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Synthesis of Geraniol Esters in a Continuous-Flow Packed-Bed Reactor of Immobilized Lipase: Optimization of Process Parameters and Kinetic Modeling

Applied Biochemistry and Biotechnology volume 184, pages 630–643 (2018)Cite this article

Abstract

With increasing demand for perfumes, flavors, beverages, and pharmaceuticals, the various associated industries are resorting to different approaches to enhance yields of desired compounds. The use of fixed-bed biocatalytic reactors in some of the processes for making fine chemicals will be of great value because the reaction times could be reduced substantially as well as high conversion and yields obtained. In the current study, a continuous-flow packed-bed reactor of immobilized Candida antarctica lipase B (Novozym 435) was employed for synthesis of various geraniol esters. Optimization of process parameters such as biocatalyst screening, effect of solvent, mole ratio, temperature and acyl donors was studied in a continuous-flow packed-bed reactor. Maximum conversion of ~ 87% of geranyl propionate was achieved in 15 min residence time at 70 °C using geraniol and propionic acid with a 1:1 mol ratio. Novozym 435 was found to be the most active and stable biocatalyst among all tested. Ternary complex mechanism with propionic acid inhibition was found to fit the data.

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References

  1. World Demand for Flavor, Fragrances to Exceed $26 Billion in 2020. (2016). Retrieved 3 February 2017, from http://www.preparedfoods.com/articles/118094-world-demand-for-flavor-fragrances-to-exceed-26-billion-in-2020.

  2. Yadav, G. D., & Lathi, P. S. (2003). Kinetics and mechanism of synthesis of butyl isobutyrate over immobilised lipases. Biochemical Engineering Journal, 16(3), 245–252.

    CAS  Article  Google Scholar 

  3. Jakovetić, S. M., Jugović, B. Z., Gvozdenović, M. M., Bezbradica, D. I., Antov, M. G., Mijin, D. Z., & Knezevic-Jugovic, Z. D. (2013). Synthesis of aliphatic esters of cinnamic acid as potential lipophilic antioxidants catalyzed by lipase B from Candida antarctica. Applied Biochemistry and Biotechnology, 170(7), 1560–1573.

    Article  Google Scholar 

  4. Shinde, S. D., & Yadav, G. D. (2014). Microwave irradiated immobilized lipase catalyzed synthesis of alkyl benzoate esters by transesterification: mechanism and kinetic modeling. Industrial and Engineering Chemistry Research, 53(21), 8706–8713.

    CAS  Article  Google Scholar 

  5. Paroul, N., Grzegozeski, L. P., Chiaradia, V., Treichel, H., Cansian, R. L., Oliveira, J. V., & De Oliveira, D. (2012). Solvent-free production of bioflavors by enzymatic esterification of citronella (Cymbopogon winterianus) essential oil. Applied Biochemistry and Biotechnology, 166(1), 13–21.

    CAS  Article  Google Scholar 

  6. Kamble, M. P., Shinde, S. D., & Yadav, G. D. (2016). Kinetic resolution of (R,S)-α-tetralol catalyzed by crosslinked Candida antarctica lipase B enzyme supported on mesocellular foam: a nanoscale enzyme reactor approach. Journal of Molecular Catalysis B: Enzymatic, 132, 61–66.

    CAS  Article  Google Scholar 

  7. Gotor-Fernández, V., Busto, E., & Gotor, V. (2006). Candida antarctica lipase B: an ideal biocatalyst for the preparation of nitrogenated organic compounds. Advanced Synthesis and Catalysis, 348(7–8), 797–812.

    Article  Google Scholar 

  8. Isah, A. A., Mahat, N. A., Jamalis, J., Attan, N., Zakaria, I. I., Huyop, F., & Abdul, R. (2017). Synthesis of geranyl propionate in a solvent-free medium using Rhizomucor miehei lipase covalently immobilized on chitosan–graphene oxide beads. Preparative Biochemistry and Biotechnology, 47(2), 199–210.

    CAS  Article  Google Scholar 

  9. Nicoletti, G., Cipolatti, E. P., Valério, A., Carbonera, N. G., Soares, N. S., Theilacker, E., et al. (2015). Evaluation of different methods for immobilization of Candida antarctica lipase B (CalB lipase) in polyurethane foam and its application in the production of geranyl propionate. Bioprocess and Biosystems Engineering, 38(9), 1739–1748.

    CAS  Article  Google Scholar 

  10. Mohamad, N., Huyop, F., Aboul-Enein, H. Y., Mahat, N. A., & Wahab, R. A. (2015). Response surface methodological approach for optimizing production of geranyl propionate catalysed by carbon nanotubes nanobioconjugates. Biotechnology & Biotechnological Equipment, 29(4), 732–739.

    CAS  Article  Google Scholar 

  11. Paroul, N., Grzegozeski, L. P., Chiaradia, V., Treichel, H., Cansian, R. L., Oliveira, J. V., & De Oliveira, D. (2010). Production of geranyl propionate by enzymatic esterification of geraniol and propionic acid in solvent-free system. Journal of Chemical Technology and Biotechnology, 85(12), 1636–1641.

    CAS  Article  Google Scholar 

  12. Ferraz, L. I. R., Possebom, G., Valandro Alvez, E., Luiz Cansian, R., Paroul, N., de Oliveira, D., & Treichel, H. (2015). Application of home-made lipase in the production of geranyl propionate by esterification of geraniol and propionic acid in solvent-free system. Biocatalysis and Agricultural Biotechnology, 4(1), 44–48.

    Article  Google Scholar 

  13. Etchells, J. C. (2005). Process intensification. Process Safety and Environmental Protection, 83(2), 85–89.

    CAS  Article  Google Scholar 

  14. Cvjetko, M., Vorkapic-Furac, Z.-P., & P. (2012). Isoamyl acetate synthesis in imidazolium-based ionic liquids using packed bed enzyme microreactor. Process Biochemistry, 47(9), 1344–1350.

    CAS  Article  Google Scholar 

  15. Ma, B. D., Yu, H. L., Pan, J., & Xu, J. H. (2016). High-yield production of enantiopure 2-hydroxy-2-(2′-chlorophenyl) acetic acid by long-term operation of a continuous packed bed reactor. Biochemical Engineering Journal, 107, 45–51.

    CAS  Article  Google Scholar 

  16. Ganguly, S., & Nandi, S. (2015). Process optimization of lipase catalyzed synthesis of diesters in a packed bed reactor. Biochemical Engineering Journal, 102, 2–5.

    CAS  Article  Google Scholar 

  17. Couto, R., Vidinha, P., Peres, C., Ribeiro, A. S., Ferreira, O., Oliveira, M. V., et al. (2011). Geranyl acetate synthesis in a packed-bed reactor catalyzed by novozym in supercritical carbon dioxide and in supercritical ethane. Industrial and Engineering Chemistry Research, 50(4), 1938–1946.

    CAS  Article  Google Scholar 

  18. Damnjanović, J. J., Žuža, M. G., Savanović, J. K., Bezbradica, D. I., Mijin, D. Ž., Bošković-Vragolović, N., & Knežević-Jugovića, Z. D. (2012). Covalently immobilized lipase catalyzing high-yielding optimized geranyl butyrate synthesis in a batch and fluidized bed reactor. Journal of Molecular Catalysis B: Enzymatic, 75, 50–59.

    Article  Google Scholar 

  19. Shinde, S. D., & Yadav, G. D. (2014). Insight into microwave-assisted lipase catalyzed synthesis of geranyl cinnamate: optimization and kinetic modeling. Applied Biochemistry and Biotechnology, 175(4), 2035–2049.

    Article  Google Scholar 

  20. Patel, V., Shah, C., Deshpande, M., & Madamwar, D. (2016). Zinc oxide nanoparticles supported lipase immobilization for biotransformation in organic solvents: a facile synthesis of geranyl acetate, effect of operative variables and kinetic study. Applied Biochemistry and Biotechnology, 178(8), 1630-1651.

  21. Tang, X. H., Li, B. J., Han, C. L., Wang, J., & Li, C. W. (2012). Preparation of mesoporous MCM-41 in open-vessel for catalytic synthesis of geranyl propionate. Advanced Materials Research, 550–553, 358–361.

    Google Scholar 

  22. Singh, N., Raj kumar, Sachan, P. K., Singh, N., Raj kumar, & Sachan, P. K. (2013). Kinetic study of catalytic esterification of butyric acid and ethanol over amberlyst 15. ISRN Chemical Engineering, 2013, 1–6.

    Google Scholar 

  23. Yadav, G. D., & Borkar, I. V. (2009). Synthesis of n-butyl acetamide over immobilized lipase. Journal of Chemical Technology & Biotechnology, 84(3), 420-426.

  24. Yadav, G. D., & Dhoot, S. B. (2009). Immobilized lipase-catalysed synthesis of cinnamyl laurate in non-aqueous media. Journal of Molecular Catalysis B: Enzymatic, 57(1–4), 34–39.

    CAS  Article  Google Scholar 

  25. Yadav, G. D., & Borkar, I. V. (2008). Kinetic modeling of immobilized lipase catalysis in synthesis of n-Butyl Levulinate. Industrial & Engineering Chemistry Research, 47(10), 3358–3363.

  26. Yadav, G. D., & Borkar, I. V. (2010). Lipase-catalyzed hydrazinolysis of phenyl benzoate: kinetic modeling approach. Process Biochemistry, 45(4), 586–592.

    CAS  Article  Google Scholar 

  27. Yadav, G. D., & Lathi, P. S. (2004). Synergism between microwave and enzyme catalysis in intensification of reactions and selectivities: transesterification of methyl acetoacetate with alcohols. Journal of Molecular Catalysis A: Chemical, 223(1–2), 51–56.

    CAS  Google Scholar 

  28. Kamble, M. P., & Yadav, G. D. (2017). Kinetic resolution of (R,S)-α-tetralol by immobilized Candida antarctica lipase B: comparison of packed bed over stirred tank batch bioreactor. Industrial & Engineering Chemistry Research, 56(7), 1750-1757.

  29. Badgujar, K. C., & Bhanage, B. M. (2014). Synthesis of geranyl acetate in non-aqueous media using immobilized Pseudomonas cepacia lipase on biodegradable polymer film: kinetic modelling and chain length effect study. Process Biochemistry, 49(8), 1304–1313.

    CAS  Article  Google Scholar 

  30. Kamble, M. P., Chaudhari, S. A., Singhal, R. S., & Yadav, G. D. (2017). Synergism of microwave irradiation and enzyme catalysis in kinetic resolution of (R,S)-1-phenylethanol by cutinase from novel isolate Fusarium ICT SAC1. Biochemical Engineering Journal, 117, 121–128.

    CAS  Article  Google Scholar 

  31. Yadav, G. D., & Thorat, P. A. (2012). Microwave assisted lipase catalyzed synthesis of isoamyl myristate in solvent-free system. Journal of Molecular Catalysis B: Enzymatic, 83, 16–22.

    CAS  Article  Google Scholar 

  32. Paroul, N., Grzegozeski, L. P., Chiaradia, V., Treichel, H., Cansian, R. L., Oliveira, J. V., & De Oliveira, D. (2011). Solvent-free geranyl oleate production by enzymatic esterification. Bioprocess and Biosystems Engineering, 34(3), 323–329.

    CAS  Article  Google Scholar 

  33. Diaz, M. D. R., Gómez, J. M., Díaz-Suelto, B., & García-Sanz, A. (2010). Enzymatic synthesis of short-chain esters in n-hexane and supercritical carbon dioxide: effect of the acid chain length. Engineering in Life Sciences, 10(2), 171–176.

    CAS  Google Scholar 

  34. Kumar, A., Dhar, K., Kanwar, S. S., & Arora, P. K. (2016). Lipase catalysis in organic solvents: advantages and applications. Biological Procedures Online, 18, 2.

    Article  Google Scholar 

  35. Yadav, G. D., & Magadum, D. B. (2017). Kinetic modelling of enzyme catalyzed biotransformation involving activations and inhibitions. Chapter 4, in  Enzyme Inhibitors and Activators, Ed. Murat Senturk, pp 1–53;  Publisher: InTechOpen; DOI: 10.5772/63325 

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Acknowledgements

HMS and MPK received JRF and SRF fellowship, respectively, from the University Grants Commission, Government of India under UGC-BSR program. GDY acknowledges support from R.T. Mody Distinguished Professor Endowment and J. C. Bose National Fellowship of Department of Science and Technology (Govt. of India).

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Authors and Affiliations

  1. Department of Chemical Engineering, Institute of Chemical Technology, Nathalal Parekh Marg, Matunga, Mumbai, 400019, India

    Harshada M. Salvi, Manoj P. Kamble & Ganapati D. Yadav

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  1. Harshada M. Salvi
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  2. Manoj P. Kamble
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  3. Ganapati D. Yadav
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Correspondence to Ganapati D. Yadav.

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Salvi, H.M., Kamble, M.P. & Yadav, G.D. Synthesis of Geraniol Esters in a Continuous-Flow Packed-Bed Reactor of Immobilized Lipase: Optimization of Process Parameters and Kinetic Modeling. Appl Biochem Biotechnol 184, 630–643 (2018). https://doi.org/10.1007/s12010-017-2572-7

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  • DOI: https://doi.org/10.1007/s12010-017-2572-7

Keywords

  • Flow chemistry
  • Biocatalysis
  • Immobilized Candida antarctica lipase B
  • Geraniol
  • Enzyme kinetics