Abstract
In this paper, the reaction of enzymatic trans-esterification of glycerides with ethanol in a reaction medium containing hexane at a temperature of 37 °C has been studied. The enzyme was Lipase from Mucor miehei, immobilized on ionic exchange resin, aimed at achieving high catalytic specific surface and recovering, regenerating and reusing the biocatalyst. A kinetic analysis has been carried out to identify the reaction path; the rate equation and kinetic parameters have been also calculated. The kinetic model has been validated by comparison between predicted and experimental results. Mass transport resistances estimation was undertaken in order to verify that the kinetics found was intrinsic. Model potentialities in terms of reactors design and optimization are also shown.
Similar content being viewed by others
Abbreviations
- CSTBR:
-
Continuous stirred tank bio-reactor
- D:
-
Diolein (in reaction mechanism)
- d p :
-
Catalyst particle diameter
- [e]:
-
Enzyme concentration (g/l)
- E:
-
Enzyme (in reaction mechanism)
- E′:
-
Activate complex (in reaction mechanism)
- E–Et:
-
Enzyme–ethanol complex (in reaction mechanism)
- E–D:
-
Enzyme–diolein complex (in reaction mechanism)
- E–M:
-
Enzyme–monolein complex (in reaction mechanism)
- E–P:
-
Enzyme–product complex (in reaction mechanism)
- E–T:
-
Enzyme–triolein complex (in reaction mechanism)
- EO:
-
Ethyloleate (in reaction mechanism)
- [EO]:
-
Ethyloleate molar concentration (mol/l)
- Δ[EO]:
-
Ethyloleate production (mol/l)
- Et:
-
Ethanol (in reaction mechanism)
- [Et]:
-
Ethanol molar concentration (mol/l)
- G:
-
Glycerol (in reaction mechanism)
- [G]:
-
Glycerol molar concentration (mol/l)
- Ki:
-
Kinetic parameters (various dimension)
- k s :
-
Mass transport coefficient (m/s)
- M:
-
Monolein (in reaction mechanism)
- me:
-
Mass of enzyme (g)
- mso:
-
Mass of simulating oil (g)
- MW:
-
Molecular weight [Da]
- P:
-
Products in terms of total sum of glycerol, monolein and diolein (M + D + G) (in reaction mechanism)
- [P]:
-
Concentration of products in terms of total sum of glycerol, monolein and diolein (M + D + G) (mol/l)
- Sh:
-
Sherwood number
- T:
-
Triolein (in reaction mechanism)
- [t]:
-
Triolein mass concentration (g/l)
- [T]:
-
Triolein molar concentration (mol/l)
- t :
-
Time (h)
- t D :
-
Diffusion time (h)
- t v :
-
Reaction time (h)
- U:
-
Units of enzyme (Unit)
- [U]:
-
Concentration of enzyme in terms of Unit (Unit/l)
- v :
-
Reaction rate (mol/l h)
- V H :
-
Hexane volume (ml) or (l)
- V SO :
-
Simulating oil volume (ml) or (l)
- 0:
-
Referring to initial conditions
- α, β:
-
Kinetic parameters
- δ, ε:
-
Functions of Et0
- δ0, δ1, ε0, ε1, ε2:
-
Parameters
- τ :
-
CSTBR mean residence time (h)
References
Billaud F, Dominguez V, Broutin P, Buston C (1995) Production of hydrocarbons by pyrolysis of methyl esters from rapeseed oil. J Am Oil Chem Soc 72:1149–1154
Ziejewski M, Kaufman KR, Schwab AW, Pryde EH (1984) Diesel engine evaluation of a nonionic sunflower oil-aqueous ethanol microemulsion. J Am Oil Chem Soc 61:1620–1626
Fukuda H, Kondo A, Noda H (2001) Biodiesel fuel production by trans-esterification of oils. J Biosci Bioeng 92:405–416
Ma F, Hanna MA (1999) Biodiesel production: a review. Bioresource Technol 70:1–15
Schwab AW, Bagby MO, Freedman B (1987) Preparation and properties of diesel fuels from vegetable oils. Fuel 66:1372–1378
Clark SJ, Wangner L, Schrock MD, Piennaar PG (1984) Methyl and ethyl soybean esters as renewable fuels for diesels engines. J Am Oil Chem Soc 61:1632–1638
Freedman B, Pryde EH, Mounts TL (1984) Variables affecting the yields of fatty esters from trans-esterified vegetable oils. J Am Oil Chem Soc 61:1638–1643
Srivastava A, Prasad R (2000) Triglycerides-based diesel fuels. Renew Sus Energ Rev 4:111–133
Formo MW (1954) Ester reactions of fatty materials. J Am Oil Chem Soc 31:548–559
Wright HJ, Segur JB, Clark HV, Coburn SK, Langdon EE, DuPuis RN (1944) A report on ester interchange. Oil Soap 21:145–148
Eckey EW (1956) Esterification and interesterification. J Am Oil Chem Soc 33:575–579
Freedman B, Butterfield RO, Pryde EH (1986) Transesterification kinetics of soybean oil. J Am Oil Chem Soc 63:1375–1380
Mittelbach M (1990) Lipase catalyzed alcoholysis of sunflower oil. J Am Oil Chem Soc 67:168–170
Abigor R, Uadia P, Foglia T, Haas M, Jones K, Okpefa E, Obibuzor J, Bafor M (2000) Lipase-catalyzed production of biodiesel fuel from some Nigerian lauric oils. Biochem Soc Trans 28:979–981
Shimada Y, Sugihara A, Nakano H, Kuramoto T, Nagao T, Gemba M, Tominaga Y (1997) Purification of docosahexanoic acid by selective esterification of fatty acids from tuna oil with Rhizopus delemar lipase. J Am Oil Chem Soc 74:97–101
Nelson LA, Foglia A, Marmer WN (1996) Lipase-catalyzed production of biodiesel. J Am Oil Chem Soc 73:1191–1195
Shimada Y, Watanabe Y, Samukawa T, Sugihara A, Noda H, Fukuda H, Tominaga Y (2000) Conversion of vegetable oil to biodiesel using immobilized Candida antarctica lipase. J Am Oil Chem Soc 77:355–360
Shimada Y, Watanabe Y, Sugihara A, Tominaga Y (2002) Enzymatic alcoholysis for biodiesel fuel production and application of reaction to oil processing. J Mol Catal B Enz 17:133–142
Samukawa T, Kaieda M, Matsumoto T, Ban K, Kondo A, Shimada Y, Noda H, Fukuda H (2000) Pretreatment of immobilized Candida antarctica lipase for biodiesel fuel production from plant oil. Biosci Bioeng 90:180–183
Kaieda M, Samukawa T, Kondo A, Fukuda H (2001) Effect of methanol and water contents on production of biodiesel fuel from plant oil catalyzed by various lipases in a solvent-free system. J Biosci Bioeng 91:12–15
Kaieda M, Samukawa T, Matsumoto T, Ban K, Kondo A, Shimada Y, Noda H, Nomoto F, Ohtsuka K, Izumoto E, Fukuda H (1999) Biodiesel fuel production from plant oil catalyzed by Rhizopus oryzae lipase in a water-containing system without an organic solvent. J Biosci Bioeng 88:627–631
Dossat V, Combes D, Marty A (2002) Lipase-catalysed transesterification of high oleic sunflower oil. Enzyme Microb Technol 30:90–94
Al-Zuhair S (2005) Production of biodiesel by lipase-catalyzed transesterification of vegetable oils: a kinetic study. Biotechnol Prog 21:1442–1448
Al-Zuhair S, Ling FW, Jun LS (2007) Proposed kinetic mechanism of the production of biodiesel from palm oil using lipase. Process Biochem 42:951–960
Al-Zuhair S, Dowaidar A, Kamal H (2009) Dynamic modeling of biodiesel production from simulated waste cooking oil using immobilized lipase. Biochem Eng J 44:256–262
Jeong GT, Park DH (2008) Lipase-catalyzed transesterification of rapeseed oil for biodiesel production with tert-butanol. Appl Biochem Biotechnol 148:131–139
Soumanou MM, Bornscheuer UT (2003) Improvement in lipase-catalyzed synthesis of fatty acid methyl esters from sunflower oil. Enz Microb Technol 33:97–103
Du W, Xu Y (2005) Study on acyl migration in immobilized Lipozyme TL catalyzed transesterification of soybean oil for biodiesel production. J Mol Cat B 37:68–71
Levenspiel O (1999) Chemical reaction engineering, 3rd edn. Wiley, New York, p 63
Cheirsilp B, H-Kittikun A, Limkatanyu S (2008) Impact of transesterification mechanisms on the kinetic modeling of biodiesel production by immobilized lipase. Biochem Eng J 42:261–269
Bird RB, Stewart WE, Lightfoot EN (1960) Transport phenomena. Wiley, New York
Berben PH, Groen C, Christensen MW, Holm HC (2001) Interesterification with immobilized enzymes. SCI Lecture Paper Series, p 121
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Calabrò, V., Ricca, E., De Paola, M.G. et al. Kinetics of enzymatic trans-esterification of glycerides for biodiesel production. Bioprocess Biosyst Eng 33, 701–710 (2010). https://doi.org/10.1007/s00449-009-0392-z
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00449-009-0392-z