土壤無機相對揮發性有機污染物吸∕脫附行為之影響

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曾文妮(Wen-Ni Tseng ) 查詢紙本館藏

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環境工程研究所

論文名稱

土壤無機相對揮發性有機污染物吸∕脫附行為之影響
(The effect of soil mineral structure on the adsorption/desorption of volatile organic compounds)

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摘要(中)

土壤對有機污染物的吸持作用，包括無機相的吸附及有機相的兩相分佈。探究吸∕脫附機制的困難在於環境基質的複雜性，所以本研究摒除水分的干擾，針對土壤無機相的構造與其吸附作用進行探討。
實驗係透過量測BET表面積、孔洞體積、孔洞大小、孔徑分布、晶格間距及推測孔洞連結，並配合電子顯微鏡之表面影像而得土樣基本結構參數；再使用Cahn D-200電動天平並控制溫度，測量苯及正己烷在鈣─蒙特石與鈦─蒙特石上之等溫吸∕脫附曲線。
結果顯示，鈣─蒙特石經由過渡金屬鈦離子取代後，表面積、孔洞體積及平均孔徑均增加、孔徑分布趨向不均勻化、晶格C層間距改變且氣態吸∕脫附曲線不具遲滯迴圈，顯示了蒙特石的結構發生改變，也使得孔洞連結度變得更佳。鈦─蒙特石提供較多吸附位置，又無立體阻礙，所以在達單層飽和吸附量時，其吸附平衡所需的時間均較鈣─蒙特石為快，單層吸附量也較高，且等溫吸∕脫附曲線沒有迴圈，無遲滯現象。實驗所得之吸附熱則受到吸附劑的孔洞及氣體分子在孔洞內之排列影響，對於孔徑體積較小的鈣─蒙特石，其吸附熱須考量吸附劑與吸附質間的作用以及吸附分子間之作用力。

摘要(英)

The objective of this research is to evaluate the effect of soil structure on the adsorption/desorption of volatile organic compounds (VOCs). The migration and the fate of nonionic organic pollutants in soils are highly depended on their vapor-phase sorptive behavior. However, it is difficult to explicit the mechanism of adsorption/desorption due to complexity of environmental medium. In order to show the effects of soil structure on adsorption/desorption of VOCs, two kinds of montmorillnite with different exchange cation, calcium and titanium were individually used to examine the isotherms for the vapor uptake of benzene and n-hexane under 288K and 298 K.
After exchanged with metal cation, the porous structure of the mineral samples was changed. These changes were explored by quantifying the BET surface area, total pore volume, micropore volume, pore size distribution, surface fractal dimension (calculated from N2 adsorption/desorption isotherms), c-spacing (by XRD) and surface image (by SEM) of mineral phase. The results demonstrate that Ti-montmorillnite has higher surface area, extensive pore size distribution, and better pore connection.
The influences of temperature and soil properties were also investigated. A gravimetric adsorption apparatus was developed and used to generate adsorption/desorption isotherms of benzene and hexane on two dry soil samples at 288 and 298 K. Isosteric heats of adsorption were calculated and heat curves were established. Equilibrium isotherms were all Type II, characterizing vapor condensation to form multilayers. The sorption capacity of soils is positively correlated with specific surface area, pore size distribution and pore connection. Nevertheless, Ti-montmorillnite didn’t reveal hysteresis loop, which might be attributed to better pore size distribution and pore connection. Isosteric heats of adsorption on Ca-montmorillnite were influenced by the reaction between adsorbent and adsorbate as well as among adsorbate molecules.
The results of this study are to further understanding of soil properties, as a basis for desorption predictions. Findings, apply not only to environment applications but also to theoretical development.

關鍵字(中)

★ 揮發性有機化合物
★ 等溫吸∕脫附曲線
★ 蒙特石結構
★ 遲滯現象

關鍵字(英)

★ adsorption/desorption isotherm
★ montmorillnite
★ porous structure

論文目次

目錄…………………………………………………..I
圖目錄…………………………………………………….V
表目錄………………………………………………….VII
1第一章前言8
1-1研究緣起8
1-2研究流程11
1-3研究目的與內容13
2第二章文獻回顧15
2-1吸附理論15
2-2影響土壤吸附VOCs的因子17
2-2-1黏土礦物的差異18
2-2-2不同VOCs 的影響20
2-2-3水份之影響21
2-2-4土壤有機質的影響23
2-2-5溫度的影響23
2-3氣態等溫吸附線24
2-4土壤吸附氣態有機污染物之相關文獻28
2-5土壤無機相之組成30
2-5-1矽酸鹽礦物31
2-5-2交換性陽離子32
2-5-3蒙特石簡介33
2-6碎形幾何簡介34
2-6-1碎形理論35
2-6-2碎形理論與土壤無機相結構35
3第三章實驗設備、材料與方法37
3-1實驗內容37
3-2實驗設備39
3-2-1氮氣吸附孔隙儀(ASAP)39
3-2-2X光繞射儀(XRD)42
3-2-3場放射掃描式電子顯微鏡(SEM+EDS)43
3-2-4微量電子天平44
3-2-5恆溫水浴槽45
3-2-6真空抽氣機45
3-2-7真空冷凍乾燥機45
3-3實驗材料46
3-3-1吸附劑46
3-3-2吸附質49
3-4實驗內容52
3-4-1實驗設備配置52
3-4-2實驗步驟55
4第四章結果與討論59
4-1土壤基本性質59
4-1-1氮氣吸∕脫附曲線60
4-1-2X-ray繞射圖譜68
4-1-3掃描式電子顯微鏡70
4-2苯及正己烷之等溫吸∕脫附實驗71
4-2-115℃及25℃等溫吸∕脫附實驗71
4-2-2等溫吸∕脫附實驗之比較76
4-3吸附熱78
4-4等溫吸∕脫附動力曲線83
5第五章結論與建議85
5-1結論85
5-2建議86
6參考文獻 88
圖目錄
目次頁次
圖 1.1 研究流程11
圖 2.1 等溫吸附線之基本形態25
圖 3.1 蒙特石之構造47
圖 3.2 苯分子之結構49
圖 3.3 正己烷分子之結構50
圖 3.4 實驗設備及配置53
圖 3.5 實驗裝置54
圖 3.6 實驗流程56
圖 4.1 氮氣吸附等溫線60
圖 4.2 孔徑分布圖(PSD)62
圖 4.3 氮氣吸∕脫附曲線64
圖 4.4 實驗數據和碎形FHH方程式之擬合67
圖 4.5 XRD繞射圖譜69
圖 4.6 土樣之表面影像（放大2萬倍）70
圖 4.7 15℃及25℃之等溫吸附曲線72
圖 4.8 15℃之等溫吸∕脫附曲線74
圖 4.9 25℃之等溫吸∕脫附曲線75
圖 4.10 苯在鈣─蒙特石15℃及25℃的吸附曲線78
圖 4.11 苯在鈣─蒙特石上的等容吸附熱79
圖 4.12 蒙特石吸附苯及正己烷的吸附反應熱81
表目錄
目次頁次
表 3?1 非離子性有機化合物基本性質表51
表 3?2 各文獻之系統操作參數55
表 4?1 鈣─蒙特石與鈦─蒙特石基本性質比較表63
表 4?2 土樣表面結構參數67
表 4?3 BET法求得之吸附係數(C)與單層飽和吸附量77

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指導教授

李俊福(Jiunn-Fwu Lee)

審核日期

2001-7-13

推文