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研究生:李志遠
研究生(外文):Chih-Yuan Lee
論文名稱:運用冰晶法探討乙醇對甲烷及二氧化碳水合物解離之效應
論文名稱(外文):Application of the Ice Seed Method to Study the Effect of Ethanol on the Dissociation of Methane and Carbon Dioxide Hydrates
指導教授:陳立仁陳立仁引用關係
指導教授(外文):Li-Jen Chen
口試委員:陳延平陳柏淳
口試日期:2013-07-17
學位類別:碩士
校院名稱:國立臺灣大學
系所名稱:化學工程學研究所
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2013
畢業學年度:101
語文別:中文
論文頁數:121
中文關鍵詞:冰晶法甲烷水合物二氧化碳水合物乙醇催化劑快速合成快速解離
外文關鍵詞:ice seed methodCH4 hydrateCO2 hydrateethanolcatalyst
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本研究以冰晶法合成甲烷及二氧化碳水合物,並且探討乙醇蒸氣對甲烷及二氧化碳水合物之合成與解離過程所造成的影響。第一部分會先以拉曼光譜鑑定兩種合成方法(添加乙醇與否)所合成之水合物,經實驗結果得知兩種方法所合成之水合物為相同物質。
第二部分則探討合成前添加乙醇與否對合成過程之影響,發現乙醇可使甲烷及二氧化碳水合物在低溫時即可快速合成,在只經過一次加熱循環即可與不添加乙醇者經過兩次循環有相同之九成以上的轉化率,由上述兩部份證明乙醇所扮演之角色為催化劑。
第三部分是比較合成前添加乙醇與否對解離過程之影響,發現添加乙醇合成之甲烷及二氧化碳水合物在解離時明顯比未添加乙醇合成之甲烷及二氧化碳水合物快速許多,得知乙醇既可加速甲烷及二氧化碳水合物合成亦能加速水合物解離,並使甲烷及二氧化碳水合物之自我保存效應消失。
最後一部分為合成完後在高壓下加入5 ml乙醇,觀察只讓乙醇參與甲烷水合物之解離過程時,是否同樣也具有加速解離效果。實驗結果為其解離行為與合成前先添加乙醇之解離結果相似。此一發現可應用在開採自然界中之天然氣水合物,因為其可大大縮短開採甲烷水合物所需之時間。


In this study, we synthesized CH4 hydrate and CO2 hydrate using ice crystal method, and investigated the effect of ethanol vapor on hydrate synthesis and dissociation processes. In the first part of this research, Raman spectrum was applied to examine whether the addition of ethanol alters gas hydrates spectroscopic properties. According to the experimental spectra, the two substances are identical.
In the second part of this research, we investigated the influence of adding at the bottom of the reactor before synthesizing gas hydrate on formation. It is found that CH4 and CO2 hydrate can be synthesized at lower temperature when ethanol vapor exists. When ethanol vapor is added, the conversion of gas hydrates is over 90 % through one heating cycle, which is the same as the conversion of gas hydrates through two heating cycles without adding ethanol vapor. The two research results above prove that ethanol behaves as catalyst.
In the third part of this research, the influence of adding ethanol before hydrate formation on dissociation was investigated. It is shown that ethanol vapor can accelerate CH4 and CO2 hydrate synthesis and dissociation, and there is no self-preservation of CH4 and CO2 hydrate.
In the last part of this research, we injected 5 ml ethanol after CH4 hydrate was synthesized. The results show that adding ethanol before or after hydrate formation does not cause significant difference in dissociation behavior.
This finding can be applied to extract CH4 from hydrate in nature because ethanol significantly accelerates CH4 h hydrate dissociation.

摘要 I
Abstract II
目錄 IV
圖目錄 VII
表目錄 XII
第一章 緒論 1
1-1氣體水合物基本性質 2
1-2自我保存效應 4
1-3水合物工業上之應用及天然氣水合物開採方法 6
第二章 文獻回顧 14
2-1一般水合物合成方法 14
2-1-1攪拌法 14
2-1-2冰晶法 15
2-2影響水合物自我保存效應之因素 17
2-2-1晶格上之缺陷、冰的遮蔽效應(ice shielding)、晶格結構 17
2-2-2客體氣體(guest gas) 18
2-2-3 surface/volume ratio 18
2-3水合物解離過程比較 19
2-4以拉曼光譜測量水合物(添加乙醇當催化劑之差別) 20
第三章 實驗方法 38
3-1實驗設備及合成材料 38
3-1-1實驗設備 38
3-1-2合成材料 41
3-2實驗方法 42
3-2-1探討不同溫度對解離行為的影響 42
3-2-2合成完後打乙醇實驗流程 44
第四章 結果與討論 57
4-1拉曼光譜 57
4-1-1甲烷水合物之拉曼光譜 57
4-1-2 CO2 hydrate之拉曼光譜 58
4-2 甲烷水合物及二氧化碳水合物合成途徑 58
4-2-1甲烷水合物及甲烷水合物(乙醇)合成途徑比較 58
4-2-2二氧化碳水合物及二氧化碳水合物(乙醇)合成途徑比較 60
4-3甲烷水合物及二氧化碳水合物及解離結果 61
4-3-1甲烷水合物解離結果 61
4-3-2二氧化碳水合物解離結果 63
4-4以乙醇當催化劑之二氧化碳水合物及甲烷水合物解離結果 64
4-4-1以乙醇當催化劑之甲烷水合物解離結果 64
4-4-2以乙醇當催化劑之二氧化碳水合物解離結果 66
4-5甲烷水合物合成完後高壓下打入乙醇之實驗結果 66
4-6 甲烷水合物以HDPE包覆樣品之實驗結果 69
4-7 質量控制流量計校正方法與排水集氣法所造成之水合物不連續解離現象 70
4-7-1質量控制流量計校正方法 70
4-7-2排水集氣法所造成之水合物不連續解離現象 72
第五章 結論 108
第六章 參考文獻 110
附錄1.甲烷水合物合成後打乙醇實驗流程 114
附錄2. 質量控制流量計氣體體積換算方法 115
附錄3. 二氧化碳水合物解離時溫度及解離速率變化情形 116


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