表面氧化磁黄铁矿的高效捕收研究
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摘要
针对硫化铜镍矿石中有用矿物易被氧化造成浮选回收率降低的问题,选用磁黄铁矿作为研究对象,通过单矿物浮选试验、吸附量测试和X射线光电子能谱检测,揭示了羟肟酸类捕收剂和黄药类捕收剂与氧化的磁黄铁矿的作用机理.结果表明:选择能直接与矿物表面的氧化产物作用的捕收剂是浮选表面氧化硫化矿的一种可行思路.弱碱性条件下苯甲羟肟酸是表面氧化磁黄铁矿的高效捕收剂,苯甲羟肟酸与氧化的磁黄铁矿表面的氧化膜主要发生"O,O"螯合,苯甲羟肟酸作用后矿物表面亲水性的Fe(OH)_3相对含量减少了37.18%.弱碱性环境下,丁基钠黄药对表面氧化的磁黄铁矿捕收能力弱,主要是因为丁基钠黄药虽然能够较好吸附在氧化的磁黄铁矿表面,但氧化的磁黄铁矿表面的亲水性物质不会减少.
The valuable minerals in copper and nickel sulphide minerals can be easily oxidized and lead to the reduction of flotation recovery.To solve the problem,the reaction mechanism of the hydroximic acid and xanthate on pyrrhotite was revealed through flotation experiments,adsorption measurements and X-ray photoelectronic spectroscopy.The results show that it is feasible to find a special collector that can directly react with oxidation layer on the surface of sulfide ore.Benzohydroxamic acid can efficiently recycle oxidized pyrrhotite under weak alkaline environment.The X-ray photoelectronic spectroscopy indicates that two oxygen atoms from benzohydroxamic acid anion can chelate Fe(OH)_3on the surface of oxidized pyrrhotite and form hydrophobic Fe(Ⅲ)hydroxamate.Meanwhile,the relative content of hydrophilic Fe(OH)_3on the surface of oxidized pyrrhotite falls by 37.18%.Surface oxidized pyrrhotite can adsorb sodium butyl xanthate under weak alkaline environment.The reason why sodium butyl xanthate can not recover surface oxidized pyrrhotite is that hydrophilic Fe(OH)_3on the surface of oxidized pyrrhotite has no change after being treated with sodium butyl xanthate.
The valuable minerals in copper and nickel sulphide minerals can be easily oxidized and lead to the reduction of flotation recovery.To solve the problem,the reaction mechanism of the hydroximic acid and xanthate on pyrrhotite was revealed through flotation experiments,adsorption measurements and X-ray photoelectronic spectroscopy.The results show that it is feasible to find a special collector that can directly react with oxidation layer on the surface of sulfide ore.Benzohydroxamic acid can efficiently recycle oxidized pyrrhotite under weak alkaline environment.The X-ray photoelectronic spectroscopy indicates that two oxygen atoms from benzohydroxamic acid anion can chelate Fe(OH)_3on the surface of oxidized pyrrhotite and form hydrophobic Fe(Ⅲ)hydroxamate.Meanwhile,the relative content of hydrophilic Fe(OH)_3on the surface of oxidized pyrrhotite falls by 37.18%.Surface oxidized pyrrhotite can adsorb sodium butyl xanthate under weak alkaline environment.The reason why sodium butyl xanthate can not recover surface oxidized pyrrhotite is that hydrophilic Fe(OH)_3on the surface of oxidized pyrrhotite has no change after being treated with sodium butyl xanthate.
引文
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[22]BUNKHOLT I,KLEIV R A.Pyrrhotite oxidation and its influence on alkaline amine flotation[J].Minerals Engineering,2015,71:65-72.
[23]XU H,ZHONG H,TANG Q,et al.A novel collector 2-ethyl-2-hexenoic hydroxamic acid:Flotation performance and adsorption mechanism to ilmenite[J].Applied Surface Science,2015,353:882-889.
[24]许志平.疏水性的理论计算[J].化学物理学报,1996(4):345-350.XU Zhiping.Theretical calculation of hydrophobicity[J].Chinese Journal of Chemical Physics,1996(4):345-350.
[25]BOZKURT V,XU Z,FINCH J A.Pentlandite/pyrrhotite interaction and xanthate adsorption[J].International Journal of Mineral Processing,1998,52(4):203-214.
[26]NATARAJAN R,SHARMA J,NIRDOSH I.Adsorption of N-hydrocinnamoyl-N-phenylhydroxylamine on pure minerals[J].Adsorption,2010,16(6):541-548.
[27]高玉德,钟传刚,邱显扬,等.苯甲羟肟酸浮选黑钨矿体系中铅离子的活化作用机理[J].中国有色金属学报,2016,26(9):1999-2006.GAO Yude,ZHONG Chuangang,QIU Xianyang,et al.Activation mechanism of Pb2+in flotation of wolframite with benzohydroxamic acid as collector[J].The Chinese Journal of Nonferrous Metals,2016,26(9):1999-2006.
[28]BUCKLEY A N,PARKER G K.Adsorption of noctanohydroxamate collector on iron oxides[J].International Journal of Mineral Processing,2013,121:70-89.
[2]RAICHUR A M,WANG X H,PAREKH B K.Quantifying pyrite surface oxidation kinetics by contact angle measurements[J].Colloids&Surfaces APhysicochemical&Engineering Aspects,2000,167(3):245-251.
[3]LEGRAND D L,BANCROFT G M,NESBITT H W.Surface characterization of pentlandite,(Fe,Ni)9S8,by X-ray photoelectron spectroscopy[J].International Journal of Mineral Processing,1997,51(1/4):217-228.
[4]NANTHAKUMAR B,KELEBEK S,KATSABANISP D.Impact of oxidation on flotation of Ni-Cu sulphide ore with respect to grinding[J].Mineral Processing and Extractive Metallurgy,2007,116(3):197-206.
[5]张维庆.几种不同的煤炭脱硫方法[J].煤炭科学技术,1993(8):36-39.ZHANG Weiqing.Several different methods of coal desulfurization[J].Coal Science and Technology,1993(8):36-39.
[6]ACRES R G,HARMER S L,BEATTIE D A.Synchrotron PEEM and ToF-SIMS study of oxidized heterogeneous pentlandite,pyrrhotite and chalcopyrite.[J].Journal of Synchrotron Radiation,2010,17(5):606-615.
[7]BUCKLEY A N,WOODS R.Surface composition of pentlandite under flotation-related conditions[J].Surface&Interface Analysis,2004,17(9):675-680.
[8]高喜潮.金川硫化铜镍矿床中镍黄铁矿的浮选[J].中国矿山工程,2015,44(6):12-16.GAO Xichao.Flotation of pentlandiet in Jinchuan copper-nickel sulfide deposit[J].China Mine Engineering,2015,44(6):12-16.
[9]董英择,卢毅屏,马忠鑫,等.调浆强度对磁黄铁矿表面组分的影响[J].中南大学学报(自然科学版),2017,48(2):277-281.DONG Yingze,LU Yiping,MA Zhongxin,et al.Effect of mixing intensity on the surface components of pyrrhotite[J].Journal of Central South University(Science and Technology),2017,48(2):277-281.
[10]冯其明,张国范,卢毅屏.蛇纹石对镍黄铁矿浮选的影响及其抑制剂研究现状[J].矿产保护与利用,1997(5):19-22.FENG Qiming,ZHANG Guofan,LU Yipin.The effect of serpentine on blucite flotation and present status for studies of its depressant[J].Conservation and Utilization of Mineral Resources,1997(5):19-22.
[11]PENG Y,WANG B,BRADSHAW D.Pentlandite oxidation in the flotation of a complex nickel ore in saline water[J].Minerals Engineering,2011,24(1):85-87.
[12]SOTO H,LASKOWSKI J.Redox conditions in the flotation of malachite with a sulphidizing agent[J].Transactions of the Institution of Mining and Metallurgy:Section C,1973,82:153-157.
[13]LEGRAND,BANCROFT D L,NESBITT G M,et al.Oxidation/alteration of pentlandite and pyrrhotite surfaces at pH 9.3:Part 1.Assignment of XPS spectra and chemical trends[J].American Mineralogist,2005,90(7):1042-1054.
[14]BUCKLEY A N,WOODS R.X-ray photoelectron spectroscopy of oxidised pyrrhotite surfaces[J].Applications of Surface Science,1985,20(4):472-480.
[15]PRATT A R,MUIR I J,NESBITT H W.X-ray photoelectron and Auger electron spectroscopic studies of pyrrhotite and mechanism of air oxidation[J].Geochimica Et Cosmochimica Acta,1994,58(2):827-841.
[16]JONES C F,LECOUNT S,SMART R S C,et al.Compositional and structural alteration of pyrrhotite surfaces in solution:XPS and XRD studies[J].Applied Surface Science,1992,55(1):65-85.
[17]BUSWELL A M,NICOL M J.Some aspects of the electrochemistry of the flotation of pyrrhotite[J].Journal of Applied Electrochemistry,2002,32(12):1321-1329.
[18]MILLER J D,LI J,DAVIDTZ J C,et al.A review of pyrrhotite flotation chemistry in the processing of PGM ores[J].Minerals Engineering,2005,18(8):855-865.
[19]KHAN A,KELEBEK S.Electrochemical aspects of pyrrhotite and pentlandite in relation to their flotation with xanthate.Part-I:Cyclic voltammetry and rest potential measurements[J].Journal of Applied Electrochemistry,2004,34(8):849-856.
[20]BELZILE N,CHEN Y W,CAI M F,et al.A review on pyrrhotite oxidation[J].Journal of Geochemical Exploration,2004,84(2):65-76.
[21]NEWELL A,BRADSHAW D J,HARRIS P J.The effect of heavy oxidation upon flotation and potential remedies for Merensky type sulfides[J].Minerals Engineering,2006,19(6/8):675-686.
[22]BUNKHOLT I,KLEIV R A.Pyrrhotite oxidation and its influence on alkaline amine flotation[J].Minerals Engineering,2015,71:65-72.
[23]XU H,ZHONG H,TANG Q,et al.A novel collector 2-ethyl-2-hexenoic hydroxamic acid:Flotation performance and adsorption mechanism to ilmenite[J].Applied Surface Science,2015,353:882-889.
[24]许志平.疏水性的理论计算[J].化学物理学报,1996(4):345-350.XU Zhiping.Theretical calculation of hydrophobicity[J].Chinese Journal of Chemical Physics,1996(4):345-350.
[25]BOZKURT V,XU Z,FINCH J A.Pentlandite/pyrrhotite interaction and xanthate adsorption[J].International Journal of Mineral Processing,1998,52(4):203-214.
[26]NATARAJAN R,SHARMA J,NIRDOSH I.Adsorption of N-hydrocinnamoyl-N-phenylhydroxylamine on pure minerals[J].Adsorption,2010,16(6):541-548.
[27]高玉德,钟传刚,邱显扬,等.苯甲羟肟酸浮选黑钨矿体系中铅离子的活化作用机理[J].中国有色金属学报,2016,26(9):1999-2006.GAO Yude,ZHONG Chuangang,QIU Xianyang,et al.Activation mechanism of Pb2+in flotation of wolframite with benzohydroxamic acid as collector[J].The Chinese Journal of Nonferrous Metals,2016,26(9):1999-2006.
[28]BUCKLEY A N,PARKER G K.Adsorption of noctanohydroxamate collector on iron oxides[J].International Journal of Mineral Processing,2013,121:70-89.