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.
- benzene;selective hydrogenation;cyclohexene;ruthenium;reaction modifier
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Selective Hydrogenation of Benzene to Cyclohexene over Nano-Sized Ru Catalyst Modified by Zn4Si2O7(OH)2H2O Salt

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