研究生: |
許詩韓 Shr-Han Shiu |
---|---|
論文名稱: |
氧化銅載氧體之化學迴圈釋氧機制及其應用於石墨燃燒之探討 Reaction Mechanisms of Cu-based Oxygen Carriers for Chemical Looping with Oxygen Uncoupling and Its Application with Graphite Combustion |
指導教授: |
顧洋
Young Ku |
口試委員: |
曾迪華
Dyi-Hwa Tseng 蔣本基 Pen-Chi Chiang 郭俞麟 Yu-Lin Kuo 曾堯宣 Yao-Hsuan Tseng |
學位類別: |
碩士 Master |
系所名稱: |
工程學院 - 化學工程系 Department of Chemical Engineering |
論文出版年: | 2012 |
畢業學年度: | 100 |
語文別: | 英文 |
論文頁數: | 163 |
中文關鍵詞: | 化學迴圈程序 、化學迴圈釋氧程序 、載氧體 、石墨燃燒 、二氧化碳捕獲與封存 |
外文關鍵詞: | Chemical looping process, chemical looping with oxygen uncoupling, oxygen carrier, graphite combustion, CO2 capture and sequestration |
相關次數: | 點閱:252 下載:3 |
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本研究之主要目的為製備適合化學迴圈釋氧程序之銅系載氧體,探討氧化銅釋氧與氧化之反應動力,並應用於石墨燃燒。實驗結果顯示:氧化銅於氮氣氣氛下進行釋氧程序時,隨著反應溫度提高,氧化銅分解速率隨之增加;而氧化過程中,反應溫度提高,不僅提高氧化反應速率,也加速氧化銅釋氧,因此造成氧化轉化率下降。研究結果亦發現,氧化銅與合成氣反應,會生成熔點低的銅金屬,因此易產生凝結團聚現象。
本研究並將氧化銅與氧化鋯混合,以製備具有高機械強度及反應特性的複合載氧體。結果顯示氧化銅與氧化鋯比例為2比3時,於合成氣及氮氣反應操作下具有50次氧化還原迴圈數。然而當氧化銅含量高於氧化鋯時,易造成氧化銅與合成氣反應時,會生成較多的液相銅,燒結並覆蓋氧化鋯,導致粒徑增加、比表面積減少以及氧化還原迴圈數下降。本研究亦利用澱粉作為載氧體孔洞生成劑,可有效提升載氧體之反應性,載氧體並可穩定進行2000圈的氧化還原操作,然而,添加過多澱粉於氧化銅/氧化鋯複合載氧體會導致機械強度降低。
本研究亦將氧化銅/氧化鋯複合載氧體與石墨置入固定床反應器進行測試,調整載氧體顆粒尺寸與反應溫度,探討載氧體與石墨之化學迴圈釋氧程序(CLOU)及化學迴圈程序(CLP)反應,實驗結果顯示於CLOU程序中以氧化銅/氧化鋯載氧體與石墨之燃燒良好。相對於CLP程序中,先將石墨被氣化後再與載氧體燃燒,完全轉換燃料所耗費的時間降低3倍。
Preparation of Cu-based oxygen carrier and combustion of graphite in CLOU was investigated in this study. The reaction kinetics for decomposition and oxidation of CuO oxygen carrier in CLOU was studied. Experimental results indicated that in decomposition process, the decomposition rate was increased with increasing reaction temperature thus decomposition conversion was increased. On the contrary, in oxidation processes, the oxidation conversion decreased due to decomposition rate was tent to oxidation rate with increasing reaction temperature. The experiment also revealed that CuO reacted with syngas was obvious agglomeration due to reducing CuO to Cu, and Cu was exhibited lower melting temperature.
In order to increase the mechanical strength of carriers and increase the reactivity for carriers with syngas, CuO oxygen carriers were prepared with ZrO2 as inert support by mechanical mixing. The results showed that CuO/ZrO2 composed of 60 % ZrO2 was better redox reactivity than that reactivity of CuO under nitrogen and syngas atmosphere after 50 redox cycles. Higher ratio of CuO to ZrO2 was disadvantageous since liquid sintering lead to increase in particle size, decrease in surface area and number of redox cycles. Annealed at 1000 oC of CuO/ZrO2 was found adequate mechanical strength and induce the highest reduction conversion under syngas and nitrogen atmosphere due to smaller average particle size. After sintering process, the reactivity was decreased thus mixing 1.25 mg starch could be increased reactivity and number of 2000 redox cycles. However, the crush strength of CuO/ZrO2 was decreased with increasing starch content.
CuO/ZrO2 oxygen carrier was used in subsequent experiment of graphite combustion in fixed bed reactor. The combustion mechanism of graphite and oxygen carrier in CLOU was investigated with various particle sizes of CuO/ZrO2 and reaction temperatures. It revealed that CuO/ZrO2 oxygen carrier with particle size between 0.3-0.5 mm reacted at 950 oC in CLOU has three times lower time for 100% conversion of graphite than gasification of graphite and combustion in CLP.
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