在都市垃圾焚化處理過程中，由於垃圾分類未能確實執行，使得焚化垃圾中夾雜許多有害物質，而這些有害物質往往無法藉由焚化或空氣污染控制設備予以去除。在都市垃圾成份中以重金屬物質最難處理，其中又以含汞污染物較為人們所重視，其對環境及人體健康之危害甚鉅。汞金屬及其化合物（如：氯化汞）因具有較高之蒸氣壓，故在焚化爐高溫環境下極易揮發而隨廢氣排出，若未能以空氣污染控制設備（Air Pollution Control Devices; APCD）予以有效去除，則會排放至大氣中，再經由不同的傳播途徑對環境生物造成嚴重傷害。
污染物在多孔性吸附劑進行吸附時，吸附質經分子擴散作用，由濃度較高的外界環境進入吸附劑的過程，一般區分為下列三個步驟：外部擴散(external diffusion)、內部擴散(internal diffusion)及表面吸附(surface adsorption)。由於一般吸附反應速率相當快(約10-6 sec)，所以控制污染物吸附速率之快慢主要與擴散步驟有關。
若能了解控制氣相氯化汞在活性碳中之傳輸與平衡機制，並求得最佳參數，將有助於設計更有效率更可靠之且吸附設備。國內外相關研究多集中於污染物(如: VOCs)在吸附劑中吸/脫附平衡與動力探討；相對而言，氣相重金屬在高溫之吸附平衡與動力之研究則甚少，因此值得深入探討。本研究旨在探討球狀活性碳對於氣相氯化汞之吸附能力，並模擬室溫(30℃)及高溫(70℃及150℃)條件對氯化汞吸附模式之影響，建立球狀活性碳吸附氣相氯化汞之等溫吸附模式及吸附動力模式。
本研究之實驗結果發現在恆溫操作條件下，球狀活性碳之氯化汞吸附容量因氣固平衡反應之故，隨氯化汞初始濃度之增加而有升高之趨勢。球狀活性碳於高溫操作條件下，氯化汞吸附容量較室溫為低。
由等溫吸附模式結果得知，在30 ℃及70℃時，球狀活性碳吸附氣相氯化汞行為偏向Freundlich Isotherm,由n值可判斷球狀活性碳吸附氣相氯化汞為有利吸附(n<1)且屬於單層吸附反應。但在150 ℃時則為不利吸附(n>1)。由實驗結果與模式比較後證明，經修改後的孔隙擴散模式能夠用於模擬室溫及高溫條件下活性碳對氯化汞之吸附行為。

This study investigated the adsorptive capacity and isotherm of HgCl2 onto spherical activated carbons (SAC) via thermogravimetric analysis (TGA). Activated carbon injection (ACI) is thought as the best available control technology (BACT) for mercury removal from flue gas. There are two major forms of vapor-phase mercury, Hgo and Hg2+, of which HgCl2 accounts for 60-95% of total mercury. Mercury emitted from the incineration of municipal solid wastes (MSW) could cause severely adverse effects on human health and ecosystem since it exists mainly in vapor phase due to high vapor pressure. Although the adsorptive capacity of HgCl2 onto activated carbon has been studied in previous adsorption column tests, only a few studies have thoroughly investigated the adsorption isotherms of HgCl2 onto SAC.
Equilibrium and kinetic studies are important towards obtaining a better understanding of mercury adsorption. Many investigations have addressed the relationship between sorption kinetics and equilibrium for different adsorbent/adsorbate combinations. For the removal of vapor-phase mercury, several bench-pilot, and full-scale tests have be proceeded to examine the influence of carbon types, carbon structures, carbon surface characteristics, injection methods (dry or wet), amount of carbon injected, and flue gas temperature on mercury removal. In addition, the dynamics of spherical activated carbons (SAC) adsorbers for the uptake of gas-phase mercury was evaluated as a function of temperature, influent concentration of mercury, and empty-bed residence time. However, only a few studies investigated the adsorption isotherms of HgCl2 onto activated carbons.
In this study, TGA was applied to obtain the adsorptive capacity of HgCl2 onto SAC with adsorption temperature (30~150oC) and influent HgCl2 concentration (50~1,000μg/m3). Experimental results indicated that the adsorptive capacity of HgCl2 onto SAC was 0.67and 0.20 mg/gC at 30、70 and 150oC, respectively. This study investigated the adsorptive capacity of HgCl2 vapor onto SAC via TGA analysis. Experimental results indicated that the adsorptive capacity of SAC decreased with the increase of the adsorption temperature. Furthermore, the results suggested that that the adsorption of SAC on HgCl2 vapor was favorable equilibrium at 30 and 70℃ and unfavorable equilibrium at 150℃. In comparison of the experimental data with isotherm equations, Freundlich isotherm fitted the experimental results better than Langmuir isotherm. The model simulations were found to fit very well to the high concentration experimental kinetic data for both adsorption and desorptionusing two adjust parameter, effective diffusivity, and the Freundlich isothermexponent.　The extracted model parameter, effective diffusivity and n, were then used to predict the experimental kinetic data for the same combination at other concentrations.

目 錄
中文摘要……………………………………………………….. Ⅰ
英文摘要……………………………………………………….. Ⅲ
目錄………………………………………………………………. Ⅳ
表目錄…………………………………………………………… Ⅷ
圖目錄…………………………………………………………….. Ⅸ
第一章 前言…………………………………………………… 1-1
1-1 研究緣起…………………………………………………… 1-1
1-2 研究目的……………………………………………………… 1-2
第二章 文獻回顧……………………………………………… 2-1
2-1 含汞污染物之來源及種類………………………………. 2-1
2-1-1 含汞污染物之來源………………………………… 2-1
2-1-2 含汞污染物之傳輸途徑………………………….. 2-3
2-2 含汞污染物之排放標準與控制技術…………………… 2-6
2-2-1 都市垃圾焚化爐含汞污染物之排放標準…… 2-6
2-2-2 含汞污染物之控制技術………………………….. 2-7
2-3 汞之物化特性及影響……………………………………… 2-9
2-3-1 汞之物理化學特性………………………………… 2-9
2-3-2 汞對人體健康之影響………………………….. 2-11
2-4 活性碳之種類與特性……………………………………… 2-13
2-4-1 活性碳之種類……………………………………… 2-13
2-4-2 活性碳之物化特性……………………………….. 2-15
2-4-3 活性碳之吸附機制……………………………….. 2-17
2-5吸附模式及理論……………………………………………… 2-18
2-5-1 吸附擴散模式……………………………………… 2-19
2-5-2 恆溫吸附模式……………………………………… 2-19
2-5-2-1 Langmuir Isotherm……………………..… 2-20
2-5-2-2 Freundlich Isotherm……………………… 2-22
2-5-2-3 Redlich and Peterson Isotherm…………… 2-23
2-5-2-4 Toth Isotherm Isotherm………………… 2-24
2-5-2-5 Brunauer-Emmett-Teller Isotherm…….. 2-25
2-5-3 恆溫吸附曲線特性… …………………………… 2-25
2-5-3-1恆溫吸附曲線類型………………………. 2-25
2-5-3-2滯後(Hysteresis loop)現象………………. 2-27
2-5-4 動力吸附模式………………………………... 2-31
2-6 活性碳脫附機制與動力模式………………………. 2-35
2-7 吸附劑之孔隙曲折度……………………………….. 2-36
2-8 熱重分析儀(TGA)之應用…………………………… 2-38
第三章 研究方法……………………………………………… 3-1
3-1 實驗設計與流程…………………………………………….. 3-1
3-2 實驗設備………………………………………………………. 3-3
3-3 實驗方法……………………………………………….……… 3-4
3-4 數據處理………………………………………………………. 3-10
第四章 結果與討論…………………………………………… 4-1
4-1 活性碳物理特性分析結果………………………..………. 4-1
4-1-1 活性碳外觀構造特性……………………….……….. 4-1
4-1-2 比表面積及孔隙分析結果…………………………. 4-1
4-2 活性碳吸附氣相氯化汞之結果…………………………. 4-5
4-3 氣相氯化汞恆溫吸附模式之結果………………………. 4-9
4-4 活性碳吸附動力分析………………………………………. 4-15
4-4-1 外部擴散…………………………………….….………. 4-15
4-4-2 分子擴散………………………………………………... 4-15
4-4-3 紐森擴散…………………………….………….…….… 4-16
4-4-4 孔隙擴散…………………………………………….….. 4-16
4-5室溫下活性碳吸附動力模式預測結果………………… 4-17
4-6高溫下活性碳吸附動力模式預測結果………………… 4-22
4-6-1 70℃下活性碳吸附動力模式預測結果………..… 4-24
4-6-2 150℃下活性碳吸附動力模式預測結果………… 4-25
4-7吸附劑之孔隙曲折度……………………………….………. 4-36
第五章 結論與建議……………………………….…………………… 5-1
5-1結論……………………………………………………..……….. 5-1
5-2建議………………………….……………………….……….…. 5-2
參考文獻……………………………………………………..………….… 6-1

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