物理化学学报 >> 2012, Vol. 28 >> Issue (05): 1243-1251.doi: 10.3866/PKU.WHXB201203081

催化和表面科学 上一篇    下一篇

La-Ni-Mo-B非晶态催化剂的制备及其苯酚加氢脱氧催化性能

王威燕, 张小哲, 杨运泉, 杨彦松, 彭会左, 罗和安   

  1. 湘潭大学化工学院, 湖南湘潭 411105
  • 收稿日期:2012-01-01 修回日期:2012-02-27 发布日期:2012-04-26
  • 通讯作者: 杨运泉 E-mail:yangyunquan@xtu.edu.cn
  • 基金资助:

    湘潭大学资助基金(2011XZX11)和湖南省教育厅开放基金(10K062)资助项目

Preparation of La-Ni-Mo-B Amorphous Catalyst and Its Catalytic Properties for Hydrodeoxygenation of Phenol

WANG Wei-Yan, ZHANG Xiao-Zhe, YANG Yun-Quan, YANG Yan-Song, PENG Hui-Zuo, LUO He-An   

  1. School of Chemical Engineering, Xiangtan University, Xiangtan 411105, Hunan Province, P. R. China
  • Received:2012-01-01 Revised:2012-02-27 Published:2012-04-26
  • Contact: YANG Yun-Quan E-mail:yangyunquan@xtu.edu.cn
  • Supported by:

    The project was supported by the Sustentation Fund of Xiangtan University, China (2011XZX11) and Scientific Research Fund of Hunan Provincial Education Department, China (10K062).

摘要: 以NaBH4为还原剂采用化学还原法制备出La-Ni-Mo-B 非晶态催化剂, 用扫描电子显微镜(SEM)、X射线衍射(XRD)、电感耦合等离子发射光谱(ICP-AES)、X射线光电子能谱(XPS)等手段对催化剂进行表征, 研究了助剂La 对Ni-Mo-B 催化剂催化性能的影响. 结果显示, 加入适量助剂La 能显著减小催化剂粒径, 增加Ni0含量, 促进Mo6+还原生成Mo4+, 但过量La 会覆盖Ni0和Mo4+的活性位点. 催化剂的高加氢活性主要归因于其非晶态结构和高Ni0含量, 高脱氧活性主要归因于其高Mo4+含量. 在苯酚的加氢脱氧(HDO)反应中, La-Ni-Mo-B非晶态催化剂催化苯酚HDO反应主要按照加氢-氢解的路径进行的, 显著降低了产物中芳烃含量. 通过优化反应条件, 催化苯酚的转化率和脱氧率都可达到99.0%. 高温下La-Ni-Mo-B 非晶态催化剂失活的主要原因是非晶态结构的破坏.

关键词: 非晶态催化剂, La-Ni-Mo-B, 加氢脱氧, 苯酚, 生物油

Abstract: Lanthanum-promoted Ni-Mo-B amorphous catalysts were prepared by chemical reduction of the corresponding metal salts with sodium borohydride aqueous solution. Scanning electron microscopy (SEM), X-ray diffraction (XRD), inductively coupled plasma atomic emission spectrometry (ICP-AES), and X-ray photoelectron spectroscopy (XPS) were used to characterize the resulting materials. Phenol was used as model compound to test the hydrodeoxygenation (HDO) activity of the La-Ni-Mo-B amorphous catalysts. Adding lanthanum could decrease the particle size, increase the content of Ni0 and promote the reduction of Mo6+ to Mo4+ . But excess lanthanum would cover some of the Ni0, and Mo4+ active sites. The high hydrogenation activity was attributed to the amorphous structure of the catalyst and the high content of Ni0 and the high degree of deoxygenation was attributed to the high content of MoO2. The HDO reation of phenol on the La-Ni-Mo-B amorphous catalyst proceeded with a hydrogenation-dehydration route, thus decreasing the aromatic content of the HDO products. Both the conversion and the total deoxygenation degree were up to 99.0%. The deactivation of the La-Ni-Mo-B amorphous catalysts during the HDO reation of phenol at high temperature was mainly caused by the crystallization of the amorphous structure.

Key words: Amorphous catalyst, La-Ni-Mo-B, Hydrodeoxygenation, Phenol, Bio-oil

MSC2000: 

  • O643.36