物理化学学报 >> 2014, Vol. 30 >> Issue (3): 527-534.doi: 10.3866/PKU.WHXB201401072

催化和表面科学 上一篇    下一篇

Cs取代对Ni-H3PW12O40/SiO2催化剂结构性质和催化性能的影响

金浩1,2, 孙晓丹1, 董澍3, 吴义志3, 孙素华1, 刘杰1, 朱慧红1, 杨光1, 伊晓东2, 方维平2   

  1. 1 中国石油化工股份有限公司抚顺石油化工研究院, 辽宁抚顺113001;
    2 厦门大学化学化工学院, 固体表面物理化学国家重点实验室, 醇醚酯化工清洁生产国家工程实验室, 福建厦门361005;
    3 中国石油抚顺石化公司石油二厂, 辽宁抚顺113004
  • 收稿日期:2013-10-08 修回日期:2014-01-06 发布日期:2014-02-27
  • 通讯作者: 金浩, 伊晓东 E-mail:jinhao.fshy@sinopec.com;xdyi@xmu.edu.cn
  • 基金资助:

    国家重点基础研究发展规划项目(973) (2010CB226903),国家自然科学基金(21073147,21303140)和教育部长江学者和创新团队发展计划项目(IRT1036)资助

Influence of Cs Substitution on the Structural Properties and Catalytic Performance of Ni-H3PW12O40/SiO2 Catalysts

JIN Hao1,2, SUN Xiao-Dan1, DONG Shu3, WU Yi-Zhi3, SUN Su-Hua1, LIU Jie1, ZHU Hui-Hong1, YANG Guang1, YI Xiao-Dong2, FANG Wei-Ping2   

  1. 1 Fushun Research Institute of Petroleum and Petrochemicals, SINOPEC, Fushun 113001, Liaoning Province, P. R. China;
    2 State Key Laboratory for Physical Chemistry of the Solid Surfaces, National Engineering Laboratory for Green Chemical Productions of Alcohols, Ethers and Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian Province, P. R. China;
    3 PetroChina Fushun Petrochemical Company No.2 Refinery, Fushun 113004, Liaoning Province, P. R. China
  • Received:2013-10-08 Revised:2014-01-06 Published:2014-02-27
  • Contact: JIN Hao, YI Xiao-Dong E-mail:jinhao.fshy@sinopec.com;xdyi@xmu.edu.cn
  • Supported by:

    The project was supported by the National Key Basic Research Program of China (973) (2010CB226903), National Natural Science Foundation of China (21073147, 21303140), and Program for Changjiang Scholars and Innovative Research Team in University, China (IRT1036).

摘要:

采用两步浸渍法和载体上的原位反应制备了一系列Cs部分取代的Ni-CsxH3-xPW12O40/SiO2催化剂,并用N2吸附比表面积测定(BET)、电感耦合等离子体发射光谱(ICP)、X射线衍射(XRD)、拉曼光谱(Raman)、原位X射线衍射(in situ XRD)、NH3程序升温脱附(NH3-TPD)、H2程序升温还原(H2-TPR)、H2程序升温脱附(H2-TPD)、吡啶吸附傅里叶变换红外(FTIR)光谱等分析测试技术对催化剂进行了表征. 以正癸烷为模型化合物,对催化剂的加氢裂化性能进行了评价. 结果表明,8%Ni-50%Cs1.5H1.5PW/SiO2催化剂具有最高的C5+收率,明显优于8%Ni-50%H3PW/SiO2催化剂和工业催化剂. 随着Cs 在CsxH3-xPW中比例的增加,正癸烷的转化率逐渐降低,而C5+选择性则逐渐提高. 当催化剂具有合适的孔径时,选择性的提高是由于催化剂酸性的减弱,而转化率的降低则是由于催化剂加氢能力的减弱.

关键词: 加氢裂化, 正癸烷, 双功能催化剂, Ni, Cs, H3PW12O40

Abstract:

Cs-substituted Ni-CsxH3-xPW12O40/SiO2 catalysts were prepared by two-step impregnation and in situ reaction on the support. The catalysts were characterized by N2 adsorption measurements, inductively coupled plasma atomic emission spectrometry, Raman spectroscopy, in situ X-ray diffraction, NH3-temperature programmed desorption (TPD), H2-temperature programmed reduction, H2-TPD, and Fourier transform infrared spectroscopy. The hydrocracking of n-decane was used to study the catalytic performance of the Ni-CsxH3-xPW12O40/SiO2 catalysts. The highest C5+ yield obtained for 8%Ni-50%Cs1.5H1.5PW/SiO2 was superior to those of 8%Ni-50% H3PW/SiO2 and an industrial catalyst. The conversion of n-decane slightly decreased and the C5+ selectivity increased with increasing Cs content in the CsxH3-xPW catalysts. Ni-CsxH3-xPW12O40/SiO2 catalysts possessed relatively large pore sizes, so the improved selectivity might have been due to a weaker acidity of the catalysts. The reduced conversion might have been due to a weaker hydrogenation ability.

Key words: Hydrocracking, n-Decane, Bifunctional catalyst, Ni, Cs, H3PW12O40

MSC2000: 

  • O643