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Preparation of Nanocatalyst Cu/ZnO Supported on Zirconia and Its Application on Steam Reforming of Methanol
|關鍵字:||steam reforming of methanol;甲醇蒸汽重組;weight hourly space velocity;promoter;precursors;分散劑;擔體;重量空間流速;鍛燒||出版社:||化學工程學系所||引用:||M-C. Tsai, T.-K. Yeh, C-H Tasi, “An improved electrodeposition technique for preparing platinum and platinum-ruthenium nano-particles on carbon nano-tubes directly grow on carbon cloth for methanol oxidation”, Electrochemistry Comunicaitons, 8 (2006) 1445-1452 K. Takeda, A. Baba, Y. Hishinuma, T. Chikahisa, “Performance of methanol reforming system for a fuel cell powered vehicle and system evaluation of a PEFC system”, JSAEReview, 23 (2002) 183-188 G. T. Wu, C. S. Wang , “Lithium insertion into CuO/carbon nanotubes ”, Journal of power sources, 75 (1998) 175-179 X. Wang, W. Li, Z. Chen, M. Waje, Y. Yan,“Durability investigation of carbon nanotube as catalyst support for proton exchange membrane fuel cell”, Journal of Power Sources, 158 (2006) 154-159 J. Xu, H. Kaifeng, G. Sun, C. Wang, X. Lv, Y. 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Gomez, “Sol-Gel preparation of supported metal catalysts”, Catalysis Today, 35 (1997) 293-317 N. Takezawa, N. Iwasa, “Steam reforming and dehydrogenation of methanol: Difference in the catalytic functions of copper and group VIII metals”, Catalysis Today, 36 (1997) 45-56||摘要:||
本論文之研究目的為製備出奈米結構之氧化鋯，將銅與氧化鋅擔持於其表面，運用在甲醇蒸汽重組反應上。擔體條件之變數包含有不同溶劑的選用、不同H2O與Zr(OC3H7)4之莫耳數比、磁石攪拌與超音波攪拌的比較、鍛燒溫度的不同、添加不同分散劑。甲醇蒸汽重組反應之變數包括有不同H2O與CH3OH之莫耳數比、重量空間速度(Weight Hourly Space Velocity)、銅之含量、氧化鋅之含量以及觸媒活性測試。
使用氧化鋅加入Cu/ZrO2中當促進劑時，在甲醇蒸汽重祖產氫的過程中，可以大幅的提升甲醇的轉化率與氫氣的產率。在觸媒中添加銅，會使得觸媒在甲醇蒸汽重組中有較高活性，而在甲醇蒸汽重組反應中，添加14%之活性金屬銅與5%氧化鋅有最好的反應效果。當我們使用Cu/ZnO/ZrO2(14 % Cu,5 % ZnO)觸媒時，在水與甲醇莫耳數比例為1.3的情形下，360℃之氫氣產率已達96%以上。更高之氫氣產率、二氧化碳選擇率與較低之一氧化碳濃度都可以在裡面觀察到。以分序製備出之觸媒，在10小時的活性測試過程中，有很良好的穩定性，氫氣產率經過10小時的操作後約維持在82%，二氧化碳選擇率均在99%以上，一氧化碳體積濃度約為0.06～0.22%。另外以同步製備出Cu/ZnO/ZrO2 所獲得氫氣產率比分序製備低上許多，雖然氫氣產率約為20%，但是二氧化碳之選擇率維持在92%以上。
In the dissertation, the purpose of this study is to prepare nanocatalyst Cu/ZnO supported on Zirconia and to apply it on steam reforming of methanol. The operating parameters, including the choice of the solvent, the molar ratio of H2O to Zr(OC3H7)4, the difference between agitation and ultrasound, the concentration of Zr(OC3H7)4 dissolved in n-propanol and the temperature of calcination, were all performed to find the optimal preparation conditions. The operatiy parameters of methanol steam reforming were included the weight hourly space velocity, the H2O/CH3OH molar ratio, the amount of copper, the amount of ZnO and time-on-stream activity testing.
The results show that the particle size of ZrO2 is related to the of choice the solvent, the molar ratio of H2O to Zr(OC3H7)4, the concentration of Zr(OC3H7)4 dissolved in n-propanol, the stirring method, the temperature of calcinations and the addition of dispersant. And adding the dispersant influenced the pore size of catalyst. The optimum operating conditions were obtained, the n-propanol as solvent, the molar ratio of H2O to Zr(OC3H7)4 is 0.25M of the concentration of 4.5 Zr(OC3H7)4 dissolved in n-propanol with ultrasound agitation,400℃ of the calcinations temperature for 5 hours and the CTAB as the dispersant for the support.
When ZnO-promoter was added to Cu/ZrO2 catalyst ,the methanol conversion and H2 yield improved greatly by methanol steam reforming. The catalyst with active Cu metal shows higher activity for the reaction of methanol steam reforming and the best weight ratio of Cu/ZnO/ZrO2 was 14/5/81. Using Cu/ZnO/ZrO2 as the catalyst, we obtained the hydrogen yield to be 96.44% at 320℃ with 1.3 of molar ratio of water to methanol. The higher hydrogen production, higher selectivity of CO2 and lower CO concentration were also observed. 10-hour duration of test for Zr-1 catalyst showed that the catalyst had good stability with H2 yield kept at 82 % and CO2 selectivity > 99 % , and CO Vol % 0.06-0.22 %. But another method of simultaneous adding Cu and ZnO precursors for the preparation Cu/ZnO/ZrO2 (Zr-2) obtained the H2 yield much lower than with by which Zr-1. H2 yield was kept at 20 %, and CO2 selectivity >92%
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