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研究生： 林慧美
Hui-Mei Lin
論文名稱： 有機污染物於含醇類水溶液中揮發特性之研究
The Study Volatile Characteristic of Organic Compounds from Aqueous System with Alcohol
指導教授： 李俊福
Jiunn-Fwu Lee
口試委員:
學位類別： 碩士
Master
系所名稱： 工學院 - 環境工程研究所
Graduate Institute of Environmental Engineering
畢業學年度： 96
語文別： 中文
論文頁數： 95
中文關鍵詞： 醇類 、界面特性參數(αA) 、質傳係數(KOL) 、揮發
外文關鍵詞： mass transfer coefficient (KOL), alcohol, Characteristic coefficient of interface ( αA), Volatilization
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    • 本研究群在先前已針對揮發性有機物自廢水中揮發的行為進行一系列之研究，由結果得知當溶解性大分子有機質或界面活性劑存在系統中時，會對其他有機物揮發造成抑制，但在研究過程中卻發現當系統中有醇類存在時，有機物的揮發速率會比沒有醇類存在時增加，特別是有風吹過液面時增加之情況更為明顯，此結果已偏離了預期之現象，本研究將以一系列的醇類添加及不同的氣相擾流條件來釐清醇類存在於溶液中對有機物揮發行為的影響機制。
    本研究所使用之有機化合物為11種單環類的芳香族化合物，其具有相似的結構及相近的亨利常數值(0.085~0.395)，但卻有差異相當大的水溶解度(1780~0.56mg/L)，依其水溶解度的高低共分成三大類來進行實驗分析，而添加之醇類以乙醇及正庚醇為主，濃度為100 mg/L ~ 500 mg/L，氣相擾動條件則為0 m/s ~ 1.0 m/s。
    由研究結果得知，推測正庚醇將有機污染物吸引至溶液界面之親和力遠大於乙醇，於靜置條件下乙醇確實會對有機污染物造成抑制作用，當加入氣相擾動條件後，風速增加至1.0 m/s時，才會造成有機污染物揮發量的增加；而正庚醇則有助於有機污染物的揮發，且添加微量風速(0.2 m/s)即可造成有機污染物之揮發量明顯上升。此外，亦得知低水溶解度化合物受風速條件之影響將大於高水溶解度之化合物；由所獲得之結果彙整後發現，有機污染物本身之物理化學特性除了亨利常數外，分子量及水溶解度為影響揮發速率最為顯著之因子。

    Abstract
    Our previous researches have been conducted on a series studies for the volatilization behavior of volatile organic matters from the waste water. From the results, it has been shown presented that, when the dissolving macromolecular organic matter or surfactant presented in the system, the volatilization rate of organic matters show dramatically decrease. During the investigation, we have also found that, when alcohol is existing in the system, the volatilization rate of organic matters will increase as compare to the systems without alcohol. The phenomenon is more obvious especially when wind is blowing through the surface of the liquid. This research carried out a series of different gaseous phase conditions to evaluate the influence of alcohol on the volatilization behavior of organic matters.
    The selected compounds consist of 11 kinds of mono-aromatic hydrocarbon, with similar structure and Henry''s constant value (0.085 to 0.395), but there is great difference of water solubility (1780 mg/L to 0.56 mg/L). We divided the compounds into three classes according with the level of water solubility during the experiment ranged. The alcohol adding is mainly ethanol and heptanol, the concentration ranged from 100 mg/L to 500 mg/L and gaseous phase turbulence changed from 0 m/s to 1.0 m/s.
    As the result, we could conclude that the ability of heptanol able to attract the organic pollution to the solution interface is much greater than that of ethanol. At still condition, the ethanol could truly cause the inhibition on the organic vaporization. However, under the condition of gaseous phase turbulence 1.0m/s, the organic volatilization is increased. Moreover, the heptanol could increase the organic compounds volatilization. The volatilization rate of the organic compounds would obviously be risen when the condition of micro-wind speed (0.2 m/s) is added in.
    In addition, we also found that the chemical compounds with low water solubility could be affected by the gaseous phase turbulence condition which is greater than that of compounds with high water solubility.
    Key word：Volatilization, alcohol, mass transfer coefficient (KOL), characteristic coefficient of interface ( αA)

    目 錄 第一章 前言 1 1-1研究緣起 1 1-2研究目的 2 1-3研究架構 3 第二章 文獻回顧 5 2-1基本理論介紹 5 2-1-1勞特定律(Raoult，s Law) 5 2-1-2亨利定律(Henry，s Law) 6 2-1-3二相分佈理論(Partitioning) 6 2-1-4二層膜理論(Two-film Theory) 8 2-1-5表面損失揮發模式(Surface Depletion Rate-limiting , SDRL) 11 2-1-6增溶作用 14 2-2醇類之結構及其性質 15 2-3揮發性有機物(VOCs)之揮發特性 16 2-3-1揮發性有機物(VOCs)之定義及其特性 16 2-3-2揮發性有機物自自然水體中揮發之行為 17 2-3-3揮發性有機物自廢水中揮發之行為 19 2-4影響揮發之因子 21 2-4-1有機物本身之物理化學性質 22 2-4-2溶劑性質 23 2-4-3環境條件 23 2-5 有機物揮發之先期探討 25 2-5-1 一階反應測試 25 2-5-2 參考化合物之概念 26 2-5-3共同溶質揮發干擾效應 29 2-6 氣相擾流對有機物自水中揮發之影響 31 2-7界面活性劑如何影響有機物之揮發 33 第三章 實驗流程及研究方法 35 3-1實驗材料 35 3-1-1有機物之基本理化特性及其來源 36 3-1-2醇類之基本理化特性及其來源 37 3-1-3其他試劑 37 3-2實驗設備 38 3-2-1實驗模廠設計 38 3-2-2其他實驗儀器設備 40 3-3實驗方法 41 3-3-1增容實驗 41 3-3-2揮發實驗 42 3-3-3環境條件 43 3-4研究方法 44 3-4-1計算質傳系數KOL 44 3-4-2 有機物之增溶效應 45 3-4-3 計算界面特性參數αA 47 第四章 結果與討論 48 4-1 有機污染物揮發反應先期測試 48 4-1-1 一階反應測試 48 4-1-2 醇類對有機污染物增溶效應之測試 50 4-1-3 有機污染物於醇類溶液中之揮發干擾效應 52 4-2 不同風速條件下有機污染物在醇類溶液之質量傳送係數 55 4-2-1 靜置條件下有機污染物於醇類溶液之KOL值 55 4-2-2 不同風速條件下有機污染物於乙醇溶液之KOL值 57 4-2-3 不同風速條件下有機污染物於正庚醇溶液之KOL值 62 4-3 醇類之增溶效應對有機污染物揮發速率之影響 66 4-3-1 有機污染物於乙醇溶液中在靜置條件下之ψ值變化 67 4-3-2 有機污染物於正庚醇溶液中在靜置條件下之ψ值變化 68 4-3-3 風速對特性參數ψ之影響 69 4-3-4 風速條件與醇類添加之影響比較 74 4-4 高亨利常數化合物在醇類溶液中之質傳系數比值 77 4-4-1 高水溶解度化合物在不同環境條件下之θ值 77 4-4-2 低水溶解度化合物在不同環境條件下之θ值 79 4-5 界面干擾對有機污染物揮發速率之影響 81 4-5-1 醇類特性所造成之界面干擾效應 81 4-5-2 風速對界面干擾效應之影響 85 4-6 在含醇類與界面活性劑溶液中有機污染物揮發特性之差異 88 第五章 結論與建議 90 5-1 結論 90 5-2 建議 92 第六章 參考文獻 93 圖 目 錄 圖1- 1 增溶實驗流程架構圖 3 圖1- 2 揮發實驗流程架構圖 4 圖2- 1 二相分佈示意圖 6 圖2- 2 二層膜理論揮發示意圖 9 圖2- 3 揮發性有機物一階反應測試(Lee et al., 2004) 26 圖2- 4 在不同的混合強度下kBen及kOrg之關係圖(Lee et al., 2004) 28 圖2- 5 在不同的界面活性劑濃度下kBen及kOrg之關係圖(Lee et al., 2004) 29 圖2- 6 苯單一化合物及苯與其他化合物混合時在不同的液相及氣相擾流下之KOL值(Chao et al., 2005) 30 圖2- 7 不同風速條件下之KOL比值與風速之關係 (Chao, 2008) 31 圖3- 1 實驗模廠設計圖 39 圖4- 1 有機污染物於不同環境條件下其濃度變化與時間之關係 49 圖4- 2 五氯苯單一化合物及五氯苯與其他化合物混合時在不同環境條件下之KOL相關性 52 圖4- 3 五氯苯單一化合物及五氯苯與其他化合物混合時在不同正庚醇濃度下之KOL值 53 圖4- 4 不同風速條件下第一類化合物於乙醇溶液中之KOL值 60 圖4- 5 不同風速條件下第二類化合物於乙醇溶液中之KOL值 61 圖4- 6 不同風速條件下第三類化合物於乙醇溶液中之KOL值 62 圖4- 7 不同風速條件下第一類化合物於正庚醇溶液中之KOL值 65 圖4- 8 不同風速條件下第二類化合物於正庚醇溶液中之KOL值 66 圖4- 9 不同風速條件下第三類化合物於正庚醇溶液中之KOL值 66 圖4- 10 有機污染物於乙醇溶液中在不同風速條件下之整體特性參數ψ值 71 圖4- 11 有機污染物於正庚醇溶液中在不同風速條件下之整體特性參數ψ值 73 圖4- 12 第一類化合物KOL值受風速條件及乙醇作用影響之結果 75 圖4- 13 第三類化合物KOL值受風速條件及乙醇作用影響之結果 75 表 目 錄 表3- 1 有機物之物理化學性質 36 表3- 2 醇類之物理化學性質 37 表4- 1 有機污染物於不同濃度乙醇下水溶解度改變量之比值(S/S0) 51 表4- 2 有機污染物於不同濃度正庚醇下水溶解度改變量之比值(S/S0) 51 表4- 3 有機污染物於乙醇溶液中在靜置條件下之KOL(cm/min) 56 表4- 4 有機污染物於正庚醇溶液中在靜置條件下之KOL(cm/min) 56 表4- 5 有機污染物於乙醇溶液中在不同風速條件下之KOL(cm/min) 57 表4- 6 有機污染物於正庚醇溶液中在不同風速條件下之KOL(cm/min) 63 表4- 7 有機污染物於乙醇溶液中在靜置條件下之特性參數ψ值 67 表4- 8 有機污染物於正庚醇溶液中在靜置條件下之特性參數ψ值 69 表4- 11 有機污染物於純水中在不同風速條件下之α值 83 表4- 12 有機污染物在靜置之情況下於不同濃度乙醇溶液中之αA值 84 表4- 13 有機污染物在靜置之情況下於不同濃度正庚醇溶液中之αA值 85 表4- 14 有機污染物於乙醇溶液中在不同風速條件下之αA值 86 表4- 15 有機污染物於正庚醇溶液中在不同風速條件下之αA值 87 表4- 16 有機污染物於不同溶液中在靜置與風速條件下其αA值之變化 87

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