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Kinetic Modeling of Solvent-Free Lipase-Catalyzed Partial Hydrolysis of Palm Oil

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Abstract

This work reports the experimental data and kinetic modeling of diacylglycerol (DAG) production from palm oil using a commercial immobilized lipase (Lipozyme RM IM) in a solvent-free medium. The experiments were performed in batch mode, at 55 °C and 400 rpm, and the effects of enzyme concentration (0.68–2.04 wt% related to the mass of substrates), initial water concentration (5–15 wt% related to the mass of oil), and reaction time were evaluated. A novel kinetic model is presented based on the ordered-sequential bi–bi mechanism considering hydrolysis and esterification steps, in which a correlation between water-in-oil solubility and surfactant molecules concentration in the oil allowed the model to describe the induction period in the beginning of the hydrolysis reaction. Moreover, mass transfer limitations related to the enzyme concentration in the system were also taken into account. The proposed model presented a very satisfactory agreement with the experimental data, thus allowing a better understanding of the reaction kinetics. The best conditions obtained for the product (partially hydrolyzed palm oil) in terms of DAG yield (35.91 wt%) were 2.87 wt% enzyme/substrate, 2.10 wt% water/oil, and 72 h of reaction.

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Abbreviations

a r :

Relative activity

DAG:

Diacylglycerol

E:

Free enzyme

EMM:

Enzyme molar mass (grams per mole)

fc:

Correction factor

FFA:

Free fatty acid

G:

Glycerol

H2O:

Water in the oil phase

H2Oins :

Water not solubilized in the oil

H2Ot :

Total water in the system

k l :

Mass transfer limitation constant (grams substrate per gram enzyme)

k r (r = 1,…,22):

Rate constants

K r (r = 1,…,7):

Apparent rate constants (g substrate2/mmol2)

MAG:

Monoacylglycerol

NMR:

Nuclear magnetic resonance

NOBS:

Number of observations

M FFA :

Molar mass of the free fatty acid of palm oil (grams per mole)

M DAG :

Molar mass of the diacylglycerol of palm oil (grams per mole)

M MAG :

Molar mass of the monoacylglycerol of palm oil (grams per mole)

M TAG :

Molar mass of the triacylglycerol of palm oil (grams per mole)

Q r (r = 1,…,6):

Apparent rate constants (g substrate2/(mol enzyme h mmol))

rmsd:

Root–mean–square deviation

TAG:

Triacylglycerol

V r (r = 1,…,6):

Apparent rate constants (g substrate2/(g enzyme h mmol))

\( \left[ {x_{\text{surf}}^{\text{oil}}} \right] \) :

Molar fraction of surfactants in the oil

\( \left[ {w_{{io}}^{{\exp }}} \right] \) :

Experimental mass fraction of pseudo-component i in observation o

\( \left[ {w_{{io}}^{\text{calc}}} \right] \) :

Calculated mass fraction of pseudo-component i in observation o

[DAG]:

Diacylglycerol concentration (millimoles per gram substrate)

[DAG × E × FFA]:

Diacylglycerol × enzyme × free fatty acid complex concentration (millimoles per gram substrate)

[DAG × E × H2O]:

Diacylglycerol × enzyme × water complex concentration (millimoles per gram substrate)

[E]:

Free enzyme concentration (millimoles per gram substrate)

[ET]:

Total enzyme concentration (millimoles per gram substrate)

[ET]:

Total enzyme concentration (grams enzyme per gram substrate)

[ETa]:

Total enzyme concentration available to substrate (grams enzyme per gram substrate)

[FFA]:

Free fatty acids concentration (millimoles per gram substrate)

[H2O]:

Water concentration in the oil phase (millimoles per gram substrate)

[H2O]0 :

Initial water concentration in the oil phase (millimoles per gram substrate)

[H2Oins]:

Concentration of water not solubilized in the oil phase (millimoles per gram substrate)

[H2Oins]0 :

Initial concentration of water not solubilized in the oil phase (millimoles per gram substrate)

[H2Ot]:

Total water concentration in the system (millimoles per gram substrate)

[H2Ot]0 :

Total initial water concentration in the system (millimoles per gram substrate)

[G]:

Glycerol concentration (millimoles per gram substrate)

[G × E × FFA]:

Glycerol × enzyme × free fatty acid complex concentration (millimoles per gram substrate)

[MAG]:

Monoacylglycerol concentration (millimoles per gram substrate)

[MAG × E × FFA]:

Monoacylglycerol × enzyme × free fatty acid complex concentration (millimoles per gram substrate)

[MAG × E × H2O]:

Monoacylglycerol × enzyme × water complex concentration (millimoles per gram substrate)

[TAG]:

Triacylglycerol concentration (millimoles per gram substrate)

[TAG × E × H2O]:

Triacylglycerol × enzyme × water complex concentration (millimoles per gram substrate)

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Acknowledgments

The authors are grateful to CNPq and CAPES/NANOBIOTEC for the financial support and scholarships.

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Authors and Affiliations

  1. Department of Chemical Engineering, Federal University of Paraná, Polytechnic Center, Jardim das Américas, Curitiba, PR, 82530-990, Brazil

    Fernando Augusto Pedersen Voll & Marcos Lúcio Corazza

  2. Department of Chemical Engineering, Maringá State University (UEM), Av. Colombo 5790, Maringá, PR, 87020-900, Brazil

    Andreia Fatima Zanette, Vladimir Ferreira Cabral & Lucio Cardozo Filho

  3. Institute of Technology and Research, Tiradentes University, Av. Murilo Dantas, 300, 49032-490, Aracaju, Sergipe, Brazil

    Claudio Dariva

  4. Biocatalysis and Organic Synthesis Group, Technology Center, Federal University of Rio de Janeiro, Bloco A, Ilha do Fundão, 21941-909, Rio de Janeiro, Brazil

    Rodrigo Octavio Mendonça Alves De Souza

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  1. Fernando Augusto Pedersen Voll
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  2. Andreia Fatima Zanette
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  3. Vladimir Ferreira Cabral
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Correspondence to Fernando Augusto Pedersen Voll.

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Voll, F.A.P., Zanette, A.F., Cabral, V.F. et al. Kinetic Modeling of Solvent-Free Lipase-Catalyzed Partial Hydrolysis of Palm Oil. Appl Biochem Biotechnol 168, 1121–1142 (2012). https://doi.org/10.1007/s12010-012-9846-x

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