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研究生： 許鴻升
Hung-Sheng Hsu
論文名稱： 以高分子聚合物模擬土壤有機質特定官能基對氣態有機污染物吸附行為之影響
The effect of specific functional groups in soil organic matter on the adsorption of vapor-phase organic compounds
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： 92
語文別： 中文
論文頁數： 85
中文關鍵詞： 非線性吸附 、特定作用力 、高分子聚合物 、土壤有機質
外文關鍵詞： nonlinear isotherm, polymer, soil organic matter (SOM)
相關次數： 點閱：8  下載：0 
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    • 摘要
    本研究選用四種已知結構之高分子聚合物模擬土壤有機質，利用Cahn D200型電子微量天平，摒除水分的干擾，以重量法對氣態有機污染物吸附行為之影響進行探討，並著重於低相對壓力下，吸附等溫線非線性吸附程度與有機質特定官能基及吸附質之物化特性間之相關性。
    實驗結果顯示，於相對壓力P/Po=0.1~0.8之範圍內，各吸附組合之氣態吸附等溫線均為線性，說明以高分子聚合物模擬土壤有機質吸持有機污染物，符合分佈作用吸附等溫線為線性之特徵。低相對壓力P/Po=0~0.1之範圍內，各組合之氣態吸附等溫線均出現凹口向下且彎曲程度不一之非線性吸附，彎曲程度與吸附質之極性大小明顯相關，當吸附質極性程度愈大，則非線性吸附程度愈大；極性程度愈小，則非線性程度愈小。吸附劑之特定官能基與非線性彎曲程度亦有高度相關性，實驗結果顯示，如羧酸基，氰基等極性官能基對非線性吸附程度有顯著的影響，主要是此類官能基與吸附質間產生氫鍵、偶極-偶極力等吸附作用力，使吸附劑吸附位址在低相對壓力下即達飽和。整體而言，本研究實驗結果說明分佈作用吸附等溫線於低相對壓力下之非線性彎曲程度與土壤有機質官能基及吸附質極性程度有明顯相關性。

    Abstract
    In researches of the sorption nonionic organic compounds by soil, the soil organic matters (SOM) has been recognized to behave as a partition medium. The unique isotherm shape which means the isotherms show nonlinear at low Ce/Sw but virtually linear at other Ce/Sw in soil/water system, implies that more than one mechanism is in effect over the entire range Ce/Sw. In order to evaluate the effect of specific functional groups in SOM on the adsorption of organic compounds, especially at low pressure, we chose polymers with known functional groups as the adsorbents in this experiment to simplify the complex characteristics of soil organic phase. To deliberate on the cause of such nonlinear sorption for organic contaminants at low pressure, several polar organic compounds were used to be the adsorbates.
    The surface area and adsorption/desorption characteristics isotherms were analyzed to realize the adsorbent structure and the surface images display the microcosmic appearances of the adsorbent. Vapor-phase adsorption isotherms of cyclohexane, benzene, acetonitrile, and methanol on polymers, such as Poly(acrylic-acid)、Poly(benzyl-methacrylate)、Poly(acrylonitrile)、and Carbowax, were gravimerically measured under 25℃.In all experimental data, the adsorption isotherms show nonlinearity with concave-downward curvatures at low relative pressure but exhibit a linear shape at higher pressure. The nonlinearity of isotherms coincides with solute polarity. The sorption capacities are greater for polar solutes than for nonpolar solutes. The nonlinear capacity increases progressively with increasing solute polarity for other solutes. In addition to the polarity, the functional groups of the adsorbents affect on the nonlinear sorption as well. There are the specific interaction, like H-bond and Van der Waal’s force adsorbent, between organic compounds and adsorbents with functional group of OH bond、COOH bond. In summary, the final results are fit with the specific-interaction model.

    目錄 目次 頁次 目錄……………………………………………………………......І 圖目錄…………………………………………………………….. IV 表目錄…………………………………………………………….. VI 第一章 前言…………………………………………………….. 1 1-1 研究緣起…………………………………………………1 1-2 研究目的與內容……………………………………... 2 第二章 文獻回顧…………………………………………….… 4 2-1 土壤………………………………………………………..4 2-1-1 土壤無機相………………………………………….. 4 2-1-2 土壤有機質…………………………….…………….. 7 2-1-3 土壤表面積………………………………………….. 8 2-1-4 土壤陽離子交換容量………………………….…..… 9 2-2 吸附理論……………………………………………...…10 2-2-1 吸附現象…………………………………………...… 10 2-2-2 土壤之吸持作用……………………………….…….. 11 2-2-2-1 土壤吸持之主要機制………………………….. 12 2-2-2-2 分佈作用(partitioning) ………………………… 15 2-3 影響吸附揮發性有機化合物的因子…………………. 17 2-3-1 不同黏土礦物的差異…………………………..…… 17 2-3-2 不同有機污染物的影響……………………………... 18 2-3-3 水份之影響………………...………………………… 19 2-3-4 土壤有機質的影響………………………………...… 20 2-3-5 溫度的影響…………...……………………………… 21 2-4 氣態吸附等溫線…………………………...………….22 2-5 土壤有機質吸附有機污染物…………………………..25 2-5-1 Glassy-Rubbery SOM Model……………………......25 2-5-2 Internal Hole Model………………………………….26 2-5-3 HSACM Model………………...………………..…… 26 2-5-4 SI model…………………………………….………...27 第三章 實驗設備、材料及方法……………………….………..29 3-2 實驗設備……………………………………………... 31 3-2-1 氮氣吸附孔隙儀(ASAP)…………………………….. 31 3-2-2 場放射掃描式顯微鏡…………………………….….. 34 3-2-3 微量天平…………………………………………..… 34 3-2-4 恆溫水浴槽………………………….….………….… 35 3-2-5 真空抽氣機……………………………..…………… 35 3-2-6 電子天平…………………………..………………… 35 3-3 實驗材料………………………………..……………. 36 3-3-1 吸附劑…….………………………..........……… 36 3-3-2 吸附質……………………………...………………… 39 3-4 實驗方法……………………………..………………..43 3-4-1 實驗配置……………………………..……………… 43 3-4-2 實驗步驟……………………………..……………… 46 第四章 結果與討論…………………………………………….. 49 4-1 吸附劑基本性質………………….…………………….49 4-1-1 氮氣吸/脫附曲線……………………………………. 49 4-1-2 掃描式電子顯微鏡……………………………….….. 53 4-2 氣態吸附等溫線………………………………………..55 4-2-1 不同吸附劑對環己烷的吸附等溫線……………….. 58 4-2-2 不同吸附劑對苯的吸附等溫線…………………….. 60 4-2-3 不同吸附劑對氰甲烷的吸附等溫線…………….….. 62 4-2-4 不同吸附劑對甲醇的吸附等溫線…………….…….. 64 4-2-5 各吸附組合之動力曲線…………………………….. 66 4-2-6 不同吸附質對吸附行為之影響…………………….. 69 4-3 有機質官能基對低濃度吸附行為之影響……………..72 4-3-1 低相對壓力環己烷之吸附等溫線…………………... 74 4-3-2 低相對壓力苯之吸附等溫線………………….…….. 75 4-3-3 低相對壓力氰甲烷之吸附等溫線…………….…….. 77 4-3-4 低相對壓力甲醇之吸附等溫線………………….….. 78 4-4 吸附質之極性對低濃度下吸附行為之影響……………80 第五章 結論與建議…………………………………………….. 83 5-1 結論………………………………………………………83 5-2 建議………………………………………………………85 參考文獻 ……………..…………………………………………86 圖 目 錄 目次 頁次 圖2-1 矽四面體與鋁八面體之構造示意圖……………......5 圖2-2 高嶺石之構造示意圖………......................6 圖2-3 蒙特石之構造示意圖……………………………….. 7 圖2-4 不同水份相對含量(R.H.)對吸附的影響………......19 圖2-5 吸附等溫線之基本形態…………………………….. 22 圖3-1 研究架構圖………………………………………….. 30 圖3-2 BET原理適用範圍示意圖………………………….. 32 圖3-3 苯之分子結構……………………………………….. 40 圖3-4 環己烷的椅式構形和船式構形…………………….. 41 圖3-5 實驗設備配置圖…………………………………….. 45 圖3-6 實驗流程…………………………………………….. 47 圖4-1 吸附劑PAACID、PBM與Carbowax之氮氣吸附等溫線………………………………………………….. 50 圖4-2 吸附劑Poly(acrylonitrile)之氮氣吸附等溫線……50 圖4-3 相對壓力P/Po=0.5下吸附劑對不同吸附質之吸附量…………………………………………………….. 57 圖 4-4 25℃下四種吸附劑對環己烷之氣態吸附等溫線….. 59 圖 4-5 25℃下四種吸附劑對苯之氣態吸附等溫線……….. 61 圖 4-6 25℃下三種吸附劑對氰甲烷之氣態吸附等溫線….. 63 圖 4-7 25℃下三種吸附劑對甲醇之氣態吸附等溫線…….. 65 圖 4-8 不同土壤與環境反應所需平衡時間範圍 ………… 66 圖 4-9 Poly(benzyl methacrylate)對四種吸附質之吸附動力曲線…………………………………………...……..68 圖 4-10 圖 4-11 Poly(acrylic acid)對四種吸附質之吸附等溫線…….. Poly(benzyl methacrylate)對四種吸附質之吸附等溫線…………………………………………………….. 70 70 圖 4-12 Poly(acrylonitrile)對四種吸附質之吸附等溫線…71 圖 4-13 Carbowax對兩種吸附質之吸附等溫線……………. 71 圖 4-14 相對壓力P/Po＜0.05下環己烷之氣態吸附等溫線... 76 圖 4-15 相對壓力P/Po＜0.05下苯之氣態吸附等溫線…….. 76 圖 4-16 相對壓力P/Po＜0.05下氰甲烷之氣態吸附等溫線.. 79 圖 4-17 相對壓力P/Po＜0.05下甲醇之氣態吸附等溫線…... 79 表 目 錄 目次 頁次 表2-1 partitioning和adsorption之比較……………………11 表3-1 吸附劑之物理性質………………………………….. 38 表3-2 吸附質之理化性質………………………………….. 39 表3-3 文獻之系統操作參數……………………………….. 46 表4-1 吸附劑相關結構參數……………………………….. 52 表4-2 各吸附劑之表面影像(左為放大1000倍、右為放大2000倍)……………………………………………… 54 表4-3 土壤有機質(SOM)中重要的官能基一覽表…… 73 表4-4 各吸附組合之明顯非線性吸附量………………….. 81

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