ESTERIFICATION KINETICS OF ETHYLENE

GLYCOL WITH ACETIC ACID USING CATALYST

By
P. SHASI VAMSI KRISHNA
R. VARUN KUMAR
K. PRAMOD KUMAR
V. ARNEETH REDDY
 INTRODUCTION:

• The growing international energy crisis coupled with rising oil prices and increasing awareness of
the environment and pollution has intensified The research on renewable fuels derived from
biomass.
• The bio-oil produced by the process of biomass pyrolysis is nowadays an emerging technology for
the production of renewable fuels and value-added chemicals.
• The bio-oil was first separated into aqueous and non-aqueous fractions by the addition of water.
• The aqueous fraction of bio-oils containing sugars, anhydrosugars, acetic acid, hydroxyacetone,
furfural, and small amounts of guaiacols is a potential source of alkanes (ranging from C1 to C6)
and polyols (ethylene glycol, 1,2-propanediol,1,4-butanediol etc).
• The ethylene glycol obtained from bio-oil fraction can be utilized to produce ethylene glycol
mono- and di-acetate suitable for application as solvent for coating, paints, and oxygenated
diesel fuel additives.
 USES:

The esterification process is widely used in industry to produce esters for a wide range of applications such as

1. Plasticizers

2. Solvent

3. Perfumery

4. Flavor chemicals

5. Precursors for Pharmaceuticals

6. Agrochemicals and

7. other fine chemicals.

Batch Reactor:
Reactions Involved:

Ref: V. P. YADAV et al., Kinetics of Esterification of Ethylene Glycol with Acetic Acid …, Chem. Biochem. Eng. Q.
25 (3) 359–366 (2011)
MODELLING:

• The esterification of ethylene glycol with acetic acid and hydrolysis as reverse
reaction are SN2 type reactions and hence, the reactions were considered as
second order in the developed empirical model.

• The rates of formation of five different components involved in the reaction

were therefore represented by the following five ordinary differential
equations.
dCEG /dt = -k1cEGcAA + k-1cEGMAcw

dCAA/dt = -k1cEGcAA + k-1cEGMAcw – k2cEGMAcAA + k-2cEGDAcw

dCEGMA/dt = -k2cEGMAcAA + k-2cEGMAcw + k1cEGcAA – k-1cEGMAcw

dCEGDA /dt = k2cEGMAcAA – k-2cEGMAcw

dCw /dt = K1cEGcAA – k-1cEGMAcw + k2cEGMAcAA – k-2cEGDAcw

KINETIC DATA:

Temperature Rate constant Rate constant Rate constant Rate constant

(K) (k1) (k-1) (k2) (k-2)

333 9.7 * 10-4 7.91 * 10-4 3.17 * 10-3 6.82 * 10-3

343 1.19 * 10-3 8.39 * 10-4 3.26 * 10-3 7.42 * 10-3

353 1.69 * 10-3 1.04 * 10-3 6.07 * 10-3 1.27 * 10-2

363 3.49 * 10-3 1.34 * 10-3 9.07 * 10-3 2.27 * 10-2

Ref: V. P. YADAV et al., Kinetics of Esterification of Ethylene Glycol with Acetic Acid …,
Chem. Biochem. Eng. Q. 25 (3) 359–366 (2011)
Results and discussion:

• From the kinetic data by using matlab simulation we obtained the

following results.

• The graph between concentration and reaction time at different

temperatures are plotted.

• The graph between selectivity of EGDA(%) and reaction time is

also plotted.
 ARRHENIUS PLOT:

From the figure:

1.The Activation energy for K1 is

-5028.5
2. The Activation energy for K2 is
-4534.9
3. The Activation energy for K-1 is
-2156.5
4. The Activation energy for K-2 is
-4973.1
• We have done the simulation in matlab using ODE45 solver.
• With the help of matlab we can find conversion for any given kinetic data in between
the temperatures of 333k to 363k for example the plot between concentration and
reaction time at 357k is as follows:
Selectivity:

• Selectivity is defined as the ratio of number of moles of desired product

formed to number of moles of reactant consumed.
After certain reaction time the selectivity of EGDA becomes constant so we can stop the analysis after
certain time by using selectivity plot.
 Conclusion:

• In the present work, the kinetics of the esterification of ethylene glycol with acetic acid has been investigated in
presence of a strongly acidic cation-exchange resin, seralite SRC-120 as catalyst.
• The acetic acid to ethylene glycol mole ratio was found to have enormous effect on the product selectivity
where higher mole ratio favors selective formation of EGDA.
• The increase in temperature has been found to enhance the reaction rate without significantly affecting the
product selectivity. The empirical kinetic model were developed to correlate the experimental data.
• The rate constants and equilibrium constants of the developed kinetic model were estimated using the
experimental data at different temperatures using non-linear least square techniques based on Levenberg-
Marquardt algorithm.
• The concentration of different components calculated based on estimated Parameters were then compared with
experimental data found to fit the experimental data.
• The activation energies and frequency factors of the rate constants of the empirical kinetic model were then
determined from the intercept and slope of the Arrhenius plot of ln(rate constants) versus 1/T.
REFERENCES:

• V. P. YADAV et al., Kinetics of Esterification of Ethylene Glycol

with Acetic Acid …, Chem. Biochem. Eng. Q. 25 (3) 359–366 (2011)

• Vispute, T. P., Huber, G. W., Green Chem. 11 (9) (2009) 1433.

• Widdecke, H., Hodge, P., Syntheses and Separations using

Functional Polymers. Wiley, New York, 1988.

• Yadav, G. D., Thathagar, M. B., React. Polym. 52 (2002) 99.