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研究生:陳威誌
研究生(外文):Wei-Chih Chen
論文名稱:雙金屬觸媒Pt-Sn/BN在巴豆醛選擇性氫化之研究
論文名稱(外文):Selective Hydrogenation of Crotonaldehyde Using Bimetallic Pt-Sn/BN Catalyst
指導教授:吳紀聖
指導教授(外文):C.-S. Wu
學位類別:碩士
校院名稱:國立臺灣大學
系所名稱:化學工程學研究所
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2004
畢業學年度:92
語文別:中文
論文頁數:106
中文關鍵詞:選擇性氫化Pt-Sn/BN巴豆醛雙金屬觸媒
外文關鍵詞:bimetallicselectivet hydrogenationPt-Sn/BNcrotonaldehyde
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本研究主要為以BN支撐的雙金屬觸媒在巴豆醛的選擇性氫化反應,將鉑與錫雙金屬利用共臨界沾濕法負載於BN上,鉑含量皆為1.1 wt%而錫含量則從0.25至0.75 wt%。除外,我們也製備單金屬觸媒1.1wt%Pt/BN及1.0wt%Sn/BN且另選用商業觸媒載體γ-Al2O3及活性碳做為比較。反應結果顯示Pt-Sn/BN中錫的添加量越多,巴豆醇的選擇率與產率越高,Pt-Sn(0.75)/BN在轉化率為60% 下,選擇率可達0.63,推測應為Pt-Sn/BN中的Snn+扮演路易士酸基而能吸附與活化C=O鍵所致。觸媒所使用的檢測有N2吸附BET比表面積測定、氫氣與一氧化碳化學吸附測定、Temperature programmed reduction(TPR)、X-ray diffraction(XRD)、X-ray photoelectron spectroscopy(XPS)及Transmission electron microscope(TEM)。從XPS分析,發現大部分的錫的價態在氫氣300℃還原後仍維持為2+,而Pt-Sn/BN則有部分Sn2+被還原為金屬態而形成PtxSn合金。Pt-Sn/γ-Al2O3在XRD上沒有出現任何PtxSn合金,但有可能因其晶粒太小以致無法由XRD所偵測。從TPR與TEM可知,BN相較γ-Al2O3對於金屬前軀物的固定力較差,以致於在氫氣還原後,金屬聚集較為嚴重。Pt-Sn/γ-Al2O3在相同反應溫度,巴豆醇選擇率亦隨著錫的含量增多而提高,但丁醛的產率大幅降低,且巴豆醇產率也無法顯著提升,其因與Snn+的周圍環境有關,而丁醛的產率大幅下降則可能由Pt的分散度降低及可能出現的PtxSn雙金屬小粒子所引起。Pt-Sn/AC的反應結果與Pt-Sn/γ-Al2O3相似。

In the present study we focused on the selective hydrogenation of crotonaldehyde over bimetallic BN-supported catalysts which were prepared by co-incipient wetness impregnation. The compositions of the catalysts were platinum 1.1 wt% and tin from 0.25 to 0.75 wt%. Besides we also prepared monometallic catalysts 1.1wt%Pt/BN and 1.0wt%Sn/BN. We chose some commercial catalyst supports γ-Al2O3 and activated carbon to compare with BN. The reaction results revealed that the more tin in Pt-Sn/BN, the higher the selectivity to crotyl alcohol. The Pt-Sn(0.75)/BN has the selectivity to crotyl alcohol 0.63 under the conversion 60%. The improvement of the selectivity to crotyl alcohol was contributed to Snn+ as Lewis acid sites that adsorb and activate C=O bond. The catalysts were characterized by N2 adsorption BET method, hydrogen and carbon monoxide selective chemisorption, temperature programmed reduction (TPR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscope (TEM) technique. By the XPS analysis, we found mostly the tin remained Sn2+ after reduction in flowing hydrogen at 300oC and PtxSn alloys were formed in Pt-Sn/BN. However we could not find any PtxSn alloys in Pt-Sn/γ-Al2O3 by XRD as the PtxSn particles might be possibly too small to be detected by XRD. BN is more inert than γ-Al2O3 and interacts weakly with metal precursors, and therefore the metal aggregation is more severe. The selectivity to crotyl alcohol in Pt-Sn/γ-Al2O3 was also increased as the tin content increased at the same reaction temperature. However the yield of the butyraldehyde was decreased appreciably and it may be caused by the decrease of the Pt dispersion and the possibly small bimetallic clusters PtxSn. The yield of the crotyl alcohol was not improved apparently due to the different surroundings of the Sn2+. The reaction results of the Pt-Sn/AC were similar to those of Pt-Sn/γ-Al2O3.



中文摘要 Ⅰ
英文摘要 Ⅲ
目錄 Ⅴ
表目錄 Ⅷ
圖目錄 Ⅸ

第一章 緒論 1

第二章 文獻回顧 2
2.1 ? β-未飽和醛的選擇性氫化 2
2.1.1觸媒金屬效應 4
2.1.2載體效應 6
2.2 分散金屬觸媒 8
2.2.1 氧化鋁載體 9
2.2.2 BN載體 10
2.2.3 活性碳載體 11
2.3 雙金屬觸媒 13
2.3.1 幾何效應 14
2.3.2 雙金屬觸媒在? β-未飽和醛選擇性氫化的研究 14

第三章 實驗方法 23
3.1 觸媒製備 23
3.2 觸媒檢測 24
3.2.1 N2吸附BET比表面積測定 28
3.2.2 氫氣與一氧化碳化學吸附測定 29
3.2.3 雷射光繞射法粒徑分析 31
3.2.4 程溫規劃還原(Temperature Programmed Reduction, TPR) 31
3.2.5 X光繞射(X-ray Diffraction, XRD) 32
3.2.6 X射線光電子分光儀(X-ray Photoelectron Spectroscopy, XPS) 34
3.2.7 穿透式電子顯微鏡(Transmission Electron Microscope, TEM) 35
3.3反應裝置及操作步驟 37
3.4標準校正線製作 39

第四章 觸媒特性分析與討論 45
4.1 載體檢測 45
4.1.1 N2吸附BET比表面積測定結果 45
4.1.2 雷射繞射法測粒徑分佈結果 45
4.1.3 XRD測定結果 47
4.2 氫氣與一氧化碳化學吸附測定 50
4.3 XRD分析 56
4.4 穿透式電子顯微鏡(TEM) 62
4.5 程溫規劃還原(TPR) 66
4.6 X射線光電子分光儀(XPS) 69
4.7 結果討論 74

第五章 巴豆醛反應結果與討論 77
5.1 以BN支撐不同金屬組成觸媒的反應結果 79
5.2 以其他載體支撐觸媒的反應結果 83
5.3 氫氣還原溫度對觸媒反應的影響 88
5.4 以BN支撐各產物淨反應活化能比較 90
5.5 結果討論 93

第六章 結論 100
第七章 參考文獻 101
附錄 106


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