负载Ni催化剂用于乙二醇蒸汽重整制氢催化性能研究.pdf

第43卷第5期
燃料化学学报
Vol 43 No
2015年5月
Journal of Fuel Chemistry and Technology
May 2015
文章编号:0253-2409(2015)050581-08
负载Ni催化剂用于乙二醇蒸汽重整制氢催化性能研究
赵星岭,吕衍安,廖卫平,金明善,索掌怀
(烟台大学应用催化研究所,山东烟台264005
摘要:采用等体积浸渍法和共沉淀法制备了i催化剂,在固定床反应器上考察了Ni负载量、焙烧温度、反应温度等因素对
乙二醇低温重整制氧反应活性和选择性的影响。应用X射线衍射、氮物理吸附、H2程序升温还原等技术对负载型M催化剂
进行了表征。结果表明,共沉淀法制备的 Niceo2催化剂具有较小的NiO颗粒与CeO2载体颗粒粒径,催化活性较高。蕍加少
量氧化钴到Ni/CeO2催化剂中可使H2收率达72.6%,EG转化率达93.1%。在CeO2中添加Al,O,能提高负载Ni催化剂的活
性,乙二醇转化率达94-.0%,H2收率达67.0%;但添加SiO2则使其活性明配变差
关键词:乙二醇;蒸汽重整;负载镍催化剂;制氢
中图分类号:O643文献标识码:A
Hydrogen production from
steam reforming of ethylene glycol over supported nickel catalysts
ZHAO Xing-ling, LU Yan-an, LIAO Wei-ping, JIN Ming-shan, SUO Zhang-huai
(institute of Applied Catalysis, Yantai University, Yantai 264005, China)
Abstract: A series of nickel catalysts were prepared by the impregnation and co-precipitation methods and
characterized by X-ray diffraction, nitrogen physisorption, and H temperature-programmed reduction
effects of nickel loading, calcination temperature, reaction temperature, support modification and cobalt oxide
ddition on the catalytic activity and selectivity to H in the steam reforming of ethylene glycol were investigated
he results indicate that the nickel catalyst prepared by co-precipitation has smaller particle size and relatively
higher activity in comparison with the catalyst prepared by impregnation. Adding a Small amount of cobalt oxide
to the Ni/Ceo catalysts can enhance the catalytic activity; over the Ni-co bimetallic catalyst, the yield of
hydrogen reaches 72. 6%o. Moditying Ceo, with Al,O,, TIO, and Zro also has a certain influence on the
catalytic activity and the Ni/Ceo, -A1, O, catalyst exhibits the highest activity, with an ethylene glycol conversion
of 94%o to gaseous products and a hydrogen yield of 67.0%o. However, Ni/Ceo, -SIO, shows a very low activit
in spite of its large surface area and pore volume
Key words: ethylene glycol; steam reforming; supported nickel catalyst; hydrogen production
近年来,生物质制氢技术受到关注。以生物质600℃以上获得了接近100%EG转化率和H2选择
或生物质衍生物为原料,通过热裂解、催化重整等方性。Tupy等]发现,活性炭负载Ni-Pt双金属催
法制氢不仅具有原料廉价易得、可再生等优点,而且化剂在270℃下可将34%EG转化,氢气选择性接
反应条件缓和、氢收率高,可望成为新的工业制氢技近70%。与贵金属相比,Ni催化剂具有资源丰富、
术
价格低廉的优势。 Shabaker等17制备了Sn改性
乙二醇(EG)是一种简単的二元停,工业上主要的 Raney-ni催化剂,发现加入少量Sm能显著提高
通过环氧乙烷制取。近年来,纤维素催化转化制选择性,而降低烷烃选择性。Pan等制备的类
FG研究取得很大进展,这为EG重整制氢技术研水滑石Ni/Sn/AI-HT催化剂不仅貝有高的H12生成
究提供了原料保证。研究发现,P、Pd、Rh、Ni等金速率和选择性,而且具有很好的稳定性,反应120h
属具有强的断裂C-C鍵能力,是良好的重整制氢催未失活。 Haasterecht等发现,碳纤维负载Ni催
化剂活性组分+。 Shabaker等比较了PvAl2O、化剂在碱性条件下连续反应50h后对H2,选择性仍
催化剂上甲醇与EG蒸汽重整反应的速率,发现两
达到99%。
者基本相同,认为C-C键断裂不是EG重整反应的
EG重整制氢催化剂不仅要有高的EG转化率、
决速步骤。 Izquierdo等0山使用负载Rh催化剂在
收稿日期:2015-01-22;修回日期:2015-03-10。
基金项目:国家自然科学基金(21273193);山东省自然科学基金(ZR201IBMO24)。
联系作者:索掌怀,Tel:05356902514,E-mail:zhuo@ytu.edu.cn。
本文的英文电子版由Elsevier出版社在Sciencedirect上出版(htp://www.sciencedirect.com/science,/journal/18725813