貴金屬對CuO/ZnO/Al2O3觸媒於甲醇部分氧化/蒸汽重組複合式反應的影響

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許哲銓(Che-chuan Hsu) 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

貴金屬對CuO/ZnO/Al2O3觸媒於甲醇部分氧化/蒸汽重組複合式反應的影響
(Oxidative steam reforming over noble metal-CuO/ZnO/ZrO2/Al2O3 catalysts)

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摘要(中)

複合式甲醇蒸汽重組反應(OSRM)，常用觸媒多以銅基觸媒為主，近年有研究報導指出Pt、Pd擔載在ZnO上，應用於甲醇產氫反應具有不錯的活性表現且有較低的CO選擇率，與一般貴金屬行為表現不同。本研究以CuO/ZnO/Al2O3(30/60/10)觸媒為參考，引入不等量Pd、Pt、Ru、Rh並進行OSRM反應活性測試，另以Me/Al2O3及Me/ZnO/Al2O3(Me=Pd、Pt、Ru、Rh)觸媒於SRM及OSRM反應條件下進行反應測試，釐清貴金屬所扮演的角色。再於活性最佳之觸媒中引入CeO2及ZrO2，了解促進劑對貴金屬-CuO/ZnO/Al2O3觸媒於OSRM反應的影響，以設計出具有高活性及高穩定性的產氫觸媒。
以共沉澱法引入貴金屬於CuO/ZnO/Al2O3(30/60/10)觸媒中可大幅促進觸媒於OSRM反應活性；以臨濕含浸法引入貴金屬於觸媒中其促進效果無法彰顯，甚至抑制觸媒活性，也增加產物中CO濃度。單獨貴金屬觸媒於SRM及OSRM反應條件下仍進行MD反應，ZnO存在時則以SRM及OSRM反應為主，且進料中含有O2時，貴金屬觸媒會進行CO oxidation反應。添加貴金屬不影響觸媒比表面積及整體分散性，但可有效提升觸媒還原能力，也促進甲醇解離吸附及反應中間物脫氫，加速反應的進行，適量添加1%Pd、Pt、Ru、Rh皆可提升CuO/ZnO/Al2O3觸媒於OSRM反應活性，Pt促進效果最佳，Pd次之。Pd、Ru、Rh會增加產物中CO的濃度，Pt則不影響觸媒CO選擇率。於最佳比例觸媒中引入CeO2、ZrO2雖增加觸媒比表面積及整體分散性，但削弱Pd、Pt對觸媒活性之促進效果。
1%Pt-CuO/ZnO/Al2O3(30/60/10)觸媒反應活性遠優於商用觸媒，並有較低的CO選擇率，觸媒穩定性也有不錯的表現，為極具發展潛力之產氫觸媒。

摘要(英)

The oxidative steam reforming of methanol (OSRM) was usually studied over Cu-based catalysts. Recently, numerous researchers indicate that Pt and Pd over ZnO have great activity and low CO concentration for hydrogen production by methanol. Their behavior is different from normal noble metals′. In this research, commercial catalysts G66B (Nisson-Gridler) with weight ratio of 30/60/10 (CuO/ZnO/Al2O3) is used as a starting reference and introduce distinct proportions of Pd,Pt,Ru and Rh which is prepared by co-precipitation method for OSRM activity test. Besides we use Me/Al2O3 and Me/ZnO/Al2O3 catalysts for SRM and OSRM condition to figure out what role noble metals play in catalysts. Finally we introduce CeO2 and ZrO2 to the catalysts having best activity in order to find out how promoters effect catalysts then design the best Me- CuO/ZnO/Al2O3 catalyst for OSRM.
Catalysts activity are much enhanced with introducing noble metals by co-precipitation method. Noble metals would carry out MD but noble metal over ZnO lead SRM and OSRM for SRM and OSRM condition. Further, noble metal catalyst carry out CO oxidation when input include O2. Catalyst surface area and dispersion have no difference after introducing noble metal, but reduction ability, methanol dissociation and adsorption and H2 dissociation of reaction intermedium are largely enhanced so that speed up reaction proceeding. Although introducing CeO2 and ZrO2 to catalyst increase surface area and dispersion but weaken the Pd and Pt enhancement. 1%Pt-CuO/ZnO/Al2O3(30/60/10) catalyst have well activity and stability and low CO selectivity which is very potential catalyst for H2 production.

關鍵字(中)

★ 氧化鋯
★ 甲醇蒸汽重組複合式反應
★ 貴金屬
★ 銅觸媒
★ 氧化鈰

關鍵字(英)

★ Oxidative Steam Reforming of Methanol(OSRM)、Copp

論文目次

摘要 i
Abstract ii
目錄 iii
圖目錄 v
表目錄 vii
第一章緒論 1
第二章文獻回顧 3
2-1 甲醇產氫反應 4
2-2 甲醇產氫的反應路徑 5
2-2-1 甲醇分解反應(MD) 5
2-2-2 甲醇蒸汽重組反應(SRM) 7
2-2-3 複合式甲醇蒸汽重組反應(OSRM) 17
2-3 甲醇產氫觸媒 22
2-3-1 銅基觸媒 23
第三章實驗方法與設備 36
3-1 貴金屬-CuO/ZnO/ZrO2/Al2O3觸媒之製備 36
3-2 觸媒性質鑑定 38
3-2-1 比表面積測定(BET) 38
3-2-2 X-射線繞射分析(XRD) 39
3-2-3 氫-程溫還原(H2-TPR) 39
3-2-4 原位漫反射傅利葉紅外線光譜儀(In situ DR-FTIR) 42
3-3 複合式甲醇蒸汽重組反應活性測試 43
3-4 轉化率與選擇率之計算 47
3-5 實驗藥品及氣體 47
第四章結果與討論 49
4-1 貴金屬添加方法對CuO/ZnO/Al2O3(30/60/10)觸媒的影響 49
4-2 貴金屬對CuO/ZnO/Al2O3(30/60/10)觸媒的影響 51
4-2-1 Pd的影響 51
4-2-2 Pt的影響 60
4-2-3 Ru負載量的影響 69
4-2-4 Rh負載量的影響 74
4-3 添加ZrO2對貴金屬-CuO/ZnO/Al2O3(30/60/10)觸媒的影響 80
4-4 添加CeO2對貴金屬-CuO/ZnO/Al2O3(30/60/10)觸媒的影響 85
4-5 觸媒穩定性測試 87
第五章結論 89
總結 90
參考文獻 91

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指導教授

陳吟足、廖炳傑
(Yin-Zu Chen、Biing-Jye Liaw)

審核日期

2011-7-12

推文