Skip to main content
Log in

Reduction of Free Fatty Acids in Acidic Nonedible Oils by Modified K10 Clay

  • Original Paper
  • Published:
Journal of the American Oil Chemists' Society

Abstract

Biodiesel is a biofuel obtained from vegetable oils. The oils used as raw materials are usually refined edible vegetable oils. Nonedible acidic oils are unsuitable for biodiesel production unless reduction of the high content in free fatty acids (FFA) of these materials had been achieved. Obtaining a good raw material from unprofitable oils becomes an important research field. Additionally clays have a long history in industrial sorption and catalysis, some being commercially available and with properties that can be modified. In this work we present the results of the use of the montmorillonite clay K10 and two acid modified clays K10(I) and K10(II), in the esterification of stearic acid with methanol and 95 % of methyl stearate was obtained with K10(II). These clays were then used for the first time to reduce the acidity of enhanced FFA sunflower oil and they show to be very effective. Reduction of FFA from 11 to 4 % was obtained with K10(II) mainly due to 94 % conversion of FFA into fatty acid methyl esters (FAME). These clays were also tested with two waste oils, one from domestic use and the other gathered from different restaurants, and showed their ability to lower the acidity of these oils. Reactions were followed by 1H NMR as well as quantitative determination of FFA and FAME. Clays were characterized by FTIR and XRD.

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

Similar content being viewed by others

References

  1. Demirbas A (2008) Biodiesel, a realistic fuel alternative for diesel engines. Springer, London

    Google Scholar 

  2. Ma F, Hanna MA (1999) Biodiesel production: a review. Bioresour Technol 70:1–15

    Article  CAS  Google Scholar 

  3. van Gerpen JV (2005) Biodiesel processing and production. Fuel Process Technol 86:1097–1107

    Article  Google Scholar 

  4. Murugesan A, Umarani C, Chinnusamy TR, Krishnan M, Subramanian R, Neduzchezhain N (2009) Production and analysis of bio-diesel from non-edible oils—A review. Renew Sustain Energy Rev 13:825–834

    Article  CAS  Google Scholar 

  5. Meher LC, Sagar DV, Naik SN (2006) Technical aspects of biodiesel production by transesterification—a review. Renew Sustain Energy Rev 10:248–268

    Article  CAS  Google Scholar 

  6. Di Serio M, Tesser R, Lu Pengmei L, Santacesaria E (2008) Heterogeneous catalysts for biodiesel production. Energy Fuels 22:207–217

    Article  Google Scholar 

  7. De Stefanis A, Tomlinson AAG (2006) Towards designing pillared clays for catalysis. Catal Today 114:126–141

    Article  Google Scholar 

  8. Velde B (1992) Introduction to clay minerals. Chapman and Hall, London

    Book  Google Scholar 

  9. Kuźniarska-Biernacka I, Pereira C, Carvalho AP, Pires J, Freire C (2011) Epoxidation of olefins catalyzed by manganese(III) salen complexes grafted to porous heterostructured clays. Applied Clay Science (article in press) doi:10.1016/j.clay.2010.12.0

  10. Issariyakul T, Dalai AK (2010) Biodiesel production from greenseed canola oil. Energy Fuels 24:4652–4658

    Article  CAS  Google Scholar 

  11. Neji BS, Trabelsi M, Frikha MH (2009) Esterification of fatty acids with short-chain alcohols over commercial acid clays in a semi-continuous reactor. Energies 2(4):1107–1117

    Article  CAS  Google Scholar 

  12. Weller MT (1994) Inorganic materials chemistry. Oxford Science Publications, Oxford

    Google Scholar 

  13. Kuźniarska-Biernacka I, Pereira C, Carvalho AP, Pires J, Freire C (2009) K10-Montmorillonite as support for a cationic Manganese(III)-salen complex. J Braz Chem Soc 20(7):1320–1326

    Google Scholar 

  14. Espantaleo AG, Nieto JÁ, Fernandez M, Marsal A (2003) Use of activated clays in the removal of dyes and surfactants from tannery waste waters. Appl Clay Sci 24:105–110

    Article  Google Scholar 

  15. Satyarthi JK, Srinivas D, Ratnasamy P (2009) Estimation of free fatty acid content in oils, fats, and biodiesel by 1H NMR spectroscopy. Energy Fuels 23:2273–2277

    Article  CAS  Google Scholar 

  16. Gelbard G, Bres O, Vargas RM, Vielfaure F, Schuchardt UF (1995) 1H nuclear magnetic resonance determination of the yield of the transesterification of rapeseed oil with methanol. J Am Oil Chem Soc 72(10):1239–1241

    Article  CAS  Google Scholar 

  17. Guillén MD, Ruiz A (2001) High resolution 1H nuclear magnetic resonance in the study of edible oils and fats. Trends Food Sci Technol 12:328–338

    Article  Google Scholar 

  18. van den Berg JDJ, van den Berg KJ, Boon JB (2002) Identification of non-cross-linked compounds in methanolic extracts of cured and aged linseed oil-based paint films using gas chromatography-mass spectrometry. J Chromatogr A 950:195–211

    Article  Google Scholar 

  19. Grim RE (1968) Clay Mineralogy. McGraw-Hill, New York

    Google Scholar 

  20. Sasra E, Bergaya F, Fripiat JJ (1994) Infrared spectroscopy study of tetrahedral and octahedral substitutions in an interstratified illite-smectite clay. Clays Clay Miner 42(3):237–241

    Article  Google Scholar 

  21. Schroeder PA (2002) Infrared Spectroscopy in clay science. In: Rule A, Guggenheim S (eds) CMS Workshop Lectures, vol. 11. Teaching Clay Science, The Clay Mineral Society, Aurora, pp 181–206

  22. Kris-Ethertona PM, Griela AE, Psotaa TL, Gebauera SK, Zhanga J, Ethertona TD (2005) Dietary stearic acid and risk of cardiovascular disease: intake, sources, digestion, and absorption. Lipids 40:1193–1200

    Article  Google Scholar 

  23. Schmid A (2011) The role of meat fat in the human diet. Crit Rev Food Sci Nutr 51:50–66

    Article  Google Scholar 

  24. Chung KH, Chang DK, Park BG (2008) Removal of free fatty acid in waste frying oil by esterification with methanol on zeolite catalyst. Bioresour Technol 99:7438–7443

    Article  CAS  Google Scholar 

  25. Dokic M, Kesic K, Krstic J, Jovanovic D, Skala D (2012) Decrease of free fatty acid content in vegetable oil using silica supported ferric sulfate catalyst. Fuel 97:595–602

    Article  CAS  Google Scholar 

  26. Zatta L, Ramos LP, Wypych F (2012) Acid activated montmorillonite as catalyst in methyl esterification reactions of lauric acid. J Oleo Sci 61(9):497–504

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This work was carried out under FCT (Portugal) funding for the PEst-OE/QUI/UI0612/2011project.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to M. Eduarda M. Araújo.

About this article

Cite this article

Pires, J., Brasil, B. & Araújo, M.E.M. Reduction of Free Fatty Acids in Acidic Nonedible Oils by Modified K10 Clay. J Am Oil Chem Soc 90, 555–561 (2013). https://doi.org/10.1007/s11746-012-2192-x

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11746-012-2192-x

Keywords

Navigation