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

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

Research output: Chapter in Book/Report/Conference proceedingConference 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
Distillation columns
Plasticizers
Catalysts
Organic acids
Petroleum
Batch reactors
Binary mixtures
Kinetic parameters
Phase equilibria
Fermentation
Feedstocks
MATLAB
ethyl citrate
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: Chapter in Book/Report/Conference proceedingConference 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.
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