铜阳极泥低温碱性熔炼浸出液中杂质分离
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摘要
铜阳极泥经低温碱性熔炼-浸出处理后,铅、砷、硒等进入强碱性浸出液,其中铅和砷分别以Pb(OH)_n~(2-n)和AsO_4~(3-)形式存在。为分离其中的铅、砷等主要杂质元素,通过计算PbS-H_2O体系电势-pH图、Ca-As-H_2O体系溶解平衡浓度-pH图后,采用硫化沉淀和钙盐沉淀的方式有效去除铅、砷,同时保证硒的低分散度。实验结果表明:采用硫化沉淀,硫化钠过量系数2.5,反应温度20℃,反应时间15 min。在此条件下,铅和铜沉淀率都达到99.99%以上,硒损失5%;采用钙盐沉淀,控制溶液pH=10,钙砷比3.5,反应温度90℃,反应时间1.5 h。在此条件下,砷沉淀率达到99%以上,硒沉淀率为2.81%。
The leaching solution of low-temperature alkaline smelting-leaching process contains selenium, arsenic and lead, which exist in forms of SeO_4~(2-), Pb(OH)_n~(2-n) and AsO_4~(3-), respectively. In order to recover selenium, it is necessary to fully precipitate the lead and arsenic. After calculating the potential-p H diagram of Pb S-H_2O system and the solubility-pH diagram of Ca-As-H_2O system, the lead and arsenic were removed by the sulfurized precipitation and calcified precipitation progress, while ensured the low dispersion of selenium. The results show that the lead can be effectively separated from other metals under the optimum conditions which are stoichiometric requirement of Na_2S of 2.5, reaction temperature of 20 ℃, reaction time of 15 min. The copper and lead precipitation can reach 99.99% when the arsenic and selenium precipitation rate is less than 5%. The arsenic precipitation ratio reaches 99% when the reaction conditions are pH=10, n(Ca)/n(As)=3.5, bath temperature of 90 ℃ and reaction time of 1.5 h.
The leaching solution of low-temperature alkaline smelting-leaching process contains selenium, arsenic and lead, which exist in forms of SeO_4~(2-), Pb(OH)_n~(2-n) and AsO_4~(3-), respectively. In order to recover selenium, it is necessary to fully precipitate the lead and arsenic. After calculating the potential-p H diagram of Pb S-H_2O system and the solubility-pH diagram of Ca-As-H_2O system, the lead and arsenic were removed by the sulfurized precipitation and calcified precipitation progress, while ensured the low dispersion of selenium. The results show that the lead can be effectively separated from other metals under the optimum conditions which are stoichiometric requirement of Na_2S of 2.5, reaction temperature of 20 ℃, reaction time of 15 min. The copper and lead precipitation can reach 99.99% when the arsenic and selenium precipitation rate is less than 5%. The arsenic precipitation ratio reaches 99% when the reaction conditions are pH=10, n(Ca)/n(As)=3.5, bath temperature of 90 ℃ and reaction time of 1.5 h.
引文
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[20]GUO X,YI Y,SHI J,TIAN Q.Leaching behavior of metals from high-arsenic dust by Na OH-Na2S alkaline leaching[J].Transactions of Nonferrous Metals Society of China,2016,26(2):575-580.
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[25]郭学益,刘静欣,田庆华,李栋.有色金属复杂资源低温碱性熔炼原理与方法[J].有色金属科学与工程,2013,4(2):8-13.GUO Xue-yi,LIU Jing-xin,TIAN Qing-hua,LI Dong.Principle and method of low temperature alkaline smelting in non-ferrous metallurgy complicated resources[J].Nonferrous Metals Science and Engineering,2013,4(2):8-13.
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[31]DUCHESNE J,REARDON E J.Measurement and prediction of portlandite solubility in alkali solutions[J].Cement and Concrete Research,1995,25(5):1043-1053.
[32]PARKER V B,EVANS W H,NUTTALL R L.The thermochemical measurements on rubidium compounds:a comparison of measured values with those predicted from the NBS tables of chemical and thermodynamic properties[J].Journal of Physical and Chemical Reference Data,1987,16(1):7-59.
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[34]何绪文,胡建龙,李静文,等.硫化物沉淀法处理含铅废水[J].环境工程学报,2013,7(4):1394-1398.HE Xu-wen,HU Jian-long,LI Jing-wen,ZHANG Jing-jing,WANG Jian-bing,GE Peng.Treatment of wastewater containing lead by sodium sulfide precipitation[J].Chinese Journal of Environmental Engineering,2013,7(4):1394-1398.
[35]李莉.碱性体系下As(Ⅲ)的催化氧化及其机理研究[D].长沙:中南大学,2009.LI Li.Efficiency and mechanism of As(III)catalytic oxidation in alkaline system[D].Changsha:Central South University,2009.
[2]郭学益,许志鹏,田庆华,李栋.低温碱性熔炼分离富集铜阳极泥中的有价金属[J].中国有色金属学报,2015,25(8):2243-2250.GUO Xue-yi,XU Zhi-peng,TIAN Qing-hua,LI Dong.Valuable metals separation from copper anode slime by low-temperature alkaline smelting process[J].The Chinese Journal of Nonferrous Metals,2015,25(8):2243-2250.
[3]曹伟,傅佩玉.天然沸石处理含铅废水的试验研究[J].环境导报,1998(2):20-22.CAO Wei FU Pei-yu,HAN Zhong-hua,XU Jie,LI Xu-zhi.Treating the Pb in waste water by zeolite[J].Environment Herald,1998(2):20-22.
[4]孙洪良,朱利中.表面活性剂改性的螯合剂有机膨润土对水中有机污染物和重金属的协同吸附研究[J].高等学校化学学报,2007,28(8):1475-1479.SUN Hong-liang,ZHU Li-zhong.Simultaneous adsorption of organic pollutant and heavy metal onto surfactant-modified organ bentonites with chelating ligands[J]Chemical Journal of Chinese Universities,2007,28(8):1475-1479.
[5]何翊,牛盾,门阅.高岭石对铅离子吸附性能的特征研究[J].金属矿山,2005(10):60-64.HE Yi,NIU Dun,MEN Yue.Studies on characteristics of Pb2+adsorption to kaolinite[J].Metal Mine,2005(10):60-64.
[6]杨津津,徐晓军,王刚,王盼,韩振宇,管堂珍,田蕊.微电解絮凝耦合技术处理含重金属铅锌冶炼废水[J].中国有色金属学报,2012,22(7):2125-2132.YANG Jin-jin,XU Xiao-jun,WANG Gang,WANG Pan,HAN Zhen-yu,GUAN Tang-zhen,TIAN Rui.Treatment of zinc and lead smelting wastewater containing heavy metals by combined process of micro-electrolysis with flocculation[J].The Chinese Journal of Nonferrous Metals,2012,22(7):2125-2132
[7]SRINIVASA RAO K,DASH P K,SARANGI D,DASH P K,ROY CHAUDHURY G.Treatment of wastewater containing Pb and Fe using ion-exchange techniques[J].Journal of Chemical Technology and Biotechnology,2005,80(8):892-898.
[8]HUANG Ling-zhi,ZENG Guang-ming,HUANG Dan-lian,LI Li-feng,HUANG Peng-mian,XIA Chang-bin.Adsorption of lead(Ⅱ)from aqueous solution onto hydrilla verticillata[J].Biodegradation,2009,20(5):651-660.
[9]PENG Y,ZHENG Y,ZHOU W,CHEN W.Separation and recovery of Cu and As during purification of copper electrolyte[J].Transactions of Nonferrous Metals Society of China,2012,22(9):2268-2273.
[10]ZHENG Y,PENG Y,KE L,CHEN W.Separation and recovery of Cu and As from copper electrolyte through electrowinning and SO2 reduction[J].Transactions of Nonferrous Metals Society of China,2013,23(7):2166-2173.
[11]刘伟锋,杨天足,刘又年,陈霖,张杜超,唐谟堂.脱除铅阳极泥中贱金属的预处理工艺选择[J].中国有色金属学报,2013,23(2):549-558.LIU Wei-feng,YANG Tian-zu,LIU You-nian,CHEN Lin,ZHANG Du-chao,TANG Mo-tang.Selection of pretreatment process for removing base metals from lead anode slime[J].The Chinese Journal of Nonferrous Metals,2013,23(2):549-558
[12]施勇,王学谦,郭晓龙,马懿星,王郎郎,宁平.采用硫化铵去除冶炼烟气中的重金属[J].中国有色金属学报,2014,24(11):2900-2905.SHI Yong,WANG Xue-qian,GUO Xiao-long,MA Yi-xing,WANG Lang-lang,NING Ping.Removal of heavy metals from smelting flue gas by ammonium sulfide[J].The Chinese Journal of Nonferrous Metals,2014,24(11):2900-2905.
[13]CHAKRAVARTY S,DUREJA V,BHATTACHARYYA G,et al.Removal of arsenic from groundwater using low cost ferruginous manganese ore[J].Water Research,2002,36(3):625-632.
[14]喻德忠,邹菁,艾军.纳米二氧化锆对砷(Ⅲ)和砷(Ⅴ)的吸附性质研究[J].武汉化工学院化工与制药学院,2004,26(3):1-3.YU De-zhong,ZOU Jing,AI Jun.Study on the adsorption properties of nanometer sized zirconium dioxide to As(Ⅲ)and As(Ⅴ)[J].J Wuhan Inst Chem Tech,2004,26(3):1-3.
[15]KORNGOLD E,BELAYEV N,ARONOV L.Removal of arsenic from drinking water by anion exchangers[J].Desalination,2001,141(1):81-84.
[16]郭恒萍.冶炼含砷污酸与酸性含砷废水处理试验及应用研究[D].西安:长安大学,2010.GUO Hen-ping.Smelting contains the arsenie wastewater disposal experiment and applied research including the arsenic dirt acid and the acidity[D].Xi’an:Chang’an University,2010.
[17]HANSEN H K,NUNEZ P,JIL C.Removal of arsenic from wastewaters by airlift electrocoagulation.Part 1:Batch reactor experiments[J].Separation Science and Technology,2008,43(1):212-224.
[18]王勇,曹龙文,罗园.硫酸装置含砷废水处理及三氧化二砷制备[J].硫酸工业,2010(4):21-25.WANG Yong,CAO Long-wen,LUO Yuan.Treatment of arsenic-containing waste water from sulphuric acid plants and preparation of As2O3[J].Sulphuric Acid Industry,2010(4):21-25.
[19]陈维平,牛秋雅,田一庄.铟生产过程中As H3气体污染治理的研究[J].环境工程,2002,20(5):31-33.CHEN Wei-pin,NIU Qiu-ya,TIAN Yi-zhuang.Study on the treatment of As H3 gas pollution in the process of indium production[J].Environmental Engineering,2002,20(5):31-33.
[20]GUO X,YI Y,SHI J,TIAN Q.Leaching behavior of metals from high-arsenic dust by Na OH-Na2S alkaline leaching[J].Transactions of Nonferrous Metals Society of China,2016,26(2):575-580.
[21]李鹏,唐谟堂,鲁君乐.由含砷烟灰直接制取砷酸铜[J].中国有色金属学报,1997,7(1):40-42.LI Peng,TANG Mo-tang,LU Jun-le.Direct production of copper arsenate from bearing arsenic dusts[J].The Chinese Journal of Nonferrous Metals,1997,7(1):40-42.
[22]易宇,石靖,田庆华,郭学益.高砷烟尘碱浸渣制备焦锑酸钠的新工艺[J].中国有色金属学报,2015,25(1):241-249.YI Yu,SHI Jing,TIAN Qing-hua,GUO Xue-yi.Novel technology for preparation of sodium pyroantimonate from alkali leaching residue of high arsenic dust[J].The Chinese Journal of Nonferrous Metals,2015,25(1):241-249
[23]BUSETTI F,BADOER S,CUOMO M,et al.occurrence and removal of potentially toxic metals and heavy metals in the wastewater treatment plant of Fusina(Venice,Italy)[J].Industrial&Engineering Chemistry Research,2005,44(24):9264-9272
[24]廖敏,王锐.菌藻共生体去除废水中砷初探[J].环境污染与防治,1997,19(2):11-12.LIAO Ming,WANG Rui.A primary study on removal of arsenic in wastewater by arsenic-resistant helotism[J]Environmental Pollution&Control,1997,19(2):11-12.
[25]郭学益,刘静欣,田庆华,李栋.有色金属复杂资源低温碱性熔炼原理与方法[J].有色金属科学与工程,2013,4(2):8-13.GUO Xue-yi,LIU Jing-xin,TIAN Qing-hua,LI Dong.Principle and method of low temperature alkaline smelting in non-ferrous metallurgy complicated resources[J].Nonferrous Metals Science and Engineering,2013,4(2):8-13.
[26]郝润蓉,方锡义,钮少冲.无机化学丛书(第三卷):碳硅锗分族[M].北京:科学出版社,1988.HE Run-rong,FANG Xi-yi,NIU Shao-chong.Inorganic chemistry(Vol III):Carbon group[M].Beijing:Science Press,1988.
[27]DEAN J A.兰氏化学手册[M].魏俊发,译.北京:科学出版社,2003.DEAN J A.Lange’s handbook of chemistry[M].WEI Jun-fa,transl.Beijing:Science Press,2003.
[28]李洪桂.冶金原理[M].北京:科学出版社,2005.LI Hong-gui.Metallurgical theory[M].Beijing:Science Press,2005.
[29]彭容秋.铅冶金[M].长沙:中南大学出版社,2004.PENG Rong-qiu.Lead metallurgy[M].Changsha:Central South University Press,2004.
[30]BOTHE JR.J V,BROWN P W.The stabilities of calcium arsenates at(23±1)℃[J].Journal of Hazardous Materials,1999,69(2):197-207.
[31]DUCHESNE J,REARDON E J.Measurement and prediction of portlandite solubility in alkali solutions[J].Cement and Concrete Research,1995,25(5):1043-1053.
[32]PARKER V B,EVANS W H,NUTTALL R L.The thermochemical measurements on rubidium compounds:a comparison of measured values with those predicted from the NBS tables of chemical and thermodynamic properties[J].Journal of Physical and Chemical Reference Data,1987,16(1):7-59.
[33]李静文.硫化钠沉淀法处理含铅废水研究[J].赤峰学院学报(自然科学版),2013,29(2):8-10.LI Jin-wen.Study on treatment of wastewater containing lead sulfide precipitation method[J].Journal of Chifeng University(Natural Science Edition),2013,29(2):8-10.
[34]何绪文,胡建龙,李静文,等.硫化物沉淀法处理含铅废水[J].环境工程学报,2013,7(4):1394-1398.HE Xu-wen,HU Jian-long,LI Jing-wen,ZHANG Jing-jing,WANG Jian-bing,GE Peng.Treatment of wastewater containing lead by sodium sulfide precipitation[J].Chinese Journal of Environmental Engineering,2013,7(4):1394-1398.
[35]李莉.碱性体系下As(Ⅲ)的催化氧化及其机理研究[D].长沙:中南大学,2009.LI Li.Efficiency and mechanism of As(III)catalytic oxidation in alkaline system[D].Changsha:Central South University,2009.