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Enhancing the selective hydrogenation of benzene to cyclohexene over Ru/TiO2 catalyst in the presence of a very small amount of ZnO

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Abstract

Highly efficient and greener hydrogenation of benzene to cyclohexene is of great importance but is challenging. In this work, Ru/TiO2 catalyst was prepared by a simple chemical-reduction method. The catalyst was characterized by transmission electron spectroscopy (TEM), X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption-desorption techniques. It was shown that the Ru nanoparticles with average size of about 2.2 nm were dispersed uniformly on the surface of the TiO2 support. The effect of a very small amount of ZnO in NaOH solution on the selectivity to cyclohexene was investigated under different conditions by using Ru/TiO2 catalyst. It was found that the addition of a small amount of ZnO to the NaOH solution could effectively enhance the selectivity to cyclohexene and that the yield of cyclohexene could reach 41.5%. Control experiments revealed that the main reason for the enhancement of the selectivity to cyclohexene was the presence of ZnO in the form of Na2Zn(OH)4 in the alkaline solution, which effectively retarded the further hydrogenation of cyclohexene. A recycling experiment showed that the yield of cyclohexene was not obviously decreased after four reuses.

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References

  1. Hu SC, Chen YW. Partial hydrogenation of benzene on Ru-Zn/SiO2 catalysts. Ind Eng Chem Res, 2001, 40: 6099–6104

    Article  CAS  Google Scholar 

  2. Fan C, Zhu YA, Zhou XG, Liu ZP. Catalytic hydrogenation of benzene to cyclohexene on Ru(0001) from density functional theory investigations. Catal Today, 2011, 160: 234–241

    Article  CAS  Google Scholar 

  3. Zhang P, Wu TB, Jiang T, Wang WT, Liu HZ, Fan HL, Zhang ZF, Han BX. Ru-Zn supported on hydroxyapatite as an effective catalyst for partial hydrogenation of benzene. Green Chem, 2013, 15: 152–159

    Article  CAS  Google Scholar 

  4. Tavoularis G, Keane MA. Direct formation of cyclohexene via the gas phase catalytic dehydrohalogenation of cyclohexyl halides. Appl Catal A, 1999, 182: 309–316

    Article  CAS  Google Scholar 

  5. Akiya N, Savage PE. Kinetics and mechanism of cyclohexanol dehydration in high-temperature water. Ind Eng Chem Res, 2001, 40: 1822–1831

    Article  CAS  Google Scholar 

  6. Feng H, Elam JW, Libera JA, Pellin MJ, Stair PC. Oxidative dehydrogenation of cyclohexane over alumina-supported vanadium oxide nanoliths. J Catal, 2010, 269: 421–431

    Article  CAS  Google Scholar 

  7. Liu HZ, Liang SG, Wang WT, Jiang T, Han BX. The partial hydrogenation of benzene to cyclohexene over Ru-Cu catalyst supported on ZnO. J Mol Catal A, 2011, 341: 35–41

    Article  CAS  Google Scholar 

  8. Wang WT, Liu HZ, Ding GD, Zhang P, Wu TB, Jiang T, Han BX. Ru-Cd/bentonite for the partial hydrogenation of benzene: a catalyst without additives. ChemCatChem, 2012, 4: 1836–1843

    Article  CAS  Google Scholar 

  9. Hu SC, Chen YW. Partial hydrogenation of benzene to cyclohexene on ruthenium catalysts supported on La2O3-ZnO binary oxides. Ind Eng Chem Res, 1997, 36: 5153–5159

    Article  CAS  Google Scholar 

  10. Zhou GB, Liu JL, Tan XH, Pei Y, Qiao MH, Fan KN, Zong BN. Effect of support acidity on liquid-phase hydrogenation of benzene to cyclohexene over Ru-B/ZrO2 catalysts. Ind Eng Chem Res, 2012, 51: 12205–12213

    CAS  Google Scholar 

  11. Liu JL, Zhu LJ, Pei Y, Zhuang JH, Li H, Li HX, Qiao MH, Fan KN. Ce-promoted Ru/SBA-15 catalysts prepared by a “two solvents” impregnation method for selective hydrogenation of benzene to cyclohexene. Appl Catal A, 2009, 353: 282–287

    Article  CAS  Google Scholar 

  12. Liu JL, Zhu Y, Liu J, Pei Y, Li ZH, Li H, Li HX, Qiao MH, Fan KN. Discrimination of the roles of CdSO4 and ZnSO4 in liquid phase hydrogenation of benzene to cyclohexene. J Catal, 2009, 268: 100–105

    Article  CAS  Google Scholar 

  13. Bu J, Liu JL, Chen XY, Zhuang JH, Yan SR, Qiao MH, He HY, Fan KN. Ru/SBA-15 catalysts for partial hydrogenation of benzene to cyclohexene: tuning the Ru crystallite size by Ba. Catal Commun, 2008, 9: 2612–2615

    Article  CAS  Google Scholar 

  14. Fan GY, Jiang WD, Wang JB, Li RX, Chen H, Li XJ. Selective hydrogenation of benzene to cyclohexene over RuCoB/γ-Al2O3 without additive. Catal Commun, 2008, 10: 98–102

    Article  CAS  Google Scholar 

  15. da-Silva JW, Cobo AJG. The role of the titania and silica supports in Ru-Fe catalysts to partial hydrogenation of benzene. Appl Catal A, 2003, 252: 9–16

    Article  CAS  Google Scholar 

  16. Liu HZ, Jiang T, Han BX, Liang SG, Wang WT, Wu TB, Yang GY. Highly selective benzene hydrogenation to cyclohexene over supported Ru catalyst without additives. Green Chem, 2011, 13: 1106–1109

    Article  CAS  Google Scholar 

  17. Zhou GB, Tan XH, Dou RF, Pei Y, Fan KN, Qiao MH, Sun B, Zong BN. The size effect of Ru/ZrO2 catalyst on partial hydrogenation of benzene to cyclohexene. Scientia Sinica Chimica, 2014, 44: 121–130

    Article  CAS  Google Scholar 

  18. Mazzieri V, Fígoli NS, Pascual FC, L’Argentière PC. Effect of the support on the selective hydrogenation of benzeneover ruthenium catalysts. 1. Al2O3 and SiO2. Catal Lett, 2005, 102: 79–82

    Article  CAS  Google Scholar 

  19. Spinacé EV, Vaz JM. Liquid-phase hydrogenation of benzene to cyclohexene catalyzed by Ru/SiO2 in the presence of water-organic mixtures. Catal Commun, 2003, 4: 91–96

    Article  Google Scholar 

  20. Zanutelo C, Landers R, Carvalho WA, Cobo AJG. Carbon support treatment effect on Ru/C catalyst performance for benzene partial hydrogenation. Appl Catal A, 2011, 409–410: 174–180

    Article  Google Scholar 

  21. Ronchin L, Toniolo L. Selective hydrogenation of benzene to cyclohexene using a Ru catalyst suspended in an aqueous solution in a mechanically agitated tetraphase reactor: a study of the influence of the catalyst preparation on the hydrogenation kinetics of benzene and of cyclohexene. Appl Catal A, 2001, 208: 77–89

    Article  CAS  Google Scholar 

  22. Zhou GB, Tan XH, Pei Y, Fan KN, Qiao MH, Sun B, Zong BN. Structural and catalytic properties of alkaline post-treated Ru/ZrO2 catalysts for partial hydrogenation of benzene to cyclohexene. ChemCatChem, 2013, 5: 2425–2435

    Article  CAS  Google Scholar 

  23. Sun HJ, Dong YY, Li SH, Jiang HB, Zhang YX, Liu ZY, Liu SC. The role of La in improving the selectivity to cyclohexene of Ru catalyst for hydrogenation of benzene. J Mol Catal A, 2013, 368–369: 119–124

    Article  Google Scholar 

  24. Schwab F, Lucas M, Claus P. Simple selective hydrogenation of benzene to cyclohexene in the presence of sodium dicyanamide. Green Chem, 2013, 15: 646–649

    Article  CAS  Google Scholar 

  25. Struijk J, Moene R, van der Kamp T, Scholten JJF. Partial liquidphase hydrogenation of benzene to cyclohexene over ruthenium catalysts in the presence of an aqueous salt solution: II. Influence of various salts on the performance of the catalyst. Appl Catal A, 1992, 89: 77–102

    Article  CAS  Google Scholar 

  26. Suppino RS, Landers R, Cobo AJG. Partial hydrogenation of benzene on Ru catalysts: effects of additives in the reaction medium. Appl Catal A, 2013, 452: 9–16

    Article  CAS  Google Scholar 

  27. Sun HJ, Wang HX, Jiang HB, Li SH, Liu SC, Liu ZY, Yuan XM, Yang KJ. Effect of (Zn(OH)2)3(ZnSO4)(H2O)5 on the performance of Ru-Zn catalyst for benzene selective hydrogenation to cyclohexene. Appl Catal A, 2013, 450: 160–168

    Article  CAS  Google Scholar 

  28. Mazzieri V, L’Argentière PC, Fígoli NS. Influence of methanol addition during selective hydrogenation of benzene to cyclohexene. React Kinet Catal Lett, 2004, 81: 107–112

    Article  CAS  Google Scholar 

  29. Fan GY, Li RX, Li XJ, Chen H. Effect of organic additives on partial hydrogenation of benzene. Catal Commun, 2008, 9: 1394–1397

    Article  CAS  Google Scholar 

  30. Sun HJ, Pan YJ, Wang HX, Dong YY, Liu ZY, Liu SC. Selective hydrogenation of benzene to cyclohexene over a Ru-Zn catalyst with diethanolamine as an additive. Chin J Catal, 2012, 33: 610–620

    Article  CAS  Google Scholar 

  31. Liu HZ, Jiang T, Han BX, Liang SG, Zhou YX. Selective phenol hydrogenation to cyclohexanone over a dual supported Pd-Lewis acid catalyst. Science, 2009, 326: 1250–1252

    Article  CAS  Google Scholar 

  32. Li HX, Bian ZF, Zhu J, Zhang DQ, Li GS, Huo YN, Li H, Lu YF. Mesoporous titania spheres with tunable chamber stucture and enhanced photocatalytic activity. J Am Chem Soc, 2007, 129: 8406–8407

    Article  CAS  Google Scholar 

  33. Li GS, Li LP, Boerio-Goates J, Woodfield BF. High purity anatase TiO2 nanocrystals: near room-temperature synthesis, grain growth kinetics, and surface hydration chemistry. J Am Chem Soc, 2005, 127: 8659–8666

    Article  CAS  Google Scholar 

  34. Mazzieri V, Coloma-Pascual F, Arcoya A, L’Argentière PC, Fígoli NS. XPS, FTIR and TPR characterization of Ru/Al2O3 catalysts. Appl Surf Sci, 2003, 210: 222–230

    Article  CAS  Google Scholar 

  35. Hu SC, Chen YW. Liquid phase hydrogenation of benzene to cyclohexene on ruthenium catalysts supported on zinc oxide-based binary oxides. J Chem Technol Biotechnol, 2001, 76: 954–958

    Article  CAS  Google Scholar 

  36. House JE. Inorg Chem. Amsterdam: Elsevier, 2008. 384

    Google Scholar 

  37. Struijk J, d’Angremond M, Lucas-de Regt WJM, Scholten JJF. Partial liquid phase hydrogenation of benzene to cyclohexene over ruthenium catalysts in the presence of an aqueous salt solution: I. Preparation, characterization of the catalyst and study of a number of process variables. Appl Catal A, 1992, 83: 263–295

    Article  CAS  Google Scholar 

  38. Odenbrand CUI, Lundin ST. Hydrogenation of benzene to cyclohexene on a ruthenium catalyst: influence of some reaction parameters. J Chem Technol Biotechnol, 1980, 30: 677–687

    Article  CAS  Google Scholar 

  39. Ning JB, Xu J, Liu J, Lu F. Selective hydrogenation of benzene to cyclohexene over colloidal ruthenium catalyst stabilized by silica. Catal Lett, 2006, 109: 175–180

    Article  CAS  Google Scholar 

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Wu, T., Zhang, P., Jiang, T. et al. Enhancing the selective hydrogenation of benzene to cyclohexene over Ru/TiO2 catalyst in the presence of a very small amount of ZnO. Sci. China Chem. 58, 93–100 (2015). https://doi.org/10.1007/s11426-014-5249-x

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  • DOI: https://doi.org/10.1007/s11426-014-5249-x

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