辛基羟肟酸浮选锡石的机理
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摘要
为探明辛基羟肟酸对锡石的捕收性能及其吸附机理,本文通过单矿物浮选实验,考察了辛基羟肟酸、水杨羟肟酸和苯甲羟肟酸体系中锡石的浮选行为,通过吸附量测定、红外光谱测试、动电位、光电子能谱分析、溶液化学计算研究了辛基羟肟酸对锡石的作用机理.浮选实验结果表明:辛基羟肟酸对锡石的捕收能力明显强于水杨羟肟酸和苯甲羟肟酸,当辛基羟肟酸质量浓度为50mg/L,pH为10左右时,锡石的回收率最高达到91.79%.吸附量测试结果显示:在pH为10时,辛基羟肟酸在锡石表面的吸附量最大为0.23mg/g,与浮选结果一致.XPS分析,Zeta电位和红外光谱测试结果表明:辛基羟肟酸在锡石表面主要发生化学吸附,同时也可能存在物理吸附.辛基羟肟酸的溶液化学计算得出:对锡石浮选起主导作用的是离子-分子缔合物.辛基羟肟酸在锡石表面形成强疏水性的缔合物,可作为锡石的强效捕收剂.
To explore the collecting capacity of octanohydroxamic acid on cassiterite,flotation tests using octanohydroxamic acid,benzohydroxamic acid and salicylhydroxamic acid as collectors were conducted.The adsorption mechanism was analyzed by adsorption measurement,infrared spectroscopic analysis,Zeta potential measurements,X-ray photoelectron spectroscopy detection and solution chemistry calculations.The flotation experiment results show that the collecting ability of the octanohydroxamic acid is stronger than that of benzohydroxamic acid and salicylhydroxamic acid.The best flotation recovery of 91.79% can be obtained with octanohydroxamic mass concentration of 50 mg/L and pH value at about 10.The adsorption capacity test results show that the maximum adsorption amount of octanohydroxamic acid is 0.23 mg/g when the pH value is 10,which is in line with the flotation tests of cassiterite.XPS detection,Zeta potential and FT-IR spectra results show that the chemical adsorption mainly occurs on the surface of cassiterite for octanohydroxamic acid,while the physical adsorption may also exist.Floatability of cassiterite is dominated by the ion and molecular association component formed by the interaction between octanohydroxamic acid and cassiterite surface.Octanohydroxamic acid can be used as an efficient collector because of the formation of strong hydro-phobic association component on the surface of cassiterite.
To explore the collecting capacity of octanohydroxamic acid on cassiterite,flotation tests using octanohydroxamic acid,benzohydroxamic acid and salicylhydroxamic acid as collectors were conducted.The adsorption mechanism was analyzed by adsorption measurement,infrared spectroscopic analysis,Zeta potential measurements,X-ray photoelectron spectroscopy detection and solution chemistry calculations.The flotation experiment results show that the collecting ability of the octanohydroxamic acid is stronger than that of benzohydroxamic acid and salicylhydroxamic acid.The best flotation recovery of 91.79% can be obtained with octanohydroxamic mass concentration of 50 mg/L and pH value at about 10.The adsorption capacity test results show that the maximum adsorption amount of octanohydroxamic acid is 0.23 mg/g when the pH value is 10,which is in line with the flotation tests of cassiterite.XPS detection,Zeta potential and FT-IR spectra results show that the chemical adsorption mainly occurs on the surface of cassiterite for octanohydroxamic acid,while the physical adsorption may also exist.Floatability of cassiterite is dominated by the ion and molecular association component formed by the interaction between octanohydroxamic acid and cassiterite surface.Octanohydroxamic acid can be used as an efficient collector because of the formation of strong hydro-phobic association component on the surface of cassiterite.
引文
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[13]ZHANG W,HONAKER R Q,GROPPO J G.Flotation of monazite in the presence of calcite Part I:Calcium ion effects on the adsorption of hydroxamic acid[J].Minerals Engineering,2017,100:40-48.
[14]LI F,ZHONG H,ZHAO G,et al.Flotation performances and adsorption mechanism ofα-hydroxyoctyl phosphinic acid to cassiterite[J].Applied Surface Science,2015,353:856-864.
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[16]XIONG F,LI Y J,ZHANG Z H,et al.Flotation response of the refractory Yangla copper oxide ores with hydroxamate collectors[J].Advanced Materials Research,2013,803:131-136.
[17]孙伟,柯丽芳,孙磊.苯甲羟肟酸在锡石浮选中的应用及作用机理研究[J].中国矿业大学学报,2013,42(1):62-68.SUN Wei,KE Lifang,SUN Lei.Study of the application and mechanism of benzohydroxamic acid in the flotation of cassiterite[J].Journal of China University of Mining&Technology,2013,42(1):62-68.
[18]ISHIDA N,YOTSUMOTO H.Direct Measurements of the interaction force between particle and bubble in aqueous surfactant solutions[J].Shigen-to-Sozai,2004,120(120):400-405.
[19]QIN W,XU Y,LIU H,et al.Flotation and surface behavior of cassiterite with salicylhydroxamic acid[J].Industrial&Engineering Chemistry Research,2011,50(18):10778-10783.
[20]GIESEKKE E W.A review of spectroscopic techniques applied to the study of interactions between minerals and reagents in flotation systems[J].International Journal of Mineral Processing,1983,11(1):19-56.
[21]朱玉霜,朱建光.浮选药剂的化学原理[M].长沙:中南工业大学出版社,1996:114-185.
[22]QIN W Q,REN L Y,XU Y B,et al.Adsorption mechanism of mixed salicylhydroxamic acid and tributyl phosphate collectors in fine cassiterite electroflotation system[J].Journal of Central South University,2012,19(6):1711-1717.
[23]WU X Q,ZHU J G.Selective flotation of cassiterite with benzohydroxamic acid[J].Minerals Engineering,2006,19(14):1410-1417.
[24]WANG P P,QIN W Q,REN L Y,et al.Solution chemistry and utilization of alkyl hydroxamic acid in flotation of fine cassiterite[J].Transactions of Nonferrous Metals Society of China,2013,23(6):1789-1796.
[25]BOGDANOVA N F,KLEBANOV A V,ERMAKOVA L E,et al.Adsorption of ions on the surface of tin dioxide and its electro kinetic characters in 1∶1electrolyte solutions[J].Colloid Journal,2004,66(4):409-417.
[26]QIN Wenqing,REN Liuyi,XU Yangbao,et al.Adsorption mechanism of mixed salicylhydroxamic acid and tributyl phosphate collectors in fine cassiterite electro-flotation system[J].Journal of Central South University,2012,19(6):1711-1717.
[27]张国范,朱阳戈,冯其明,等.油酸钠对微细粒钛铁矿的捕收机理[J].中国有色金属学报,2009,19(2):372-377.ZHANG Guofan,ZHU Yangge,FENG Qiming,et al.Flotation mechanism of fine ilmenite by sodium oleate[J].The Chinese Journal of Nonferrous Metals,2009,19(2):372-377.
[28]MURUGANANTHAM G,RAVICHANDRAN K,SARAVANAKUMAR K,et al.Effect of doping level on physical properties of antimony doped nanocrystalline tin oxide films fabricated using low cost spray technique[J].Surface Engineering,2011,27(5):376-381.
[29]NI X,LIU Q.The adsorption and configuration of octyl hydroxamic acid on pyrochlore and calcite[J].Colloids&Surfaces A Physicochemical&Engineering Aspects,2012,411(19):80-86.
[30]FENG Q,ZHAO W,WEN S,et al.Activation mechanism of lead ions in cassiterite flotation with salicylhydroxamic acid as collector[J].Separation&Purification Technology,2017,178:193-199.
[31]ALAGTA A,FELHSI I,BERTOTI I,et al.Corrosion protection properties of hydroxamic acid selfassembled monolayer on carbon steel[J].Corrosion Science,2008,50(6):1644-1649.
[32]王淀佐,胡岳华.浮选溶液化学[M].长沙:湖南科学技术出版社,1987:18-49.
[33]QIN W,WEI Q,JIAO F,et al.Effect of sodium pyrophosphate on the flotation separation of chalcopyrite from galena[J].International Journal of Mining Science and Technology,2012,22(3):345-349.
[2]ANGADI S I,SREENIVAS T,JEON H S,et al.A review of cassiterite beneficiation fundamentals and plant practices[J].Minerals Engineering,2015,70:178-200.
[3]王晓,童雄,周永诚.锡石工艺矿物学与选矿工艺[J].矿冶,2011,20(4):15-19.WANG Xiao,TONG Xiong,ZHOU Yongcheng.Process mineralogy and ore-dressing process of cassiterite[J].Mining&Metallurgy,2011,20(4):15-19.
[4]许道刚,张雪峰,陈伟丽,等.我国锡石选矿研究现状与发展趋势[J].矿山机械,2015(6):8-12.XU Daogang,ZHANG Xuefeng,CHEN Weili,et al.Research status and development tendency of cassiterite benefi ciation in China[J].Mining&Processing Equipment,2015(6):8-12.
[5]ZHOU Yongcheng,TONG Xiong,SONG Shaoxian,et al.Beneficiation of cassiterite fines from a tin tailing slime by froth flotation[J].Separation Science&Technology,2014,49(3):458-463.
[6]吕晋芳,童雄,周永诚.微细粒锡石浮选药剂研究概况[J].湿法冶金,2010,29(2):71-74.LYU Jinfang,TONG Xiong,ZHOU Yongcheng.Research status on flotation reagents for fine cassiterite[J].Hydrometallurgy,2010,29(2):71-74.
[7]见百熙,张泾生.近年来锡石浮选药剂的发展[J].矿冶工程,1982(2):67-71.JIAN Baixi,ZHANG Jingsheng.Recent development of cassiterite flotation reagent[J].Mining&Metallurgical Engineering,1982(2):67-71.
[8]高玉德,邱显扬,钟传刚,等.羟肟酸类捕收剂性质及浮选钨矿物特性[J].中国钨业,2012,27(2):10-14.GAO Yude,QIU Xianyang,ZHONG Chuangang,et al.Property and surface chemistry of hydroxamic acids using as collectors in tungsten minerals flotation[J].China Tungsten Industry,2012,27(2):10-14.
[9]黄林旋.国外异羟肟酸的研究[J].有色金属工程,1973(12):41-45.HUANG Linxuan.Different hydroxyl oxime acid research abroad[J].Nonferrous Metal Engineering,1973(12):41-45.
[10]罗家珂.异羟肟酸合成及其在浮选中的应用[J].国外金属矿选矿,1983(2):7-17.LUO Jiake.Different hydroxyl oxime acid synthesis and its application in flotation[J].Metallic Ore Dressing Abroad,1983(2):7-17.
[11]刘文刚,王本英,代淑娟,等.羟肟酸类捕收剂在浮选中的应用现状及发展前景[J].有色矿冶,2006,22(4):25-27.LIU Wengang,WANG Benying,DAI Shujuan.Current application and development prospect of hydroximic acid in flotation[J].Non-Ferrous Mining and Metallurgy,2006,22(4):25-27.
[12]YOON R H,NAGARAJ D R,WANG S S,et al.Beneficiation of kaolin clay by froth flotation using hydroxamate collectors[J].Minerals Engineering,1992,5(3/5):457-467.
[13]ZHANG W,HONAKER R Q,GROPPO J G.Flotation of monazite in the presence of calcite Part I:Calcium ion effects on the adsorption of hydroxamic acid[J].Minerals Engineering,2017,100:40-48.
[14]LI F,ZHONG H,ZHAO G,et al.Flotation performances and adsorption mechanism ofα-hydroxyoctyl phosphinic acid to cassiterite[J].Applied Surface Science,2015,353:856-864.
[15]FUERSTENAU D W,PRADIP P.Mineral flotation with hydroxamate collectors[M].London:The Institution of Mining and Metallurgy,1984:165.
[16]XIONG F,LI Y J,ZHANG Z H,et al.Flotation response of the refractory Yangla copper oxide ores with hydroxamate collectors[J].Advanced Materials Research,2013,803:131-136.
[17]孙伟,柯丽芳,孙磊.苯甲羟肟酸在锡石浮选中的应用及作用机理研究[J].中国矿业大学学报,2013,42(1):62-68.SUN Wei,KE Lifang,SUN Lei.Study of the application and mechanism of benzohydroxamic acid in the flotation of cassiterite[J].Journal of China University of Mining&Technology,2013,42(1):62-68.
[18]ISHIDA N,YOTSUMOTO H.Direct Measurements of the interaction force between particle and bubble in aqueous surfactant solutions[J].Shigen-to-Sozai,2004,120(120):400-405.
[19]QIN W,XU Y,LIU H,et al.Flotation and surface behavior of cassiterite with salicylhydroxamic acid[J].Industrial&Engineering Chemistry Research,2011,50(18):10778-10783.
[20]GIESEKKE E W.A review of spectroscopic techniques applied to the study of interactions between minerals and reagents in flotation systems[J].International Journal of Mineral Processing,1983,11(1):19-56.
[21]朱玉霜,朱建光.浮选药剂的化学原理[M].长沙:中南工业大学出版社,1996:114-185.
[22]QIN W Q,REN L Y,XU Y B,et al.Adsorption mechanism of mixed salicylhydroxamic acid and tributyl phosphate collectors in fine cassiterite electroflotation system[J].Journal of Central South University,2012,19(6):1711-1717.
[23]WU X Q,ZHU J G.Selective flotation of cassiterite with benzohydroxamic acid[J].Minerals Engineering,2006,19(14):1410-1417.
[24]WANG P P,QIN W Q,REN L Y,et al.Solution chemistry and utilization of alkyl hydroxamic acid in flotation of fine cassiterite[J].Transactions of Nonferrous Metals Society of China,2013,23(6):1789-1796.
[25]BOGDANOVA N F,KLEBANOV A V,ERMAKOVA L E,et al.Adsorption of ions on the surface of tin dioxide and its electro kinetic characters in 1∶1electrolyte solutions[J].Colloid Journal,2004,66(4):409-417.
[26]QIN Wenqing,REN Liuyi,XU Yangbao,et al.Adsorption mechanism of mixed salicylhydroxamic acid and tributyl phosphate collectors in fine cassiterite electro-flotation system[J].Journal of Central South University,2012,19(6):1711-1717.
[27]张国范,朱阳戈,冯其明,等.油酸钠对微细粒钛铁矿的捕收机理[J].中国有色金属学报,2009,19(2):372-377.ZHANG Guofan,ZHU Yangge,FENG Qiming,et al.Flotation mechanism of fine ilmenite by sodium oleate[J].The Chinese Journal of Nonferrous Metals,2009,19(2):372-377.
[28]MURUGANANTHAM G,RAVICHANDRAN K,SARAVANAKUMAR K,et al.Effect of doping level on physical properties of antimony doped nanocrystalline tin oxide films fabricated using low cost spray technique[J].Surface Engineering,2011,27(5):376-381.
[29]NI X,LIU Q.The adsorption and configuration of octyl hydroxamic acid on pyrochlore and calcite[J].Colloids&Surfaces A Physicochemical&Engineering Aspects,2012,411(19):80-86.
[30]FENG Q,ZHAO W,WEN S,et al.Activation mechanism of lead ions in cassiterite flotation with salicylhydroxamic acid as collector[J].Separation&Purification Technology,2017,178:193-199.
[31]ALAGTA A,FELHSI I,BERTOTI I,et al.Corrosion protection properties of hydroxamic acid selfassembled monolayer on carbon steel[J].Corrosion Science,2008,50(6):1644-1649.
[32]王淀佐,胡岳华.浮选溶液化学[M].长沙:湖南科学技术出版社,1987:18-49.
[33]QIN W,WEI Q,JIAO F,et al.Effect of sodium pyrophosphate on the flotation separation of chalcopyrite from galena[J].International Journal of Mining Science and Technology,2012,22(3):345-349.