稻殼灰分-氧化鋅複合擔體銅觸媒應用於氧化性甲醇蒸氣重組產氫之研究

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葉元婷(Yuan-ting Yeh) 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

稻殼灰分-氧化鋅複合擔體銅觸媒應用於氧化性甲醇蒸氣重組產氫之研究
(Hydrogen Production by Oxidative Steam Reforming of Methanol over Cu/RHA-ZnO Catalysts)

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摘要(中)

本研究是利用桃園縣之廢棄稻殼，經酸洗、碳燒跟熱解處理後的稻殼灰份(rice husk ash，RHA )，採用初濕含浸法先製備出ZnO、RHA的複合擔體，再以沈澱固著法製備出不同Si/Zn原子比的Cu/ZnO-RHA複合擔體觸媒。催化反應測試方面，利用甲醇在常壓下進行氧化性蒸氣重組反應(oxidative steam reforming of methanol, ORSM)，由於反應物中包含了水與氧，同時具備了甲醇蒸氣重組反應(steam reforming of methanol, SRM)和甲醇部份氧化反應(partial oxidation of methanol, POM)的優點，擁有較高的氫氣產率也能有效降低一氧化碳選擇率，減少燃料電池Pt電極的毒化。在觸媒與擔體特性分析方面，利用感應耦合電漿原子發射光譜儀(ICP-AES)、X射線繞射儀(XRD)、程式升溫還原(TPR)、N2O分解吸附(dissociative adsorption of nitrous oxide)、穿透式電子顯微鏡(TEM)、掃描式電子顯微鏡(SEM)等技術，進一步了解各種不同操作變數對觸媒的影響。
由XRD的結果可得知Zn含量越多，Cu0的繞射峰就越明顯也越高。在TPR圖譜中，Zn含量越多Cu的還原溫度也越高。由N2O分解吸附結果顯示Zn含量越多反而造成粒徑變大、分散度變差的問題。但是在活性測試中，擔體中的Si/Zn的原子比為9/1的反應性最好，可以瞭解到加入少量的ZnO能增加觸媒活性，而N2O分解吸附結果對於不同煅燒溫度探討，煅燒溫度在673 K時有最佳的分散度與最小粒徑。在TEM與SEM顯微圖中可得知粒徑大小，其與N2O分解吸附計算出來的結果相似。在氧化性蒸氣重組反應中，可得知在Si/Zn原子比9/1、進料莫耳比O2/CH3OH=0.3與H2O/CH3OH=1及反應溫度為523 K時，觸媒擁有最佳甲醇轉化率、氫氣產率與最低的一氧化碳選擇率。

摘要(英)

Cu/RHA-ZnO catalysts were studied for oxidative steam reforming of methanol (OSRM, CH3OH + 0.5H2O + 0.25O2 → 2.5H2 + CO2) to produce hydrogen. Rice husk ash (RHA) was used to prepare RHA-ZnO binary supports by incipient wetness impregnation method and the catalysts were prepared by deposition-precipitation method with the binary support. The catalysts and supports were characterized by ICP-AES, XRD, TPR, N2O titration, TEM and SEM analyses. The average diameter of Cu particles was determined by TEM and N2O titration. XRD was used to study the crystallinity of the catalysts. The TPR results stated that redox properties of catalysts depended on the RHA/ZnO molar ratios. From N2O titration, TEM and SEM results, it was concluded that ZnO played minor role on controlling particle size of copper. However, the appropriate amount of Zn in catalysts is beneficial for activity. The effects of several experimental parameters of this study such as Si/Zn ratio, calcination temperature, reduction temperature, composition of feeding and reaction temperature had been discussed. The Cu/RHA-ZnO catalyst with Si/Zn atomic ratio at 9/1, calcined at 673 K and reduced at 573 K exhibits the optimum CH3OH conversion, H2 production rate and CO selectivity. The most suitable reaction temperature is 523 K with the feed ratio of H2O/CH3OH/O2 = 1/1/0.3 for OSRM reaction.

關鍵字(中)

★ 銅觸媒
★ 產氫
★ 氧化性甲醇蒸氣重組
★ 稻殼灰分

關鍵字(英)

★ Hydrogen
★ Cu catalyst
★ Rice husk ash
★ Oxidative Steam Reforming of Methanol

論文目次

中文摘要.............................................i
英文摘要.............................................iii
誌謝.................................................iv
目錄.................................................v
圖目錄...............................................ix
表目錄...............................................xiii
第一章緒論..........................................1
1-1前言..............................................1
1-2 燃料電池簡介.....................................2
1-3 燃料電池工作原理.................................4
1-4 燃料電池種類.....................................6
1-5氫能經濟..........................................6
1-6甲醇產氫..........................................9
1-7內容與論文架構....................................10
第二章文獻回顧......................................12
2-1 稻殼的組成、性質與製備...........................12
2-2 銅觸媒的簡介.....................................14
2-3 觸媒的製備.......................................15
2-4 擔體效應.........................................16
2-5 銅金屬表面積的測定...............................17
2-6 銅的活性位置.....................................18
2-7 氧化性甲醇蒸氣重組反應...........................18
第三章實驗方法與製備................................23
3-1 稻殼灰分的製備...................................23
3-1-1 水洗程序.......................................23
3-1-2 酸洗程序.......................................23
3-1-3 熱解程序.......................................24
3-1-4 碳燒程序.......................................27
3-2 複合擔體的製備 ...................................29
3-3 擔載銅觸媒的製備.................................30
3-4 擔體銅觸媒的鑑定分析.............................31
3-4-1 感應耦合電漿原子放射光譜儀(ICP-AES)............32
3-4-2 X射線繞射分析儀(XRD)...........................32
3-4-3 程式升溫還原(TPR)..............................33
3-4-4 銅金屬表面積的量測.............................37
3-4-5 穿透式電子顯微鏡(TEM)..........................40
3-4-6 掃描式電子顯微鏡(SEM)..........................40
3-5 觸媒活性測試－氧化性甲醇蒸氣重組產氫反應.........45
3-6 實驗流程與操作變數...............................47
3-7 數據的計算與實例.................................49
3-7-1 銅觸媒理論載量的定義與計算.....................49
3-7-2 轉化率的定義與計算.............................49
3-7-3 選擇率的定義與計算.............................54
3-7-4 產生速率的定義與計算...........................54
3-8 藥品、氣體及儀器設備.............................55
3-8-1 藥品...........................................55
3-8-2 氣體...........................................55
3-8-3 設備儀器.......................................56
第四章結果與討論....................................58
4-1 稻殼灰分組成分析.................................58
4-2 物性分析.........................................58
4-2-1 X射線繞射(XRD)分析結果.........................60
4-2-2 程式升溫還原(TPR)分析結果......................62
4-2-3 N2O分解吸附反應結果(N2O-Titration )分析結果....65
4-2-4 穿透式電子顯微鏡(TEM)分析結果..................68
4-2-5 掃描式電子顯微鏡(SEM)分析結果..................71
4-3 化性分析.........................................74
4-3-1 擔體Si/Zn原子比對觸媒活性的影響................74
4-3-2 煅燒溫度對觸媒活性的影響.......................79
4-3-3 進料比對觸媒活性的影響.........................83
4-3-3-1 不同O2/CH3OH莫耳比的影響.....................83
4-3-3-2 不同H2O/CH3OH莫耳比的影響....................87
4-3-4 反應溫度對觸媒活性的影響.......................91
4-3-5 Cu/RHA-ZnO與Cu/SiO2-ZnO觸媒在反應活性的比較....93
第五章結論..........................................101
參考文獻.............................................104

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指導教授

張奉文(Feg-wen Chang)

審核日期

2009-6-25

推文