固相法合成铜铝尖晶石催化甲醇重整反应

郗宏娟; 李光俊; 庆绍军; 侯晓宁; 赵金珍; 刘雅杰; 高志贤

固相法合成铜铝尖晶石催化甲醇重整反应

1.
中国科学院山西煤炭化学研究所, 山西太原 030001;
2.
中国科学院大学北京 100049

详细信息

通讯作者:
高志贤

中图分类号: O643.32⁺2
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出版历程
- 收稿日期: 2013-05-31
- 修回日期: 2013-06-23
- 刊出日期: 2013-08-30

Cu-Al spinel catalyst prepared by solid phase method for methanol steam reforming

1.
Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China;
2.
University of Chinese Academy of Sciences, Beijing 100049, China

摘要

摘要: 以氢氧化铜和拟薄水铝石为原料(Cu/Al物质的量比为1/2),采用固相法经过不同温度焙烧后获得了一系列Cu-Al氧化物催化剂.当焙烧温度由500 ℃提高到900 ℃时,催化剂的主要铜物种由CuO渐变为CuAl₂O₄,比表面积由75.0 m²/g降低至16.6 m²/g.在甲醇重整反应过程中,以CuAl₂O₄为主要成分且具有较高比表面积的催化剂表现了优异的催化性能.另外,以CuAl₂O₄为主要成分的催化剂不经过预还原处理时,在反应过程中同时存在活性铜的释放和烧结,其催化活性呈现先增加后降低的趋势.在本研究催化剂制备条件下,优选800 ℃焙烧的催化剂,其催化性能优于商业Cu-Zn-Al催化剂,且具有可再生性.当催化剂不经过预还原处理时,在水醇物质的量比为1、240 ℃、1.01×10⁶ Pa、质量空速为1.75 h^-1的条件下,甲醇起始转化率为55.2%;反应进行288.3 h时,甲醇转化率升高至79.3%;反应继续运行至1 000.5 h时,甲醇转化率降低至63.9%.
- CuAl₂O₄ /
- 固相法 /
- 甲醇重整 /
- 缓释铜
Abstract: A series of catalysts were prepared by calcination of copper(II) hydroxide and pseudo boehmite with a Cu/Al molar ratio of 1/2. When the calcination temperature was raised from 500 ℃ to 900 ℃, the main component of the catalysts varied from CuO to CuAl₂O₄, and the catalyst surface area declined from 75.0 to 16.6 m²/g. The catalysts, with CuAl₂O₄ as main component and high surface area, showed excellent catalytic performance in methanol steam reforming reaction (MSR). In addition, the catalyst, with CuAl₂O₄ as main component, had the copper releasing as well as sintering, hence the catalytic activity increased first and then decreased. The preferred catalyst was calcined at 800 ℃ and had better catalytic performance than commercial Cu-Zn-Al. Meanwhile, this catalyst can be regenerated after MSR. When the catalyst was not pre-reduced, the methanol conversion was 55.2% at the beginning, and then increased to 79.3% at 288.3 h, and decreased to 63.9% at 1 000.5 h, when reaction conditions were the molar ratio of alcohol to water 1, 240 ℃, 1.0×10⁶ Pa, WHSV of 1.75 h^-1.
- CuAl₂O₄ /
- solid phase method /
- methanol steam reforming /
- copper release

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参考文献(12)

洪学伦. 甲醇重整气为燃料的质子交换膜燃料电池[J]. 化工学报, 2007, 58(6): 1564-1567. (HONG Xue-lun. PEMFC system fed with methanol reformate gas[J]. Journal of Chemical Industry and Engineering(China), 2007, 58(6): 1564-1567.)

YAHIRO H, NAKAYA K, YAMAMOTA K, SAILI K, YAMAURA H. Effect of calcination temperature on the catalytic activity of copper supported on γ-alumina for the water-gas-shift reaction[J]. Catal Commun, 2006, 7(4): 228-231.

BEHRENS M, ARMBRVSTER M. Methanol steam reforming[M]. Catalysis for Alternative Energy Generation, Springer, 2012: 175-235.

AGARAS H, CERRELLA G, LABORDE M A. Copper catalysts for the steam reforming of methanol: Analysis of the preparation variables[J]. Appl Catal, 1988, 45(1): 53-60.

FUKUNAGA T, RYUMON N, ICHIKUNI N, SHIMAZU S. Characterization of Cu Mn-spinel catalyst for methanol steam reforming[J]. Catal Commun, 2009, 10(14): 1800-1803.

KAMEOKA S, TANABE T, TSAI A P. Spinel CuFe₂O₄: A precursor for copper catalyst with high thermal stability and activity[J]. Catal Lett, 2005, 100(1): 89-93.

李光俊, 郗宏娟, 张素红, 谷传涛, 庆绍军, 侯晓宁, 高志贤. 尖晶石CuM₂O₄(M= Al, Fe, Cr)催化甲醇重整反应的特性[J]. 燃料化学学报, 2012, 40(12): 1466-1471. (LI Guang-jun, XI Hong-juan, ZHANG Su-hong, GU Chuan-tao, QING Shao-jun, HOU Xiao-ning, GAO Zhi-xian. Catalytic characteristics of spinel CuM₂O₄ (M=Al, Fe, Cr) for the steam reforming of methanol[J]. Journal of Fuel Chemistry and Technology, 2012, 40(12): 1466-1471.)

隋小涛, 于乔, 姜妍彦, 唐乃岭, 谷秀梅, 宁桂玲. 纳米CuAl₂O₄粉体的合成工艺条件及其表征[J]. 传感技术学报, 2006, 19(5): 2351-2353. (SUI Xiao-tao, YU Qiao, JIANG Yan-yan, TANG Nai-ling, GU Xiu-mei, NING Gui-ling. Characterization and condition of synthesizing CuAl₂O₄ nanoparticles[J]. Chinese Journal of Sendors and Actuators, 2006, 19(5): 2351-2353.)

SHLONO T, SHIONO K, MIYIMOTO K. Synthesis and characterization of MgAl₂O₄ spinel precursor from a heterogeneous alkoxide solution containing fine MgO powder[J]. J Am Ceram Soc, 2000, 83(1): 235-237.

WRZYSZCZ J, ZAWADZKI M, TRAWCZYNSKI J, GRABOWSKA H, MITAA W. Some catalytic properties of hydrothermally synthesised zinc aluminate spinel[J]. Appl Catal A: Gen, 2001, 210(1/2): 263-269.

骆凡, 吴季怀, 林建明, 胡东红, 杨媛媛, 张云霞. 纳米晶 CuAl₂O₄ 的合成, 表征及光催化性能研究[J]. 中国科技论文在线, 2008, 3(4): 263-267. (LUO Fan, WU Ji-huai, LIN Jian-ming, HU Dong-hong, YANG Yuan-yuan, ZHANG Yun-xia. Synthesis, characterization and photocatalytic properties of nanocrystalline CuAl₂O₄[J]. Sciencepaper online, 2008, 3(4): 263-267.)

庆绍军, 侯晓宁, 郗宏娟, 邱诗铭, 高志贤. Cu-SiO₂氧化还原性能的研究. 第十三届全国青年催化学术会议论文集, 2011: 290. (QING Shao-jun, HOU Xiao-ning, XI Hong-juan, QIU shi-ming, GAO zhi-xian. Redox performance of Cu/SiO₂. The 13th national youth catalytic academic conference proceedings, 2011: 290.)

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