催化学报

催化学报 ›› 2016, Vol. 37 ›› Issue (11): 1949-1965.DOI: 10.1016/S1872-2067(16)62518-4

• 论文 • 上一篇    下一篇

制备条件对用于甘油蒸汽重整反应Ni基催化剂性能的影响

M. A. Goula, N. D. Charisiou, K. N. Papageridis, G. Siakavelas   

  1. 西马其顿技术教育学院技术应用学院环境与污染控制工程系替代燃料与环境催化实验室, 科扎尼, 希腊
  • 收稿日期:2016-05-31 修回日期:2016-07-24 出版日期:2016-11-25 发布日期:2016-11-25
  • 通讯作者: M. A. Goula,Tel:+30-2461068296; Fax:+30-2461039682; E-mail:mgoula@teiwm.gr

Influence of the synthesis method parameters used to prepare nickel-based catalysts on the catalytic performance for the glycerol steam reforming reaction

M. A. Goula, N. D. Charisiou, K. N. Papageridis, G. Siakavelas   

  1. Technological Education Institution of Western Macedonia, School of Technological Applications, Department of Environmental and Pollution Control Engineering, Laboratory of Alternative Fuels and Environmental Catalysis, GR-50100 Koila, Kozani, Greece
  • Received:2016-05-31 Revised:2016-07-24 Online:2016-11-25 Published:2016-11-25
  • Contact: M. A. Goula,Tel:+30-2461068296; Fax:+30-2461039682; E-mail:mgoula@teiwm.gr

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740

被引次数

7

摘要：

研究了制备参数对用于甘油蒸汽重整反应的Ni基催化剂性能的影响.采用过量浸渍法、等体积浸渍法和改进的平衡沉积过滤（EDF）法制备了一系列Al2O3负载的8 wt% Ni催化剂，运用X射线衍射（XRD）、电感耦合等离子体光谱仪、N2吸附-脱附、扫描电镜（SEM）、透射电镜和H2程序升温还原（TPR）表征了催化剂的表面和体相性质；采用CHN分析仪和SEM表征了使用后催化剂以测定其表面沉积的碳及其形貌.结果表明，制备方法对所制催化剂的织构、结构和表面性质影响很大，导致氧化铝表面Ni物种的分散和种类的不同.即使XRD和TPR结果证实形成了铝酸镍晶相，但Ni/Al-edf催化剂中β峰的贡献大于其它两个催化剂的，表明在这种情况下铝酸镍更容易还原.在550℃以上CO2选择性增加和CO选择性不变，表明Ni/Al-wet和Ni/Al-edf催化剂可成功催化水汽变换反应.另外，650℃时Ni/Al-edf催化剂上甘油生成气相产物的转化率、氢气产率以及烯丙醇、乙醛和乙酸选择性最高，且它在所有催化剂中的积炭量也最低.将催化剂结构性质、分散度和还原性与其催化性能相关联，发现EDF法制得的催化剂比表面积和活性相分散度更高，更易被还原，因而其活性和生成H2的选择性更高，也更抗积碳.

关键词: 甘油, 氢气, 蒸汽重整, 负载型镍催化剂, 催化剂制备

Abstract:

The influence of the synthesis method parameters used to prepare nickel-based catalysts on the catalytic performance for the glycerol steam reforming reaction was studied. A series of Al2O3-supported Ni catalysts were synthesized, with nickel loading of 8 wt%, using the incipient wetness, wet impregnation, and modified equilibrium deposition filtration methods. The catalysts' surface and bulk properties were determined by inductively coupled plasma (ICP), N2 adsorp-tion-desorption isotherms (BET), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and temperature-programmed reduction (TPR). Used catalysts were characterized by techniques such as elemental analysis and SEM in order to deter-mine the level of carbon that was deposited and catalyst morphology. The results indicated that the synthesis method affected the textural, structural and surface properties of the catalysts, differenti-ating the dispersion and the kind of nickel species on alumina's surface. The formation of nickel aluminate phases was confirmed by the XRD and TPR analysis and the β-peak of the Ni/Al-edf cata-lyst was higher than in the other two catalysts, indicating that the nickel aluminate species of this catalyst were more reducible. Both Ni/Al-wet and Ni/Al-edf catalysts showed increasing CO2 selec-tivities and approximately constant CO selectivities for temperatures above 550℃, indicating that these catalysts successfully catalyze the water gas shift reaction. It was also confirmed that the Ni/Al-edf catalyst had the highest values for glycerol to gaseous products conversion, hydrogen yield, allyl alcohol, acetaldehyde, and acetic acid selectivities at 650℃ and the lowest carbon depo-sition of the catalysts tested. The correlation of the catalysts' structural properties, dispersion and reducibility with catalytic performance reveals that the EDF method can provide catalysts with higher specific surface area and active phase's dispersion, that are easier to reduce, more active and selective to hydrogen production, and more resistant to carbon deposition.

Key words: Glycerol, Hydrogen, Steam reforming, Supported nickel catalyst, Catalyst preparation