臺灣博碩士論文加值系統

以不同合成溫度(70、100及130℃)及反應時間(24、72小時)製備出不同孔徑的SBA-15，將不同孔徑的SBA-15進行官能化，再將官能化後的SBA-15經逐步聚合接枝成丙烯酸甲酯胺基樹枝狀聚合物。探討吸附劑的接枝效率與二氧化碳的吸附效果，改善孔填充的問題。
經BET分析的數據可了解，孔徑隨著水熱合成溫度增加由3.55 nm提高至7.91 nm，再增加反應時間由7.91 nm提高至10.91 nm，但溫度過高或反應時間過長可能會造成孔壁破裂。FT-IR結果顯示2900 cm-1、1500 cm-1、700 cm-1左右多出了SBA-15所沒有的峰值，表示成功將SBA-15官能化。接枝反應後將濾液以滴定法進行胺含量之滴定，70℃-SBA-15 G1至G2的接枝效率由11.67%提高至12.50%，但在G3後有可能是孔填充的問題使得接枝效率降低至10.28%，100℃-SBA-15與70℃-SBA-15情形相同，而130℃-SBA-15與130℃-3D-SBA-15 G1-G3的接枝效率沒有降低的情形發生(130℃-SBA-15:10.30、11.42、11.76%,130℃-3D-SBA-15:9.77、10.82、11.60%)，表示改善了孔填充的問題。以固定反應床模擬煙氣(28% CO2與72% N2)於室溫下進行二氧化碳的吸附及吸附劑的再生，實驗數據進行分析比較，130℃-SBA-15/G3吸附量最高 (82.25 mg/g) ，100℃-SBA-15/G2吸附劑經過了五次吸附-脫附循環吸附量為65.80、63.26、61.53、62.71、64.8 mg。
研究發現比表面積和孔徑影響了接枝的效率、可接枝的次數及二氧化碳吸附量。提高水熱溫度與合成時間可有效增加孔徑的大小、提高接枝次數並改善孔填充的問題，達到更高的吸附量，吸附劑的重複再利用性高，可減少處裡二氧化碳的成本。

Different synthetic temperatures (70, 100 and 130℃) and reaction times (24 and 72 hours) are used to make SBA-15 of pore diameters, which is functionalized. The acrylate-based amine dendrimers is grafted by stepwise polymerization the functionalized SBA-15. The grafting efficiency of the absorbent and the absorption effect of carbon dioxide are discussed, and problems such as pore filling are improved.
The data of BET analysis shows that the pore diameter will increase from 3.55 nm to 7.91 nm as the hydrothermal temperature increases, and will also increase from 7.91 nm to 10.91 nm if the reaction time is additionally increased. However, the pore wall may break if the temperature or reaction time is too high or long. The FT-IR result shows the peak value that is not possessed by SBA-15 appears both sides of 2900 cm-1, 1500 cm-1, and 700 cm-1, which indicate SBA-15 is successfully functionalized. After grafting reaction, the amine content of the filtrate is determined by the titration. As for 70℃-SBA-15, the grafting efficiencies of G1 to G2 are increased from 11.67% to 12.50%, but they may decrease to 10.28% due to problems like pore filling after G3. The grafting efficiencies are the same for 100℃-SBA-15 and 70℃-SBA-15, but the grafting efficiencies of G1 to G3 are not decreased as for 130℃-SBA-15 and 130℃-3D-SBA-15 (130℃-SBA-15:10.30,11.42,11.76%,130℃-3D-SBA-15:9.77,10.82,11.60%), which indicate the pore filling is improved. The fixed-bed reactor is used to simulate flue gas by carbon dioxide adsorption at room temperature and the regeneration of adsorbent. The test data shows that the adsorption capacity of 130℃-SBA-15/G3 is maximum (82.25 mg/g), and the cyclic adsorption capacity of 100℃-SBA-15/G2 is respectively 65.80, 63.26, 61.53, 62.71, and 64.8 mg after adsorption and desorption for 5 times.
The study finds that the specific surface area and the pore diameter affect the grafting efficiency, the graftable number and the adsorption capacity of carbon dioxide. The pore diameter and the grafting number can be effectively increased, and the pore filling can be improved by increasing the hydrothermal temperature and the synthetic time. As a result, the adsorption capacity is increased, the reusability of adsorbent is increased, and the cost for treating carbon dioxide is decreased.

摘要 I
Abstract III
誌謝 V
圖目錄 VIII
表目錄 X
第一章 前言 1
1-1 研究緣起 1
1-2 研究目的 3
1-3 研究內容 3
第二章 文獻回顧 5
2-1 二氧化碳捕集技術 5
2-1-1吸附法 5
2-1-2吸收法 8
2-1-3薄膜分離法 10
2-2吸附劑之種類介紹 11
2-3 SBA-15　合成機制 15
2-4 SBA-15表面改質方法介紹 18
2-4-1共結合法 (co-condenstation)： 18
2-4-2無水有機溶劑法 (silylation)： 18
2-4-3加水有機溶劑法 (coating)： 19
2-4-4含浸法(Impregnation method)： 19
2-4-5接枝/嫁接到表面法(graft-to method)： 19
2-5接枝/嫁接方法 21
2-5-1幅照法 22
2-5-2光化學法 23
2-5-3低溫等離子法 25
2-5-4偶合接枝 26
2-5-5添加接枝共聚物 27
2-6胺與二氧化碳 28
2-6-1 胺的種類 28
2-6-2 各類胺之比較 28
2-6-3 胺與二氧化碳之反應 30
2-7 吸附等溫線 31
2-8文獻總結 33
第三章 實驗設備與方法 35
3-1 實驗試藥 35
3-2 SBA-15之製備方法與接枝 36
3-2-1 SBA-15製備方法 36
3-2-2 SBA-15官能化之方法 38
3-2-3 SBA-15 接枝方法 40
3-3 SBA-15上胺含量之定量(滴定法) 42
3-4固定床反應設備 44
3-5 分析儀器 46
3-6 實驗流程 47
3-6-1 吸附-脫附反應 47
3-6-2 BET測定 50
3-6-3 FTIR 測定 50
第四章 結果與討論 52
4-1BET分析 53
4-2傅立葉轉換紅外光譜(FTIR)分析 63
4-3胺含量分析(滴定) 65
4-4二氧化碳吸附分析 69
4-4-1二氧化碳吸附 69
4-4-2 二氧化碳吸附-脫附循環 79
第五章 結論與建議 81
5-1 結論 81
5-2 建議 82
參考文獻 84

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