γ-环糊精固载淀粉的制备及其对废水中染料去除性能研究
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摘要
以环氧氯丙烷为交联剂,将功能主体分子γ-环糊精引入淀粉中,合成了γ-环糊精固载淀粉CS-γCD。通过单因素实验优化了反应条件。采用红外/拉曼光谱(IR/RAM)、扫描电镜(SEM)和X射线衍射谱(XRD)表征了产物结构。考察了CS-γCD对亚甲基蓝、甲基紫及刚果红3种不同结构染料的吸附性,对模拟混合染料废水的脱色性能,及其材料自身的降解性能。结果表明,CS-γCD对各染料的吸附量不仅较其他吸附材料显著提高,并对不同结构种类的染料具有了更为广泛的吸附能力,其对混合染料废水的脱色率接近90%。CS-γCD可被酶降解,但降解速率较天然淀粉缓慢,稳定性有所提高,使用寿命相对延长,更利于其在污水处理方面的推广应用。
Theγ-cyclodextrin immobilized starch(CS-γCD)was synthesized by introducing host functional moleculeγ-Cyclodextrin into starch in the presence of epichlorohydrin.The reaction conditions were optimized by single factor experiments.The structures of the products were characterized by infrared spectrum/raman spectroscopy(IR/RAM),scanning electron microscope(SEM),X-ray diffraction(XRD).The adsorption of CS-γCD on dyes with three different structuring forms including methylene blue,methyl purple and congo red,and its decolorizing performance on simulate mixed dye waste water were studied,as well as the degradation property.The results showed that,compared with other adsorbents,CS-γCD not only had a significant improved dyestuff adsorption quantity,but also had a broader adsorbing capacity for dyes with different structures.Its decolorization rate on mixed dye waste-water was close to 90%.CS-γCD could be enzymatic degraded,while its degradation speed was much lower then native starch,showed CS-γCD had relatively higher stability and longer useful life,which could be beneficial for its popularization and application in dyestuff waste-water treatment field.
Theγ-cyclodextrin immobilized starch(CS-γCD)was synthesized by introducing host functional moleculeγ-Cyclodextrin into starch in the presence of epichlorohydrin.The reaction conditions were optimized by single factor experiments.The structures of the products were characterized by infrared spectrum/raman spectroscopy(IR/RAM),scanning electron microscope(SEM),X-ray diffraction(XRD).The adsorption of CS-γCD on dyes with three different structuring forms including methylene blue,methyl purple and congo red,and its decolorizing performance on simulate mixed dye waste water were studied,as well as the degradation property.The results showed that,compared with other adsorbents,CS-γCD not only had a significant improved dyestuff adsorption quantity,but also had a broader adsorbing capacity for dyes with different structures.Its decolorization rate on mixed dye waste-water was close to 90%.CS-γCD could be enzymatic degraded,while its degradation speed was much lower then native starch,showed CS-γCD had relatively higher stability and longer useful life,which could be beneficial for its popularization and application in dyestuff waste-water treatment field.
引文
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[29]Hu R,Lin L,Liu T,et al.Reducing sugar content in hemicellulose hydrolysate by dns method:a revisit[J].Journal of Biobased Materials &Bioenergy,2008,2(2):156-161.
[2]Gil A,Assis F C C,Albeniz S,et al.Removal of dyes from wastewaters by adsorption on pillared clays[J].Chemical Engineering Journal,2011,168(3):1032-1040.
[3]俞洁,庞二牛,陆泉芳,等.蛭石/聚乙二醇/丙烯酸水凝胶对阳离子染料的吸附研究[J].化工新型材料,2014(12):139-142.
[4]刘宏波,陈渊,郑鹏鹏,等.带氨基磁性微球的制备及其对活性艳兰KN-R吸附行为[J].化工新型材料,2012,40(1):101-104.
[5]Ngah W S W,Teong L C,Hanafiah M A K M.Adsorption of dyes and heavy metal ions by chitosan composites:a review[J].Carbohydrate Polymers,2011,83(4):1446-1456.
[6]Dotto G L,Pinto L A A.Adsorption of food dyes onto chitosan:optimization process and kinetic[J].Carbohydrate Polymers,2011,84(1):231-238.
[7]Juang R,Tseng R,Wu F,et al.Adsorption behavior of reactive dyes from aqueous solutions on chitosan[J].Journal of Chemical Technology &Biotechnology Biotechnology,2010,70(4):391-399.
[8]张庆乐,王丽平,李业云,等.杨树叶干粉吸附结晶紫染料的响应曲面法研究[J].化工新型材料,2016(10):194-197.
[9]沈海民,纪红兵,武宏科,等β.-环糊精的固载及其应用最新研究进展[J].有机化学,2014,34(8):1549-1572.
[10]López-De-Dicastillo C,Gallur M,CataláR,et al.Immobilization ofβ-cyclodextrin in ethylene-vinyl alcohol copolymer for active food packaging applications[J].Journal of Membrane Science,2010,353(1):184-191.
[11]Yi Y,Wang Y,Zhang W.Synthesis of a new chitosan immobilized withβ-cyclodextrins and its adsorption properties for bilubin[J].Journal of Applied Polymer Science,2006,99(3):1264-1268.
[12]Sulaiman S,Cieh N L,Mokhtar M N,et al.Covalent immobilization of cyclodextrin glucanotranferase on kenaf cellulose nanofiber and its application in ultrafiltration membrane system[J].Process Biochemistry,2017,55:85-95.
[13]Lu D D,Yang L Q,Zhou T H,et al.Synthesis,characterization and properties of biodegradable polylactic acid-β-cyclodextrin cross-linked copolymer microgels[J].European Polymer Journal,2008,44(7):2140-2145.
[14]Liu B,Li H,Xu X,et al.Optimized synthesis and crystalline stability ofγ-cyclodextrin metal-organic frameworks for drug adsorption[J].International Journal of Pharmaceutics,2016,514(1):212.
[15]Zhao D,Zhao L,Zhu C S,et al.Comparative study of polymer containing beta-cyclodextrin and—COOH for adsorption toward aniline,1-naphthylamine and methylene blue[J].Journal of Hazardous Materials,2009,171(1-3):241.
[16]Liu H,Zheng-Biao G U,Hong Y,et al.Hyperchromic spectrophotometric determination ofγ-cyclodextrin with bromocresol green[J].Journal of Food Science &Biotechnology,2009.
[17]康琪.模拟染料废水化学絮凝法脱色的过程分析方法研究[D].济南:山东大学,2006.
[18]Emami Meybodi Z,Imani M,Atai M.Kinetics of dextran crosslinking by epichlorohydrin:a rheometry and equilibrium swelling study[J].Carbohydr Polym,2013,92(2):1792-1798.
[19]李铭慧,郭明,高兴军,等.玉米淀粉接枝顺丁烯二酸酐高分子吸水树脂的制备和保水性能研究[J].化工新型材料,2012,40(12):147-149.
[20]高和军.多孔阳离子淀粉的制备与应用[J].化工新型材料,2013,41(12):168-170.
[21]高和军,付洪权,胡星琪,等.疏水性阳离子淀粉的制备与应用[J].高分子材料科学与工程,2011,27(9):164-167.
[22]Zhang H,Wang J K,Liu W J,et al.Microwave-assisted synthesis,characterization,and textile sizing property of carboxymethyl corn starch[J].Fibers &Polymers,2015,16(11):2308-2317.
[23]王秀艳,董丽松.变性淀粉结晶性和形态研究[J].中国粮油学报,2005,20(3):26-29.
[24]矫娜,王东升,段晋明,等.改性硅藻土对三种有机染料的吸附作用研究[J].环境科学学报,2012,32(6):1364-1369.
[25]Kalkan E.Experimental study to remediate acid fuchsin dye using laccase-modified zeolite from aqueous solutions[J].Polish Journal of Envonmental Studies,2015,24:115-124.
[26]贺君,杨耕耘,陈国忠,等.改性沸石去除染料废水中性红的研究[J].燕山大学学报,2015,39(1):68-72.
[27]Shen H M,Zhu G Y,Yu W B,et al.Surface immobilization ofβ-cyclodextrin on hybrid silica and its fast-adsorption performance to p-nitrophenol from aqueous phase[J].Rsc Advances,2015,5(103):84410-84422.
[28]董晓蕾,李莉,陈晴川,等β.-环糊精聚合物的合成及其对苯酚的选择性吸附研究[J].化工新型材料,2012,40(10):86-89.
[29]Hu R,Lin L,Liu T,et al.Reducing sugar content in hemicellulose hydrolysate by dns method:a revisit[J].Journal of Biobased Materials &Bioenergy,2008,2(2):156-161.
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