Skip to main content
SpringerLink
Log in

Adsorption microcalorimetry characterization of K-doped MgAl mixed oxide catalysts for soybean oil transesterification synthesized by impregnation and ball milling techniques

  • Published:
Journal of Thermal Analysis and Calorimetry Aims and scope Submit manuscript

Abstract

Layered double hydroxides were prepared by pH-controlled co-precipitation method with a Mg/Al molar ratio between 1.5 and 4.0 and used as precursors for obtaining, through calcination, a series of MgAl mixed oxides, which were used as catalysts for soybean oil transesterification with methanol. The mixed oxide with the highest Mg/Al ratio was doped with potassium for obtaining highly basic catalysts. Three different potassium salts (K2CO3, KNO3, CH3COOK) were used for loading potassium on the support (K loading ca. 3 mass%) by two different techniques, namely conventional incipient wetness impregnation and innovative mechanical milling. All the catalysts were characterized as to their chemical composition, structure and texture by inductively coupled plasma atomic emission spectroscopy, X-ray diffraction and N2 physisorption, respectively. Their basic and acid features were assessed by adsorption microcalorimetry, using CO2 and NH3 as probe molecules, respectively. Catalytic testing was carried out in a slurry batch reactor operated at 343 K and atmospheric pressure. The occurrence of potassium leaching into the liquid phase was checked for the K-doped catalysts. The initial activity of the heterogeneous catalysts was interpreted in terms of surface basicity, by taking into account a possible role of acidity in determining the mechanism.

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

Access this article

Log in via an institution

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

Instant access to the full article PDF.

Institutional subscriptions

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

Similar content being viewed by others

References

  1. Gerpen JV. Biodiesel processing and production. Fuel Process Technol. 2005;86:1097–107.

    Article  Google Scholar 

  2. Wilson K, Lee AF. Rational design of heterogeneous catalysts for biodiesel synthesis. Catal Sci Technol. 2012;2:884–97.

    Article  CAS  Google Scholar 

  3. Suppes GJ, Dasari MA, Doskocil EJ, Mankidy PJ, Goff MJ. Transesterification of soybean oil with zeolite and metal catalysts. Appl Catal A Gen. 2004;257:213–23.

    Article  CAS  Google Scholar 

  4. Derrien A, Renard G, Brunel D. Guanidine linked to micelle-templated mesoporous silicates as base catalyst for transesterification. Stud Surf Sci Catal. 1998;117:445–52.

    Article  CAS  Google Scholar 

  5. Gelbard G, Vielfaure-Joly F. Polynitrogen strong bases as immobilized catalysts for the transesterification of vegetable oils. CR Acad Sci Ser IIc Chim. 2000;3:563–7.

    CAS  Google Scholar 

  6. Schuchardt U, Sercheli R, Vargas RM. Transesterification of vegetable oil: a review. J Braz Chem Soc. 1998;9(1):199–210.

    CAS  Google Scholar 

  7. Schuchardt U, Vargas RM, Gelbard G. Transesterification of soybean oil catalyzed by alkylguanidines heterogenized on different substituted polystyrenes. J Mol Catal A. 1996;109:37–44.

    Article  CAS  Google Scholar 

  8. Sercheli R, Vargas RM, Schuchardt U. Alkylguanidine-catalyzed heterogeneous transesterification of soybean oil. J Am Oil Chem Soc. 1999;76(10):1207–10.

    Article  CAS  Google Scholar 

  9. Meloni D, Monaci R, Zedde Z, Cutrufello MG, Fiorilli S, Ferino I. Transesterification of soybean oil on guanidine base-functionalized SBA-15 catalysts. Appl Catal B. 2011;102:505–14.

    Article  CAS  Google Scholar 

  10. Suppes GJ, Bockwinkel K, Lucas S, Botts JB, Mason MH, Heppert JA. Calcium carbonate catalyzed alcoholysis of fats and oils. J Am Oil Chem Soc. 2001;78:139–45.

    Article  CAS  Google Scholar 

  11. Peterson GR, Sacarrah WP. Rapeseed oil transesterification by heterogeneous catalysis. J Am Oil Chem Soc. 1984;61:1593–6.

    Article  CAS  Google Scholar 

  12. Ebiura T, Echizen T, Ishikawa A, Murai K, Baba T. Selective transesterification of triolein with methanol to methyl oleate and glycerol using alumina loaded with alkali metal salt as a solid-base catalyst. Appl Catal A Gen. 2005;283:111–6.

    Article  CAS  Google Scholar 

  13. Xie WL, Peng H, Chen LG. Transesterification of soybean oil catalyzed by potassium loaded on alumina as a solid-base catalyst. Appl Catal A Gen. 2006;300:67–74.

    Article  CAS  Google Scholar 

  14. Xie WL, Huang XM. Synthesis of biodiesel from soybean oil using heterogeneous KF/ZnO catalyst. Catal Lett. 2006;107:53–9.

    Article  CAS  Google Scholar 

  15. Leclercq E, Finiels A, Moreau C. Transesterification of rapeseed oil in the presence of basic zeolites and related solid catalysts. J Am Oil Chem Soc. 2001;78:1161–5.

    Article  CAS  Google Scholar 

  16. Xie WL, Peng H, Chen LG. Calcined Mg-Al hydrotalcites as solid base catalysts for methanolysis of soybean oil. J Mol Catal A. 2006;246:24–32.

    Article  CAS  Google Scholar 

  17. Cantrell DG, Gillie LJ, Lee AF, Wilson K. Structure-reactivity correlations in MgAl hydrotalcite catalysts for biodiesel synthesis. Appl Catal A Gen. 2005;287:183–90.

    Article  CAS  Google Scholar 

  18. Di Serio M, Ledda M, Cozzolino M, Minutillo G, Tesser R, Santacesaria E. Transesterification of soybean oil to biodiesel by using heterogeneous basic catalysts. Ind Eng Chem Res. 2006;45:3009–14.

    Article  Google Scholar 

  19. J Di Cosimo JI, Diez VK, Xu M, Iglesia E, Apesteguia CR. Structure and surface and catalytic properties of Mg-Al basic oxides. J Catal. 1998;178:499–510.

  20. Trakarnpruk W, Porntangjitlikit S. Palm oil biodiesel synthesized with potassium loaded calcined hydrotalcite and effect of biodiesel blend on elastomer properties. Renew Energy. 2008;33:1558–63.

    Article  CAS  Google Scholar 

  21. Xu C, Suna J, Zhao B, Liu Q. On the study of KF/Zn(Al)O catalyst for biodiesel production from vegetable oil. Appl Catal B. 2010;99:111–7.

    Article  CAS  Google Scholar 

  22. Teng G, Gao L, Xiao G, Liu H, Lv J. Biodiesel preparation from Jatropha curcas oil catalyzed by hydrotalcite loaded with K2CO3. Appl Biochem Biotechnol. 2010;162:1725–36.

    Article  CAS  Google Scholar 

  23. Salinas D, Araya P, Guerrero S. Study of potassium-supported TiO2 catalysts for the production of biodiesel. Appl Catal B. 2012;117–118:260–7.

    Article  Google Scholar 

  24. Valente JS, Hernandez-Cortez J, Cantu MS, Ferrat G, López-Salinas E. Calcined layered double hydroxides Mg–Me–Al (Me: Cu, Fe, Ni, Zn) as bifunctional catalysts. Catal Today. 2010;150:340–5.

    Article  CAS  Google Scholar 

  25. McKenzie AL, Fishel CT, Davis RJ. Investigation of the surface structure and basic properties of calcined hydrotalcites. J Catal. 1992;138:547–61.

    Article  CAS  Google Scholar 

  26. Kuśtrowski P, Chmielarz L, Bożek E, Sawalha M, Roessner F. Acidity and basicity of hydrotalcite derived mixed Mg-Al oxides studied by test reaction of MBOH conversion and temperature programmed desorption of NH3 and CO2. Mater Res Bull. 2004;39:263–81.

    Article  Google Scholar 

  27. Gravelle PC. Heat-Flow Microcalorimetry and Its Application to Heterogeneous Catalysis. Adv Catal. 1972;2:191–263.

    Google Scholar 

  28. Auroux A. Catalyst characterization, fundamental and applied catalysis, physical techniques for solid materials. In: Imelik B, Védrine JC, editors. Plenum Press. New York: 1994. p. 611–50.

  29. Cardona-Martinez N, Dumesic JA. Applications of adsorption microcalorimetry to the study of heterogeneous catalysis. Adv Catal. 1992;38:149–244.

    CAS  Google Scholar 

  30. Andersen PJ, Kung HH. Catalysis, specialist periodical reports. In: Bond GC, Webb G, editors. The Royal Society of Chemistry. London: 1994. Ch. 11.

  31. Solinas V, Ferino I. Microcalorimetric characterization of acid-basic catalysts. Catal Today. 1998;41:179–89.

    Article  CAS  Google Scholar 

  32. Tichit D, Lhouty MH, Guida A, Chiche BH, Figueras F, Auroux A, Bartalini D, Garrone E. Textural properties and catalytic activity of hydrotalcites. J Catal. 1995;151:50–9.

    Article  CAS  Google Scholar 

  33. Occelli ML, Olivier JP, Auroux A, Kalwei M, Eckert H. Basicity and porosity of a calcined hydrotalcite-type material from nitrogen porosimetry and adsorption microcalorimetry methods. Chem Mater. 2003;15:4231–8.

    Article  CAS  Google Scholar 

  34. Dussault L, Dupin JC, Dumitriu E, Auroux A, Guimon C. Microcalorimetry, TPR and XPS studies of acid–base properties of NiCuMgAl mixed oxides using LDHs as precursors. Thermochim Acta. 2005;434:93–9.

    Article  CAS  Google Scholar 

  35. Prescott HA, Li ZJ, Kemnitz E, Trunschke A, Deutsch J, Lieske H, Auroux A. Application of calcined Mg–Al hydrotalcites for michael additions: an investigation of catalytic activity and acid–base properties. J Catal. 2005;234:119–30.

    Article  CAS  Google Scholar 

  36. Dussault L, Dupin JC, Martinez H, Dumitriu E, Auroux A, Guimon C. Influence of the metal nature (Ni, Cu, Mg) on the surface acid-base properties of mixed oxides elaborated from LDH. Surf Interface Anal. 2006;38:234–7.

    Article  CAS  Google Scholar 

  37. Leóna M, Díaza E, Bennici S, Vega A, Ordóñez S, Auroux A. Adsorption of CO2 on Hydrotalcite-Derived Mixed Oxides: sorption Mechanisms and Consequences for Adsorption Irreversibility. Ind Eng Chem Res. 2010;49:3663–71.

    Article  Google Scholar 

  38. Leóna M, Díaza E, Vega A, Ordóñez S, Auroux A. Consequences of the iron–aluminium exchange on the performance of hydrotalcite-derived mixed oxides for ethanol condensation. Appl Catal B. 2011;102:590–9.

    Article  Google Scholar 

  39. Meloni D, Sini MF, Cutrufello MG, Monaci R, Rombi E, Ferino I. Characterization of the active sites in MgNiAl mixed oxides by microcalorimetry and test reaction. J Therm Anal Calorim. 2012;108:783–91.

    Article  CAS  Google Scholar 

  40. Meloni D, Sini MF, Cutrufello MG, Monaci R, Rombi E, Ferino I. Acid-base features of ex-hydrotalcites Mg-containing and Mg-free mixed oxides. J Therm Anal Calorim. 2013;112:489–98.

    Article  CAS  Google Scholar 

  41. Reichle WT. Anionic clay minerals. CHEMTECH. 1986;16:58–63.

    CAS  Google Scholar 

  42. Cantrell DG, Gillie LJ, Lee AF, Wilson K. Structure-reactivity correlations in MgAl hydrotalcitecatalysts for biodiesel synthesis. Appl Catal A Gen. 2005;287:183–90.

    Article  CAS  Google Scholar 

  43. Barrault J, Derouault A, Courtois G, Maissant JM, Dupin JC, Guimon C, Martinez H, Dumitriu E. On the catalytic properties of mixed oxides obtained from the Cu-Mg-Al LDH precursors in the process of hydrogenation of the cinnamaldehyde. Appl Catal A Gen. 2004;262:43–51.

    Article  CAS  Google Scholar 

  44. Ruthven DM. Principles of adsorption & adsorption processes. New York: Wiley; 1984.

  45. Reid RC, Pransuitz JM, Sherwood TK. The properties of gases and liquids. 3rd ed. vol 27. New York: Mc Graw-Hill; 1977. p. 403–35.

  46. Dossin TF, Reyniers MF, Marin GB. Kinetics of heterogeneously MgO-catalyzed transesterification. Appl Catal B. 2006;62:35–45.

    Article  CAS  Google Scholar 

Download references

Acknowledgements

Thanks are due to Dr Carla Cannas for TEM images.

Author information

Authors and Affiliations

  1. Dipartimento di Scienze Chimiche e Geologiche, Università di Cagliari, Complesso Universitario Monserrato, s.s. 554, Bivio per Sestu, 09042, Monserrato, CA, Italy

    D. Meloni, R. Monaci, M. G. Cutrufello, E. Rombi & I. Ferino

Authors
  1. D. Meloni
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. R. Monaci
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. M. G. Cutrufello
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. E. Rombi
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. I. Ferino
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to I. Ferino.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (PDF 123 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Meloni, D., Monaci, R., Cutrufello, M.G. et al. Adsorption microcalorimetry characterization of K-doped MgAl mixed oxide catalysts for soybean oil transesterification synthesized by impregnation and ball milling techniques. J Therm Anal Calorim 119, 1023–1036 (2015). https://doi.org/10.1007/s10973-014-4283-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10973-014-4283-4

Keywords

Search

Navigation