亚铁氰化镍钾/羧甲基魔芋凝胶微球对Cs~+的吸附性能及吸附机制
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摘要
以魔芋葡苷聚糖(KGM)改性后的羧甲基魔芋葡苷聚糖(CKGM)为基体,通过溶胶-凝胶法将CKGM与亚铁氰化镍钾(KNiFC)复合后制备亚铁氰化镍钾/羧甲基魔芋凝胶微球(KNiFC/CKGM)生物质吸附剂,用于去除废水中的Cs+。从pH值、吸附时间、Cs+的初始浓度、温度及竞争离子等方面研究KNiFC/CKGM对Cs+的吸附性能,分析了其吸附动力学和热力学行为;并利用FTIR、SEM、EDX、XPS和XRD分析吸附作用机制。实验结果表明:当吸附剂用量为1g·L-1、反应温度为298.15K、初始浓度为20mg·L-1、吸附时间为18h时,该吸附剂对Cs+的去除率可达94.8%。吸附过程符合准二级动力学模型(R2=0.999)和Freundlich等温吸附模型(R2=0.985)。在288.15~328.15K范围内,KNiFC/CKGM对Cs+的吸附量与温度呈正相关,吸附过程为自发、吸热的过程。FTIR、SEM和XPS等表征结果说明,KNiFC能较好的负载于CKGM上,且在吸附实验中KNiFC/CKGM能保持完整的骨架结构;EDX和XRD结果表明,KNiFC/CKGM对Cs+吸附机制是K+与Cs+发生了离子交换。
Potassium nickel hexacyanoterrate/carboxymethyl konjac glucomannan gel microspheres(KNiFC/CKGM)biomass adsorbent was synthesized by the sol-gel method via composite with KNiFC,using CKGM as the substrate material,which was prepared by carboxymethylation modification of konjac glucomannan(KGM).The KNiFC/CKGM adsorbent was used to remove Cs+in wastewater.Batch adsorption experiments such as pH value,contact time,initial Cs+concentration,temperature and competing ions were investigated to analyze the adsorption properties of KNiFC/CKGM,and the adsorption process was studied by kinetic and thermodynamic analysis.The corresponding adsorption mechanisms were also analyzed by FTIR,SEM,EDX,XPS and XRD.Under the adsorption condition that the temperature is 298.15 K,the adsorption dosage is 1 g·L-1,adsorption time is 18 hand ini-tial Cs+concentration is 20 mg·L-1,the removal rate of the adsorbent material can reach 94.8%.The experimental results show that the adsorption data is well fitted with in line Freundlich isotherm model(R2=0.985)and pseudosecond-order kinetics model(R2=0.999).In the range of 288.15-328.15 K,there is a positive correlation between temperature and the Cs+adsorption quantity.And the adsorption progress is a spontaneous endothermic reaction.The results of FTIR,SEM and XPS demonstrate that the KNiFC is loaded well on CKGM,and KNiFC/CKGM can keep the complete structure during adsorption experiments.EDX and XRD results show that adsorption of KNiFC/CKGM to Cs+on adsorbents is mainly due to ion exchange between K+and Cs+.
Potassium nickel hexacyanoterrate/carboxymethyl konjac glucomannan gel microspheres(KNiFC/CKGM)biomass adsorbent was synthesized by the sol-gel method via composite with KNiFC,using CKGM as the substrate material,which was prepared by carboxymethylation modification of konjac glucomannan(KGM).The KNiFC/CKGM adsorbent was used to remove Cs+in wastewater.Batch adsorption experiments such as pH value,contact time,initial Cs+concentration,temperature and competing ions were investigated to analyze the adsorption properties of KNiFC/CKGM,and the adsorption process was studied by kinetic and thermodynamic analysis.The corresponding adsorption mechanisms were also analyzed by FTIR,SEM,EDX,XPS and XRD.Under the adsorption condition that the temperature is 298.15 K,the adsorption dosage is 1 g·L-1,adsorption time is 18 hand ini-tial Cs+concentration is 20 mg·L-1,the removal rate of the adsorbent material can reach 94.8%.The experimental results show that the adsorption data is well fitted with in line Freundlich isotherm model(R2=0.985)and pseudosecond-order kinetics model(R2=0.999).In the range of 288.15-328.15 K,there is a positive correlation between temperature and the Cs+adsorption quantity.And the adsorption progress is a spontaneous endothermic reaction.The results of FTIR,SEM and XPS demonstrate that the KNiFC is loaded well on CKGM,and KNiFC/CKGM can keep the complete structure during adsorption experiments.EDX and XRD results show that adsorption of KNiFC/CKGM to Cs+on adsorbents is mainly due to ion exchange between K+and Cs+.
引文
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[18]陈婧,谢水波,曾涛涛,等.羟基铁插层膨润土的制备及其对铀(Ⅵ)的吸附特性与机制[J].复合材料学报,2016,33(11):2649-2656.CHEN J,XIE S B,ZENG T T,et al.Preparation of hydroxy-Fe intercalated bentonite and its adsorption characteristics and Mechanism of uranium(Ⅵ)[J].Acta Materiae Compositae Sinica,2016,33(11):2649-2656(in Chinese).
[19]ZONG Y L,ZHANG Y D,LIN X Y,et al.Preparation of a novel microsphere adsorbent of prussian blue capsulated in carboxymethyl cellulose sodium for Cs(Ⅰ)removal from contaminated water[J].Journal of Radioanalytical and Nuclear Chemistry,2017,311(3):1577-1591.
[20]HO Y S,MCKAY G.Pseudo-second order model for sorption processes[J].Process Biochemistry,1999,34(5):451-465.
[21]张晓涛,王喜明.木质纤维素/纳米蒙脱土复合材料对废水中Cu(Ⅱ)的吸附及解吸[J].复合材料学报,2015,32(2):385-394.ZHANG X T,WANG X M.Adsorption and desorption of Cu(Ⅱ)in lignocellulose/by wastewater nano montmorillonite composites[J].Acta Materiae Compositae Sinica,2015,32(2):385-394(in Chinese).
[22]马锋锋,赵保卫,刁静茹.小麦秸秆生物炭对水中Cd2+的吸附特性研究[J].中国环境科学,2017,37(2):551-559.MA F F,ZHAO B W,DIAO J R.Adsorptive characteristics of cadmium onto biochar produced from pyrolysis of wheat straw in aqueous solution[J].China Environmental Science,2017,37(2):551-559(in Chinese).
[23]LANGMUIR I.Constitution and fundamental properties of solids and liquids:I,Solids[J].Journal of the American Chemical Society,1916,183:102-105.
[24]ADEBOWALE K O,UNUABONAH E I,OLU-OWOLABI B I.Kinetic and thermodynamic aspects of the adsorption of Pb2+and Cd2+ions on tripolyphosphate-modified kaolinite clay[J].Chemical Engineering Journal,2008,136(2):99-107.
[25]MALANDRINO M,ABOLINO O,GIACOMINO A,et al.Adsorption of heavy metals on vermiculite:Influence of pH and organic ligands[J].Journal of Colloid and Interface Science,2006,299(2):537-546.
[26]KANRAR S,DEBNATH S,DE P,et al.Preparation,characterization and evaluation of fluoride adsorption efficiency from water of iron-aluminium oxide-graphene oxide composite material[J].Chemical Engineering Journal,2016,306:269-279.
[27]刘星群,谢水波,曾凡勇,等.亚铁铝类水滑石吸附铀的性能与吸附机制[J].复合材料学报,2017,34(1):183-190.LIU X Q,XIE S B,ZENG F Y,et al.Characteristics and mechanism of uranium(Ⅵ)adsorption by Fe(Ⅱ)-Al LDH[J].Acta Materiae Compositae Sinica,2017,34(1):183-190(in Chinese).
[28]ISMAIL I,El-SOUROUGY M,MONEIM N,et al.Equilibrium and kinetic studies of the sorption of cesium by potassium nickel hexacyanoferrate complex[J].Journal of Radioanalytical and Nuclear Chemistry,1999,240(1):59-67.
[29]LIU S Q,LI H,SUN W H,et al.Photoinducedly electrochemical preparation of Prussian blue film and electrochemical modification of the film with cetyltrimethylammonium cation[J].Electrochimica Acta,2011,56(11):4007-4014.
[30]FARAH A M,SHOOTO N D,THEMA F T,et al.Fabrication of Prussian blue/multi-walled carbon nanotubes modified glassy carbon electrode for electrochemical detection of hydrogen peroxide[J].International Journal of Electrochemical Science,2012,7(5):4302-4313.
[31]沈舞婷.核应急废水处理用普鲁士蓝/碳纳米管海绵吸附材料及性能[D].南京:南京航空航天大学,2014.SHEN W T.Nuclear emergency wastewater treatment with Prussian blue/carbon nanotube sponge absorbing material and performance[D].Nanjing:Nanjing University of Aeronautics and Astronautics,2014(in Chinese).
[32]秦艳敏,王敦球,梁美娜,等.桑树杆活性炭/铁锰氧化物复合吸附剂的制备及其对Cr(Ⅵ)的吸附[J].环境化学,2016,35(4):783-792.QIN Y M,WANG D Q,LIANG M N,et al.Preparation of mulberry stem activated carbon/Fe-Mn oxide composite sorbent and its effects on the adsorption of Cr(Ⅵ)[J].Environmental Chemistry,2016,35(4):783-792(in Chinese).
[33]NAIDU G,LOGANATHAN P,JEONG S,et al.Rubidium extraction using an organic polymer encapsulated potassium copper hexacyanoferrate sorbent[J].Chemical Engineering Journal,2016,306:31-42.
[34]HU B,FUGETSU B,YU H,et al.Prussian blue caged in spongiform adsorbents using diatomite and carbon nanotubes for elimination of cesium[J].Journal of Hazardous Materials,2012,217-218:85-91.
[35]VINCENT C,HERTZ A,VINCENT T,et al.Immobilization of inorganic ion-exchanger into biopolymer foams-application to cesium sorption[J].Chemical Engineering Journal,2014,236(2):202-211.
[36]VIPIN A K,HU B,FUGETSU B.Prussian blue caged in alginate/calcium beads as adsorbents for removal of cesium ions from contaminated water[J].Journal of Hazardous Materials,2013,258-259:93-101.
[2]JANG S C,KANG S M,HALDORAI Y,et al.Synergistically strengthened 3D micro-scavenger cage adsorbent for selective removal of radioactive cesium[J].Scientific Reports,2016,6:38384.
[3]TORAD NL,HU M,IMURA M,et al.Large Cs adsorption capability of nanostructured Prussian blue particles with high accessible surface areas[J].Journal of Materials Chemistry,2012,22(35):18261-18267.
[4]DWIVEDI C,PATHAK S K,KUMAR M,et al.Potassium cobalthexacyanoferrate-gel beads for cesium removal:Kinetics and sorption studies[J].RSC Advances,2013,3(44):22102-22110.
[5]KAZEMIAN H,ZAKERI H,RABBANI M S.Cs and Sr removal from solution using potassium nickel hexacyanoferrate impregnated zeolites[J].Journal of Radioanalytical and Nuclear Chemistry,2006,268(2):231-236.
[6]BREIER C F,PIKE S M,SEBESTA F,et al.New applications of KNiFC-PAN resin for broad scale monitoring of radiocesium following the Fukushima Dai-ichi nuclear disaster[J].Journal of Radioanalytical and Nuclear Chemistry,2015,307(3):2193-2200.
[7]DU Z,JIA M,WANG X.Cesium removal from solution using PAN-based potassium nickel hexacyanoferrate(Ⅱ)composite spheres[J].Journal of Radioanalytical and Nuclear Chemistry,2013,298(1):167-177.
[8]BONDAR Y,KUZENKO S,HAN D H,et al.Development of novel nanocomposite adsorbent based on potassium nickel hexacyanoferrate-loaded polypropylene fabric[J].Nanoscale Research Letters,2014,9(1):1-6.
[9]MILONJI S,BISPO I,FEDOROFF M,et al.Sorption of cesium on copper hexacyanoferrate/polymer/silica composites in batch and dynamic conditions[J].Journal of Radioanalytical and Nuclear Chemistry,2002,252(3):497-501.
[10]RAJEC P,ORECHOVSKA J,NOVAK I.NIFSIL:A new composite sorbent for cesium[J].Journal of Radioanalytical and Nuclear Chemistry,2000,245(2):317-321.
[11]MIMURA H,KIMURA M,AKIBA K,et al.Separation of cesium and strontium by potassium nickel[J].Journal of Nuclear Science and Technology,1999,36(3):307-310.
[12]LALHRIATPUIA C,TIWARI D,LEE S M.Immobilized nickel hexacyanoferrate on activated carbons for efficient attenuation of radio toxic Cs(Ⅰ)from aqueous solutions[J].Applied Surface Science,2014,321:275-282.
[13]DING D,ZHAO Y,YANG S,et al.Adsorption of cesium from aqueous solution using agricultural residue-Walnut shell:Equilibrium,kinetic and thermodynamic modeling studies[J].Water Research,2013,47(7):2563-2571.
[14]OFOMAJA A E,PHOLOS A,NAIDOO E B.Application of raw and modified pine biomass material for cesium removal from aqueous solution[J].Ecological Engineering,2015,82:258-266.
[15]WU L P,LIN X Y,WU J,et al.Adsorption behavior of carboxymethyl konjac glucomannan microspheres for fluoride from aqueous solution[J].RSC Advances,2016,6(92):89417-89429.
[16]牛春梅,吴文辉,王著,等.羧甲基魔芋葡甘聚糖的制备及应用[J].精细化工,2006,23(8):806-808+821.NIU C M,WU W H,WANG Z,et al.Preparation and application of carboxymethyl konjac glucomannan[J].Fine Chemical Industry,2006,23(8):806-808+821(in Chinese).
[17]QING Y H,LI J,KANG B,et al.Selective sorption mechanism of Cs+on potassium nickel hexacyanoferrate(Ⅱ)compounds[J].Journal of Radioanalytical and Nuclear Chemistry,2015,304(2):527-533.
[18]陈婧,谢水波,曾涛涛,等.羟基铁插层膨润土的制备及其对铀(Ⅵ)的吸附特性与机制[J].复合材料学报,2016,33(11):2649-2656.CHEN J,XIE S B,ZENG T T,et al.Preparation of hydroxy-Fe intercalated bentonite and its adsorption characteristics and Mechanism of uranium(Ⅵ)[J].Acta Materiae Compositae Sinica,2016,33(11):2649-2656(in Chinese).
[19]ZONG Y L,ZHANG Y D,LIN X Y,et al.Preparation of a novel microsphere adsorbent of prussian blue capsulated in carboxymethyl cellulose sodium for Cs(Ⅰ)removal from contaminated water[J].Journal of Radioanalytical and Nuclear Chemistry,2017,311(3):1577-1591.
[20]HO Y S,MCKAY G.Pseudo-second order model for sorption processes[J].Process Biochemistry,1999,34(5):451-465.
[21]张晓涛,王喜明.木质纤维素/纳米蒙脱土复合材料对废水中Cu(Ⅱ)的吸附及解吸[J].复合材料学报,2015,32(2):385-394.ZHANG X T,WANG X M.Adsorption and desorption of Cu(Ⅱ)in lignocellulose/by wastewater nano montmorillonite composites[J].Acta Materiae Compositae Sinica,2015,32(2):385-394(in Chinese).
[22]马锋锋,赵保卫,刁静茹.小麦秸秆生物炭对水中Cd2+的吸附特性研究[J].中国环境科学,2017,37(2):551-559.MA F F,ZHAO B W,DIAO J R.Adsorptive characteristics of cadmium onto biochar produced from pyrolysis of wheat straw in aqueous solution[J].China Environmental Science,2017,37(2):551-559(in Chinese).
[23]LANGMUIR I.Constitution and fundamental properties of solids and liquids:I,Solids[J].Journal of the American Chemical Society,1916,183:102-105.
[24]ADEBOWALE K O,UNUABONAH E I,OLU-OWOLABI B I.Kinetic and thermodynamic aspects of the adsorption of Pb2+and Cd2+ions on tripolyphosphate-modified kaolinite clay[J].Chemical Engineering Journal,2008,136(2):99-107.
[25]MALANDRINO M,ABOLINO O,GIACOMINO A,et al.Adsorption of heavy metals on vermiculite:Influence of pH and organic ligands[J].Journal of Colloid and Interface Science,2006,299(2):537-546.
[26]KANRAR S,DEBNATH S,DE P,et al.Preparation,characterization and evaluation of fluoride adsorption efficiency from water of iron-aluminium oxide-graphene oxide composite material[J].Chemical Engineering Journal,2016,306:269-279.
[27]刘星群,谢水波,曾凡勇,等.亚铁铝类水滑石吸附铀的性能与吸附机制[J].复合材料学报,2017,34(1):183-190.LIU X Q,XIE S B,ZENG F Y,et al.Characteristics and mechanism of uranium(Ⅵ)adsorption by Fe(Ⅱ)-Al LDH[J].Acta Materiae Compositae Sinica,2017,34(1):183-190(in Chinese).
[28]ISMAIL I,El-SOUROUGY M,MONEIM N,et al.Equilibrium and kinetic studies of the sorption of cesium by potassium nickel hexacyanoferrate complex[J].Journal of Radioanalytical and Nuclear Chemistry,1999,240(1):59-67.
[29]LIU S Q,LI H,SUN W H,et al.Photoinducedly electrochemical preparation of Prussian blue film and electrochemical modification of the film with cetyltrimethylammonium cation[J].Electrochimica Acta,2011,56(11):4007-4014.
[30]FARAH A M,SHOOTO N D,THEMA F T,et al.Fabrication of Prussian blue/multi-walled carbon nanotubes modified glassy carbon electrode for electrochemical detection of hydrogen peroxide[J].International Journal of Electrochemical Science,2012,7(5):4302-4313.
[31]沈舞婷.核应急废水处理用普鲁士蓝/碳纳米管海绵吸附材料及性能[D].南京:南京航空航天大学,2014.SHEN W T.Nuclear emergency wastewater treatment with Prussian blue/carbon nanotube sponge absorbing material and performance[D].Nanjing:Nanjing University of Aeronautics and Astronautics,2014(in Chinese).
[32]秦艳敏,王敦球,梁美娜,等.桑树杆活性炭/铁锰氧化物复合吸附剂的制备及其对Cr(Ⅵ)的吸附[J].环境化学,2016,35(4):783-792.QIN Y M,WANG D Q,LIANG M N,et al.Preparation of mulberry stem activated carbon/Fe-Mn oxide composite sorbent and its effects on the adsorption of Cr(Ⅵ)[J].Environmental Chemistry,2016,35(4):783-792(in Chinese).
[33]NAIDU G,LOGANATHAN P,JEONG S,et al.Rubidium extraction using an organic polymer encapsulated potassium copper hexacyanoferrate sorbent[J].Chemical Engineering Journal,2016,306:31-42.
[34]HU B,FUGETSU B,YU H,et al.Prussian blue caged in spongiform adsorbents using diatomite and carbon nanotubes for elimination of cesium[J].Journal of Hazardous Materials,2012,217-218:85-91.
[35]VINCENT C,HERTZ A,VINCENT T,et al.Immobilization of inorganic ion-exchanger into biopolymer foams-application to cesium sorption[J].Chemical Engineering Journal,2014,236(2):202-211.
[36]VIPIN A K,HU B,FUGETSU B.Prussian blue caged in alginate/calcium beads as adsorbents for removal of cesium ions from contaminated water[J].Journal of Hazardous Materials,2013,258-259:93-101.