膨润土对U(Ⅵ)的吸附机理研究
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摘要
以高庙子膨润土为研究对象,通过静态吸附实验,考查了高庙子膨润土对U(Ⅵ)的吸附特征,研究了接触时间、固液比、铀的初始浓度、pH、离子类型和离子浓度等因素对U(Ⅵ)吸附特征的影响,并讨论了膨润土对U(Ⅵ)的吸附动力学和热力学过程。结果表明:吸附过程在24 h后达到动态平衡;最佳吸附固液比为1:300;最佳吸附初始浓度为40 mg·L~(-1);在pH为5时,膨润土对U(Ⅵ)的吸附效果最好,过酸或过碱都会影响膨润土对U(Ⅵ)的吸附;溶液中Ca~(2+)、CO_3~(2-)显著降低了膨润土对U(Ⅵ)的吸附效果,影响程度随着离子浓度的增加而增大;Freundlich等温吸附模型和准二级动力学模型对吸附过程的拟合效果较好,主要表现为多层吸附。
[Background] The research on the disposal of clay rock in high-level waste is still in the initial stage,and little attention has been paid to the migration mechanism of nuclide in clay rock treatment system in previous work. [Purpose] This study aims at the adsorption behavior of U(Ⅵ) in Gaomiaozi bentonite and provide reference for the safety evaluation system of high level waste disposal storehouse. [Methods] The sorption behavior of U(Ⅵ)on Gaomiaozi bentonite was studied as a function of adsorption time, solid-to-liquid ratio, initial concentration of U(Ⅵ), pH value, the type of ionic species and ionic concentration by the static experimental method. Both scanning elextron microscope(SEM) and infrared spectrometer were employed to experimental observation. The adsorption kinetics and thermodynamic of U( Ⅵ) in bentonite was discussed. [Results] Experimental results showed that the equilibrium time of U( Ⅵ) sorption on bentonite was about 24 h. The optimum adsorption ratio was 1: 300. The optimum initial concentration was 40 mg·L~(-1). When the pH value was 5, the ability of absorption reaches the best, the acid or alkaloid would affect the adsorption of bentonite on U(VI). Ca~(2+) and CO_3~(2-) in solution significantly reduce the adsorption of U(VI) by bentonite, and the degree of influence increaseds with the increase of ion concentration.[Conclusions] The sorption isotherm of U(Ⅵ) can be simulated very well using the Freundlich and follow the quasi-2 nd order kinetic equation, indicating that the adsorption is a multi-layer adsorption model.
[Background] The research on the disposal of clay rock in high-level waste is still in the initial stage,and little attention has been paid to the migration mechanism of nuclide in clay rock treatment system in previous work. [Purpose] This study aims at the adsorption behavior of U(Ⅵ) in Gaomiaozi bentonite and provide reference for the safety evaluation system of high level waste disposal storehouse. [Methods] The sorption behavior of U(Ⅵ)on Gaomiaozi bentonite was studied as a function of adsorption time, solid-to-liquid ratio, initial concentration of U(Ⅵ), pH value, the type of ionic species and ionic concentration by the static experimental method. Both scanning elextron microscope(SEM) and infrared spectrometer were employed to experimental observation. The adsorption kinetics and thermodynamic of U( Ⅵ) in bentonite was discussed. [Results] Experimental results showed that the equilibrium time of U( Ⅵ) sorption on bentonite was about 24 h. The optimum adsorption ratio was 1: 300. The optimum initial concentration was 40 mg·L~(-1). When the pH value was 5, the ability of absorption reaches the best, the acid or alkaloid would affect the adsorption of bentonite on U(VI). Ca~(2+) and CO_3~(2-) in solution significantly reduce the adsorption of U(VI) by bentonite, and the degree of influence increaseds with the increase of ion concentration.[Conclusions] The sorption isotherm of U(Ⅵ) can be simulated very well using the Freundlich and follow the quasi-2 nd order kinetic equation, indicating that the adsorption is a multi-layer adsorption model.
引文
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6夏良树,谭凯旋,王晓,等.铀在榕树叶上的吸附行为及其机理分析[J].原子能科学技术,2010,44(3):278-284.XIA Liangshu,TAN Kaixuan,WANG Xiao,et al.Adsorption behavior of uranium and mechanism analysis on banyan leaves[J].Atomic Energy Science and Technology,2010,44(3):278-284.
7邓晓颖,庹先国,王勋来,等.239Pu在高庙子膨润土中的吸附特征研究[J].核技术,2012,35(9):32-36.DENG Xiaoying,TUO Xianguo,WANG Xunlai,et al.Adsorption behavior of239Pu by Gaomiaozi bentonite[J].Nuclear Techniques,2012,35(9):32-36.
8毛文静,刘峙嵘.RGO/FeOOH凝胶制备及其对铀的吸附性[J].核技术,2014,37(9):090302.DOI:10.11889/j.0253-3219.2014.hjs.37.090302.MAO Wenjing,LIU Zhirong.Preparation of RGO/FeOOH aerogels and its adsorption for U(VI)[J].Nuclear Techniques,2014,37(9):090302.DOI:10.11889/j.0253-3219.2014.hjs.37.090302.
9杜浪,李玉香,马雪,等.偶氮胂Ⅲ分光光度法测定微量铀[J].冶金分析,2015,35(1):68-71.DOI:10.13228/j.b0yuan.issn1000-7571.009388.DU Lang,LI Yuxiang,MA Xue,et al.Determination of micro uranium by arsenazoⅢspectrophotometry[J].Metallurgical Analysis,2015,35(1):68-71.DOI:10.13228/j.b0yuan.issn 1000-7571.009388.
10岳萍,庹先国,宿吉龙,等.239Pu在膨润土中的吸附和迁移实验研究[J].科学技术与工程,2014,14(8):168-171.DOI:10.3969/j.issn.1671-1815.2014.08.031.YUE Ping,TUO Xianguo,SU Jilong,et al.Application of back off diagnosis technology in downhole operation[J].Science Technology and Engineering,2014,14(8):168-171.DOI:10.3969/j.issn.1671-1815.2014.08.031.
11刘勇,李晖,张永丽,等.羟基铝柱撑蛭石的制备及其吸附磷酸根性能研究[J].四川大学学报(工程科学版),2008,40(4):80-85.LIU Yong,LI Hui,ZHANG Yongli,et al.The preparation and application of Al-pillared vermiculite in phosphate adsorption[J].Journal of Sichuan University(Engineering Science),2008,40(4):80-85.
12刘艳,易发成,王哲.膨润土对铀的吸附研究[J].非金属矿,2010,33(1):52-53.DOI:10.3969/j.issn.1000-8098.2010.01.018.LIU Yan,YI Facheng,WANG Zhe.Study on sorption of bentonite to uranium[J].Non-Metallic Mines,2010,33(1):52-53.DOI:10.3969/j.issn.1000-8098.2010.01.018.
13赖捷,刘畅,冷阳春,等.粘土岩对铀(Ⅵ)的吸附特征研究[J].四川大学学报(自然科学版),2017,54(4):815-821.DOI:10.3969/j.issn.0490-6756.2017.04.025.LAI Jie,LIU Chang,LENG Yangchun,et al.Study of adsorption characteristic uranium(Ⅵ)on clay rock[J].Journal of Sichuan University(Natural Science Edition),2017,54(4):815-821.DOI:10.3969/j.issn.0490-6756.2017.04.025.
14 Wang Z,Zachara J M,Boily J F,et al.Determining individual mineral contributions to U(Ⅵ)adsorption in a contaminated aquifer sediment:a fluorescence spectroscopy study[J].Geochimica Et Cosmochimica Acta,2011,75(10):2965-2979.DOI:10.1016/j.gca.2011.03.008.
15张虹,冷阳春,王彦惠,等.温度对U(Ⅵ)在高岭土上的吸附影响[J].核技术,2018,41(7):070302.DOI:10.11889/j.0253-3219.2018.hjs.41.070302.ZHANG Hong,LENG Yangchun,WANG Yanhui,et al.Effect of temperature on adsorption of U(Ⅵ)onto kaolin[J].Nuclear Techniques,2018,41(7):070302.DOI:10.11889/j.0253-3219.2018.hjs.41.070302.
16凌辉,唐振平,谢水波,等.铁负载膨润土对铀(Ⅵ)的吸附特性及机理研究[J].南华大学学报(自然科学版),2014,(3):26-32.DOI:10.3969/j.issn.1673-0062.2014.03.007.LING Hui,TANG Zhenping,XIE Shuibo,et al.Adsorption characteristics and mechanism of uranium by Fe-immobilized bentonite[J].Journal of University of South China(Science and Technology),2014,(3):26-32.DOI:10.3969/j.issn.1673-0062.2014.03.007.
17宋文玉,降青梅,刘亚东,等.铬(Ⅲ)离子催化铈(Ⅳ)离子氧化异丁醇的反应动力学及机理[J].河北大学学报(自然科学版),2004,24(6):594-599.DOI:10.3969/j.issn.1000-1565.2004.06.008.SONG Wenyu,JIANG Qingmei,LIU Yadong,et al.Kinetics and mechanism of chromium(III)ion catalysis cerium(IV)ions dation isobutanol[J].Journal of Hebei University(Natural Science Edition),2004,24(6):594-599.DOI:10.3969/j.issn.1000-1565.2004.06.008.
18梁诗敏,于涛.铀在高岭土上的吸附动力学及热力学研究[J].河北大学学报(自然科学版),2016,36(6):596-603.DOI:10.3969/j.issn.1000-1565.2016.06.006.LIANG Shimin,YU Tao.Kinetic and thermodynamic study of U(Ⅵ)adsorption onto kaolin[J].Journal of Hebei University(Natural Science Edition),2016,36(6):596-603.DOI:10.3969/j.issn.1000-1565.2016.06.006.
2卢嘉炜,苏伟,谢华.地质特种水泥对模拟含铀废液的静态吸附动力学研究[J].核技术,2017,40(9):090501.DOI:10.11889/j.0253-3219.2017.hjs.40.090501.LU Jiawei,SU Wei,XIE Hua.Study on static adsorption kinetics of simulated uranium-bearing wastewater by geological specialty cement[J].Nuclear Techniques,2017,40(9):090501.DOI:10.11889/j.0253-3219.2017.hjs.40.090501.
3 Olivelli M S,Curutchet G A,Sánchez R M T.Uranium uptake by montmorillonite-biomass complexes[J].Industrial&Engineering Chemistry Research,2013,52(6):2273-2279.DOI:10.1021/ie301773p.
4 Yuan L Y,Liu Y L,Shi W Q,et al.High performance of phosphonate-functionalized mesoporous silica for U(Ⅵ)sorption from aqueous solution[J].Dalton Transactions,2011,40(28):7446-7453.DOI:10.1039/C1DT10085H.
5黄彬,周佳玮.用改性膨润土吸附处理含铀(Ⅵ)废水试验研究[J].湿法冶金,2018,(2):128-134.DOI:10.13355/j.cnki.sfyj.2018.02.010.HUANG Bin,ZHOU Jiawei.Adsorption of uranium(Ⅵ)from wastewater using modified bentonite[J].Hydrometallurgy of China,2018,(2):128-134.DOI:10.13355/j.cnki.sfyj.2018.02.010.
6夏良树,谭凯旋,王晓,等.铀在榕树叶上的吸附行为及其机理分析[J].原子能科学技术,2010,44(3):278-284.XIA Liangshu,TAN Kaixuan,WANG Xiao,et al.Adsorption behavior of uranium and mechanism analysis on banyan leaves[J].Atomic Energy Science and Technology,2010,44(3):278-284.
7邓晓颖,庹先国,王勋来,等.239Pu在高庙子膨润土中的吸附特征研究[J].核技术,2012,35(9):32-36.DENG Xiaoying,TUO Xianguo,WANG Xunlai,et al.Adsorption behavior of239Pu by Gaomiaozi bentonite[J].Nuclear Techniques,2012,35(9):32-36.
8毛文静,刘峙嵘.RGO/FeOOH凝胶制备及其对铀的吸附性[J].核技术,2014,37(9):090302.DOI:10.11889/j.0253-3219.2014.hjs.37.090302.MAO Wenjing,LIU Zhirong.Preparation of RGO/FeOOH aerogels and its adsorption for U(VI)[J].Nuclear Techniques,2014,37(9):090302.DOI:10.11889/j.0253-3219.2014.hjs.37.090302.
9杜浪,李玉香,马雪,等.偶氮胂Ⅲ分光光度法测定微量铀[J].冶金分析,2015,35(1):68-71.DOI:10.13228/j.b0yuan.issn1000-7571.009388.DU Lang,LI Yuxiang,MA Xue,et al.Determination of micro uranium by arsenazoⅢspectrophotometry[J].Metallurgical Analysis,2015,35(1):68-71.DOI:10.13228/j.b0yuan.issn 1000-7571.009388.
10岳萍,庹先国,宿吉龙,等.239Pu在膨润土中的吸附和迁移实验研究[J].科学技术与工程,2014,14(8):168-171.DOI:10.3969/j.issn.1671-1815.2014.08.031.YUE Ping,TUO Xianguo,SU Jilong,et al.Application of back off diagnosis technology in downhole operation[J].Science Technology and Engineering,2014,14(8):168-171.DOI:10.3969/j.issn.1671-1815.2014.08.031.
11刘勇,李晖,张永丽,等.羟基铝柱撑蛭石的制备及其吸附磷酸根性能研究[J].四川大学学报(工程科学版),2008,40(4):80-85.LIU Yong,LI Hui,ZHANG Yongli,et al.The preparation and application of Al-pillared vermiculite in phosphate adsorption[J].Journal of Sichuan University(Engineering Science),2008,40(4):80-85.
12刘艳,易发成,王哲.膨润土对铀的吸附研究[J].非金属矿,2010,33(1):52-53.DOI:10.3969/j.issn.1000-8098.2010.01.018.LIU Yan,YI Facheng,WANG Zhe.Study on sorption of bentonite to uranium[J].Non-Metallic Mines,2010,33(1):52-53.DOI:10.3969/j.issn.1000-8098.2010.01.018.
13赖捷,刘畅,冷阳春,等.粘土岩对铀(Ⅵ)的吸附特征研究[J].四川大学学报(自然科学版),2017,54(4):815-821.DOI:10.3969/j.issn.0490-6756.2017.04.025.LAI Jie,LIU Chang,LENG Yangchun,et al.Study of adsorption characteristic uranium(Ⅵ)on clay rock[J].Journal of Sichuan University(Natural Science Edition),2017,54(4):815-821.DOI:10.3969/j.issn.0490-6756.2017.04.025.
14 Wang Z,Zachara J M,Boily J F,et al.Determining individual mineral contributions to U(Ⅵ)adsorption in a contaminated aquifer sediment:a fluorescence spectroscopy study[J].Geochimica Et Cosmochimica Acta,2011,75(10):2965-2979.DOI:10.1016/j.gca.2011.03.008.
15张虹,冷阳春,王彦惠,等.温度对U(Ⅵ)在高岭土上的吸附影响[J].核技术,2018,41(7):070302.DOI:10.11889/j.0253-3219.2018.hjs.41.070302.ZHANG Hong,LENG Yangchun,WANG Yanhui,et al.Effect of temperature on adsorption of U(Ⅵ)onto kaolin[J].Nuclear Techniques,2018,41(7):070302.DOI:10.11889/j.0253-3219.2018.hjs.41.070302.
16凌辉,唐振平,谢水波,等.铁负载膨润土对铀(Ⅵ)的吸附特性及机理研究[J].南华大学学报(自然科学版),2014,(3):26-32.DOI:10.3969/j.issn.1673-0062.2014.03.007.LING Hui,TANG Zhenping,XIE Shuibo,et al.Adsorption characteristics and mechanism of uranium by Fe-immobilized bentonite[J].Journal of University of South China(Science and Technology),2014,(3):26-32.DOI:10.3969/j.issn.1673-0062.2014.03.007.
17宋文玉,降青梅,刘亚东,等.铬(Ⅲ)离子催化铈(Ⅳ)离子氧化异丁醇的反应动力学及机理[J].河北大学学报(自然科学版),2004,24(6):594-599.DOI:10.3969/j.issn.1000-1565.2004.06.008.SONG Wenyu,JIANG Qingmei,LIU Yadong,et al.Kinetics and mechanism of chromium(III)ion catalysis cerium(IV)ions dation isobutanol[J].Journal of Hebei University(Natural Science Edition),2004,24(6):594-599.DOI:10.3969/j.issn.1000-1565.2004.06.008.
18梁诗敏,于涛.铀在高岭土上的吸附动力学及热力学研究[J].河北大学学报(自然科学版),2016,36(6):596-603.DOI:10.3969/j.issn.1000-1565.2016.06.006.LIANG Shimin,YU Tao.Kinetic and thermodynamic study of U(Ⅵ)adsorption onto kaolin[J].Journal of Hebei University(Natural Science Edition),2016,36(6):596-603.DOI:10.3969/j.issn.1000-1565.2016.06.006.