Advertisement

Journal of Porous Materials

, Volume 24, Issue 2, pp 411–419 | Cite as

Preparation, characterization and thermal stability improvement of mesoporous sulfated zirconia for converting deodorizer distillate to methyl esters

  • Hong Khanh Dieu Nguyen
  • Phong Van Pham
  • Anh Duc Vo
Article

Abstract

This article reported a new procedure for synthesizing ordered mesoporous sulfated zirconia (m-SZ), an effective oxophosphate process for strengthening thermal stability of the as-synthesized m-SZ catalyst forming mesoporous phosphated sulfated zirconia (m-PSZ). The study also afforded a new reaction routine for synthesizing the m-SZ through condensation method using Zr(SO4)2 solution precursor in the incipient wetness impregnation method. The m-PSZ contained dense surface superacid sites being suitable for methanolysis of almost vegetable oils or animal fats producing methyl ester. The temperature of the condensation process was varied in the range of 70–100 °C, and the time periods were surveyed from 12 to 72 h for well self-assembling the mesoporous structure. The precipitation obtained from the condensations was calcined at 450 °C for 3 h after completely removing of the surface water overnight at 100 °C. The after calcination powder was the m-SZ catalyst. The H3PO4 was used as precursor for oxophosphate process producing the m-PSZ catalyst. The m-PSZ catalyst was applied to the methyl ester synthesis using deodorizer distillate collected from vegetable oil refinery in Vietnam as feedstock. The methanolysis was established at 130 °C for 4 h to obtain the refined methyl esters after passing through a purification process. The refined biodiesel characteristics were determined for its using in diesel engine, and the results showed almost positive values. Some techniques were used in the research such as XRD, TEM, BET, TG–DTA, NH3–TPD and GC–MS.

Keywords

Mesoporous zirconia Superacid Methyl esters Deodorizer distillate Oxophosphate 

References

  1. 1.
    M.E. Borges, L. Díaz, Recent developments on heterogeneous catalysts for biodiesel production by oil esterification and transesterification reactions: a review. Renew. Sustain. Energy Rev. 16(5), 2839–2849 (2012)CrossRefGoogle Scholar
  2. 2.
    Kamchai Nuithitikul, Jumras Limtrakul, Comparison in catalytic activities of sulfated zirconia and sulfated tin oxide for converting free fatty acids in crude palm oil to their methyl esters. Int. J. Chem. Reactor Eng. 10(1), 1–29 (2012)CrossRefGoogle Scholar
  3. 3.
    T. Yamaguchi, K. Tanabe, Y.C. Kung, Preparation and characterization of ZrO2 and SO4 2−-promoted ZrO2. Mater. Chem. Phys. 16(1), 67–77 (1987)CrossRefGoogle Scholar
  4. 4.
    A. Corma, V. Fornés, M.I. Juan-Rajadell, J.M. López Nieto, Influence of preparation conditions on the structure and catalytic properties of SO4 2−/ZrO2 superacid catalysts. Appl. Catal. A 116(1–2), 151–163 (1994)CrossRefGoogle Scholar
  5. 5.
    Dan Farcasiu, J.Q. Li, Preparation of sulfated zirconia catalysts with improved control of sulfur content. Appl. Catal. A: Gen. 128(1), 97–105 (1995)CrossRefGoogle Scholar
  6. 6.
    V.G. Deshmanea, Y.G. Adewuyi, Synthesis of thermally stable, high surface area, nanocrystalline mesoporous tetragonal zirconium dioxide (ZrO2): effects of different process parameters. Microporous Mesoporous Mater. 148(1), 88–100 (2012)CrossRefGoogle Scholar
  7. 7.
    K. Saravanan, B. Tyagi, R.S. Shukla, H.C. Bajaj, Esterification of palmitic acid with methanol over template-assisted mesoporous sulfated zirconia solid acid catalyst. Appl. Catal. B 172–173, 108–115 (2015)CrossRefGoogle Scholar
  8. 8.
    N.G. Shao, R. Sheikh, A. Hilonga, J.E. Lee, Y.H. Park, H.T. Kim, Biodiesel production by sulfated mesoporous titania–silica catalysts synthesized by the sol–gel process from less expensive precursors. Chem. Eng. J. 215–216, 600–607 (2013)CrossRefGoogle Scholar
  9. 9.
    X.R. Chen, Y.H. Ju, C.Y. Mou, Direct synthesis of mesoporous sulfated silica–zirconia catalysts with high catalytic activity for biodiesel via esterification. J. Phys. Chem. C 111, 18731–18737 (2007)CrossRefGoogle Scholar
  10. 10.
    H.R. Chen, J.L. Shi, Z.L. Hua, M.L. Ruan, D.S. Yan, Parameter control in the synthesis of ordered porous zirconium oxide. Mater. Lett. 51, 187–193 (2001)CrossRefGoogle Scholar
  11. 11.
    Ulrike Ciesla, Michael Froba, Galen Stucky, Ferdi Schuth, Highly ordered porous zirconias from surfactant-controlled syntheses: zirconium oxide-sulfate and zirconium oxo phosphate. Chem. Mater. 11, 227–234 (1999)CrossRefGoogle Scholar
  12. 12.
    U. Ciesla, S. Schacht, G.D. Stucky, K.K. Unger, F. Schuth, Formation of a porous zirconium oxo phosphate with a high surface area by a surfactant-assisted synthesis. Angew. Chem. Int. Ed. Engl. 35(5), 541–543 (1996)CrossRefGoogle Scholar
  13. 13.
    M. Risch, E.E. Wolf, Effect of the preparation of a mesoporous sulfated zirconia catalyst in n-butane isomerization activity. Appl. Catal. A 206, 283–293 (2001)CrossRefGoogle Scholar
  14. 14.
    D. Zhao, Y. Wan, W. Zhou, in Introduction, in Ordered Mesoporous Materials (Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, Germany, 2013). doi: 10.1002/9783527647866.ch1 CrossRefGoogle Scholar
  15. 15.
    C.T. Kresge, M.E. Leonowicz, W.J. Roth, J.C. Vartuli, J.S. Beck, Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism. Nature 359, 710–712 (1992)CrossRefGoogle Scholar
  16. 16.
    A. Monnier, F. Schuth, Q. Huo, D. Kumar, D. Margolese, R.S. Maxwell, G.D. Stucky, M. Krishnamurty, P. Petroff, A. Firouzi, M. Janicke, B.F. Chmelka, Cooperative formation of inorganic–organic interfaces in the synthesis of silicate mesostructures. Science 261, 1299–1303 (1993)CrossRefGoogle Scholar
  17. 17.
    U. Ciesla, D. Demuth, R. Leon, P. Petroff, G.D. Stucky, K. Unger, F. Schiith, Surfactant controlled preparation of mesostructured transition-metal oxide compounds. J. Chem. Sol Chem. Commun. 11, 1387–1388 (1994)CrossRefGoogle Scholar
  18. 18.
    A. Stein, M. Fendorf, T.P. Jarvie, K.T. Mueller, A.J. Benesi, T.E. Mallouk, Salt-gel synthesis of porous transition metal oxides. Chem. Mater 7, 304–313 (1995)CrossRefGoogle Scholar
  19. 19.
    U. Ciesla, G. Stucky, F. Schtith, Improvement of the thermal stability of mesostructured metal oxides with zirconia as the example, mesoporous molecular sieves 1998. Stud. Surf. Sci. Catal. 117, 527–534 (1998)CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2016

Authors and Affiliations

  • Hong Khanh Dieu Nguyen
    • 1
  • Phong Van Pham
    • 2
  • Anh Duc Vo
    • 3
  1. 1.Hanoi University of Science and TechnologyHanoiVietnam
  2. 2.Vietnam Oil and Gas GroupHanoiVietnam
  3. 3.Industrial University of Ho Chi Minh CityHo Chi MinhVietnam

Personalised recommendations