新型三叔胺萃取剂的合成及其萃取性能
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摘要
合成一种新型三叔胺萃取剂并对其萃取性能进行研究。以二乙烯三胺、溴代正己烷和溴代正辛烷为原料,合成N,N,N′,N″,N″-五烷基(己基,辛基)二乙烯三胺,分别用红外光谱、核磁共振氢谱对其进行表征。比较N,N,N′,N″,N″-五己基二乙烯三胺、N,N,N′,N″,N″-五辛基二乙烯三胺与N235的萃取性能,研究N,N,N′,N″,N″-五辛基二乙烯三胺的反萃性能。研究结果表明:N,N,N′,N″,N’’-五辛基二乙烯三胺萃取性能优于N,N,N′,N″,N″-五己基二乙烯三胺性能,而与N235性能类似;以2 mol/L NaOH作反萃剂,当反萃温度为25℃,振荡时间为5 min,油与水的体积比即相比(V(O)/V(A))为2:1时,单级反萃率达97.48%;水相中钼质量浓度最高可富集到55 g/L。
A novel three-tri-amine extractant was firstly synthesized, and its extraction performance was investigated. Two new chemicals of N,N,N′,N″,N″-pentahexyldiethylenetriamine and N,N,N′,N″,N″-pentaoctyldiethylenetriamine were synthesised using diethylenetriamine,1-bromohexane and 1-bromooctane as raw materials, respectively. IR and 1H-NMR were employed to characterize the structures of both chemicals. The performance of extraction of molybdenum with N,N,N′,N″,N″-pentahexyldiethylenetriamine, N,N,N′,N″,N″-pentaoctyldiethylenetriamine and N235 were investigated. The performance of stripping of molybdenum with N,N,N′,N″,N″-pentaoctyldiethylenetriamine was researched. The solution of 2 mol/L Na OH was used to strip molybdenum from the loaded organic. The results show that N,N,N′,N″,N″-pentaoctyldiethylenetriamine has better extraction performance than N,N,N′,N″,N″-pentahexyldiethylenetriamine and is similar to N235. The stripping of Mo reaches 97.48% with volume ratio V(O)/V(A) of 2:1 at 25 ℃ for 5 min in single stage. The mass concentration of molybdenum in strip liquor reaches 55 g/L.
A novel three-tri-amine extractant was firstly synthesized, and its extraction performance was investigated. Two new chemicals of N,N,N′,N″,N″-pentahexyldiethylenetriamine and N,N,N′,N″,N″-pentaoctyldiethylenetriamine were synthesised using diethylenetriamine,1-bromohexane and 1-bromooctane as raw materials, respectively. IR and 1H-NMR were employed to characterize the structures of both chemicals. The performance of extraction of molybdenum with N,N,N′,N″,N″-pentahexyldiethylenetriamine, N,N,N′,N″,N″-pentaoctyldiethylenetriamine and N235 were investigated. The performance of stripping of molybdenum with N,N,N′,N″,N″-pentaoctyldiethylenetriamine was researched. The solution of 2 mol/L Na OH was used to strip molybdenum from the loaded organic. The results show that N,N,N′,N″,N″-pentaoctyldiethylenetriamine has better extraction performance than N,N,N′,N″,N″-pentahexyldiethylenetriamine and is similar to N235. The stripping of Mo reaches 97.48% with volume ratio V(O)/V(A) of 2:1 at 25 ℃ for 5 min in single stage. The mass concentration of molybdenum in strip liquor reaches 55 g/L.
引文
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[16]罗逸,任以伟,刘伦华,等.双叔胺缔合相变—两步反萃法处理萘磺酸系废[J].化工环保,2007,27(1):67-69.LUO Yi,REN Yiwei,LIU Lunhua,et al.Treatment of waste liquor containing naphthalenesulfonic acid compounds by association phase change with di-tertiary amine and two-step back-extraction processes[J].Environmental Protection of Chemical Industry,2007,27(1):67-69.
[2]杨幼明,蓝桥发,邓声华,等.P507与N235混合溶剂的稳定性及对Nd Cl3的协萃效应[J].中国稀土学报,2013,31(4):386-390.YANG Youming,LAN Qiaofa,DENG Shenghua,et al.Chemical stability of P507-N235 system and its synergistic extraction for Nd Cl3[J].Journal of the Chinese Society of Rare Earths,2013,31(4):386-390.
[3]向铁根.钼冶金[M].长沙:中南大学出版社,2002:87-89.XIANG Tiegen.Molybdenum metallurgy[M].Changsha:Central South University Press,2002:87-89.
[4]BANDA R,SOHN S H,LEE M S.Process development for the separation and recovery of Mo and Co from chloride leach liquors of petroleum refining catalyst by solvent extraction[J].Hazard Mater,2012,213(6):1-6.
[5]钟宏,符剑刚,刘凌波.采用N235从含Mo,Mn酸浸液中萃取回收Mo[J].过程工程学报,2006,6(1):29-31.ZHONG Hong,FU Jiangang,LIU Lingbo.Recovery of Mo from acid leaching solution containing Mo and Mn by solvent extraction of N235[J].The Chinese Journal of Process Engineering,2006,6(1):29-31.
[6]肖朝龙,肖连生,龚柏凡.采用N235从镍钼矿盐酸浸出液中萃取钼的研究[J].中国钼业,2011,35(1):8-11.XIAO Chaolong,XIAO Liansheng,GONG Baifan.A study of extracting molybdenum from hydrochloric acid leach liquor of Ni-Mo ore using N235[J].China Molybdenum Industry,2011,35(1):8-11.
[7]ZHAO Zhongwei,LIANG Yang,HUO Guangsheng,et al.Solvent extraction of molybdenum blue from alkaline leaching solution of the Ni-Mo ore[J].Journal of Refractory Metals and Hard Materials,2011,29(1):232-236.
[8]李青刚,廖宇龙,张启修,等.白钨矿酸性化学选矿浸出液的钨钼萃取研究[J].稀有金属与硬质合金,2011,39(3):2-5.LI Qinggang,LIAO Yulong,ZHANG Qixiu,et al.Extraction of tungsten and molybdenum from scheelite chemical beneficiation acidic leachate[J].Rare Metals and Cemented Carbides,2011,39(3):2-5.
[9]朱薇,肖连生,肖超,等.N235萃取镍钼矿硫酸浸出液中钼的研究[J].稀有金属与硬质合金,2010,38(1):2-4.ZHU Wei,XIAO Liansheng,XIAO Chao,et al.Molybdenum extraction with N235 from the sulphuric acid leach liquor in Ni-Mo Ore[J].Rare Metals and Cemented Carbides,2010,38(1):2-4.
[10]谢琦莹,陈景,杨项军,等.N235萃取HCl体系中TBP消除第3相的作用机理[J].无机化学学报,2007,23(1):58-62.XIE Qiying,CHEN Jing,YANG Xiangjun,et al.Mechanism of third-phase elimination by TBP in N235/HCI solvent extraction system[J].Chinese Journal of Inorganic Chemistry,2007,23(1):58-62.
[11]谢琦莹,陈景,杨项军.叔胺N235萃取盐酸时酸度对产生第3相的影响[J].无机化学学报,2008,24(6):897-901.XIE Qiying,CHEN Jing,YANG Xiangjun.Effect of HCl concentration on formation of third-phase in N235-C12H26-HCl solvent extraction system[J].Chinese Journal of Inorganic Chemistry,2008,24(6):897-901.
[12]刘立华,吴俊,肖乐体,等.N,N,N′,N″,N″-四烯丙基乙二胺的合成与表征[J].精细石油化工,2010,27(2):5-7.LIU Lihua,WU Jun,XIAO Leti,et al.Synthesis and characterization of N,N,N′,N″,N″-tetraallylethylenediamine[J].Speciality Petrochemicals,2010,27(2):5-7.
[13]许兴友,魏祥,高健,等.N,N,N′,N″,N″-五(2-氰基乙基)二乙烯三胺的合成及表征[J].淮海工学院学报,2004,13(2):39-40.XU Xingyou,WEI Xiang,GAO Jian,et al.Synthesis and characterization of N,N,N′,N″,N″-penta(2-nitrilethyl)diethylenetriamine[J].Journal of Huaihai Institute of Technology,2004,13(2):39-40.
[14]阎峰,程侣柏,赵鸣玉.双叔胺新型离子缔合萃取剂研究[J].大连理工大学学报,2000,40(6):686-687.YAN Feng,CHENG Lübai,ZHAO Mingyu.Study of new types of di-tertiary amine ion-associating extracting agent[J].Journal of Dalian University of Technology,2000,40(6):686-687.
[15]阎峰,赵鸣玉,程侣柏.一种新的双叔胺化学萃取剂的研究[J].精细化工,1999,16(3):44-46.YAN Feng,ZHAO Mingyu,CHENG Lübai.Research on a new di-tertiary amine chemical extractant[J].Fine Chemicals,1999,16(3):44-46.
[16]罗逸,任以伟,刘伦华,等.双叔胺缔合相变—两步反萃法处理萘磺酸系废[J].化工环保,2007,27(1):67-69.LUO Yi,REN Yiwei,LIU Lunhua,et al.Treatment of waste liquor containing naphthalenesulfonic acid compounds by association phase change with di-tertiary amine and two-step back-extraction processes[J].Environmental Protection of Chemical Industry,2007,27(1):67-69.