制备条件对Ni/ZrO<sub>2</sub>-SiO<sub>2</sub>催化剂煤气甲烷化的影响

刘文燕; 赵安民; 张海涛; 应卫勇; 房鼎业

制备条件对Ni/ZrO₂-SiO₂催化剂煤气甲烷化的影响

华东理工大学大型工业反应器工程教育部工程研究中心化学工程联合国家重点实验室, 上海 200237

基金项目: 国家科技支撑计划课题。

详细信息

作者简介:
刘文燕(1985- ), 女, 河南温县人, 硕士研究生, 主要从事催化反应工程研究。

通讯作者:
应卫勇, Tel:021-64252192, Fax:021-64252192, E-mail:wying@ecust.edu.cn。

中图分类号: TQ536.9
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出版历程
- 收稿日期: 2011-02-19
- 修回日期: 2011-05-23
- 刊出日期: 2012-01-31

Effect of preparation condition on catalytic performance of Ni/ZrO₂-SiO₂ for methanation of coal gas

Engineering Research Center of Large Scale Reactor Engineering and Technology, Ministry of Education, State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China

摘要

摘要: 采用浸渍法制备了ZrO₂-SiO₂复合载体和Ni质量分数为6%的Ni/ZrO₂-SiO₂催化剂,考察了载体制备时浸渍溶液pH值、焙烧温度和催化剂制备时的焙烧温度对Ni/ZrO₂-SiO₂催化剂煤气甲烷化反应性能的影响。采用X射线衍射、程序升温还原和扫描电子显微镜等方法对催化剂进行了表征。结果表明,载体浸渍溶液pH值为8.0～9.0, 载体焙烧温度为550 ℃,催化剂焙烧温度为450 ℃时,Ni/ZrO₂-SiO₂催化剂在煤气甲烷化反应中显示了最优的催化性能,CO转化率100%,CO₂转化率1.8%,CH₄生成速率16.6 mmol/(h·g)。进一步表征发现,制备ZrO₂-SiO₂复合载体时,增大浸渍溶液的pH值有利于形成粒径较小的亚稳态四方晶相ZrO₂,可见四方晶相ZrO₂更有利于甲烷化反应;载体焙烧温度会影响到NiO粒径的大小和其在催化剂表面的分散,温度过高和过低都会导致NiO粒径大小的不适宜以及分散性的降低;催化剂焙烧温度过高则会导致NiO与载体间的相互作用减弱,NiO分散性降低。
- 镍 /
- ZrO₂-SiO₂ /
- 一氧化碳 /
- 二氧化碳 /
- 甲烷化
Abstract: Ni/ZrO₂-SiO₂ catalysts with 6% Ni loading amount were prepared by impregnation. The ZrO₂-SiO₂ support was also synthesized by impregnation. Effects of pH value of the impregnating solution and calcination temperature of support and catalyst on activities of Ni/ZrO₂-SiO₂ catalysts were investigated. The catalysts were characterized using XRD,TPR and SEM measurements. Ni/ZrO₂-SiO₂(S5) catalyst exhibited excellent catalytic activity with 100% of CO conversion, 1.8% of CO₂ conversion and 16.6 (mmol·h^-1·g^-1) of CH₄ formation rate. The preparation conditions were as follows:pH value of the impregnating solution, 8.0～9.0, calcination temperature of support and catalyst, 550 ℃ and 450 ℃.The mathanation activity of Ni/ZrO₂-SiO₂ was strongly influenced by the ZrO₂ phase change. The catalyst with tetragonal zirconia showed higher catalytic activity. The increase of pH value of the impregnating solution was in favor of forming small tetragonal zirconia. The calcination temperature of support influenced the grain size and the dispersity of NiO, unsuitable temperature might lead to ill-fitted grain size and aggregation. Exorbitant calcination temperature could weaken interaction between NiO and the support, and lowered the dispersity of NiO.
- nickel /
- ZrO₂-SiO₂ /
- carbon monoxide /
- carbon dioxide /
- methanation

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