氨基改質之鋁鎂氧氣凝膠應用於二氧化碳／環氧丙烷之環加成反應

Amino Group Modification of Al-Mg-O Aerogels for Carbon Dioxide／Propylene Oxide Cycloaddition Reaction

林詠傑(Yong-Jie Lin)

指導教授 ： 林義峯

中原大學/工學院/化學工程研究所/碩士(2017年)

https://doi.org/10.6840/cycu201700448

摘要

二氧化碳一直是大氣中最需要被解決的主要溫室氣體，近年依然以二氧化碳捕捉與封存(Carbon-dioxide Capture and Storage, CCS)為主要減排技術，但將捕捉到之二氧化碳進行封存已有安全的疑慮，因此近年來許多學者都致力於如何將二氧化碳進行再利用以利於有效減少大氣中之二氧化碳。過去，曾有學者大力研究於二氧化碳與環氧化物之環加成反應，此反應可以利用環氧化物與二氧化碳藉由觸媒合成出具有高經濟效益之環碳酸酯類。
　　因此，本研究將利用環氧化物起始凝膠法製備鋁鎂氧氣凝膠，並應用於二氧化碳/環氧丙烷之環加成反應中，並從實驗結果中找到鋁鎂氧氣凝膠之最佳鋁鎂莫耳比例，但從實驗結果可以發現鋁鎂氧氣凝膠對於環碳酸酯類之產率依然沒有很顯著的效果，所以本研究希望藉由氣凝膠之易改質特性，使其表面進行改質接枝氨基官能基，使氣凝膠可以除了鋁鎂兩樣金屬當作活性點外，多出氨基加入反應，藉此提升環碳酸酯類之產率。而在實驗過程中，我們也探討了不同的實驗參數對實驗結果之影響，並從中找到最佳參數條件為反應溫度150oC、反應時間15hr與反應壓力10kgw。最後，本實驗成功製備出氨基改質鋁鎂氧氣凝膠之異相觸媒應用於二氧化碳之環加成反應中，並將實驗參數最佳化後得到將近99%的碳酸丙烯酯產率觸媒效果。

關鍵字

氧化鋁氣凝膠 ； 鋁鎂氧氣凝膠 ； 氨基改質之鋁鎂氧凝膠 ； 二氧化碳再利用 ； 環加成反應 ； 環氧丙烷 ； 碳酸丙烯酯

並列摘要

CO2 is the primary greenhouse gas which causes global warming in recent years. As the carbon capture and storage (CCS) getting maturing, the reuse of carbon dioxide which made from CCS is the important issue. In this way, the most common method is the synthesis of cyclic carbonate chemicals from the cycloaddition reaction of carbon dioxide and epoxide. The catalyst plays an important role in the CO2/epoxide cycloaddition reactions. The Lewis acidic and basic sites are both needed on the catalyst surface for the help of epoxide ring opening, leading to the synthesis of cyclic carbonate. Furthermore, the larger specific surface area and more active site of the catalyst are also needed to enhance the efficiency of the CO2/epoxide cycloaddition reactions.
　　Aerogel is a mesoporous nanomaterial (pore size between 2~50 nm) with high specific surface area and porosity (at least 90%) and low density. In this study, for the first time, the ternary metal oxide aerogels, Mg-doped Al2O3 aerogels, with higher specific surface area and Lewis acidic and basic sites on the aerogel surface are successfully prepared using a facile sol-gel reaction. The as-prepared Mg-doped Al2O3 aerogels are also served as a heterogeneous catalyst for the CO2/propylene oxide cycloaddition reaction. Compared to the pristine Al2O3 aerogels, the Mg-doped Al2O3 aerogels possessed both Lewis acidic and basic sites on the surface are able to enhance the efficiency of the CO2/propylene oxide cycloaddition reactions. As a result, the as-prepared Mg-doped Al2O3 aerogels are a promising and novel catalyst for the CO2/epoxide cycloaddition reactions.

並列關鍵字

Alumina aerogel ； Al-Mg-O aerogel ； Amine Al-Mg-O aerogel ； CO2 recovery ； cycloaddition ； propylene oxide ； propylene carbonate

參考文獻

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