甲醇於CuO/ZnO/ZrO2/Al2O3之SRM、OSRM產氫反應研究─ZrO2的影響

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王志煒(Chih-wei Wang) 查詢紙本館藏

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化學工程與材料工程學系

論文名稱

甲醇於CuO/ZnO/ZrO2/Al2O3之SRM、OSRM產氫反應研究─ZrO2的影響
(Steam reforming and oxidative steam reforming of methanol over CuO/ZnO/ZrO2/Al2O3 ─ the influnce of ZrO2)

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摘要(中)

氫氣為燃料電池主要的能量來源，多採碳氫化合物蒸汽重組為主,其中又以甲醇產氫系統最為簡單，適用於移動式供氫。甲醇產氫常見的反應有甲醇蒸汽重組(SRM)、甲醇部分氧化(POM)與複合式甲醇蒸汽重組(OSRM)，其中SRM與OSRM反應產氫效率較高，CO選擇率低。
本實驗室過去產氫觸媒設計的研究以商業觸媒G66B(CuO/ZnO/Al2O3=30/60/10)成分為基礎，以共沉澱法製備不同比例之CuO/ZnO/CeO2/ZrO2/Al2O3觸媒，進行SRM及OSRM反應，發現CeO2與Al2O3為負面影響，ZrO2則有不錯促進活性與增進穩定性的效果，但較高CuO負載量(大於30%)時ZrO2促進效果無法顯現，甚至有負面的效果，本研究固定CuO/ZnO/Al2O3觸媒中Al2O3含量為10 wt%，在不同CuO負載量(10~40 wt%)觸媒中引入不等量ZrO2取代部分ZnO，進行SRM及OSRM反應，藉以近一步探討ZrO2對CuO/ZnO/Al2O3觸媒的影響。研究發現ZrO2可提升觸媒的還原能力、分散性，也增進觸媒的穩定。DRFTIR分析發現ZrO2可增加甲醇吸附，適量添加可促進反應活性。觸媒中CuO/ZnO比值為影響觸媒活性的重要因素，CuO/ZnO比值小於0.8，ZrO2對觸媒活性有促進效果，如過量添加ZrO2取代ZnO，使CuO/ZnO比值大於0.8，減少 CuO/ZnO之間的交互周界，ZrO2的促進效果無法顯現，甚至對觸媒活性有負面影響。

摘要(英)

Abstract
The proton exchange membrane fuel cells (PEMFC) usually use hydrogen as feed, and the methanol hydrogenation which is the most simply hydrogen production system therefore the system also apply to onboard equipment. The steam reforming of methanol (SRM) and oxidative steam reforming of methanol (OSRM) are two of the best hydrogen production of methanol reaction.
In our past research, commercial catalysts G66B (Nisson-Gridler) with weight ratio of 30/60/10 (CuO/ZnO/Al2O3) was used as a starting reference for designing CuO/ZnO/ZrO2/Al2O3 catalysts which were prepared by co-precipitation method for SRM and OSRM. We find out that the CeO2 and Al2O3 were negative to the catalyst activity, ZrO2 had excellent performance on catalytic activity and stability, nevertheless when high loading ZrO2 (above 30 wt %), the promotion of ZrO2 had disappeared. In this research, we fixed Al2O3 composition in the CuO/ZnO/ZrO2/Al2O3 catalyst as 10 wt%, and change the composition of rest of the species of catalyst, and introducing ZrO2 replace the partial ZnO in the catalyst test in SRM and OSRM reactions try to figure out the influence of ZrO2 in CuO/ZnO/Al2O3-based catalysts.
ZrO2 could improve the catalytic reducibility and the copper dispersion on catalyst and increase the stability of catalyst, in DRIFT we also note the obvious evidence that ZrO2 could increase the methanol adsorption on catalyst. The CuO/ZnO ratio is extremely important to the catalytic activity, when the ratio is above 0.8, introducing ZrO2 show no improvement ,when the ratio below 0.8, introducing ZrO2 improve the catalytic activity and the stability.

關鍵字(中)

★ 產氫反應
★ 銅觸媒
★ 氧化鋯
★ 甲醇蒸汽重組
★ 複合式甲醇蒸汽重組

關鍵字(英)

★ steam reforming of methanol(SRM)
★ ZrO2
★ Copper catalyst
★ oxidative steam reforming of methanol(OSRM)

論文目次

目　錄 iii
圖目錄 v
表目錄 vii
第一章緒　論 1
第二章文獻回顧 2
2-1 甲醇產氫反應 3
2-2 銅觸媒與甲醇產氫常用之CuO/ZnO/Al2O3觸媒 3
2-3 甲醇產氫的反應路徑 7
2-3-1 甲醇蒸汽重組反應(SRM) 7
2-3-2 甲醇蒸汽重組(SRM)的反應路徑 10
2-3-3 複合式甲醇蒸汽重組反應(OSRM) 16
2-3-4 複合式甲醇蒸汽重組(OSRM)的反應路徑 19
2-4 引入ZrO2至觸媒中的影響 20
2-4-1 引入ZrO2對觸媒特性及反應活性的影響 21
2-4-2 引入ZrO2對觸媒穩定性的影響 26
第三章實驗方法與設備 29
3-1 CuO/ZnO/ZrO2/Al2O3觸媒之製備 29
3-2 觸媒性質鑑定 31
3-2-1元素組成分析(ICP) 31
3-2-2 X-射線繞射分析(XRD) 31
3-2-3 氫-程溫還原(H2-TPR) 32
3-2-4漫反射傅利葉紅外線光譜儀(DR-FTIR) 35
3-3 甲醇蒸汽重組反應活性測試 36
3-4 複合式甲醇蒸汽重組反應活性測試 37
3-5 轉化率與選擇率之計算 40
3-6 實驗藥品及氣體 40
第四章結果與討論 42
4-1觸媒基本性質鑑定 43
4-2 觸媒活性測試與探討 43
4-2-1 CuO/ZnO/Al2O3觸媒在SRM與OSRM的活性 44
4-2-2 ZrO2對CuO/ZnO/Al2O3(30/60/10)觸媒的影響 49
4-2-3 ZrO2對CuO/ZnO/Al2O3(40/50/10)觸媒的影響 59
4-2-4 ZrO2對CuO/ZnO/Al2O3(20/70/10)觸媒的影響 69
4-2-5 ZrO2對CuO/ZnO/Al2O3(10/80/10)觸媒的影響 79
4-2-6 ZrO2與CuO/ZnO比值對觸媒反應活性的影響 89
4-3觸媒穩定性測試 96
第五章結論 100
總結 101
參考文獻 102

參考文獻

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指導教授

陳吟足(Yin zu chen)

審核日期

2010-8-2

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