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Citation: SUN Hai-Jie, ZHOU Xiao-Li, ZHAO Ai-Juan, WANG Zhen-Zhen, LIU Shou-Chang, LIU Zhong-Yi. Selective Hydrogenation of Benzene to Cyclohexene over Nano-Sized Ru Catalyst Modified by Zn4Si2O7(OH)2H2O Salt[J]. Chinese Journal of Inorganic Chemistry, ;2015, 31(7): 1287-1295. doi: 10.11862/CJIC.2015.162 shu

Selective Hydrogenation of Benzene to Cyclohexene over Nano-Sized Ru Catalyst Modified by Zn4Si2O7(OH)2H2O Salt

  • 1.

    1 College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001, China;

  • 2.

    2 Institute of Environmental and Catalytic Engineering, College of Chemistry and Chemical Engineering, Zhengzhou Normal University, Zhengzhou 450044, China;

  • 3.

    3 Solid Waste Management Center of Henan, Zhengzhou 210036, China

  • Corresponding author: LIU Zhong-Yi, 
  • Received Date: 7 February 2015
    Available Online: 17 April 2015

    Fund Project: 国家自然科学基金(No.21273205, U1304204) (No.21273205, U1304204)河南省博士后科研项目(No.2013006)资助项目。 (No.2013006)

  • A nano-sized Ru catalyst was prepared using the precipitation method. The performance of the catalyst for selective hydrogenation of benzene to cyclohexene with Na2SiO3·9H2O and diethanolamine as modifiers was investigated in the presence of ZnSO4. The catalyst after and before hydrogenation was characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF), and transmission electron microscopy-energy dispersive spectroscopy (TEM-EDS). The results show that Na2SiO3 in the solution could react with ZnSO4 to form a Zn4Si2O7(OH)2H2O salt, H2SO4 and Na2SO4, and the Zn4Si2O7(OH)2H2O salt chemisorbed on the surface of the Ru catalyst plays a key role in improving the selectivity to cyclohexene of the Ru catalyst. The increased dosage of Na2SiO3·9H2O will result in the increased amount of the formed Zn4Si2O7(OH)2H2O salt, the decreased activity of the Ru catalyst and the increased selectivity to cyclohexene. The diethanolamine added into the slurry could neutralize the H2SO4 formed by reacting Na2SiO3 with ZnSO4. This could shift the chemical equilibrium to the direction of the formation of the Zn4Si2O7(OH)2H2O salt, resulting in the increase of the selectivity to cyclohexene of the Ru catalyst. When the mass ratio of the Ru catalyst, ZnSO4·7H2O, Na2SiO3·9H2O, diethanolamine and the dispersant ZrO2 was at 1.0:24.6:0.4:0.2:5.0, 2 g of the Ru catalyst will give a selectivity to cyclohexene of 75% and a cyclohexene yield of 55% at a benzene conversion of 73%. Moreover, this catalytic system shows a good reusability and an excellent stability.
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