微晶纤维素改性制备Cu~(2+)吸附材料的研究
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摘要
以微晶纤维素为原料,通过接枝胺化反应制备一种对水体中Cu~(2+)具有较强去除能力的吸附材料,并采用FTIR、SEM、XRD和TG/DTG对其进行表征,模拟吸附水体中的重金属Cu~(2+)。结果表明:接枝聚合反应在微晶纤维素、引发剂、单体的质量比为100∶3.89∶175,反应温度为70℃、反应时间为3 h的条件下进行最佳,接枝率可达到91.44%。胺化反应在温度为60℃、时间为1 h的条件下进行,其效率可达到78.14%。微晶纤维素接枝胺化改性保留了间隙结构、降低了结晶度、提高了热稳定性。改性前后的微晶纤维素对Cu~(2+)的吸附量分别为1.50和83.07 mg·g~(-1)。微晶纤维素的接枝胺化改性改善了其与水体的可及度,增强了对Cu~(2+)的络合能力,大大提高了微晶纤维素对水体中重金属Cu~(2+)的吸附能力。
In this research,microcrystalline cellulose( MCC) was chosen as raw material,to prepare a type of adsorbent for copper ions in water. A copolymer of microcrystalline cellulose( MCC-g-PGMA) was prepared by graft polymerization of glycidyl methacrylate( GMA) with potassium persulfate( KPS) as an initiator and MCC as a substrate. This was followed by EDA which was introduced into the side chains of the MCC-g-PGMA. An adsorption experiment for copper ions in water and characterization methods of FTIR,SEM,XRD,and TG/DTG were conducted. The results showed that the optimal weight ratios of cellulose,initiator,monomer should be 100 ∶ 3.89 ∶ 175. In addition,the optimal temperature was found to be 70 ℃,the optimal reaction time was 3 h,and the graft yield could reach 91.44%. The cellulose-based adsorbent was obtained by amination modification of MCC-g-PGMA,the amination efficiency could reach 78.14% under 60 ℃ for 1 hour. The modifications of MCC maintained its gap structure,lowered its degree of crystallinity,and improved its thermal stability. Adsorption capacities of unmodified and modified MCC for copper ions in water reached 1.50 and 83.07 mg·g~(-1),respectively. This chemical modification could promote accessibility between water and MCC,strengthen its complexing capability for copper ions,and considerably improve its adsorption capability for copper ions in water.
In this research,microcrystalline cellulose( MCC) was chosen as raw material,to prepare a type of adsorbent for copper ions in water. A copolymer of microcrystalline cellulose( MCC-g-PGMA) was prepared by graft polymerization of glycidyl methacrylate( GMA) with potassium persulfate( KPS) as an initiator and MCC as a substrate. This was followed by EDA which was introduced into the side chains of the MCC-g-PGMA. An adsorption experiment for copper ions in water and characterization methods of FTIR,SEM,XRD,and TG/DTG were conducted. The results showed that the optimal weight ratios of cellulose,initiator,monomer should be 100 ∶ 3.89 ∶ 175. In addition,the optimal temperature was found to be 70 ℃,the optimal reaction time was 3 h,and the graft yield could reach 91.44%. The cellulose-based adsorbent was obtained by amination modification of MCC-g-PGMA,the amination efficiency could reach 78.14% under 60 ℃ for 1 hour. The modifications of MCC maintained its gap structure,lowered its degree of crystallinity,and improved its thermal stability. Adsorption capacities of unmodified and modified MCC for copper ions in water reached 1.50 and 83.07 mg·g~(-1),respectively. This chemical modification could promote accessibility between water and MCC,strengthen its complexing capability for copper ions,and considerably improve its adsorption capability for copper ions in water.
引文
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[10]陈培珍,刘瑞来,赵瑨云,等.丁二酸酐接枝纤维素纳米纤维膜及其重金属离子吸附[J].应用化学,2017,34(8):891-898.
[11]刘志江,李檬,肖惠宁,等.改性纤维素的制备及分光光度法对Cu2+吸附研究[J].影像科学与光化学,2017,35(3):274-280.
[12]蔡志江,张青,朱聪,等.纤维素/二氧化钛复合纳米纤维膜的制备及对Cu2+吸附性能[J].高分子材料科学与工程,2018,34(5):131-136.
[13]潘祖仁.高分子化学[M].北京:化学工业出版社,2007:60-107.
[14]石淑兰,何福望.制浆造纸分析与检测[M].北京:中国轻工业出版社,2010:283-285.
[15]SEGAL L,CREELY J J,MARTIN JR A E,et al.An empirical method for estimating the degree of crystallinity of native cellulose using the X-Ray diffractometer[J].Textile Research Journal,1959,29(10):786-794.
[16]陈秋艳,苗庆显,黄六莲.粉碎处理提高竹溶解浆的反应性能[J].森林与环境学报,2017,37(3):277-282.(:)
[2]MONIER M,AYAD D M,SARHAN A A.Adsorption of Cu(II),Hg(II),and Ni(II)ions by modified natural wool chelating fibers[J].Journal of Hazardous Materials,2010,176(1/2/3):348-355.
[3]WU F C,TSENG R L,JUANG R S.Kinetic modeling of liquid-phase adsorption of reactive dyes and metal ions on chitosan[J].Water Research,2001,35(3):613-618.
[4]ZHOU L,WANG Y,LIU Z,et al.Characteristics of equilibrium,kinetics studies for adsorption of Hg(II),Cu(II),and Ni(II)ions by thiourea-modified magnetic chitosan microspheres[J].Journal of Hazardous Materials,2009,161(2/3):995-1 002.
[5]EVANS J R,DAVIDS W G,MACRAE J D,et al.Kinetics of cadmium uptake by chitosan-based crab shells[J].Water Research,2002,36(13):3 219-3 226.
[6]RANGEL-MENDEZ J R,MONROY-ZEPEDA R,LEYVA-RAMOS E,et al.Chitosan selectivity for removing cadmium(II),copper(II),and lead(II)from aqueous phase:p H and organic matter effect[J].Journal of Hazardous Materials,2009,162(1):503-511.
[7]高鹤,梁大鑫,李坚.纤维素气凝胶材料研究进展[J].科技导报,2016,34(19):138-142.
[8]林珊,曹石林,黄六莲,等.纤维素的溶解及其成膜研究进展[J].科学技术与工程,2014,14(4):124-130.
[9]刘毅,闻海峰,彭阳,等.ADA螯合纤维素的合成及吸附性能[J].净水技术,2018,37(1):97-105.
[10]陈培珍,刘瑞来,赵瑨云,等.丁二酸酐接枝纤维素纳米纤维膜及其重金属离子吸附[J].应用化学,2017,34(8):891-898.
[11]刘志江,李檬,肖惠宁,等.改性纤维素的制备及分光光度法对Cu2+吸附研究[J].影像科学与光化学,2017,35(3):274-280.
[12]蔡志江,张青,朱聪,等.纤维素/二氧化钛复合纳米纤维膜的制备及对Cu2+吸附性能[J].高分子材料科学与工程,2018,34(5):131-136.
[13]潘祖仁.高分子化学[M].北京:化学工业出版社,2007:60-107.
[14]石淑兰,何福望.制浆造纸分析与检测[M].北京:中国轻工业出版社,2010:283-285.
[15]SEGAL L,CREELY J J,MARTIN JR A E,et al.An empirical method for estimating the degree of crystallinity of native cellulose using the X-Ray diffractometer[J].Textile Research Journal,1959,29(10):786-794.
[16]陈秋艳,苗庆显,黄六莲.粉碎处理提高竹溶解浆的反应性能[J].森林与环境学报,2017,37(3):277-282.(:)
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