Chinese Journal of Catalysis

Chinese Journal of Catalysis ›› 2017, Vol. 38 ›› Issue (6): 1087-1100.DOI: 10.1016/S1872-2067(17)62813-4

• Articles • Previous Articles    

Acid-activated and WOx-loaded montmorillonite catalysts and their catalytic behaviors in glycerol dehydration

Weihua Yua,b, Pengpeng Wangb, Chunhui Zhoub,c,d, Hanbin Zhaob, Dongshen Tongb, Hao Zhangb, Huimin Yange, Shengfu Jif, Hao Wangc   

  1. a. Zhijiang College, Zhejiang University of Technology, Hangzhou 310024, Zhejiang, China;
    b. Research Group for Advanced Materials & Sustainable Catalysis (AMSC), Research Center for Clay Minerals, State Key Laboratory Breeding Base of Green Chemistry Synthesis Technology, Discipline of Industrial Catalysis, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032, Zhejiang, China;
    c. Centre for Future Materials, University of Southern Queensland, Toowoomba, Queensland 4350, Australia;
    d. Engineering Research Center of Non-metallic Minerals of Zhejiang Province, Zhejiang Institute of Geology and Mineral Resource, Hangzhou 310007, Zhejiang, China;
    e. Key Laboratory of High Efficient Processing of Bamboo of Zhejiang Province, China National Bamboo Research Center, Hangzhou 310012, Zhejiang, China;
    f. State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China
  • Received:2017-01-13 Revised:2017-03-10 Online:2017-06-18 Published:2017-06-08
  • Supported by:

    The work was supported by the National Natural Science Foundation of China (21373185, 41672033, 21506188, 21404090), the Open Project Programs of Engineering Research Center of Non-metallic Minerals of Zhejiang Province (ZD2015k07), of State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology (GCTKF2014006), of Key Laboratory of High Efficient Processing of Bamboo of Zhejiang Province (2016), and of State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology (CRE-2016-C-303)

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Abstract:

The use of H2SO4-, HCl-, H3PO4-, and CH3COOH-activated montmorillonite (Mt) and WOx/H3PO4- activated Mt as catalysts for the gas-phase dehydration of glycerol was investigated. The WOx/H3PO4-activated Mt catalysts were prepared by an impregnation method using H3PO4-activated Mt (Mt-P) as the support. The catalysts were characterized using powder X-ray diffraction, Fourier-transform infrared spectroscopy, N2 adsorption-desorption, diffuse reflectance ultraviolet-visible spectroscopy, temperature-programmed desorption of NH3, and thermogravimetric analysis. The acid activation of Mt and WOx loaded on Mt-P affected the strength and number of acid sites arising from H+ exchange, the leaching of octahedral Al3+ cations from Mt octahedral sheets, and the types of WOx (2.7 ≤ x ≤ 3) species (i.e., isolated WO4/WO6-containing clusters, two-dimensional [WO6] polytungstates, or three-dimensional WO3 crystals). The strong acid sites were weakened, and the weak and medium acid sites were strengthened when the W loading on Mt-P was 12 wt% (12%W/Mt-P). The 12%W/Mt-P catalyst showed the highest catalytic activity. It gave a glycerol conversion of 89.6% and an acrolein selectivity of 81.8% at 320 ℃. Coke deposition on the surface of the catalyst led to deactivation.

Key words: Glycerol, Acrolein, Dehydration, WOx, Acid-activated nanoclay, Catalyst