臺灣博碩士論文加值系統

硒是人體與動物體內必要的微量元素，但過量攝取則會危害人體。硒的來源大多來自地質經雨侵蝕流至水庫或地下水。有一部份硒來自於工廠排放的廢水，當工廠過度排放含硒廢水，會使水中的硒濃度達到危害人體濃度。吸持作用對於環境中的硒分佈有相當大的影響，因此討論吸持作用與硒的分佈以及去除微量污染物是有其必要性。自然環境中，鐵、鋁氧化物是相當普遍的化合物，無定形二氧化矽具有低零電點，高比表面積的特性，但單一元氧化物存於環境中的並不多，因此本研究以氧化鐵或氧化鋁與無定形二氧化矽 (SiO2(s)) 形成之二元氧化物來吸持水溶液中的硒酸鹽與亞硒酸鹽，進而討論硒酸鹽與亞硒酸鹽和不同二元氧化物之間吸附的關係。以 100 mL 10 g SiO2(s)/ L與 10 mL 0.5 M Fe(NO3)3或Al(NO3)3混合，將pH值調整為約5和8，定量至1 L，震盪合成24小時，形成本研究所使用的二元氧化物。鐵、矽二元氧化物系統在吸附硒酸鹽與亞硒酸鹽隨pH下降，而移除率上升，系統pH約5下合成之二元氧化物移除率最大 (Se(IV) 94.7%；Se(VI) 53.3%)；鋁、矽二元氧化物系統中，也是pH約5下合成移除率最大 (Se(IV) 81.7%；Se(VI) 71.4%)，在高pH值的環境中，OH-會與硒酸根與亞硒酸根競爭吸附位置，所以高pH值下吸附力會下降。等溫吸附實驗中Se(IV)與Se(VI) 鐵、矽二元氧化物系統的最大吸附量分別為20.4 mg g-1及2.4 mg g-1；鋁、矽二元氧化物系統的最大吸附量Se(IV) 32.7 mg g-1及Se(VI) 11.3 mg g-1。動力吸附實驗結果顯示硒酸鹽與亞硒酸鹽系統分別在15與60分鐘後達平衡。吸附硒酸鹽系統中，由於二氧化矽之低零電點影響，使得鐵、矽二元氧化物系統之表面電位較低，以致於吸附硒酸鹽的能力較純氧化鐵低；雖然鋁、矽二元氧化物系統之表面電位與純氧化鋁並無差異，但由於純氧化鋁的比表面積可提供較多可吸附硒酸鹽位置，所以吸附能力也是較鋁、矽二元氧化物系統大。在脫附實驗研究中，亞硒酸鹽與吸附材料會產生內層吸附，而脫附平衡時間需要較久；硒酸鹽與吸附劑是水合外層吸附，因此30分鐘內可達脫附平衡。

目錄
口試委員會審定書………………………………………………………i
中文摘要…………………………………………………………………..i
英文摘要…………………………………………………………………iii
第一章 前言……………………………………………………… 1
第二章 文獻回顧………………………………………………… 3
2.1 硒的特性.............................................................................. 3
2.2 氧化鐵、鋁形成.................................................................. 5
2.3 氧化鐵、鋁表面特性.......................................................... 7
2.4 吸附現象理論...................................................................... 8
2.5 固液界面模式..................................................................... 10
2.6 氧化物 (氧化鐵、鋁) 對陰離子之吸附特性…............... 11
2.7 二相氧化物 (binary oxides) ............................................... 13
第三章 材料與方法……………………………………………… 14
3.1 實驗設計………………………………………………… 14
3.2 合成吸附劑……………………………………………… 15
3.3 吸附劑物化性質的研究………………………………… 15
3.4 吸附特性的研究………………………………………… 19
第四章 結果與討論……………………………………………… 22
4.1 合成吸附劑之物化特性………………………………… 22
3
4.2 吸附特性………………………………………………… 29
第五章 結論與建議……………………………………………… 51
5.1 結論………………………………………………………51
5.2 建議……………………………………………………….51
第六章 參考文獻………………………………………………… 52

官文惠（1994），氧化鋁覆膜於石英砂吸附水中硒之研究，國立台灣大學環境工程學研究所碩士論文。
陳宗永（1994），氧化鐵覆膜於石英砂吸附水中硒之研究，國立台灣大學環境工程學研究所碩士論文。
王尚禮（1993），過氯酸鋁之水解反應與水鋁氧石之生成機制，國立台灣大學農業化學研究所碩士論文。
Alaejos, M. S., F. J. Díaz Romero, and C. Díaz Romero, 2000, “Selenium and Cancer: Some Nutritional Aspects,” Nutrition, Vol. 16, pp. 376-383.
Bailey, R. P., T. Bennett, and M. M. Benjamin, 1992, “Sorption onto and recovery of Cr(VI) using iron-oxide-coated sand,” Wat. Sci. Tech., Vol. 26, pp 1239-1244.
Balistrieri, L., and T. T. Chao, 1990, “Adsorption of selenium by amorphous iron oxyhydroxide and manganese dioxide, ”Geochim. Cosmochim. Acta, Vol. 54, pp. 739-751.
Barrow, N. J., L. Madrid and A. M. Posner, (1981) “A partial model for the rate of adsorption and desorption of phosphate by goethite,” J. Soil Sci., Vol. 32, pp. 399-407.
Blesa, M. A. and E. Matijevic, 1989, “Phase transformations of iron oxide, oxyhydroxides, and hydrous oxide in aqueous media,” Adv. Colloid Interface Sci., Vol. 29, pp. 173-221.
Bruggeman, C., A. Maes , J. Vancluysen, and P. Vandemussele, 2005, “Selenite reduction in Boom clay: Effect of FeS2, clay minerals and dissolved organic matter,” Environmental Pollution, Vol. 137, pp. 209-221.
Chao, T. T., M. E. Harward, and S. C. Fang,1962, “Movement of S35 tagged sulfate tough soil columns,” J. Soil Sci. Soc. Am. Proc., Vol. 26, pp. 27-32.
Davis, J. A. and J. O. Leckie, 1980, “Surface ionization and complexation at the oxide/water interface III adsorption of anion,” Journal of Colloid and Interface Science, Vol. 74, pp. 32-34.
Davis, S. A. and M. Misra, 1997, “Transport Model for the Adsorption of Oxyanions of Selenium ( IV) and Arsenic (V) from Water onto Lanthanumand Aluminum-Based Oxides,” Journal of Colloid and Interface Science, Vol. 188, pp. 340-350.
Dong D., Y. M. Nelson, L. W. Lion, M. L. Shuler and W. C. Ghiorse, 2000, “Adsorption of Pb and Cd onto metal oxides and organic material in natural surface coating as dtermined by selective extractions: new evidence for the importance of Mn and Fe oxides,” Water Research, Vol. 34, pp. 427-436.
Dousma, J. and P. L. de Bruyu, 1976, “Hydrolysis precipitation studies of iron solution. I. Model for hydrolysis and precipitation from Fe(III) nitrate solution,” Journal of Colloid and Interface Science, Vol. 56, pp. 527-539.
Edwards, M. and M. M. Benjamin, 1989, “Adsorptive filtration using coated sand: a new approach for treatment of metal-bearing wastes,” WPCF, Vol. 61, pp. 1523-1533.
Elliott, H. A., M. R. Liberati, and C. P. Huang,1986, “Effect of iron oxide removal on heavy metal sorption by acid subsoils,” Water, Air, & Soil Pollution, Vol. 27, pp. 379-389.
Genç-Fuhrman, H., P. S. Mikkelsen, A. Ledin, 2007, “Simultaneous removal of As, Cd, Cr, Cu, Ni and Zn from stormwater: Experimental comparison of 11 different sorbents,” Water Research, Vol. 41, pp. 591-602.
Goh, K. H. and T. T. Lim, 2004, “Geochemistry of inorganic arsenic and seleniumin a tropical soil: effect of reaction time, pH, and competitive anions on arsenic and selenium adsorption,” Chemosphere, Vol.55, pp. 849-859.
Gupta, V. K., V. K. Saini and N. Jain, 2005, “Adsorption of As(III) from aqueous solutions by iron oxide-coated sand,” Journal of Colloid and Interface Science, Vol. 288, pp.55-60.
Hayes, K. F., 1987, “Equilibrium, spectroscopic and kinetic studies of ion adsorption at the oxide/aqueous interface,” Ph. D. Dissertation, Stanford University.
Hayes, K. F., A. L. Roe, G. E. Brown, K. O. Hodgson, J. O. Leckie, G. A. Parks, 1987, “In situ X-ray adsorption study of surface complexes: selenium oxyanions on α-FeOOH,” Science, Vol. 238, pp. 783-786.
Hayes, K. F., C. Papelis and J. O. Leckie, 1988, “Modeling ionic strength effects on anion adsorption at hydrous oxide/solution interfaces,” Journal of Colloid and Interface Science, Vol. 125, pp. 717-726.
Hlavay, J. and K. Polyák, 2005, “Determination of surface properties of iron hydroxide-coated alumina adsorbent prepared for removal of arsenic from drinking water,” Journal of Colloid and Interface Science, Vol. 284, pp. 71-77.
Hsu, P. H. and T. F. Bates, 1964, “Formation of X-ray amorphous and crystalline aluminum hydroxides,” Mineral Mag., Vol. 33, pp. 749-768.
Kameda, T., T. Yoshioka, T. Mitsuhashia, M. Uchidaa and A Okuwaki, 2003, “The simultaneous removal of calcium and chloride ions from calcium chloride solution using magnesium–aluminum oxide,” Water Research. Vol. 37, pp. 4045-4050.
Koningsberger, D. C. and R. Prins., 1988, X-ray absorption: principles, applications, techniques of EXAFS, SEXAFS, and XANES, pp.53-83.
Kuan W. H., S. L. Lo, M. K. Wang and C. F. Lin, 1998, “Removal of Se(IV) and Se(VI) from water by aluminum-oxide-coated sand,” Water Research, Vol. 32, pp. 915-923.
Kuan W. H., S. L. Lo and M. K. Wang, 2004, “Modeling and electrokinetic evidences on the processes of the Al(III)sorption continuum in SiO2(s) suspension,” Journal of Colloid and Interface Science, Vol. 272, pp. 489-497.
Lai C. H. and C. Y. Chen, 2001, “Removal of metal ions and humic acid from water by iron-coated filter media,” Chemosphere, Vol. 44(5), pp. 1177-84.
Lavander, O. A., 1988, “Selenium, chromium, and manganese,” In: Modern Nutrition in Health and Disease. 7th ed., M.E. Shils and V.R. Young (eds.), Lea Febiger, Phialadelphia, PA, pp. 263-267.
Liu, Y. T., M. K. Wang, T. Y. Chen, P. N. Chiang, P. M. Huang and J. F. Lee, 2006, “Arsenate Sorption on Lithium/Aluminum Layered Double Hydroxide Intercalated by Chloride and on Gibbsite: Sorption Isotherms, Envelopes, and Spectroscopic Studies,” Environ. Sci. Technol., Vol. 40, pp. 7784-7789.
Lo, S. L. and T. Y. Chen, 1997, “Adsorption of Se(IV) and Se(VI) on an iron-coated sand from water,” Chemosphere, Vol. 35, pp. 919-930.
Lützenkirchen, J. and Ph. Behra, 1997, “A new approach for modeling potential effects in cation adsorption onto binary (hydr)oxides,” J. of Contaminant Hydrology, Vol. 26, pp. 257-268.
Manahan, S. E, 1984, “Environmental Chemistry,” 4th ed., Prindle Weber and Schmidt Publishers, Boston, MA., pp.106-151.
Meng, X. and R. D. Letterman, 1993, “Effect of component oxide interaction on the adsorption properties of mixed oxides,” Environ. Sci. Technol., Vol. 27, pp. 970-975.
Morril, L. G., B. C. Mahilum and S. H. Mohiuddin, 1982, “Sorption, Degradation and Persistence,” In: Organic Compounds in soils, Ann Arbor Sci. Publisher, Inc..
Parida, K. M., B. Gorai, N.N. Das, and S. B. Rao, 1997, “Studies on Ferric Oxide Hydroxides III. Adsorption of Selenite (SeO32-) on Different Forms of Iron Oxyhydroxides,” Journal of Colloid and Interface Science, Vol. 185, pp.355-362.
Poulton, S. W., M. D. Kroma, J. Van Rijn, and R. Raiswell, 2002, “The use of hydrous iron (III) oxides for the removal of hydrogen sulphide in aqueous systems,” Water Research, Vol. 36, pp. 825–834.
Pulker, H. K., 1984, “Coating on Glass,” Elsveier, Amsterdam, Oxford, New York.
Ramakrishna, D. M.; T. Viraraghavan, and Y. C. Jin, 2006, “Iron Oxide Coated Sand for Arsenic Removal: Investigation of Coating Parameters Using Factorial Design Approach,” Practice Periodical of Hazardous, Toxic, and Radioactive Waste Management, Vol. 10, pp. 198-206.
Schwertmann, U. and R. M. Taylor, 1989, “Iron oxide,” In: Minerals in Soil Environments, Dixon, J. B., Weed S. B. (ed.), 2nd ed., Soil Sci. Soc. Am. J., Medison, Wisconsin, USA, pp. 379-428.
Stumm W., “Chemistry of the solid-water interface”, John Wiley & Sons, New York, USA (1992).
Teo, B. K., 1986, EXAFS: Basic Principles and Data Analysis, pp. 21-78.
Violante, A., and M. L. Jackson, 1981, “Clay influence on the crystallization of aluminum hydroxide polymorphs in the presence of citrate, sulfate or chrolide,” Geoderma, Vol. 25, pp. 199-214.
Wu, C. H., C. F. Lin and S. L. Lo, 2003, “Modeling Competitive Adsorption of Chromate, Sulfate and Selenate on γ-Al2O3: Comparison between the Triple-Layer Model and a Freundlich-type Multi-component Isotherm,” J. of the Chinese Inst. of Environ. Eng., Vol. 13, pp. 87-94.
Xu Y. and L. Axe, 2005, “Synthesis and characterization of iron oxide-coated silica and its effect on metal adsorption,” Journal of Colloid and Interface Science, Vol. 282, pp. 11-19.
Yuan, T., Hu, J. Y., Ong, S. L., Luo, Q. F., and Ng, W. J., 2002, “Arsenic removal from household drinking water by adsorption.” J. Environ. Sci. Health, Part A: Toxic/Hazard. Subst. Environ. Eng., A37 9, pp. 1721–1736.
Zeng, L, 2003, “A method for preparing silica-containing iron(III) oxide adsorbents for arsenic removal,” Water Research, Vol. 37, pp. 4351-4358.
Zhang, G. S., J. H. Qu, H. J. Liu, R. P. Liu, and R. C. Wu, 2007, “Preparation and evaluation of a novel Fe–Mn binary oxide adsorbent for effective arsenite removal,” Water Research, Vol. 41, pp. 1921-1928.