臺灣博碩士論文加值系統

近年來，由於世界各國的工業科技發展迅速，導致石化燃料被大量使用，造成大氣中二氧化碳濃度逐年增加及全球暖化效應，如此嚴重的環境問題也引發了全球關注。為了減緩二氧化碳的排放量，許多國家也開始進行研究二氧化碳捕獲與分離的方法，根據研究分析指出，捕獲每噸二氧化碳成本需要50〜70美元，但要符合經濟效益則需控制在每噸30美元以下，因此捕獲技術中所使用的吸附材料著重於高吸附性、高選擇性、循環穩定性及低成本等方向來改進，以提高最佳的應用可能性。
本研究主要是利用氧化鈣(CaO)以不同含量負載於奈米結構之中孔洞碳材(SMC)製備二氧化碳吸附劑，材料的合成首先是以一界面活性劑做為軟模板，有機化合物當做碳源，再以不同含量(7 wt%、18 wt%、28 wt%)比例的Ca(NO3)2．4H2O作為氧化鈣之前驅物，藉由有機-有機自組裝(organic-organic self-assembly)的方式聚合而成，經高溫碳化後移除軟模板即可得鈣基吸附劑之中孔碳材(CaO-x/SMC)。製備出的吸附劑經由各種物化特性分析，如X光粉末繞射儀(XRD)、氮氣等溫吸附/脫附(N2 adsorption/desorption isotherm)、傅立葉紅外線吸收光譜(FTIR)、穿透式電子顯微鏡(TEM)、X光光電子能譜(XPS) 等儀器鑑定。另外，再以熱重分析儀(TGA)進行二氧化碳吸脫附效能測試，探討不同鈣含量之吸附劑於常溫、中高溫及高溫的捕獲能力與脫附效能，再分別針對樣品與99%氧化鈣進行多次循環吸脫附測試，探討樣品的穩定性及再利用性。
實驗結果顯示，吸附劑負載之鈣含量及吸脫附溫度都會影響二氧化碳吸附效能，在高溫下的吸附量有提升之趨勢，氧化鈣負載於高表面積與孔體積的中孔碳材確實能抑制鈣顆粒團聚的發生，且穩定性較佳。

In recent years, global warming has triggered enormous public concerns and severe environmental problems. The increases of CO2 concentration in the atmosphere due to the rapid development of industrial has been caused by the consumption of huge amounts of fossil fuels. In order to reduce CO2 emissions, many researchers focus on developments of CO2 capture and sequestration. A preliminary analysis from US indicated that an economically feasible approach for CO2 capture should further cost-down to less than US $30. Thus, it is urgent to develop low cost and cyclic stability of adsorbents for practical applications.
The objectives of this research are to prepare nanostructured mesoporous carbon supported nanosized calcium oxide (CaO) materials as the CO2 adsorbents. A one- pot route is proposed by crosslinking phenolic resins with block-copolymer surfactant templates in the presence of different amounts of Ca precursors. After high temperature of carbonization, mesoporous carbon materials supported nanocrystalline calcium oxides (CaO-x/SMC) can be obtained. The structural and chemical properties of CaO-x/SMC by different spectroscopic and analytical techniques, such as powder X-ray diffraction (XRD), nitrogen adsorption/desorption isotherms (BET), fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS). The CO2 sorption/desorption performance was also investigated in terms of various adsorption and desorption temperatures by using thermogravimetric analyzer (TGA). To compare the stability and recyclability of commercially avaliable CaO and CaO-x/SMC, the cyclic adsorption-desoprtion tests were also studied.
The experimental results show that CO2 adsorption-desorption performance was affected by the operation temperatures and calcium contents. In addition, mesoporous carbon support could effectively restrict the growth of calcium oxides and thus avoid sintering during the high-temperature cycling processes.

中文摘要 I
Abstract III
誌謝 V
目錄 VII
表目錄 XI
圖目錄 XII
第一章 緒論 1
1.1前言 1
1.2研究動機 3
第二章 文獻回顧 5
2.1 溫室氣體相關議題之探討 5
2.1.1何謂溫室效應 5
2.1.2溫室氣體種類 7
2.1.3 二氧化碳捕獲路徑與優缺點 9
2.1.4 二氧化碳捕獲與分離技術 12
2.2 孔洞分子篩之發展 16
2.3 中孔洞氧化矽 SBA-15 19
2.3.1 SBA-15簡介 19
2.3.2 SBA-15合成機制 19
2.3.3 SBA-15表面改質與修飾 20
2.4 中孔洞碳材料 23
2.4.1中孔洞碳材料簡介 23
2.4.2 中孔洞碳材合成機制 26
2.4.3 自組裝合成中孔洞碳材簡介 27
2.4.4 自組裝合成奈米中孔洞碳材之合成方法 28
2.4.5 中孔洞碳材之應用 34
2.5 氧化鈣之簡介與應用 35
2.5.1 氧化鈣(Calcium oxide)之特性 35
2.5.2 氧化鈣之應用 36
2.6 氧化鈣用於二氧化碳之捕獲與分離 36
2.6.1 氧化鈣用於二氧化碳捕獲與分離之優缺點 36
2.6.2 負載氧化鈣於孔洞性碳材料用於二氧化碳捕獲 40
第三章 實驗方法與步驟 42
3.1 化學藥品與試劑 42
3.2 實驗步驟與樣品製備 43
3.2.1 自組裝合成中孔洞碳材負載氧化鈣(CaO-x/SMC)的製 備 43
3.2.2 二氧化碳吸脫附效能測試 45
3.3 樣品物化特性鑑定 46
3.3.1 X-光粉末繞射儀(XRD) 47
3.3.2 小角度X光散射儀(SAXS) 48
3.3.3 等溫氮氣吸附/脫附比表面積分析儀(BET) 49
3.3.4 傅立葉轉換紅外線光譜儀(FT-IR) 50
3.3.5 穿透式電子顯微鏡(TEM) 52
3.3.6 X-ray光電子光譜儀(XPS) 54
3.3.7 熱重分析儀(TGA) 54
第四章 實驗結果與討論 57
4.1 中孔碳材負載氧化鈣吸附劑 57
4.2 SAXS與XRD分析 57
4.3 BET分析 60
4.4 FT-IR分析 63
4.5 XPS分析 65
4.6 TEM分析 71
4.7 二氧化碳吸附效能測試 76
4.7.1 單一溫度之各含量吸附 76
4.7.2 單一含量之各溫度吸附 80
4.7.3 各吸附溫度之脫附效率測試 84
4.7.4 熱穩定性測試 88
4.7.5 循環穩定性測試 90
第五章 結論 93
參考文獻 95
自傳 103

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