Resource utilization of copper smelter slag——a state-of-the-arts review

doi:10.16085/j.issn.1000-6613.2016-2366

Abstract

Abstract: Large quantities of slag dumped in the open are contributing to the absence of recovery and utilization of valuable metals as well as potential environmental pollution to water and soil arisen by heavy metal contamination. The mineralogical characteristics and researches on recovering valuable metals from typical copper slag produced by pyrometallurgical process were summarized in the present work. The advantage and limitation of outstanding treatment methods which are presently performed to dispose of the slag for the recovery of iron and copper contained were analyzed and discussed,such as mineral separation,hydrometallurgical extraction,pyrometallurgical impoverishment,high temperature oxidation and high temperature reduction,etc. The prospective trends were predicted. The analyzing results obtained showed that the slow cooling followed by flotation and hydrometallurgical extraction are high effective method for recycling of copper contained in the smelting slag with a high content copper. Especially the process of high pressure oxidative acid leaching has excellent application prospect as it can inhibit the leaching of iron. Mineral phase reconfiguration for utilizing resource is effective to recover copper and iron in the slag with low content of copper. The process that calcium oxide is added into the molten slag prior to modification and cooling slow followed by flotation and magnetic separation is prospective to be applied,as the reason that copper and iron contained in the slag can be effectively recycled,and that flotation tailings can be directly used in building materials industry.

Key words: waste treatment, reaction engineering, recovery, metallurgical slag

摘要： 火法冶炼废弃渣大量露天堆存，存在铜、铁等有价金属资源未能回收利用和重金属污染土壤及水体等环境问题。本文综述了铜火法冶炼过程中产生的典型废弃渣的物相特征，以及渣中铜、铁等有价金属回收利用的研究现状。分析和讨论了选矿分离、湿法提取、火法贫化、高温氧化、高温还原等工艺处理铜冶炼废渣、回收利用铜和铁的优势及存在的缺陷，展望研究趋势。分析表明：缓冷-浮选、湿法提取都能有效回收利用高品位的冶炼铜渣，湿法酸浸中的加压浸出能抑制铁的浸出而具有应用优势；矿相资源化重构是有效利用低含量铜渣中铜和铁资源的有效方法；在熔融态炉渣中加入氧化钙改性重构后缓冷，再进行浮选和磁选，既能回收炉渣中的铜和铁，且浮选尾渣可以直接用于建材行业，更具备应用前景。

关键词: 废物处理, 反应工程, 回收, 冶炼渣

CLC Number:

TQ09

LIAO Yalong, YE Chao, WANG Yiyang, CAO Lei. Resource utilization of copper smelter slag——a state-of-the-arts review[J]. Chemical Industry and Engineering Progress, 2017, 36(08): 3066-3073.

廖亚龙, 叶朝, 王祎洋, 曹磊. 铜冶炼渣资源化利用研究进展[J]. 化工进展, 2017, 36(08): 3066-3073.

References

[1] BARON S,CARIGNAN J,PLOQUIN A. Dispersion of heavy metals(metalloids)in soils from 800-year-old pollution(mont-loze're,France)[J]. Environ. Sci. Technol.,2006,40:5319-5326.
[2] DUTREÁ V,VANDECASTEELE C. Immobilization mechanism of arsenic in waste solidified using cement and lime[J]. Environ. Sci. Technol.,1998,32:2782-2787.
[3] 唐谱,李秋菊,洪新. 铜渣浸出毒性的鉴别和处置方式[J]. 有色金属,2011,63(2):302-304. TANG P,LI Q J,HONG X. Identification of leaching toxicity and their safe disposal method of copper slag[J]. Nonferrous Metals,2011,63(2):302-304.
[4] RIVEROSA G,UTIGARD T A. Disposal of arsenic in copper discharge slags[J]. Journal of Hazardous Materials,2000,B77:241-252.
[5] HARVEY Alter. The composition and environmental hazard of copper slags in the context of the Basel Convention[J]. Resources,Conservation and Recycling,2005,43:353-360.
[6] 陈远望. 智利铜炉渣贫化方法概述[J]. 世界有色金属,2001(9):56-62. CHEN Y W. Review on impoverishment process of copper slag in Chily[J]. World Nonferrous Metals,2001(9):56-62.
[7] LIAO Y L,CHAI X J,LI J T,et al. Study on the reduction of ferrous compounds disseminated in fayalite,vitreous and magnetite in dumped copper slag by means of carbonthermic method[J]. Advanced Materials Research,2011,233/234/235:684-688.
[8] SARRAFI A,RAHMATI B,HASSANI H R. Recovery of copper from reverberatory slag by flotation[J]. Minerals Engineering,2004,17(3):457-459.
[9] 王衍. 炼铜转炉渣中铜铁的选矿研究[J]. 有色矿山,2003,32(4):19-23. WANG H. Study on copper and iron concentrating from coverter slag of copper smelting[J]. Nonferrous Mines,2003,32(4):19-23.
[10] 汤雁冰. 诺兰达炉渣选矿工艺探讨[J]. 有色矿冶,2000,16(4):15-20. TANG Y B. Discussion on mineral processing of slag of noranda reactor[J]. Non-Ferrous Mining and Metallurgy,2000,16(4):15-20.
[11] 张林楠,张力,王明玉,等. 铜渣的处理与资源化[J]. 矿产综合利用,2005(5):22-26. ZHANG L N,ZHANG L,WANG M Y,et al. Treatment and resourceful disposal of copper slag[J]. Multipurpose Utilization of Mineral Resources,2005(5):22-26.
[12] CARRANZA F,IGLESIAS N,MAZUELOS A,et al. Ferric leaching of copper slag flotation tailings[J]. Minerals Engineering,2009,22:107-110.
[13] KAKSONEN A H,LAVONEN Leena,KUUSENAHO Mari,et al. Bioleaching and recovery of metals from final slag waste of the copper smelting industry[J]. Minerals Engineering,2011,24:1113-1121.
[14] 王彤,朱维东,赵平原,等. 黄铜水平连铸覆盖物渣中Cu、Zn的浸出[J]. 贵州科学,2007,25(s1):79-81. WANG T,ZHU W D,ZHAO P Y,et al. Leaching of copper and zinc in mantle from horizontal continuous casting of brass[J]. Guizhou Science,2007,25(s1):79-81.
[15] SHEN H T,FORSSBERG E. An overview of recovery of metals from slags[J]. Waste Management,2003,23:933-949.
[16] AGRAWAl A,SAHU K K,PANDEY B D. Solid waste management in non-ferrous industries in India[J]. Resources,Conservation and Recycling,2004,42:99-120.
[17] LIFSET R J,GORDON R B. Where has all the copper gone:the stocks and flows project,part 1[J]. JOM,2002,54(10):21-26.
[18] LI Y J,PEREDERIY I,PAPANGELAKIS V G. Cleaning of waste smelter slags and recovery of valuable metals by pressure oxidative leaching[J]. Journal of Hazardous Materials,2008,152:607-615.
[19] LI Y J,PAPANGELAKIS V G,PEREDERIY I. High pressure oxidative acid leaching of nickel smelter slag:characterization of feed and residue[J]. Hydrometallurgy,2009,97:185-193.
[20] BANZA A N,GOCK E,KONGOLO K. Base metals recovery from copper smelter slag by oxidizing leaching and solvent extraction[J]. Hydrometallurgy,2002,67(1/2/3):63-69.
[21] ABDEL B S M,MAHMOUD A R. Hydrometallurgical recovery of metal values from brass melting slag[J]. Hydrometallurgy,1999,53:31-44.
[22] HERREROS O,QUIROZ R,MANZANO E,et a1. Copper extraction from reverberatory and flash furnace slags by chlorine 1eaching[J]. Hydrometallurgy,1998,49(1/2):87-101.
[23] BESE A V,ATA O N,CELIK C,et a1. Determination of the optimum conditions of dissolution of copper in converter slag with chlorine gas in aqueous media[J]. Chemical Engineering and Processing,2003,42(4):291-298.
[24] ALTUNDOGAN H S,TUMEN F. Metal recovery from copper converter slag by roasting with ferric sulphate[J]. Hydrometallurgy,1997,44(1/2):261-267.
[25] RUDNIK E,BURZYLLSKA L,GUMOWSKA W. Hydrometallurgical recovery of copper and cobalt from reduction-roasted copper converter slag[J]. Mineral Engineering,2009,22(1):88-95.
[26] ARSLAN C,ARSLAN F. Recovery of copper,cobalt,and zinc from copper sn1elter and converter slags[J]. Hydrometallurgy,2002,67(1/2/3):1-7.
[27] 马国军,王战仁,李光强,等. 诺兰达铜渣中有价元素的回收[J]. 武汉科技大学学报,2008,31(5):473-477. MA G J,WANG Z R,LI G Q,et al. Recovery of valuable elements from Noranda copper slag[J]. Journal of Wuhan University of Science and Technology,2008,31(5):473-477.
[28] VAISBURD S,BEMER A,BRANDON D G,et a1. Slags and mattes in vanyukov's process for the extraction of copper[J]. Metallurgical and Materials Transactions B,2002,33:551-559.
[29] VAISBURD S,BRANDON D G,KOZHAKHMETOV S,et al. Physicochemical properties of matte-slag melts taken from vanyukov's furnace for copper extraction[J]. Metallurgical and Materials Transactions B,2002,33:561-564.
[30] 陈海清,李沛兴,刘水根,等. 铜渣火法强化贫化工艺研究[J]. 湖南有色金属,2006,22(3):16-18. CHEN H Q,LI P X,LIU S G,et al. Study on the strengthening depletion of copper from copper smelter slag by pyro-process[J]. Hunan Nonferrous Metals,2006,22(3):16-18.
[31] 张林楠. 铜渣中有价组分选择性析出研究[D]. 沈阳:东北大学,2005. ZHANG L N. Study on selective precipitation valuable constituent in copper smelting slags[D]. Shenyang:Northeastern University,2005.
[32] 魏国忠,吾特W,叶国瑞. 直流矿热电炉中铜转炉渣的贫化[J]. 东北大学学报,1989,10(4):388-393. WEI G Z,WUTH W,YE G R. Impoverishment of copper converter slags by a laboratory DC electric furnace[J]. Journal of Northeast University of Technology,1989,10(4):388-393.
[33] 杜清枝. 炉渣真空贫化的物理化学[J]. 昆明工学院学报,1995,20(2):107-110. DU Q Z. Physical chemistry of vacuum slag cleaning[J]. Journal of Kunming Institute of Technology,1995,20(2):107-110.
[34] 曹洪杨,张力,付念新,等. 国内外铜渣的贫化[J]. 材料与冶金学报,2009,8(1):33-39. CAO H Y,ZHANG L,FU N X,et al. Review of copper slag impoverishment[J]. Journal of Materials and Metallurgy,2009,8(1):33-39.
[35] 隋智通,郭振中,张力,等. 含钛高炉渣中钛组分的绿色分离技术[J]. 材料与冶金学报,2006,5(2):93-97. SUI Z T,GUO Z Z,ZHANG L,et al. Green separation technique of Ti component from Ti-bearing blast furnace slag[J]. Journal of Materials and Metallurgy,2006,5(2):93-97.
[36] WANG M Y,WANG X W,HE Y H,et a1. Isothermal precipitation and growth process of perovskite phase in oxidized titanium bearing slag[J]. Transactions of Nonferrous Metals Society of China,2008,2:459-462.
[37] 王明玉,张力,张林楠,等. 含钛高炉熔渣氧化过程性能变化特征[J]. 有色金属,2008,60(2):59-61. WANG M Y,ZHANG L,ZHANG L N,et al. Characteristics change of Ti-bearing molten blast furnace slag under dynamic oxidation condition[J]. Nonferrous Metals,2008,60(2):59-61.
[38] WANG M Y,ZHANG L N,ZHANG L,et a1. Selective enrichment of TiO₂ and precipitation behavior of perovskite phase in titania bearing slag[J]. Trans Nonferous Met. Soc. China,2006,2:421-425.
[39] 张林楠,张力,王明玉,等. 铜渣贫化的选择性还原过程[J]. 有色金属,2005,57(3):44-47. ZHANG L N,ZHANG L,WANG M Y,et al. Research on selective reducing impoverishment process of copper salg[J]. Nonferrous Metals,2005,57(3):44-47.
[40] 曹洪杨,付念新,张力,等. 铜冶炼熔渣中铁组分的迁移与析出行为[J]. 过程工程学报,2009(2):284-288. CAO H Y,FU N X,ZHANG L,et al. Migration and precipitation behavior of Fe components in copper smelting slag[J]. The Chinese Journal of Process Engineering,2009(2):284-288.
[41] 刘纲,朱荣,王昌安,等. 铜渣熔融氧化提铁的试验研究[J]. 中国有色冶金,2009(1):71-74. LIU G,ZHU R,WANG C A,et al. Experiment of molten oxidation iron extraction in copper slag[J]. Chinese Nonferrous Metallurgy,2009(1):71-74.
[42] 黄自力,罗凡,李密,等. 从炼铜水淬渣中回收铁的试验研究[J]. 矿产保护与和利用,2009(3):51-54. HUANG Z L,LUO F,LI M,et al. Experimental study on iron recovery from water quenched slag of copper smelting[J]. Conservation and Utilization of Mineral Resources,2009(3):51-54.
[43] 廖曾丽,唐谱,张波. 等. 铜渣在中低温下氧化改性的实验研究[J]. 中国有色冶金,2012(4):74-78. LIAO Z L,TANG P,ZHANG B,et al. Experimental study on oxidation modificatiion of copper slag at middle-low temperature[J]. Chinese Nonferrous Metallurgy,2012(4):74-78.
[44] 杨慧芬,景丽丽,党春阁. 铜渣中铁组分的直接还原与磁选回收[J]. 中国有色金属学报,2011,21(5):1165-1170. YANG H F,JING L L,DANG C G. Iron recovery from copper-slag with lignite-based direct reduction followed by magnetic separation[J]. The Chinese Journal of Nonferrous Metals,2011,21(5):1165-1170.
[45] CHENG X L,ZHAO K,QI Y H,et al. Direct reduction experiment on iron-bearing waste slag[J]. Journal of Iron and Steel Research,International,2013,20(3):24-29.
[46] ZHAI X J,LI N J,ZHANG X,et al. Recovery of cobalt from converter slag of Chambishi copper smelter using reduction smelting process[J]. Trans. Nonferrous Met. Soc. China,2011,21:2117-2121.
[47] 李磊,胡建杭,王华. 铜渣熔融还原炼铁过程反应热力学分析[J]. 材料导报,2011,25(7):114-117. LI L,HU J H,WANG H. Thermodynamic analysis of iron smelting reduction from copper residue[J]. Materials Review,2011,25(7):114-117.
[48] 胡建杭,王华,刘慧利,等. 铜渣在不同煅烧温度的晶相结构[J]. 湖南科技大学学报(自然科学版),2011,26(2):97-100. HU J H,WANG H,LIU H L,et al. Polycrystalline structure of copper slag at different calcining temperature[J]. Journal of Hunan University of Science & Technology (Natural Science Edition),2011,26(2):97-100.
[49] AL-JABRI K S,HISADA M,AL-ORAIMI S K. Copper slag as sand replacement for high performance concrete[J]. Cement & Concrete Composites,2009,31:483-488.
[50] KHANZADI M,BEHNOOD A. Mechanical properties of high-strength concrete incorporating copper slag as coarse aggregate[J]. Construction and Building Materials,2009,23:2183-2188.
[51] SHI C J,Meyer C,Behnood A. Utilization of copper slag in cement and concrete[J]. Resources,Conservation and Recycling,2008,52:1115-1120.
[52] WU W,ZHANG W D,MA G W. Optimum content of copper slag as a fine aggregate in high strength concrete[J]. Materials and Design,2010,31:2878-2883.
[53] WU W,ZHANG W D,MA G W. Mechanical properties of copper slag reinforced concrete under dynamic compression[J]. Construction and Building Materials,2010,24:910-917.
[54] AL-JABRI K S,AL-SAIDY A H,Taha R. Effect of copper slag as a fine aggregate on the properties of cement mortars and concrete[J]. Construction and Building Materials,2011,25:933-938.
[55] ALI A,SALIM A. Mechanical activation of silicomanganese slag and its influence on the properties of Portland slag cement[J]. Powder Technology,2014,251:41-51.
[56] 秦守婉,申建军,吴春丽. 熔渣、铜矿渣在水泥生产中的应用研究[J]. 硅酸盐通报,2013,32(4):572-576,582. QIN S W,SHEN J J,WU C L. Utilization of blast furnace slag,copper slag in the production of clinker[J]. Bulletin of the Chinese Ceramic Society,2013,32(4):572-576,582.
[57] 胡纯清,衡晓志,喻国安. 钢铜渣碱性膨胀造成建筑物破坏的调查研究[J]. 土工基础,2000,14(1):35-38. HU C Q,HENG X Z,YU G A. The investigation and research of structures destruction caused by basic expansion of steel or copper slag[J]. Soil Engineering and Foundation,2000,14(1):35-38.
[58] 王枫,高波. 某学校混凝土爆裂事故原因分析[J]. 混凝土与水泥制品,2011(12):53-55. WANG F,GAO B. The reason analysis on concrete blowout happened in a school[J]. China Concrete and Cement Products,2011(12):53-55.
[59] LIAO YALONG L,CHAI XIJUAN J,LI JIANGTAO T,et al. Study on recovering iron from smelting slag by carbothermic reduction[J]. Advanced Materials Research,2012,382:422-426.
[60] LIAO Y L,ZHOU J,HUANG F R. Separating and recycling of Fe,Cu, from dumped copper slag by microwave irradiation assisted carbothermic method[J]. Journal of Residuals Science & Technology,2016,13(s1):155-160.
[61] 韩伟,秦庆伟. 从炼铜炉渣中提取铜铁的研究[J]. 矿冶,2009,18(2):9-12. HAN W,QIN Q W. Recovery of copper and iron from copper slag[J]. Mining & Metallurgy,2009,18(2):9-12.
[62] 吴礼杰. 转炉渣中有价金属的选别[J]. 矿业研究与开发,2001,21(4):29-32. WU L J. Selective recovery of valuable metals from rotary furnace slag[J]. Mining Research and Design,2001,21(4):29-32.
[63] 廖亚龙,黄斐荣,周娟,等. 低冰镍转炉渣中钴的氧压酸浸行为及其动力学[J]. 化工学报,2015,66(10):3971-3978. LIAO Y L,HUANG F R,ZHOU J,et al. Kinetics and behavior of cobalt extraction from low nickel matte converter slag by pressure oxidative leaching with sulfuric acid[J]. CIESC Journal,2015,66(10):3971-3978.
[64] 黄斐荣,廖亚龙,王祎洋,等. 响应曲面法优化镍转炉渣氧压选择性浸出工艺[J]. 环境科学研究,2016,29(6):894-899. HUANG F R,LIAO Y L,WANG Y Y,et al. Optimization of pressure oxidative acid leaching of nickel converter slag by response surface methodology[J]. Research of Environmental Sciences,2016,29(6):894-899.
[65] HUANG F R,LIAO Y L,ZHOU J,et al. Selective recovery of valuable metals from nickel converter slag at elevated temperature with sulfuric acid solution[J]. Separation and Purification Technology,2015,156(2):572-581.