Reaction kinetics of the catalytic esterification of citric acid with ethanol

被引：74

作者：

Kolah, Aspi K. ^{[1
]}

Asthana, Navinchandra S. ^{[1
]}

Vu, Dung T. ^{[1
]}

Lira, Carl T. ^{[1
]}

Miller, Dennis J. ^{[1
]}

机构：

[1] Michigan State Univ, Dept Chem Engn & Mat Sci, E Lansing, MI 48824 USA

来源：

INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH | 2007年 / 46卷 / 10期

关键词：

D O I：

10.1021/ie060828f

中图分类号：

TQ [化学工业];

学科分类号：

0817 [化学工程与技术];

摘要：

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 degrees 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 by product 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.

引用

页码：3180 / 3187

页数：8

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