Enzymatic esterification/transesterification of rice bran acid oil for subsequent γ-oryzanol recovery

Document Type : Research Paper

Authors

1 Department of Biotechnology, Faculty of Engineering and Industrial Technology, Silpakorn University, Amphoe Muang, Nakhon Pathom 73000, Thailand.

2 Bio-Circular-Green-economy Technology & Engineering Center, BCGeTEC, Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn University, Phayathai Road, Patumwan, Bangkok 10330, Thailand.

3 School of Chemical Engineering, College of Engineering, Universiti Teknologi MARA (UiTM), 40450 Shah Alam, Selangor, Malaysia.

Abstract

This study recovered γ-oryzanol from rice bran acid oil (RBAO), following an initial enzymatic esterification/transesterification to selectively convert its glyceride impurities into fatty acid ethyl esters (FAEEs) or biodiesel. γ-oryzanol was then deprotonated and separated from the biodiesel into the resulting aqueous phase via acid-base extraction. Herein, we determine the effects of varying reaction conditions, i.e., ethanol:RBAO molar ratio, temperature, reaction time, enzyme loading, and agitation speed, on the degrees of glyceride removal, γ-oryzanol loss, free fatty acid (FFA) remaining, and biodiesel content. Up to 100% glyceride removal was achieved with a relatively high biodiesel yield (84%) and γ-oryzanol loss as low as 26% under our most suitable reaction conditions (5:1 ethanol:RBAO molar ratio, 40 °C, 24 h reaction time, 10%wt enzyme loading, 200 rpm agitation). Furthermore, of the remaining oryzanol, up to 94% was recovered by the acid-base extraction with 2-4 M ethanolic NaOH solution. Our results suggest that a combination of enzymatic esterification/transesterification with subsequent acid-base extraction offers an efficient alternative approach to the simultaneous production of biodiesel and γ-oryzanol recovery from low-cost RBAO. Based on our analysis of techno-economic and environmental sustainability, integration of the present method into a rice bran oil refinery would make the process profitable, with the minimum use of toxic chemicals and energy.

Graphical Abstract

Enzymatic esterification/transesterification of rice bran acid oil for subsequent γ-oryzanol recovery

Highlights

  • Rice bran acid oil is esterified/transesterified before γ-oryzanol extraction.
  • Suitable conditions for enzymatic esterification/transesterification are found.
  • 100% glyceride removal is achieved with high biodiesel yield and low γ-oryzanol loss.
  • γ-oryzanol in biodiesel was efficiently recovered using acid-base extraction.
  • The highest γ-oryzanol recovery (94%) was achieved by a 2-4 M ethanolic NaOH solution.

Keywords

References

  1. Aguieiras, E.C., Cavalcanti-Oliveira, E.D., de Castro, A.M., Langone, M.A., Freire, D.M., 2017. Simultaneous enzymatic transesterification and esterification of an acid oil using fermented solid as biocatalyst. J. Am. Oil Chem. Soc. 94(4), 551-558.
  2. Akkarawatkhoosith, N., Tongtummachat, T., Kaewchada, A., Jaree, A., 2021. Non-catalytic and glycerol-free biodiesel production from rice bran oil fatty acid distillate in a microreactor. Energy Convers. Manage.: X 11, 100096.
  3. Al-Zuhair, S., Ramachandran, K.B., Hasan, M., 2008. Effect of enzyme molecules covering of oil-water interfacial area on the kinetic of oil hydrolysis. Chem. Eng. J. 139(3), 540-548.
  4. Amelia, Song, C.P., Chang, M.Y., Adiiba, S.H., Chan, E.S., 2023. Retention of high-value tocols during enzymatic esterification of palm fatty acid distillate using liquid lipase for improving the economics and sustainability of biodiesel production. Ind. Crops Prod. 194, 116271.
  5. Anjinta, A., Usaku, C., Boonnoun, P., Daisuk, P., Shotipruk, A., 2023. Method Development for Purification of γ-oryzanol from Hydrolyzed Rice Bran Acid Oil by Semi-preparative Chromatography. J. Oleo Sci. 72(1), 39-47.
  6. Balat, M., 2011. Potential alternatives to edible oils for biodiesel production-a review of current work. Energy Convers. Manage. 52(2), 1479-1492.
  7. Bhaskaragoud, G., Rajath, S., Mahendra, V.P., Kumar, G.S., Krishna, A.G., Kumar, G.S., 2016. Hypolipidemic mechanism of oryzanol components- ferulic acid and phytosterols. Biochem. Biophys. Res. Commun. 476(2), 82-89.
  8. Brenna, E., De Fabritiis, V., Parmeggiani, F., Tentori, F., Tessaro, D., 2023. Lipase-mediated synthesis of oleoyl ethanolamide starting from high-oleic sunflower oil soapstock. ACS Sustainable Chem. Eng. 11(7), 2764-2772.
  9. Business Development Bank of Canada, 2023. Gross profit margin.
  10. Chandra, P., Enespa, Singh, R., Arora, P.K., 2020. Microbial lipases and their industrial applications: a comprehensive review. Microb. Cell Fact. 19, 169.
  11. Cheng, C., Jiang, T., Wu, Y., Cui, L., Qin, S., He, B., 2018. Elucidation of lid open and orientation of lipase activated in interfacial activation by amphiphilic environment. Int. J. Biol. Macromol. 119, 1211-1217.
  12. Chigorimbo-Murefu, N.T.L., Riva, S., Burton, S.G., 2009. Lipase-catalysed synthesis of esters of ferulic acid with natural compounds and evaluation of their antioxidant properties. J. Mol. Catal. B: Enzym. 56(4), 277-282.
  13. Choi, N., Lee, J.S., Kwak, J., Lee, J., Kim, I.H., 2016. Production of biodiesel from acid oil via a two-step enzymatic transesterification. J. Oleo Sci. 65(11), 913-921.
  14. Compton, D.L., Laszlo, J.A., Berhow, M.A., 2000. Lipase-catalyzed synthesis of ferulate esters. J. Am. Oil Chem. Soc. 77, 513-519.
  15. Das, P.K., Chaudhuri, A., Kaimal, T.N.B., Bhalerao, U.T., 1999. Process for the isolation of oryzanols from crude dark acid oil (rice bran). U.S. Patent 5,869,708.
  16. Das, P.K., Chaudhuri, A., Kaimal, T.N.B., Bhalerao, U.T., 1998. Isolation of γ-oryzanol through calcium ion induced precipitation of anionic micellar aggregates. J. Agric. Food Chem. 46(8), 3073-3080.
  17. Deleuze, H., Langrand, G., Millet, H., Baratti, J., Buono, G., Triantaphylides, C., 1987. Lipase-catalyzed reactions in organic media: competition and applications. Biochim. Biophys. Acta - Protein Struct. Mol. Enzymol. 911(1), 117-120.
  18. dos Santos, K.C., Hamerski, F., Pedersen Voll, F.A., Corazza, M.L., 2018. Experimental and kinetic modeling of acid oil (trans)esterification in supercritical ethanol. Fuel. 224, 489-498.
  19. Ghosh, S., Bhattacharyya, D.K., 1995. Utilization of acid oils in making valuable fatty products by microbial lipase technology. J. Am. Oil Chem. Soc. 72, 1541-1544.
  20. Goswami, D., De, S., Basu, J.K., 2012. Effects of process variables and additives on mustard oil hydrolysis by porcine pancreas lipase. Braz. J. Chem. Eng. 29(3), 449-460.
  21. Griffin, J.M., Atherton, J.H., Page, M.I., Powles, N.T., 2016. Lipase catalysed conversion of triglycerides to amides in liquid ammonia. J. Phys. Org. Chem. 29(12), 768-772.
  22. Hakala, P., Lampi, A.M., Ollilainen, V., Werner, U., Murkovic, M., Wähälä, K., Karkola, S., Piironen, V., 2002. Steryl phenolic acid esters in cereals and their milling fractions. J. Agric. Food Chem. 50(19), 5300-5307.
  23. Hoang, A.T., Tabatabaei, M., Aghbashlo, M., Carlucci, A.P., Ölçer, A.I., Le, A.T., Ghassemi, A., 2021. Rice bran oil-based biodiesel as a promising renewable fuel alternative to petrodiesel: a review. Renew. Sust. Energy Rev. 135, 110204.
  24. Ito, J., Sawada, K., Ogura, Y., Xinyi, F., Rahmania, H., Mohri, T., Kohyama, N., Kwon, E., Eitsuka, T., Hashimoto, H., Kuwahara, S., Miyazawa, T., Nakagawa, K., 2019. Definitive evidence of the presence of 24-methylenecycloartanyl ferulate and 24-methylenecycloartanyl caffeate in barley. Sci. Rep. 9(1), 12572.
  25. Jesus, S.P., Grimaldi, R., Hense, H., 2010. Recovery of γ-oryzanol from rice bran oil byproduct using supercritical fluid extraction. J. Supercrit. Fluids. 55(1), 149-155.
  26. Ju, Y.H., Zullaikah, S., 2013. Effect of acid-catalyzed methanolysis on the bioactive components of rice bran oil. J. Taiwan Inst. Chem. Eng. 44(6), 924-928.
  27. Kaewboonnum, P., Vechpanich, J., Santiwattana, P., Shotipruk, A., 2010. γ-Oryzanol recovery from rice bran oil soapstock. Sep. Sci. Technol. 45(9), 1186-1195.
  28. Kamal, M.Z., Yedavalli, P., Deshmukh, M. V, Rao, N.M., 2013. Lipase in aqueous-polar organic solvents: activity, structure, and stability. Protein Sci. 22(7), 904-915.
  29. Krishna, A.G.G., Khatoon, S., Shiela, P.M., Sarmandal, C.V, Indira, T.N., Mishra, A., 2001. Effect of refining of crude rice bran oil on the retention of oryzanol in the refined oil. J. Am. Oil Chem. Soc. 78(2), 127-131.
  30. Kulkarni, M.G., Gopinath, R., Meher, L.C., Dalai, A.K., 2006. Solid acid catalyzed biodiesel production by simultaneous esterification and transesterification. Green Chem. 8(12), 1056-1062.
  31. Laleh, P., Yaser, K., Alireza, O., 2019. Oleoylethanolamide: a novel pharmaceutical agent in the management of obesity-an updated review. J. Cell. Physiol. 234(6), 7893-7902.
  32. Ma, L., Persson, M., Adlercreutz, P., 2002. Water activity dependence of lipase catalysis in organic media explains successful transesterification reactions. Enzyme Microb. Technol. 31(7), 1024-1029.
  33. Manova, D., Gallier, F., Tak-Tak, L., Yotava, L., Lubin-Germain, N., 2018. Lipase-catalyzed amidation of carboxylic acid and amines. Tetrahedron Lett. 59(21), 2086-2090.
  34. Marchetti, J.M., Errazu, A.F., 2008. Esterification of free fatty acids using sulfuric acid as catalyst in the presence of triglycerides. Biomass Bioenergy. 32(9), 892-895.
  35. Meedam, A., Usaku, C., Daisuk, P., Shotipruk, A., 2022. Comparative study on physicochemical hydrolysis methods for glycerides removal from rice bran acid oil for subsequent γ-oryzanol recovery. Biomass Convers. Biorefin. 12, 245-252.
  36. Minatel, I.O., Francisqueti, F.V., Corrêa, C.R., Lima, G.P.P., 2016. Antioxidant activity of γ-oryzanol: a complex network of interactions. Int. J. Mol. Sci. 17(8), 1107.
  37. Monteiro, R.R.C., Arana-Peña, S., da Rocha, T.N., Miranda, L.P., Berenguer-Murcia, Á., Tardioli, P.W., dos Santos, J.C.S., Fernandez-Lafuente, R., 2021. Liquid lipase preparations designed for industrial production of biodiesel. Is it really an optimal solution?. Renew. Energy. 164, 1566-1587.
  38. Murphy, C.B., 2022. How Do Gross Profit and Gross Margin Differ?. Investopedia.
  39. Naylor, R.L., Higgins, M.M., 2017. The political economy of biodiesel in an era of low oil prices. Renew. Sust. Energy Rev. 77, 695-705.
  40. Noor, I.., Hasan, M., Ramachandran, K.., 2003. Effect of operating variables on the hydrolysis rate of palm oil by lipase. Process Biochem. 39(1), 13-20.
  41. Piacentini, E., Mazzei, R., Giorno, L., 2021. Comparison between lipase performance distributed at the O/W interface by membrane emulsification and by mechanical stirring. Membranes. 11(2), 137.
  42. Raghuvanshi, S., Gupta, R., 2010. Advantages of the immobilization of lipase on porous supports over free enzyme. Protein Pept. Lett. 17(11), 1412-1416.
  43. Reis, P., Holmberg, K., Watzke, H., Leser, M.E., Miller, R., 2009a. Lipases at interfaces: a review. Adv. Colloid Interface Sci. 147-148, 237-250.
  44. Reis, P., Miller, R., Leser, M., Watzke, H., 2009b. Lipase-catalyzed reactions at interfaces of two-phase systems and microemulsions. Appl. Biochem. Biotechnol. 158, 706-721.
  45. Ribeiro, B.D., de Castro, A.M., Coelho, M.A.Z., Freire, D.M.G., 2011. Production and use of lipases in bioenergy: a review from the feedstocks to biodiesel production. Enzyme Res. 2011, 615803.
  46. Sombutsuwan, P., Nakornsadet, A., Aryusuk, K., Akepratumchai, S., Jeyashoke, N., Lilitchan, S., Krisnangkura, K., 2018. Recovery of γ-oryzanol from rice bran acid oil by an acid-base extraction method with the assistance of response surface methodology. J. Oleo Sci. 67(11), 1405-1415.
  47. Szcześniak, K.A., Ostaszewski, P., Ciecierska, A., Sadkowski, T., 2016. Investigation of nutriactive phytochemical-gamma-oryzanol in experimental animal models. J. Anim. Physiol. Anim. Nutr. 100(4), 601-617.
  48. Thai Edible Oil Co. Ltd., 2018. Price of rice bran acid oil in Thailand.
  49. Urrutia, C., Sangaletti-Gerhard, N., Cea, M., Suazo, A., Aliberti, A., Navia, R., 2016. Two step esterification-transesterification process of wet greasy sewage sludge for biodiesel production. Bioresour. Technol. 200, 1044-1049.
  50. Van Hoed, V., Depaemelaere, G., Ayala, J.V., Santiwattana, P., Verhé, R., De Greyt, W., 2006. Influence of chemical refining on the major and minor components of rice bran oil. J. Am. Oil Chem. Soc. 83(4), 315-321.
  51. van Rantwijk, F., Hacking, M.A.P.J., Sheldon, R.A., 2000. Lipase-catalyzed synthesis of carboxylic amides: Nitrogen nucleophiles as acyl acceptor. Biocatalysis. 131, 23-43.
  52. Vaysse, L., Ly, A., Moulin, G., Dubreucq, E., 2002. Chain-length selectivity of various lipases during hydrolysis, esterification and alcoholysis in biphasic aqueous medium. Enzyme Microb. Technol. 31(5), 648-655.
  53. Wang, Xiaosan, Wang, Xingguo, Wang, T., 2017. An effective method for reducing free fatty acid content of high-acid rice bran oil by enzymatic amidation. J. Ind. Eng. Chem. 48, 119-124.
  54. Wongwaiwech, D., Weerawatanakorn, M., Tharatha, S., Ho, C.T., 2019. Comparative study on amount of nutraceuticals in by-products from solvent and cold pressing methods of rice bran oil processing. J. food drug Anal. 27(1), 71-82.
  55. Yusoff, M.F.M., Xu, X., Guo, Z., 2014. Comparison of fatty acid methyl and ethyl esters as biodiesel base stock: a review on processing and production requirements. J. Am. Oil Chem. Soc. 91, 525-531.
  56. Zaidel, D.N.A., Muhamad, I.I., Daud, N.S.M., Muttalib, N.A.A., Khairuddin, N., Lazim, N.A.M., 2019. 18-Production of biodiesel from rice bran oil, in: Biomass, Biopolymer-Based Materials, and Bioenergy: Construction, Biomedical, and Other Industrial Applications. 409-447.
  57. Zuyi, L., Ward, O.P., 1993. Stability of microbial lipase in alcoholysis of fish oil during repeated enzyme use. Biotechnol. Lett. 15, 393-398.

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