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系统总结了近年来铜渣综合利用的最新研究成果,主要包括铜渣中有价金属单独提取、有价组元协同还原高值化转化、铜渣协同处置制备建筑材料以及铜渣在环保治理等方面的研究进展,梳理出铜渣综合利用存在的问题,并对其未来发展趋势进行了预测。目前,铜渣缓冷浮选贫化后,渣铜残留量可降至0.23%～0.26%,但选矿尾渣难以利用;传统火法贫化后渣中铜残留量仍在0.6%～1%以上,大量的铜仍未得到有效回收利用,需再次贫化;利用熔融铜渣适度涡流贫化—熔融原位还原制备含铜抗菌不锈钢/耐磨铸铁,联产水泥熟料,渣中铜残留量可降至0.27%左右,不仅实现了铜渣的无渣化资源化高值利用,同时有效利用了铜渣的余热,铜、铁、铅、锌的回收率分别为>98%、>95%、>90%、>95%,是未来最具发展潜力的铜渣大规模高值化资源化综合利用新技术。
Abstract：The latest research results in comprehensive utilization of copper slag in recent years were systematically summarized,including extraction of valuable metals,preparation of high value-added copper slag alloys,co-processing of copper slag to prepare building materials,and application of copper slag in environmental protection and progress of other fields.Problems in comprehensive utilization of copper slag were sorted out and future development was predicted.After flotation,residual amount of copper in depleted slag can be reduced to 0.23%—0.26%,but the beneficiation tailings cannot be used.Pyrolysis process can only effectively recover part of copper in copper slag,and copper residue in depleted slag is still 0.6%-1% above.Using molten copper smelting slag to moderately deplete-eddy current smelting reduction to prepare copper-containing antibacterial stainless steel/wear-resistant cast iron,and co-produce cement clinker,which not only realizes high-value utilization of copper slag without slag,but also effectively utilizes copper slag waste heat.Recovery of Cu,Fe,Pb,and Zn is >98%,>95%,>90%,and>95%,respectively.It is a new technology for comprehensive utilization of large-scale high-value copper slag resources with the most development potential in the future.
[1]顾晓薇,胥孝川,王青,等．世界铜资源格局[J]．金属矿山,2015(3):8-13.GU X W,XU X C,WANG Q,et al.The world pattern of copper resource[J].Metal Mine,2015(3):8-13．
[2]熊靓辉,李调丽,张会琼．国内外铜矿资源供需现状及趋势分析[J]．矿产勘查,2019,10(2):159-163.XIONG L H,LI D L,ZHANG H Q.Current situation and trend analysis of copper resources supply and demand at home and abroad[J].Mineral Exploration,2019,10(2):159-163．
[3]马茁卉．国内外铜资源竞争力对比研究[J]．中国国土资源经济,2015,28(10):28-30.MA Z H.Comparative study oncompetitiveness of copper resources at home and abroad[J].Natural Resource Economics of China,2015,28(10):28-30．
[4]刘金生,姜平国,肖义钰,等．从铜渣中回收铁的研究现状及其新方法的提出[J]．有色金属科学与工程,2019,10(2):19-24.LIU J S,JIANG P G,XIAO Y J,et al.Research status and new method of recovering iron from copper slag[J].Nonferrous Metals Science and Engineering,2019,10(2):19-24．
[5]ZHOU H,LI B,WEI Y G,et al.Magnetite reduction in copper converter slag using biodiesel produced from waste cooking oil[J].Canadian Metallurgical Quarterly,2019,58(2):187-195．
[6]AYBIN R,AHMET G,YAVUZ A T,et al.Effects of some additives on copper losses to matte smelting slag[J].JOM,2016.DOI:10.1007?s11837-016-1825-1．
[7]ELLIOTT J F,MOUNIER M.Surface and interfacial tensions in copper matte-slag systems,1 200℃[J].Canadian Metallurgical Quarterly,2013,21 (4):415-428．
[8]SHI Y,WEI Y,ZHOU S,et al.Effect of B2O3content on the viscosity of copper slag[J].Journal of Alloys and Compounds,2019:153478.DOI:10.1016?j.jallcom.2019.153478．
[9]LI B,WANG X B,WANG H,et al.Smelting reduction and kinetics analysis of magnetic iron in copper slag using waste cooking oil[J].Entific Reports,2017,7(1):2406.DOI:10.1038?s41598-017-02696-y．
[10]LI B,WEI Y G,WANG H,et al.Reduction of magnetite from copper smelting slag using petro-diesel and biodiesel[J].ISIJ International,2018,58(6):1168-1174．
[11]ZHOU S W,WEI Y G,LI B,et al.Cleaner recycling of iron from waste copper slag by using walnut shell char as green reductant[J].Journal of Cleaner Production,2019,217(20):423-431．
[12]ZHOU H,LI B,WEI Y,et al.Magnetite reduction in copper converter slag using biodiesel produced from waste cooking oil[J].Canadian Metallurgical Quarterly,2018,58(2):1-9．
[13]QU G R,WEI Y G,LI B,et al.Distribution of copper and iron components with hydrogen reduction of copper slag[J].Journal of Alloys and Compounds,2020,824:153910.DOI.org?10.1016?j.jallcom.2020.153910．
[14]李丽萍,何金戈．地沟油生物柴油在发动机上的应用现状和发展趋势[J]．油脂化工,2014,39(8):52-56LI L P,HE J G.Application status and development trend of cooking oil biodiesel in engine[J].China Oils and Fats,2014,39(8):52-56．
[15]姜保成．铜渣涡流还原冶炼含铜耐磨铸铁的研究[D]．沈阳：东北大学,2019.JIANG B C.Study on eddy current reduction of copper slag for smelting copper-bearing wear resistant cast iron[D].Shenyang:Northeastern University,2019．
[16]张东亮．铜渣涡流贫化过程的研究[D]．沈阳：东北大学,2017.ZHANG D L.The research on vortex dilution process of copper slag[D].Shenyang:Northeastern University,2017．
[17]李志强．含铜铁水喷吹CO2脱碳研究[D]．沈阳：东北大学,2017.LI Z Q.The research on decarburization of coppercontaining hot metal smelted by CO2 injection[D].Shenyang:Northeastern University,2017．
[18]郑超．铜渣氢气还原过程的研究[D]．沈阳：东北大学,2017.ZHENG C.The Research on reduction process of copper slag by hydrogen[D].Shenyang:Northeastern University,2017．
[19]刘帅．铜渣还原的含铜铁水中砷的脱除[D]．沈阳：东北大学,2017.LIU S.Removal of arsenic from copper-containing molten iron reduced by copper slag[D].Shenyang:Northeastern University,2017．
[20]GUO Z Q,ZHU D Q,PAN J,et al.Mechanism of mineral phase reconstruction for improving the beneficiation of copper and iron from copper slag[J].JOM,2016,68(9):2341-2348．
[21]ZUO Z L,YU Q B,XIE H Q,et al.Mechanical and reduction characteristics of cold-pressed copper slag pellets composited within biomass and lignite[J].Renewable Energy,2018,125:206-224．
[22]ZUO Z L,YU Q B,WEI M Q,et al.Thermogravimetric study of the reduction of copper slag by biomass[J].Journal of Thermal Analysis&Calorimetry,2016,126(2):1-11．
[23]ZUO Z L,YU Q B,XIE H Q,et al.Thermogravimetric analysis of the biomass pyrolysis with copper slag as heat carrier[J].Journal of Thermal Analysis&Calorimetry,2017,129:1233-1241．
[24]ZUO Z L,YU Q B,XIE H Q,et al.Direct reduction of copper slag-carbon composite pellets by coal and biochar[J].Environmental Technology,2020,41(17):2240-2252．
[25]WEI R R,YANG M R,LV X W,et al.Preparing ferrosilicon alloy with copper slag[J].The Minerals,Metals&Materials Society,2017:301-310.DOI:10.1007?978-3-319-52192-3_30．
[26]GUO Z Q,ZHU D Q,PAN J,et al.Innovative methodology for comprehensive and harmless utilization of waste copper slag via selective reductionmagnetic separation process[J].Journal of Cleaner Production,2018,187:910-922．
[27]GUO Z Q,PAN J,ZHU D Q,et al.Co-reduction of copper smelting slag and nickel laterite to prepare Fe-Ni-Cu alloy for weathering steel[J].JOM,2018,70(2):150-154．
[28]牛丽萍,刘捷元,宋锦波,等．熔融铜渣天然气还原过程的研究[J]．材料与冶金学报,2016,15(3):200-204.NIU L P,LIU J Y,SONG J B,et al.Study on reduction process of melting copper slag with natural gas[J].Journal of Materials and Metallurgy,2016,15(3):200-204．
[29]张保敬．铜渣还原冶炼含铜抗菌不锈钢的基础研究[D]．沈阳：东北大学,2019.ZHANG B J.Afundamental study on copper slag reduced to smelt copper-containing antibacterial stainless steel[D].Shenyang:Northeastern University,2019．
[30]张廷安,牛丽萍,豆志河,等．一种从冶炼铜渣中直接还原回收铜铁的方法：201210364451.4[P].2012-09-26.ZHANG T A,NIU L P,DOU Z H,et al.A method to recover copper and iron from smelting copper slag by direct reduction:201210364451.4[P].2012-09-26．
[31]张廷安,牛丽萍,豆志河,等．一种利用铜渣还原铁水直接冶炼含铜抗菌不锈钢的方法：201410345197.2[P].2014-07-21.ZHANG T A,NIU L P,DOU Z H,et al.A method to directly smelt copper containing antibacterial stainless steel from melted iron reduced from copper slag:201410345197.2[P].2014-07-21．
[32]东北大学．熔融铜渣适度贫化-涡流还原制备含铜抗菌不锈钢?耐磨铸铁关键技术与装备开发[Z]．沈阳：东北大学,2019.Northeastern University.Key technology and equipment development for preparation of antibacterial stainless steel?wear-resistant cast iron containing copper by eddy reduction with moderate dilution of molten copper slag[Z].Shenyang:Northeastern University,2019．
[33]ZHANG B J,NIU L P,ZHANG T A,et al.Alternative reduction of copper matte in reduction process of copper slag[J].ISIJ International,2017,57(5):775-781．
[34]ZHANG B J,ZHANG T A,NIU L P,et al.Moderate dilution of copper slag by natural gas[J].JOM,2018,70(1):47-52．
[35]张廷安,张保敬,牛丽萍,等．一种喷吹CO2脱除高碳含铜铁水中碳的方法：ZL201610851740.5[P].2016-12-07.ZHANG T A,ZHANG B J,NIU L P,et al.Method for removing carbon from high-carbon copper-containing molten iron by blowing CO2:ZL201610851740.5[P].2016-12-07．
[36]张廷安,刘燕,豆志河,等．一种涡流搅拌熔融还原炼铁方法：ZL201610854514.2[P].2017-02-22.ZHANG T A,LIU Y,DOU Z H,et al.Eddy current stirring smelting reduction ironmaking method:ZL201610854514.2[P].2017-02-22．
[37]张廷安,豆志河,牛丽萍,等．一种搅拌协同喷吹气体携带硫化剂贫化铜渣的方法：ZL201610144808.6[P].2016-06-15.ZHANG T A,DOU Z H,NIU L P,et al.A method for depleting copper slag with agitation and coordinated injection of gas carrying sulfiding agent:ZL201610144808.6[P].2016-06-15．
[38]张廷安,牛丽萍,豆志河,等．一种铜冶炼渣的贫化方法：ZL201610144793.3[P].2016-07-20.ZHANG T A,NIU L P,DOU Z H,et al.A method of depletion of copper smelting slag:ZL201610144793.3[P].2016-07-20．
[39]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(2):933-938．
[40]LORI A R,HASSANI A,SEDGHI R.Investigating the mechanical and hydraulic characteristics of pervious concrete containing copper slag as coarse aggregate[J].Construction and Building Materials,2019,197:130-142．
[41]PREM P R,VERMA M,AMBILY P S.Sustainable cleaner production of concrete with high volume copper slag[J].Journal of Cleaner Production,2018,193:43-58．
[42]RAJASEKAR A,ARUNACHALAM K,KOTTAISAMY M.Assessment of strength and durability characteristics of copper slag incorporated ultra high strength concrete[J].Journal of Cleaner Production,2019,208:402-414．
[43]BABU K M,RAVITHEJA A.Effect of copper slag as fine aggregate replacement in high strength concrete[J].Materials Today:Proceedings,2019,19(2):409-414．
[44]RAJU S,DHARMAR B.Durability characteristics of copper slag concrete with fly ash[J].Gradevinar,2017,69(11):1031-1040．
[45]WANG Z J,ZHANG T A,ZHOU L.Investigation on electromagnetic and microwave absorption properties of copper slag-filled cement mortar[J].Cement and Concrete Composites,2016,74:174-181．
[46]AMERI F,BRITO J D,MADHKHAN M,et al.Steel fibre-reinforced high-strength concrete incorporating copper slag:Mechanical,gamma-ray shielding,impact resistance,and microstructural characteristics[J].Journal of Building Engineering,2020,29:101118.DOI.org?10.1016?j.jobe.2019.101118．
[47]FAN Y,ZHANG B,et al.An innovated application of reutilize copper smelter slag for cement-based electromagnetic interference composites[J].Scientific Reports,2018,8(1):16155.DOI:10.1038?s41598-018-34680-5．
[48]LIM S,LEE W,CHOO H,et al.Utilization of high carbon fly ash and copper slag in electrically conductive controlled low strength material[J].Construction and Building Materials,2017,157:42-50．
[49]LEMOUGNA P N,YLINIEMI J,ADESANYA E,et al.Reuse of copper slag in high-strength duilding ceramics containing spodumene tailings as fluxing agent[J].Minerals Engineering,2020,155:106448.DOI.org?10.1016?j.mineng.2020.106448．
[50]杨洁,徐龙华,王周杰,等．锂辉石浮选尾矿制备建筑装饰陶瓷材料及其性能[J]．化工进展,2020,39(9):3777-3785.YANG J,XU L H,WANG Z J,et al.Preparation and properties of building decoration ceramic materials from spodumene flotation tailings[J].Chemical Industry and Engineering Progress,2020,39 (9):3777-3785．
[51]LIU M K,MA G J,ZHANG X,et al.Preparation of black ceramic tiles using waste copper slag and stainless steel slag of electric arc furnace[J].Materials,2020,13(3):776.DOI:10.3390?ma13030776．
[52]LI J L,MOU Q Q,ZENG Q,et al.Experimental study on precipitation behavior of spinels in stainless steelmaking slag under heating treatment[J].Processes,2019,7(8):487.DOI:10.3390?pr7080487．
[53]杜龙．不锈钢粉尘制备黑色瓷砖的物理性质和浸出行为[D]．武汉：武汉科技大学,2017.DU L.Physicalproperties and leaching behaviour of the black ceramic tiles prepared by stainless steel dust[D].Wuhan:Wuhan University of Science and Technology,2017．
[54]SMOTHERS W J.Cobalt-Free Black Pigments[M]ACollection of Papers Presented at the 1978,1979,and1980Meetings of the Materials&Equipment?Whitewares.Ceramic Engineering and Science Proceedings,American Ceramic Society Bulletin,2008,60(5):863-870．
[55]陈政,黄清娥,黄保坤,等．水合状态的无定形氧化铁用作高效水氧化催化剂[J]．催化学报,2019,40(1):38-42.CHEN Z,HUANG Q E,HUANG B K,et al.Ahydrated amorphous iron oxide nanoparticle as active water oxidation catalyst[J].Chinese Journal of Catalysis,2019,40(1):38-42．
[56]白书立,张晓玉,薛瑶佳,等．碳化硅负载氧化铜催化剂低温NH3选择性催化还原NOx的性能[J]．燃料化学学报,2020,48(6):723-727.BAI S L,ZHANG X Y,XUE Y J,et al.Silicon carbonsupported copper oxide catalysts for the selective catalytic reduction of NOx with NH3 at low temperature[J].Journal of Fuel Chemistry and Technology,2020,48(6):723-727．
[57]夏慧．乙炔黑?二氧化锰催化臭氧微气泡氧化有机废水[D]．武汉：中南民族大学,2019.XIA H.Acetylene black?manganese dioxide catalyzed oxidation of organic wastewater by ozone microbubbles[D].Wuahn:South-Central University for Nationalities,2019．
[58]叶智青．燃煤烟气脱汞处理技术[J]．环境科学导刊,2020,39(3):58-63.YE Z Q.Theremoval technology of mercury from the flue gas of fired coal[J].Environmental Science Survey,2020,39(3):58-63．
[59]LI H L,ZHANG W L,WANG J,et al.Copper slag as a catalyst for mercury oxidation in coal combustion flue gas[J].Waste Management,2018,74:253-259．
[60]RABIEE F,MAHANPOOR K.Experimental scale photocatalytic oxidation SO2from simulated flue gas in the presence of Mn?copper slag as a novel nanocatalyst:Optimizations by Hybrid Box-Behnken experimental design and genetic algorithm[J].Russian Journal of Applied Chemistry,2018,91(4):687-700．
[61]吴立军．改性柱状活性炭脱硫脱硝性能研究[D]．安徽马鞍山：安徽工业大学,2016.WU L J.Study on SO2and NOxremoval performance of modified columnar activated carbon[D].Maanshan:Anhui University of Technology,2016．
[62]袁博．铁基催化剂催化氧化脱硫脱硝脱汞实验研究[D]．北京：华北电力大学,2019.YUAN B.Experimentalstudy on the catalytic oxidation for removing sulfur dioxide,nitrogen oxides and mercury over iron-based catalysts[D].Beijing:North China Electric Power University,2019．
[63]林爽．Fe3O4污水预处理及电动处理污泥重金属减量研究[D]．辽宁大连：大连海事大学,2019.LIN S.Heavymetal reduction study on sewage pretreatment by Fe3 O4 and sludge treatment by electrokinetic method[D].Dalian:Dalian Maritime University,2019．
[64]赵雅光,万俊锋,刘奉滨,等．零价铁(ZVI)治理水体砷污染研究进展[J]．环境化学,2013,32(10):1943-1949.ZHAO Y G,WANG J F,LIU F B,et al.Application of zero-valent iron(ZVI)technology for arsenic removal from aqueous environment[J].Environmental Chemistry,2013,32(10):1943-1949．
[65]LIU Z W,DONG S S,ZOU D,et al.Electrochemically mediated nitrate reduction on nanoconfined zerovalent iron:Properties and mechanism[J].Water Research,2020,173:115596.DOI.org?10.1016?j.watres.2020.115596．
[66]RONAVARI A,BALAZS M,TOLMACSOV P,et al.Impact of the morphology and reactivity of nanoscale zero-valent iron(NZVI)on dechlorinating bacteria[J].Water Research,2016,95:165-173．
[67]ZOU Y D,WANG X X,KHAN A,et al.Environmental remediation and application of nanoscale zero-valent iron and its composites for the removal of heavy metal ions:A review[J].Environmental Science&Technology,2016,50(14):7290-7304．
[68]胡美世,乐成涛,王淼,等．铜渣改性制备多孔硅酸盐负载微纳米零价铁及其去除废水中的Cr(Ⅵ)[J]．矿产保护与利用,2020,40(3):40-45.HU M S,LE C T,WANG M,et al.Preparation of porous silicate supported micro-nano ZVI from copper slag and its application for removing Cr(Ⅵ)from wastewater[J].Conservation and Utilization of Mineral Resources,2020,40(3):40-45．
[69]LI J,CHEN C L,ZHU K R,et al.Nanoscale zerovalent iron particles modified on reduced graphene oxides using aplasma technique for Cd(Ⅱ)removal[J].Journal of the Taiwan Institute of Chemical Engineers,2015,59:389-394．
[70]LAI B,ZHANG Y,CHEN Z,et al.Removal of pnitrophenol(PNP)in aqueous solution by the micronscale iron-copper(Fe?Cu)bimetallic particles[J].Applied Catalysis B:Environmental,2014,144:816-830．
[71]唐琼瑶,黄磊,刘浩,等．铜渣制备微电解填料及其处理甲基橙废水的研究[J]．金属矿山,2018,47(1):183-186.TANG Q Y,HUANG L,LIU H,et al.Study on the preparation of microelectrolyte filler with copper slag and its treatment on methyl orange wastewater[J].Metal Mine,2018,47(1):183-186．
[72]李永奎,祝星,祁先进,等．铜渣与含砷污酸反应行为及除砷机理[J]．中国环境科学,2019,39(10):4228-4238.LI Y K,ZHU X,QI X J,et al.Reaction behavior of copper slag with waste acid and its arsenic removal mechanism[J].China Environmental Science,2019,39(10):4228-4238．
[73]REZVAN Z,KAZEM M.Preparation and characterization of nano-spherical CoFe2O4 supported on copper slag as a catalyst for photocatalytic degradation of 2-nitrophenol in water[J].Journal of Nanostructure in Chemistry,2017,7(1):67-74．
[74]梁艳莉,马剑琪,郭少波．核壳型磁性纳米复合材料CoFe2O4@PDA@Pt的制备及催化性能[J]．复合材料学报,2021,38.DOI:10.13801?j.cnki.fhclxb.20200925.001.LIANG Y L,MA J Q,GUO S B.Preparation and catalytic properties of CoFe2O4@PDA@Pt magnetic nanocomposite catalyst with core shell structure[J].Acta Materiae Compositae Sinica,2021,38.DOI:10.13801?j.cnki.fhclxb.20200925.001.
基本信息:
中图分类号:X758
引用信息:
[1]李小凡,豆志河,张廷安,等.铜冶炼渣综合利用进展[J].有色金属(冶炼部分),2021(04):108-118.
基金信息:
国家自然科学基金云南联合基金重点项目(U1702253)
2021-04-12
2021-04-12