本研究探討磷化鎳之粒徑效應於4-甲基愈創木酚的加氫脫氧反應。利用低比表面積二氧化矽(SiO2-L)、高比表面積二氧化矽(SiO2-H)及中孔結構之二氧化矽(SBA-15)作為觸媒載體合成具有不同粒徑之磷化鎳。觸媒的物化性鑑定包括:氮氣物理吸附(BET)、X-ray繞射圖譜(XRD)、X射線光電子能譜(XPS)、感應耦合電漿原子發射光譜分析(ICP-AES)、穿透式電子顯微鏡(TEM)、氫氣程溫還原反應(H2-TPR)、氫氣程溫脫附反應(H2-TPD) 、一氧化碳的化學吸附(CO chemisorption)、一氧化碳程溫脫附(CO-TPD)以及氨氣的程溫脫附反應 (NH3-TPD)。
本實驗以程溫還原法合成三種二氧化矽擔載磷化鎳觸媒，載體比表面積較高者擁有較小粒徑之磷化鎳。此粒徑差異影響磷化鎳之加氫脫氧活性：較小粒徑之磷化鎳擁有較高氫氣吸附量及較高的鎳離子價態(Niδ+)；較大的磷化鎳活性點則具有相反的趨勢。利用批次式反應器於250℃及40 bar氫氣壓力下進行4-甲基愈創木酚加氫脫氧，發現觸媒物化性質的差異也反應在活性測試上；Ni2P/SiO2-L擁有最大轉化率但加氫活性與脫氧程度較弱，相對而言，Ni2P/SBA-15雖轉化率略低於其他兩種觸媒，但具有最佳加氫活性及脫氧程度。推測氫氣吸附量及鎳離子的氧化態對於4-甲基愈創木酚加氫脫氧扮演著重要的關鍵。

The aim of this study is to understand the particle size effect of nickel phosphide in hydrodeoxygenation (HDO) of 4-mathylguaiacol. Different surface areas of silica were used as the supports to synthesize nickel phosphide with varying particle sizes. Commercial SiO2 supports of low surface area (SiO2-L, 96 m2/g), high surface area (SiO2-H, 205 m2/g) and mesoporous SBA-15 (687 m2/g) were selected as the supports. Catalyst characterizations, including N2 physisorption, XRD, XPS, ICP-AES, TEM, H2-TPR, H2-TPD, CO chemisorption, CO-TPD, and NH3-TPD were performed.
Silica-supported nickel phosphide catalysts were prepared by temperature-programmed reduction. High surface area support had small particle size of nickel phosphide, while the low surface area counterpart has large nickel phosphide size. The particle size affects HDO activity of 4-methylguaiacol. The HDO of 4-methylguaiacol at 250℃ and 40 bar H2 in a batch reactor is used as a model reaction to explore the particle size effect of nickel phosphide. The small particle size of nickel phosphide had higher H2 uptake amount and higher partial positive charged Ni cations (Niδ+) than large counterpart. The activity test showed that the small particle size of nickel phosphide had lower conversion but higher hydrogenation and deoxygenation ability than large counterparts. H2 uptake was proposed to play a key role in 4-methylguaiacol hydrodeoxygenation reaction.

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