Acta Chimica Sinica ›› 2019, Vol. 77 ›› Issue (10): 1054-1062.DOI: 10.6023/A19060219 Previous Articles    



成诗婕a, 曾杨a, 裴燕a, 范康年a, 乔明华a*(), 宗保宁b*()   

  1. a 复旦大学化学系 上海市分子催化和功能材料重点实验室 上海 200438
    b 中国石化石油化工科学研究院 催化材料与反应工程国家重点实验室 北京 100083
  • 投稿日期:2019-06-18 发布日期:2019-08-12
  • 通讯作者: 乔明华,宗保宁;
  • 基金资助:

Synthesis and Catalysis of Pt/W-s-SBA-15 Catalysts with Short Channel for Glycerol Hydrogenolysis to 1,3-Propanediol

Cheng, Shijiea, Zeng, Yanga, Pei, Yana, Fan, Kangniana, Qiao, Minghuaa*(), Zong, Baoningb*()   

  1. a Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Department of Chemistry, Fudan University, Shanghai 200438
    b State Key Laboratory of Catalytic Materials and Reaction Engineering, Research Institute of Petroleum Processing, SINOPEC, Beijing 100083
  • Received:2019-06-18 Published:2019-08-12
  • Contact: Qiao, Minghua,Zong, Baoning;
  • Supported by:
    Project supported by the National Key Research and Development Project of China(2016YFB0301602);the National Natural Science Foundation of China(21872035);Science and Technology Commission of Shanghai Municipality(08DZ2270500);State Key Laboratory of Catalytic Materials and Reaction Engineering (RIPP, SINOPEC)

The mesoporous SBA-15 molecular sieves doped in situ by W with channels parallel to the short axis (W-s-SBA-15) were synthesized by using decane as cosolvent and trimethylbenzene (TMB) as pore-expanding agent, which were used as the supports for the preparation of the Pt/W-s-SBA-15 catalysts. The effect of the loadings of Pt and W on the catalytic performance in glycerol hydrogenolysis to 1,3-propanediol (1,3-PDO) was investigated. The morphology, chemical states of Pt and W, and acidity of the catalysts were systematically characterized by using Brunauer-Emmett-Teller (BET), scanning electron microscopy (SEM), transmission electron microscopy (TEM), CO pulsed adsorption, X-ray photoelectron spectroscopy (XPS), Raman, ultraviolet-visible diffuse reflectance spectra (UV-Vis DRS), Fourier transform infrared spectroscopy (FT-IR) and FT-IR of adsorbed pyridine analysis (Py-IR). The BET and TEM results revealed that there are two kinds of pores in the structure: the mesoporous channels parallel to the short axis and honeycomb-like macropores. The Pt dispersion and active surface area calculated from CO chemical adsorption, firstly increased and then decreased with the increase in the Pt and W loadings. The highly dispersed tungsten species were assigned to the single-site WO4 on the basis of the characterization results of Raman, UV-Vis DRS, and FT-IR. The XPS results indicated that the amount of the Pt-O-Si/W linkages and the Pt δ+/(Pt 0+Pt δ+) ratio are the highest on the 4Pt/W-s-SBA-15(1/480) catalyst which promote the dispersion of the Pt particles on the catalyst surface. With the increase in the loadings of Pt and W, the conversion of glycerol and the conversion of glycerol to liquid products (CTL) increased monotonically, while the selectivity to 1,3-PDO experienced a volcanic-type evolution. At the reaction temperature of 433 K, H2 pressure of 4.0 MPa, and reaction time of 24 h, the highest yield of 1,3-PDO of 49.0% was resulted on the 4Pt/W-s-SBA-15(1/480) catalyst. It is identified that the conversion of glycerol on the Pt/W-s-SBA-15 catalysts is proportional to the active surface area of Pt on the catalyst, while the small Pt particle size and the strong synergy between Pt and the highly dispersed WO4 species are advantageous to the formation of 1,3-PDO.

Key words: short-channel W-SBA-15, glycerol hydrogenolysis, 1,3-propanediol, Pt, W