Continuous process for esterification of citric acid: Formation of triethyl citrate

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

    Research output: ResearchConference contribution

    Abstract

    Organic acids and alcohols, produced by fermentation of carbohydrate feedstocks, constitute an important class of biorenewable platform chemicals that can be further converted to useful products. Tri-ethyl citrate is currently gaining a lot of attention because it is a non-toxic, biocompatible plasticizer that can be used in place of hazardous petroleum-based phthalate compounds. The potential application of tri-ethyl citrate is currently limited by the lack of large-scale, efficient, and economic production facilities. Though, there is a glut of published literature on synthesis of tri-ethyl citrate from citric acid and ethanol, relatively little information on the kinetics and thermodynamics of its formation is available. We present here a continuous process for the formation of triethyl citrate using cationic exchange resins as catalysts in a reactive distillation column and batch reactor. Vapor-liquid equilibrium studies for important binary mixtures have also been conducted. In a standard batch reaction, equilibrium was achieved after 16 hours; 99% of the citric acid was converted to a mixture of monoethyl, diethyl, and triethyl citrate, with a batch triethyl citrate selectivity of 64%. Kinetic parameters that include both ion-exhcanged catalyzed reactions and self-catalyzed reactions were generated by non-linear regression of batch experimental data in MATLAB. Chemical and physical parameters thus obtained were inserted into AspenPlus process simulation software to model citric acid esterification in our semi-pilot reactive distillation column (5 cm diameter × 4 m height) and various column performance parameters (liquid holdup, catalyst efficiency) were determined by comparing pilot-scale column results with model predictions.

    LanguageEnglish (US)
    Title of host publicationACS National Meeting Book of Abstracts
    StatePublished - 2007
    Event233rd ACS National Meeting - Chicago, IL, United States
    Duration: Mar 25 2007Mar 29 2007

    Other

    Other233rd ACS National Meeting
    CountryUnited States
    CityChicago, IL
    Period3/25/073/29/07

    Profile

    Esterification
    Citric Acid
    ethyl citrate
    Distillation columns
    Catalysts
    Plasticizers
    Organic acids
    Petroleum
    Batch reactors
    Binary mixtures
    Kinetic parameters
    Phase equilibria
    Fermentation
    Feedstocks
    MATLAB
    Ethanol
    Resins
    Alcohols
    Carbohydrates
    Thermodynamics

    ASJC Scopus subject areas

    • Chemistry(all)

    Cite this

    Asthana, N. S., Kolah, A., Miller, D., Vu, D., & Lira, C. (2007). Continuous process for esterification of citric acid: Formation of triethyl citrate. In ACS National Meeting Book of Abstracts

    Continuous process for esterification of citric acid : Formation of triethyl citrate. / Asthana, Navinchandra S.; Kolah, Aspi; Miller, Dennis; Vu, Dung; Lira, Carl.

    ACS National Meeting Book of Abstracts. 2007.

    Research output: ResearchConference contribution

    Asthana, NS, Kolah, A, Miller, D, Vu, D & Lira, C 2007, Continuous process for esterification of citric acid: Formation of triethyl citrate. in ACS National Meeting Book of Abstracts. 233rd ACS National Meeting, Chicago, IL, United States, 3/25/07.
    Asthana NS, Kolah A, Miller D, Vu D, Lira C. Continuous process for esterification of citric acid: Formation of triethyl citrate. In ACS National Meeting Book of Abstracts. 2007.
    Asthana, Navinchandra S. ; Kolah, Aspi ; Miller, Dennis ; Vu, Dung ; Lira, Carl. / Continuous process for esterification of citric acid : Formation of triethyl citrate. ACS National Meeting Book of Abstracts. 2007.
    @inbook{e922dc291ae14bd6a1d5e19317cb6ce0,
    title = "Continuous process for esterification of citric acid: Formation of triethyl citrate",
    abstract = "Organic acids and alcohols, produced by fermentation of carbohydrate feedstocks, constitute an important class of biorenewable platform chemicals that can be further converted to useful products. Tri-ethyl citrate is currently gaining a lot of attention because it is a non-toxic, biocompatible plasticizer that can be used in place of hazardous petroleum-based phthalate compounds. The potential application of tri-ethyl citrate is currently limited by the lack of large-scale, efficient, and economic production facilities. Though, there is a glut of published literature on synthesis of tri-ethyl citrate from citric acid and ethanol, relatively little information on the kinetics and thermodynamics of its formation is available. We present here a continuous process for the formation of triethyl citrate using cationic exchange resins as catalysts in a reactive distillation column and batch reactor. Vapor-liquid equilibrium studies for important binary mixtures have also been conducted. In a standard batch reaction, equilibrium was achieved after 16 hours; 99% of the citric acid was converted to a mixture of monoethyl, diethyl, and triethyl citrate, with a batch triethyl citrate selectivity of 64%. Kinetic parameters that include both ion-exhcanged catalyzed reactions and self-catalyzed reactions were generated by non-linear regression of batch experimental data in MATLAB. Chemical and physical parameters thus obtained were inserted into AspenPlus process simulation software to model citric acid esterification in our semi-pilot reactive distillation column (5 cm diameter × 4 m height) and various column performance parameters (liquid holdup, catalyst efficiency) were determined by comparing pilot-scale column results with model predictions.",
    author = "Asthana, {Navinchandra S.} and Aspi Kolah and Dennis Miller and Dung Vu and Carl Lira",
    year = "2007",
    isbn = "084127438X",
    booktitle = "ACS National Meeting Book of Abstracts",

    }

    TY - CHAP

    T1 - Continuous process for esterification of citric acid

    T2 - Formation of triethyl citrate

    AU - Asthana,Navinchandra S.

    AU - Kolah,Aspi

    AU - Miller,Dennis

    AU - Vu,Dung

    AU - Lira,Carl

    PY - 2007

    Y1 - 2007

    N2 - Organic acids and alcohols, produced by fermentation of carbohydrate feedstocks, constitute an important class of biorenewable platform chemicals that can be further converted to useful products. Tri-ethyl citrate is currently gaining a lot of attention because it is a non-toxic, biocompatible plasticizer that can be used in place of hazardous petroleum-based phthalate compounds. The potential application of tri-ethyl citrate is currently limited by the lack of large-scale, efficient, and economic production facilities. Though, there is a glut of published literature on synthesis of tri-ethyl citrate from citric acid and ethanol, relatively little information on the kinetics and thermodynamics of its formation is available. We present here a continuous process for the formation of triethyl citrate using cationic exchange resins as catalysts in a reactive distillation column and batch reactor. Vapor-liquid equilibrium studies for important binary mixtures have also been conducted. In a standard batch reaction, equilibrium was achieved after 16 hours; 99% of the citric acid was converted to a mixture of monoethyl, diethyl, and triethyl citrate, with a batch triethyl citrate selectivity of 64%. Kinetic parameters that include both ion-exhcanged catalyzed reactions and self-catalyzed reactions were generated by non-linear regression of batch experimental data in MATLAB. Chemical and physical parameters thus obtained were inserted into AspenPlus process simulation software to model citric acid esterification in our semi-pilot reactive distillation column (5 cm diameter × 4 m height) and various column performance parameters (liquid holdup, catalyst efficiency) were determined by comparing pilot-scale column results with model predictions.

    AB - Organic acids and alcohols, produced by fermentation of carbohydrate feedstocks, constitute an important class of biorenewable platform chemicals that can be further converted to useful products. Tri-ethyl citrate is currently gaining a lot of attention because it is a non-toxic, biocompatible plasticizer that can be used in place of hazardous petroleum-based phthalate compounds. The potential application of tri-ethyl citrate is currently limited by the lack of large-scale, efficient, and economic production facilities. Though, there is a glut of published literature on synthesis of tri-ethyl citrate from citric acid and ethanol, relatively little information on the kinetics and thermodynamics of its formation is available. We present here a continuous process for the formation of triethyl citrate using cationic exchange resins as catalysts in a reactive distillation column and batch reactor. Vapor-liquid equilibrium studies for important binary mixtures have also been conducted. In a standard batch reaction, equilibrium was achieved after 16 hours; 99% of the citric acid was converted to a mixture of monoethyl, diethyl, and triethyl citrate, with a batch triethyl citrate selectivity of 64%. Kinetic parameters that include both ion-exhcanged catalyzed reactions and self-catalyzed reactions were generated by non-linear regression of batch experimental data in MATLAB. Chemical and physical parameters thus obtained were inserted into AspenPlus process simulation software to model citric acid esterification in our semi-pilot reactive distillation column (5 cm diameter × 4 m height) and various column performance parameters (liquid holdup, catalyst efficiency) were determined by comparing pilot-scale column results with model predictions.

    UR - http://www.scopus.com/inward/record.url?scp=37349127411&partnerID=8YFLogxK

    UR - http://www.scopus.com/inward/citedby.url?scp=37349127411&partnerID=8YFLogxK

    M3 - Conference contribution

    SN - 084127438X

    SN - 9780841274389

    BT - ACS National Meeting Book of Abstracts

    ER -