銅/氧化釤-氧化鈰觸媒之製備及其催化甲醇蒸汽重組反應之研究

Preparation of Copper/Samarium Oxide-Cerium Oxide Catalyst for Steam Reforming of Methanol

王翔平

甲醇蒸汽重組 ； 導氧離子材料 ； 奈米觸媒 ； 氫氣 ； steam reforming of methanol ； oxygen-iron-conducting material ； nanocatalyst ； hydrogen

中興大學化學工程學系所學位論文

2009年

碩士

楊鴻銘

繁體中文

本論文研究目的為將活性金屬銅擔持於氧化釤摻混氧化鈰表面，將其應用於甲醇蒸汽重組反應。觸媒製備變數包括不同銅含量、氧化釤和氧化鈰不同比例、不同煅燒溫度、不同種類分散劑、不同分散劑添加量、不同攪拌方式、促進劑不同添加量、不同先驅物濃度。甲醇蒸汽重組反應之變數包括不同水量對甲醇莫耳數比、不同重量空間流速與觸媒穩定性測試。 實驗結果顯示，銅添加量為25wt%之觸媒反應活性較高。氧化釤和氧化鈰的比例為Sm2O3(25)-CeO2(75)其氫氣產率最佳。不同煅燒溫度會影響其顆粒大小且在煅燒溫度500℃時可以提升氫氣產率。添加分散劑溴化十六烷基三甲基四級銨鹽(CTMAB)其表面積較大且有很高的反應活性。分散劑不同添加量會影響表面積和孔洞體積。超音波製備的觸媒活性比超音波和攪拌還要好。添加少量氧化鋅為促進劑時，氫氣產率在280℃，即達到約95%。先驅物濃度0.007M與0.005M的顆粒大小較小，但產氫速率卻比先驅物濃度0.01M時低。 以觸媒[Cu(80)/ZnO(20)](25)/[Sm2O3(25)-CeO2(75)](75)進行甲醇蒸汽重組反應變因中，當水與甲醇莫耳數比為1.3mol/mol與反應溫度280℃時，氫氣產率為95%，單位產氫速率可達到110.3mmmol/s*kg.cat。重量空間流速以7.7hr-1為反應活性最好。觸媒穩定性測試過程中，反應時間達100小時時，活性衰退63%，其二氧化碳選擇率可以持續維持在96%以上。

In the thesis, the purpose of this study is to prepare nanocatalyst Cu supported on Sm2O3-CeO2 and to apply it on steam reforming of methanol. The parameters of catalyst preparation include the different amounts of Cu, ratio of samarium oxide to cerium oxide, temperature of calcinations, types of dispersant, amount of dispersant, method of mixing, amount of promoter, concentration of precursor. Operating conditions in steam reforming of methanol are molar ratio of H2O/CH3OH, weight hourly space velocity, and stability of catalysts. The results show that the amount of copper at 25wt% has a higer activity than others. The ratios of samarium oxide to cerium oxide at 25wt% and 75wt% made the best hydrogen yield. Different calcination temperatures can influence the pore size of catalyst, and the temperature of calcination at 500℃ enhanced the hydrogen yield greatly. Adding the dispersant of 1-Hexadecyl trimethyl ammonium bromide can make the catalyst obtain large surface area and have high activities. The content of dispersant can influence the surface area and total pore size of the that using catalyst. The catalystic activity using method of ultrasound is better than ultrasound and stirring. Adding few ZnO as promoter to Cu/Sm2O3-CeO2, the hydrogen yield was obtained near 95% at 280℃. The concentrations of precursor at 0.007M and 0.005M made the particles more smaller, but the hydrogen production rate was lower than that at 0.01M. The catalyst of [Cu(80)/ZnO(20)](25)/[Sm2O3(25)-CeO2(75)](75) was used to proceed the reaction of steam reforming of methanol. With 1.3 of molar ratio of water to methanol, the hydrogen yield was 95% and the hydrogen production rate was 110.3mmmol/s*kg.cat at 280℃. The best performance of the catalyst was at 7.7hr-1 of weight hourly space velocity. In 100-hour duration of test, the activity decreased about 63%, and CO2 selectivity still kept at above 96% after 100h of reaction.

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