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完整後設資料紀錄
DC 欄位 | 值 | 語言 |
---|---|---|
dc.contributor.advisor | 鄭淑芬 | |
dc.contributor.author | Chun-Wei Lin | en |
dc.contributor.author | 林君威 | zh_TW |
dc.date.accessioned | 2021-06-17T00:32:19Z | - |
dc.date.available | 2012-03-19 | |
dc.date.copyright | 2012-03-19 | |
dc.date.issued | 2012 | |
dc.date.submitted | 2012-02-10 | |
dc.identifier.citation | [1] Katryniok, B.; Paul, S.; Belli`ere-Baca, V.; Reye, P.; Dumeignil, F. Green Chem. 2010, 12, 2079.
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dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/66368 | - |
dc.description.abstract | 鎢鋯氧化物當作觸媒在許多酸催化反應中表現出色。甘油脫水形成丙烯醛的反應在工業上具有高度經濟價值,而介孔洞材料SBA-15具有高表面積,以及均勻六方角柱規則孔洞,加上良好的水熱穩定性,使其成為具潛力的觸媒載體。本研究使用超臨界乙醇將鎢鋯金屬前驅物帶入SBA-15材料孔洞中,接著煆燒處理,使其形成金屬氧化物,藉此增加觸媒表面積及金屬氧化物顆粒分散性,此外並使用不含載體的觸媒,和使用含浸法負載之觸媒來做比較。從X光繞射、氮氣吸脫附和電子顯微鏡實驗得知,利用超臨界乙醇法製成的鎢鋯氧化物複合材料保有原本SBA-15的規則六角柱狀排列。相較於直接含浸法,複合材料具有較高表面積以及保有介孔洞。實驗中改變不同的初始含浸溶劑、不同的SBA-15載體型態、不同煆燒溫度,以及鎢和鋯的負載順序,藉此觀察樣品在催化活性上的差異。
觸媒活性測試中,氣相甘油脫水反應在固定床反應器進行,將產物以氣相層析儀進行分析。實驗結果得知,對所有觸媒丙烯醛 (acrolein) 皆為主要產物,選擇率約80%,伴隨甘油一次脫水的副產物丙酮醇(hydroxyacetone)和其他副產物。使用扁狀SBA-15做為載體,和甲醇/水 (1:2, v/v)做為初始含浸溶劑的觸媒,有最好的甘油轉化率,且觸媒煆燒再生後,活性維持不變。煆燒溫度最佳化實驗中,以775 oC煆燒之樣品活性最佳,失活速率最慢。 | zh_TW |
dc.description.abstract | Tungstated zirconia has been found to be efficient catalysts in many acid-catalyzed reactions. The gas-phase dehydration of glycerol to acrolein is of great economical value. Mesoporous SBA-15 has great potential as catalyst support due to its ordered pore structure, high surface area and good hydrothermal stability. In the present study, mesoporous SBA-15 was used as the support for preparing supported tungstated zirconia (WZ) catalysts in order to increase the surface area and the dispersion of metal oxides. The catalysts prepared through pre-impregnation and subsequent supercritical treatment were found to retain ordered porous structure and well-dispersed W/Zr catalytic sites based on the results of XRD, N2 physisorption and EM photos. Factors of catalyst preparation such as the pre-impregnation solvents, supporting sequences of active phases, and morphology differences of silica supports in influencing the catalytic performances were examined.
The gas-phase dehydration of glycerol in the presence of water was investigated using fixed-bed reactor, and product analysis was performed by gas chromatography. From the catalytic results, all samples facilitated the same acrolein selectivity around 80%, with hydroxyacetone as the major by-product. The combination of platelet SBA-15 as support and MeOH/H2O (1:1 v:v) as pre-impregnation solvent gave catalysts having higher glycerol conversion. Moreover, the catalytic activities were retained after several cycles. The optimal calcination temperature for preparing the catalysts of the lowest deactivation rate was at 775 oC. | en |
dc.description.provenance | Made available in DSpace on 2021-06-17T00:32:19Z (GMT). No. of bitstreams: 1 ntu-101-R98223127-1.pdf: 8582181 bytes, checksum: e9c404c3e850a0fa6db8b8fa92d97ec9 (MD5) Previous issue date: 2012 | en |
dc.description.tableofcontents | 謝誌 I
中文摘要 II Abstract III 目錄 IV 表目錄 VI 圖目錄 VIII Chapter 1 序論 1 1-1 研究背景 1 1-2 甘油脫水觸媒、反應機制及其產物分布 2 1-3 鎢鋯氧化物的研究與發展 6 1-4 介孔材料的簡介 12 1-5 超臨界流體 16 1-6 研究目標 19 Chapter 2 實驗部分 21 2-1 化學藥品 21 2-2 觸媒的製備 22 2-2-1 鎢鋯氧化物製備 22 2-2-2 鎢鋯氧化物負載於SBA-15載體觸媒製備 22 2-3 鑑定觸媒材料的儀器 23 2-4 催化反應 30 2-5 產物鑑定 32 Chapter 3 觸媒的鑑定 35 3-1 鎢鋯氧化物觸媒 35 3-2 鎢鋯氧化物負載於SBA-15: 直接含浸法與超臨界乙醇法的比較 37 3-3 超臨界乙醇合成鎢鋯氧化物負載於介孔洞SBA-15 40 3-3-1 改變鎢與鋯的負載順序 40 3-3-2 改變初濕含浸溶劑 43 3-3-3 改變載體型態探討 47 3-3-4 改變觸媒煆燒溫度 50 3-3-5 在分次負載樣品製備中改變含浸溶劑和載體型態 53 3-4 鎢LIII-edge X光吸收光譜 55 3-5 觸媒酸性的測量 58 Chapter 4 催化反應 63 4-1 觸媒製備對催化活性的影響 63 4-1-1 載體與超臨界處理的影響 63 4-1-2 負載順序的影響 66 4-1-3 初濕含浸溶劑的影響 68 4-1-4 載體型態的影響 71 4-1-5 煆燒溫度的影響 73 4-1-6 在分次負載樣品製備中改變含浸溶劑和載體型態 75 4-1-7 與文獻報導之觸媒活性做比較 76 4-2 觸媒酸性與活性之關連 77 4-3 觸媒的重複使用 78 Chapter 5 結論 82 Chapter 6 參考文獻 83 | |
dc.language.iso | zh-TW | |
dc.title | 介孔洞SBA-15負載之鎢鋯氧化物用於氣相甘油脫水反應 | zh_TW |
dc.title | Gas-phase Dehydration of Glycerol Catalyzed by SBA-15 Supported W/Zr Mixed Oxides | en |
dc.type | Thesis | |
dc.date.schoolyear | 100-1 | |
dc.description.degree | 碩士 | |
dc.contributor.oralexamcommittee | 牟中原,萬本儒 | |
dc.subject.keyword | 鎢鋯氧化物,固體酸,丙烯醛,甘油,SBA-15, | zh_TW |
dc.subject.keyword | WO3/ZrO2,Solid acid,Acrolein,Glycerol,SBA-15, | en |
dc.relation.page | 85 | |
dc.rights.note | 有償授權 | |
dc.date.accepted | 2012-02-10 | |
dc.contributor.author-college | 理學院 | zh_TW |
dc.contributor.author-dept | 化學研究所 | zh_TW |
顯示於系所單位: | 化學系 |
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