采用萃取剂[Omim][BF_4]分离提取铬渣中的Cr_2O_7~(2-)
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摘要
铬渣是重要的工业固体废物,具有极其严重的环境危害性,分离提取铬的资源化利用是减少铬渣环境污染和资源浪费的有效途径。以1-辛基-3-甲基咪唑四氟硼酸盐离子液体([Omim][BF_4])为萃取剂,戊醇为稀释剂,对铬渣酸浸液进行萃取和反萃取实验。在萃取实验过程中,分别考察萃取剂浓度、时间、pH等条件的影响作用。采用斜率法及红外光谱分析进行了萃取机理研究,最后进行了反萃取实验研究。结果表明:在萃取剂浓度ρ([Omim][BF_4])=50.0 g/L、6.0 min、pH为1.408~2.006条件下,Cr_2O_7~(2-)的萃取率达到94.81%;[Omim][BF_4]对Cr_2O_7~(2-)的萃取主要是根据软硬酸碱理论通过离子缔合形成萃合物达到较高的萃取率;在pH=10、反萃取剂为0.5mol/L NaBr+0.5 mol/L(NH_4)_2SO_3、15.0 min的条件下,铬的反萃率达到99.35%。实现了铬渣中铬资源的分离提取。
Chromic slags are vital industrial solid wastes which possess extremely serious environmental perniciousness.Separating and extracting chromium is effective means to reduce its environmental pollution and resources waste.The extraction behavior of chromium from chromium slag acidic leaching solution with[Omim][BF_4]dissolved in pentanol was studied as concentration of extractant,time,acidity,and so on.The results show that extraction rate of chromate can reach up to 94.81%under the conditions of[Omim][BF_4]concentration of 50.0 g/L,shaking time of 6.0 min,pH of 1.408-2.006.The extraction mechanism results show that the extraction proceeds via ionic association based on HSAB to product adduct.The back-extraction rate of chromate can reach up to 99.35%under the conditions of pH=10,stripping agent 0.5 mol/L NaBr+0.5 mol/L(NH_4)_2SO_3,shaking time 15.0 min.The purification of chromium from chromium slags is achieved.
Chromic slags are vital industrial solid wastes which possess extremely serious environmental perniciousness.Separating and extracting chromium is effective means to reduce its environmental pollution and resources waste.The extraction behavior of chromium from chromium slag acidic leaching solution with[Omim][BF_4]dissolved in pentanol was studied as concentration of extractant,time,acidity,and so on.The results show that extraction rate of chromate can reach up to 94.81%under the conditions of[Omim][BF_4]concentration of 50.0 g/L,shaking time of 6.0 min,pH of 1.408-2.006.The extraction mechanism results show that the extraction proceeds via ionic association based on HSAB to product adduct.The back-extraction rate of chromate can reach up to 99.35%under the conditions of pH=10,stripping agent 0.5 mol/L NaBr+0.5 mol/L(NH_4)_2SO_3,shaking time 15.0 min.The purification of chromium from chromium slags is achieved.
引文
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[8]邱胤轩,杨丽梅,黄松涛,李岩,张歌,胡祎罕娜.协同萃取法分离和回收废水中重金属离子的研究现状[J].稀有金属,2015,39(8):749-758.QIU Yin-xuan,YANG Li-mei,HUANG Hai-tao,LI Yan,ZHANG Ge,HU Yi-han-na.Progress in separation and recycled of heavy metals from wastewater by synergistic solvent extraction method[J].Rare Metals,2015,39(8):749-758.
[9]孙盼,黄焜,刘会洲.采用酸化伯胺A-N1923-酒石酸钠体系从强碱性溶液萃取分离钒铬[J].中国有色金属学报,2016,26(7):1559-1567.SUN Pan,HUANG Kun,LIU Hui-zhou.Seperation V and Cr from alkaline aqueous solutins using acidified primary amine A-N1923-sodium tartrate system[J].The Chinese Journal of Nonferrous Metals,2016,26(7):1559-1567.
[10]LUO Jian-hong,LI Jun,YANG Zhao-peng,LIU Xue-feng.Removal of chromium(Ⅲ)from aqueous waste solution by predispersed solvent extraction[J].Transactions of Nonferrous Metals Society of China,2013,23(2):524-529.
[11]PANDEY B D,COTE G,BAUER D.Extraction of chromium(Ⅲ)from spent tanning baths[J].Hydrometallury,1996,40(3):343-357.
[12]ZHANG Li-hua,ZHU Zhi-liang,Chromium extraction from sewage sludge using polyepoxysuccinic acid[J].Pedosphere,2012,22(1):131-136.
[13]刘梦莹,车佳宁,吴蔚闳,卢运祥,彭昌军,刘洪来,卢浩,杨强,汪华林.功能性离子液体萃取水中Cu2+的实验与理论[J].化学学报,2015,73:117.LIU Meng-ying,CHE Jia-ning,WU Wei-hong,LU Yun-xiang,PENG Chang-jun,LIU Hong-lai,LU Hao,YANG Qiang,WANG Hua-lin.Extraction of copper from aqueous solution with functional ionic liquids:Experiment and theoretical calculation[J].Acta Chimica Sinica,2015,73:117.
[14]陈仁坦,刘植昌,孟祥海,张睿.离子液体萃取重金属离子的研究进展[J].化工进展,2013,32(11):2758.CHEN Ren-tan,LIU Zhi-chang,MENG Xiang-hai,ZHANG Rui.Advances in heavy metal ion extraction with ionic liquids[J].Chemical Industry and Engineering Progress,2013,32(11):2758.
[15]CHIAPPE C,PIERACCINI D.Ionic liquids:Solvent properties and organic reactivity[J].Journal of Physical Organic Chemistry,2005,18(4):275-297.
[16]ROONER D,JACQUEMIN J,GARDAS R.Thermoph-ysical properties of ionic liquids[J].Ionic Liquids,2004,49(4):954-964.
[17]TOKUDA H,ISHII K,SUSAN H B A,WATANABE M.Physicochemical properties and structures of room temperature ionic liquids:Variation of anionic species[J].Journal of Physical Chemistry,2004,108(42):16593-16600.
[18]PLECHKOVA N,SEDDON K R.Applications of ionic liquids in the chemical industry[J].Chemical Society Reviews,2008,37(1):123-150.
[19]SUN Ping,ARMSTRONG D W.Ionic liquids in analytical chemistry[J].Analytica Chimical Acta,2010,661(1):1-16.
[20]SUN Xiao-qi,LUO Hui-ming,DAI Sheng.Ionic liquids-based extraction:A promising strategy for the advanced nuclear fuel cycle[J].Chemical Reviews,2012,112(4):2100-2128.
[21]GALINSKI M,LEWANDOWSKI A,STEPNIAK I.Ionic liquids as electrolytes[J].Electro chimical Acta,2006,51(26):5567-5580.
[22]PARVULESCU V I,HARDARE C.Catalysis in ionic liquids[J].Chemical Reviews,2007,107(6):2615-2665.
[23]VISSER A E,JENSEN M P,LASZAK I,NASH K L,GREGORY R,ROGERS R D.Uranyl coordination environment in hydrophobic ionic liquids:An in situ investigation[J].Inorg Chem,2003,42(7):2197-2199.
[24]VISSER A E,ROGERS R D.Room-temperature ionic liquids:New solvents for F-element separations and associated solutionchemistry[J].Solid State Chem,2003,171:109-113.
[25]VISSER A E,SWATLOSKI R P,REICHERT W M.MAYTON R,SHEFF S,WIERZBICKI A,DAVIS J H,ROGERS R D.Task-specific ionic liquids incorporating novel cations for the coordination and extraction of Hg2+and Cd2+:Synthesis,characterization,and extraction studies[J].Environmental Science&Technology,2002,36(11):2523-2529.
[26]VISSER A E,SWATLOSKI R P,REICHERT W M,MAYTON R,SHEFF S,WIERZBICKE A,DAVIS J H,ROGERS R D.Task-specific ionic liquids for the extraction of metal ions from aqueous solutions[J].Chem Comun,2001:135-136.
[27]NAKASHIMA K,KUBOTA F,MARUYAMA T.Ionic liquids as a novel solvent for lanthanide extraction[J].Anal SCI,2003,8(19):1097-1098.
[28]WHITEHEAD J A,LAWRANCE G A,MCCLUSKEY A.Green leaching:Recyclable and selective leaching of gold-bearing ore in an ionic liquid[J].Green Chem,2004,6(7):313-315.
[29]DOMANSKA U,KOZLOWSKA M,ROGALSKI M.Solubility of imidazoles in alcohols[J].Journal of Chemical&Engineering Data,2002,47(1):8-16.
[30]DOMANSKA U,KOZLOWSKA M K,ROGALSKI M.Solubilities,partition coefficients,density,and surface tension for imidazoles+octan1ol or+water or+n-decane[J].Journal of Chemical&Engineering Data,2002,47(3):456-466.
[31]DOMANSKA U,KROLIKOWSKA M,ARASIMOWICZ M.Phase equilibria of(1-hexyl-3-methylimidazolium thiocyanate+water,alcohol,or hydrocarbon)binary systems[J].Journal of Chemical&Engineering Data,2010,55(2):773-777.
[32]郑丽丽,郭晨,刘会洲.离子液体的红外光谱研究[J].光谱学与光谱分析,2006,26(7):33-34.ZHENG Li-li,GUO Chen,LIU Hui-zhou.The FTIR study of the 1-butyl-3-methylimidazolium based ionic liquids[J].Spectriscopy and Spectral Analysis,2006,26(7):33-34.
[33]葛战勤,杨永会,孙思修,沈静兰.伯胺N1923萃取22 7Cr O-的研究[J].应用化学,1995,12(3):59.GE Zhan-qin,YANG Yong-hui,SUN Si-xiu,SHEN Jing-lan.Extraction dichromate with primary amine N1923[J].Chinese Journal of Applied Chemistry,1995,12(3):59.
[2]景学森,蔡木林,杨亚提.铬渣处理处置技术研究进展[J].环境技术,2006(3):33.JING Xue-sen,CAI Mu-lin,YANG Ya-ti.Research progress of treatment and disposal of chromium slags[J].Environmental Technology,2006(3):33.
[3]陈果,王鑫.浅析我国铬渣解毒技术的研究[J].科技与企业,2015(6):245-246.CHEN Guo,WANG Xin.Detoxification techniques of chromium slag in China:A review[J].Technology and Business,2015(6):245-246.
[4]孟超,孟庆庆.化学沉淀法处理含铬电镀废水的工程应用研究[J].环境科学与管理,2013,38(4):106-110.MENG Chao,MENG Qing-qing.Applied research on chromium-containing electroplating wastewater by chemical precipitation method[J].Environmental Science and Management,2013,38(4):106-110.
[5]范力,张建强,程新,刘伟,夏明芳,王志良.离子交换法以及吸附法处理含铬废水的研究进展[J].水处理技术,2009,35(1):30-33.FAN Li,ZHANG Jiang-qiang,CHENG Xin,LIU Wei,XIA Ming-fang,WANG Zhi-liang.Progress of treatment of waste water containing chromium by ion-exchange method and adsorption method[J].Water Treatment Technology,2009,35(1):30-33.
[6]覃奇贤,刘淑兰,成旦红,郭鹤桐.铬酸溶液中金属铬电沉积的机理[J].物理化学学报,1992,8(4):571-575.TAN Qi-xian,LIU Shu-lan,CHENG Dan-hong,GUO He-tong.The mechanism of chromium electrodeposition of from chromic acid solution[J].Acta Physico-Chimica Sinica,1992,8(4):571-575.
[7]王拥军,张宇飞,许刚,蒋兴祥.高纯金属铬的电解生产实践[J].湿法冶金,2009,28(2):99-100.WANG Yong-jun,ZHANG Yu-fei,XU Gang,JIANG Xing-xiang.Electrolysis production practice of high purity metal chromium[J].Hydrometallurgy,2009,28(2):99-100.
[8]邱胤轩,杨丽梅,黄松涛,李岩,张歌,胡祎罕娜.协同萃取法分离和回收废水中重金属离子的研究现状[J].稀有金属,2015,39(8):749-758.QIU Yin-xuan,YANG Li-mei,HUANG Hai-tao,LI Yan,ZHANG Ge,HU Yi-han-na.Progress in separation and recycled of heavy metals from wastewater by synergistic solvent extraction method[J].Rare Metals,2015,39(8):749-758.
[9]孙盼,黄焜,刘会洲.采用酸化伯胺A-N1923-酒石酸钠体系从强碱性溶液萃取分离钒铬[J].中国有色金属学报,2016,26(7):1559-1567.SUN Pan,HUANG Kun,LIU Hui-zhou.Seperation V and Cr from alkaline aqueous solutins using acidified primary amine A-N1923-sodium tartrate system[J].The Chinese Journal of Nonferrous Metals,2016,26(7):1559-1567.
[10]LUO Jian-hong,LI Jun,YANG Zhao-peng,LIU Xue-feng.Removal of chromium(Ⅲ)from aqueous waste solution by predispersed solvent extraction[J].Transactions of Nonferrous Metals Society of China,2013,23(2):524-529.
[11]PANDEY B D,COTE G,BAUER D.Extraction of chromium(Ⅲ)from spent tanning baths[J].Hydrometallury,1996,40(3):343-357.
[12]ZHANG Li-hua,ZHU Zhi-liang,Chromium extraction from sewage sludge using polyepoxysuccinic acid[J].Pedosphere,2012,22(1):131-136.
[13]刘梦莹,车佳宁,吴蔚闳,卢运祥,彭昌军,刘洪来,卢浩,杨强,汪华林.功能性离子液体萃取水中Cu2+的实验与理论[J].化学学报,2015,73:117.LIU Meng-ying,CHE Jia-ning,WU Wei-hong,LU Yun-xiang,PENG Chang-jun,LIU Hong-lai,LU Hao,YANG Qiang,WANG Hua-lin.Extraction of copper from aqueous solution with functional ionic liquids:Experiment and theoretical calculation[J].Acta Chimica Sinica,2015,73:117.
[14]陈仁坦,刘植昌,孟祥海,张睿.离子液体萃取重金属离子的研究进展[J].化工进展,2013,32(11):2758.CHEN Ren-tan,LIU Zhi-chang,MENG Xiang-hai,ZHANG Rui.Advances in heavy metal ion extraction with ionic liquids[J].Chemical Industry and Engineering Progress,2013,32(11):2758.
[15]CHIAPPE C,PIERACCINI D.Ionic liquids:Solvent properties and organic reactivity[J].Journal of Physical Organic Chemistry,2005,18(4):275-297.
[16]ROONER D,JACQUEMIN J,GARDAS R.Thermoph-ysical properties of ionic liquids[J].Ionic Liquids,2004,49(4):954-964.
[17]TOKUDA H,ISHII K,SUSAN H B A,WATANABE M.Physicochemical properties and structures of room temperature ionic liquids:Variation of anionic species[J].Journal of Physical Chemistry,2004,108(42):16593-16600.
[18]PLECHKOVA N,SEDDON K R.Applications of ionic liquids in the chemical industry[J].Chemical Society Reviews,2008,37(1):123-150.
[19]SUN Ping,ARMSTRONG D W.Ionic liquids in analytical chemistry[J].Analytica Chimical Acta,2010,661(1):1-16.
[20]SUN Xiao-qi,LUO Hui-ming,DAI Sheng.Ionic liquids-based extraction:A promising strategy for the advanced nuclear fuel cycle[J].Chemical Reviews,2012,112(4):2100-2128.
[21]GALINSKI M,LEWANDOWSKI A,STEPNIAK I.Ionic liquids as electrolytes[J].Electro chimical Acta,2006,51(26):5567-5580.
[22]PARVULESCU V I,HARDARE C.Catalysis in ionic liquids[J].Chemical Reviews,2007,107(6):2615-2665.
[23]VISSER A E,JENSEN M P,LASZAK I,NASH K L,GREGORY R,ROGERS R D.Uranyl coordination environment in hydrophobic ionic liquids:An in situ investigation[J].Inorg Chem,2003,42(7):2197-2199.
[24]VISSER A E,ROGERS R D.Room-temperature ionic liquids:New solvents for F-element separations and associated solutionchemistry[J].Solid State Chem,2003,171:109-113.
[25]VISSER A E,SWATLOSKI R P,REICHERT W M.MAYTON R,SHEFF S,WIERZBICKI A,DAVIS J H,ROGERS R D.Task-specific ionic liquids incorporating novel cations for the coordination and extraction of Hg2+and Cd2+:Synthesis,characterization,and extraction studies[J].Environmental Science&Technology,2002,36(11):2523-2529.
[26]VISSER A E,SWATLOSKI R P,REICHERT W M,MAYTON R,SHEFF S,WIERZBICKE A,DAVIS J H,ROGERS R D.Task-specific ionic liquids for the extraction of metal ions from aqueous solutions[J].Chem Comun,2001:135-136.
[27]NAKASHIMA K,KUBOTA F,MARUYAMA T.Ionic liquids as a novel solvent for lanthanide extraction[J].Anal SCI,2003,8(19):1097-1098.
[28]WHITEHEAD J A,LAWRANCE G A,MCCLUSKEY A.Green leaching:Recyclable and selective leaching of gold-bearing ore in an ionic liquid[J].Green Chem,2004,6(7):313-315.
[29]DOMANSKA U,KOZLOWSKA M,ROGALSKI M.Solubility of imidazoles in alcohols[J].Journal of Chemical&Engineering Data,2002,47(1):8-16.
[30]DOMANSKA U,KOZLOWSKA M K,ROGALSKI M.Solubilities,partition coefficients,density,and surface tension for imidazoles+octan1ol or+water or+n-decane[J].Journal of Chemical&Engineering Data,2002,47(3):456-466.
[31]DOMANSKA U,KROLIKOWSKA M,ARASIMOWICZ M.Phase equilibria of(1-hexyl-3-methylimidazolium thiocyanate+water,alcohol,or hydrocarbon)binary systems[J].Journal of Chemical&Engineering Data,2010,55(2):773-777.
[32]郑丽丽,郭晨,刘会洲.离子液体的红外光谱研究[J].光谱学与光谱分析,2006,26(7):33-34.ZHENG Li-li,GUO Chen,LIU Hui-zhou.The FTIR study of the 1-butyl-3-methylimidazolium based ionic liquids[J].Spectriscopy and Spectral Analysis,2006,26(7):33-34.
[33]葛战勤,杨永会,孙思修,沈静兰.伯胺N1923萃取22 7Cr O-的研究[J].应用化学,1995,12(3):59.GE Zhan-qin,YANG Yong-hui,SUN Si-xiu,SHEN Jing-lan.Extraction dichromate with primary amine N1923[J].Chinese Journal of Applied Chemistry,1995,12(3):59.