Advances in the Ruthenium Catalysts for Partial Hydrogenation of Benzene toCyclohexene
WANG Hongqin, XIE Jiyang, AN Nihong, DAI Yunsheng, TANG Chun, LIU Jun, SHEN Yafeng, ZHOU Wei
State Key Laboratory of Advanced Technologies for Comprehensive Utilization of Platinum Metals, Sino-Platinum Metals Co. Ltd., Kunming Institute of Precious Metals, Kunming 650106
Abstract: Cyclohexene with an active double bond is widely used in the synthesis of pharmaceuticals, pesticides, food and other high value-added fine chemicals. Cyclohexene can be synthesized by several ways, such as dehydrogenation of cyclohexane, dehydration of cyclohexanol, dehydrohalogenation of halogenated cyclohexane, Birch reduction or partial hydrogenation of benzene. Compared with other methods, the technology of partial hydrogenation of benzene to cyclohexene is of the advantage of safety, high atom-economy, environmentally friendly, and has caused a wide range of concerns by different researcher in recent years. The hydrogenation of benzene to cyclohexane is thermodynamically much more favorable since the cyclohexane is at least 75 kJ/mol more stable than cyclohexene in terms of the Gibbs free energy. In addition, cyclohexene is easily hydrogenated to cyclohexane, because the chemical properties of conjugated π bonds of benzene ring are more stable than that of double bond of cyclohexene. Development of new catalyst is the key to enhance the selectivity to cyclohexene for partial hydrogenation of benzene in the tetra-phase reaction system. The partial hydrogenation of benzene to cyclohexene has been known for more than 100 years. Only in 1957 was the products identified in the hydrogenation of benzene catalyzed by Ni membrane. Since then, the production of cyclohexene in the hydrogenation of benzene at low degrees of conversion has been reported by several researchers, and ruthenium catalysts have been especially suiting for the reaction. One of the most important advances was the adoption of agitated tetra-phase reactors containing an organic phase, an aqueous phase, a gas phase (H2) and a solid phase (catalysts), to which transition metal salts are added, and can achieve yields as high as 60%. In 1989, the Ru-Zn catalyst for benzene partial hydrogenation was industrialised for the first time in Japan by Asahi-Kasei Chemical Co., Ltd.. The technology was introduced from Japan into Shenma Group Company in 1995. Along with the introduction of advanced technology, many research institutes and universities also have stated further research in the partial hydrogenation of benzene in our country. Research work has been dedicated to the optimization of reaction conditions, the development of new catalysts and the exploration of the nature of improving selectivity. In recent years, the great number of scientific articles show that the selectivity of cyclohexene could be improved by reasonably designing ruthenium catalysts. For example, a series of Ru-Zn/ZrO2 catalysts are prepared by post-treatment of a binary Ru-catalyst using NaOH aqueous solutions. Alkaline post-treatment removed metallic Zn, the surface hydroxyl groups content and the hydrophilicity of the catalysts was increased. The Ru-catalysts could be modified by adding a suitable accessory ingredient in order to enhance reaction selectivity. Promoter could modify Ru active sites and dramatically improve the selectivity to cyclohexene. Although several kinds of Ru-based catalysts are developed, the unsupported Ru-Zn catalyst remains the only one used in industry, which pivotal preparation technique has been controlled by Asahi. The research on liquid-phase partial hydrogenation of benzene in recent years was reviewed, including the influence of precursors, preparation methods, supports, promoters and additives on catalyst activity and the selectivity of the products. The remaining challenges and development trend of partial hydrogenation of benzene to cyclohexene is pointed out at the end.
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2019, Vol. 33 
