臺灣博碩士論文加值系統

本研究嘗試探討應用多種廢棄資材作為稻稈氣化過程催化劑之可行性，其中廢棄資材分別包括自來水廠衍生之含鐵錳淨水污泥、建築廢棄物之紅磚及煅燒白雲石等。藉由控制在氣化溫度900℃及改變不同催化劑添加配比(0%~15%)之條件下，探討稻稈氣化過程提昇產能之效率、減少焦油之產量及降低微量污染物排放等影響。研究結果顯示，添加5%至15%之含鐵錳淨水污泥試驗條件下，合成氣中可燃性氣體之產生量有明顯之增加，相較於未添加催化劑之試驗結果，可燃性氣體產量可由0.61 Nm3/kg增加至0.71 Nm3/kg。建築廢棄物紅磚對於稻稈氣化過程之可燃氣體產量之提昇，受其比表面積較含鐵錳淨水污泥為低，無法提供較多活性位置之影響，其可燃氣體產量僅增加至0.66 Nm3/kg。至於含鈣基之煅燒白雲石試驗結果顯示，可燃性氣體產量則可增加至0.72 Nm3/kg至0.75 Nm3/kg。
添加不同種類之含鐵基/鈣基礦物型催化劑，對於稻稈氣化後合成氣熱值提昇之影響結果顯示，含鐵基之鐵錳淨水污泥及建築廢棄物紅磚等催化劑，其合成氣之低位發熱量可由未添加催化劑之14.76 MJ/Nm3約可增加至15.73-16.47 MJ/Nm3，而含鈣基之煅燒白雲石試驗結果，其合成氣之低位發熱量可增加至16.36 MJ/Nm3，整體而言，試驗添加不同配比及種類之礦物型催化劑，約可提昇6-12%之合成氣熱值。另若以能源密度(energy density)作為比較基準，其中未添加催化劑對稻稈氣化產能之能源密度而言，其合成氣體之熱值約為稻稈生質物熱值之1.63倍，然當添加試驗之含鐵基/鈣基礦物型催化劑後，其合成氣之熱值增加為稻稈生質物熱值之1.73-1.91倍。
含鐵基/鈣基催化劑對稻稈氣化衍生焦油減量及提昇合成氣品質之影響結果顯示，含鐵錳淨水污泥及建築廢棄物紅磚對焦油減量之效果最為明顯，其焦油含量可由19.92 g/kg biomass(未添加催化劑)降低至13.10 g/kg biomass，焦油減量率可達34.25%。然含鈣基礦物型催化劑(煅燒白雲石)則受到高溫再聚合作用之影響，其焦油減量率僅為13%，焦油減量效果較不明顯。至於含鐵基/鈣基催化劑對微量污染物(H2S及HCl)減量效果之評估結果顯示，含鐵基之礦物型催化劑受孔隙結構改變及KCl鹽類毒化之影響，對微量污染物之減量並無顯著之效果，而以含鈣基礦物型催化劑對H2S有較高之吸附去除效果，其減量幅度高達70.27-70.63%，可有效降低合成氣中微量污染物濃度，進而提昇合成氣之利用品質。整體而言，本研究利用之含鐵基/鈣基廢棄資材，可作為稻稈氣化過程之催化劑，研究結果並可提供後續稻稈氣化催化反應過程產能效率提昇、焦油減量及微量污染物排放策略研擬之參考。

摘要……………………………………………...…………………………… i
目錄………………………………………...………………………………… v
圖目錄………………………………………...……………………………… vii
表目錄……………………………………………...………………………… x
第一章 前言………………………………..…….…………..……………… 1
第二章 文獻回顧……………………………….…………………………… 4
2-1 生質物與催化劑之現況…………….…………………………… 4
2-2 氣化技術原理與應用……….…………………………………… 6
2-3 氣化產能效率…………………………………………………… 8
2-3-1 調整操作參數法(self-modification)…..…………………… 9
2-3-2 添加催化劑……………………..……………………..…… 17
2-4 焦油減量及去除技術…………….…………….……………… 25
2-4-1 機械方法(mechanism methods)…………………………… 27
2-4-2 調整操作參數法(self-modification)………………………. 28
2-4-3 催化劑分解法(catalytic cracking)………………..……….. 31
……第三章 研究材料與方法…...…………………………………………… 38
3-1 實驗材料………….……………………………………………… 38
3-1-1 生質物………..……………………………………………… 38
3-1-2 催化劑………………..……………………………………… 38
3-2 實驗方法……………….………………………………………… 38
3-2-1 實驗設備…………..………………………………………… 38
3-2-2 催化劑製備…..……………………………………………… 39
3-2-3 操作條件……….……….…………………………………… 40
3-2-4 實驗步驟…………………………………………………….. 41
3-3 分析項目與方法…………….…………………………………… 42
3-3-1 實驗材料………………..…………………………………… 42
3-3-2 氣化產物……………..……………………………………… 45
……第四章 結果與討論……………………………………………………… 53
4-1 實驗材料之物化特性分析結果………………………………… 53
4-1-1 生質物………….…………………………………………… 53
4-1-2 催化劑………………………………………………….…… 54
4-2 催化劑對稻稈氣化產氣組成變化之影響……………………… 57
4-2-1氣化試驗再現性分析……………………………………..… 57
4-2-2 總產氣及可燃性氣體產氣量之比較……………………… 58
4-2-3 氣體組成變化之分析結果……………………….………… 60
4-2-4 催化劑對單位生質物氣體量變化之影響……….………… 70
4-3 氣化稻稈之焦油產量變化……………………………………… 77
4-4 產能效率評估…………………………………………………… 80
4-4-1 碳及氫轉換率分析結果…………………………………... 80
4-4-2 氣體熱值變化………………………..……………………... 90
4-4-3 Fe2O3與CaO含量對於稻稈氣化產能之影響評估……… 97
4-5 微量氯化氫與硫化物之排放評估……………………………… 101
4-5-1 硫化氫排放濃度變化之分析結果………………………… 101
4-5-2 氯化氫排放濃度變化之分析結果………………………… 111
第五章 結論與建議……………………………………………………… 117
5-1 結論……………………………………………………………… 117
5-1-1 催化劑對稻稈氣化反應之產能效率影響分析之結果…… 117
5-1-2 催化劑對稻稈氣化合成氣品質及焦油減量效果之結果…. 118
5-1-3 催化劑對稻稈氣化過程之微量污染物排放特性影響之結
果…………………………………………………………….. 118
5-2 建議……………………………………………………………… 119
參考文獻……………………………………………………..……………… 120

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