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________ ISSN 2278 – 9472

Research Journal of Engineering Sciences ___________________________________________


Vol. 6(3), 10-15, March (2017)) Res. J. Engineering Sci.

Modeling of esterification
esterification-pervaporation
pervaporation integrated system of acrylic acid
with ethanol
Ghoshna Jyoti*, Amit Keshav and J. Anand Kumar
Department of Chemical Engineering, National Institute of Technology Raipur (CG), India
ghoshna2006@gmail.com
Available online at: www.isca.in, www.isca.me
Received 30th November 2016, revised 20th February 2017, accepted 14th March 2017
201
Abstract
Kinetic model for esterification of acrylic acid with ethanol using sulphuric acid (H2SO4) as a catalyst coupled pervaporation
process was established in this work. The major effects of different parameters such as reaction temperature, ratios of initial
initi
molar quantity of reactants, membrane area, catalyst concentration and membrane permeability on the esterification
reaction and the permeation kinetics of water removed by pervaporation were taken into consideration in this kinetic model.
The developed model equations are solved by the ODE solver, ode45 implemented in the MATLAB. The esterification of
acrylic acid with ethanol usingH2SO4 was carried out at a temperature range of 50 50–70°C,
70°C, catalyst concentration of 1-3%
1 of
reaction mixture and initial reactant molar ratio of 1:11:1-1:3.
1:3. The conversion of acrylic acid or yield of ethyl acrylate was
enhanced in a pervaporation reactor as compared to a conventional reactor. The result indicates that the esterification
pervaporation integrated system accelerates the rate of ester formation by removing water.

Keywords: Pervaporation, Esterification, Membrane, Modeling, Acrylic acid.

Introduction In present paper experiments were conducted


co for esterification
of acrylic acid with ethanol integrated with pervaporation and
Nowadays, merging reactor with separation unit has become a without pervaporation. Modeling of the esterification reaction
current trend in the chemical industry in order to obtain more coupled with PV process has also been presented for the
efficient processes and lower energy consumption1. This esterification of acrylic acid with ethanol. The Th model was
combination is advantageous for the production of esters from validated using experimental data. Besides, the effect of various
esterification reaction as this reaction is thermodynamically process variables, such as process temperature (T), initial mole
limited. Pervaporation process shifts the chemical equilibrium ratio of reactants (MR), and the ratio of the effective membrane
towards the production on of ester by removing water area over the volume of reacting mixture (S/V),catalyst
(S/V),c content
continuously. Pervaporation
ervaporation (PV) is useful for dehydration of (CC) on the performance of pervaporation reactor for
organicchemicals2. esterification reaction were discussed.

Moreover, PV enhances both conversion and reaction rates as it Materials and methods
can remove water simultaneously from the reactor.
Mathematical modeling of coupled reaction-membrane
membrane systems The hydrophilic PVA membrane, used in this work was
has attracted great interest because it can provide an insight into supplied by Permionics Membranes Pvt. Ltd., India. India All
the industrial design and optimal operation of theseprocesses3. reactants (acrylic acid, ethanol) and catalyst (sulfuric acid) were
of analytical grade with purity higher than 99% and obtained
In present work the resulting
ulting ester ethyl acrylate from the from Merck.
esterification reaction between acrylic acid and ethyl alcohol
can be used as a reactive building block to produce coatings and The experimental set-up
up used for the PV couple desterification
inks, adhesives, sealants, textiles, plastics and elastomers4,5. reaction was performed in situ batch operation mode. The
Pervaporation membrane reactors assisted with esterification membrane
rane was placed just below the reactor in a particular cell.
butanol6, lactic acid and
have been studied of acrylic acid and n-butanol The effective membrane area which was in contact with the feed
iso-propanol , acetic acid and iso-propanol8, acetic acid and iso
7
iso- mixture was 78.5 cm2. Reactants were added to the reactor
butanol9, acetic acid and ethanol10, lactic acid and ethanol11. along with catalyst and heated up to the desired reaction
Limited work related to esterification- pervaporation hybrid temperature. The stirrer was started at 300 rpm speed for the
system of acrylic acid with ethanol has been available on proper mixing of reaction mixture. A thermostat has been used
literature12. Truong et al. 201312 used a polymer based to maintain the temperature within the accuracy of ±1°C during
membrane to improve the synthesis of acrylic esters and the reaction. With the help of hydrophilic membrane (PVA),
investigated the chemical stability of the membrane. water was separated from thehe feed mixture simultaneously. The

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Research Journal of Engineering Sciences________________________________________________________ ISSN 2278 – 9472
Vol. 6(3), 10-15, March (2017) Res. J. Engineering Sci.

pressure on the permeate side was held constant at 5 mbar and Equation (3) can be written as
chiller temperature was maintained at -5°C. During the
d (C i )  γ γ C C 
experiment samples were withdrawn from the reactor at regular − ri = = k1 C C  γ A γ B C A C B − E W E W  (4)
dt  K eq 
intervals.  
Samples collected from the reactor and the permeate were Where: the equilibrium constant, Keq can be calculated from the
analyzed by NUCON series 5700 gas chromatograph (GC) with given equation below as
porapak column (id 2mm, od 1/8”, length 2 m) hydrogen gas
taken as carrier gas with flow rate 60 ml/min equipped with a k1 γ E C E γ W CW
TCD detector. Sample has injected in chromatograph with K eq = = (4)
k −1 γ A C A γ B C B
amount of 1µl. To obtain accurate results, each sample was
analyzed two times. For simplifying the mathematical model following assumptions
can be made: i. constant selectivity of the PVA membrane, ii.
The operating conditions for the gas chromatograph are: i. isothermal reaction and pervaporation, iii. constant catalyst
Temperature (ᵒC), ii. Injector: 150, iii. Detector: 180, iv. Oven: activity, and iv. the partial molar volume in a mixture is the
180. same as that of a pure component3.

Modeling of the membranereactor: The mathematical model By combining pervaporation with the esterification, the change
of a hybrid system of a batch reactor for esterification coupled of concentration can be written as follows:
with pervaporation is based on three aspects: (a) reaction
kinetics of esterification, (b) membrane perm selectivity in
d (C i ) S
pervaporation, and (c) mass balance. = ri − Ji (5)
dt V0
The esterification reaction between acrylic acid (A) and ethyl
alcohol (B) to produce ethyl acrylate (E) and water (W) can be In present work a hydrophilic PVA membrane was used so the
represented by an elementary reversible reaction having second partial fluxes of components acrylic acid, ethanol and ethyl
order. The reaction can be written as follows: acrylate were neglected (JEthanol∼JAcid∼ Jester∼ 0). The water
balance in the PV coupled reactor can be written as:
‫ܣ‬+‫ܧ ⇌ ܤ‬+ܹ
d (CW )  γ γ C C  S
The rate expression for second order reversible reaction can be = k1 C C  γ A γ B C A C B − E W E W  − JW
written as: dt  K eq  V
  0
(6)
− dC A
− rA = = k1C A C B C C − k −1C E CW C C (1)
dt
The relationship between flux and feed water concentration is
Where: CA, CB, CE, CW and CC represents the concentration nonlinear and varies throughout the reaction. Hence the
(mol/m3) of acrylic acid, ethanol, ethyl acrylate, water and following modified relation can be used 2.
catalyst respectively. k1 and k-1 are the forward and backward J W = k PV 1CW − k PV 2 CW2
reaction rate constants and t is the reaction time. (7)
Where: kPV1 and kPV2 are empirical constants.
The change in concentration of acrylic acid, ethyl alcohol, ester
and water can be deduced from the material balance and can be Solution methodology: The model equations described in the
presented as previous section consists of non-linear differential equations.
− dC A − dCB dCE dCW These ODEs along are solved by an ODE solver, ode45 in
ri = = = = = k1C AC B CC − k −1C E CW CC (2)
dt dt dt dt Matlab, to get the solutions of concentration profile of reactants
and product. The set of kinetic parameters are estimated by a
To consider non-ideal thermodynamic behavior of the reaction nonlinear optimization technique. The error between the model
mixtures, the chemical activities instead of concentrations can and experimental data serves as the objective function to be
be used in the reaction rate equation: minimized by using combination of optimization routine
fmincon and Genetic Algorithm from the Matlab Optimization
ri = k1C Aγ A C B γ B CC − k −1C E γ E CW γ W CC (3) Toolbox. The objective function of the optimization problem is

NC
Where, γA, γB, γE and γW represent the activity coefficient of
φ = ∑ (C ical − C iexp )
2
acrylic acid, ethanol, ethyl acrylate, water and catalyst
i =1 (8)
respectively.

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Research Journal of Engineering Sciences________________________________________________________ ISSN 2278 – 9472
Vol. 6(3), 10-15, March (2017) Res. J. Engineering Sci.

Where: NC is the number of experimental data points for reaction temperature of 50°C, molar ratio of reactants of 1:1 and
concentration of acrylic acid. The kinetic parameters are catalyst loading of 3% (vol). Acrylic acid conversion was
obtained by solving the model equation based on the successive increased from its equilibrium value of 46% to 57.2% in 7 hr by
guess values of the kinetic parameters. using PVA membrane reactor.

In order to study the non-ideality associated with the reaction The increment in the amount of the any reactant shifts the
mixture, we need to consider the activity coefficients along with chemical equilibrium towards the product side. Figure-2
the concentrations to determine the equilibrium constant. Here presents the effect of initial mole ratio of acrylic acidto ethanol,
we considered UNIFAC method to determine the activity MR, on the performance of the pervaporation-esterification
coefficients. The coefficients are directly obtained from Aspen coupled reactor. The simulations were carried out under the
Plus software. operating conditions as temperature of 60°C, CC of 3%, S/V of
14.13 m-1. The reaction rate of esterification increases with an
Results and discussion increase in amount of ethanol. The conversion increased from
78% to 98.8% with changing molar ratio from 1:1 to 1:3.
The main parameters which affect the esterification-PV aided
process can be classified into three groups: i. Factors affecting In esterification catalyst concentration is also another way to
only the esterification kinetics: catalyst concentration, and initial accelerate reaction rate. For the analysis, the catalyst
molar ratio of methanol to salicylic acid. ii. Factors affecting concentration was varied from 1 to 3% of initial volume of the
only the pervaporation kinetics: ratio of effective membrane reacting mixture. The simulation results for conversion of
area to volume of reaction mixture. iii. Factors affecting both acrylic acid during esterification aided PV process over various
the esterification and pervaporation kinetics: temperature. catalyst loadings were presented in Figure-3. It can be seen that
as catalyst concentration increased the conversion of acrylic
The esterification reactions were carried out in aninsitu acid increases due to the availability of more H+ ions enhancing
pervaporation membrane reactor with and without conversion. A catalyst increases the rate of the chemical
pervaporation. The experiments were carried out by changing reaction by making available a new low energy pathway for the
different process parameters such as temperature (50-70oC), conversion of reactants to products5.
initial mole ratio of acrylic acid to ethanol (1:1-1:3), catalyst
concentration (1-3%) and the ratio between the effective An increase in the temperature enhances the esterification
membrane area and reaction volume (14.13-25.505 m-1) were reaction because a higher temperature favors both water
carried out. The results are discussed in further section. removal by pervaporation and the rate of reaction3. Effect of
temperature on the esterification-PV process of acrylic acid and
For the validation of the developed model the obtained results ethanol was studied for the fixed molar ratio of acrylic acid to
are compared with experimental data and are presented in ethanol of 1:1 and 3% (vol) of catalyst by varying temperature
Figure-1. The suggested model predicted results were in good from 50 to 70°C. Figure-4 shows that increasing in temperature
agreement with the experimental data. It was observed that the increases the conversion of acrylic acid. The accelerating of the
PV intensified the conversion of acrylic acid for the PV coupled rate of reaction with the increase of the temperature for the
esterification reaction than for the esterification without PV. For forward reaction was faster than the backward process.
this experiment the operating conditions are considered as

0.7

0.6
Conversion of acid XA

0.5

0.4

0.3

0.2 Series
1
0.1

0
0 100 200 300 400 500
Time (min)
Figure-1: Dependence of conversion on time with and without PV. The solid lines indicate the values predicted by the kinetic
model. (T=50°C, CC=3%, MR=1:1, S/V=14.13m-1).

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Research Journal of Engineering Sciences________________________________________________________ ISSN 2278 – 9472
Vol. 6(3), 10-15, March (2017) Res. J. Engineering Sci.

1.2

Conversion of acid XA
0.8

0.6
1:3
0.4 1:2
1:1
0.2

0
0 100 200 300 400 500
Time (min)
Figure-2: Effect of change in molar ratio on conversion of acrylic acid (T=60°C, CC=3%, S/V=14.13m-1).

0.9
0.8
0.7
Conversion of acid XA

0.6
0.5
0.4
1%
0.3
2%
0.2
3%
0.1
0
0 100 200 300 400 500
Time (min)
Figure-3: Effect of change in concentration of catalyst on conversion of acrylic acid (T=60°C, MR=1:1, S/V=14.13m-1).

0.9
0.8
conversion of acid XA

0.7
0.6
0.5
0.4
70C
0.3
60C
0.2
50C
0.1
0
0 100 200 300 400 500
Time (min)
Figure-4: Effect of the reaction temperature on the conversion of the PV-aided esterification of acrylic acid and ethanol (MR= 1:1,
CC=3%, S/V=14.13m-1).

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Research Journal of Engineering Sciences________________________________________________________ ISSN 2278 – 9472
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1
0.9
0.8

Conversion of acid XA
0.7
0.6
0.5 25.404 m-1
0.4 17.66 m-1
0.3 14.13 m-1
0.2
0.1
0
0200100 300 400 500
Time (min)
Figure-5: Effect of the ratio between the membrane area and reaction volume on the conversion of the PV coupled esterification of
acrylic acid and ethanol (T=60°C, MR= 1:1, CC=3%).

The larger membrane area could remove the byproduct water γE= activity coefficient of ethyl acrylate, γW= activity coefficient
3 2 2
sufficiently, and thus the esterification was enhanced. of water, k1 = forward reaction rate constant((m ) /kmol .min),
Simulations were carried out with changing the ratio of 3 2 2
membrane area to initial reaction volume as 14.13, 17.66 and k-1 = backward reaction rate constant ((m ) /kmol .min), t =
25.404 m-1 and the obtained results were presented in Figure-5. reaction time (min), T = reaction temperature (°C), Keq =
The values for the other operating parameters were the equilibrium constant, S = membrane area (m2), J = total flux
following: molar ratio of initial reactant, 1, catalyst loading, 3%, (gm/m2.min), R = rate constant (8.314 J/mol K), V = volume of
and reaction temperature 60°C. As increasing S/V, the water initial reaction mixture.
removal rate will be more and hence leading to enhanced
conversion. References
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Pervaporation for Production of n -Butyl Acetate. Chinese
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