一种新型壳聚糖交联树脂的制备及对Cr(Ⅵ)吸附性能研究
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摘要
采用改进的滴加成球法合成壳聚糖树脂,用环氧氯丙烷对树脂进行交联,制备新型壳聚糖交联树脂。研究了交联树脂对Cr(VI)的吸附效果,探讨了溶液pH值、吸附时间、温度、Cr(VI)初始质量浓度等因素对吸附性能的影响及吸附热力学和动力学。结果表明,各因素中pH值对壳聚糖交联树脂吸附Cr(VI)影响较大。对初始质量浓度为120mg/L的Cr(VI)溶液,壳聚糖交联树脂投加量为1 g/L,pH=3,温度为25℃,吸附2h时可达到最大吸附容量(72mg/g)。用Langmuir等温模型和Pseudo second-order动力学模型对树脂的吸附过程进行线性拟合,R2分别为0.999 9和0.999 7,模型计算的饱和吸附容量qmax(73.53 mg/g)和平衡吸附量qe(29.23 mg/g)与试验结果(72.10 mg/g和27.73 mg/g)基本吻合。Fick扩散模型表明,树脂对Cr(VI)的吸附可分为3个阶段,说明Cr(VI)的去除是物理吸附和化学吸附共同作用的结果。
In this study,a kind of novel chitosan cross-linked resin was prepared by an improved drop-sphere-forming method.epichlorohydrin was used to cross-link the resin in enhancing its rigidity.The characterization of chitosan cross-linked resin showed that the specific surface area and the mean diameter of the pores of the resins were 1.59 m2/g and 20 nm,respectively.Besides,the average diameter of the resin particles was 0.2 mm.The adsorption of Cr(VI) onto the cross-linked chitosan has been investigated.The resin showed a higher affinity towards the uptake of Cr(VI) from the simulated wastewater,but the adsorption ability was influenced by time,pH value,temperature and the initial concentration of the solution.The results showed that the pH was the main influencing factor,and the maximum adsorption was observed at a pH value of 3.0;in addition,the temperature has also influenced the adsorption ability.The chitosan resins were added in the solution as initial concentration as 120 mg/L,at pH=3 and 25 ℃with an adsorbent dosage of 1 g/L.The system underwent an upward trend dramatically for 2 hours,and the adsorption capacity reached the highest point at 72 mg/g.Under the room temperature,the data of the equilibrium sorption experiments was fitted well with Langmuir isotherm,and the related coefficient of the model was 0.999 9.Besides,under the adsorption temperatures of 25 ℃,the experimental kinetic data were well correlated with Pseudo-second-order model,and the related coefficient of the model was 0.999 7.Fick diffusion law describes the adsorption reactions take place through 3 steps:(i) external film diffusion,(ii) intraparticle diffusion and(iii) interaction between adsorbate and active site(—NH2).The results shown the cross-linked chitosan resin could remove Cr(VI) efficiently and the removal of Cr(VI) may include both physical adsorption of Cr(VI) on the surface or inside of the resin and ion exchange between Cr(VI) and the chitosan resin.
In this study,a kind of novel chitosan cross-linked resin was prepared by an improved drop-sphere-forming method.epichlorohydrin was used to cross-link the resin in enhancing its rigidity.The characterization of chitosan cross-linked resin showed that the specific surface area and the mean diameter of the pores of the resins were 1.59 m2/g and 20 nm,respectively.Besides,the average diameter of the resin particles was 0.2 mm.The adsorption of Cr(VI) onto the cross-linked chitosan has been investigated.The resin showed a higher affinity towards the uptake of Cr(VI) from the simulated wastewater,but the adsorption ability was influenced by time,pH value,temperature and the initial concentration of the solution.The results showed that the pH was the main influencing factor,and the maximum adsorption was observed at a pH value of 3.0;in addition,the temperature has also influenced the adsorption ability.The chitosan resins were added in the solution as initial concentration as 120 mg/L,at pH=3 and 25 ℃with an adsorbent dosage of 1 g/L.The system underwent an upward trend dramatically for 2 hours,and the adsorption capacity reached the highest point at 72 mg/g.Under the room temperature,the data of the equilibrium sorption experiments was fitted well with Langmuir isotherm,and the related coefficient of the model was 0.999 9.Besides,under the adsorption temperatures of 25 ℃,the experimental kinetic data were well correlated with Pseudo-second-order model,and the related coefficient of the model was 0.999 7.Fick diffusion law describes the adsorption reactions take place through 3 steps:(i) external film diffusion,(ii) intraparticle diffusion and(iii) interaction between adsorbate and active site(—NH2).The results shown the cross-linked chitosan resin could remove Cr(VI) efficiently and the removal of Cr(VI) may include both physical adsorption of Cr(VI) on the surface or inside of the resin and ion exchange between Cr(VI) and the chitosan resin.
引文
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[10]CHEN Xiaochun(陈小春),TANG Jiapeng(汤佳鹏),CHEN Yong(陈勇),et al.Preparation,properties and application of pH/thermo-sensitive PNIPA/CS sem-i IPN hydrogel beads[J].Journal of ChemicalEngineering of Chinese Universities(高校化学工程学报),2008,22(3):538-542.
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[12]REN Hui(任慧),DING Yigang(丁一刚),WU Yuanxin(吴元欣),et al.Study on preparation method and absorb capability of cross link-age aspheric shape chitosan resin[J].New Chemical Materials(化工新型材料),2003,31(4):33-35.
[13]GB 7467—87 Water quality—determination of chromium(VI)—1,5diphenyl-carbohydrazide spectrophotometric method(水质——六价铬的测定——二苯碳酰二肼分光光度法[S].
[14]HE Xiaojin(贺小进),ZHANG Bingling(张冰凌),TAN Tianwei(谭天伟),et al.Study on adsorption properties to metal ion and physicalproperties ofbead Ni2+templated chitosan chelated resins[J].Journalof Chemical Engineering of Chinese Universities(高校化学工程学报),2001,15(1):23-28.
[15]YANG Jinqing(杨晋青),GUO Siyuan(郭祀远).Study on the struc-tural analysis and adsorption of crosslinked hydroxypropyl chitosan withCr(VI)[J].Ion Exchange and Adsorption(离子交换与吸附),2010,26(3):248-255.
[16]KYZAS G Z,KOSTOGLOU M,LAZARIDIS N K.Copper andchromium(VI)removal by chitosan derivatives—equilibrium and kinet-ic studies[J].Chemical Engineering Journal,2009,152(2/3):440-448.
[17]BABEL S,KURNIAWAN T A.Cr(VI)removal from syntheticwastewater using coconut shell charcoal and commercial activated car-bon modi?edwith oxidizing agents and/or chitosan[J].Chemosphere,2004,54(7):951-967.
[18]WANG Jinsong(王劲松),CHEN Siguang(陈思光),XU Hua(徐华),et al.Comparing the adsorption properties of chromium(VI)on-to crosslinked chitosan and impriting chitosan[J].Journal of Universityof South China:Science and Technology(南华大学学报:自然科学版),2010,24(1):74-77.
[19]LI Zengxin(李增新),WANG Guoming(王国明),WANG Tong(王彤),et al.Adsorption of chromium(VI)in the sewage with atta-pulgite-chitosan adsorbent[J].Journal of Safety and Environment(安全与环境学报),2008,8(3):52-55.
[20]ROJAS G,SILVA J,FLORES JA,et al.Adsorptionofchromium on-to cross-linked chitosan[J].Separation and Purification Technology,2005,44(1):31-36.
[21]QUAN Guixiang(全桂香),YAN Jinlong(严金龙).Kinetic model ofadsorption of chromium(VI)by chitosan[J].Leather and Chemicals(皮革与化工),2008,8(25):5-8.
[22]GUPATA K C,MAJETIN V,KUMAR R.Studies on sem-i interpene-trating polymer network beads of chitosan-poly(ethylene glycol)for thecontrolled release of drugs[J].Journal of Applied Polymer Science,2001,80(4):639-649.
[2]LIU Cunhai(刘存海),ZHU Yufeng(朱玉凤),ZHANGGuanghua(张光华).The preparation of the modified chitosan and its application intreating the electroplating chromium-containing wastewater[J].Journalof Shaanxi Normal University:Natural Science Edition(陕西师范大学学报:自然科学版),2009,37(6):47-50.
[3]XIA Qing(夏清).Study on technology conditions of treatment ofchromium-contained wastewater by chemical reduction[J].InorganicChemicals Industry(无机盐工业),2003,35(3):37-39.
[4]FANGYunru(方云如),ZHANG Zhihong(张智宏),YANG Jiannan(杨建男),et al.Treatment of wastewater containing chromium andcadmium by producing ferrite[J].Journal of Jiangsu Institute of Petro-chemical Technology(江苏石油化工学院学报),1999,11(4):8-10.
[5]LIU Yongjun.Simultaneous oxidation ofphenol and reduction ofCr(VI)induced by contact glow discharge electrolysis[J].Journal ofHazardousMaterials,2009,168(2/3):992-996.
[6]SARDOHAN T,KIR E,GULEC A,et al.Removal of Cr(III)andCr(VI)through the plasmamodified and unmodified ion-exchangemem-branes[J].Separation and PurificationTechnology,2010,74(1):14-20.
[7]ACOSTA I,RODRIGUEZ X,GUTIERREZ C,et al.Biosorption ofchromium(VI)from aqueous solutions onto fungal biomass[J].Bioinorganic Chemistry and Applications,2004,2(1/2):1-7.
[8]ZHANG Chunhua(仉春花),DONG Yuying(董玉瑛),SHI Wen(施文),et al.Preventive effects ofmembrane fouling by chitosan floccula-tion[J].Journal of Safety and Environment(安全与环境学报),2011,11(6):39-42.
[9]LI Aiyang(李爱阳),CAI Ling(蔡玲),HE Hui(贺惠).Study on theadsorption behavior of As(III)by MnO2 loaded chitosan[J].Journal ofSafety and Environment(安全与环境学报),2011,11(4):61-64.
[10]CHEN Xiaochun(陈小春),TANG Jiapeng(汤佳鹏),CHEN Yong(陈勇),et al.Preparation,properties and application of pH/thermo-sensitive PNIPA/CS sem-i IPN hydrogel beads[J].Journal of ChemicalEngineering of Chinese Universities(高校化学工程学报),2008,22(3):538-542.
[11]HE Xiaojin(贺小进),TAN Tianwei(谭天伟),QI Yizheng(戚以政),et al.Study on synthesis and adsorption properties to metal ofchitosan chelated resins[J].Ion Exchange and Adsorption(离子交换与吸附),2000,16(10):47-53.
[12]REN Hui(任慧),DING Yigang(丁一刚),WU Yuanxin(吴元欣),et al.Study on preparation method and absorb capability of cross link-age aspheric shape chitosan resin[J].New Chemical Materials(化工新型材料),2003,31(4):33-35.
[13]GB 7467—87 Water quality—determination of chromium(VI)—1,5diphenyl-carbohydrazide spectrophotometric method(水质——六价铬的测定——二苯碳酰二肼分光光度法[S].
[14]HE Xiaojin(贺小进),ZHANG Bingling(张冰凌),TAN Tianwei(谭天伟),et al.Study on adsorption properties to metal ion and physicalproperties ofbead Ni2+templated chitosan chelated resins[J].Journalof Chemical Engineering of Chinese Universities(高校化学工程学报),2001,15(1):23-28.
[15]YANG Jinqing(杨晋青),GUO Siyuan(郭祀远).Study on the struc-tural analysis and adsorption of crosslinked hydroxypropyl chitosan withCr(VI)[J].Ion Exchange and Adsorption(离子交换与吸附),2010,26(3):248-255.
[16]KYZAS G Z,KOSTOGLOU M,LAZARIDIS N K.Copper andchromium(VI)removal by chitosan derivatives—equilibrium and kinet-ic studies[J].Chemical Engineering Journal,2009,152(2/3):440-448.
[17]BABEL S,KURNIAWAN T A.Cr(VI)removal from syntheticwastewater using coconut shell charcoal and commercial activated car-bon modi?edwith oxidizing agents and/or chitosan[J].Chemosphere,2004,54(7):951-967.
[18]WANG Jinsong(王劲松),CHEN Siguang(陈思光),XU Hua(徐华),et al.Comparing the adsorption properties of chromium(VI)on-to crosslinked chitosan and impriting chitosan[J].Journal of Universityof South China:Science and Technology(南华大学学报:自然科学版),2010,24(1):74-77.
[19]LI Zengxin(李增新),WANG Guoming(王国明),WANG Tong(王彤),et al.Adsorption of chromium(VI)in the sewage with atta-pulgite-chitosan adsorbent[J].Journal of Safety and Environment(安全与环境学报),2008,8(3):52-55.
[20]ROJAS G,SILVA J,FLORES JA,et al.Adsorptionofchromium on-to cross-linked chitosan[J].Separation and Purification Technology,2005,44(1):31-36.
[21]QUAN Guixiang(全桂香),YAN Jinlong(严金龙).Kinetic model ofadsorption of chromium(VI)by chitosan[J].Leather and Chemicals(皮革与化工),2008,8(25):5-8.
[22]GUPATA K C,MAJETIN V,KUMAR R.Studies on sem-i interpene-trating polymer network beads of chitosan-poly(ethylene glycol)for thecontrolled release of drugs[J].Journal of Applied Polymer Science,2001,80(4):639-649.
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