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研究生:劉玉城
研究生(外文):Yu-Chern Liu
論文名稱:被擔持釩氧化物觸媒之表面特性與丙烷氧化反應之反應動力模式之研究
論文名稱(外文):Fundamental Studies of Propane Oxidation over Model Supported Vanadia Catalysts: Molecular Structure-Reactivity/Selectivity
指導教授:鄭紀民
指導教授(外文):Jih-Mirn Jehng
學位類別:碩士
校院名稱:國立中興大學
系所名稱:化學系
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:1999
畢業學年度:87
語文別:中文
中文關鍵詞:被擔持釩氧化物觸媒丙烷氧化脫氫反應還原能力表面酸性拉曼光譜反應動力紅外線光譜表面積
外文關鍵詞:Supported Vanadium OxidePropane OxidationRaman SpectroscopyReducibilityAcditykinetic modelsFT-IR spectroscopy
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由於近十年來,烷類產量過剩及成本低之因素,在石油及石油化學工業中將烷類催化氧化轉變成烯類及含氧化物之製程日漸提高研究者之注意及興趣。被擔持金屬氧化物觸媒已廣泛被應用在於化學工業界,其中的研究結果顯示以釩氧化物為主之觸媒最能有效應用於烷類之氧化反應。被擔持釩氧化物和擔體之鍵結性質在氧化脫氫反應上扮演一個重要的角色,因為擔體不僅提供高表面積而且可分散表面金屬氧化物。被擔持釩氧化物之活性是藉由特定的擔體與表面釩氧化物之覆蓋率及鍵結關係所決定的。在以釩氧化物為主之觸媒中,又以被擔持釩氧化物為最理想之模式系統做為對烷類氧化之基礎研究,因為表面釩氧化物之兩度空間特性可利用光譜儀在反應狀態下測得,進而提供對此觸媒分子結構設計及分析之幫助。故有系統探討模式被擔持釩氧化物觸媒應用於烷類氧化反應為此研究之主要方向。
模式被擔持釩氧化物觸媒及混合表面氧化物金屬均擁有雙功能之性質(氧化還原/酸性或氧化還原/鹼性),製備之模式被擔持釩氧化物觸媒,以不同濃度之V2O5/TiO2、V2O5/SiO2、V2O5/Al2O3為主,利用沈浸法製備並運用拉曼(Raman)、傅利葉紅外線光譜做表面特性分析,對被擔持釩氧化物金屬探討表面路易士酸和表面布郎士酸的基位,以了解表面活性金屬氧化物之分子結構。觸媒之表面化學、及還原能力將運用傅利葉紅外線光譜之砒碇吸附及程式控溫還原/脫附實驗求得。模式被擔持釩氧化物觸媒之丙烷氧化反應測試將可得知此觸媒對此反應之活性及選擇性。且利用Langmuir-Hinshelwood mechanism 建立反應動力模式。由分子結構特性分析及反應動力結果之結合可建立丙烷氧化反應之分子結構與活性/選擇性間之關係性。故此基礎研究之結果可提供建立丙烷反應與觸媒間之分子觀反應動力模式,及幫助釩氧化物觸媒在烷類氧化反應之設計與改善。

The current abundance and low cost of alkanes has generated much interest in the oxidative catalytic conversion of alkanes to alkene and oxygenates in the petroleum and petrochemical industries. A review of the literature reveals that the oxidation of alkanes is most efficient over vanadia-based catalysts and that essentially no systematic studies with well-characterized catalysts have been performed to date. Among vanadia—based catalysts, supported vanadia catalysts are oxidation and ideal model catalytic system for investigating the fundamental aspects of alkane oxidation because the two-dimensional nature of the surface vanadia overlayer allows such catalysts to be molecularly designed as well as molecularly characterized with in situ spectroscopies under rection conditions. Thus, a research opportunity currently exists to systematically investigate the fundamental aspects of alkane oxidation over well-characterized model supported vanadia catalysts.
The model supported vanadia catalysts, as well as mixed metal oxide monolayers possessing dual functionality (redox/acid and redox/base), will be synthesized and characterized with molecular spectroscopies (Raman and FT-IR spectroscopy) to confirm that the desired molecular arrangements of the active surface metal oxide phases have been achieved. The molecular characterization studies will also be conducted in situ under reaction conditions to obtain information about the dynamics of the surface metal oxide species (possible structure transformations and extent of reduction) and potential hydrocarbon intermediates. Information about the surface chemistry of the model supported vanadia catalysts, acid/base and redox properties, will be obtained with FTIR pyridine/CO2 adsorption and temperature programmed reduction and deosrtion experiments. The reactivity/selectivity properties of the model catalysts will be chemically probed with steady-state catalytic studies of propane oxidation. Combination of the structural characterization and kinetic information will allow for the development of molecular structure-reactivity/selectivity relationships for this important class of catalytic reactions. This fundamental information will provide a foundation to develop molecular-level kinetic models as well as assist in the molecular design of improved catalysts for alkane oxidation over vanadia-based catalysts.

目錄
中文摘要…………………………………………………Ⅰ
英文摘要…………………………………………………Ⅲ
致謝………………………………………………………Ⅴ
圖目錄……………………………………………………Ⅸ
表目錄……………………………………………………XII
第一章 緒論…………………………………………… 1
1.1 前言…………………………………………………1
1.2 研究動機及目的……………………………………1
1.3 丙烯在化學工業的重要性…………………………2
1.4 丙烯及丁烯的來源:脫氫及氧化脫氫……………3
1.5 文獻回顧……………………………………………6
1.6 反應的關鍵步驟……………………………………10
第二章 實驗方法及裝置……………………………… 13
2.1 觸媒之製備…………………………………………13
2.1-1 被擔持釩氧化物觸媒之製備……………………15
2.2 觸媒特性分析………………………………………15
2.2-1.1 BET表面積之測定原理……………………… 15
2.2-1.2 孔徑大小之測定原理.……………………… 20
2.2-1.3 BET表面積及孔徑大小之測定實驗………… 22
2.2-1.4 BET表面積及孔徑大小之計算……………… 23
2.2-2 砒碇吸附紅外線光譜儀之應用…………………24
2.2-2.1 傅立葉轉換紅外線光譜儀之原理……………24
2.2-2.2 FTIR砒碇吸附之定性分析……………………25
2.2-3 TPR溫控程式還原反應之定量分析…………… 28
2.2-3.1 TPR溫控程式還原反應之定量分析原理…… 28
2.2-3.2 TPR溫控程式還原反應之定量分析………… 28
2.2-4 拉曼光譜之測定…………………………………30
2.3 GC分析………………………………………………30
2.3-1 GC分析原理………………………………………30
2.3-2 GC實驗……………………………………………32
2.3-3 被擔持金屬觸媒之丙烷氧化脫氫反應之計算方法...36
第三章 實驗結果與討論……………………………… 40
3.1 BET和平均孔徑大小的偵測結果………………… 40
3.2 砒碇吸附紅外線光譜之偵測結果…………………44
3.3 TPR之定量分析結果……………………………… 45
3.4 拉曼光譜之分析結果………………………………49
3.5 GC反應之分析結果…………………………………57
第四章 動力模式……………………………………… 84
4.1 前言…………………………………………………84
4.2 反應動力經驗方程式………………………………85
4.2-1 Langmuir-Hinshelwood模式之反應機構………88
4.2-2 丙烷及氧之反應級數……………………………90
4.2-3 應用Arrhenius 方程式計算活化能……………90
4.2-3 可能反應之步驟…………………………………93
第五章 結論與建議…………………………………… 94
第六章 參考文獻……………………………………… 98
第七章附錄………………………………………… 101

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