QCM定量分析天然有机物的吸附特性及在混凝中的应用
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摘要
消毒副产物(DBPs)的去除是当今饮用水安全的重大课题,强化混凝成本低、效率高,成为控制DBPs前驱物最佳可行性技术。本论文建立了利用石英晶体微天平(QCM)定量分析有机物在氧化铝表面吸附性能,并应用于有机物与絮凝剂作用机理研究。
本文首次利用石英晶体微天平(QCM)技术研究氧化铝对水中有机物的吸附效果及影响因素,从而得出铝系混凝剂去除水中有机物的影响因素。QCM实验证明,铝系混凝剂去除有机物受有机物浓度、溶液PH值、分子量大小,分子极性影响。水体中有机物的浓度越大,氧化铝吸附有机物达到平台值的时间越短；当有机物的溶液为偏酸性时,氧化铝吸附有机物的量最大,吸附率速率也快,形成的吸附膜比较紧密牢固,吸附效果优于中性及偏碱性溶液；大分子量的有机物被氧化铝吸附的更多,各种分子量的有机物在氧化铝表面上的吸附机制与吸附层性质没有明显的差别；有机物的分子极性对吸附的影响比较大,憎水性有机物的吸附量远大于亲水性有机物。
实际水体的QCM实验也证明,有机物在氧化铝表面的吸附特性与腐植酸配水在氧化铝表面的吸附特性相同,同时也证明了SUVA(UV254／TOC)值越高,NOM在氧化铝表面吸附的越多。
实验室混凝实验采用氯化铝、聚十三铝及工业PAC为混凝剂,确定去除腐殖酸配水、松花江源水及钱塘江源水中的有机物,实验结果证明,水样品中憎水性、分子量大、及在每种混凝剂的最佳PH值等条件下,水中的有机物去除率会比其它条件下混凝实验对有机物的去除率高,混凝实验为两个实际水体提供最佳的混凝方案,并对比研究了不同结果的影响因素。
Nowadays one of the most important issue in water treatment is to removal the Disinfentions by Products (DBPs).Enhanced coagulation is the best available technology to control Disinfentions by Products (DBPs) for its high efficiency and low cost to removal DBPs precursor (TOC).The paper first use the technology of Quartz Crystal Microbalance (QCM) to study the Adorption characteristic of Natural orgnic matter on alumina which is coated on wafer.
The experiment that using a quartz crystal microbalance with dissipation monitoring (QCM-D) to investigate humic acid (HA) adsorption onto alumina (Al2O3) could prove the degree of adsorption and layer structures of HA by the real-time monitoring of resonance frequency and energy dissipation changes (Δf andΔD).The effect of HA concentration, HA molecular characteristics (molecular weight and polarity), and pH on HA adsorption onto Al2O3 were investigated. HA is more adsorbable onto alumina at weakly acidic pH values because the adsorbed layer is more non-rigid. This reveals that efficient HA removal by coagulation at weakly acidic pH values is not just due to the hydrolysis of Al ions as previously presumed. HA of hydropHobic character and high molecular weight is more adsorbable onto alumina than HA of hydropHilic character and low molecular weight. The mass adsorption for the hydropHobic fraction is about four times high than the hydropHilic fraction (120 ng cm-2 and 30 ng cm-2). The adsorbed layer of hydropHobic HA is more non-rigid than hydropHobic HA.These result could be useful in subsequent research to establish a quantified calculation model for the coagulation process.
The study of real water using QCM proved the same conclusions which humic acid (HA) adsorption onto alumina has educed before.And also proved that the NOM adsorbed mmuch when the value of SUVA is hight.
The FeCl3 AlCl3 Al13 and PAC were used to do the Jar Test in the lab.The waters one was made in the lab,the others were took from two river that is songhuajiang and qiantangjian.when the HA contents large percent of hydropHobic orgnic matter,large molecule,the removal of HA is much.This is consistent with the conclusion obtained of QCM experiment.
The Jar Test also provides scheme to the two real waters and analysised the factors which hold back the removal of HA. Hopes this can privde some evidences to latter researches.
本文首次利用石英晶体微天平(QCM)技术研究氧化铝对水中有机物的吸附效果及影响因素,从而得出铝系混凝剂去除水中有机物的影响因素。QCM实验证明,铝系混凝剂去除有机物受有机物浓度、溶液PH值、分子量大小,分子极性影响。水体中有机物的浓度越大,氧化铝吸附有机物达到平台值的时间越短；当有机物的溶液为偏酸性时,氧化铝吸附有机物的量最大,吸附率速率也快,形成的吸附膜比较紧密牢固,吸附效果优于中性及偏碱性溶液；大分子量的有机物被氧化铝吸附的更多,各种分子量的有机物在氧化铝表面上的吸附机制与吸附层性质没有明显的差别；有机物的分子极性对吸附的影响比较大,憎水性有机物的吸附量远大于亲水性有机物。
实际水体的QCM实验也证明,有机物在氧化铝表面的吸附特性与腐植酸配水在氧化铝表面的吸附特性相同,同时也证明了SUVA(UV254／TOC)值越高,NOM在氧化铝表面吸附的越多。
实验室混凝实验采用氯化铝、聚十三铝及工业PAC为混凝剂,确定去除腐殖酸配水、松花江源水及钱塘江源水中的有机物,实验结果证明,水样品中憎水性、分子量大、及在每种混凝剂的最佳PH值等条件下,水中的有机物去除率会比其它条件下混凝实验对有机物的去除率高,混凝实验为两个实际水体提供最佳的混凝方案,并对比研究了不同结果的影响因素。
Nowadays one of the most important issue in water treatment is to removal the Disinfentions by Products (DBPs).Enhanced coagulation is the best available technology to control Disinfentions by Products (DBPs) for its high efficiency and low cost to removal DBPs precursor (TOC).The paper first use the technology of Quartz Crystal Microbalance (QCM) to study the Adorption characteristic of Natural orgnic matter on alumina which is coated on wafer.
The experiment that using a quartz crystal microbalance with dissipation monitoring (QCM-D) to investigate humic acid (HA) adsorption onto alumina (Al2O3) could prove the degree of adsorption and layer structures of HA by the real-time monitoring of resonance frequency and energy dissipation changes (Δf andΔD).The effect of HA concentration, HA molecular characteristics (molecular weight and polarity), and pH on HA adsorption onto Al2O3 were investigated. HA is more adsorbable onto alumina at weakly acidic pH values because the adsorbed layer is more non-rigid. This reveals that efficient HA removal by coagulation at weakly acidic pH values is not just due to the hydrolysis of Al ions as previously presumed. HA of hydropHobic character and high molecular weight is more adsorbable onto alumina than HA of hydropHilic character and low molecular weight. The mass adsorption for the hydropHobic fraction is about four times high than the hydropHilic fraction (120 ng cm-2 and 30 ng cm-2). The adsorbed layer of hydropHobic HA is more non-rigid than hydropHobic HA.These result could be useful in subsequent research to establish a quantified calculation model for the coagulation process.
The study of real water using QCM proved the same conclusions which humic acid (HA) adsorption onto alumina has educed before.And also proved that the NOM adsorbed mmuch when the value of SUVA is hight.
The FeCl3 AlCl3 Al13 and PAC were used to do the Jar Test in the lab.The waters one was made in the lab,the others were took from two river that is songhuajiang and qiantangjian.when the HA contents large percent of hydropHobic orgnic matter,large molecule,the removal of HA is much.This is consistent with the conclusion obtained of QCM experiment.
The Jar Test also provides scheme to the two real waters and analysised the factors which hold back the removal of HA. Hopes this can privde some evidences to latter researches.
引文
[1]晏明全高碱度微污染水体强化混凝及系统优化研究,中国科学院研究生院博士学位论文,2006年
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[2]汤鸿霄,钱易,文湘华.水体颗粒物和难降解有机物的特性与控制技术原理[M]：上卷水体颗粒物.第一版.北京：中国环境科学出版社,2000.
[3]许葆玖,安鼎年.给水处理理论与设计[M].中国建筑工业出版社,1992.11.
[4]Hatcher P. G., Breger I. A., Maciel G E., Szeverenyi N. M., Geochemistry of humin In Humic Substances in Soil, Sediment, and Water[M] Wiley, New York,1985.
[5]Hatcher P. G, Spiker E. C., Selective degradation of plant biomolecules. In Aquatic and Terrestrial Humic Materials[M]. Ann Arbor Science, Ann Arbor,,1983.
[6]Hedges J I, Polymerization of humic substances in natural environments. In Humic Substances and Their Role in Environment [M]. Wiley, New York,1988.
[7]Karanfil T., Kilduff J. E., Schlautman M. A., Weber Jr. W. J., Adsorption of organic macromolecules by granular activated carbon.1. Influence of molecular propertiesunder anoxic solution conditions[J]. Environ. Sci. Technol.,1996.30:2187-2194.
[8]Rice J.A., MacCarthy P., A model of humin. [J] Environment. Sci. Technol.,1990.24:1875-1877.
[9]王琳,王宝贞,饮用水深度处理技术[M],化学工业出版社,2002.2
[10]Frederick W. P., Water quality and treatment [M],The Fourth Edition,1990.
[11]Rook J.J., Formation of haloforms during chlorination of natural waters [J]. Water Treat. Exam,1974. 28(4):234.
[12]]Symons J.M., Nellar T.A., Carswell J.K., et al., National organics reconnaissance survey for halogenated organics in drinking water.[J].JAWWA,1975.67:634.
[13]晏明全,聚合氯化铝强化混凝去除天然水体中有机污染物的机理及优化改性研究,北京大学博士后研究工作报告,2008年。
[14]http://www.instrument.com.cn/show/download/shtml/017476.shtml
[15]USEPA.Guidance Manual for Compliance with the Interim Enhanced Surface Water Treatment Rule.[M]:Turbidity Provisions.1999
[16]建设部.城市供水水质标准[M].2005.
[17]Stumm W., Morgan J.J., Aquatic Chemistry. New York:Wiley-Interscience[M],1981.
[18]Verwey E. J. W., Overbeek J. Th. G.., Theory of the stability of lyopHobic colloids.[M],Amsterdam, 1948.
[19]Verwey E. J. W., Colloid Chemistry, Ⅴ,Ⅶ.[M], Reinhold,1950.
[20]吕亚林,石英晶体微天平研究进展与展望[J]北大口腔医院
[21]Fung Y S, Wong Y Y. Self—assembled monolayers as the coating in quartz piezoelectric crystal immunosensor to detect salmonella in aqueous solution [J].Anal. Chem,2001,53-75
[22]Patolsky F, Lichtenstein A, Wilner 1. Amplified micro-gravimetric quartz-crystal-microbalance assay of DNA using oligonucleotide-functional liposomes or biotinylated liposome [J]. Am.Chem.Soc.2000,12-18
[23]刘光昌线阵CCD高准确度检测技术[J]仪器仪表与传感器,1993.12
[24]赵子龙,楚霞.基于蛋白质修饰的纳米金探针的石英晶体微天平分析[J],化学传感器,2004.12
[25]Schneider T W, Buttry D A. Electrochemical quartz crystal microbalance studies of asorption and desorption of self-assembled monolayer of alky thiods on gold [J]Chem.Soc.,1993,121-23
[26]Michael R.Jarrett and Harryo Finklea.Anal.Chem.1999,71:353-357
[27]Sauerbrey G. Z. PHys.,1959,155:206
[28]汤鸿霄,钱易,文湘华.水体颗粒物和难降解有机物的特性与控制技术原理：上卷水体颗粒物,第一版,北京：中国环境科学出版社,2000
[29]王东升,刘海龙,晏明全,余剑锋,汤鸿霄,强化混凝与优化混凝：必要性、目标和发展方向；中国化学会第七届水处理化学会暨学术研讨会,山东大学,2004.9.13～9.15.
[30]北京青年报,2005.2.16,我国水资源仅为世界平均水平的四分之一
[31]Edzwald J. K. and Van Benschoten J.,Aluminum coagulation of natural organic matter. in Chemical Water and Wastewater Treatment, Proceedings of the 4th International Gothenburg Symposium (edited by Hahn, H.H. and Klute, R.).[M] October 1-3,1990. Madrid, Spain. Springer-Verlag, Berlin. p.341-359.
[32]Hundt T. R. and O'Melia C. R., Aluminum-Fulvic Acid Interactions:Mechanisms and Applications.[J]Journal of the American Water Works Association,1988.80(4):176-186.
[33]Gregor J.E., Nokes C. J., Fenton E.Optimising natural organic matter removal. from low turbidity waters by controlled pH adjustment of aluminium coagulation. [J] Water Research,1997. 31(12):2949-2958.
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