臺灣博碩士論文加值系統

淨水程序中添加含氯消毒劑，具有確保水質安全衛生之功用。但消毒劑與存在於水中之有機物發生反應會生成消毒副產物(DBPs)，如三鹵甲烷(THMs)、鹵化乙酸(HAAs)等，使飲用水的致癌風險明顯增加，最近對鹵化乙酸的致癌性研究逐漸增加。原水中有機酸常是淨水場加氯消毒形成消毒副產物之主要反應物，本研究利用單壁奈米碳管(Single-walled Carbon Nanotube, SWCNT) 吸附去除水中黃酸，探討奈米碳管吸附水中黃酸、鹵化乙酸潛勢(Haloacetic Acid Formation Potential, HAAFP)之平衡與吸附行為，最後再利用動力吸附模式及等溫吸附模式模擬並對吸附速率及平衡作模式預測，並計算其熱力學參數ΔG、ΔS及ΔH以便對奈米碳管吸附的機制有更深入的了解。
在黃酸濃度0.893至3.342mg TOC/L 下利用Langmuir Model 求出單壁奈米碳管其飽和吸附量為61.88mg /g，比商業用之粒狀活性碳有較佳的吸附量。(一般粒狀活性碳GAC之吸附量為10.69 mg/g)。奈米碳管吸附黃酸的量隨著溫度降低、水溶液pH下降而有增加的趨勢；在恆溫25℃狀態下，經過平衡吸附試驗後分析HAAFP，求得HAAFP去除效率可達到40.76%。動力吸附實驗結果以Modified Freundlich Equation、Pseudo-1st-order Equation、Pseudo-2nd-order Equation三模式套用，結果以Modified Freundlich Equation模擬最佳；由Intraparticle Diffusion Equation模式解析，顯示吸附過程由孔隙擴散所掌控；計算奈米碳管吸附黃酸反應的活化能，顯示膜擴散為反應速率控制因子，根據熱力學參數的求取顯示奈米碳管吸附黃酸的過程為自發、放熱反應。
奈米碳管在吸附容量和反應速率特性上均較活性碳佳，雖然奈米碳管目前售價仍相當昂貴，其作為吸附劑的應用是有潛力。若能結合奈米碳管技術與消毒技術用於家用處理設施或小型簡易淨水場之飲用水處理單元末端設計，有助於民眾飲用水安全技術與市場發展機會。

Disinfectants, such as chlorine, are widely used in water treatment plants to ensure the safety and quality of drinking water. However, these disinfectants easily react with some natural or man-made organic compounds in raw water and form disinfection by-products (DBPs). For example, halogenated acetic acid (HAAs) and trihalomethanes (THMs) are two main components of DBPs. These DBPs contained in drinking water will increase the risk of cancer in human body. Therefore, researches on halogenated acetic acid’s potential of causing cancer have increased currently. Organic acids are usually the reactants which proceed in chlorination reaction into products of disinfection by-products in water treatment plant. The purpose of this study is to investigate adsorption characteristics in solution by using tests of kinetics and equilibrium adsorptions and kinetic model evaluations of selected fulvic acids (FA) extracted from raw water. Therefore, we use commercial single-walled carbon nanotube (SWCNT) for the adsorbents, and calculate thermodynamic parameters (ΔG, ΔS and ΔH) in order to further understand the adsorption mechanism of CNTs.
The maximum adsorbed amounts of FA onto SWCNTs was calculated by the Langmuir model at 25℃, reaching 61.88mg / g which were much higher than that onto commercially available granular activated carbon (10.69 mg/g). The adsorption capacity of FA onto CNTs increased with decreasing outer diameter of CNTs (dp), molecular weight of FA, trmperature and pH value in all texts. In the condition of constant temperature 25℃, we analyzed HAAFP after the test of equilibrium adsorption and that the removal efficiency of HAAFP could reach 40.76%. The best selection in kinetic models evaluation, fitting models such as Modified Freundlich equation, Pseudo-1st-order equation and Pesudo-2nd-oder equation, is Modified Freundlch equation model. In addition, intraparticle diffusion equation model was fitted well and showed adsorption process was controlled by pore diffusion. We calculated the activation energy of carbon nanotube adsorption of FA and found that film diffusion was the main factor for controlling reaction rate. According to results of thermodynamic parameters indicated that the adsorption was spontaneously and an exothermic reaction.
It is obvious that the adsorption capacity as well as the reaction rate of CNTs are superior to that of granular activated carbon in raw water. These results suggest that CNTs possess highly potential applications in environmental protection. In the future, if we can combine nanotube technology with disinfection technology and apply such technique on the end of processing unit for design of either the domestic treatment facilities or small simple water treatment in drinking water. Thus it will enhance the new treatment technology of drinking water and the safety of the public health. Another possibility will be to promote the opportunity of marketing development in drinking water.

謝誌........................................................................................ I
摘要......................................................................................... I
英文摘要............................................................................... III
目錄........................................................................................ V
表目錄.................................................................................... X
圖目錄....................................................................................XI
第一章 緒論........................................................................... 1
1.1 研究緣起......................................................................... 1
1.2 研究目的及內容............................................................. 3
第二章 文獻回顧................................................................... 5
2.1 水體中有機物之來源..................................................... 5
2.2 水中背景有機物之性質與結構分析............................. 6
2.2.1 腐植質...........................................................................6
2.2.2 非腐植質類.................................................................. 7
2.2.3 水中背景有機物之結構分析...................................... 8
2.3 有機物對淨水工程的影響........................................... 10
2.4 消毒副產物................................................................... 13
2.5 鹵化乙酸與鹵化乙酸生成潛勢................................... 17
2.5.1 鹵化乙酸的來源....................................................... 17
2.5.2 鹵化乙酸之分類....................................................... 17
2.5.3 鹵化乙酸生成因素................................................... 19
2.5.4 鹵化乙酸之法規管制標準....................................... 21
2.5.5 鹵化乙酸生成潛勢................................................... 22
2.6 奈米碳管的材料特性與應用....................................... 23
2.6.1 奈米碳管的特性與結構........................................... 23
2.6.2 奈米碳管的吸附能力............................................... 26
2.6.3 奈米碳管的界達電位............................................... 27
2.6.4 奈米碳管之應用....................................................... 29
2.7 吸附原理....................................................................... 31
2.8 影響吸附能力因子....................................................... 34
2.9 吸附模式....................................................................... 36
2.9.1 動力吸附模式........................................................... 36
2.9.2 等溫吸附模式........................................................... 38
2.10 熱力學模式................................................................ 41
第三章實驗方法與步驟..................................................... 42
3.1 實驗流程....................................................................... 42
3.2 實驗材料與設備........................................................... 43
3.2.1 實驗材料................................................................... 43
3.2.2 實驗設備................................................................... 44
3.2.3 實驗藥品................................................................... 45
3.3 黃酸製備及前置實驗................................................... 47
3.3.1 黃酸萃取前置實驗................................................... 47
3.3.2 黃酸製備方法........................................................... 49
3.3.3 定量分析................................................................... 51
3.3.4 定性分析................................................................... 52
3.4 鹵化乙酸分析方法....................................................... 54
3.4.1 HAAs 分析步驟........................................................ 55
3.4.2 採樣與保存............................................................... 58
3.4.3 氣相層析儀分析條件............................................... 59
3.4.4 檢量線之建立........................................................... 59
3.4.5 鹵化乙酸生成潛勢分析方法................................... 60
3.5 奈米碳管之特性分析.................................................. 61
3.5.1 掃描式電子顯微鏡(SEM)........................................ 61
3.5.2 比表面積分析儀(BET)............................................. 61
3.5.3 霍氏轉換紅外線光譜(FTIR) ................................... 62
3.5.4 熱重量分析儀(TGA) ................................................ 62
3.6 吸附實驗...................................................................... 64
3.6.1 實驗裝置................................................................... 64
3.6.2 吸附動力實驗........................................................... 64
3.6.3 等溫吸附平衡實驗................................................... 65
3.6.4 不同溫度之吸附平衡實驗....................................... 66
3.6.5 奈米碳管對不同黃酸初始濃度之HAAFP 去除量.. 67
第四章 結果與討論............................................................ 69
4.1 奈米碳管與粒狀活性碳(GAC)之特性分析................ 69
4.1.1 SEM 量測.................................................................. 69
4.1.2 孔隙結構................................................................... 71
4.1.3 霍氏轉換紅外線光譜(FTIR) ................................... 73
4.1.4 熱重分析(TGA) ........................................................ 75
4.1.5 能量散佈光譜(EDS)................................................ 75
4.2 奈米碳管吸附原水中黃酸之特性研究....................... 76
4.2.1 吸附平衡動力實驗................................................... 76
4.2.2 吸附動力實驗之探討............................................... 77
4.2.3 不同溫度之吸附平衡實驗....................................... 80
4.2.4 吸附熱力學之探討................................................... 82
4.3 奈米碳管與GAC 吸附黃酸效果之比較..................... 85
4.4 鹵化乙酸生成潛勢(HAAFP)之去除........................... 88
4.5 與文獻其它吸附劑之比較.......................................... 94
第五章 結論與建議............................................................ 96
5.1 結論............................................................................... 96
5.2 建議............................................................................... 97
參考文獻............................................................................. 98
附錄-口試委員意見回覆.................................................. 106

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