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Selective Hydrogenation of Benzene to Cyclohexene over Ru-Zn Catalysts: Mechanism Investigation on NaOH as a Reaction Additive

Institute of Environmental and Catalytic Engineering, College of Chemistry and Chemical Engineering, Zhengzhou Normal University, Zhengzhou 450044, China
Zhengzhou Tobacco Research Institute of CNTC, Zhengzhou 450001, China
College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001, China
Authors to whom correspondence should be addressed.
Catalysts 2018, 8(3), 104;
Received: 16 January 2018 / Revised: 23 February 2018 / Accepted: 28 February 2018 / Published: 2 March 2018
PDF [4396 KB, uploaded 2 March 2018]


Ru-Zn catalysts were synthesized via a precipitation method, and the mechanism of NaOH modifying Ru-Zn catalysts on the selective hydrogenation of benzene to cyclohexene was thoroughly investigated. Fresh as well as used catalysts were characterized via X-ray diffraction (XRD), X-ray Fluorescence (XRF), transmission electron microscope (TEM), scanning electron microscope (SEM), Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT), respectively. Before catalytic experiments, metallic Ru and rodlike ZnO were detected from fresh Ru-Zn catalysts. Notably, with the increasing concentration of NaOH added into the reaction medium (e.g., from 0 to 0.6 mol·L−1), the dispersion of ZnO on the Ru surface significantly improved, resulting in the enhancement Ruδ+ species of electron deficiency. The catalytic activity towards benzene conversion was therefore retarded and the selectivity towards cyclohexene was improved. When the added NaOH concentration reached 0.6 mol·L−1, the atomic ratio of Zn/Ru decreased from 0.27 (when no NaOH was added) to 0.16, benzene conversion of 45.3%, and cyclohexene selectivity of 89.3% was achieved using a batch reactor after 25 min of reaction time. However, with continually increasing the NaOH concentration, i.e., to 1.2 mol·L−1, parts of ZnO could react with the over-added NaOH, leading to the unfavorable consumption of uniformly dispersed ZnO. This causes the increasing of catalytic activity towards benzene conversion, as well as the decreasing of the selectivity towards cyclohexene. Moreover, no loss of catalytic activity and selectivity towards cyclohexene formation from selective hydrogenation of benzene was observed after 10 times of catalytic experiments without any regeneration. View Full-Text
Keywords: benzene; selective hydrogenation; cyclohexene; Ru; Zn; reaction additives benzene; selective hydrogenation; cyclohexene; Ru; Zn; reaction additives

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Sun, H.; Chen, Z.; Li, C.; Chen, L.; Peng, Z.; Liu, Z.; Liu, S. Selective Hydrogenation of Benzene to Cyclohexene over Ru-Zn Catalysts: Mechanism Investigation on NaOH as a Reaction Additive. Catalysts 2018, 8, 104.

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