, IYE CSP R. Determination of tungsten in low−grade tungsten ores by dual−column ion chromatography[J]. Analytica Chimica Acta, 1994, 287(3): 229−234.
[17] 杨华玲, 王华来, 赵玲, 等. 用氯化焙烧—水浸工艺从钨尾矿中提取有价金属铷锂钾[J]. 湿法冶金, 2019, 38(4): 267−270.
YANG H L, WANG H L. ZHAO L, et al. Extraction of rubidium, lithium and potassium from a tungsten tailings using chlorination roasting−water leaching process[J]. Hydrometallurgy of China, 2019, 38(4): 267−270.
[18] WANG F Y, LIU H, YAN L. Construction of layered double hydroxide composites derived from tungsten tailing particles for simultaneously enhancing fire protection and anti−ageing properties of intumescent fire−resistant coatings applied in wood surface[J]. Journal of Building Engineering, 2023, 77: 107−409.
[19] LI S M, SHOU K, WANG L, et al, Temperature effect of tungsten tailings activated by NaOH[J]. Case Studies in Construction Materials, 2022, 17: e01291.
[20] 何桂春, 肖策环. 江西某钨尾矿浮选试验[J]. 有色金属科学与工程, 2015, 6(6): 82−87.
HE G C, XIAO C H. Experimental study on flotation of wolframite tailings in a Jiangxi tungsten mine[J]. Nonferrous Metals Science and Engineering, 2015, 6(6): 82−87.
[21] 陈江安, 朱作伟, 彭征, 等. 离心机回收某钨选矿厂尾矿中钨的试验研究[J]. 中国钨业, 2012, 27(4): 20−22.
CHEN J A, ZHU Z W, PENG Z, et al. Recovering tungsten by centrifuge from tailings of a tungsten dressing plant[J]. China Tungsten Industry, 2012, 27(4): 20−22.
[22] 邓巧娟, 车小奎, 郑其, 等. 某钨尾矿综合回收钨铜锌的试验研究[J]. 稀有金属, 2019, 43(5): 541−550.
DENG Q J, CHEN X K, ZHENG Q, et al. Comprehensive recovery of tungsten, copper and zinc from tungsten tailings[J]. Chinese Journal of Rare Metals, 2019, 43(5): 541−550.
[23] 彭康, 伦惠林, 李阿鹏, 等. 钨尾矿综合利用的研究进展[J]. 中国资源综合利用, 2013, 31(2): 35−38. doi: 10.3969/j.issn.1008-9500.2013.02.011
PENG K, LUN H L, LI A P, et al. Research progress on the comprehensive utilization of tungsten tailings[J]. China Resources Comprehensive Utilization, 2013, 31(2): 35−38. doi: 10.3969/j.issn.1008-9500.2013.02.011
[24] 陈杜娟, 苗梁, 彭建城, 等. 江西某钨重选尾矿钼回收试验[J]. 金属矿山, 2013(3): 152−154+157.
CHEN D J, MIAO L, PENG J C, et al. Tests of molybdenum recovery from tungsten tailings by gravity in jiangxi[J]. Metal Mine, 2013(3): 152−154+157.
[25] 王晨亮, 邱显扬, 邹坚坚, 等. 从钨重选尾矿中回收铋钼选矿试验研究[J]. 矿山机械, 2016, 44(8): 53−57.
WANG C L, QIU X Y, ZOU J J, et al. Beneficiation test study on recovery of bismuth and molybdenum from tailings of tungsten gravity separation[J]. Mining& Processing Equipment, 2016, 44(8): 53−57.
[26] 杨斌清. 钨尾矿综合回收铋钼新工艺的研究[J]. 矿产保护与利用, 1997(5): 53−55.
YANG B Q. A study on new process of comprehensive recovery of Bi and Mo from a tailings separated of tungsten[J]. Conservation and Utilization of Mineral Resources, 1997(5): 53−55.
[27] 冯章标, 阳华玲, 王长福. 某高钙钨尾矿反—正浮选工艺回收铷的研究[J]. 矿产保护与利用, 2024, 44(1): 89−94.
FENG Z B, YANG H L, WANG C F. Recovery of rubidium from a tungsten tailings containing high calcite by reverse−positive flotation process[J]. Conservation and Utilization of Mineral Resources, 2024, 44(1): 89−94.
[28] 王威, 柳林, 刘红召, 等. 从钨尾矿中提取铷的研究[J]. 有色金属(冶炼部分), 2018(7): 17−20.
WANG W, LIU L, LIU H Z, et al. Study on extraction of rubidium from tungsten tailings[J]. Nonferrous Metals(Extractive Metallurgy), 2018(7): 17−20.
[29] 王威, 常学勇, 柳林, 等. 赣州某钨尾矿中锂的浮选回收与浸出试验[J]. 金属矿山, 2018(11): 185−188.
WANG W, CHANG X Y, LIU L, et al. Experiment of flotation recovery and leaching of lithium from a tungsten tailings in ganzhou[J]. Metal Mine, 2018(11): 185−188.
[30] 彭康. 钨尾矿高值化加工与利用的研究[D]. 长沙: 中南大学, 2014.
PENG K. Study on high value processing and utilization of tungsten tailing[D]. Changsha: Central South University, 2014.
[31] XIE R Q, ZHAO Z H, WANG X, et al. Flotation separation of scheelite from fluorite by new depressant nitrilotriacetic acid and its mechanism[J]. Journal of the Taiwan Institute of Chemical Engineers, 2023, 152: 105153.
[32] 汪志平, 王成行, 邹坚坚, 等. 磁—浮联合工艺回收矽卡岩型钨尾矿中萤石试验研究[J]. 金属矿山, 2023(5): 260−265.
WANG Z P. WANG C X, ZOU J J, et al. Experimental study on recovery of fluorite from skarn type tungsten tailings by magnetic and flotation combined process[J]. Metal Mine, 2023(5): 260−265.
[33] 冯青舒, 陈文胜, 王舰, 等. 从湖南某钨多金属矿尾矿中回收伴生萤石试验研究[J]. 矿冶工程, 2022, 42(1): 68−71. doi: 10.3969/j.issn.0253-6099.2022.01.016
FENG Q S, CHEN W S, WANG J, et al. Recovering associated fluorite from tailings of tungsten−containing polymetallic ore[J]. Mining and Metallurgical Engineering, 2022, 42(1): 68−71. doi: 10.3969/j.issn.0253-6099.2022.01.016
[34] 龙冰. 从湖南某常温浮钨尾矿中浮选回收萤石试验[J]. 金属矿山, 2019(9): 195−198.
LONG B. Experimental study on recovery of fluorite by flotation from the tailings of tungsten flotation at room temperature in Hu’nan Province[J]. Metal Mine, 2019(9): 195−198.
[35] 邵伟华, 常学勇, 王守敬, 等.湖南某铍矿综合回收实验[J]. 矿产综合利用, 2024, 45(5): 31−37+56.
SHAO W H, CHANG X Y, WANG S J, et al. Experimental study on multipurpose recovery of beryllium ore in Hunan Province[J]. Multipurpose Utilization of Mineral Resources, 2024, 45(5): 31−37+56.
[36] 张志峰. 滇西某选钨尾矿中回收绿柱石的研究[J]. 矿产综合利用, 2014(4): 56−59. doi: 10.3969/j.issn.1000-6532.2014.04.013
ZHANG Z F. Research on beryl recovery from wolfram tailings in western yunnan[J]. Multipurpose Utilization of Mineral Resources, 2014(4): 56−59. doi: 10.3969/j.issn.1000-6532.2014.04.013
[37] 谢义莲. 从江西某黑钨矿重选尾矿中回收绿柱石[J]. 矿产综合利用, 1983(2): 21−26.
XIE Y L. Beryl recovered from a wolframite gravity concentration tailings of Jiangxi[J]. Multipurpose Utilization of Mineral Resources, 1983(2): 21−26.
[38] 吴夫彬. 黑钨尾矿回收绿柱石的浮选试验[J]. 有色金属(冶炼部分), 1965(2): 14−16+42.
WU F B. Flotation experiment for recovering beryl from black tungsten tailings[J]. Nonferrous Metals(Extractive Metallurgy), 1965(2): 14−16+42.
[39] 朱一民, 周菁. 从黄沙坪低品位钼、铋、钨、萤石浮选尾矿中回收石榴石的回收和应用试验研究[J]. 有色矿冶, 2012, 28(3): 31−33. doi: 10.3969/j.issn.1007-967X.2012.03.010
ZHU Y M, ZHOU J. The Experiment study of recovering and appling garnet from the low grade Mo, Bi, WO3 and fluorite flotation tailings of Huangshaping[J]. Non−Ferrous Mining and Metallurgy, 2012, 28(3): 31−33. doi: 10.3969/j.issn.1007-967X.2012.03.010
[40] 田祎兰, 胡志强, 陈旭波. 从尾矿中回收石榴子石的选矿试验研究[J]. 中国矿业, 2020, 29(S1): 506−509. doi: 10.12075/j.issn.1004-4051.2020.S1.117
TIAN Y L, HU Z Q, CHEN X B. et al. Study on beneficiation test of recovering garnet from tailings[J]. China Mining Magazine, 2020, 29(S1): 506−509. doi: 10.12075/j.issn.1004-4051.2020.S1.117
[41] 王全亮, 吴明海, 周虎强, 等. 选矿尾矿中的石榴子石可选性试验研究[J]. 湖南有色金属, 2014, 30(4): 13−15. doi: 10.3969/j.issn.1003-5540.2014.04.004
WANG Q L, WU M H, ZHOU H Q, et al. The beneficability research of garnet from tailings[J]. Hunan Nonferrous Metals, 2014, 30(4): 13−15. doi: 10.3969/j.issn.1003-5540.2014.04.004
[42] PANX D, LIS Q, LiY K, et al. Resource, characteristic, purification and application of quartz: A review[J]. Minerals Engineering, 2022, 183: 107600.
[43] 赵伟康, 程明宇, 黄义威, 等. 江西某钨尾矿中石英选矿提纯试验[J]. 非金属矿, 2022, 45(3): 51−55. doi: 10.3969/j.issn.1000-8098.2022.03.013
ZHAO W K, CHENG M Y, HUANG W, et al. Experimental study on the recovery of quartz from tungsten tailings in Jiangxi[J]. Non−Metallic Mines, 2022, 45(3): 51−55. doi: 10.3969/j.issn.1000-8098.2022.03.013
[44] 赵强, 张鹏羽. 从钨尾矿中回收SiO2的试验研究[J]. 工程建设, 2023, 55(1): 1−5.
ZHAO Q, ZHANG P Y. Experimental research on recovery of SiO2 from tungsten tailings[J]. Engineering Construction, 2023, 55(1): 1−5.
[45] 程浩. 钨尾矿地聚合物人造石制备及其性能研究[D]. 赣州: 江西理工大学, 2023.
CHENG H. Study on preparation and properties of polymer artificial stonefrom tungsten tailings[D]. Ganzhou: Jiangxi University of Science and Technology, 2023.
[46] CHOI Y W, YONG J K, CHOI O, et al. Utilization of tailings from tungsten mine waste as a substitution material for cement[J]. Construction and Building Materials, 2009, 23(7): 2481−2486.
[47] 司加保, 李琳, 黄震. 用钨尾矿制备水泥混合材试验[J]. 现代矿业, 2016, 32(7): 222−225. doi: 10.3969/j.issn.1674-6082.2016.07.077
SI J B, LI L, HUANG Z. Test on preparation of cement admixture using tungsten tailings[J]. Modern Mining, 2016, 32(7): 222−225. doi: 10.3969/j.issn.1674-6082.2016.07.077
[48] 张春霖, 王海, 李静. 尾矿微晶玻璃研究进展概述[J]. 辽宁科技大学学报, 2018, 41(6): 406−411.
ZHANG C L, WANG H, LI J. Summary of research progress on glass−ceramics made from tailings[J]. Journal of University of Science and Technology Liaoning, 2018, 41(6): 406−411.
[49] PENG K, LVC Z, YANGH M. Novel preparation of glass ceramics from amorphized tungsten tailings[J]. Ceramics International, 2014, 40: 10291−10296.
[50] 王凯文, 黄景华, 朱羽, 等. 添加造孔剂法制备钨尾矿多孔陶瓷[J]. 高校化学工程学报, 2022, 36(6): 879−885. doi: 10.3969/j.issn.1003-9015.2022.00.010
WANG K W, HANG J H, ZHU Y, et al. Preparation of porous ceramics from tungsten tailings by adding pore−forming agent[J]. Journal of Chemical Engineering of Chinese Universities, 2022, 36(6): 879−885. doi: 10.3969/j.issn.1003-9015.2022.00.010
[51] 曾庆钋. 利用钨尾矿制备地质聚合物及其性能研究[D]. 赣州: 江西理工大学, 2021.
ZENG Q P. Study on the properties of geopolymer prepared bytungsten[D]. Ganzhou: Jiangxi University of Science and Technology, 2021.
[52] 郭小明. 利用钨尾矿制备矿物聚合材料的研究[D]. 赣州: 江西理工大学, 2007.
GUO X M. Study on preparation of geopolymers from tungsten tailing[D]. Ganzhou: Jiangxi University of Science and Technology, 2007.
[53] 焦向科, 罗仙平, 李佳, 等. 钨尾矿预处理制备矿物聚合材料[J]. 硅酸盐通报, 2015, 34(12): 3610−3616+3621.
JIAO X K, LUO X P, LI J, et al. Pretreatment of tungsten tailing for geopolymer synthesis[J]. bulletin of the chinese ceramic society, 2015, 34(12): 3610−3616+3621.
[54] ZENG Y L, DUAN N, FU C P, et al. Preparation and characterization of tungsten tailing−based geopolymers[J]. Ceramics International, 2023, 49(13): 22043−22053.
-