摻雜過渡金屬之觸媒在光催化及加氫脫硫反應促進效應之研究

Promoter Effect of Transition Metal Doped Catalyst for Photocatalysis and Deep Hydrodesulfurization Reaction

陳亭穆(Ting-Mu Chen)

指導教授 ： 王奕凱

國立清華大學/工學院/化學工程學系/博士(2010年)

https://doi.org/10.6843/NTHU.2010.00175

摘要

本研究中探討了摻雜過渡金屬的促進效應對於觸媒在光催化以及深度加氫脫硫反應之影響。在光催化反應上，以溶膠凝膠法及共沉澱法製備含鋯之二氧化鈦光觸媒，探討不同鍛燒溫度及鋯添加量的效應；在深度加氫脫硫反應中，則以共沉澱法製備出含釩之氧化鋁載體，含浸鈷及鉬做為深度加氫脫硫反應中之活性物質，並觀察不同釩添加量對反應轉化率及脫硫效率的影響。在觸媒特性鑑定上，則分析了摻雜過渡金屬後的觸媒其晶型結構、比表面積與孔洞特性、表面的元素組成及元素間的相對比例。
實驗結果顯示，在光催化反應中，以溶膠凝膠法製備之鋯含量為10 mol%與鍛燒溫度為500 ℃之鈦鋯混合金屬氧化物對乙醛反應進料有最佳的光催化效果，藉由使用Langmuir-Hinshelwood動力學模型，可求得模型中的參數值，並配合觸媒之鑑定結果，得到參數值與觸媒特性間相對關係的經驗式；在深度加氫脫硫反應中，含釩的氧化鋁觸媒其反應路徑傾向於氫化後脫硫而非直接脫硫，有助於移除結構阻礙程度較高的硫份化合物4,6二甲基二苯並噻吩。此外，使用傳統氧化鋁觸媒與含釩的氧化鋁觸媒經磨碎混合後的混合觸媒，可達到較佳的轉化率以及較高的脫硫效率，而達到降低柴油中硫份的效果。

關鍵字

光催化 ； 深度加氫脫硫 ； 過渡金屬 ； 促進效應

並列摘要

In this research, the promoter effect of transition metal doped catalyst for photocatalysis and deep hydrodesulfurization reaction had been discussed. The titania and zirconia mixed oxides photocatalysts were prepared by the sol-gel and co-precipitation methods with different calcination temperature and added amounts of Zr, and the vanadia containing alumina (Vx-Al2O3) was prepared by the co-precipitation method and used as a catalyst support for Co and Mo oxide (Co-Mo/Vx-Al2O3) in the hydrodesulfurization (HDS) reaction.
Detailed catalyst characterization and catalyst testing showed that the doped transition metal oxides could improve the catalyst activities. The thermal stability and photodegradation ability of acetaldehyde were enhanced by incorporated Zr into the TiO2 structure. The experiment results showed that the s-TiZr-10-500 catalyst presented the best photocatalytic ability.
The promoter effect of vanadia is due to the synergetic effect of the formation of V-Mo sulfide. A binary powder mixture with intimate contact of Co-Mo/γ-Al2O3 and Co-Mo/Vx-Al2O3 could facilitate a concerted reaction involving both hydrogenation and direct desulfurization pathways.

並列關鍵字

Photocatalyst ； Deep Hydrodesulfurization ； Transition metal ； Promoter effect

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