Journal of Porous Materials

, Volume 24, Issue 2, pp 443–454 | Cite as

Preparation of meso-structured silica–calcium mixed oxide (MSCMO) catalyst for converting Vietnamese rubber seed oil to biodiesel



This report covered some new contributions in catalyst preparation and characterization. Meso-structured silica–calcium mixed oxide catalyst possessed both acidic and basic sites was synthesized through co-condensation method in alkaline environment using tetraethylorthosilicate, CaO, and cetyltrimethylammoniumbromide. The co-condensation process was established at 90 °C for 24 h obtaining white-gel precipitate which was dried at 120 °C followed by calcination at 550 °C for 5 h. The as-synthesized catalyst was used in conversion of rich free fatty acid rubber seed oil (22 %wt) in Vietnam to fatty acid methyl esters (FAMEs) in mild conditions such as temperature of 120 °C, time of 4 h, catalyst dosage of 3 %wt, methanol/oil mass ratio of 2.5/1 and agitating speed of 550 rpm achieving the reaction yield of 95.4 %. The catalyst were characterized by various techniques such as X-ray diffraction, transmission electron spectroscopy, Nitrogen Adsorption–Desorption Analysis (BET), temperature programmed desorption (NH3 and CO2-TPD). Especially, X-ray absorption spectroscopies was applied to explain the occurrence of acid and base sites on catalysts surface. The analysis showed the sixfold coordinated calcium sites characterizing for the mixed oxide structure of CaO–SiO2. The results helped to simulate the bonding structure around the Ca sites indicating the electrostatic charge differences along the Ca–O–Si connections and the ability for occurring the defect sites containing the O2− moieties corresponding to the acidity and basicity of the catalysts respectively. Gas chromatography–mass spectroscopy was also used to determine the composition of the FAMEs showing high purity of these products.


Meso-structured silica–calcium mixed oxide X-Ray absorption spectroscopy Biodiesel Acid-base catalyst Bifunctional catalyst 



This work was financially supported by the National Foundation for Science and Technology Development, Vietnam (NAFOSTED) under grant number 104.05-2013.57.


  1. 1.
    T.-M. Hsin, S. Chen, E. Guo, C.-H. Tsai, M. Pruski, V.S.Y. Lin, Calcium containing silicate mixed oxide-based heterogeneous catalysts for biodiesel production. Top. Catal. 53, 746–754 (2010)CrossRefGoogle Scholar
  2. 2.
    S. Yan, S.O. Salley, K.Y. Simon Ng, Simultaneous transesterification and esterification of unrefined or waste oils over ZnO–La2O3 catalysts. Appl. Catal. A Gen. 353, 203–212 (2009)CrossRefGoogle Scholar
  3. 3.
    S. Yan, S.O. Salley, K.Y.S. Ng, Using mixed oxide zinc and lanthanum catalyst that has a high tolerance for the presence of water and free fatty acids (FFA) in the oil. US Patent 20100010246 (2009)Google Scholar
  4. 4.
    S. Yan, C. DiMaggio, S. Mohan, M. Kim, S.O. Salley, K.Y. Simon Ng, Advancements in Heterogeneous catalysis for biodiesel synthesis. Top. Catal. 53, 721–736 (2010)CrossRefGoogle Scholar
  5. 5.
    J. Jitputti, B. Kitiyanan, P. Rangsunvigit, K. Bunyakiat, L. Attanatho, P. Jenvanitpanjakul, Transesterification of crude palm kernel oil and crude coconut oil by different solid catalysts. Chem. Eng. J. 116, 61–66 (2006)CrossRefGoogle Scholar
  6. 6.
    Q. Shu, Q. Zhang, G. Xu, Z. Nawaz, D. Wang, J. Wang, Synthesis of biodiesel from cottonseed oil and methanol using a carbon based solid acid catalyst. Fuel Process. Technol. 90, 1002–1008 (2009)CrossRefGoogle Scholar
  7. 7.
    H.K.D. Nguyen, P. Van Pham, A.D. Vo, Preparation, characterization and thermal stability improvement of mesoporous sulfated zirconia for converting deodorizer distillate to methyl esters. J Porous Mater (2016). doi: 10.1007/s10934-016-0274-0
  8. 8.
    N.V. Dat et al., Biodiesel synthesis from rubber seed oil. Vietnam J. Sci. 21A, 105–113 (2012)Google Scholar
  9. 9.
    A.S. Ramadhas, S. Jayaraj, C. Muraleedharan, Biodiesel production from high FFA rubber seed oil. Fuel 84, 335–340 (2005)CrossRefGoogle Scholar
  10. 10.
    H.D. Eka, Y. Tajul Aris, W.A. Wan Nadiah, Potential use of Malaysian rubber (Hevea brasiliensis) seed as food, feed and biofuel. Int. Food Res. J. 17, 527–534 (2010)Google Scholar
  11. 11.
    V.S.-Y. Lin et al., Porous silica and metal oxide composite-based catalyst for conversion of fatty acids and oils to Biodiesel, US 7790651 B2 (2010).
  12. 12.
    M. Kouzu, S. Yamanaka, J. Hidaka, M. Tsunomori, Heterogeneous catalysis of calcium oxide used for transesterification of soybean oil with refluxing methanol. Appl. Catal. 355(1–2), 94–99 (2009)CrossRefGoogle Scholar
  13. 13.
    J. Zheng, S. Zhai, Y. Zhang, D. Wu, Y. Suna, Y. Yang, L. Chen, F. Deng, Hydrothermally stable MCM-41 analogue with extensive embedded voids. Catal. Today 93–95, 529–534 (2004)CrossRefGoogle Scholar
  14. 14.
    S.K. Das, M.K. Bhunia, Bhaumik, Self-assembled TiO2 nanoparticles: mesoporosity, optical and catalytic properties. Dalton Trans. 39, 4382–4390 (2010)CrossRefGoogle Scholar
  15. 15.
    K.R. Coombes, J.M. Koomen, K.A. Baggerly, J.S. Morris, R. Kobayashi, Understanding the characteristics of mass spectrometry data through the use of simulation. Cancer Inform. 1, 41–52 (2005)Google Scholar
  16. 16.
    K. Tanabe et al., New Solid Acids and Bases—Their Catalytic Properties, Studies in Surface Science and Catalysis, vol. 51 (1989)Google Scholar
  17. 17.
    A. Paul, Acid-base, surface electron donating and catalytic properties of binary oxides of Zr with rare earth elements, Thesis of Doctor of Philosophy in Chemistry, Department of Applied Chemistry, Cochin University of Science and Technology, 1997Google Scholar
  18. 18.
    A.S. Ivanova, Structure, texture, and acid-base properties of alkaline earth oxides, rare earth oxides, and binary oxide systems. Kinet. Catal. 46(5), 620–633 (2004)CrossRefGoogle Scholar

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© Springer Science+Business Media New York 2016

Authors and Affiliations

  1. 1.Hanoi University of Science and TechnologyHanoiVietnam

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