羊栖菜干藻作为生物吸附剂用于去除电镀废水中的重金属
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摘要
藻类作为一种生物吸附剂用于去除水溶液中单种重金属离子,具有较好的效果,但对共存的多种金属离子去除则相对复杂。本实验利用碱预处理后的羊栖菜藻粉作为海藻吸附剂,研究了不同环境条件对其去除电镀废水中重金属离子[Zn(Ⅱ)、Cu(Ⅱ)、Cr(Ⅵ)和Ni(Ⅱ)]的影响,并通过电镜观察和红外光谱分析其对重金属离子的吸附机理。结果发现,pH 2时Cr(Ⅵ)去除率最高,在pH 6~9时,Cu(Ⅱ)、Zn(Ⅱ)和Ni(Ⅱ)的去除率较高。海藻吸附剂在低剂量(2~4 g/L)投加时,4种重金属的去除率均有不同程度的增加,大于4 g/L时,去除率不再增加。Zn(Ⅱ)和Ni(Ⅱ)的吸附在25 min左右达到平衡,Cr(Ⅵ)和Cu(Ⅱ)稍慢;温度对海藻吸附剂去除Cu(Ⅱ)、Zn(Ⅱ)、Cr(Ⅵ)和Ni(Ⅱ)的影响并不明显。Langmuir模型能更好地描述海藻吸附剂对4种重金属离子的吸附行为,表明它们属于单分子层吸附,海藻吸附剂对Cr(Ⅵ)和Ni(Ⅱ)的最大吸附容量明显高于Cu(Ⅱ)和Zn(Ⅱ)。准二级吸附动力学方程能更好地描述吸附过程,说明吸附方式以化学吸附为主。吸附前后海藻吸附剂的红外光谱分析表明,对重金属的生物吸附主要与羧基有关。研究表明,海藻吸附剂对电镀废水中Cu(Ⅱ)、Zn(Ⅱ)、Cr(Ⅵ)和Ni(Ⅱ)都具有一定的去除效果。
Algal bioadsorbents can effectively remove the single heavy metal ion in aqueous solution, but the removal mechanism of coexisting multiple metal ions was relatively complicated. In this paper, Sargassum fusiforme biomass, pretreated by NaOH, was used to remove heavy metal ions [Cu(Ⅱ), Zn(Ⅱ), Cr(Ⅵ) and Ni(Ⅱ)] in the electroplating wastewater, and the effects of pH, temperature, contact time and biomass doses on the removal efficiency and its adsorption mechanism were investigated. The results showed that the optimum pH in the removal efficiency of Cu(Ⅱ), Zn(Ⅱ) and Ni(Ⅱ) was among 6–9, while for Cr(Ⅵ), it was 2. The removal efficiency increased when biomass doses were elevated from 2 to 4 g/L, but it maintained constant when the biomass doses were higher than 4 g/L. The adsorption equilibrium of Zn(Ⅱ) and Ni(Ⅱ) was reached at about 25 min while for Cr(Ⅵ) and Cu(Ⅱ), it was slightly slow. The influence of temperature on adsorption of heavy metal ions was not obvious. Langmuir model can closely describe the adsorption of heavy metal ions, which indicated the absorption was the monolayer adsorption. The maximum adsorption capacity for Cr(Ⅵ) and Ni(Ⅱ) was significantly higher than that for Cu(Ⅱ) and Zn(Ⅱ). The adsorption kinetic can be described by the pseudo-second order kinetic model,indicating that the adsorption process was mainly chemical adsorption. Fourier transform infrared spectroscopy analysis of the adsorbent before and after adsorption showed that the bioabsorption of heavy metals was mainly related to carboxyl group. The results suggested that the algal adsorbent could effectively remove the heavy metal ions in electroplating wastewater and exhibit a good application prospect.
Algal bioadsorbents can effectively remove the single heavy metal ion in aqueous solution, but the removal mechanism of coexisting multiple metal ions was relatively complicated. In this paper, Sargassum fusiforme biomass, pretreated by NaOH, was used to remove heavy metal ions [Cu(Ⅱ), Zn(Ⅱ), Cr(Ⅵ) and Ni(Ⅱ)] in the electroplating wastewater, and the effects of pH, temperature, contact time and biomass doses on the removal efficiency and its adsorption mechanism were investigated. The results showed that the optimum pH in the removal efficiency of Cu(Ⅱ), Zn(Ⅱ) and Ni(Ⅱ) was among 6–9, while for Cr(Ⅵ), it was 2. The removal efficiency increased when biomass doses were elevated from 2 to 4 g/L, but it maintained constant when the biomass doses were higher than 4 g/L. The adsorption equilibrium of Zn(Ⅱ) and Ni(Ⅱ) was reached at about 25 min while for Cr(Ⅵ) and Cu(Ⅱ), it was slightly slow. The influence of temperature on adsorption of heavy metal ions was not obvious. Langmuir model can closely describe the adsorption of heavy metal ions, which indicated the absorption was the monolayer adsorption. The maximum adsorption capacity for Cr(Ⅵ) and Ni(Ⅱ) was significantly higher than that for Cu(Ⅱ) and Zn(Ⅱ). The adsorption kinetic can be described by the pseudo-second order kinetic model,indicating that the adsorption process was mainly chemical adsorption. Fourier transform infrared spectroscopy analysis of the adsorbent before and after adsorption showed that the bioabsorption of heavy metals was mainly related to carboxyl group. The results suggested that the algal adsorbent could effectively remove the heavy metal ions in electroplating wastewater and exhibit a good application prospect.
引文
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[22]Zou H X,Li N,Wang L H,et al.Equilibrium and kinetic studies of Cd2+biosorption by the brown algae Sargassum fusiforme[J].PLoS ONE,2014,9(4):e95242.
[23]Salem N M,Awwad A M.Biosorption of Ni(Ⅱ)from electroplating wastewater by modified(Eriobotrya japonica)loquat bark[J].Journal of Saudi Chemical Society,2014,18(5):379-386.
[24]Shahverdi F,Ahmadi M,Avazmoghadam S,et al.Comparative study of the kinetics and equilibrium of nickel(II)biosorption from aqueous solutions by free and immobilized biomass of Aspergillus awamori[J].Environmental Progress&Sustainable Energy,2015,34(5):1356-1364.
[25]Kumar K V.Linear and non-linear regression analysis for the sorption kinetics of methylene blue onto activated carbon[J].Journal of Hazardous Materials,2006,137(3):1538-1544.
[26]Padmavathy V,Vasudevan P,Dhingra S C.Biosorption of nickel(II)ions on Baker's yeast[J].Process Biochemistry,2003,38(10):1389-1395.
[27]Yang L,Chen J P.Biosorption of hexavalent chromium onto raw and chemically modified Sargassum sp.[J].Bioresource Technology,2008,99(2):297-307.
[28]张继义,梁丽萍,蒲丽君,等.小麦秸秆对Cr(Ⅵ)的吸附特性及动力学、热力学分析[J].环境科学研究,2010,23(12):1546-1552.Zhang J Y,Liang L P,Pu L J,et al.Adsorption characteristics of Cr(VI)by wheat straw including kinetic and thermodynamics analysis[J].Research of Environmental Sciences,2010,23(12):1546-1552(in Chinese).
[29]董彩娥.三种褐藻对重金属Cu2+、Zn2+、Cr3+、Ni2+的吸附研究[D].广州:广州大学,2015.Dong C E.Studies on the absorption of heavy metalCu+2、Zn+2、Cr+3、Ni+2by three brown algal biomass[D].Guangzhou:Guangzhou University,2015(in Chinese).
[30]张丹,高健伟,马培,等.溶液中多种金属离子共存对毛木耳生物吸附能力的影响[J].生态环境,2008,17(6):1822-1827.Zhang D,Gao J W,Ma P,et al.Effect of competitive interference on the metal ions biosorption by Auricularia polytricha mycelial[J].Ecology and Environment,2008,17(6):1822-1827(in Chinese).
[31]Murphy V,Tofail S A M,Hughes H,et al.A novel study of hexavalent chromium detoxification by selected seaweed species using SEM-EDX and XPS analysis[J].Chemical Engineering Journal,2009,148(2-3):425-433.
[32]Murphy V,Hughes H,McLoughlin P.Enhancement strategies for Cu(II),Cr(III)and Cr(VI)remediation by a variety of seaweed species[J].Journal of Hazardous Materials,2009,166(1):318-326.
[33]Rahman M S,Sathasivam K V.Heavy metal biosorption potential of a Malaysian Rhodophyte(Eucheuma denticulatum)from aqueous solutions[J].International Journal of Environmental Science and Technology,2016,13(8):1973-1988.
[2]Kongsricharoern N,Polprasert C.Chromium removal by a bipolar electro-chemical precipitation process[J].Water Science and Technology,1996,34(9):109-116.
[3]Zeraatkar A K,Ahmadzadeh H,Talebi A F,et al.Potential use of algae for heavy metal bioremediation,a critical review[J].Journal of Environmental Management,2016,181:817-831.
[4]Chen Z,Ma W,Han M.Biosorption of nickel and copper onto treated alga(Undaria pinnatifida):application of isotherm and kinetic models[J].Journal of Hazardous Materials,2008,155(1-2):327-333.
[5]Sheng P X,Ting Y P,Chen J P,et al.Sorption of lead,copper,cadmium,zinc,and nickel by marine algal biomass:characterization of biosorptive capacity and investigation of mechanisms[J].Journal of Colloid and Interface Science,2004,275(1):131-141.
[6]Omar H H.Biosorption of copper,nickel and manganese using non-living biomass of marine alga,Ulva lactuca[J].Pakistan Journal of Biological Science,2008,11(7):964-973.
[7]He J S,Chen J P.A comprehensive review on biosorption of heavy metals by algal biomass:materials,performances,chemistry,and modeling simulation tools[J].Bioresource Technology,2014,160:67-78.
[8]李恺,耿存珍,张阳,等.活性和非活性海藻吸附重金属的研究[J].环境工程,2013,31(1):51-55,34.Li K,Geng C Z,Zhang Y,et al.Research on active and inactive algae absorbing heavy metal[J].Environmental Engineering,2013,31(1):51-55,34(in Chinese).
[9]Guler U A,Sarioglu M.Single and binary biosorption of Cu(II),Ni(II)and methylene blue by raw and pretreated Spirogyra sp.:equilibrium and kinetic modeling[J].Journal of Environmental Chemical engineering,2013,1(3):369-377.
[10]Yal??n S,Sezer S,Apak R.Characterization and lead(II),cadmium(II),nickel(II)biosorption of dried marine brown macro algae Cystoseira barbata[J].Environmental Science and Pollution Research,2012,19(8):3118-3125.
[11]Wu X D,Jiang W,Lu J J,et al.Analysis of the monosaccharide composition of water-soluble polysaccharides from Sargassum fusiforme by high performance liquid chromatography/electrospray ionisation mass spectrometry[J].Food Chemistry,2014,145:976-983.
[12]徐鲁荣.大型海藻对重金属的吸附研究[D].厦门:厦门大学,2002.Xu L R.Study on the adsorption of heavy metals by macroalgae[D].Xiamen:Xiamen University,2002(in Chinese).
[13]Sud D,Mahajan G,Kaur M P.Agricultural waste material as potential adsorbent for sequestering heavy metal ions from aqueous solutions-a review[J].Bioresource Technology,2008,99(14):6017-6027.
[14]Plazinski W.Binding of heavy metals by algal biosorbents.Theoretical models of kinetics,equilibria and thermodynamics[J].Advances in Colloid and Interface Science,2013,197-198:58-67.
[15]Javadian H,Ahmadi M,Ghiasvand M,et al.Removal of Cr(VI)by modified brown algae Sargassum bevanom from aqueous solution and industrial wastewater[J].Journal of the Taiwan Institute of Chemical Engineers,2013,44(6):977-989.
[16]揭诗琪,乔丽媛,李明明,等.改性生物质材料对Cr(Ⅵ)的吸附性能[J].中国有色金属学报,2015,25(5):1362-1369.Jie S Q,Qiao L Y,Li M M,et al.Adsorption properties of Cr(VI)by modified biomass materials[J].The Chinese Journal of Nonferrous Metals,2015,25(5):1362-1369(in Chinese).
[17]Sunwoo I Y,Ra C H,Jeong G T,et al.Evaluation of ethanol production and bioadsorption of heavy metals by various red seaweeds[J].Bioprocess and Biosystems Engineering,2016,39(6):915-923.
[18]Celik A,Demirba?A.Removal of heavy metal ions from aqueous solutions via adsorption onto modified lignin from pulping wastes[J].Energy Sources,2005,27(12):1167-1177.
[19]Wang X S,Li Z Z.Competitive adsorption of nickel and copper ions from aqueous solution using nonliving biomass of the marine brown alga Laminaria japonica[J].Clean,2009,37(8):663-668.
[20]Kleinübing S J,Guibal E,da Silva E A,et al.Copper and nickel competitive biosorption simulation from single and binary systems by Sargassum filipendula[J].Chemical Engineering Journal,2012,184:16-22.
[21]王宪,何园,郑盛华.褐藻对电镀废水中Au2+,Ag+,Cu2+,Ni2+生物吸附-解吸作用[J].华侨大学学报(自然科学版),2008,29(1):22-25.Wang X,He Y,Zheng S H.Biosorption and desorption of Au2+,Ag+,Cu2+and Ni2+from electroplating wastewater by brown algae Laminaria japonica[J].Journal of Huaqiao University(Natural Science),2008,29(1):22-25(in Chinese).
[22]Zou H X,Li N,Wang L H,et al.Equilibrium and kinetic studies of Cd2+biosorption by the brown algae Sargassum fusiforme[J].PLoS ONE,2014,9(4):e95242.
[23]Salem N M,Awwad A M.Biosorption of Ni(Ⅱ)from electroplating wastewater by modified(Eriobotrya japonica)loquat bark[J].Journal of Saudi Chemical Society,2014,18(5):379-386.
[24]Shahverdi F,Ahmadi M,Avazmoghadam S,et al.Comparative study of the kinetics and equilibrium of nickel(II)biosorption from aqueous solutions by free and immobilized biomass of Aspergillus awamori[J].Environmental Progress&Sustainable Energy,2015,34(5):1356-1364.
[25]Kumar K V.Linear and non-linear regression analysis for the sorption kinetics of methylene blue onto activated carbon[J].Journal of Hazardous Materials,2006,137(3):1538-1544.
[26]Padmavathy V,Vasudevan P,Dhingra S C.Biosorption of nickel(II)ions on Baker's yeast[J].Process Biochemistry,2003,38(10):1389-1395.
[27]Yang L,Chen J P.Biosorption of hexavalent chromium onto raw and chemically modified Sargassum sp.[J].Bioresource Technology,2008,99(2):297-307.
[28]张继义,梁丽萍,蒲丽君,等.小麦秸秆对Cr(Ⅵ)的吸附特性及动力学、热力学分析[J].环境科学研究,2010,23(12):1546-1552.Zhang J Y,Liang L P,Pu L J,et al.Adsorption characteristics of Cr(VI)by wheat straw including kinetic and thermodynamics analysis[J].Research of Environmental Sciences,2010,23(12):1546-1552(in Chinese).
[29]董彩娥.三种褐藻对重金属Cu2+、Zn2+、Cr3+、Ni2+的吸附研究[D].广州:广州大学,2015.Dong C E.Studies on the absorption of heavy metalCu+2、Zn+2、Cr+3、Ni+2by three brown algal biomass[D].Guangzhou:Guangzhou University,2015(in Chinese).
[30]张丹,高健伟,马培,等.溶液中多种金属离子共存对毛木耳生物吸附能力的影响[J].生态环境,2008,17(6):1822-1827.Zhang D,Gao J W,Ma P,et al.Effect of competitive interference on the metal ions biosorption by Auricularia polytricha mycelial[J].Ecology and Environment,2008,17(6):1822-1827(in Chinese).
[31]Murphy V,Tofail S A M,Hughes H,et al.A novel study of hexavalent chromium detoxification by selected seaweed species using SEM-EDX and XPS analysis[J].Chemical Engineering Journal,2009,148(2-3):425-433.
[32]Murphy V,Hughes H,McLoughlin P.Enhancement strategies for Cu(II),Cr(III)and Cr(VI)remediation by a variety of seaweed species[J].Journal of Hazardous Materials,2009,166(1):318-326.
[33]Rahman M S,Sathasivam K V.Heavy metal biosorption potential of a Malaysian Rhodophyte(Eucheuma denticulatum)from aqueous solutions[J].International Journal of Environmental Science and Technology,2016,13(8):1973-1988.