指導教授：陳延平臺灣大學：化學工程學研究所王欣薇Wang, Hsin-WeiHsin-WeiWang2014-11-252018-06-282014-11-252018-06-282014http://ntur.lib.ntu.edu.tw//handle/246246/261129本研究使用一套高壓低溫的設備，進行二氧化碳水合物之熱力學與動力學實驗研究。採用等容溫度循環法量測二氧化碳+純水+添加劑之熱力學相平衡數據，以及在等容之系統中以升壓方式進行動力學實驗。本研究選用之添加劑為環醚類之1,3-二氧六環、醯胺類之乙醯胺及醇類之環戊醇。 由本研究之實驗結果顯示當添加1,3-二氧六環，對水合物的生成有促進之效果，使二氧化碳水合物穩定存在區域擴大。而其促進效果隨著添加之濃度增加而提升，20 wt% 之1,3-二氧六環平衡溫度最多可增加約7.8 K。另外，添加乙醯胺對二氧化碳水合物有抑制效果，抑制效果隨濃度增加而變大，在20 wt% 時最大，抑制溫度約5 K。此外，為了模擬海洋環境，本研究亦進行二氧化碳＋鹽水＋添加劑之水合物系統相平衡條件的量測，由實驗結果發現當添加1,3-二氧六環至鹽水系統中亦有促進二氧化碳水合物生成之效果；而添加抑制劑乙醯胺則是使二氧化碳水合物相平衡曲線往溫度更低和壓力更高的方向移動。由於受到鹽分的影響，其促進效果較添加至純水系統時為低；抑制效果較純水系統時為高。 另外，添加環戊醇於熱力學上促進效果不明顯，促進溫度最大只達2 K，但於熱力學實驗過程中發現，其在動力學水合物生成方面具有促進的效果，故以環戊醇作為添加劑進行動力學實驗。由實驗之結果證實，相較於純水系統而言，添加環戊醇可大幅縮短水合物生成之誘導時間並增加水合物生成之速率。In this study, an apparatus which can be operated at high pressure and low temperature conditions was built and operated to measure the carbon dioxide hydrate of thermodynamics phase equilibrium and kinetics formation rate. In the thermodynamic part, this study used isochoric method to measure the carbon dioxide-hydrate-liquid water phase equilibrium boundary curve. In kinetics parts, using the pressurization in isochoric system to measure the formation rate and the amount of carbon dioxide hydrate. In this research, 1,3-Dioxane, Acetamide, and Cyclopentanol were chosen as additives. In thermodynamic experimental results showed that the addition of 1,3-Dioxane in carbon dioxide system had effective promotion effects on formation of carbon dioxide in comparison with pure water system at a given pressure, and they could broaden the hydrates stability region. Furthermore, the promotion effect could increase as the concentration of additives increased. With the concentration of 20 wt% 1,3-Dioxane additives, the dissociation temperatures were increased about 7.8 K. With 20 wt% Acetamide, the equilibrium temperature decreased about 5 K at given pressure in comparisoon to that of pure water system. In addition, the hydrate dissociation conditions for brine systems with 3.5 wt% NaCl were also measured in this study. The promotion effect for carbon dioxide hydrate formation in brine environment was also observed with 1,3-Dioxane. However, the promotion effects in the presence of 1,3-Dioxane additives in the salt system was less than those in the pure water system. On the other hand, the inhibition effects were observed when adding Acetmaide in brine system, the equilibrium conditions shifted to higher pressure and lower temperature in comparison with pure water system. Although the promotion effect of adding Cyclopentanol in carbon dioxide hydrate system was not good. It seemed that Cyclopentanol could increase the formation rate and decrease the induction time of carbon dioxide hydrates in thermodynamic experiments, so Cyclopentaonl was chosen as additive in kinetic experiments. The kinetic results proved Cyclopentaonl could reduce the induction time of forming carbon dioxide hydrates in comparison with pure water system, and the initial rate of hydrate formation was effectively increased by adding Cyclopentanol. In conclusion, Cyclopentaonl was effective kinetic promoter to form carbon dioxide hydrates in this work.摘要 I Abstract II 目錄 IV 表目錄 VII 圖目錄 IX 第一章 緒論 1 1-1 水合物介紹 2 1-2 二氧化碳水合物介紹及相關應用 4 1-3 二氧化碳捕捉與封存 (Carbon Dioxide Capture and Storage, CCS) 6 1-4 研究方向與目的 11 第二章 文獻回顧 13 2-1 水合物的相圖和相律 13 2-2 水合物生成機制 15 2-3 水合物結構之鑑定 17 2-4 水合物熱力學的相關研究 18 2-5 水合物動力學方面之研究 21 第三章 實驗方法 23 3-1 實驗設備與藥品 24 3-2 實驗步驟 25 3-2.1 熱力學實驗步驟 25 3-2.2 動力學實驗步驟 27 3-3 實驗數據分析 29 3-3.1 熱力學實驗數據分析 29 3-3.2 動力學實驗數據分析 30 第四章 結果與討論 31 A. 熱力學之水合物相平衡實驗 31 4A-1 溫度循環之流程 31 4A-2 純水對比實驗 32 4A-2.1二氧化碳水合物結構之預測 34 4A-3添加劑篩選及測試實驗 34 4A-4二氧化碳+純水+1,3-二氧六環之水合物系統相平衡數據 36 4A-4.1 二氧化碳+純水+1,3-二氧六環之水合物結構預測 37 4A-4.2 1,3-二氧六環與文獻添加劑比較 38 4A-5二氧化碳+純水+乙醯胺之水合物系統相平衡數據 39 4A-5.1 二氧化碳+純水+乙醯胺之水合物結構預測 40 4A-5.2 乙醯胺與文獻添加劑比較 40 4A-6二氧化碳+純水+環戊醇之水合物系統相平衡數據 41 4A-6.1 二氧化碳+純水+環戊醇之水合物結構預測 42 4A-6.2 環戊醇與文獻添加劑比較 42 4A-7二氧化碳+鹽水+添加劑之水合物系統相平衡數據 43 B. 動力學實驗數據量測 45 4B-1. 升壓方式之實驗流程 45 4B-2. 動力學實驗條件之選擇 46 4B-3. 動力學實驗結果討論 47 4B-3.1 純水系統與環戊醇系統之動力學實驗 47 4B-3.2 二氧化碳+純水+環戊醇系統之過冷溫度探討 48 4B-3.3二氧化碳+純水+環戊醇系統之攪拌速率探討 49 4B-3.4 二氧化碳+純水+環戊醇系統之操作壓力探討 50 第五章 結論 52 參考文獻 1183071803 bytesapplication/pdf論文使用權限：不同意授權二氧化碳水合物等容溫度循環法相平衡水合物生成動力學乙醯胺環戊醇1,3-二氧六環鹽水thesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/261129/1/ntu-103-R01524090-1.pdf