硫化矿浮选捕收剂分子结构与性能的电子态密度研究
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摘要
采用电子态密度研究了黄药、黑药和硫氨酯等硫化矿浮选捕收剂的电子结构与性能的关系。结果表明:电子态密度的离域性和轨道杂化作用较好地反映浮选药剂捕收性和选择性的强弱;黄药分子中双键硫原子的态密度最活跃,而黄药离子中单键硫原子的态密度最活跃;直链黄药(C_2～C_5)的态密度随烃基碳链的增长逐渐增强;丙基黄药和丁基黄药异构体的态密度强于相应的正构体的态密度,而正戊基黄药的态密度稍强于异戊基黄药的态密度;黑药中3418A的电子态密度相对最大,表现出更强的电子活性;不同结构的硫氨酯其氮原子的态密度变化比硫原子的大,这有利于改善硫氨酯捕收剂的螯合能力。
The density of electronic states method was used to study the relationship between structures and activity of sulfide floatation collectors such as xanthate, aerofloat and thocarbamate. The results show that delocalization and orbital hybridization could better reflect the collecting and selectivity of flotation reagents. The states density of double-bonded sulfur atom in xanthate is the most active, while that of single-bonded sulfur atom in xanthate ion. Moreover, the states density of straight chain xanthates(C_2-C_5) increases with the alkyl chain growth. The order of the states density of xanthate isomers is as follows: isopropyl xanthate>n-propyl xanthate, isobutyl xanthate>n-butyl xanthate and n-pentyl xanthate>isopentyl xanthate; The electronic states density of 3418 A in aerofloat is relatively maximum, showing the stronger electron activity. Thocarbamate with different structures changes its states density of nitrogen atom more than that of sulfur atom, which is beneficial to improve the chelating ability of thocarbamate collectors.
The density of electronic states method was used to study the relationship between structures and activity of sulfide floatation collectors such as xanthate, aerofloat and thocarbamate. The results show that delocalization and orbital hybridization could better reflect the collecting and selectivity of flotation reagents. The states density of double-bonded sulfur atom in xanthate is the most active, while that of single-bonded sulfur atom in xanthate ion. Moreover, the states density of straight chain xanthates(C_2-C_5) increases with the alkyl chain growth. The order of the states density of xanthate isomers is as follows: isopropyl xanthate>n-propyl xanthate, isobutyl xanthate>n-butyl xanthate and n-pentyl xanthate>isopentyl xanthate; The electronic states density of 3418 A in aerofloat is relatively maximum, showing the stronger electron activity. Thocarbamate with different structures changes its states density of nitrogen atom more than that of sulfur atom, which is beneficial to improve the chelating ability of thocarbamate collectors.
引文
[1]王淀佐.浮选药剂的结构与性能—浮选药剂的HLB计算法[J].有色金属(冶炼部分),1977(7):36-40.WANG Dian-zuo.The structure and properties of flotation reagents—HLB calculation method of flotation reagents[J].Nonferrous Metals(Smelting Part),1977(7):36-40.
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[8]王纪镇,印万忠.酸碱软硬度的势标度在浮选剂结构性能研究中应用[J].东北大学学报(自然科学版),2013,34(7):1035-1038.WANG Ji-zhen,YIN Wan-zhong.Application of acid-base potential scale in structure performance study of flotation reagents[J].Journal of Northeastern University(Natural Science),2013,34(7):1035-1038.
[9]周国华,孙伟,薛玉兰,蒋玉仁,何伯泉.化学反应电子转移数判据在浮选捕收剂结构与性能关系的应用研究[J].有色金属,2001,53(1):19-21.ZHOU Guo-hua,SUN Wei,XUE Yu-lan,JIANG Yu-ren,HE Bo-quan.Application of number of electronic transfer in chemical reaction to study of structure-reactivity relationship of flotation reagents[J].Nonferrous Metals,2001,53(1):19-21.
[10]NATARAJAN R,NIRDOSH I.Application of topochemical,topostructural,physicochemical and geometrical parameters to model the flotation efficiencies of N-arylhydroxamic acids[J].International Journal of Mineral Processing,2003,71(1/4):113-129.
[11]冯其明,席振伟,张国范,卢毅屏,欧乐明.脂肪酸捕收剂浮选钛铁矿性能研究[J].金属矿山,2009(5):46-49.FENG Qi-ming,XI Zhen-wei,ZHANG Guo-fan,LU Yi-ping,OU Le-ming.Collecting performance of fatty acid as collector for ilmenite[J].Metal Mine,2009(5):46-49.
[12]曹飞,孙传尧,王化军,陈飞武.烃基结构对黄药捕收剂浮选性能的影响[J].北京科技大学学报,2014,36(12):1589-1594.CAO Fei,SUN Chuan-yao,WANG Hua-jun,CHEN Fei-wu.Effect of alkyl structure on the flotation performance of xanthate collectors[J].Journal of University of Science and Technology Beijing,2014,36(12):1589-1594.
[13]孙伟,杨帆,胡岳华,何国勇,刘文莉.前线轨道在黄铜矿捕收剂开发中的应用[J].中国有色金属学报,2009,19(8):1524-1530.SUN Wei,YANG Fan,HU Yue-hua,HE Guo-yong,LIU Wen-li.Application of frontier orbital in developing new collectors of chalcopyrite[J].The Chinese Journal of Nonferrous Metals,2009,19(8):1524-1530.
[14]LIU Guang-yi,ZHONG Hong,DAI Ta-gen,XIA Liu-yin.Investigation of the effect of N-substituents on performance of thionocarbamates as selective collectors for copper sulfides by ab initio calculations[J].Minerals Engineering,2008,21(12/14):1050-1054.
[15]SARVARAMINI A,LARACHI F.Understanding the interactions of thiophosphorus collectors with chalcopyrite through DFT simulation[J].Computational Materials Science,2017,132:137-145.
[16]LIU Guang-yi,XIAO Jing-jing,ZHOU Di-wen,ZHONG Hong,CHOI Phillip,XU Zheng-he.A DFT study on the structure-reactivity relationship of thiophosphorus acids as flotation collectors with sulfide minerals:Implication of surface adsorption[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2013,434(19):243-252.
[17]张行荣,刘崇峻,朱阳戈,郑桂兵,尚衍波,韩龙,艾晶.采用密度泛函方法研究铜铅分离的抑制机理[J].中国有色金属学报,2017,27(4):843-849.ZHANG Xing-rong,LIU Chong-jun,ZHU Yang-ge,ZHENG Gui-bing,SHANG Yan-bo,HAN Long,AI Jing.Depressing mechanism of copper-lead separation by density functional theory method[J].The Chinese Journal of Nonferrous Metals,2017,27(4):843-849.
[18]张行荣,郑桂兵,艾晶,刘崇峻,尚衍波.赤铁矿反浮选淀粉抑制作用第一性原理[J].中国有色金属学报,2016,26(2):465-470.ZHANG Xing-rong,ZHENG Gui-bing,AI Jing,LIU Chong-jun,SHANG Yan-bo.First-principles of depressing mechanism of starch in reverse-flotation of hematite[J].The Chinese Journal of Nonferrous Metals,2016,26(2):465-470.
[19]陈建华.硫化矿物浮选固体物理研究[M].长沙:中南大学出版社,2015:31-35.CHEN Jian-hua.The solide physics of sulphide minerals flotation[M].Changsha:Central South University Press,2015:31-35.
[20]陈晔,陈建华,李玉琼,赵翠华.空间结构对硫化矿物表面能带结构和电子性质的影响[J].中国有色金属学报,2016,26(11):2403-2411.CHEN Ye,CHEN Jian-hua,LI Yu-qiong,ZHAO Cui-hua.Effect of spatial structure on band structure and electronic properties of sulphide minerals[J].The Chinese Journal of Nonferrous Metals,2016,26(11):2403-2411.
[21]LONG Xian-hao,CHEN Ye,CHEN Jian-hua,XU Zheng-he,LIU Qing-xia,DU Zheng.The effect of water molecules on the thiol collector interaction on the galena(Pb S)and sphalerite(Zn S)surfaces:A DFT study[J].Applied Surface Science,2016,389:103-111.
[22]JONES R O,GUNNARSSON O.The density functional formalism,its applications and prospects[J].Reviews of Modern Physics,1989,61(3):689-746.
[23]MARZARI N,VANDERBILT D,PAYNE M C.Ensemble density-functional theory for ab-initio molecular dynamics of metals and finite-temperature insulators[J].Physical Review Letters,1997,79(7):1337-1340.
[24]HUNG A,YAROVSKY I,RUSSO S P.Density-functional theory studies of xanthate adsorption on the pyrite Fe S2(110)and(111)surfaces[J].Journal of Chemical Physics,2003,118(13):6022-6029.
[25]孙传尧.选矿工程师手册(第1册)[M].北京:冶金工业出版社,2015:518-529.SUN Chuan-yao.Handbook for mineral processing engineers[M].Beijing:Metallurgical Industry Press,2015:518-529.
[26]刘凤霞,陈建华,吴伯增,朱文涛.白铅矿、褐铁矿的硫化浮选试验研究[J].矿产保护与利用,2007(1):27-30.LIU Feng-xia,CHEN Jian-hua,WU Bo-zeng,ZHU Wen-tao.Sulfidizing flotation tests of cerusite and limonite[J].Conservation and Utilization of Mineral Resources,2007(1):27-30.
[27]B.A.格列姆博茨基.浮选过程物理化学基础[M].郑飞,译.北京:冶金工业出版社,1985:299-301.GLEMBOTSKIIВА.Physical chemistry basis of flotation process[M].ZHENG Fei,transl.Beijing:Metallurgical Industry Press,1985:299-301.
[28]E.T.帕西纳-特雷维劳,周廷熙,李长根.二异丁基二硫代次膦酸钠(Aerophine 3418A)与活化和未活化的方铅矿和黄铁矿的相互作用[J].国外金属矿选矿,2004,41(6):20-26.PASINA-TREVELLAO E T,ZHOU Ting-xi,LI Chang-gen.Interaction of activated and unactivated galena and pyrite with sodium diisobutyldithiophosphinate(Aerophine 3418A)[J].Metallic Ore Dressing Abroad,2004,41(6):20-26.
[2]王淀佐.浮选药剂的结构与性能—浮选药剂性能的CMC计算法[J].有色金属(冶炼部分),1977(6):25-28.WANG Dian-zuo.The structure and properties of flotation reagents—CMC calculation method of flotation reagents performance[J].Nonferrous Metals(Smelting Part),1977(6):25-28.
[3]王淀佐.浮选药剂的结构与性能—浮选药剂性能的电负性计算法[J].有色金属(冶炼部分),1975(4):44-51.WANG Dian-zuo.The structure and properties of flotation reagents—Electronegativity calculation method of flotation reagents performance[J].Nonferrous Metals(Smelting Part),1975(4):44-51.
[4]王淀佐.浮选药剂的结构与性能—一百种含硫有机浮选剂的分子设计[J].有色金属(选矿部分),1979(2):14-28.WANG Dian-zuo.The structure and properties of flotation reagents—Molecular design of one hundred kinds of sulfur-containing organic flotation reagents[J].Nonferrous Metals(Concentrating Part),1979(2):14-28.
[5]王淀佐.矿物浮选和浮选剂[M].长沙:中南大学出版社,1986.WANG Dian-zuo.Mineral flotation and flotation reagents[M].Changsha:Central South University Press,1986.
[6]见百熙.浮选药剂的分子结构及其规律性—用高等药物化学原理探讨浮选药剂分子的设计[J].有色金属工程,1983(1):10-18.JIAN Bai-xi.Molecular structure and regularity of flotation reagents—A discussion on the design of flotation reagent molecules by the principle of higher medicinal chemistry[J].Nonferrous Metals Engineering,1983(1):10-18.
[7]王淀佐,林强,蒋玉仁.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 Dian-zuo,LIN Qiang,JIANG Yu-ren.Molecular design of mineral processing and metallurgy[M].Changsha:Central South University of Technology Press,1996.
[8]王纪镇,印万忠.酸碱软硬度的势标度在浮选剂结构性能研究中应用[J].东北大学学报(自然科学版),2013,34(7):1035-1038.WANG Ji-zhen,YIN Wan-zhong.Application of acid-base potential scale in structure performance study of flotation reagents[J].Journal of Northeastern University(Natural Science),2013,34(7):1035-1038.
[9]周国华,孙伟,薛玉兰,蒋玉仁,何伯泉.化学反应电子转移数判据在浮选捕收剂结构与性能关系的应用研究[J].有色金属,2001,53(1):19-21.ZHOU Guo-hua,SUN Wei,XUE Yu-lan,JIANG Yu-ren,HE Bo-quan.Application of number of electronic transfer in chemical reaction to study of structure-reactivity relationship of flotation reagents[J].Nonferrous Metals,2001,53(1):19-21.
[10]NATARAJAN R,NIRDOSH I.Application of topochemical,topostructural,physicochemical and geometrical parameters to model the flotation efficiencies of N-arylhydroxamic acids[J].International Journal of Mineral Processing,2003,71(1/4):113-129.
[11]冯其明,席振伟,张国范,卢毅屏,欧乐明.脂肪酸捕收剂浮选钛铁矿性能研究[J].金属矿山,2009(5):46-49.FENG Qi-ming,XI Zhen-wei,ZHANG Guo-fan,LU Yi-ping,OU Le-ming.Collecting performance of fatty acid as collector for ilmenite[J].Metal Mine,2009(5):46-49.
[12]曹飞,孙传尧,王化军,陈飞武.烃基结构对黄药捕收剂浮选性能的影响[J].北京科技大学学报,2014,36(12):1589-1594.CAO Fei,SUN Chuan-yao,WANG Hua-jun,CHEN Fei-wu.Effect of alkyl structure on the flotation performance of xanthate collectors[J].Journal of University of Science and Technology Beijing,2014,36(12):1589-1594.
[13]孙伟,杨帆,胡岳华,何国勇,刘文莉.前线轨道在黄铜矿捕收剂开发中的应用[J].中国有色金属学报,2009,19(8):1524-1530.SUN Wei,YANG Fan,HU Yue-hua,HE Guo-yong,LIU Wen-li.Application of frontier orbital in developing new collectors of chalcopyrite[J].The Chinese Journal of Nonferrous Metals,2009,19(8):1524-1530.
[14]LIU Guang-yi,ZHONG Hong,DAI Ta-gen,XIA Liu-yin.Investigation of the effect of N-substituents on performance of thionocarbamates as selective collectors for copper sulfides by ab initio calculations[J].Minerals Engineering,2008,21(12/14):1050-1054.
[15]SARVARAMINI A,LARACHI F.Understanding the interactions of thiophosphorus collectors with chalcopyrite through DFT simulation[J].Computational Materials Science,2017,132:137-145.
[16]LIU Guang-yi,XIAO Jing-jing,ZHOU Di-wen,ZHONG Hong,CHOI Phillip,XU Zheng-he.A DFT study on the structure-reactivity relationship of thiophosphorus acids as flotation collectors with sulfide minerals:Implication of surface adsorption[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2013,434(19):243-252.
[17]张行荣,刘崇峻,朱阳戈,郑桂兵,尚衍波,韩龙,艾晶.采用密度泛函方法研究铜铅分离的抑制机理[J].中国有色金属学报,2017,27(4):843-849.ZHANG Xing-rong,LIU Chong-jun,ZHU Yang-ge,ZHENG Gui-bing,SHANG Yan-bo,HAN Long,AI Jing.Depressing mechanism of copper-lead separation by density functional theory method[J].The Chinese Journal of Nonferrous Metals,2017,27(4):843-849.
[18]张行荣,郑桂兵,艾晶,刘崇峻,尚衍波.赤铁矿反浮选淀粉抑制作用第一性原理[J].中国有色金属学报,2016,26(2):465-470.ZHANG Xing-rong,ZHENG Gui-bing,AI Jing,LIU Chong-jun,SHANG Yan-bo.First-principles of depressing mechanism of starch in reverse-flotation of hematite[J].The Chinese Journal of Nonferrous Metals,2016,26(2):465-470.
[19]陈建华.硫化矿物浮选固体物理研究[M].长沙:中南大学出版社,2015:31-35.CHEN Jian-hua.The solide physics of sulphide minerals flotation[M].Changsha:Central South University Press,2015:31-35.
[20]陈晔,陈建华,李玉琼,赵翠华.空间结构对硫化矿物表面能带结构和电子性质的影响[J].中国有色金属学报,2016,26(11):2403-2411.CHEN Ye,CHEN Jian-hua,LI Yu-qiong,ZHAO Cui-hua.Effect of spatial structure on band structure and electronic properties of sulphide minerals[J].The Chinese Journal of Nonferrous Metals,2016,26(11):2403-2411.
[21]LONG Xian-hao,CHEN Ye,CHEN Jian-hua,XU Zheng-he,LIU Qing-xia,DU Zheng.The effect of water molecules on the thiol collector interaction on the galena(Pb S)and sphalerite(Zn S)surfaces:A DFT study[J].Applied Surface Science,2016,389:103-111.
[22]JONES R O,GUNNARSSON O.The density functional formalism,its applications and prospects[J].Reviews of Modern Physics,1989,61(3):689-746.
[23]MARZARI N,VANDERBILT D,PAYNE M C.Ensemble density-functional theory for ab-initio molecular dynamics of metals and finite-temperature insulators[J].Physical Review Letters,1997,79(7):1337-1340.
[24]HUNG A,YAROVSKY I,RUSSO S P.Density-functional theory studies of xanthate adsorption on the pyrite Fe S2(110)and(111)surfaces[J].Journal of Chemical Physics,2003,118(13):6022-6029.
[25]孙传尧.选矿工程师手册(第1册)[M].北京:冶金工业出版社,2015:518-529.SUN Chuan-yao.Handbook for mineral processing engineers[M].Beijing:Metallurgical Industry Press,2015:518-529.
[26]刘凤霞,陈建华,吴伯增,朱文涛.白铅矿、褐铁矿的硫化浮选试验研究[J].矿产保护与利用,2007(1):27-30.LIU Feng-xia,CHEN Jian-hua,WU Bo-zeng,ZHU Wen-tao.Sulfidizing flotation tests of cerusite and limonite[J].Conservation and Utilization of Mineral Resources,2007(1):27-30.
[27]B.A.格列姆博茨基.浮选过程物理化学基础[M].郑飞,译.北京:冶金工业出版社,1985:299-301.GLEMBOTSKIIВА.Physical chemistry basis of flotation process[M].ZHENG Fei,transl.Beijing:Metallurgical Industry Press,1985:299-301.
[28]E.T.帕西纳-特雷维劳,周廷熙,李长根.二异丁基二硫代次膦酸钠(Aerophine 3418A)与活化和未活化的方铅矿和黄铁矿的相互作用[J].国外金属矿选矿,2004,41(6):20-26.PASINA-TREVELLAO E T,ZHOU Ting-xi,LI Chang-gen.Interaction of activated and unactivated galena and pyrite with sodium diisobutyldithiophosphinate(Aerophine 3418A)[J].Metallic Ore Dressing Abroad,2004,41(6):20-26.