活性污泥胞外聚合物提取方法及其对重金属离子的吸附研究
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摘要
在污水处理工艺日益改进的今天,研究学者加大了对活性污泥胞外聚合物(EPS)的性质和功用的研究。其中包括对其提取方法的研究,其提取方法分为物理方法和化学方法,寻找出既能保证EPS的结构和又能将其提取完全的方法是急需解决的问题。另外,胞外聚合物做为一种新型的生物吸附剂来吸附重金属离子越来越受到人们的重视,人们注意到在活性污泥法处理工艺中,胞外聚合物对重金属离子的去除发挥着重要的作用,从而将提取出来的胞外聚合物做为金属离子的吸附剂加以应用成为国内外研究的热点课题。
本文从这两个研究方向入手,一方面以膜生物反应器活性污泥为原材料,通过三种物理方法:热提法、高速离心法和超声波法从中提取出胞外聚合物,对每种方法的提取条件进行适当的变化,从而找出各自的最优提取条件,在各自最优条件下分别提取出一定量的胞外聚合物,进行对比比较,从而找出最佳的提取方法。另一方面,利用最佳方法提取出一定量的胞外聚合物作为吸附剂,研究其对Cu~(2+)、Ni~(2+)和Cr~(3+)这几种重金属离子的吸附去除效果,寻求最佳的吸附条件,考察其作为金属离子的生物吸附剂的可行性。同时,研究EPS在贵重金属离子(Ag+)的回收上的实用价值。
实验的结果表明在这三种物理方法提取结果当中,热提法(80℃,15min)提取的胞外聚合物的量最多而且对细胞的破坏程度也比较小,为最佳提取方法。胞外聚合物对Cu~(2+)、Cr~(3+)和Ni~(2+)三种重金属离子吸附适宜pH值分别为3～5,4～6和4～6;适宜投加比例(EPS质量:金属离子质量)分别为1.8:1,1.6:1和2:1,EPS对不同的金属离子吸附机理不同,对一种金属离子吸附饱和后对其他金属离子同样有吸附作用。对贵重金属离子Ag~+有一定的吸附作用,从而将胞外聚合物用于贵重金属离子的回收有一定的潜力。
With the increasing advance of sewage disposal craft,research scholars increase the studies on property and funtion of active sludge extrocellular polymeric substances (EPS).The studies include the research on method of its extraction,which is divided into physical method and chemical process,and finding out the method that is both able to guarantee EPS structure and able to extract entirely is an urgent problem.In addition ,with the incresing recognition on EPS as a sort of newfashioned biosorption agent absorbing heavy metal ion, it is noticed that EPS is important for the removal of heavy metal ions in activated sludge treating process and it used as metallic ion adsorbent become both domestic and overseas researchful hotspot.
The paper starts with the above two researchful directions.On the one hand extract EPS from raw and processed materials that is membrane bio-reactor active sludge through the medium of three strain physical methods that include heating extration, supercentrifugal process and ultrasonic method. Proper changing per strain methodological abstraction condition proceeds and thereby hunts respective optimal abstraction condition. Contrast a given mass of EPS extracted in respective optimum conditions and thereby find out optimal method of extraction.On the other hand study EPS as adsorbent,which is given by best extracted way,adsorption removal effect versus heavy metal ion that includes Cu~(2+),Ni~(2+) and Cr~(3+).And seek optimal adsorption condition,review its feasibility as metallic ion biosorption agent. At the same time research the using value of EPS at reclaiming precious metal ion(Ag+).
The experiment shows optimal method of extraction is heating extraction (80℃,15min)which extracts the most EPS measure and furthermore level of destruction on cell is the smallest in three strain physical method extraction outcome. The proper pH value on Extrocellular polymer (EPS) respectively absorbing three kinds of heavy metal ion including Cu~(2+),Ni~(2+) and Cr~(3+) is 3～5,4～6和4～6. The fitting throwing scale(EPS quality:Metallic ion quality)is 1.8:1, 1.6:1 and 2.0:1 respectively. EPS has different adsorption mechanism versus different metallic ion and can also absorb the rest metallic ion after a sort of metallic ion adsorptive saturation. EPS designed to reclaim heavy metal ion has definite potential as it has definite sorption versus precious metal ion Ag~+.
本文从这两个研究方向入手,一方面以膜生物反应器活性污泥为原材料,通过三种物理方法:热提法、高速离心法和超声波法从中提取出胞外聚合物,对每种方法的提取条件进行适当的变化,从而找出各自的最优提取条件,在各自最优条件下分别提取出一定量的胞外聚合物,进行对比比较,从而找出最佳的提取方法。另一方面,利用最佳方法提取出一定量的胞外聚合物作为吸附剂,研究其对Cu~(2+)、Ni~(2+)和Cr~(3+)这几种重金属离子的吸附去除效果,寻求最佳的吸附条件,考察其作为金属离子的生物吸附剂的可行性。同时,研究EPS在贵重金属离子(Ag+)的回收上的实用价值。
实验的结果表明在这三种物理方法提取结果当中,热提法(80℃,15min)提取的胞外聚合物的量最多而且对细胞的破坏程度也比较小,为最佳提取方法。胞外聚合物对Cu~(2+)、Cr~(3+)和Ni~(2+)三种重金属离子吸附适宜pH值分别为3～5,4～6和4～6;适宜投加比例(EPS质量:金属离子质量)分别为1.8:1,1.6:1和2:1,EPS对不同的金属离子吸附机理不同,对一种金属离子吸附饱和后对其他金属离子同样有吸附作用。对贵重金属离子Ag~+有一定的吸附作用,从而将胞外聚合物用于贵重金属离子的回收有一定的潜力。
With the increasing advance of sewage disposal craft,research scholars increase the studies on property and funtion of active sludge extrocellular polymeric substances (EPS).The studies include the research on method of its extraction,which is divided into physical method and chemical process,and finding out the method that is both able to guarantee EPS structure and able to extract entirely is an urgent problem.In addition ,with the incresing recognition on EPS as a sort of newfashioned biosorption agent absorbing heavy metal ion, it is noticed that EPS is important for the removal of heavy metal ions in activated sludge treating process and it used as metallic ion adsorbent become both domestic and overseas researchful hotspot.
The paper starts with the above two researchful directions.On the one hand extract EPS from raw and processed materials that is membrane bio-reactor active sludge through the medium of three strain physical methods that include heating extration, supercentrifugal process and ultrasonic method. Proper changing per strain methodological abstraction condition proceeds and thereby hunts respective optimal abstraction condition. Contrast a given mass of EPS extracted in respective optimum conditions and thereby find out optimal method of extraction.On the other hand study EPS as adsorbent,which is given by best extracted way,adsorption removal effect versus heavy metal ion that includes Cu~(2+),Ni~(2+) and Cr~(3+).And seek optimal adsorption condition,review its feasibility as metallic ion biosorption agent. At the same time research the using value of EPS at reclaiming precious metal ion(Ag+).
The experiment shows optimal method of extraction is heating extraction (80℃,15min)which extracts the most EPS measure and furthermore level of destruction on cell is the smallest in three strain physical method extraction outcome. The proper pH value on Extrocellular polymer (EPS) respectively absorbing three kinds of heavy metal ion including Cu~(2+),Ni~(2+) and Cr~(3+) is 3～5,4～6和4～6. The fitting throwing scale(EPS quality:Metallic ion quality)is 1.8:1, 1.6:1 and 2.0:1 respectively. EPS has different adsorption mechanism versus different metallic ion and can also absorb the rest metallic ion after a sort of metallic ion adsorptive saturation. EPS designed to reclaim heavy metal ion has definite potential as it has definite sorption versus precious metal ion Ag~+.
引文
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[3] 刘萍等. 生物吸附在含重金属废水处理中的研究进展[J]. 工业用水与废水,2004,35(5):1—5.
[4] 董德明等. 天然水中细菌胞外聚合物对重金属的吸附规律[J]. 吉林大学学报(理学版), 2003,11(1):41—44.
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[13] Veiga MC et al.,Composition and Role of Extracellular in Methanogenic Granules[J],Appl.Environ.Mirobio.,1997,63(2):403—407.
[14] 王文军等.生物膜的研究进展[J].环境科学进展,1999,7(5):43—51.
[15] Sophie Comte , Gilles Guibaud,Michel Baudu.Biosorption properties of extracellular polymeric substances (EPS)resulting from activated sludge according to their type:Soluble or bound[J].Process Biochemistry, 2006,10 (41):815—823.
[16] Brown and Lester.Composition of Bacterial Extrcellular Polymer ExtractionMethods[J].App.Environ.Micro.,1980,40(2):179—185.
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[20] Carr D.F.and Ganczarcyk J. Activated Sludge Extrorface in Relation to their Settlement Characteristics[J]. Wat. Res,1985,19:527—533.
[21] Forster C F.The Production of Polymers from Activated sludge by Ethanolic Extraction and its relation to Treatment Plant Operation[J].Water Pollution Control,1993,24(6):403—433.
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[28] Nelson Y M et al.Modeling Oligotrophic Biofilm Formation and Lead Adsorption to Biofim Components[J].Envriom.Sci.Tech.,1996,30(6):2027—2036.
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[32] Houghton,J.I.;T. Quarmby,J. The impact of digester retention time on microbial extracellular polymer production and sludge dewaterability[J]. Environ.Technol.,2002,21(10):1157—1165.
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[34] Nakata,Kuniho;Kurane,Ryuichiro Production of an extracellular p olysaccharide bioflocculant by Klebsiella pneumoniae[J]. Biosci. , B iotechnol.,B iochem,1999,63(12):2064- 2068(English).
[35] Ryuichiro Kuranne.Microbia flocculation of waste liquids and oil emulsion by a bioflocculant from A alcaligenes[J].Agri Biol Chem,1991,5(4):1127—1129.
[36] Fujita.Masanor Production of a novel bioflocculant from organic wastes using bioconversion processes[J]. Yosui to Haisui. 2004,2(4):327—332.
[37] Finlayson J C et al.The Relationship between the Structure of Activated Sludge Flocs and the Sorption of Hydtophobic Pollutants[J].Wat.Sci.Tech,1998,37(4-5):307—315.
[38] Nelson Y M et al.,Modeling Oligotrophic Biofilm Formation and Lead Adsorption to Biofilm Components[J].Envrion.Sci.Tech.,1996,30(6):2027—2036.
[39] Loaec M.Uptake of lead , cadmium and Zink by Novel Bacterial Exopolysaccharides[J].Wat. Res,1997,31(5):1171—1179.
[40] Brunk B K et al.Effects of Salinity Changes and the Formation on Dissolved Organic Matter Coatings on the Sorption of Phenanthrene:Implication for Pollutant Trapping in Estuaries[J].Environ.Sci.Tech,1997,31(1):119—125.
[41] Metzner A V.Removing soluble metals from waste water[J].Wat Sewage Wks,1977,124:98—101.
[42] Cheng M H .Heavy metals uptake by activated sludge[J]. Wat Pollut Control Fed,1975,47:362—376.
[43] Uloth V C.Aerobic bio-treatment of a high-strength leachate[J].Environ Engng Div ASCE,1977,103:647—661.
[44] Stover R C.Evaluation of metals in waste water sludge[J].Wat Pollut Control Fed,1976,48:2165—2175.
[45] Peterson P.Unusual accumulation of elements by plants and animals[J].Sci Prog,1971,59:505—526.
[46] Jernelov A.Ecological implications of metal metabolism by micro-organisms[J].Swedish Water and Air Pollut Res Lab,1975,32.
[47] Yamada M.Change of mercurial compounds in activated sludge[J].Ferment Tech,1972,6:155—160.
[48] H.Horn,T.R.N–eu and M.Wulkow.Modelling the structure and function of extracellular polymeric substances in biofilms with new numerical techniques[J]. Water Science and Technology, 2001 ,10(43 ):121—127.
[49] 金若菲等.膜生物反应器中生物学特征[J]. 微生物学通报, 2004, 31(2): 121—125.
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[53] Xiaoqi Zhang,Paul L.Bishop and Brian K.Kinkle. Comparison of Extraction Methods for quantifying Extrcellular Polymers in Biofilms[J]. Wat Sci.Tech.,1999,39(7):211—218.
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[2] 昝逢宇,赵秀兰. 生物吸附剂及其吸附性能研究进展[J].青海环境,2004,14(1):15—17.
[3] 刘萍等. 生物吸附在含重金属废水处理中的研究进展[J]. 工业用水与废水,2004,35(5):1—5.
[4] 董德明等. 天然水中细菌胞外聚合物对重金属的吸附规律[J]. 吉林大学学报(理学版), 2003,11(1):41—44.
[5] 李季伦等.微生物生理学[M].北京农业大学出版社,1993.
[6] De Beer et al. Masanor Production of a novel bioflocculant from organic wastes using bioconversion processes[J].Appl Microbiol Biotechnol ,1996,12(46):1364-1366.
[7] Delia Teresa Sponza. Investigation of extracellular polymer substances (EPS) and physicochemical properties of different activated sludge flocs under steady-state conditions[J]. Enzyme and Microbial Technology,2003,10(32): 375—385.
[8] John A,Nielsen P H.Cell biomass and exopolymer compositions in sewer biofillm[J].Wat Sci Tech,1998,37(1):17—24.
[9] Goodwin,J.A.S and Forster,C.F.A further examination into the c omposition of activated sludge surfaces in relation to their settling characteristics[J]. Wat.Res,1985,19(5):527—533.
[10] Lazarova,V ,and Manem,J. Biofilm characterization and activity analysis in water and wastewater treatment[J].Wat.Res,1995,29:2227—2245.
[11] Jahn,A .;Griebe,T .;Nielsen,P .H . Accumulation of protein in the biofilm Composition of Pseudomonas putida biofilms matrix[J]. Biofouling,1999,14 (l):49—57.
[12] Andreas Jahn et al Cell. Biomass and Exopolymer Composition in Sewer Biofilms[J]. Wat.Sci .Tech, 1998,37(l):17—24.
[13] Veiga MC et al.,Composition and Role of Extracellular in Methanogenic Granules[J],Appl.Environ.Mirobio.,1997,63(2):403—407.
[14] 王文军等.生物膜的研究进展[J].环境科学进展,1999,7(5):43—51.
[15] Sophie Comte , Gilles Guibaud,Michel Baudu.Biosorption properties of extracellular polymeric substances (EPS)resulting from activated sludge according to their type:Soluble or bound[J].Process Biochemistry, 2006,10 (41):815—823.
[16] Brown and Lester.Composition of Bacterial Extrcellular Polymer ExtractionMethods[J].App.Environ.Micro.,1980,40(2):179—185.
[17] Xiaoqi Zhang et al.,Comparison of Extraction Methods for quantifying Extrcellular Polymers in Biofilms[J]. Wat Sci.Tech.,1999,39(7):211—218.
[18] Friedman BA et al.Fine structure and composition of the Zoogioeai Matrix Surrounding Zoogioea Ramtgea[J].Bacterial.,1996,9(20):2144—2155.
[19] Pavoni JL et al. , Bacterial Extrcellular Polymers and Biological Flocculation[J].Water Pollution Control,1972,44(7):413—431.
[20] Carr D.F.and Ganczarcyk J. Activated Sludge Extrorface in Relation to their Settlement Characteristics[J]. Wat. Res,1985,19:527—533.
[21] Forster C F.The Production of Polymers from Activated sludge by Ethanolic Extraction and its relation to Treatment Plant Operation[J].Water Pollution Control,1993,24(6):403—433.
[22] Fang H and Jia X.Extraction of Extrcellular Material:Extraction Methods and Problems ,ma,Nuciric Acid as a Component or Mucilage in Activated sludge[J].Wat.Res,1968,2:811—812.
[23] Gehr and Henry.Removal of Extrcellular Material[J], Wat. Res,1983,17:1743—1748.
[24] Goodwin J A .FurProc.Wat.Pollu.Res.,1998,9:250—261.
[25] Bo Frolund et al. Extraction of Extrcellular Polymers from Activated Sludge Using a Cation Exchange Resin[J].Wat. Res,1996,30(8):1749—1758.
[26] Nishikawa S. and M.Kuriyather Examination into the Composition of Activated Sludge Sulular Polymers from Anaerobic Sludges[J].Biotech.Tech.,1996,10:803—808.
[27] Azeredo J.Methods to Extract the Expolymeric Matrix from Biofilm:a Comparative Study[J].Wat.Sci.Tech.,1999,39(7):243—250.
[28] Nelson Y M et al.Modeling Oligotrophic Biofilm Formation and Lead Adsorption to Biofim Components[J].Envriom.Sci.Tech.,1996,30(6):2027—2036.
[29] 赵丹,黄勇等.改进AB工艺以达到优化脱氮的探讨[J].中国给水排水,2002,18 (8):30—32.
[30] 金雪标,高运川.吸附生物降解法的应用与讨论[J].环境保护,1997, (8):42-45.
[31] Chan,Kwong-Yu; Xu,Li-Chong;Fang,Herbert H.P. Anaerobic Electrochemical Corrosion of Mild Steel in the Presence of Extracellular Polymeric Substances Produced by a Culture Enriched in Sulfate-Reducing Bacteria[J].Source Environmental Science and Technology,2002,36(8):1720—1727.
[32] Houghton,J.I.;T. Quarmby,J. The impact of digester retention time on microbial extracellular polymer production and sludge dewaterability[J]. Environ.Technol.,2002,21(10):1157—1165.
[33] Sanin. F.D. And Vesilind. P.A(1994). Effect of centrifugation on the removal of extracellular polymer sand physical properties of activated sludge[J].Wat.Sci.Tech,2002,30(8):117—127.
[34] Nakata,Kuniho;Kurane,Ryuichiro Production of an extracellular p olysaccharide bioflocculant by Klebsiella pneumoniae[J]. Biosci. , B iotechnol.,B iochem,1999,63(12):2064- 2068(English).
[35] Ryuichiro Kuranne.Microbia flocculation of waste liquids and oil emulsion by a bioflocculant from A alcaligenes[J].Agri Biol Chem,1991,5(4):1127—1129.
[36] Fujita.Masanor Production of a novel bioflocculant from organic wastes using bioconversion processes[J]. Yosui to Haisui. 2004,2(4):327—332.
[37] Finlayson J C et al.The Relationship between the Structure of Activated Sludge Flocs and the Sorption of Hydtophobic Pollutants[J].Wat.Sci.Tech,1998,37(4-5):307—315.
[38] Nelson Y M et al.,Modeling Oligotrophic Biofilm Formation and Lead Adsorption to Biofilm Components[J].Envrion.Sci.Tech.,1996,30(6):2027—2036.
[39] Loaec M.Uptake of lead , cadmium and Zink by Novel Bacterial Exopolysaccharides[J].Wat. Res,1997,31(5):1171—1179.
[40] Brunk B K et al.Effects of Salinity Changes and the Formation on Dissolved Organic Matter Coatings on the Sorption of Phenanthrene:Implication for Pollutant Trapping in Estuaries[J].Environ.Sci.Tech,1997,31(1):119—125.
[41] Metzner A V.Removing soluble metals from waste water[J].Wat Sewage Wks,1977,124:98—101.
[42] Cheng M H .Heavy metals uptake by activated sludge[J]. Wat Pollut Control Fed,1975,47:362—376.
[43] Uloth V C.Aerobic bio-treatment of a high-strength leachate[J].Environ Engng Div ASCE,1977,103:647—661.
[44] Stover R C.Evaluation of metals in waste water sludge[J].Wat Pollut Control Fed,1976,48:2165—2175.
[45] Peterson P.Unusual accumulation of elements by plants and animals[J].Sci Prog,1971,59:505—526.
[46] Jernelov A.Ecological implications of metal metabolism by micro-organisms[J].Swedish Water and Air Pollut Res Lab,1975,32.
[47] Yamada M.Change of mercurial compounds in activated sludge[J].Ferment Tech,1972,6:155—160.
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