氨基膦酸衍生硅胶吸附剂分离铂、钯和铀
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摘要
基于曼尼希反应原理,采用化学接枝法合成了氨基膦酸衍生硅胶吸附剂,考察了其对溶液中铂、钯和铀的吸附分离性能。测试了溶液pH、吸附时间、初始金属离子浓度、离子强度和固液比对吸附的影响,吸附选择性及吸附剂的重复使用性能,分析了吸附机制,并用动态柱法对模拟高放废液中3种金属离子进行了回收。衍生硅胶对铂、钯和铀的吸附与溶液pH值关系密切,离子强度、固液比对吸附的影响不大;吸附过程符合准二级吸附动力学模型和Langmuir等温吸附模型。在pH 2时,吸附剂3 h内对铂、钯的平衡吸附容量分别为18.5和19.9mg·g-1,pH 6时3 h内的铀平衡吸附容量为62.1 mg·g-1,利用不同pH条件下的吸附差异可分离回收溶液中的铂、钯和铀。受金属离子溶液化学形态控制,吸附剂对铂、钯有较好的吸附选择性。用5 ml 5%硫脲可完全解吸吸附于衍生硅胶上的铂和钯,5 ml 0.1 mol·L-1HNO3可定量解吸铀。衍生硅胶吸附材料可回收重复使用,采用双柱联合可定量回收模拟废液中的3种金属元素。
Based on the theory of Mannich reaction,aminophosphonic acid derivative silica was synthesized by chemical grafting method,and served as the sorbent for separation of platinum,palladium and uranium from aqueous solution. The sorption performance of the sorbent for platinum,palladium and uranium was investigated under different pH,contact time,initial ion concentration,ionic strength and solid-liquid ratio. Meanwhile,the sorption selectivity of sorbent and the reusability of reclaimed sorbent was examined.The sorption capacity was strongly dependent on pH of solution but independent on the ionic strength and solid-liquid ratio. The sorption process was fitted to the pseudo-second-order kinetic model and Langmuir isotherms model. At pH = 2,the equilibrium sorption capacity of 18. 5 and 19. 9 mg·g-1 for platinum and palladium respectively were achieved within 3 h,and that value for uranium was62. 1 mg·g-1 at pH = 6. The differentia of sorption behavior at different pH could be used for sorption and separation of platinum,palladium from uranium in aqueous solution. Controlled by the speciation of metal ions in aqueous solution,the excellent sorption selectivity for platinum and palladium in binary ions systems was achieved. The adsorbed platinum and palladium could be completely stripped by using 5 ml of 5% thiourea and the appropriate eluate for uranium was 5 ml of 0. 1 mol·L-1 HNO3. Furthermore,the sorbent was stable and reusable with no decrease of sorption capacity during the desorption process. The quantitative recovery of these three metal ions from the simulated HLLW was practicable by using a dual-columns procedure.
Based on the theory of Mannich reaction,aminophosphonic acid derivative silica was synthesized by chemical grafting method,and served as the sorbent for separation of platinum,palladium and uranium from aqueous solution. The sorption performance of the sorbent for platinum,palladium and uranium was investigated under different pH,contact time,initial ion concentration,ionic strength and solid-liquid ratio. Meanwhile,the sorption selectivity of sorbent and the reusability of reclaimed sorbent was examined.The sorption capacity was strongly dependent on pH of solution but independent on the ionic strength and solid-liquid ratio. The sorption process was fitted to the pseudo-second-order kinetic model and Langmuir isotherms model. At pH = 2,the equilibrium sorption capacity of 18. 5 and 19. 9 mg·g-1 for platinum and palladium respectively were achieved within 3 h,and that value for uranium was62. 1 mg·g-1 at pH = 6. The differentia of sorption behavior at different pH could be used for sorption and separation of platinum,palladium from uranium in aqueous solution. Controlled by the speciation of metal ions in aqueous solution,the excellent sorption selectivity for platinum and palladium in binary ions systems was achieved. The adsorbed platinum and palladium could be completely stripped by using 5 ml of 5% thiourea and the appropriate eluate for uranium was 5 ml of 0. 1 mol·L-1 HNO3. Furthermore,the sorbent was stable and reusable with no decrease of sorption capacity during the desorption process. The quantitative recovery of these three metal ions from the simulated HLLW was practicable by using a dual-columns procedure.
引文
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[19]Fan Q H,Guo Z J,Wu W S.Radionuclide sorption at solid-liquid surface:models and applications[J].Progress in Chemistry,2011,23(7):1429.(范桥辉,郭治军,吴王锁.放射性核素在固-液界面上的吸附:模型及其应用[J].化学进展,2011,23(7):1429.)
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[2]Bush R P.Recovery of platinum group metals from high level radioactive waste possibilities of separation and use re-evaluated[J].Platinum Metals Rev.,1991,35(4):202.
[3]Zdenek K.Potential applications of fission platinoids in industry[J].Platinum Metals Rev.,2005,49(2):79.
[4]Pokhitonov Yu A,Romanovskii V N.Palladium in irradiated fuel.Are there any prospects for recovery and application[J].Radiochemistry,2005,47(1):1.
[5]Shi W Q,Zhao Y L,Chai Z F.A preview of nano-materials and nano-technologies applied in advanced nuclear energy system[J].Progress in Chemistry,2011,23(7):1478.(石伟群,赵宇亮,柴之芳.纳米材料与纳米技术在先进核能系统中的应用前瞻[J].化学进展,2011,23(7):1478.)
[6]Liu Y L,Yuan L Y,Yuan Y L,Lan J H,Li Z J,Feng Y X,Zhao Y L,Chai Z F,Shi W Q.A high efficient sorption of U(VI)from aqueous solution using aminofunctionalized SBA-15[J].J.Radioanal.Nucl.Chem.,2012,292:803.
[7]Yuan L Y,Liu Y L,Shi W Q,Lv Y L,Lan J H,Zhao Y L,Chai Z F.High performance of phosphonatefunctionalized mesoporous silica for U(VI)sorption from aqueous solution[J].Dalton Trans.,2011,40:7446.
[8]Wang X L,Yuan L Y,Wang Y F,Li Z J,Lan J H,Liu Y L,Feng Y X,Zhao Y L,Chai Z F,Shi W Q.Mesoporous silica SBA-15 functionalized with phosphonate and amino groups for uranium uptake[J].Science China Chemistry,2012,55(9):1705.
[9]Qi X Y,Yuan L Y,Wu H M,Shi W Q,Feng Y X,Zhao Y L,Chai Z F.Mesoporous silica functionalized with phosphonate as sorbent for Th(IV)extraction[J].Atomic Energy Science and Technology,2012,46(6):652.(戚晓燕,袁立永,吴红枚,石伟群,冯一潇,赵宇亮,柴之芳.磷酸酯功能化介孔硅材料对钍(IV)的吸附性能[J].原子能科学技术,2012,46(6):652.)
[10]Pearson R G.Hard and soft acids and bases[J].J.Am.Chem.Soc.,1963,85(22):3533.
[11]Liao C F,Jiao Y F.Review on research&application of cyanex phosphinic extractants in extractive separation of nonferrous metals[J].Nonferrous Metals,2005,57(4):76.(廖春发,焦芸芬.Cyanex系列膦类萃取剂用于有色金属分离的现状[J].有色金属,2005,57(4):76.)
[12]Zhan G Y,Su Z X,Luo X Y,Chang X J,Liu Y Q.The property of aminophsphonic acid resin for separation and enrichment of noble metals[J].Journal of Lanzhou University,1993,29(4):173.(詹光耀,苏致兴,罗兴寅,常希俊,刘永清.氨基膦酸树脂分离富集贵金属元素性能的研究[J].兰州大学学报,1993,29(4):173.)
[13]Mannich C,Kr9sche W.Ueber ein kondensationsprodukt aus formaldehyd,ammoniak und antipyrin[J].Archiv der Pharmazie,1912,250:647.
[14]Xu R N,Yan J,Xia Y.An IR-spectroscopic study of aminophosphonic resin[J].Ion Exchange and Adsorption,1986,3:25.(徐荣南,严峻,夏炎.氨基膦酸树脂的红外光谱研究[J].离子交换与吸附,1986,3:25.)
[15]Guibal E.Interactions of metal ions with chitosanbased sorbents:a review[J].Sep.Purif.Technol.,2004,38:43.
[16]Unlu N,Ersoz M.Adsorption characteristics of heavy metal ions onto a low cost biopolymeric sorbent from aqueous solutions[J].Journal of Hazardous Materials,2006,136(2):272.
[17]Ho Y S.Review of second-order models for adsorption systems[J].Journal of Hazardous Materials,2006,136(2):681.
[18]Langmuir I.The adsorption of gases on plane surfaces of glass,mica,and platinum[J].J.Am.Chem.Soc.,1918,40(8):1361.
[19]Fan Q H,Guo Z J,Wu W S.Radionuclide sorption at solid-liquid surface:models and applications[J].Progress in Chemistry,2011,23(7):1429.(范桥辉,郭治军,吴王锁.放射性核素在固-液界面上的吸附:模型及其应用[J].化学进展,2011,23(7):1429.)
[20]Hall K R,Eagleton L C,Acrivos A,Vermeule T.Por-and solid-diffusion kinetics in fixed-bed adsorption under constant-pattern conditions[J].Ind.Eng.Chem.Fund.,1966,5(2):212.
[21]Grant R A.The separation chemistry of rhodium and iridium[A].Precious Metals Recovery and Refining,Proceedings of a Seminar of the International Precious Metals Institute[C].Scottsdale,USA,1989.7.