Skip to main content
Log in

Effects of functionalization conditions of sulfonic acid grafted SBA-15 on catalytic activity in the esterification of glycerol to monoglyceride: a factorial design approach

  • Published:
Journal of Porous Materials Aims and scope Submit manuscript

Abstract

A series of propyl sulfonic acid-modified SBA-15 catalysts (SBA-15SO3H) was prepared under various conditions using post-functionalization approach. A factorial design coupled with response surface analysis were employed to evaluate the effects of the preparation conditions on the catalyst activity. Optimization of the conditions to find the most active SBA-15SO3H catalyst with the highest activity in glycerol esterification with lauric acid at 160 °C for 6 h was also made. Amount of 3-(mercaptopropyl)trimethoxysilane (MPTMS) and reflux time were chosen as parameters of the preparation conditions. The presence of propyl sulfonic acid groups in SBA-15SO3H catalysts was confirmed by FT-TIR method. The catalysts were also characterized by means of surface analysis, XRD, TEM and TGA. The results obtained from the statistical models suggested that the amount of MPTMS was more important parameter to influence the activity compared to the reflux time. The optimum preparation condition was achieved at a reflux time of 20 h and an MPTMS amount of 1 mL/gram SBA-15 to obtain the SBA-15SO3H(1) with the highest monoglyceride selectivity (70.2%) and corresponding lauric acid conversion (95%) in the esterification process.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11
Fig. 12

Similar content being viewed by others

References

  1. N. Garti, A. Asein, M. Fanum, A DSC study of water behavior in water-in-oil microemulsions stabilized by sucrose esters, butanol. Colloids Surf. A 170, 1–18 (2000)

    Article  CAS  Google Scholar 

  2. L. Sagalowicz, M.E. Leser, H.J. Watzke, M. Michel, Monoglyceride self assembly structures as delivery vehicles. Trend Food Sci. Technol. 17, 204–214 (2006)

    Article  CAS  Google Scholar 

  3. H. Moonen, H. Bas, Mono- and Diglycerides, Emulsifiers in Food Technology (Oxford, Blackwell, 2004), pp. 40–58

  4. C.A. Ferretti, R.N. Olcese, C.R. Apesteguia, J.I.D. Cosimo, Heterogeneously-catalyzed glycerolysis of fatty acid methyl esters: reaction parameter optimization. Ind. Eng. Chem. Res. 48, 10387–10394 (2009)

    Article  CAS  Google Scholar 

  5. N. Sanchez, M. Martınez, J. Aracil, Selective esterification of glycerine to 1-glycerol monooleate: 1. Kinetic modelling. Ind. Eng. Chem. Res. 36, 1524–1528 (1997)

    Article  CAS  Google Scholar 

  6. W.D. Bossaert, D.E.D. Vos, W.M.V. Rhijn, J. Bullen, Mesoporous sulfonic acids as selective heterogeneous catalysts for the synthesis of monoglycerides. J. Catal. 182, 156–164 (1999)

    Article  CAS  Google Scholar 

  7. C.S. Caetano, I.M. Fonseca, A.M. Ramos, J. Vital, J.E. Castanheiro, Esterification of free fatty acids with methanol using heteropolyacids immobilized on silica. Catal. Commun. 9, 1996–1999 (2008)

    Article  CAS  Google Scholar 

  8. R. Nakamura, K. Komura, Y. Sugi, The esterification of glycerine with lauric acid catalysts by multi-valent metal salts. Selective formation of mono- and dilaurins. Catal. Commun. 9, 511–515 (2008)

    Article  CAS  Google Scholar 

  9. L. Guerreiro, J.E. Castanheiro, I.M. Fonseca, R.M. Martin-Aranda, A.M. Ramos, J. Vital, Transesterification of soybean oil over sulfonic acid functionalised polymeric membranes. Catal. Today 118, 166–171 (2006)

    Article  CAS  Google Scholar 

  10. J. Aracil, M. Martinez, N. Sanchez, A. Corma, Formation of a jojoba oil analog by esterification of oleic acid using zeolites as catalyst. Zeolites 12, 233–236 (1992)

    Article  CAS  Google Scholar 

  11. E. Heykants, W.H. Verrelst, R.F. Parton, P.A. Jacobs, Shape-selective zeolite catalysed synthesis of monoglycerides by esterification of fatty acids with glycerol. Stud. Surf. Sci. Catal. 105, 1277–1284 (1997)

    Article  Google Scholar 

  12. Y. Pouilloux, S. Abro, C. van Hove, J. Barrault, Reaction of glycerol with fatty acids in the presence of ion-exchange resins: Preparation of monoglycerides. J. Mol. Catal. A: Chem. 149, 243–254 (1999)

    Google Scholar 

  13. J. Perez-Pariente, I. Diaz, F. Mohino, E. Satre, Selective synthesis of monoglycerides by using functionalised mesoporous catalysts. Appl. Catal. A 254, 173–188 (2003)

    Article  CAS  Google Scholar 

  14. S.M. Stevens, K. Jansson, C. Xiao, S. Asahina, M. Klingstedt, D. Grüner, Y. Sakamoto, K. Miyasaka, P. Cubillas, R. Brent, L. Han, S. Che, R. Ryoo, D. Zhao, M. Anderson, F. Schüth, O. Terasaki, An appraisal of high resolution scanning electron microscopy applied to porous materials. JEOUL News 44, 17–22 (2009)

    Google Scholar 

  15. W.M. van Rhijn, D.E. Vos, W.D. Bossaert, J. Bullen, B. Vouters, P. Grobert, P.A. Jacobs, Sulfonic acid bearing mesoporous materials as catalysts in furan and polyol derivatization. Stud. Surf. Sci. Catal. 117, 183–190 (1998)

    Article  Google Scholar 

  16. I. Hannus, M. Búza, A. Beck, L. Guczi, G. Sáfrán, Hydrodechlorination catalytic activity of gold nanoparticles supported on TiO2 modified SBA-15 investigated by IR spectroscopy. J. Molec. Struct. 924–926, 355–357 (2009)

    Article  Google Scholar 

  17. I. Dıaz, F. Mohino, E. Satre, J. Perez-Pariente, Synthesis and catalytic properties of SO3H-mesoporous materials from gels containing non-ionic surfactants. Stud. Surf. Sci. Catal. 135, 1383–1390 (2001)

    Google Scholar 

  18. F. Hoffmann, M. Cornelius, J. Morell, M. Froba, Silica-based mesoporous organic–inorganic hybrid materials. Angew. Chem. Int. Ed. 45, 3216–3251 (2006)

    Article  CAS  Google Scholar 

  19. N. Garcia, E. Benito, J. Guzman, P. Tiemblo, V. Morales, R.A. Garcıa, Functionalization of SBA-15 by an acid-catalyzed approach: A surface characterization study. Micropor. Mesopor. Mater. 106, 129–139 (2007)

    Article  CAS  Google Scholar 

  20. D. Zhao, Q. Huo, J. Feng, B.F. Chmelka, G.D. Stucky, Nonionic triblock and star diblock copolymer and oligomeric surfactant syntheses of highly ordered, hydrothermally stable mesoporous silica structures. JAOCS 120, 6024–6036 (1998)

    Article  CAS  Google Scholar 

  21. G.E.P. Box, W.G. Hunter, J.S. Hunter, Statistics for experiments, an introduction to design, data analysis and model building (Wiley, New York, 1978)

    Google Scholar 

  22. R. Molina, F. Martínez, J.A. Melero, D.H. Bremner, A.G. Chakinala, Mineralization of phenol by a heterogeneous ultrasound/Fe-SBA-15/H2O2 process: Multivariate study by factorial design of experiments. Appl. Catal. B. 66, 198–207 (2006)

    Article  CAS  Google Scholar 

  23. D. Das, J.F. Lee, S. Cheng, Selective synthesis of Bisphenol-A over mesoporous MCM silicacatalysts functionalized with sulfonic acid groups. J. Catal. 223, 152–160 (2004)

    Article  CAS  Google Scholar 

  24. T. Kang, Y. Park, J. Yi, Highly Selective adsorption of Pt2+ and Pd2+ using thiol-functionalized mesoporous silica. Ind. Eng. Chem. Res. 43, 1478–1484 (2004)

    Article  CAS  Google Scholar 

  25. C.M. Crudden, M. Sateesh, R. Lewis, Mercaptopropyl-modified mesoporous silica: A remarkable support for the preparation of a reusable, heterogeneous palladium catalyst for coupling reactions. J. Am. Chem. Soc. 127, 10045–10050 (2005)

    Article  CAS  Google Scholar 

  26. L. Hermida, A.Z. Abdullah, A.R. Mohamed, Post-synthetically functionalized SBA-15 with sulfonic acid and sulphated zirconia for esterification of glycerol to monoglyceride. J. Appl. Sci. 10(24), 3199–3206 (2010)

    Article  CAS  Google Scholar 

  27. Y.C. Yang, S.R. Vali, Y.H. Ju, A process for synthesizing high purity monoglyceride. J. Chin. Inst. Chem. Eng. 34, 617–623 (2003)

    CAS  Google Scholar 

  28. W. Volland, Organic compound identification using infrared spectroscopy, available from World Wide Web: http://www.800mainstreet.com/irsp/eir.html (accessed on August 2010)

  29. M. Kruk, M. Jaroniec, C.H. Ko, R. Ryoo, Characterization of the porous structure of SBA-15. Chem. Mater. 12, 1961–1968 (2000)

    Article  CAS  Google Scholar 

  30. B. Rac, P.F. Molnar, M. Mohai, I. Bertoti, A comparative study of solid sulfonic acid catalysts based on various ordered mesoporous silica materials. J. Molec. Catal. A 244, 46–57 (2006)

    Article  CAS  Google Scholar 

  31. M.C. Chao, C.H. Chang, H.P. Lin, C.Y. Tang, C.Y. Lin, Morphological control on SBA-15 mesoporous silicas via a slow self-assembling rate. J. Mater. Sci. 44, 6453–6462 (2009)

    Article  CAS  Google Scholar 

  32. W. Cao, C. Zhang, P. Hong, H. Ji, Response surface methodology for autolysis parameters optimization of shrimp head and amino acids released during autolysis. J. Food Chem. 109, 176–183 (2008)

    Article  CAS  Google Scholar 

Download references

Acknowledgments

A Short Term (No.6035274) and a Research University (RU) grants (No.814003 and 814004) from Universiti Sains Malaysia to support this work are gratefully acknowledged.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Ahmad Zuhairi Abdullah.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Hermida, L., Abdullah, A.Z. & Mohamed, A.R. Effects of functionalization conditions of sulfonic acid grafted SBA-15 on catalytic activity in the esterification of glycerol to monoglyceride: a factorial design approach. J Porous Mater 19, 835–846 (2012). https://doi.org/10.1007/s10934-011-9538-x

Download citation

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10934-011-9538-x

Keywords

Navigation