辛基羟肟酸在氟碳铈矿表面的吸附机理
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摘要
通过吸附量测试、纯矿物浮选、Zeta电位和XPS测试,研究辛基羟肟酸在氟碳铈矿表面的吸附行为和吸附机理。研究结果表明:辛基羟肟酸在氟碳铈矿表面吸附符合二级动力学模型,等温吸附过程符合Freundlich吸附模型,pH=9.5时辛基羟肟酸在氟碳铈矿表面的吸附速度和吸附量比pH=6.5时的大;辛基羟肟酸在氟碳铈矿表面的吸附为多层、不均匀吸附,是物理吸附和化学吸附共同作用的结果,但以化学吸附为主。吸附机理为:羟肟酸根阴离子OHA~-与氟碳铈矿表面暴露的Ce~(3+)发生螯合反应生成OHA-Ce沉淀,形成化学吸附;羟肟酸分子OHA与氟碳铈矿表面的氧以氢键形式形成物理吸附,同时,溶液中游离的羟肟酸分子OHA与氟碳铈矿表面已吸附上的OHA分子形成氢键和烃链间疏水缔合作用,产生不均匀的物理吸附。
The adsorption behavior and mechanism of octyl hydroxamic acid(OHA) on bastnaesite surface was investigated through adsorption test, single mineral flotation, Zeta potential and XPS measurements. The results show that the adsorption of OHA on bastnaesite surface agrees with the second order kinetic model, and the isothermal adsorption process correlates well with the Freundlich isotherm model. The adsorption speed and adsorption amount of OHA on bastnaesite surface at pH=9.5 are greater than that at pH=6.5. The adsorption of OHA on bastnaesite surface is multilayered and heterogeneous, which is a combined result of physical and chemical adsorption, and the later is the dominating form. The adsorption mechanism is that hydroxamate anions OHA~- can chelate react with the exposed Ce~(3+) on bastnaesite surface and form the OHA-Ce precipitate, resulting in chemical adsorption. Hydroxamic acid molecule OHA can form hydrogen bond with oxygen atom on bastnaesite surface and form physical adsorption, and meanwhile,the dissociated OHA molecule can form hydrogen bond and hydrophobic association of hydrocarbon chains with the adsorbed OHA on bastnaesite surface, resulting in heterogeneous physical adsorption.
The adsorption behavior and mechanism of octyl hydroxamic acid(OHA) on bastnaesite surface was investigated through adsorption test, single mineral flotation, Zeta potential and XPS measurements. The results show that the adsorption of OHA on bastnaesite surface agrees with the second order kinetic model, and the isothermal adsorption process correlates well with the Freundlich isotherm model. The adsorption speed and adsorption amount of OHA on bastnaesite surface at pH=9.5 are greater than that at pH=6.5. The adsorption of OHA on bastnaesite surface is multilayered and heterogeneous, which is a combined result of physical and chemical adsorption, and the later is the dominating form. The adsorption mechanism is that hydroxamate anions OHA~- can chelate react with the exposed Ce~(3+) on bastnaesite surface and form the OHA-Ce precipitate, resulting in chemical adsorption. Hydroxamic acid molecule OHA can form hydrogen bond with oxygen atom on bastnaesite surface and form physical adsorption, and meanwhile,the dissociated OHA molecule can form hydrogen bond and hydrophobic association of hydrocarbon chains with the adsorbed OHA on bastnaesite surface, resulting in heterogeneous physical adsorption.
引文
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[20]任俊,卢寿慈,池汝安.1-羟基-2-萘羟肟酸浮选氟碳铈矿作用机理[J].中国有色金属学报,1996,6(4):24-28.REN Jun,LU Shouci,CHI Ru’an.Flotation mechanism of bastnaesite with 1-hydroxy 2-naphthyl hydroxamic acid[J].The Chinese Journal of Nonferrous Metals,1996,6(4):24-28.
[21]付宏渊,邱祥,王琼,等.铁盐改性柚子皮对含铬废水的吸附性能[J].中南大学学报(自然科学版),2017,48(9):2271-2278.FU Hongyuan,QIU Xiang,WANG Qiong,et al.Adsorption performance of Fe(Ⅲ)-modified pomelo peel on wastewater containing Cr(Ⅵ)[J].Journal of Central South University(Science and Technology),2017,48(9):2271-2278.
[22]曹永丹,曹钊,张亚辉,等.Cu(II)、Ni(II)离子在蛇纹石表面的吸附及其浮选的影响[J].工程科学学报,2016,38(4):461-467.CAO Yongdan,CAO Zhao,ZHANG Yahui,et al.Effect of Cu(II)and Ni(II)adsorption on serpentine flotation[J].Chinese Journal of Engineering,2016,38(4):461-467.
[23]朱玉霜,朱丹.辛基羟肟酸在锡石表面吸附的热力学研究[J].有色金属,1994,46(1):24-28.ZHU Yushuang,ZHU Dan.Adsorption thermodynamics of octyl hydroxamic acid on cassiterite[J].Nonferrous Metals,1994,46(1):24-28.
[24]徐龙华,蒋昊,巫侯琴,等.季铵盐在高岭石表面的吸附特性[J].中南大学学报(自然科学版),2013,44(11):4379-4384.XU Longhua,JIANG Hao,WU Houqin,et al.Absorption characteristics of quaternary ammonium on kaolinite[J].Journal of Central South University(Science and Technology),2013,44(11):4379-4384.
[25]张国范,张佰发,石晴.油酸钠在闪锌矿表面的吸附机理[J].中南大学学报(自然科学版),2017,48(1):16-24.ZHANG Guofan,ZHANG Baifa,SHI Qing.Adsorption mechanism of sphalerite by sodium oleate[J].Journal of Central South University(Science and Technology),2017,48(1):16-24.
[26]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.
[27]印海,刘伟,王慧.生物炭对水中五氯酚的吸附性能研究[J].中国环境科学,2014,34(8):2017-2023.YIN Hai,LIU Wei,WANG Hui.Adsorption efficiencies of pentachlorophenol from aqueous solution onto biochars[J].China Environmental Science,2014,34(8):2017-2023.
[28]NI Xiao,LIU Qi.Notes on the adsorption of octyl hydroxamic acid on pyrochlore and calcite[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2013,430:91-94.
[29]NI Xiao,LIU Qi.The adsorption and configuration of octyl hydroxamic acid on pyrochlore and calcite[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2012,411:80-86.
[2]ZHANG Xia,DU Hao,WANG Xuming,et al.Surface chemistry aspects of bastnaesite flotation with octyl hydroxamate[J].International Journal of Mineral Processing,2014,133:29-38.
[3]程建忠,侯运炳,车丽萍.白云鄂博矿床稀土资源的合理开发及综合利用[J].稀土,2007,28(1):70-74.CHENG Jianzhong,HOU Yunbing,CHE Liping.Making rational multipurpose use of resources of RE in Bayan Obo deposit[J].Chinese Rare Earths,2007,28(1):70-74.
[4]GUPTA C K,KRISHNAMURTHY N.Extractive metallurgy of rare earths[J].International Materials Reviews,2013,37(1):197-248.
[5]JORDENS A,CHENG Y P,WATERS K E.A review of the beneficiation of rare earth element bearing minerals[J].Minerals Engineering,2013,41(1):97-114.
[6]PRADIP P.The surface properties and flotation of rare-earth minerals[D].Berkeley:University of California.Department of Materials Science and Mineral Engineering,1981:222.
[7]徐金球,徐晓军,王景伟.1-羟基2-萘甲羟肟酸的合成及对稀土矿物的捕收性能[J].有色金属,2002,54(3):72-73.XU Jinqiu,XU Xiaojun,WANG Jingwei.Synthesis of1-hydroxy-2-naphthyl hydroximic acid and application to collecting rare earth minerals[J].Nonferrous Metals,2002,54(3):72-73.
[8]REN J,LU S,SONG S,et al.A new collector for rare earth mineral flotation[J].Minerals Engineering,1997,10(12):1395-1404.
[9]CUI J L,HOPE G A,BUCKLEY A N.Spectroscopic investigation of the interaction of hydroxamate with bastnaesite(cerium)and rare earth oxides[J].Minerals Engineering,2012,36/37/38:91-99.
[10]FERRON C J,BULATOVIC S M,SALTER R S.Beneficiation of rare earth oxide minerals[J].Materials Science Forum,1991,70/71/72:251-270.
[11]REN Jun,WANG Wenmei,LUO Jiake,et al.Progress of flotation reagents of rare earth minerals in China[J].Journal of Rare Earths,2003,21(1):1-8.
[12]BULATOVIC S M.Handbook of flotation reagents:chemistry,theory and practice[M].Oxford:Elsevier Science&Technology,2010:151-173.
[13]NI X,PARRENT M,CAO M,et al.Developing flotation reagents for niobium oxide recovery from carbonatite Nb ores[J].Minerals Engineering,2012,36/37/38:111-118.
[14]罗家珂,任俊,唐芳琼,等.我国稀土浮选药剂研究进展[J].中国稀土学报,2002,20(5):385-391.LUO Jiake,REN Jun,TANG Fangqiong,et al.Development on flotation reagents of rare earth minerals in China[J].Journal of the Chinese Society of Rare Earths,2002,20(5):385-391.
[15]PRADIP P,FUERSTENAU D W.Design and development of novel flotation reagents for the beneficiation of Mountain Pass rare-earth ore[J].Minerals&Metallurgical Processing,2013,30(1):1-9.
[16]JORDENS A,MARION C,GRAMMATIKOPOULOS T,et al.Beneficiation of the Nechalacho rare earth deposit:flotation response using benzohydroxamic acid[J].Minerals Engineering,2016,99:158-169.
[17]HE X J,VAISEY M.Research on process development for Mt Weld rare earths resources of Australia[C]//Proceedings of XXVI International Mineral Processing Congress.New Delhi:New Concept Information Systems Pvt.Ltd.,2012:140.
[18]王成行,邱显扬,胡真.水杨羟肟酸对氟碳铈矿的捕收机制研究[J].中国稀土学报,2014,32(6):727-735.WANG Chenghang,QIU Xianyang,HU Zhen.Flotation mechanism of bastnaesite by salicylhydroxamic acid[J].Journal of the Chinese Society of Rare Earths,2014,32(6):727-735.
[19]饶金山,何晓娟,罗传胜,等.辛基羟肟酸浮选氟碳铈矿机制研究[J].中国稀土学报,2015,33(3):370-377.RAO Jinshan,HE Xiaojuan,LUO Chuansheng,et al.Flotation mechanism of octyl hydroximic acid on bastnaesite[J].Journal of the Chinese Society of Rare Earths,2015,33(3):370-377.
[20]任俊,卢寿慈,池汝安.1-羟基-2-萘羟肟酸浮选氟碳铈矿作用机理[J].中国有色金属学报,1996,6(4):24-28.REN Jun,LU Shouci,CHI Ru’an.Flotation mechanism of bastnaesite with 1-hydroxy 2-naphthyl hydroxamic acid[J].The Chinese Journal of Nonferrous Metals,1996,6(4):24-28.
[21]付宏渊,邱祥,王琼,等.铁盐改性柚子皮对含铬废水的吸附性能[J].中南大学学报(自然科学版),2017,48(9):2271-2278.FU Hongyuan,QIU Xiang,WANG Qiong,et al.Adsorption performance of Fe(Ⅲ)-modified pomelo peel on wastewater containing Cr(Ⅵ)[J].Journal of Central South University(Science and Technology),2017,48(9):2271-2278.
[22]曹永丹,曹钊,张亚辉,等.Cu(II)、Ni(II)离子在蛇纹石表面的吸附及其浮选的影响[J].工程科学学报,2016,38(4):461-467.CAO Yongdan,CAO Zhao,ZHANG Yahui,et al.Effect of Cu(II)and Ni(II)adsorption on serpentine flotation[J].Chinese Journal of Engineering,2016,38(4):461-467.
[23]朱玉霜,朱丹.辛基羟肟酸在锡石表面吸附的热力学研究[J].有色金属,1994,46(1):24-28.ZHU Yushuang,ZHU Dan.Adsorption thermodynamics of octyl hydroxamic acid on cassiterite[J].Nonferrous Metals,1994,46(1):24-28.
[24]徐龙华,蒋昊,巫侯琴,等.季铵盐在高岭石表面的吸附特性[J].中南大学学报(自然科学版),2013,44(11):4379-4384.XU Longhua,JIANG Hao,WU Houqin,et al.Absorption characteristics of quaternary ammonium on kaolinite[J].Journal of Central South University(Science and Technology),2013,44(11):4379-4384.
[25]张国范,张佰发,石晴.油酸钠在闪锌矿表面的吸附机理[J].中南大学学报(自然科学版),2017,48(1):16-24.ZHANG Guofan,ZHANG Baifa,SHI Qing.Adsorption mechanism of sphalerite by sodium oleate[J].Journal of Central South University(Science and Technology),2017,48(1):16-24.
[26]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.
[27]印海,刘伟,王慧.生物炭对水中五氯酚的吸附性能研究[J].中国环境科学,2014,34(8):2017-2023.YIN Hai,LIU Wei,WANG Hui.Adsorption efficiencies of pentachlorophenol from aqueous solution onto biochars[J].China Environmental Science,2014,34(8):2017-2023.
[28]NI Xiao,LIU Qi.Notes on the adsorption of octyl hydroxamic acid on pyrochlore and calcite[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2013,430:91-94.
[29]NI Xiao,LIU Qi.The adsorption and configuration of octyl hydroxamic acid on pyrochlore and calcite[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2012,411:80-86.