Advertisement

Sunflower oil transesterification with methanol using immobilized lipase enzymes

  • José María Encinar
  • Juan Félix González
  • Nuria Sánchez
  • Sergio Nogales-Delgado
Research Paper
  • 59 Downloads

Abstract

The transesterification of sunflower oil with methanol, using immobilized lipase enzymes as catalysts, was studied. The process was carried out in a semi-continuous mode. Temperature (30–50 °C), methanol flow (0.024–0.04 ml/min), kind of enzyme (Lipozyme 62350, Lipozyme TL-IM, Novozym 435 and Pseudomonas cepacia Sol–Gel-AK) and enzyme concentrations (1.25–10% by weight) were the operating variables. The final product was characterized by the EN 14214 standard. All the parameters, except for cold filter plugging point, were similar to a diesel fuel. For low methanol flows, reaction rate was proportional to methanol concentration. High flows caused catalyst deactivation. Novozyme 435, Lipozyme TL-IM and Lipozyme 62350 showed similar maximum reaction rates, but Novozyme 435 was more resistant to deactivation. Pseudomonas cepacia hardly obtained 1% conversion. The catalyst concentration, up to 2.5%, had a positive effect on the reaction rate and conversion. The optimum temperature was 40 °C. The initial reaction rate was in line with the Arrhenius law, up to 50 °C. By differential and integral methods, the Michaelis–Menten, competitive inhibition and ping-pong bi–bi kinetic parameters were determined. The transesterification of sunflower oil in a semi-continuous regime of alcohol improved the results, compared to the discontinuous regime, and those were similar to the obtained ones in a discontinuous regime with step-by-step methanol addition. The lipase that showed the best yield and higher resistance to deactivation was Novozym 435. The kinetic models that forecast the deactivation of lipases by an inhibitor described the experimental behavior properly.

Keywords

Biodiesel Catalyst Immobilized lipases Methanolysis Kinetic study 

Notes

Compliance with ethical standards

Conflict of interest

The authors declare no conflict of interest.

References

  1. 1.
    Encinar JM, González JF, Rodríguez JJ, Tejedor A (2002) Biodiesel fuels from vegetable oils: transesterification of Cynara cardunculus L. oil with ethanol. Energy Fuel 16:443–450CrossRefGoogle Scholar
  2. 2.
    Park D, Lee SY (2013) Special issue: current status of bioenergy research. Bioprocess Biosyst Eng 36:649–650CrossRefGoogle Scholar
  3. 3.
    Ghanei R, Moradi GR, Taherpourkalantari R, Arjmandzadeh E (2011) Variation of physical properties during transesterification of sunflower oil to biodiesel as an approach to predict reaction progress. Fuel Process Technol 92:1593–1598CrossRefGoogle Scholar
  4. 4.
    Srivastava A, Prasad R (2002) Triglycerides-based diesel fuels. Renew Sust Energ Rev 4:111–133CrossRefGoogle Scholar
  5. 5.
    Knothe G, Razon LF (2017) Biodiesel fuels. Progr Energy Combust Sci 58:36–59CrossRefGoogle Scholar
  6. 6.
    Reyero I, Arzamendi G, Zabala S, Gandía LM (2015) Kinetics of the NaOH-catalyzed transesterification of sunflower oil with ethanol to produce biodiesel. Fuel Process Technol 129:147–155CrossRefGoogle Scholar
  7. 7.
    Sánchez N, Sánchez R, Encinar JM, Gónzález JF, Martínez G (2015) Complete analysis of castor oil methanolysis to obtain biodiesel. Fuel 147:95–99CrossRefGoogle Scholar
  8. 8.
    Pourzolfaghar H, Abnisa F, Daud W, Aroua MK (2016) A review of the enzymatic hydroesterification process for biodiesel production. Renew Sust Energ Rev 61:245–257CrossRefGoogle Scholar
  9. 9.
    Selvakumar P, Sivashanmugam P (2017) Optimization of lipase production from organic solid waste by anaerobic digestion and its application in biodiesel production. Fuel Process Technol 165:1–8CrossRefGoogle Scholar
  10. 10.
    Ma F, Hanna MA (1999) Biodiesel production: a review. Bioresour Technol 70:1–15CrossRefGoogle Scholar
  11. 11.
    Demirbas A (2009) Progress and recent trends in biodiesel fuels. Energy Convers Manag 50:14–34CrossRefGoogle Scholar
  12. 12.
    Encinar JM, González JF, Pardal A, Martínez G (2010) Rape oil transesterification over heterogeneous catalysts. Fuel Process Technol 91:1530–1536CrossRefGoogle Scholar
  13. 13.
    Ma L, Zhou L, Jiang Y, He Y, Wang L, Gao J (2017) Lipase based static emulsions as efficient biocatalysts for biodiesel production. J Chem Technol Biotechnol 92:1248–1255CrossRefGoogle Scholar
  14. 14.
    Ye B, Qiu F, Sun C, Li Y, Yang D (2014) Biodiesel production from soybean oil using heterogeneous solid base catalyst. J Chem Technol Biotechnol 89:988–997CrossRefGoogle Scholar
  15. 15.
    Gog A, Roman M, Tosa M, Paizs C, Irimie FD (2015) Biodiesel production using enzymatic transesterification. Current state and perspectives. Renew Energy 39:10–16CrossRefGoogle Scholar
  16. 16.
    Banković-Ilić IB, Stamenković OS, Veljković VB (2012) Biodiesel production from non-edible plant oils. Renew Sust Energ Rev 16:3621–3647CrossRefGoogle Scholar
  17. 17.
    Verma P, Sharma MP, Dwivedi G (2016) Impact of alcohol on biodiesel production and properties. Renew Sust Energ Rev 56:319–333CrossRefGoogle Scholar
  18. 18.
    Lam MK, Lee KT, Mohamed AR (2010) Homogeneous, heterogeneous and enzymatic catalysis for transesterification of high free fatty acid oil (waste cooking oil) to biodiesel: A review. Biotechnol Adv 28:500–518CrossRefGoogle Scholar
  19. 19.
    Babaki M, Yousefi M, Habibi Z, Brask J, Mohammadi M (2015) Preparation of highly reusable biocatalysts by immobilization of lipases on epoxy-functionalized silica for production of biodiesel from canola oil. Biochem Eng J 101:23–31CrossRefGoogle Scholar
  20. 20.
    Kuo CH, Peng LT, Kan SC, Liu YC, Shieh CJ (2013) Lipase immobilized biocatalytic membranes for biodiesel production. Bioresour Technol 145:229–232CrossRefGoogle Scholar
  21. 21.
    Zhao X, Qi F, Yuan C, Du W, Liu D (2015) Lipase-catalyzed process for biodiesel production: enzyme immobilization, process simulation and optimization. Renew Sust Energ Rev 44:182–197CrossRefGoogle Scholar
  22. 22.
    Kalantari M, Kazemeini M, Arpanaei A (2013) Evaluation of biodiesel production using lipase immobilized on magnetic silica nanocomposite particles of various structures. Biochem Eng J 79:267–273CrossRefGoogle Scholar
  23. 23.
    Lotti M, Pleiss J, Valero F, Ferrer P (2015) Effects of methanol on lipases: molecular, kinetic and process issues in the production of biodiesel. Biotechnol J 10:22–30CrossRefGoogle Scholar
  24. 24.
    Martínez G, Sánchez N, Encinar JM, González JF (2014) Fuel properties of biodiesel from vegetable oils and oil mixtures. Influence of methyl esters distribution. Biomass Bioenergy 63:22–32CrossRefGoogle Scholar
  25. 25.
    Encinar JM, Pardal A, Sánchez N (2016) An improvement to the transesterification process by the use of co-solvents to produce biodiesel. Fuel 166:51–58CrossRefGoogle Scholar
  26. 26.
    Encinar JM, Pardal A, Martínez G (2012) Transesterification of rapeseed oil in subcritical methanol conditions. Fuel Process Technol 94:40–46CrossRefGoogle Scholar
  27. 27.
    Encinar JM, González JF, Pardal A (2012) Transesterification of castor oil under ultrasonic irradiation conditions. Preliminary results. Fuel Process Technol 103:9–15CrossRefGoogle Scholar
  28. 28.
    Encinar JM, González JF, Martínez G, Sánchez N, Pardal A (2012) Soybean oil transesterification by the use of a microwave flow system. Fuel 95:386–393CrossRefGoogle Scholar
  29. 29.
    Encinar JM, González JF, Martínez G, Román S (2009) Catalytic pyrolysis of exhausted olive oil waste. J Anal Appl Pyrolysis 85:197–203CrossRefGoogle Scholar
  30. 30.
    Prankl H (2002) High biodiesel quality required by European standards. Eur J Lipid Sci Technol 104:371–375CrossRefGoogle Scholar
  31. 31.
    Amini Z, Ilham Z, Ong HC, Mazaheri H, Chen W (2017) State of the art and prospective of lipase-catalyzed transesterification reaction for biodiesel production. Energy Convers Manag 141:339–353CrossRefGoogle Scholar
  32. 32.
    Yadav GD, Manjula Devi K (2004) Immobilized lipase-catalysed esterification and transesterification reactions in non-aqueous media for the synthesis of tetrahydrofurfuryl butyrate: comparison and kinetic modeling. Chem Eng Sci 59:373–383CrossRefGoogle Scholar
  33. 33.
    Guldhe A, Singh B, Mutanda T, Permaul K, Bux F (2015) Advances in synthesis of biodiesel via enzyme catalysis: novel and sustainable approaches. Renew Sust Energ Rev 41:1447–1464CrossRefGoogle Scholar
  34. 34.
    Vicente G, Martinez M, Aracil J (2004) Integrated biodiesel production: a comparison of different homogeneous catalysts systems. Bioresour Technol 92:297–305CrossRefGoogle Scholar
  35. 35.
    Saydut A, Erdogan S, Beycar Kalafar A, Kaya C, Aydin F, Hamamci C (2016) Process optimization for production of biodiesel from hazelnut oil, sunflower oil and their hybrid feedstock. Fuel 183:512–517CrossRefGoogle Scholar
  36. 36.
    Zuleta E, Rios LA, Benjumea PN (2012) Oxidative stability and cold flow behavior of palm, sacha-inchi, jatropha and castor oil biodiesel blends. Fuel Process Technol 102:96–101CrossRefGoogle Scholar
  37. 37.
    Lv P, Cheng Y, Yang L, Yuan Z, Li H, Luo W (2013) Improving the low temperature flow properties of palm oil biodiesel: addition of cold flow improver. Fuel Process Technol 110:61–64CrossRefGoogle Scholar
  38. 38.
    Cardone M, Mazzoncini M, Manini S, Rocco V, Senatore A, Seggiani M, Vitolo S (2003) Brassica carinata as an alternative oil crop production of biodiesel in Italy: agronomic evaluation, fuel production by transesterification and characterization. Biomass Bioenergy 25:623–636CrossRefGoogle Scholar
  39. 39.
    Drauz K, Waldmann H (2002) Enzyme catalysis in organic synthesis, 2nd edn. Wiley-VCH, WeinheimCrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • José María Encinar
    • 1
  • Juan Félix González
    • 2
  • Nuria Sánchez
    • 1
  • Sergio Nogales-Delgado
    • 1
  1. 1.Department of Chemical Engineering and Physical ChemistryUniversity of ExtremaduraBadajozSpain
  2. 2.Department of Applied Physics, Industrial Engineering SchoolUniversity of ExtremaduraBadajozSpain

Personalised recommendations