反,反,順-1,5,9-環十二碳三烯在含鎳MCM-41中孔型分子篩之氫化反應

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Title:	反,反,順-1,5,9-環十二碳三烯在含鎳MCM-41中孔型分子篩之氫化反應
Other Titles:	Catalytic hydrogenation of trans, trans, cis-1, 5, 9-cyclododecatriene over Ni/MCM-41 mesoporous molecular sieves
Authors:	許振宏
Contributors:	柯安男 Ko, An-Nan 東海大學化學系
Keywords:	反;反;順- 1;5;9- 環十二碳三烯;中孔型分子篩;氫化反應 trans;trans;cis-1;5;9-cyclododecatriene;MCM-41;Ni/MCM-41;mesoporous molecular sieves;hydrogenation
Date:	2003
Issue Date:	2011-05-19T06:06:51Z (UTC)
Abstract:	本研究探討反,反,順- 1,5,9-環十二碳三烯與氫氣在含鎳MCM-41中孔型分子篩之催化反應。利用X射線繞射儀、穿透式電子顯微鏡表面積測試儀、氨氣溫度程控脫附儀、氫氣溫度程控還原儀、固態核磁共振儀、一氧化碳化學吸附儀、以及霍式轉換紅外線光譜儀，來鑑定Ni/Si-MCM-41與Ni/Al-MCM-41觸媒的結構、表面積、酸性、觸媒還原狀況以及金屬分散度等。結果顯示，Ni/Al-MCM-41觸媒隨著矽/鋁莫爾比的增加，結構規則性提高，表面積增加，但酸量隨之減少。對Ni/Si-MCM-41觸媒而言，除了鎳含量最高的觸媒（Ni15%/Si-MCM-41）可能因為過多鎳金屬堆積的緣故，其餘觸媒的酸量、一氧化碳吸附量及TPR還原面積皆隨鎳含量的增加而增加。Ni(15%)/MCM-41系列的觸媒經由TEM與TPR的測量，可獲知鎳金屬堆積的情況，並從吸附?啶的IR圖譜中獲知觸媒具有弱的路易士（Lewis）酸性點。使用攪拌批式反應器於10大氣壓與50∼80℃下的實驗結果顯示，攪拌轉速大於800 rpm時可以忽略擴散限制，且觸媒在極性溶劑中有較好的催化活性。當觸媒重量、反應溫度、鎳含量增加時，反應物的轉化率隨之增加。而Ni(15%)/Al-MCM-41系列觸媒會隨著矽鋁比的減少，反應的轉化率隨之增加，顯示增加觸媒的路易士酸性點會增加催化的活性。Ni/MCM-41觸媒在經過反應後，BET表面積、結構規則性、酸量以及TPR實驗中的高溫波峰皆顯示出下降的趨勢，導致再生觸媒呈現出較差的催化活性。 The catalytic reaction between trans, trans, cis- 1, 5, 9- cyclododecatriene and hydrogen gas has been studied using nickel containing mesoporous molecular sieve MCM-41. The catalysts of Ni/Si-MCM-41 and Ni/Al-MCM-41 were characterized with various techniques of XRD, TEM, gas sorption analyzer, NH3-TPD, H2-TPR, solid state NMR, CO-chemisorption and FT-IR to obtain the catalyst properties, viz. the structure, the surface area, the acidity, the reducibility and the metal dispersion. Increasing the SiO2/Al2O3 mol ratio enhances the structural order and the surface area but diminishes the acid amount. An increase of nickel content in Ni/Si-MCM-41 enlarges the acid amount, the adsorbed CO and the peak area of H2-TPR except the largest amount of nickel (15%) probably due to the packing of nickel metal. With Ni (15%)/MCM-41 catalysts, the textures of nickel packing were obtained from the results of TEM and TPR. Based on FT-IR measurements, the catalysts were found to contain Lewis acid sites. The catalytic reaction was performed at 10 bar and 50~80℃ in a stirred batch reactor. The system is free of diffusional limitation at a stirring speed larger than 800 rpm and the better catalytic activity is attained by using polar solvent. The conversion of reactant increases with the catalyst weight, the reaction temperature and the nickel content. Decreasing the SiO2/Al2O3 mol ratio of Ni(15%)/Al-MCM-41enhances the catalytic activity, implying the positive effect of catalyst Lewis acidity. After reactions the Ni/MCM-41 catalysts show a decrease of BET surface area, structural order, acid amount and area of high temperature peak in TPR. Accordingly, the regenerated catalysts exhibit lower activities.
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