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研究生： 沈百淳
Shen, Bai-Chun
論文名稱： HCl對Fe2O3/SiO2載氧體於高溫化學環路燃燒之影響
Effect of Hydrogen Chloride on Fe2O3/SiO2 for High-Temperature Chemical-Looping Combustion
指導教授： 朱信
Chu, Hsin
學位類別： 碩士
Master
系所名稱： 工學院 - 環境工程學系
Department of Environmental Engineering
論文出版年： 2011
畢業學年度： 99
語文別： 中文
論文頁數： 186
中文關鍵詞： 化學環路燃燒 、載氧體 、一氧化碳 、氫氣 、氯化氫
外文關鍵詞： Chemical-looping combustion, Oxygen carrier, CO, H2, HCl
相關次數： 點閱：80  下載：1 
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    • 隨著人口增加及經濟快速發展，使得全球對能源需求益增，但在化石燃料蘊藏有限與全球溫室效應的危機下，未來針對能源改善與二氧化碳減量之議題已成為趨勢。化學環路燃燒系統乃傳統煤炭氣化技術之進一步研發，不僅提高能源效率，對於CO2與NOX也具有良好的控制效果。因此，本研究探討以自行製備之20% Fe2O3/SiO2、20% NiO/SiO2及20% Mn2O3/SiO2載氧體之性能及與CO/H2/HCl反應之研究。

    在高溫下，金屬載氧體於TGA及固定床反應管之循環測試，得知Fe2O3在高溫下多次再生後較能保有穩定的還原效果及高反應性，因此選定20% Fe2O3/SiO2為最適合之載氧體進行操作參數試驗。以反應管模擬固定床，當空間流速為400 mL hr-1 g-1時，Fe2O3具有較佳之利用率；當CO濃度大於40%，使得載氧體與CO之間的反應性下降；H2濃度大於15%，發現載氧體的利用率有停滯的現象，推測原因為負載20%的活性重金屬本身無法提供更多的活性位置給還原氣體。HCl參與反應對載氧體之影響，結果得知H2氣氛下添加HCl使得整體的利用率提升至近100%；而CO氣氛下HCl的加入對載氧體的利用率並無顯影響性。

    XRD圖譜發現還原後之Fe2O3載氧體產生Fe2+2SiO4，經由多次還原氧化後之載氧體，發現有SiO2˙(H2O)X的晶相。利用FTIR即時監測CO/H2/HCl反應過程中之氣相反應物及生成物的消長情形，推測可能的反應機制，且由動力研究發現，第一型衰退模式較適合用來描述此結果。

    The increasing demand for energy resources has been the concern of world due to the population growth and economic developments. However, reserves of fossil fuels have been limited and global warming crisis is increasing. Hence, the technology improvement and carbon dioxide capture for energy issues have become a trend in the future. Chemical-looping combustion (CLC), one of the energy efficiency and CO2 and NOX good control effects, is considered a promising option for power generation. In the present work, the handmade carriers of 20% Fe2O3/SiO2, 20% NiO/SiO2 and 20% Mn2O3/SiO2 oxygen will be reacted with CO/H2 in the TGA system, and then best one will be chosen to perform continuous fixed-bed reactions.

    20% Fe2O3/SiO2 oxygen carrier was investigated for amounts of cyclic reaction in the TGA system and fixed-bed reactor, and Fe2O3 showed high reactivity and great mechanical strength. Hence, Fe2O3 was chosen as a suitable oxygen carrier to conduct following operating parameters. The space velocity was 400 ml hr-1 g-1 which showed a better utilization; as the CO concentration is greater than 40%, the utilization decreasing. H2 concentration was added more than 15%, so consequently the utilization has the phenomenon of stagnation. The results were speculated that Fe2O3 oxygen carrier couldn’t provide more effective active sites, as increasing the concentration of reactant gas. The effect of Fe2O3 oxygen carrier in chlorine-containing hot coal gas showed that the overall utilization went near 100% in H2 atmosphere. On the contrary, there is no obvious influence on the presence of HCl process in CO atmosphere. It was likely that the positive influence of H2 overpowered the absorption reaction of CO.

    Several instruments were used for observing the structure change, elemental composition and crystal transformation. From the XRD patterns, it can be found that after the reduction of oxygen-carrier-produced Fe2+2SiO4; furthermore, the SiO2˙(H2O)X crystalline phase would be outputted after regeneration. To obtain more information of gas phase changing during the CO/H2/HCl reduction, we used FTIR real-time monitoring the by-products, and then conducting the possible reaction mechanism. The kinetic model for the reduction of Fe2O3 oxygen carrier with CO, H2 and HCl of experiment results, the first deactivation model is suitable to describe results.

    摘要 I Abstract II 表目錄 VIII 圖目錄 X 第一章 前言 1 1-1 研究動機 1 1-2 研究內容與架構 3 第二章 文獻回顧 5 2-1 發電系統簡介 5 2-1.1 IGCC發電簡介 5 2-1.2 CLC發電簡介 8 2-1.3 CLR發電簡介 11 2-1.4 CLH發電簡介 12 2-2 一氧化碳之特性 14 2-2.1 一氧化碳之來源 14 2-2.2 一氧化碳之性質 14 2-2.3 一氧化碳之形成機制與排放物性 17 2-3 氫氣之特性 19 2-3.1 氫氣之來源 19 2-3.2 氫氣之性質 19 2-4 氯化氫特性 21 2-4.1 氯化氫之來源 21 2-4.2 氯化氫之性質 21 2-4.3 氯化氫之危害 23 2-5 載氧體製備方式 24 2-5.1 溶膠凝膠法 24 2-5.2 機械混合法 24 2-5.3 臨濕含浸法 25 2-5.4 溶解法 26 2-5.4 共沉澱法 27 2-6 載氧體特性 28 2-7 載氧體之選擇 34 2-7.1 金屬氧化物載氧體 36 2-7.2 載體型載氧體 39 2-8 載氧體之活性衰退 42 2-9 CLC操作參數之影響 44 2-10 表面物理吸附等溫線 46 2-11 載氧體還原反應動力之探討 48 2-11.1 衰退模式 49 2-11.2 Arrhenius表示式 51 第三章 研究方法與實驗器材 52 3-1 研究方法 52 3-1.1 實驗規劃 52 3-1.2 實驗步驟與方法 54 3-2 實驗器材 56 3-2.1 實驗材料 56 3-2.2 實驗系統裝置 58 3-2.3 主要儀器原理介紹 64 3-3 預備實驗 76 3-3.1 載氧體之製備 76 3-3.2 檢量線製作及儀器校正 78 3-3.3 空白實驗 78 第四章 結果與討論 81 4-1 自製載氧體之特性分析 83 4-1.1 XRD分析 84 4-1.2 ICP-AES金屬元素分析 87 4-1.3 載氧體之TPR分析 88 4-1.4 溫度對載氧體之還原性能測試 92 4-1.5 改變還原氣體濃度之特性分析 95 4-1.6 不同載氧體還原-氧化反應之比較 99 4-2 改變操作參數對於20% Fe2O3/SiO2載氧容量影響之探討 105 4-2.1 空間流速之影響 105 4-2.2 一氧化碳濃度之影響 107 4-2.3 氫氣濃度之影響 109 4-2.4 混合還原性氣體之影響 111 4-2.5 氯化氫濃度之影響 113 4-3 氯化氫之還原－再生循環對吸收容量影響之探討 119 4-4 載氧體反應前後分析 122 4-4.1 XRD分析 122 4-4.2 SEM分析 126 4-4.3 SEM–EDS分析 130 4-4.4 Mapping分析 136 4-4.5 BET表面積與孔洞特性 147 4-4.6 XPS分析 152 4-5 HCl對20% Fe2O3/SiO2載氧體之反應機制探討 155 4-5.1 氫氣及一氧化碳對20% Fe2O3/SiO2之反應 155 4-5.2 添加HCl於CO氣氛下對20% Fe2O3/SiO2之反應 158 4-5.3 添加HCl於H2氣氛下對20% Fe2O3/SiO2之反應 161 4-5.4 添加HCl於CO及H2氣氛下對20% Fe2O3/SiO2之反應 163 4-6 還原反應動力模擬探討 166 4-6.1 第一型之衰退模式 166 4-5.2 第二型之衰退模式 171 第五章 結論與建議 175 5-1 結論 175 5-2 建議 178 參考文獻 179 附錄 186

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