两种天然矿物改性材料对模拟废水中Cd~(2+)的吸附特性
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摘要
为了提升天然非金属矿物对Cd~(2+)的吸附性能,采用MT(蒙脱石)和HP(海泡石)为前驱材料,依次通过酸纯化和SDS(十二烷基磺酸钠)改性后合成了有机非金属矿物材料,利用扫描电镜(SEM)、傅里叶变换红外光谱(FT-IR)、X射线荧光光谱分析(XRF)等手段对2种改性材料[SDS-MT(十二烷基磺酸钠改性蒙脱石)和SDS-HP(十二烷基磺酸钠改性海泡石)]吸附Cd~(2+)的机制进行探究,并对吸附过程分别进行了动力学拟合和等温吸附方程拟合.结果表明:(1)SDS-MT和SDS-HP吸附模拟废水中Cd~(2+)的效果分别比未改性的MT和HP平均提升约40%和19.5%.(2)改性过程没有改变2种前驱材料的基本结构,但引起其元素质量分数、阳离子交换量和比表面积的改变.(3)SDS-MT、SDS-HP对模拟废水中Cd~(2+)的吸附量受溶液的p H影响较大,最大吸附量分别达16.54、9.24 mg/g,2种改性材料对模拟废水中Cd~(2+)的吸附过程能较好地满足准二级动力学方程,并且其平衡传质时间较短.(4)SDS-MT对模拟废水Cd~(2+)的吸附模型较满足于Freundlich吸附等温模型,推测SDS-MT是一种有限吸附位点的吸附剂,吸附过程为单分子层吸附,而SDS-HP则较好的满足Langmuir吸附等温模型.研究显示,对2种天然非金属矿物材料的有机改性能够有效提升材料对Cd~(2+)的吸附容量,发挥材料的实际运用价值.
In order to enhance the removal of Cd from wastewater by natural non-metallic minerals,Montmorillonite(MT)and Sepiolite(HP)were used as precursors and were modified by acid purification and Sodium dodecyl sulphater(SDS).The mechanism of Cd~(2+)adsorption by the two modified materials was analyzed by SEM,FT-IR and XRF.The adsorption properties of the two modified materials were fully characterized by adsorption kinetics and adsorption isotherms.The results showed that:(1)The percentages of Cd adsorption by Sodium dodecyl sulfate modified montmorillonite(SDS-MT)and Sodium dodecyl sulfate modified sepiolite(SDS-HP)were about 40%and 19.5%,which are higher than those of the untreated minerals.(2)During the modification process,the basic structures of the two precursors were not changed,while elemental mass fraction,cation exchange capacity,and specific surface area of both modified materials were changed.(3)The sorption of Cd~(2+)by SDS-MT/SDS-HP was strongly p H dependent and the maximum adsorption capacities were 16.54and 9.24 mg/g.The kinetic process of Cd~(2+)adsorption on the SDS-MT/SDS-HP was well fitted by the pseudo-second-order kinetic model and the adsorption equilibrium time of the two materials was shorter.The Cd~(2+)adsorption on the SDS-MT could be better described by the Freundlich model,suggesting SDS-MT is a monolayer adsorption process with limited adsorption sites,whereas the sorption on SDS-HP could be better described with the Langmuir model.Therefore,the organic modification of two natural mineral montmorillonite and sepiolite can effectively improve the adsorption capacity of Cd~(2+)and exert the maximum use value of the materials.
In order to enhance the removal of Cd from wastewater by natural non-metallic minerals,Montmorillonite(MT)and Sepiolite(HP)were used as precursors and were modified by acid purification and Sodium dodecyl sulphater(SDS).The mechanism of Cd~(2+)adsorption by the two modified materials was analyzed by SEM,FT-IR and XRF.The adsorption properties of the two modified materials were fully characterized by adsorption kinetics and adsorption isotherms.The results showed that:(1)The percentages of Cd adsorption by Sodium dodecyl sulfate modified montmorillonite(SDS-MT)and Sodium dodecyl sulfate modified sepiolite(SDS-HP)were about 40%and 19.5%,which are higher than those of the untreated minerals.(2)During the modification process,the basic structures of the two precursors were not changed,while elemental mass fraction,cation exchange capacity,and specific surface area of both modified materials were changed.(3)The sorption of Cd~(2+)by SDS-MT/SDS-HP was strongly p H dependent and the maximum adsorption capacities were 16.54and 9.24 mg/g.The kinetic process of Cd~(2+)adsorption on the SDS-MT/SDS-HP was well fitted by the pseudo-second-order kinetic model and the adsorption equilibrium time of the two materials was shorter.The Cd~(2+)adsorption on the SDS-MT could be better described by the Freundlich model,suggesting SDS-MT is a monolayer adsorption process with limited adsorption sites,whereas the sorption on SDS-HP could be better described with the Langmuir model.Therefore,the organic modification of two natural mineral montmorillonite and sepiolite can effectively improve the adsorption capacity of Cd~(2+)and exert the maximum use value of the materials.
引文
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[20] YUAN P,HE H,BERGAYA F,et al.Synthesis and characterization of delaminated iron-pillared clay with meso-microporous structure[J].Microporous&Mesoporous Materials,2006,88(1/2/3):8-15.
[21] MARTINGS. BATISTA A L,SITTA B C,et al. Oscillatory instabilities during the electrocatalytic oxidaion of methanol on platinum[J]. Journal of the Brazilian Chemical Society,2008,19(4):679-687.
[22] LI S Z,WU P X. Characterization of sodium dodecyl sulfate modified iron pillared montmorillonite and its application for the removal of aqueous Cu(Ⅱ)and Co(Ⅱ)[J].Journal of Hazardous Materials,2010,173(1/2/3):62-70.
[23] IAFISCO M,MARCHETTI M,MORALES J G,et al. Silica gel template for calcium phosphates crystallization[J]. Crystal Growth&Design,2009,9(11):4912-4921.
[24]任爽,孟昭福,王腾,等.阳(阴)离子复配修饰两性磁性膨润土的表面特征差异及对苯酚吸附的影响[J].环境科学,2018,39(1):187-194.REN Shuang,MENG Zhaofu,WANG Teng,et al. Comparison of amphoteric-cationic and amphoteric-anionic modified magnetic bentonites:characterization and sorption capacity of phenol[J].Environmental Science,2018,39(1):187-194.
[25]徐应明,梁学峰,孙国红,等.酸和热处理对海泡石结构及吸附Pb2+、Cd2+性能的影响[J].环境科学,2010,31(6):1560-1567.XU Yingming,LIANG Xuefeng,SUN Guohong,et al.Effects of acid and heating treatments on the structure of sepiolite and its adsorption of lead and cadmium[J].Environmental Science,2010,31(6):1560-1567.
[26] GANGULY S,DANA K,GHATAK S. Thermogravimetric study of n-alkylammonium intercalated montmorillonites of different cation exchange capacity[J].Journal of Thermal Analysis&Calorimetry,2010,100(1):71-78.
[27] IRANI M,FAN M,ISMAIL H,et al. Modified-nanosepiolite as an inexpensive support of tetraethylenepentamine for CO2,sorption[J].Nano Energy,2015,11:235-246.
[28] BARBIER F,DUC G,PETIT-RAMELM. Adsorption of lead and cadmium ions from aqueous solution to the montmorillonite/water interface[J]. Colloids&Surfaces A:Physicochemical&Engineering Aspects,2000,166(1/2/3):153-159.
[29] LIN S H,JUANG R S.Heavy metal removal from water by sorption using surfactant-modified montmorillonite[J]. Journal of Hazardous Materials,2002,92(3):315-26.
[30] KARA M,YUZER H,SABAH E,et al. Adsorption of cobalt from aqueous solutions onto sepiolite[J].Water Research,2003,37(1):224-32.
[31] ZHAO D L,XIN Y,HUI Z,et al.Effect of environmental conditions on Pb(Ⅱ)adsorption onβ-Mn O2[J]. Chemical Engineering Journal,2010,164(1):49-55.
[32] YANG S,ZONG P,REN X,et al. Rapid and highly efficient preconcentration of Eu(Ⅲ)by core-shell structured Fe3O4@humic acid magnetic nanoparticles[J]. Acs Applied Materials&Interfaces,2012,4(12):6891-6900.
[33] YU S,ZHAI L,ZHONG S,et al. Synthesis and structural characterization of magnetite/sepiolite composite and its sorptive properties for Co(Ⅱ)and Cd(Ⅱ)[J]. Journal of the Taiwan Institute of Chemical Engineers,2016,59:221-228.
[34]罗钰,白波,王洪伦,等.Mn@海藻酸微球吸附去除盐酸四环素及其类Fenton再生[J].环境科学学报,2017,37(5):1732-1741.LUO Yu,BAI Bo,WANG Honglun,et al.Adsorption of tetracycline hydrochloride by Mn@alginate microspheres and their Fenton-like regeneration[J]. Acta Scientiae Circumstantiae,2017,37(5):1732-1741.
[35]陈利华,王欣,成家杨.硅藻类粗多糖生物剂的制备及其对Cd2+的吸附性能[J].环境科学研究,2018,31(8):1439-1449.CHEN Lihua,WANG Xin,CHENG Jiayang. Preparation of crude polysaccharide biological agent from diatom and its adsorption of cadmium ions[J]. Research of Environmental Sciences,2018,31(8):1439-1449.
[36] DADA A O. Langmuir,Freundlich,Temkin and DubininRadushkevich isotherms studies of equilibrium sorption of Zn2+unto phosphoric acid modified rice husk[J]. Iosr Journal of Applied Chemistry,2012,3(1):38-45.
[2] SATARUG S,BAKER J R,URBENJAPOLS,et al. A global perspective on cadmium pollution and toxicity in non-occupationally exposed population[J].Toxicology Letters,2003,137(1/2):65-83.
[3] MAHDAVINIA G R,RAHMANI Z,KARAMI S,et al.Magnetic/pHsensitive carrageenan/sodium alginate hydrogel nanocompo-site beads:preparation,swellingbehavior,and drug delivery[J]. Journal of Biomaterials Science Polymer Edition,2014,25(17):1891-1906.
[4] CRUZGUZMAN M,CELIS R,HERMOSIN M C,et al.Heavy metal adsorption by montmorillonites modified with natural organic cations[J].Soil Science Society of America Journal,2006,70(1):215-221.
[5] IJAGBEMI C O,MIHWA B,DONGSU K. Montmorillonite surface properties and sorption characteristics for heavy metal removal from aqueous solutions[J]. Journal of Hazardous Materials,2009,166(1):538-546.
[6] PADILLA-ORTEGA E,LEYVA-RAMOS R,MENDOZA-BARRON J,et al. Adsorption of heavy metal ions from aqueous solution onto sepiolite[J].Adsorption Science&Technology,2011,29(6):569-584.
[7] HE H,MA L,ZHU J,et al. Synthesis of organoclays:a critical review and some unresolved issues[J]. Applied Clay Science,2014,100(4):22-28.
[8] THENG B K G,CHURCHMAN G J,GATES W P,et al.Organically modified clays for pollutant uptake and environmental protection[M].Berlin,Germany:Theories and Applications,Springer-Verlag,2008:145-174.
[9] LAGALY G,OGAWA M,DEKANY I. Chapter 7. 3 clay mineral organic interactions[J]. Developments in Clay Science,2006,1(5):309-377.
[10] ZHU L,BAOLANG-CHEN A,SHEN X. Sorption of phenol,p-nitrophenol,and aniline to dual-cation organobentonites from water[J].National Journal of Andrology,2000,19(5):664-692.
[11] LIU H. Cd2+adsorption on thiol-modified montmorillonite and desorption by acid rain[J].Non-Metallic Mines,2013,36(3):69-72.
[12] GAJOWIAK A,GLADYSZ-PLASKA A,STERNIK D,et al.Sorption of uranyl ions on organosepiolite[J]. Chemical Engineering Journal,2013,219(3):459-468.
[13] HWANG Y,LEE J K,JEONG Y M,et al.Production and dispersion stability of nanoparticles in nanofluids[J]. Powder Technology,2008,186(2):145-153.
[14] AKPOMIE K G,DAWODU F A.Acid-modified montmorillonite for sorption of heavy metals from automobile effluent[J]. Beni-Suef University Journal of Basic and Applied Sciences,2016,5(1):1-12.
[15]杨林,吴平霄,刘帅,等.两性修饰蒙脱石对水中镉和四环素的吸附性能研究[J].环境科学学报,2016,36(6):2033-2042.YANG Lin,WU Pingxiao,LIU Shuai,et al. Adsorption of Cd(Ⅱ)and tetracycline by amphoteric surfactants modified montmorillonite[J].Acta Scientiae Circumstantiae,2016,36(6):2033-2042.
[16]周建兵,吴平霄,朱能武,等.十二烷基磺酸钠(SDS)改性蒙脱石对Cu2+、Cd2+的吸附研究[J].环境科学学报,2010,30(1):88-96.ZHOU Jianbing,WU Pingxiao,ZHU Nengwu,et al. Absorption of Cu2+and Cd2+by SDS-modified montmorillonite[J].Acta Scientiae Circumstantiae,2010,30(1):88-96.
[17] YU S,ZHAI L,ZHONG S,et al. Synthesis and structural characterization of magnetite/sepiolite composite and its sorptive properties for Co(Ⅱ)and Cd(Ⅱ)[J]. Journal of the Taiwan Institute of Chemical Engineers,2016,59:221-228.
[18] OZCAN A S,BILGE E,OZACAN A.Adsorption of acid blue 193from aqueous solutions onto BTMA-bentonite[J]. Colloids&Surfaces A Physicochemical&Engineering Aspects,2005,266(1):73-81.
[19] AKPOMIE K G,DAWODU F A.Efficient abstraction of nickel(Ⅱ)and manganese(Ⅱ)ions from solution onto an alkaline-modified montmorillonite[J].Journal of Taibah University for Science,2014,8(4):343-356.
[20] YUAN P,HE H,BERGAYA F,et al.Synthesis and characterization of delaminated iron-pillared clay with meso-microporous structure[J].Microporous&Mesoporous Materials,2006,88(1/2/3):8-15.
[21] MARTINGS. BATISTA A L,SITTA B C,et al. Oscillatory instabilities during the electrocatalytic oxidaion of methanol on platinum[J]. Journal of the Brazilian Chemical Society,2008,19(4):679-687.
[22] LI S Z,WU P X. Characterization of sodium dodecyl sulfate modified iron pillared montmorillonite and its application for the removal of aqueous Cu(Ⅱ)and Co(Ⅱ)[J].Journal of Hazardous Materials,2010,173(1/2/3):62-70.
[23] IAFISCO M,MARCHETTI M,MORALES J G,et al. Silica gel template for calcium phosphates crystallization[J]. Crystal Growth&Design,2009,9(11):4912-4921.
[24]任爽,孟昭福,王腾,等.阳(阴)离子复配修饰两性磁性膨润土的表面特征差异及对苯酚吸附的影响[J].环境科学,2018,39(1):187-194.REN Shuang,MENG Zhaofu,WANG Teng,et al. Comparison of amphoteric-cationic and amphoteric-anionic modified magnetic bentonites:characterization and sorption capacity of phenol[J].Environmental Science,2018,39(1):187-194.
[25]徐应明,梁学峰,孙国红,等.酸和热处理对海泡石结构及吸附Pb2+、Cd2+性能的影响[J].环境科学,2010,31(6):1560-1567.XU Yingming,LIANG Xuefeng,SUN Guohong,et al.Effects of acid and heating treatments on the structure of sepiolite and its adsorption of lead and cadmium[J].Environmental Science,2010,31(6):1560-1567.
[26] GANGULY S,DANA K,GHATAK S. Thermogravimetric study of n-alkylammonium intercalated montmorillonites of different cation exchange capacity[J].Journal of Thermal Analysis&Calorimetry,2010,100(1):71-78.
[27] IRANI M,FAN M,ISMAIL H,et al. Modified-nanosepiolite as an inexpensive support of tetraethylenepentamine for CO2,sorption[J].Nano Energy,2015,11:235-246.
[28] BARBIER F,DUC G,PETIT-RAMELM. Adsorption of lead and cadmium ions from aqueous solution to the montmorillonite/water interface[J]. Colloids&Surfaces A:Physicochemical&Engineering Aspects,2000,166(1/2/3):153-159.
[29] LIN S H,JUANG R S.Heavy metal removal from water by sorption using surfactant-modified montmorillonite[J]. Journal of Hazardous Materials,2002,92(3):315-26.
[30] KARA M,YUZER H,SABAH E,et al. Adsorption of cobalt from aqueous solutions onto sepiolite[J].Water Research,2003,37(1):224-32.
[31] ZHAO D L,XIN Y,HUI Z,et al.Effect of environmental conditions on Pb(Ⅱ)adsorption onβ-Mn O2[J]. Chemical Engineering Journal,2010,164(1):49-55.
[32] YANG S,ZONG P,REN X,et al. Rapid and highly efficient preconcentration of Eu(Ⅲ)by core-shell structured Fe3O4@humic acid magnetic nanoparticles[J]. Acs Applied Materials&Interfaces,2012,4(12):6891-6900.
[33] YU S,ZHAI L,ZHONG S,et al. Synthesis and structural characterization of magnetite/sepiolite composite and its sorptive properties for Co(Ⅱ)and Cd(Ⅱ)[J]. Journal of the Taiwan Institute of Chemical Engineers,2016,59:221-228.
[34]罗钰,白波,王洪伦,等.Mn@海藻酸微球吸附去除盐酸四环素及其类Fenton再生[J].环境科学学报,2017,37(5):1732-1741.LUO Yu,BAI Bo,WANG Honglun,et al.Adsorption of tetracycline hydrochloride by Mn@alginate microspheres and their Fenton-like regeneration[J]. Acta Scientiae Circumstantiae,2017,37(5):1732-1741.
[35]陈利华,王欣,成家杨.硅藻类粗多糖生物剂的制备及其对Cd2+的吸附性能[J].环境科学研究,2018,31(8):1439-1449.CHEN Lihua,WANG Xin,CHENG Jiayang. Preparation of crude polysaccharide biological agent from diatom and its adsorption of cadmium ions[J]. Research of Environmental Sciences,2018,31(8):1439-1449.
[36] DADA A O. Langmuir,Freundlich,Temkin and DubininRadushkevich isotherms studies of equilibrium sorption of Zn2+unto phosphoric acid modified rice husk[J]. Iosr Journal of Applied Chemistry,2012,3(1):38-45.
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