Log in

Optimization of Lipase-Catalyzed Synthesis of Cetyl Octanoate in Supercritical Carbon Dioxide

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

Abstract

Cetyl octanoate, a wax ester of 24 carbons, is widely used in the cosmetic industry as a base oil. The current work focuses on lipase-catalyzed synthesis of cetyl octanoate in supercritical carbon dioxide (SC-CO2) by esterification of cetyl alcohol and octanoic acid. Three immobilized lipases were screened, and 15 reaction conditions were tested in order to find the combination for maximal yield. The results showed that Novozym® 435 was the best catalyst for the synthesis, and a reaction time of 20 min was adequate for a maximal yield. Response surface methodology (RSM) with a 3-factor-3-level Box-Behnken design was employed to evaluate the effects of synthesis parameters, including reaction temperature (35–75 °C), pressure (8.27–12.41 MPa), and enzyme amount (5–15% wt of cetyl alcohol). A model for the synthesis was developed and the optimum conditions could be predicted to be reaction pressure of 10.22 MPa, reaction temperature of 63.70 °C, and enzyme amount of 11.20%. An experiment was performed under this optimum condition and a yield of 99.5% was obtained. This experimental yield correlated well with the predicted value of yield (97.6%). We concluded that, in a SC-CO2 system, nearly 100% molar conversion of cetyl octanoate could be obtained by immobilized Novozym® 435 in a short reaction time (20 min) under the predicted optimal conditions.

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

Access this article

Subscribe and save

Springer+ Basic
EUR 32.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or Ebook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

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

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

Similar content being viewed by others

References

  1. Patel S, Nelson DR, Gibbs AG (2001) Chemical and physical analyses of wax ester properties. J Insect Sci 1:1–7

    Google Scholar 

  2. Salis A, Solinas V, Monduzzi M (2003) Wax esters synthesis from heavy fraction of sheep milk fat and cetyl alcohol by immobilised lipases. J Mol Catal B Enzym 21:167–174

    Article  CAS  Google Scholar 

  3. Petersson AEV, Gustafsson LM, Nordblad M, Börjesson P, Mattiasson B, Adlercreutz P (2005) Wax esters produced by solvent-free energy-efficient enzymatic synthesis and their applicability as wood coatings. Green Chem 7:837–843

    Article  CAS  Google Scholar 

  4. Hunter KW Jr, Gault RA, Stehouwer JS, Tam-Chang SW (2003) Synthesis of cetyl myristoleate and evaluation of its therapeutic efficacy in a murine model of collagen-induced arthritis. Pharmacol Res 47:43–47

    Article  CAS  Google Scholar 

  5. Gunawan ER, Basri M, Rahman MBA, Salleh AB, Rahman RNZA (2005) Study on response surface methodology (RSM) of lipase-catalyzed synthesis of palm-based wax ester. Enzyme Microb Technol 37:739–744

    Article  CAS  Google Scholar 

  6. Kawabata T, Mizugaki T, Ebitani K, Kaneda K (2003) Highly efficient esterification of carboxylic acids with alcohols by montmorillonite-enwrapped titanium as a heterogeneous acid catalyst. Tetrahedron Lett 44:137–140

    Google Scholar 

  7. Sunitha S, Kanjilal S, Reddy PS, Prasad RBN (2007) Liquid-liquid biphasic synthesis of long chain wax esters using the Lewis acidic ionic liquid choline chloride·2ZnCl2. Tetrahedron Lett 48:6962–6965

    Article  CAS  Google Scholar 

  8. Ieda N, Mantri K, Miyata Y, Ozaki A, Komura K, Sugi Y (2008) Esterification of long-chain acids and alcohols catalyzed by ferric chloride hexahydrate. Ind Eng Chem Res 47:8631–8638

    Article  CAS  Google Scholar 

  9. Isono Y, Nabetani H, Nakajima M (1995) Wax ester synthesis in a membrane reactor with lipase-surfactant complex in hexane. J Am Oil Chem Soc 72:887–890

    Article  CAS  Google Scholar 

  10. Hadzir NM, Basri M, Rahman MBA, Razak CNA, Rahman RNZA, Salleh AB (2001) Enzymatic alcoholysis of triolein to produce wax ester. J Chem Technol Biotechnol 76:511–515

    Article  CAS  Google Scholar 

  11. Dianóczki C, Recseg K, Kovári K, Poppe L (2007) Convenient enzymatic preparation of conjugated linoleic acid alkyl esters with C6–C22 alcohols. J Mol Catal B Enzym 45:45–49

    Article  Google Scholar 

  12. Hobbs HR, Thomas NR (2007) Biocatalysis in supercritical fluids, in fluorous solvents, and under solvent-free conditions. Chem Rev 107:2786–2820

    Article  CAS  Google Scholar 

  13. Wimmer Z, Zarevúcka M (2010) A review on the effects of supercritical carbon dioxide on enzyme activity. Int J Mol Sci 11:233–253

    Article  CAS  Google Scholar 

  14. Knez Z, Laudani CG, Habulin M, Reverchon E (2007) Exploiting the pressure effect on lipase-catalyzed wax ester synthesis in dense carbon dioxide. Biotechnol Bioeng 97:1366–1375

    Article  CAS  Google Scholar 

  15. Leitner W (2002) Supercritical carbon dioxide as a green reaction medium for catalysis. Acc Chem Res 35:746–756

    Article  CAS  Google Scholar 

  16. Laudani CG, Habulin M, Knez Z, Porta GD, Reverchon E (2007) Immobilized lipase-mediated long-chain fatty acid esterification in dense carbon dioxide: bench-scale packed-bed reactor study. J Supercrit Fluid 41:74–81

    Article  CAS  Google Scholar 

  17. Habulin M, Šabeder S, Sampedro MA, Knez Z (2008) Enzymatic synthesis of citronellol laurate in organic media and in supercritical carbon dioxide. Biochem Eng J 42:6–12

    Article  CAS  Google Scholar 

  18. Chen HC, Ju HY, Twu YK, Chen JH, Chang CM, Liu YC, Chang C, Shieh CJ (2010) Optimized enzymatic synthesis of caffeic acid phenethyl ester by RSM. N Biotechnol 27:89–93

    Article  CAS  Google Scholar 

  19. Ju HY, Huang KC, Chen JH, Liu YC, Chang CMJ, Lee CC, Chang C, Shieh CJ (2010) Optimization of the extraction of Alpinia oxyphylla essence oil in supercritical carbon dioxide. J Am Oil Chem Soc 87:1063–1070

    Article  CAS  Google Scholar 

  20. AS S (1990) SAS user guide. SAS Institute, Cary

    Google Scholar 

  21. Sun S, Shan L, Liu Y, ** Q, Song Y, Wang X (2009) Solvent-free enzymatic synthesis of feruloylated diacylglycerols and kinetic study. J Mol Catal B Enzym 57:104–108

    Article  CAS  Google Scholar 

  22. Yadav GD, Dhoot SB (2009) Immobilized lipase-catalysed synthesis of cinnamyl laurate in non-aqueous media. J Mol Catal B Enzym 57:34–39

    Article  CAS  Google Scholar 

  23. Lystvet SM, Hoff BH, Anthonsen T, Jacobsen EE (2010) Chemoenzymatic synthesis of enantiopure 1-phenyl-2-haloethanols and their esters. Biocatal Biotransform 28:272–278

    Article  CAS  Google Scholar 

  24. Varma MN, Madras G (2010) Effect of chain length of alcohol on the lipase-catalyzed esterification of propionic acid in supercritical carbon dioxide. Appl Biochem Biotechnol 160:2342–2354

    Article  CAS  Google Scholar 

  25. Habulin M, Šabeder S, Knez Z (2008) Enzymatic synthesis of sugar fatty acid esters in organic solvent and in supercritical carbon dioxide and their antimicrobial activity. J Supercrit Fluid 45:338–345

    Article  CAS  Google Scholar 

  26. Olsen T, Kerton F, Marriott R, Grogan G (2006) Biocatalytic esterification of lavandulol in supercritical carbon dioxide using acetic acid as the acyl donor. Enzyme Microb Technol 39:621–625

    Article  CAS  Google Scholar 

  27. Peterson J (1993) A general approach to ridge analysis with confidence intervals. Technometrics 35:204–214

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding authors

Correspondence to Yung-Chuan Liu or Chwen-Jen Shieh.

About this article

Cite this article

Kuo, CH., Ju, HY., Chu, SW. et al. Optimization of Lipase-Catalyzed Synthesis of Cetyl Octanoate in Supercritical Carbon Dioxide. J Am Oil Chem Soc 89, 103–110 (2012). https://doi.org/10.1007/s11746-011-1895-8

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11746-011-1895-8

Keywords

Navigation