Selective hydrogenation of benzene to cyclohexene over monometallic ruthenium catalysts in the presence of CeO2 and ZnSO4 as co-modifiers

稀土学报(英文版), 2013, (10): 1023-1028. doi: 10.1016/S1002-0721(12)60397-4

孙海杰 ^1, , 陈凌霞 ^2, , 李帅辉 ^3, , 江厚兵 ^4, , 张元馨 ^5, , 任保增 ^6, , 刘仲毅 ^7, , 刘仲毅 ^8,

1.College of Chemistry and Molecular Engnineering, Zhengzhou University, Zhengzhou 450001, China

2.Institute of Environmental and Catalytic Engineer-ing, Department of Chemistry, Zhengzhou Normal University, Zhengzhou 450044, China

3.College of Chemistry and Molecular Engnineering, Zhengzhou University, Zhengzhou 450001, China

4.College of Chemistry and Molecular Engnineering, Zhengzhou University, Zhengzhou 450001, China

5.College of Chemistry and Molecular Engnineering, Zhengzhou University, Zhengzhou 450001, China

6.School of Chemical Engineering and Energy, Zhengzhou University, Zhengzhou 450001, China

7.College of Chemistry and Molecular Engnineering, Zhengzhou University, Zhengzhou 450001, China

8.College of Chemistry and Molecular Engnineering, Zhengzhou University, Zhengzhou 450001, China

基金项目: the Innovation Fund for Technology Based Firms of China(10C26214104505) National Natural Science Foundation of China(21273205)

Selective hydrogenation of benzene to cyclohexene over monometallic ruthenium catalysts in the presence of CeO2 and ZnSO4 as co-modifiers

SUN Haijie ^1, , CHEN Lingxia ^2, , LI Shuaihui ^3, , JIANG Houbing ^4, , ZHANG Yuanxin ^5, , REN Baozeng ^6, , LIU Zhongyi ^7, , LIU Shouchang ^8,

1.College of Chemistry and Molecular Engnineering, Zhengzhou University, Zhengzhou 450001, China

2.Institute of Environmental and Catalytic Engineer-ing, Department of Chemistry, Zhengzhou Normal University, Zhengzhou 450044, China

3.College of Chemistry and Molecular Engnineering, Zhengzhou University, Zhengzhou 450001, China

4.College of Chemistry and Molecular Engnineering, Zhengzhou University, Zhengzhou 450001, China

5.College of Chemistry and Molecular Engnineering, Zhengzhou University, Zhengzhou 450001, China

6.School of Chemical Engineering and Energy, Zhengzhou University, Zhengzhou 450001, China

7.College of Chemistry and Molecular Engnineering, Zhengzhou University, Zhengzhou 450001, China

8.College of Chemistry and Molecular Engnineering, Zhengzhou University, Zhengzhou 450001, China

Keywords： hydrogenation

The monometallic Ru catalysts with the CeO2 without calcination and ZnSO4 as co-modifiers gave a cyclohexene yield of 58.5% at the optimum nominal CeO2/Ru molar ratio of 0.15. Moreover, this catalyst had a good stability. The chemisorbed (Zn(OH)2)3(ZnSO4)(H2O)3 salt on Ru surface, which was formed by the CeO2 reacting with ZnSO4, created the new Ru active sites suitable for the formation of cyclohexene and improved the selectivity to cyclohexene. In addition, the Zn2+in the aqueous phase could form a stable complex with cyclohexene, stabilizing the cyclohexene in the liquid phase and improving the selectivity to cyclo-hexene. The calcination treatment of CeO2 was not beneficial for the enhancement of the selectivity to cyclohexene since it is difficult for the CeO2 calcinated to react with ZnSO4 to form the (Zn(OH)2)3(ZnSO4)(H2O)3 salt.

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