請用此 Handle URI 來引用此文件:
http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/28895
完整後設資料紀錄
DC 欄位 | 值 | 語言 |
---|---|---|
dc.contributor.advisor | 張慶源 | |
dc.contributor.author | De-Sheng Lu | en |
dc.contributor.author | 盧德笙 | zh_TW |
dc.date.accessioned | 2021-06-13T00:28:20Z | - |
dc.date.available | 2012-07-27 | |
dc.date.copyright | 2007-07-27 | |
dc.date.issued | 2007 | |
dc.date.submitted | 2007-07-24 | |
dc.identifier.citation | Allcock, H. R. and F. W. Lampe, “Contemporary polymer Chemistry”, Upper Saddle River, New Jersey: Prentice Hall (1990).
Ayranci, E. and E. Bayram, “Adsorption of phthalic acid and its esters onto high-area activated carbon-cloth studied by in situ UV-spectroscopy,” J. Hazardous Materials B, 122(1-2), 147-153 (2005). Braunauer, S., L.S. Deming, W.S. Deming and E. Teller, “On a theory of the van der Walls adsorption of gases,” J. Am. Chem. Soc., 62(7), 1723-1732 (1940). Brunauer, S., P.H. Emmett and E. Teller, “Adsorption of gases in multimolecular layers,” J. Am. Chem. Soc., 60(2), 309-317 (1938). Chang, C.F., C.Y. Chang and W.T Tsai., “Adsorption equilibrium of polyethylene glycol in the copper electroplating solution on activated carbon,” J. Colloid Interface Sci., 232(1), 207-209 (2000). Colborn, T.,D. Dumanoski and J. P. Myers, “Our Stolen Future,” Penguin Books, NewYork, NY (1996) (失竊的未來,臺灣譯本). Costa, L., M. Avataneo, P. Bracco and V. Brunella, “Char formation in polyvinyl polymers,” Polymer Degradation and Stability, 77(3), 503-510 (2002). Den, W., H.C. Liu, S.F. Chan, K.T. Kin and C. Huang, “Adsorption of phthalate esters with multiwalled carbon nanotubes and its application,” J. Environ. Eng. Manag., 16(4), 275-282 (2006). Dharmalingam, K., K. Ramachandran and P. Sivagurunathan, “FTIR and dielectric studies of molecular interaction between alkyl methacrylates and primary alcohols,” Physica B: Phyaics of Condensed Matter, 392(2), 127-131 (2007). Edeskuty, F.J. and N.R. Amundson, “Mathmatics of Adsorption. 4. Effect ofIntraparticle Diffusion in Agitated Static Systems,” J. Phys. Chem., 56(A1),148-152 (1952). Freundlich, H., “Über die Adsorption in Lösungen,” Z. Phys. Chem., 57, 385-470 (1906). Geankoplis, C.J., “Transport processes and unit operations,” Allyn and Bacon series in engineering, Prentice Hall PTR, Upper Saddle River, NJ, pp. 712-736 (1983). Hasany, S.M., M.M. Saeed and M. Ahmed, “Sorption of traces of silver ions onto polyurethane foam from acidic solution,” Talanta, 54(1),89-98 (2001). Hauduk, W. and H. Laudie, “Prediction of diffusion coefficients for nonelectrolytes in dilute aqueous solutions,” AIChE. J., 20(3), 611-615 (1974). Ho, Y.S. and G. Mckay, “A comparison of chemisorption kinetic models applied to pollutant removal on various sorbents,” Trans. I. Chem. E., 76(B4), 332-340 (1998). Kaczmarek, H., A. Podgórski and K. Bajer, “Photochemical reactions in poly(vinyl chloride)/poly(vinyl alcohol) blends,” J. Photochemistry Photobiology, A:Chemistry, 171(2), 187-195 (2005). Lagergren, S., “About the theory of so-called adsorption of soluble substances,” Kungliga Svenska Vetenskapsakademien, Handlingar, 24(4), 1-39 (1898). Langmuir, I., “The adsorption of gases on plane surfaces of glass, mica and platinum,” J. Am. Chem. Soc., 40(9), 1361-1403 (1918). Li, H., Y. Zhang, X. Chen, K. Shi, Z. Yuan, B. Liu, B. Shen and B. He, “Synthesis and adsorption aspect of crosslinked PVA-based blood compatible adsorbents for LDL apheresis,” Reactive & Functional Polymers, 58(1), 53-63 (2004). Liu, B.J. and Q.L. Ren, ”Sorption of levulinic acid onto weakly basic anion exchangers: Equilibrium and kinetic studies,” J. Colloid and Interface Science, 294(2), 281-287 (2006). Liu, X., M.D. Kaminski, Y. Guan, H. Chen, H. Liu and A. J. Rosengart, “Preparation and characterization of hydrophobic superparamagnetic magnetite gel,” J. Magnetism and Magnetic Materials, 306(2), 248-253 (2006). Low, M.J.D., “Kinetics of chemisorption of gases on solids,” Chem. Rev., 60(3), 267-312 (1960). Lowell, S. and J.E. Shields, “Powder Surface Area and Porosity,” 3rd Ed., Chapman & Hall, New York, NY, USA (1991). Majumdar, S. and B. Adhikari, “Polyvinyl alcohol: A taste sensing material,” Sensors & Actuators: B. Chemical, 114(2), 747-755 (2006). McNeill, I.C., S. Ahmed and L. Memetea, “Thermal degradation of vinyl acetatemethacrylic acid copolymer and homopolymers. I. An FTIR spectroscopic investigation of structural changes in the degrading material,” Polymer Degradation and Stability, 47(3), 423-433 (1995). Özacar, M. and İ. A. Şengil, “A kinetic study of metal complex dye sorption onto pine sawdust,” Process Biochemistry, 40(2), 565-572 (2005). Özcan, A. S., B. Erdem and A. Özcan, “Adsorption of Acid Blue 193 from aqueous solutions onto BTMA-bentonite,” Colloids and Surfaces A, 266(1-3), 73-81 (2005). Rosen, J.B., “Kinetics of a fixed bed system for solid diffusion into spherical particles,” J. Chem. Phys., 20(3), 387-394(1952). Ruthven, D.M., “Principles of Adsorption & Adsorption Process,” John Wiley and Sons, New York, NY (1984). Shibayama, M., M. Sato, Y. Kimura, H. Fujiwara and S. Nomura, “11B n.m.r. study on the reaction of poly(vinyl alcohol) with boric acid,” Polym, 29(2), 336-340 (1988). Sontheimer, H., B. R. Frick, J. Fettig, G. Hörner, C. Hubele and G. Zimmer, “Active Carbon for Water Treatment,” 2nd Ed., DVGW-Forschungss telle, Engler-Bunte-Institut, Universität Karlsruhe, Karlsruhe, Germany, pp. 258-348 (1998). Stoeckli, F., “Dubinin’s theory and its contribution to adsorption science” Russian Chemical Bulletin, 50(12), 2265-2272 (2001). Tseng, J.Y., C.Y. Chang, Y.H. Chen, C.F. Chang and P.C. Chiang, “Synthesis of micro-size magnetic polymer adsorbent and its application for removal of Cu(Ⅱ) ion,” Colloids and Surfaces A, 295(1-3), 209-216 (2007). Tseng, R.L., F.C. Wu, R.S. Juang, “Liquid-phase adsorption of dynes and phenols using pinewood-based activated carbons,” Carbon, 41(3), 487-495 (2003). Wilke, C.R. and P. Chang, “Correlation of diffusion coefficients in dilute solutions,” AIChE. J., 1(2), 264-270 (1955). 下飯坂達,「粉体液相中凝集分散」,粉体粉末冶金, 12(6), 263, (1966)。 王正雄,「環境荷爾蒙―地球村二十一世紀之熱門課題」,環境檢驗雙月刊第29期 (2000)。 杜逸虹著,「聚合體學」,三民書局股份有限公司,台灣台北,201-269 (1978)。 林敬二,「儀器分析上冊」,美亞書版股份有限公司,台灣台北,356-398 (1997)。 許國恩,「應用新穎吸附劑吸附去除水體中農藥之研究」,國立台灣大學環境工程學研究所碩士論文 (2006)。 許紫菱,「以奈米超順磁性二氧化鋯吸附處理陰離子溶液」,國立台灣大學環境工程學研究所碩士論文 (2006)。 廖健森,張碧芬,袁紹英,「環境荷爾蒙—塑膠添加物鄰苯二甲酸二甲酯之環境流佈」,環境檢驗雙月刊第38期 (2001)。 薛敬和編,「黏著劑全書-材料與技術」,高立圖書公司,台灣台北,759-783 (1985)。 行政院環境保護署環境檢驗所,「台灣地區疑似環境荷爾蒙物質管理及環境流布調」,微生物與環境荷爾蒙研討會論文集 (2000)。 行政院環保署,「物質安全資料表95年版」。http://www.eric.org.tw/Chm_/95MSDS/080-01.doc | |
dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/28895 | - |
dc.description.abstract | 鄰苯二甲酸二甲酯(DMP)屬於環境荷爾蒙,其存在濃度極低,同時其極低濃度的暴露量即可對生化與細胞作用機制造成巨大的改變。故本研究以吸附的方式濃縮DMP,欲達到提高單位體積的汙染物濃度,以利於氧化、降解或其他處理處置程序。
本研究以化學共沉法製備四氧化三鐵,再以懸浮聚合法的方式合成之磁性聚醋酸乙烯酯(M-PVAC),最後進行表面改質形成吸附劑磁性聚乙烯醇(M-PVAL)。其飽和磁化強度分別為57.2、26.0和43.2 emu g-1。皆具有超順磁性。吸附劑屬於微米等級而其粒數平均粒徑為0.75 μm。 以完全攪拌槽進行動力實驗,整體性動力學部份,分別以假性一階動力方程式、假性二階動力方程式和Elovich rate equation。傳統動力學部分以孔擴散及表面擴散模式進行探討。結果顯示隨著初始濃度越高,固液之間濃度梯度越大,其達到平衡的時間越快。 等溫吸附曲線實驗分為不調整初始pH值、初始pH值為5及7三組,皆以Langmuir等溫吸附方程式、Freundlich等溫吸附方程式及Dubinin-Radushkevich (D-R)等溫吸附方程式進行模擬。三組實驗之Langmuir isotherm之單層飽和吸附量qL分別為5.21、4.01和4.22 mg g-1。三組之Freundlich isotherm之異質性常數nF值分別為2.19、2.59、2.59,皆大於1。顯示本DMP/M-PVAL系統屬於有利吸附。三組實驗由D-R等溫方程式推估之每莫耳吸附質吸附的自由能EF值分別6.48、7.04和7.19 kJ mol-1,其EF皆小於8 kJ mol-1,整體的吸附程序是屬於物理自然發生的形式。 調整含有甲醇比例為0、10 及50 vol.%進行等溫吸附實驗,其qL值分別為5.21、4.03及1.18 mg g-1。顯示甲醇之含量越高,則M-PVAL之qL值越低。同時三組之EF值分別為6.48、5.89和4.68 kJ mol-1,顯示甲醇與DMP可形成良好之鍵結,以致親合力較吸附劑為高。利用此特性以50 vol.%甲醇進行脫附實驗,經過兩次脫附單元後,其脫附效率高達95%。 | zh_TW |
dc.description.abstract | Dimethyl phthalate (DMP) is a member of environmental hormones. It exists with low concentration and is harmful to biological and cell`s mechanism even with a very low exposed concentration. Adsorption is chosen to remove and concentrate DMP for further oxidizing, degrading or other treating processes.
Fe3O4 (M) is prepared by precipitation method and then synthesized to magnetic polyvinyl acetate (M-PVAC) by suspension polymerization. Its surface is modified by alcoholization to produce a polymer adsorbent of magnetic polyvinyl alcohol (M-PVAL). The saturated magnetizations of particles M, M-PVAC and M-PVAL are 57.2, 26.0 and 43.2 emu g-1 with super-para-magnetism, respectively. The average particle size of M-PVAL by number is 0.75 μm in micro size. Global kinetic expressions are simulated by pseudo-first-order equation, pseudo-second-order equation and Elovich rate equation in completely stirred tank reactor (CSTR) system. Traditional kinetic models of pore and surface diffusions are also employed. As a result, time to reach equilibrium is faster when the initial concentration of DMP is higher because of the high gradient of concentrations between solid and liquid. The isotherm experiments include three cases: (1) with no adjustment of initial pH (pH0) of solution, (2) pH0 = 5 and (3) pH0 = 7. The results are simulated by Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherms. The saturated amounts of adsorption of unimolecular layer (qL) of Langmuir isotherm are 5.21, 4.21 and 4.22 mg g-1 in these three cases and the values of heterogeneity factor nF of Freundlich isotherm are 2.19, 2.59 and 2.59 which are greater than 1. It reveals the DMP/M-PVAL system is belong to favorable adsorption. The values of adsorption activation energy per mole (EF) of D-R isotherm in these cases are 6.48, 7.04 and 7.19 kJ mol-1which are less than 8 kJ mol-1, indicating that the adsorption process is belong to the form of physical nature. The values of qL for the adsorption of DMP in three solutions containing 0, 10 and 50 vol.% alcohol are 5.21, 4.03 and 1,18 mg g-1, respectively. It shows the more content of methnol the less the concentration in solid M-PVAL (qL). The values of EF in these three experimental sets are 6.48, 5.89 and 4.68 kJ mol-1 , indicating that stable bond forms between the methanol and DMP so that the affinity between them is better than that between the adsorbent and DMP. Using the characteristics between methanol and DMP to desorption process, the desorption efficiency is as high as 95 % by twice desorption units applying 50 vol.% methnol. | en |
dc.description.provenance | Made available in DSpace on 2021-06-13T00:28:20Z (GMT). No. of bitstreams: 1 ntu-96-R94541119-1.pdf: 2013271 bytes, checksum: e5ce15da2df3e94239a8c30deee40119 (MD5) Previous issue date: 2007 | en |
dc.description.tableofcontents | 中文摘要 i
英文摘要 iii 目錄 v 表目錄 x 圖目錄 xii 符號說明 xvi 第一章 緒論 1 1.1 研究背景 1 1.2 研究目的 2 第二章 文獻回顧 4 2.1 環境荷爾蒙 4 2.1.1 環境荷爾蒙簡介 4 2.1.2 環境荷爾蒙使用情形及分類 4 2.1.3 鄰苯二甲酸二甲酯 6 2.1.4 鄰苯二甲酸二甲酯處理相關文獻 6 2.2 磁性吸附劑相關研究 8 2.2.1磁鐵礦 (Magnetite)合成─化學共沉法(Percipitation Method) 8 2.2.1.1 磁鐵礦表面化學原理 9 2.2.2聚乙烯醇之製備 9 2.2.2.1 懸浮聚合 11 2.2.2.2 自由基鎖鏈聚合反應機構 11 2.2.2.3 聚醋酸乙烯酯之特性 13 2.2.2.4 聚乙烯醇之特性 13 2.3吸附原理 14 2.3.1 吸附基本理論 14 2.3.2 等溫吸附方程式 14 2.3.2.1 Freundlich等溫吸附方程式 16 2.3.2.2 Ladgmuir等溫吸附方程式 18 2.3.2.3 Dubinin-Radushkevich 等溫吸附方程式 18 2.3.2.4 BET多層吸附方程式 20 2.3.3 吸附動力理論 21 2.3.3.1 假性ㄧ階動力方程式(Pseudo-first-order Rate Equation) 22 2.3.2.2 假性二階動力方程式(Pseudo-second-order Rate Equation) 23 2.3.2.3 Elovich-Rate Equation 23 2.3.2.4 外部質量傳送 24 2.3.2.5 內部質量傳送 26 第三章 實驗設備與研究方法 29 3.1 藥品 29 3.2 實驗設備 30 3.2.1 磁性吸附劑合成設備 30 3.2.2 吸附劑物理化學特性分析 30 3.3.3 吸脫附實驗系統 31 3.3 實驗步驟 31 3.3.1 磁性聚乙烯醇之製備 35 3.3.1.1 化學共沉法製備磁性凝膠 35 3.3.1.2 懸浮聚合法製備磁性聚醋酸乙烯酯 37 3.3.1.3 醇解改質 38 3.3.2 吸附劑特性分析 38 3.3.2.1表面官能基 38 3.3.2.2磁特性 41 3.3.2.3掃瞄式電子顯微鏡 41 3.3.2.4 比表面積 41 3.3.2.5 粒徑分佈 41 3.3.2.6 表面電位 42 3.3.2.7 密度及孔隙度 42 3.3.3 吸脫附行為之探討 43 3.3.3.1 完全攪拌槽動力實驗 43 3.3.3.2 等溫吸脫附曲線 43 3.3.3.3 磁性吸附劑脫附再生與磁性分離 44 3.4 實驗分析方法與條件 44 3.4.1分光光度計 44 3.4.2高效能液相層析儀 45 第四章 結果與討論 47 4.1 吸附劑之物理化學特性 47 4.1.1 磁滯曲線 47 4.1.2 表面官能基 47 4.1.3 吸附劑物理特性分析 50 4.1.4 界達電位 54 4.2 完全攪拌槽吸附動力 57 4.2.1 吸附背景參數設定 57 4.2.2 吸附動力實驗 60 4.2.3 整體性動力分析 60 4.2.4 外部質量傳送 63 4.2.5 內部質量傳送 63 4.2.6 質量傳送綜合討論 67 4.3 鄰苯二甲酸二甲酯之等溫吸附行為 68 4.4 磁性吸附劑脫附再生與磁性分離 77 4.4.1 等溫脫附曲線 77 4.4.2 鄰苯二甲酸二甲酯吸脫附之質量平衡 81 4.4.2.1 理論質量平衡式 81 4.4.2.2 實際質量平衡式 84 4.4.3 綜合結果比較 87 4.4.4 M-PVAL之應用與磁性分離 91 第五章 結論與建議 93 5.1 結論 93 5.1.1 合成磁性聚乙烯醇之物理化學特性 93 5.1.2 DMP吸附行為 93 5.1.3 DMP脫附行為 94 5.2 建議 94 參考文獻 96 附錄A:中英名詞及英文縮寫對照 101 附錄B:合成照片 105 | |
dc.language.iso | zh-TW | |
dc.title | 應用磁性吸附劑吸附環境荷爾蒙-以鄰苯二甲酸二甲酯為例 | zh_TW |
dc.title | Adsorption of Environmental Hormones Using Magnetic Adsorbent: A Case Study of Dimethyl Phthalate | en |
dc.type | Thesis | |
dc.date.schoolyear | 95-2 | |
dc.description.degree | 碩士 | |
dc.contributor.oralexamcommittee | 蔣本基,張瓊芬 | |
dc.subject.keyword | 環境荷爾蒙,鄰苯二甲酸二甲酯,吸附,磁鐵礦,懸浮聚合,聚乙烯醇,吸附動力, | zh_TW |
dc.subject.keyword | environmental hormones,dimethyl phthalate,magnetite,polyvinyl alcohol,suspended polymerization,adsorption isotherm,adsorption kinetic, | en |
dc.relation.page | 106 | |
dc.rights.note | 有償授權 | |
dc.date.accepted | 2007-07-26 | |
dc.contributor.author-college | 工學院 | zh_TW |
dc.contributor.author-dept | 環境工程學研究所 | zh_TW |
顯示於系所單位: | 環境工程學研究所 |
文件中的檔案:
檔案 | 大小 | 格式 | |
---|---|---|---|
ntu-96-1.pdf 目前未授權公開取用 | 1.97 MB | Adobe PDF |
系統中的文件,除了特別指名其著作權條款之外,均受到著作權保護,並且保留所有的權利。