负载Ni催化剂上低温甘油蒸汽重整制氢.pdf

第43卷第6期
燃料化学学报
2015年6月
Journal of Fuel
try and Technology
Jun.2015
文章编号:0253-2409(2015)06-0684-08
负载N催化剂上低温甘油蒸汽重整制氢
吕衍安,赵星岭,索掌怀,廖卫平,金明善
(烟台大学应用催化研究所,山东烟台264005)
摘要:采用等体积浸渍法制备了A2O3、CeO2、TiO2及MgO负载i催化剂,考察了它们对甘油蒸汽重整制氢反应的催化性
能。采用Ⅹ射线衍射、N2吸附、透射电镜及H2程序升温还原等方法对催化剂进行了表征。结果表明,载体对催化剂的活
性有显著影响。在400℃下NCeO2的催化活性明显好于其他催化剂,活性次序为 Nicec2>NiAl2O2>Ni/TiO2~
Ni/MgO。Ni/CeO2也具有好的稳定性,反应20h未见活性下降,甘油转化率70%,氢气收率69.2%。这与CeO2的本性及其
与活性组分的相互作用有关。Al2O。具有较大的比表面积与孔体积,有利于O吸附及甲烷化反应的进行,使得N/Al2O、催
化剂在较高温度下具有很高的甘油转化率85.7%,但H2选择性较差。由于MgO载体与活性组分强的相互作用而生成
Nimgo2固溶体,导致Ni/MgO低温活性差。
关键词:甘油;蒸汽重整;制氢;负载Mi催化剂
中图分类号:O643文献标识码:A
Low-temperature steam reforming of glycerol
or hydrogen production over supported nickel catalysts
LU Yan-an, ZHAO Xing-ling, SUO Zhang-huai, LIAO Wei-ping, JIN Ming-shan
(Institute of Applied Catalysis, Yantai University, Yantai 264005, China)
Abstract: Al2], Ceo2, Tio and Mgo supported Ni catalysts were prepared by incipient impregnation. The
activities in glycerol steam reforming to hydro en production were evaluated at 300 500 t. The catalysts were
characterized by XRD, N, adsorption, TEM, and H, -TPR techniques. A strong effect of support on the activity
of Ni catalyst was detected. Ni/Ceo, catalyst gives the highest activity among all catalysts at 400C and the
following activity order is shown Ni/Ceo2 Ni/Al, O N/Tio Ni/Mgo. On Niceo there was almost no
deactivation detected after 20 h reaction with 70 conversion of glycerol and 69. 2% H yield. Good activity and
stability of the catalyst is attributed to the intrinsic property of Ceo and strong interaction between Ceo and
active nickel species. Relatively high glycerol conversion(857% with low H selectivity on NA1 O catalyst
at 500 C is achieved due to its high surface area and large pore volume. The formation of solid solution Nimgo
phase observed in Ni/Mgo catalyst does not show the desired activity at low temperatures though it enhanced the
interactions between active phase and the support. Base oxide supports(Ceo, MO) seem to be more effective
than acid oxide supports in preventing the formation of CO and CH, as by-products
Key words: glycerol; steam reforming; hydrogen production; supported nickel catalyst
生物质的催化转化是目前催化研究的热点课题
Co+H20→H12+CO2,△F=-41k/mol
之一。甘油是由动植物脂肪和油制肥皂时的副产
(2)
品。在生物柴油生产中,也产生一定量的甘油。因
总反应C3H2Oっ+3H2O→7H12+3CO2,
此,甘油被看作可再生的生物质资源。目前,对甘油
△=+127kI/mol(3
的利用主要集中于催化氢解制丙二醇2及蒸汽重
该反应是一个典型的强吸热过程,高温有助于
整制氢3“等方面。氢能源是理想的清洁能源,甘反应的进行。此外,整个过程还会伴随甲烷化、积炭
油重整制氢具有明显的资源优势。
等副反应的发生。
一般认为,甘油蒸汽催化重整制氢包括以下
些研究6?表明,P、Ir、Ru、Rh、Ni等金属具
过程:
有很强的C-C断裂能力,是良好的甘油蒸汽重整制
CH2O3→4H2+3C0,△=+250kJ/mol
氢催化剂。虽然Pt、催化剂具有更好的低温活性
(1)和稳定性6”),但Mi催化剂以其价格低廉,能促进
收稿日期:2014-12-19;修回日期:2015-03-21。
基金项目:国家自然科学基金(21273193);山东省自然科学基金(ZR2011BMO24
联系作者;索掌怀,Tel:05356902514,E-mail:zhuo@ytu,edu.cn