菱镁矿、白云石和方解石的浮选第一性原理研究
|
摘要
为了更好地实现菱镁矿的浮选脱钙,基于密度泛函理论,通过Materials Studio(MS)软件模拟优化了菱镁矿、白云石和方解石的晶体结构、解理面、与常见浮选药剂的作用模型,计算了这3种矿物的能带结构、态密度、表面能、与常见浮选药剂的前线轨道以及相互作用能等参数,从微观角度研究了钙镁碳酸盐矿物的浮选机理。理论研究表明:菱镁矿、白云石和方解石均为绝缘体,六偏磷酸钠和水玻璃比油酸钠和十二胺更容易与这3种矿物结合;菱镁矿{104}、白云石{110}、方解石{104}是这3种矿物的完全解理面;这3种矿物的钙镁离子与油酸钠的羰基氧发生了化学吸附,与十二胺是物理吸附,N—H…O氢键起了重要作用;推测出十二胺对钙镁碳酸盐矿物浮选有一定的选择性。第一性原理的推测结果基本得到了纯矿物浮选试验的验证,因此,第一性原理对浮选分离药剂的选择和机理研究有一定的指导意义。
In order to better achieve the flotation decalcification of magnesite,the crystal structure,cleavage surface,minerals and the interaction model with common flotation reagents of magnesite,dolomite and calcite were simulated by Materials Studio(MS)software based on density functional theory. The energy band structure,density of states,surface energy of the three minerals,the frontier orbital,as well as interaction energy between the minerals and common flotation reagents were calculated,which helps to study flotation mechanism of calcium-magnesium carbonate minerals from microscopic view. Theoretical studies indicated that magnesite,dolomite and calcite are all insulators. Sodium hexametaphosphate and water glass are interacted with these three minerals easily,compared with sodium oleate and dodecylamine. The complete cleavage surface of magnesite,dolomite and calcite are {104}plane,{110}plane and {104}plane respectively. The calcium ions and magnesium ions of these three minerals are chemically adsorbed with the carbonyl oxygen of sodium oleate,and the interaction with dodecylamine is the physical adsorption accompanied with the formation of N-H…O hydrogen bonds,indicating a selectivity interaction between dodecylamine and calcium magnesium carbonate minerals in flotation. The speculative results of the first principles are basically verified by the pure minerals flotation experiments,which indicates that the first-principles has guiding significance for the selection of flotation separation agents and its mechanism research.
In order to better achieve the flotation decalcification of magnesite,the crystal structure,cleavage surface,minerals and the interaction model with common flotation reagents of magnesite,dolomite and calcite were simulated by Materials Studio(MS)software based on density functional theory. The energy band structure,density of states,surface energy of the three minerals,the frontier orbital,as well as interaction energy between the minerals and common flotation reagents were calculated,which helps to study flotation mechanism of calcium-magnesium carbonate minerals from microscopic view. Theoretical studies indicated that magnesite,dolomite and calcite are all insulators. Sodium hexametaphosphate and water glass are interacted with these three minerals easily,compared with sodium oleate and dodecylamine. The complete cleavage surface of magnesite,dolomite and calcite are {104}plane,{110}plane and {104}plane respectively. The calcium ions and magnesium ions of these three minerals are chemically adsorbed with the carbonyl oxygen of sodium oleate,and the interaction with dodecylamine is the physical adsorption accompanied with the formation of N-H…O hydrogen bonds,indicating a selectivity interaction between dodecylamine and calcium magnesium carbonate minerals in flotation. The speculative results of the first principles are basically verified by the pure minerals flotation experiments,which indicates that the first-principles has guiding significance for the selection of flotation separation agents and its mechanism research.
引文
[1]普拉蒂普,汪镜亮,李长根.浮选药剂的分子模拟及合理设计[J].国外金属矿选矿,2004(10):28-34.Pratip,Wang Jingliang,Li Changgen.Molecular simulation and rational design of flotation reagents[J].Foreign Metal Ore Dressing,2004(10):28-34.
[2]周乐光.矿石学基础[M].北京:冶金工业出版社,2007.Zhou Leguang.The Basis of Ore Science[M].Beijing:Metallurgical Industry Press,2007.
[3]于海林.单键立方相氮的第一性原理研究[D].湘潭:湘潭大学,2006.Yu Hailin.First-principles Study of Single-button Cubic Phase Nitrogen[D].Xiangtan:Xiangtan University,2006.
[4]赵珊茸.结晶学及矿物学[M].北京:高等教育出版社,2017.Zhao Shanrong.Crystallography and Mineralogy[M].Beijing:Higher Education Press,2017.
[5]常丽华.透明矿物薄片鉴定手册[M].北京:地质出版社,2006.Chang Lihua.Handbook of Identification of Transparent Mineral Flakes[M].Beijing:Geological Publishing House,2006.
[6]高志勇.三种含钙矿物晶体各向异性与浮选行为关系的基础研究[D].长沙:中南大学,2013.Gao Zhiyong.Basic Research on the Relationship between Crystal Anisotropy and Flotation Behavior of three Calcium-bearing Minerals[D].Changsha:Central South University,2013.
[7]张英.白钨矿与含钙脉石矿物浮选分离抑制剂的性能与作用机理研究[D].长沙:中南大学,2012.Zhang Ying.Study on the Performance and Mechanism of Flotation Separation Inhibitors of Scheelite and Calcium-containing Gangue Minerals[D].Changsha:Central South University,2012.
[8]王杰.方解石晶体结构及表面吸附浮选药剂的第一性原理研究[D].贵阳:贵州大学,2016.Wang Jie.First-principles Study on Crystal Structure and Surface Adsorption Flotation Reagent of Calcite[D].Guiyang:Guizhou University,2016.
[9]Li R,Zhong Y,Huang C,et al.Surface energy and surface self-diffusion of Al calculated by embedded atom method[J].Physica B:Condensed Matter,2013,422:51-55.
[10]Wang J,Wang S.Surface energy and work function of fcc and bcc crystals:Density functional study[J].Surface Science,2014,630:216-224.
[11]Titiloye J O,de Leeuw N H,Parker S C.Atomistic simulation of the differences between calcite and dolomite surfaces[J].Geochimica et Cosmochimica Acta,1998,62(15):2637-2641.
[12]Hossain F M,Dlugogorski B Z,Kennedy E M,et al.Electronic,optical and bonding properties of MgCO[3J].Solid State Communications,2010,150:848-851.
[13]Hossain F M,Murch G E,Belova I V,et al.Electronic,optical and bonding properties of CaCO3calcite[J].Solid State Communications,2009,149:1201-1203.
[14]孙家钟,何福城.定性分子轨道理论[M].长春:吉林大学出版社,1999:197.Sun Jiazhong,He Fucheng.Qualitative Molecular Orbital Theory[M].Changchun:Jilin University Press,1999:197.
[15]陈华强.几种无机、有机抑制剂对方解石浮选抑制行为的研究[J].四川有色金属,1998(2):42-45.Chen Huaqiang.Study on the inhibition behavior of several inorganic and organic inhibitors of calcite flotation[J].Sichuan Nonferrous Metals,1998(2):42-45.
[16]王淀佐.选矿与冶金药剂分子设计[M].长沙:中南工业大学出版社,1996.Wang Dianzuo.Molecular Design of Mineral Processing and Metallurgical Agents[M].Changsha:Central South University of Technology Press,1996.
[17]王正烈.物理化学[M].北京:化学工业出版社,2006.Wang Zhenglie.Physical Chemistry[M].Beijing:Chemical Industry Press,2006.
[2]周乐光.矿石学基础[M].北京:冶金工业出版社,2007.Zhou Leguang.The Basis of Ore Science[M].Beijing:Metallurgical Industry Press,2007.
[3]于海林.单键立方相氮的第一性原理研究[D].湘潭:湘潭大学,2006.Yu Hailin.First-principles Study of Single-button Cubic Phase Nitrogen[D].Xiangtan:Xiangtan University,2006.
[4]赵珊茸.结晶学及矿物学[M].北京:高等教育出版社,2017.Zhao Shanrong.Crystallography and Mineralogy[M].Beijing:Higher Education Press,2017.
[5]常丽华.透明矿物薄片鉴定手册[M].北京:地质出版社,2006.Chang Lihua.Handbook of Identification of Transparent Mineral Flakes[M].Beijing:Geological Publishing House,2006.
[6]高志勇.三种含钙矿物晶体各向异性与浮选行为关系的基础研究[D].长沙:中南大学,2013.Gao Zhiyong.Basic Research on the Relationship between Crystal Anisotropy and Flotation Behavior of three Calcium-bearing Minerals[D].Changsha:Central South University,2013.
[7]张英.白钨矿与含钙脉石矿物浮选分离抑制剂的性能与作用机理研究[D].长沙:中南大学,2012.Zhang Ying.Study on the Performance and Mechanism of Flotation Separation Inhibitors of Scheelite and Calcium-containing Gangue Minerals[D].Changsha:Central South University,2012.
[8]王杰.方解石晶体结构及表面吸附浮选药剂的第一性原理研究[D].贵阳:贵州大学,2016.Wang Jie.First-principles Study on Crystal Structure and Surface Adsorption Flotation Reagent of Calcite[D].Guiyang:Guizhou University,2016.
[9]Li R,Zhong Y,Huang C,et al.Surface energy and surface self-diffusion of Al calculated by embedded atom method[J].Physica B:Condensed Matter,2013,422:51-55.
[10]Wang J,Wang S.Surface energy and work function of fcc and bcc crystals:Density functional study[J].Surface Science,2014,630:216-224.
[11]Titiloye J O,de Leeuw N H,Parker S C.Atomistic simulation of the differences between calcite and dolomite surfaces[J].Geochimica et Cosmochimica Acta,1998,62(15):2637-2641.
[12]Hossain F M,Dlugogorski B Z,Kennedy E M,et al.Electronic,optical and bonding properties of MgCO[3J].Solid State Communications,2010,150:848-851.
[13]Hossain F M,Murch G E,Belova I V,et al.Electronic,optical and bonding properties of CaCO3calcite[J].Solid State Communications,2009,149:1201-1203.
[14]孙家钟,何福城.定性分子轨道理论[M].长春:吉林大学出版社,1999:197.Sun Jiazhong,He Fucheng.Qualitative Molecular Orbital Theory[M].Changchun:Jilin University Press,1999:197.
[15]陈华强.几种无机、有机抑制剂对方解石浮选抑制行为的研究[J].四川有色金属,1998(2):42-45.Chen Huaqiang.Study on the inhibition behavior of several inorganic and organic inhibitors of calcite flotation[J].Sichuan Nonferrous Metals,1998(2):42-45.
[16]王淀佐.选矿与冶金药剂分子设计[M].长沙:中南工业大学出版社,1996.Wang Dianzuo.Molecular Design of Mineral Processing and Metallurgical Agents[M].Changsha:Central South University of Technology Press,1996.
[17]王正烈.物理化学[M].北京:化学工业出版社,2006.Wang Zhenglie.Physical Chemistry[M].Beijing:Chemical Industry Press,2006.