Startseite One-Pot Isomerization of n-Alkanes by Super Acidic Solids: Sulfated Aluminum-Zirconium Binary Oxides
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One-Pot Isomerization of n-Alkanes by Super Acidic Solids: Sulfated Aluminum-Zirconium Binary Oxides

  • Abhishek Dhar EMAIL logo , Abhishek Dutta , Carlos O. Castillo-Araiza EMAIL logo , V.A. Suárez-Toriello , Dhananjoy Ghosh und Uttam Raychaudhuri
Veröffentlicht/Copyright: 19. Januar 2016
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Abstract

Super acidic nanostructured sulfated aluminum-zirconium binary oxides in mole ratios of Zr4+: Al3+ as 2:1 (SAZ-1), 1:1 (SAZ-2), 1:2(SAZ-3) and the reference catalyst super acidic sulfated zirconia (SZ) were synthesized by a precipitation method. Firstly, the catalytic performance of these four catalysts was evaluated during the isomerization of n-hexane to 2-methyl pentane and 3-methyl pentane, n-heptane and n-octane to their corresponding branched chain isomers at low temperature and pressure conditions (40°C and 1 atm). SAZ-1 performed the highest active and selective isomerization of n-hexane, n-heptane, and n-octane into their corresponding branched chain isomers. The catalytic activity of the reference catalyst SZ was the lowest among the four synthesized catalysts. TEM analysis applied to SAZ-1 and SZ indicated the presence of particle-bulks having average size of 20 nm; moreover, these materials presented an amorphous nature, having no particular surface morphology. XRD confirmed the amorphous structure of SAZ-1 and SZ as well as indicated their internal phase structure. FTIR generated ideas about different linkages and bond connectivities between atoms and groups in SAZ-1 and SZ. Ammonia-TPD of these two materials confirmed the higher super acidic nature of SAZ-1 and lower super acidic nature of SZ. Catalyst evaluation and characterization allowed to propose a reaction mechanism, elucidating a possible role of Brønsted and Lewis acid sites on the studied reaction-catalyst, being the former active sites the main factor leading to isomerization reaction. AFM and SEM pictures indicated the nature of the surface of the catalysts. Nevertheless, SEM analysis before and after the reaction displayed that catalyst morphology was modified and could influence the activity of the catalyst. The use of SAZ-1 is cost saving as well as energy saving.

Acknowledgement

Abhishek Dhar is thankful to Dr. Kaushik Gupta, Presidency University, Kolkata and Mr. Smriti Ranjan Maji, Bose Institute, Kolkata for their co-operation in instrumentation analysis. Abhishek Dutta acknowledges Prof. Denis Constales, Ghent University for help with the understanding of the FTIR spectra analysis. Abhishek Dhar is particularly grateful to University Grant Commission (UGC) India for a doctoral scholarship (UGC/1018/Jr. Fellow (Sc)).

References

1. Adeeva, V., Dehaan, J.W., Janchen, J., Lei, G.D., Schunemann, V., Vandeven, L.J.M., et al., 1995. Acid sites in sulfated and metal-promoted zirconium dioxide catalysts. Journal of Catalysis 151, 364–372.10.1006/jcat.1995.1039Suche in Google Scholar

2. Arata, K., Hino, M., 1990. Preparation of Superacids by metal oxides and their catalytic action. Materials Chemistry and Physics 26, 213–237.10.1016/0254-0584(90)90012-YSuche in Google Scholar

3. Arata, K., Matsuhashi, H., Hino, M., Nakamura, H., 2003. Synthesis of solid superacids and their activities for reactions of alkanes. Catalysis Today 81, 17–30.10.1016/S0920-5861(03)00098-1Suche in Google Scholar

4. Belloum, M., Travers, C., Bournonville, J.P., 1998. Isomérisation Des Paraffines De C4 À C7 Sur Catalyseurs Zéolithiques. Revue Bibliographique. Catalysts Courier 33, 1–6.10.2516/ogst:1991004Suche in Google Scholar

5. Bieletzki, M., Hynninen, T., Soini, T.M., Pivetta, M., Henry, C.R., Foster, A.S., et al., 2010. Topography and work function measurements of thin MgO(001) films on Ag(001) by Nc-AFM and KPFM. Physical Chemistry Chemical Physics 12, 3203–3209.10.1039/b923296fSuche in Google Scholar PubMed

6. Boronat, M., Viruela, P., Corma, A., 1996a. A Theoretical study on the mechanism of the superacid-catalyzed unimolecular isomerization of N-Alkanes and N-Alkenes. Comparison between Ab Initio and density functional results. The Journal of Physical Chemistry 100, 16514–16521.10.1021/jp961179wSuche in Google Scholar

7. Boronat, M., Viruela, P., Corma, A., 1996b. Theoretical study on the mechanism of the superacid-catalyzed unimolecular isomerization of N-Butane and 1-Butene. The Journal of Physical Chemistry 100, 633–637.10.1021/jp9514077Suche in Google Scholar

8. Brown, A.S.C., Hargreaves, J.S.J., 1999. Sulfated metal oxide catalysts. Superactivity through superacidity? Green Chemistry 1, 17–20.10.1039/a807963cSuche in Google Scholar

9. Chakrabarty, D.K., Viswanathan, B., 2009. Heterogeneous Catalysis, International, India: New Age Science.Suche in Google Scholar

10. Chao, K.J., Wu, H.C., Leu, L.J., 1995. Skeletal isomerization of N-Butane on Zeolites and sulfated zirconium oxide promoted by platinum: effect of reaction pressure. Journal of Catalysis 157, 289–293.10.1006/jcat.1995.1293Suche in Google Scholar

11. Chen, W.H., Ko, H.H., Sakthivel, A., Huang, S.J., Liu, S.H., Lo, A.Y., et al., 2006. A solid-state NMR, FT-IR and TPD Study on acid properties of sulfated and metal-promoted zirconia: influence of promoter and sulfation treatment. Catalysis Today 116, 111–120.10.1016/j.cattod.2006.01.025Suche in Google Scholar

12. Choudhary, V.R., Karkamkar, A.J., 2003. Temperature-programmed desorption of water and ammonia on Sulphated zirconia catalysts for measuring their strong acidity and acidity distribution. Journal of Chemical Sciences 115, 281–286.10.1007/BF02704219Suche in Google Scholar

13. Das, D., Mishra, H.K., Dalai, A.K., Parida, K.M., 2004. Iron, and manganese doped SO4 2-/ZrO2-TiO2 mixed oxide catalysts: studies on acidity and benzene isopropylation activity. Catalysis Letters 93, 185–193.10.1023/B:CATL.0000017075.91301.4bSuche in Google Scholar

14. Davis, B.H., Keogh, R.A., Srinivasan, R., 1994. Sulfated zirconia as a hydrocarbon conversion catalyst. Catalysis Today 20, 219–256.10.1016/0920-5861(94)80004-9Suche in Google Scholar

15. Dhar, A., Bhattacharya, S., Chowdhuri, U.R., 2012. The Hydoisomerization of Petroium Naphta by Pt-Doped G-Alumina catalysts: synthesis, characterization and mechanistic study. International Journal of Chemical and Analytical Science 3, 1634–1638.Suche in Google Scholar

16. Furuta, S., 2003. The effect of electric type of platinum complex ion on the isomerization activity of Pt-Loaded Sulfated Zirconia-Alumina. Applied Catalysis A: General 251, 285–293.10.1016/S0926-860X(03)00360-0Suche in Google Scholar

17. Gao, Z., Xia, Y., Hua, W., Miao, C., 1998. New catalyst of SO 4 2-/Al2O3-ZrO2 for N-butane isomerization. Topics in Catalysis 6, 101–106.10.1023/A:1019122608037Suche in Google Scholar

18. Heinemann, H., 1981. A Brief History of Industrial Catalysis, Springer, Berlin.Suche in Google Scholar

19. Hino, M., Arata, K., 1994. Synthesis of highly active superacids of SO4/ZrO2 with Ir, Pt, Rh, Ru, Os, and Pd substances for reaction of butane. Catalysis Letters 30, 25–30.10.1007/BF00813669Suche in Google Scholar

20. Holló, A., Hancsók, J., Kalló, D., 2002. Kinetics of Hydroisomerization of C5–C7 Alkanes and Their Mixtures over platinum containing mordenite. Applied Catalysis A: General 229, 93–102.10.1016/S0926-860X(02)00018-2Suche in Google Scholar

21. Hsu, C.S., Robinson, P., 2006. Practical Advances in Petroleum Processing, Springer-Verlag, New York.10.1007/978-0-387-25789-1Suche in Google Scholar

22. Ibragimov, A.A., Shiriyazdanov, R.R., Davletshin, A.R., Rakhimov, M.N., 2013. Isomerization of light alkanes catalyzed by ionic liquids: an analysis of process parameters. Theoretical Foundations of Chemical Engineering 47, 66–70.10.1134/S0040579513010028Suche in Google Scholar

23. Keogh, R.A., Srinivasan, R., Davis, B.H., 1995. Pt-SO2−4-ZrO2 catalysts: the impact of water on their activity for hydrocarbon conversion. Journal of Catalysis 151, 292–299.10.1006/jcat.1995.1030Suche in Google Scholar

24. Kimura, T., 2003. Development of Pt/SO42−/ZrO2 catalyst for isomerization of light naphtha. Catalysis Today 81, 57–63.10.1016/S0920-5861(03)00102-0Suche in Google Scholar

25. Kustov, L.M., Kazansky, V.B., Figueras, F., Tichit, D., 1994. Investigation of the acidic properties of ZrO2 Modified by SO2−4 anions. Journal of Catalysis 150, 143–149.10.1006/jcat.1994.1330Suche in Google Scholar

26. Laha, S.C., Venkatesan, C., Sakthivel, A., Komura, K., Kim, T.H., Cho, S.J., et al., 2010. Highly stable Aluminosilicates with a dual pore system: simultaneous formation of Meso- and Microporosities with Zeolitic BEA building units. Microporous and Mesoporous Materials 133, 82–90.10.1016/j.micromeso.2010.04.018Suche in Google Scholar

27. Lei, T., Xu, J.S., Hua, W.M., Tang, Y., Gao, Z., 1999. High-activity catalyst of SO 4 2- /ZrO2 supported on gamma-Al2O3 for N-Butane Isomerization. Catalysis Letters 61, 213–218.10.1023/A:1019057929918Suche in Google Scholar

28. Ling, H., Wang, Q., Shen, B.X., 2009. Hydroisomerization and hydrocracking of hydrocracker bottom for producing lube base oil. Fuel Processing Technology 90, 531–535.10.1016/j.fuproc.2009.01.006Suche in Google Scholar

29. Martens, J.A., Jacobs, P.A., Weitkamp, J., 1986. Attempts to rationalize the distribution of hydrocracked products. I qualitative description of the primary hydrocracking modes of long chain Paraffins in open zeolites. Applied Catalysis 20, 239–281.10.1016/0166-9834(86)80020-3Suche in Google Scholar

30. Mastikhin, V.M., Nosov, A.V., Filimonova, S.V., Terskikh, V.V., Kotsarenko, N.S., Shmachkova, V.P., et al., 1995. High-resolution solid-state NMR studies of sulfate-promoted zirconia in relation to N-Pentane isomerization. Journal of Molecular Catalysis A: Chemical 101, 81–90.10.1016/1381-1169(95)00080-1Suche in Google Scholar

31. Matsuhashi, H., Shibata, H., Nakamura, H., Arata, K., 1999. Skeletal isomerization mechanism of alkanes over solid superacid of sulfated zirconia. Applied Catalysis A: General 187, 99–106.10.1016/S0926-860X(99)00194-5Suche in Google Scholar

32. Morterra, C., Cerrato, G., Ardizzone, S., Bianchi, C.L., Signoretto, M., Pinna, F., 2002. Surface features and catalytic activity of sulfated zirconia catalysts from hydrothermal precursors. Physical Chemistry Chemical Physics 4, 3136–3145.10.1039/b110444fSuche in Google Scholar

33. Nakamoto, K. 2009. Infrared and Raman Spectra of Inorganic and Coordination Compounds. Part B, 6th ed, Wiley, New York.10.1002/9780470405888Suche in Google Scholar

34. Olah, G.A., Surya, G.K., Sommer, J., 1985. Superacids, John Wiley and Sons, New York.Suche in Google Scholar

35. Peak, D., Ford, R.G., Sparks, D.L., 1999. An in Situ ATR-FTIR investigation of sulfate bonding mechanisms on goethite. Journal of Colloid and Interface Science 218, 289–299.10.1006/jcis.1999.6405Suche in Google Scholar

36. Ramos, M.J., Gómez, J.P., Dorado, F., Sánchez, P., Valverde, J.L., 2005. Hydroisomerization of a refinery naphtha stream over agglomerated Pd zeolites. Industrial & Engineering Chemistry Research 44, 9050–9058.10.1021/ie050765lSuche in Google Scholar

37. Roldán, R., Beale, A.M., Sánchez-Sánchez, M., Romero-Salguero, F.J., Jiménez-Sanchidrián, C., Gómez, J.P., et al., 2008. Effect of the impregnation order on the nature of metal particles of Bi-functional Pt/Pd-supported zeolite beta materials and on their catalytic activity for the hydroisomerization of alkanes. Journal of Catalysis 254, 12–26.10.1016/j.jcat.2007.10.022Suche in Google Scholar

38. Romero, M.D., Calles, J.A., Rodríguez, A., 1997. Influence of the preparation method and metal precursor compound on the Bifunctional Ni/HZSM-5 catalysts. Industrial & Engineering Chemistry Research 36, 3533–3540.10.1021/ie960775+Suche in Google Scholar

39. Sarkar, D., Mohapatra, D., Ray, S., Bhattacharyya, S., Adak, S., Mitra, N., 2007. Synthesis and characterization of Sol–Gel derived ZrO2 Doped Al2O3 nanopowder. Ceramics International 33, 1275–1282.10.1016/j.ceramint.2006.05.002Suche in Google Scholar

40. Sing, K., 1985. Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (Recommendations 1984). Pure and Applied Chemistry 57, 603–619.10.1351/pac198557040603Suche in Google Scholar

41. Srinivasan, R., Watkins, T.R., Hubbard, C.R., Davis, B.H., 1995. Sulfated zirconia catalysts. The crystal phases and their transformations. Chem. Mater 8, 836–730.10.1021/cm00052a018Suche in Google Scholar

42. Tatsumi, T., Matsuhashi, H., Arata, K., 1996. A study of the preparation procedures of sulfated zirconia prepared from zirconia gel. The effect of the pH of the mother solution on the isomerization activity of N-Pentane. Bulletin of the Chemical Society of Japan 69, 1191–1194.10.1246/bcsj.69.1191Suche in Google Scholar

43. Wan, K.T., Khouw, C.B., Davis, M.E., 1996. Studies on the catalytic activity of zirconia promoted with sulfate, iron, and manganese. Journal of Catalysis 158, 311–326.10.1006/jcat.1996.0030Suche in Google Scholar

44. Weyda, H., Köhler, E., 2003. Modern refining concepts – an update on naphtha-isomerization to modern gasoline manufacture. Catalysis Today 81, 51–55.10.1016/S0167-2991(03)80165-9Suche in Google Scholar

45. Zarkalis, A.S., Hsu, C.-Y., Gates, B.C., 1996. Butane disproportionation catalyzed by sulfated zirconia promoted with iron and manganese. Catalysis Letters 37, 1–4.10.1007/BF00813510Suche in Google Scholar

46. Zarkalis, A.S., Hsu, C.Y., Gates, B.C., 1994. Solid superacid catalysis: kinetics of butane isomerization catalyzed by a sulfated oxide containing iron, manganese, and zirconium. Catalysis Letters 29, 235–239.10.1007/BF00814269Suche in Google Scholar

47. Zhang, R., Meng, X., Liu, Z., Meng, J., Xu, C., 2008. Isomerization of N-pentane catalyzed by acidic Chloroaluminate ionic liquids. Industrial & Engineering Chemistry Research 47, 8205–8210.10.1021/ie801013jSuche in Google Scholar

Received: 2015-4-14
Revised: 2015-11-9
Accepted: 2015-12-1
Published Online: 2016-1-19
Published in Print: 2016-6-1

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