CS-EGDE/Fe_3O_4凝胶微球对水中重金属离子的吸附性能及机理研究
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摘要
以壳聚糖为代表的天然生物质自身含有大量活性基团能选择性吸附重金属离子,为重金属废水的高效经济处理提供了可能.本实验以壳聚糖为基材,采用原位共沉淀法和乙二醇二缩水甘油醚(EGDE)交联法共同作用制得CS-EGDE/Fe_3O_4凝胶微球吸附剂,通过电子扫描显微镜(SEM)、透射电镜(TEM)、X射线能谱(EDS)、傅里叶红外光谱(FTIR)、饱和磁强分析(VSM)对样品进行了充分表征.通过静态吸附批实验及模拟固定床动态吸附实验,较系统的考察了凝胶微球在不同初始pH、接触时间和初始浓度下对多元重金属Pb(II)、Cu(II)、Zn(II)的吸附性能.结果表明:①CS-EGDE/Fe_3O_4凝胶微球内部孔隙发达,具有良好的超顺磁性;②吸附剂能够快速与重金属离子发生螯合反应,主要作用基团为-NH_3和-OH,且对重金属离子吸附符合准二级动力学,吸附过程可用Langmuir等温吸附方程描述,为单层化学吸附;③在多元吸附体系中发生拮抗作用,重金属竞争吸附顺序为Pb(II)>Cu(II)>Zn(II),主要是3种离子共价指数的差异导致了这一结果;④固定床在多元重金属模拟废水处理中表现出良好的去除效能,对Pb(II)、Cu(II)、Zn(II)的饱和吸附时间分别为13、8、2 h.研究显示, CS-EGDE/Fe_3O_4凝胶微球对水中重金属离子具有良好的吸附性能,有望为重金属废水处理提供一种新的研究思路和技术路线.
The natural biomass represented by chitosan contains a large number of active groups to selectively adsorb heavy metal ions, which provides a possibility for efficient and economical treatment of heavy metal wastewater. The adsorbent was prepared by a combination of in situ-coprecipitation and ethylene glycol diglycidyl ether crosslinking using chitosan as raw material. The samples were characterized by scanning electron microscopy(SEM), transmission electron microscopy(TEM), energy dispersive X-ray spectroscopy(EDS), Fourier transform infrared spectroscopy(FTIR), and vibrating sample magnetometry(VSM). The static adsorption experiments and simulated fixed bed dynamic adsorption experiments were carried out to investigate the adsorption behavior of Pb(II), Cu(II) and Zn(II) by the gel microspheres under different initial pH, contact time and initial concentrations. The results show that: ①CS-EGDE/Fe_3O_4 gel microsphere has well-developed internal porosity and good magnetic properties;②The adsorbent can rapidly chelate with heavy metal ions. The main groups are —NH_3 and —OH, and the adsorption of heavy metal ions conforms to quasi-secondary kinetics. The adsorption process can be described by Langmuir isotherm adsorption equation, which is single-layer chemical adsorption;③Antagonism occurred in the ternary adsorption system, and the competitive adsorption order of heavy metals was Pb(II)>Cu(II)>Zn(II), mainly owing to the difference in the covalent index of the three ions;④The fixed bed shows good adsorption performance in the treatment of ternary heavy metal simulated wastewater. The adsorption saturation times of heavy metal Pb(II), Cu(II), and Zn(II) were 13, 8, and 2 h, respectively. The study indicates that CS-EGDE/Fe_3O_4 gel microsphere has good adsorption performance for heavy metals and it is expected to provide a new technical route for heavy metal wastewater treatment.
The natural biomass represented by chitosan contains a large number of active groups to selectively adsorb heavy metal ions, which provides a possibility for efficient and economical treatment of heavy metal wastewater. The adsorbent was prepared by a combination of in situ-coprecipitation and ethylene glycol diglycidyl ether crosslinking using chitosan as raw material. The samples were characterized by scanning electron microscopy(SEM), transmission electron microscopy(TEM), energy dispersive X-ray spectroscopy(EDS), Fourier transform infrared spectroscopy(FTIR), and vibrating sample magnetometry(VSM). The static adsorption experiments and simulated fixed bed dynamic adsorption experiments were carried out to investigate the adsorption behavior of Pb(II), Cu(II) and Zn(II) by the gel microspheres under different initial pH, contact time and initial concentrations. The results show that: ①CS-EGDE/Fe_3O_4 gel microsphere has well-developed internal porosity and good magnetic properties;②The adsorbent can rapidly chelate with heavy metal ions. The main groups are —NH_3 and —OH, and the adsorption of heavy metal ions conforms to quasi-secondary kinetics. The adsorption process can be described by Langmuir isotherm adsorption equation, which is single-layer chemical adsorption;③Antagonism occurred in the ternary adsorption system, and the competitive adsorption order of heavy metals was Pb(II)>Cu(II)>Zn(II), mainly owing to the difference in the covalent index of the three ions;④The fixed bed shows good adsorption performance in the treatment of ternary heavy metal simulated wastewater. The adsorption saturation times of heavy metal Pb(II), Cu(II), and Zn(II) were 13, 8, and 2 h, respectively. The study indicates that CS-EGDE/Fe_3O_4 gel microsphere has good adsorption performance for heavy metals and it is expected to provide a new technical route for heavy metal wastewater treatment.
引文
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Kong J J,Gu R,Yuan J N,et al.2018.Adsorption behavior of Ni(II) onto activated carbons from hide waste and high-pressure steaming hide waste[J],Ecotoxicology and Environmental Safety,156:294-300
刘晨.2017.生物质基聚合物功能材料的组装及吸附性能研究[D].北京:中国地质大学.
李建军,鲍旭,吴先锋,等.2017.磁性壳聚糖复合微球的制备及其Cu2+吸附性能[J].无机化学学报,33(3):383-388
梁莎,冯宁川,郭学益.2009.生物吸附法处理重金属废水研究进展[J].水处理技术,35(3):13-17
林霞,陈培丰,黄风华,等.2010.SiO2表面包覆对Fe3O4磁性微球性能的影响[J].合成化学,18(4):507-510
李一民,廖建和,赵艳芳,等.2011.微波辐射凝固天然橡胶的性能研究[J].弹性体,21(6):29-33
林志艳,陈亮,陈东辉.2003.壳聚糖分子量与絮凝剂投加量的关系模型[J].环境科学研究,5:45-47
Ma H,Pu S Y,Hou Y Q,et al.2018.A highly efficient magnetic chitosan "fluid" adsorbent with a high capacity and fast adsorption kinetics for dyeing wastewater purification[J].Chemical Engineering Journal,345:556-565
Ma H,Pu S Y,Ma J,et al.2018.Formation of multi-layered chitosan honeycomb spheres via breath-figure-like approach in combination with co-precipitation processing[J].Materials Letters,211:91-95
Pu S Y,Ma H,Zinchenko A,et al.2017.Novel highly porous magnetic hydrogel beads composed of chitosan and sodium citrate:an effective adsorbent for the removal of heavy metals from aqueous solutions[J].Environmental Science and Pollution Research,24:16520-16530
Ribeiro C,Scheufele F B,Espinoza-Quinones F R.et al.2018.A comprehensive evaluation of heavy metals removal from battery industry wastewaters by applying bio-residue,mineral and commercial adsorbent materials[J].Journal of Materials Science,53:7976-7995
Reddy D H K,Lee S M.2013.Application of magnetic chitosan composites for the removal of toxic metal and dyes from aqueous solutions[J].Advances in Colloid and Interface Science,201:68-93
Rosique M,Angosto J M,Guibal E,et al.2016.Fernandez-lopez,factorial design methodological approach for enhanced cadmium ions bioremoval by opuntia biomass[J].Clean-Soil Air Water,44:959-966
Rio S,Delebarre A.2003.Removal of mercury in aqueous solution by fluidized bed plant fly ash[J].Fuel,82(2):153-159
施晓文,杜予民,覃采芹,等.2003.交联羧甲基壳聚糖微球的制备及其对Pb2+的吸附性能[J].应用化学,20(8):715-718
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Wang Q,Wang B,Lee X Q,et al.2018.Sorption and desorption of Pb(II) to biochar as affected by oxidation and pH[J].The Science of the total environment,634:188-194
王帅.2017.磁性壳聚糖微球吸附剂的制备及对水中重金属离子去除性能[D].郑州:华北水利水电大学
万仲豪,李孟,张倩.2018.间苯二胺改性磁性壳聚糖对六价铬的还原-吸附协同作用机制研究[J].环境科学学报,38(8):3118-3126
王泽红,陶士杰,于福家,等.2012.天然沸石的改性及其吸附Pb2+,Cu2+的研究[J].东北大学学报(自然科学版),33(11):1637-1640
邢云,李素娟,李步海.2014.交联壳聚糖对常见金属离子的吸附性能及机理探讨[J].冶金分析,34(9):58-65
俞洁,郑继东,陆泉芳,等.2017.壳聚糖/聚乙二醇/丙烯酸吸附剂对Cu2+、Co2+和Ni2+的吸附选择性和重复利用性[J].环境科学学报,37(3):1003-1012
杨虎城,龚继来,曾光明.2017.掺杂聚乙烯醇的壳聚糖小球对铜离子-腐殖酸的单一和连续吸附行为[J].环境科学学报,37(10):3735-3745
余宙,仵彦卿,刘预.2009.新型交联壳聚糖材料对地下水重金属Zn2+的吸附性能[J].生态环境学报,18(6):2102-2107
Zhang C M,Duan N,Jiang L H,et al.2018.Influence of Mn2+ ions on the corrosion mechanism of lead-based anodes and the generation of heavy metal anode slime in zinc sulfate electrolyte[J].Environmental Science and Pollution Research International,25:11958-11969
张淑琴,童仕唐.2008.活性炭对重金属离子铅镉铜的吸附研究[J].环境科学与管理,33(4):91-94
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朱再盛,罗三来,钟娜,等.2008.交联壳聚糖对Zn2+的吸附性能[J].应用化学,25(5):617-621
Bhattacharya A,Naik S N,Khare S K.2018.Harnessing the bio-mineralization ability of urease producing Serratia marcescens and Enterobacter cloacae EMB19 for remediation of heavy metal cadmium (II)[J].Journal of Environmental Management,215:143-152
Bailey S E,Olin T J,Bricka R M,et al.1999.A review of potentially low-cost sorbents for heavy metals[J].Water Research,33(11):2469-2479
Chen C H,Lin Y S,Wu S J,et al.2018.Mutlifunctional nanoparticles prepared from arginine-modified chitosan and thiolated fucoidan for oral delivery of hydrophobic and hydrophilic drugs[J].Carbohydrate Polymers,193:163-172
Chen C,Wang J.2007.Influence of metal ionic characteristics on their biosorption capacity bySaccharomyces cerevisiae[J].Applied Microbiology and Biotechnology,74(4):911-917
Luk C J,Yip J,Yuen C M,et al.2014.A comprehensive study on adsorption behaviourof direct,reactive and acid dyes on crosslinked and non-crosslinked chitosan beads[J].Journal of Fiber Bioengineering and Informatics,7 (1) 35-52
Chen M,Shafer-Peltier K,Randtke S J.et al.2018.Competitive association of cations with poly(sodium 4-styrenesulfonate) (PSS) and heavy metal removal from water by PSS-assisted ultrafiltration[J].Chemical Engineering Journal,344:155-164
Chang Y C,Chen D H.2005.Preparation and adsorption properties of monodisperse chitosan-bound Fe3O4 magnetic nanoparticles for removal of Cu(II) ions[J].Journal of Colloid & Interface Science,283(2):446-451
陈志军,彭凯,路文忠,等.2006.Fe3O4/聚合物磁性高分子微球的制备[J].材料导报,20(s2):198-200
曹佐英,张启修,赖声礼.2001.微波辐射下模板法乙二醇双缩水甘油醚交联壳聚糖树脂的制备及吸附性能的研究[J].湿法冶金,20(4)
丁述理,孙晨光.2006.膨润土吸附水中Cr(Ⅵ)的影响因素研究[J] 非金属矿,29(3):45-48
丁纯梅,宋庆平,孔霞,等.2004.壳聚糖/Pb(Ⅱ)模板壳聚糖膜与Pb(Ⅱ)螯合反应的动力学及机理探讨[J].无机化学学报,20(6):711-714
Nieboer E,Richardson D H S.1980.The replacement of the nodescript term ‘heavy metals’ by a biologically and chemicall significant classification of metal ions[J].Environmental Pollution Series B,Chemical and Physical 1(1):3-26
Fu F L,Wang Q.2011.Removal of heavy metal ions from wastewaters:a review[J].Journal of Environmental Management,92(3):407-418
郭晶,李利强,黄代中,等.2016.洞庭湖表层水和底泥中重金属污染状况及其变化趋势[J].环境科学研究,29(1):44-51
王宇,高建峰,胡拖平,等.2016.乙二醇双缩水甘油醚交联壳聚糖印迹材料对稀土中 Cu(Ⅱ)的选择性吸附[J].材料导报,30(4):29-32
黄鸽,姜霞,完颜华,等.2012.不同稳定剂对污染沉积物中重金属的稳定效果[J].环境科学研究,25(5):563-567
解春雨.2018.功能性材料对铀的吸附行为及机制研究[D].上海:中国科学院大学(中国科学院上海应用物理研究所).
季君晖.2000.Cu2+—壳聚糖螯合物及壳聚糖吸附Cu2+机理的XPS研究[J].应用化学,1:115-116
Jacob J M,Karthik C,Saratale R G,et al.2018.Biological approaches to tackle heavy metal pollution:A survey of literature[J].Journal of Environmental Management,217:56-70
Jó wiak,Tomasz,Filipkowska U,Szymczyk P,et al.2017.Effect of ionic and covalent crosslinking agents on properties of chitosan beads and sorption effectiveness of Reactive Black 5 dye[J].Reactive and Functional Polymers,114:58-74
Kong J J,Gu R,Yuan J N,et al.2018.Adsorption behavior of Ni(II) onto activated carbons from hide waste and high-pressure steaming hide waste[J],Ecotoxicology and Environmental Safety,156:294-300
刘晨.2017.生物质基聚合物功能材料的组装及吸附性能研究[D].北京:中国地质大学.
李建军,鲍旭,吴先锋,等.2017.磁性壳聚糖复合微球的制备及其Cu2+吸附性能[J].无机化学学报,33(3):383-388
梁莎,冯宁川,郭学益.2009.生物吸附法处理重金属废水研究进展[J].水处理技术,35(3):13-17
林霞,陈培丰,黄风华,等.2010.SiO2表面包覆对Fe3O4磁性微球性能的影响[J].合成化学,18(4):507-510
李一民,廖建和,赵艳芳,等.2011.微波辐射凝固天然橡胶的性能研究[J].弹性体,21(6):29-33
林志艳,陈亮,陈东辉.2003.壳聚糖分子量与絮凝剂投加量的关系模型[J].环境科学研究,5:45-47
Ma H,Pu S Y,Hou Y Q,et al.2018.A highly efficient magnetic chitosan "fluid" adsorbent with a high capacity and fast adsorption kinetics for dyeing wastewater purification[J].Chemical Engineering Journal,345:556-565
Ma H,Pu S Y,Ma J,et al.2018.Formation of multi-layered chitosan honeycomb spheres via breath-figure-like approach in combination with co-precipitation processing[J].Materials Letters,211:91-95
Pu S Y,Ma H,Zinchenko A,et al.2017.Novel highly porous magnetic hydrogel beads composed of chitosan and sodium citrate:an effective adsorbent for the removal of heavy metals from aqueous solutions[J].Environmental Science and Pollution Research,24:16520-16530
Ribeiro C,Scheufele F B,Espinoza-Quinones F R.et al.2018.A comprehensive evaluation of heavy metals removal from battery industry wastewaters by applying bio-residue,mineral and commercial adsorbent materials[J].Journal of Materials Science,53:7976-7995
Reddy D H K,Lee S M.2013.Application of magnetic chitosan composites for the removal of toxic metal and dyes from aqueous solutions[J].Advances in Colloid and Interface Science,201:68-93
Rosique M,Angosto J M,Guibal E,et al.2016.Fernandez-lopez,factorial design methodological approach for enhanced cadmium ions bioremoval by opuntia biomass[J].Clean-Soil Air Water,44:959-966
Rio S,Delebarre A.2003.Removal of mercury in aqueous solution by fluidized bed plant fly ash[J].Fuel,82(2):153-159
施晓文,杜予民,覃采芹,等.2003.交联羧甲基壳聚糖微球的制备及其对Pb2+的吸附性能[J].应用化学,20(8):715-718
王建龙,陈灿.2010.生物吸附法去除重金属离子的研究进展[J].环境科学学报,30(4):673-701
Wang Q,Wang B,Lee X Q,et al.2018.Sorption and desorption of Pb(II) to biochar as affected by oxidation and pH[J].The Science of the total environment,634:188-194
王帅.2017.磁性壳聚糖微球吸附剂的制备及对水中重金属离子去除性能[D].郑州:华北水利水电大学
万仲豪,李孟,张倩.2018.间苯二胺改性磁性壳聚糖对六价铬的还原-吸附协同作用机制研究[J].环境科学学报,38(8):3118-3126
王泽红,陶士杰,于福家,等.2012.天然沸石的改性及其吸附Pb2+,Cu2+的研究[J].东北大学学报(自然科学版),33(11):1637-1640
邢云,李素娟,李步海.2014.交联壳聚糖对常见金属离子的吸附性能及机理探讨[J].冶金分析,34(9):58-65
俞洁,郑继东,陆泉芳,等.2017.壳聚糖/聚乙二醇/丙烯酸吸附剂对Cu2+、Co2+和Ni2+的吸附选择性和重复利用性[J].环境科学学报,37(3):1003-1012
杨虎城,龚继来,曾光明.2017.掺杂聚乙烯醇的壳聚糖小球对铜离子-腐殖酸的单一和连续吸附行为[J].环境科学学报,37(10):3735-3745
余宙,仵彦卿,刘预.2009.新型交联壳聚糖材料对地下水重金属Zn2+的吸附性能[J].生态环境学报,18(6):2102-2107
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