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: Research - peer-reviewArticle

    • 35 Citations

    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
    Esterification
    Reaction kinetics
    Ethanol
    Kinetics
    citric acid
    reaction kinetics
    ethanol
    kinetics
    Citric Acid
    ethyl citrate
    Ethers
    ether
    Ion exchange resins
    Catalysts
    resin
    ion exchange
    catalyst
    rate
    Ether

    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: Research - peer-reviewArticle

    @article{343c23ea440444089c27c8f824a3bb26,
    title = "Reaction kinetics of the catalytic esterification of citric acid with ethanol",
    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.",
    author = "Kolah, {Aspi K.} and Asthana, {Navinchandra S.} and Vu, {Dung T.} and Lira, {Carl T.} and Miller, {Dennis J.}",
    year = "2007",
    month = "5",
    doi = "10.1021/ie060828f",
    volume = "46",
    pages = "3180--3187",
    journal = "Industrial & Engineering Chemistry Product Research and Development",
    issn = "0888-5885",
    publisher = "American Chemical Society",
    number = "10",

    }

    TY - JOUR

    T1 - Reaction kinetics of the catalytic esterification of citric acid with ethanol

    AU - Kolah,Aspi K.

    AU - Asthana,Navinchandra S.

    AU - Vu,Dung T.

    AU - Lira,Carl T.

    AU - Miller,Dennis J.

    PY - 2007/5/9

    Y1 - 2007/5/9

    N2 - 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.

    AB - 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.

    UR - http://www.scopus.com/inward/record.url?scp=34248994158&partnerID=8YFLogxK

    UR - http://www.scopus.com/inward/citedby.url?scp=34248994158&partnerID=8YFLogxK

    U2 - 10.1021/ie060828f

    DO - 10.1021/ie060828f

    M3 - Article

    VL - 46

    SP - 3180

    EP - 3187

    JO - Industrial & Engineering Chemistry Product Research and Development

    T2 - Industrial & Engineering Chemistry Product Research and Development

    JF - Industrial & Engineering Chemistry Product Research and Development

    SN - 0888-5885

    IS - 10

    ER -