载铁活性炭的制备及其吸附水溶液中铀离子的性能
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摘要
采用液相还原法制备载铁活性炭,对负载铁前后及吸附铀离子U(VI)后的活性炭进行表征,考察了其吸附性能.结果表明,铁以球形疏散负载于活性炭的孔隙中,载铁后比表面积为10.3 m~2/g,孔容为0.0245 cm~3/g,最可几孔径为10.5 nm.吸附U(VI)过程中铁表面发生腐蚀并形成新晶体,比表面积增至16.7 m~2/g,孔容增至0.0955 cm~3/g,最可几孔径增至17.9 nm.载铁活性炭对水溶液中铀离子的吸附机理为吸附、氧化还原和沉淀.在Fe SO4?7H2O与活性炭质量比1.25/1、载铁活性炭投加量0.6 mg/m L、反应时间60 min及pH值5.00的条件下,水溶液中U(VI)的去除率最佳,达99.9%,U(VI)初始浓度和反应温度的影响较小.载铁活性炭吸附U(VI)的过程符合Freundlich(R2=0.992)和Langmuir(R2=0.943)吸附等温模型,动力学过程符合准二级动力学模型(R2=0.999),扩散速率主要由液膜扩散控制.
The Fe-loaded activated carbon was prepared by liquid-phase chemical reduction procedure. The activated carbon, Fe-loaded activated before and after adsorption uranium ion were analyzed, its absorption property to uranium ion was studied. The results showed that Fe was embedded loosely as spheres in the pores of activated carbon which had a specific surface area of 10.3 m~2/g, pore size of 0.0245 cm~3/g and pore diameter of 10.5 nm. Some erosion and new crystals on iron surface were detected after adsorption uranium ion, contributing a rise in specific surface area of 16.7 m~2/g, pore size of 0.0955 cm~3/g and pore diameter of 17.9 nm. Redox, together with adsorption and precipitate, dominant the uranium ion removal efficiency. The maximum removal rate was 99% with mass ratio of Fe SO4?7H2O to activated carbon of 1.25:1, Fe-AC concentration of 0.6 mg/m L, reaction time of 60 min, and pH value of 5.00. The uranium ion adsorption by Fe-loaded activated carbon matched Langmuir(R2=0.943) and Freundich(R2=0.992) models. The adsorption reaction could be described by a pseudo-second order kinetics equation(R2=0.999), and diffusion rate agreed with the membrane diffusion.
The Fe-loaded activated carbon was prepared by liquid-phase chemical reduction procedure. The activated carbon, Fe-loaded activated before and after adsorption uranium ion were analyzed, its absorption property to uranium ion was studied. The results showed that Fe was embedded loosely as spheres in the pores of activated carbon which had a specific surface area of 10.3 m~2/g, pore size of 0.0245 cm~3/g and pore diameter of 10.5 nm. Some erosion and new crystals on iron surface were detected after adsorption uranium ion, contributing a rise in specific surface area of 16.7 m~2/g, pore size of 0.0955 cm~3/g and pore diameter of 17.9 nm. Redox, together with adsorption and precipitate, dominant the uranium ion removal efficiency. The maximum removal rate was 99% with mass ratio of Fe SO4?7H2O to activated carbon of 1.25:1, Fe-AC concentration of 0.6 mg/m L, reaction time of 60 min, and pH value of 5.00. The uranium ion adsorption by Fe-loaded activated carbon matched Langmuir(R2=0.943) and Freundich(R2=0.992) models. The adsorption reaction could be described by a pseudo-second order kinetics equation(R2=0.999), and diffusion rate agreed with the membrane diffusion.
引文
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[31]李小燕,张明,刘义保,等.离子强度、阴阳离子和腐殖酸对纳米零价铁去除溶液中U(VI)的影响[J].中国有色金属学报,2015,25(12):3505-3512.
[32]李小燕,刘义保,张明,等.纳米零价铁去除溶液中U(VI)的还原动力学研究[J].原子能科学技术,2014,48(1):7-13.
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[35]Donia A M,Atia A A,El-Boraey H,et al.Uptake Studies of Copper(II)on Glycidyl Methacrylate Chelating Resin Containing Fe2O3 Particles[J].Sep.Purif.Technol.,2006,49(1):64-70.
[36]Yang W,Liu W,Liu H,et al.Adsorption and Correlation with Their Thermodynamic Properties of Triazine Herbicides on Soils[J].J.Environ.Sci,.2003,15(4):443-448.
[2]Bransfield S J,Cwiertny D M,Roberts A L,et al.Influence of Copper Loading and Surface Coverage on the Reactivity of Granular Iron toward 1,1,1-Trichloroethane[J].Environ.Sci.Technol.,2006,40(5):1485-1490.
[3]张巍,左军,韩晓琳,等.负载纳米零价铁/钯(ZVI/Pd)双金属活性炭去除水中三氯乙烯(TCE)的研究[J].净水技术,2013,32(1):67-73.
[4]Tseng H H,Su J G,Liang C.Synthesis of Granular Activated Carbon/Zero Valent Iron Composites for Simultaneous Adsorption/Dechlorination of Trichloroethylene[J].J.Hazard.Mater.,2011,192(2):500-506.
[5]Kakavandi B,Kalantary R R,Farzadkia M,et al.Enhanced Chromium(VI)Removal Using Activated Carbon Modified by Zero Valent Iron and Silver Bimetallic Nanoparticles[J].Iran J.Environ.Healt.,2014,12(1):1-10.
[6]王长柏,李小燕,刘义保,等.包覆型纳米零价铁去除溶液中Pb(II)-210的研究[J].辐射研究与辐射工艺学报,2014,32(3):56-60.
[7]Crane R A,Scott T.The Removal of Uranium onto Carbon-supported Nanoscale Zero-valent Iron Particles[J].J.Nat.Prod.,2014,16(12):1-13.
[8]Hu S,Yao H,Wang K,et al.Intensify Removal of Nitrobenzene from Aqueous Solution Using Nano-Zero Valent Iron/Granular Activated Carbon Composite as Fenton-like Catalyst[J].Water Air Soil.Pollut.,2015,226(5):1-13.
[9]Zhang H,Jin Z,Lu H,et al.Synthesis of Nanoscale Zero-valent Iron Supported on Exfoliated Graphite for Removal of Nitrate[J].Trans.Nonferrous Met.Soc.China,2006,16:s345-s349.
[10]Zhan J,Zheng T,Piringer G,et al.Transport Characteristics of Nanoscale Functional Zerovalent Iron/Silica Composites for in situ Remediation of Trichloroethylene[J].Environ.Sci.Technol.,2008,42(23):8871-8876.
[11]Ponder S M,Darab J G,Bucher J,et al.Surface Chemistry and Electrochemistry of Supported Zerovalent Iron Nanoparticles in the Remediation of Aqueous Metal Contaminants[J].Chem.Mater.,2001,13(2):479-486.
[12]Kim H,Hong H J,Jung J,et al.Degradation of Trichloroethylene(TCE)by Nanoscale Zero-valent Iron(n ZVI)Immobilized in Alginate Bead[J].J.Hazard.Mater.,2010,176(1):1038-1043.
[13]颜小星,柳听义,王中良.壳聚糖-纳米零价铁球去除水中二价镉的研究[J].天津师范大学学报(自然科学版),2014,34(3):42-46.
[14]Xu J,Li Y,Jing C,et al.Removal of Uranium from Aqueous Solution Using Montmorillonite-supported Nanoscale Zero-valent Iron[J].J.Radioanalm Nucl.Chem.,2014,299(1):329-336.
[15]De León M A,Sergio M,Bussi J,et al.Application of a Montmorillonite Clay Modified with Iron in Photo-Fenton Process:Comparison with Goethite and n ZVI[J].Environ.Sci.Pollut.Res.Int.,2015,22(2):864-869.
[16]Kim S A,Kamala-Kannan S,Lee K J,et al.Removal of Pb(II)from Aqueous Solution by a Zeolite–Nanoscale Zero-valent Iron Composite[J].Chem.Eng.J.,2013,217:54-60.
[17]Foo K Y,Hameed B H.Potential of Activated Carbon Adsorption Processes for the Remediation of Nuclear Effluents:A Recent Literature[J].Desalin and Water Treatment,2012,41(1/3):72-78.
[18]刘诺.负载纳米零价铁活性炭去除水中CAHs的可行性研究[D].上海:华东理工大学,2013.11.
[19]Choi H,Al-Abed S R,Agarwal S,et al.Synthesis of Reactive Nano-Fe/Pd Bimetallic System?Iimpregnated Activated Carbon for the Simultaneous Adsorption and Dechlorination of PCBs[J].Chem.Mater.,2008,20(11):3649-3655.
[20]曾淦宁,武晓,郑林,等.负载纳米零价铁铜藻基活性炭的制备及其去除水中Cr(VI)的研究[J].环境科学,2015,36(2):530-536.
[21]朱慧杰,王红强.负载型纳米铁制备条件对As(V)吸附的影响[J].生态学杂志,2011,30(9):1988-1992.
[22]唐敏康,肖爱红,许建红,等.活性炭负载亚铁离子去除水中溴酸盐研究[J].水处理技术,2015,41(5):58-62.
[23]伍秀琼.活性炭负载纳米零价铁去除溴酸盐的研究[D].长沙:湖南大学,2013.16.
[24]王琼,陈维芳,潘玲,等.纳米零价铁/活性炭复合材料去除水中六氯苯的影响因素研究[J].水资源与水工程学报,2015,26(1):91-95.
[25]王正芳.载铁活性炭的制备及对P(V)的吸附性能研究[D].南京:南京大学,2011.27-28.
[26]Wang Q,Snyder S,Kim J,et al.Aqueous Ethanol Modified Nanoscale Zerovalent Iron in Bromate Reduction:Synthesis,Characterization,and Reactivity[J].Environ.Sci.Technol.,2009,43(9):3292-3299.
[27]吴丽梅,吕国诚,廖立兵.活性炭负载纳米零价铁去除污水中六价铬的研究[J].矿物学报,2012,S1:181-182.
[28]张小毛,陈维芳,晏长成,等.液相还原和碳热法制备纳米零价铁/活性炭复合材料的比较研究[J].水资源与水工程学报,2015,26(3):129-135.
[29]肖静.载铁活性炭吸附剂的制备及除砷机理研究[D].湘潭:湘潭大学,2013.37-38.
[30]刘凤莲,刘兴荣.零价铁脱除水中六价铬的实验研究[J].环境与健康杂志,2009,26(2):139-141.
[31]李小燕,张明,刘义保,等.离子强度、阴阳离子和腐殖酸对纳米零价铁去除溶液中U(VI)的影响[J].中国有色金属学报,2015,25(12):3505-3512.
[32]李小燕,刘义保,张明,等.纳米零价铁去除溶液中U(VI)的还原动力学研究[J].原子能科学技术,2014,48(1):7-13.
[33]Freundlich H M F.Over the Adsorption in Solution[J].J.Hazard.Mater.,1906,57(25):385-471.
[34]Xu T,Liu X Q.Peanut Shell Activated Carbon:Characterization,Surface Modification and Adsorption of Pb2+from Aqueous Solution[J].Chin.J.Chem.Eng.,2008,16(3):401-406.
[35]Donia A M,Atia A A,El-Boraey H,et al.Uptake Studies of Copper(II)on Glycidyl Methacrylate Chelating Resin Containing Fe2O3 Particles[J].Sep.Purif.Technol.,2006,49(1):64-70.
[36]Yang W,Liu W,Liu H,et al.Adsorption and Correlation with Their Thermodynamic Properties of Triazine Herbicides on Soils[J].J.Environ.Sci,.2003,15(4):443-448.