Reaction kinetics of the catalytic esterification of citric acid with ethanol

Aspi K. Kolah, Navinchandra S. Asthana, Dung T. Vu, Carl T. Lira, Dennis J. Miller

Research output: Contribution to journalArticle

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Abstract

Reaction kinetics are presented for the reversible esterification reaction of citric acid with ethanol to form tri-ethyl citrate via mono-ethyl and di-ethyl citrates. The reaction was studied in batch isothermal experiments, self-catalyzed homogeneously by citric acid and the formed mono- and di-ethyl citrates, and heterogeneously catalyzed by macroporous Amberlyst-15 ion-exchange resin catalyst. Experimental data were obtained between 78 and 120 °C at different mole ratios of ethanol to citric acid and catalyst concentrations up to 5 wt % ion-exchange resin. The kinetics of ethanol etherification to form di-ethyl ether were included in the investigation. Kinetic modeling was performed using a pseudo-homogeneous UNIQUAC-based activity model, taking into consideration the rate of self-catalyzed esterification and the side reaction to form diethyl ether. The activity coefficients for the tri-ethyl citrate-ethanol and tri-ethyl citrate-water binary pairs were obtained from experimental vapor-liquid equilibrium data. Kinetics of the di-ethyl citrate to tri-ethyl citrate reaction limit the overall tri-ethyl citrate formation rate, as citric acid and mono-ethyl citrate are esterified rapidly to their equilibrium compositions. Higher temperatures lead to faster reaction kinetics but significantly increase the production of the undesired byproduct di-ethyl ether. The kinetic model developed is useful for the design and simulation of processes such as reactive distillation for tri-ethyl citrate formation.

LanguageEnglish (US)
Pages3180-3187
Number of pages8
JournalIndustrial and Engineering Chemistry Research
Volume46
Issue number10
DOIs
StatePublished - May 9 2007

Profile

citric acid
Citric acid
Esterification
reaction kinetics
Reaction kinetics
Citric Acid
ethanol
Ethanol
ether
Ethers
kinetics
Kinetics
Ion exchange resins
resin
ion exchange
catalyst
Catalysts
activity coefficient
Ether
Activity coefficients

ASJC Scopus subject areas

  • Polymers and Plastics
  • Environmental Science(all)
  • Chemical Engineering (miscellaneous)

Cite this

Reaction kinetics of the catalytic esterification of citric acid with ethanol. / Kolah, Aspi K.; Asthana, Navinchandra S.; Vu, Dung T.; Lira, Carl T.; Miller, Dennis J.

In: Industrial and Engineering Chemistry Research, Vol. 46, No. 10, 09.05.2007, p. 3180-3187.

Research output: Contribution to journalArticle

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abstract = "Reaction kinetics are presented for the reversible esterification reaction of citric acid with ethanol to form tri-ethyl citrate via mono-ethyl and di-ethyl citrates. The reaction was studied in batch isothermal experiments, self-catalyzed homogeneously by citric acid and the formed mono- and di-ethyl citrates, and heterogeneously catalyzed by macroporous Amberlyst-15 ion-exchange resin catalyst. Experimental data were obtained between 78 and 120 °C at different mole ratios of ethanol to citric acid and catalyst concentrations up to 5 wt {\%} ion-exchange resin. The kinetics of ethanol etherification to form di-ethyl ether were included in the investigation. Kinetic modeling was performed using a pseudo-homogeneous UNIQUAC-based activity model, taking into consideration the rate of self-catalyzed esterification and the side reaction to form diethyl ether. The activity coefficients for the tri-ethyl citrate-ethanol and tri-ethyl citrate-water binary pairs were obtained from experimental vapor-liquid equilibrium data. Kinetics of the di-ethyl citrate to tri-ethyl citrate reaction limit the overall tri-ethyl citrate formation rate, as citric acid and mono-ethyl citrate are esterified rapidly to their equilibrium compositions. Higher temperatures lead to faster reaction kinetics but significantly increase the production of the undesired byproduct di-ethyl ether. The kinetic model developed is useful for the design and simulation of processes such as reactive distillation for tri-ethyl citrate formation.",
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