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Esterification of acrylic acid with ethanol using pervaporation membrane

reactor

Article  in  Korean Journal of Chemical Engineering · May 2017

DOI: 10.1007/s11814-017-0088-z

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 Korean J. Chem. Eng., 34(3), 1-8 (2017) pISSN: 0256-1115
DOI: 10.1007/s11814-017-0088-z eISSN: 1975-7220
INVITED REVIEW PAPER INVITED REVIEW PAPER

Esterification of acrylic acid with ethanol using pervaporation membrane reactor

Ghoshna Jyoti, Amit Keshav†, and Jayapal Anandkumar

Department of Chemical Engineering, National Institute of Technology Raipur (CG), India

(Received 13 December 2016 • accepted 22 March 2017)

Abstract−Esterification of acrylic acid with ethanol was carried out using an in-situ reactor with an integrated per-
vaporation assembly (IPAE) made of polyvinyl alcohol (PVA) membrane and was compared with a non-integrated
(NIE) system. Effect of reaction temperature (Tr), catalyst loading (CC), molar ratios of reactants (MR) and ratio of
effective membrane area to unit volume of reaction mixture (S/Vo) on kinetics of esterification reaction were studied.
Conversions achieved in IPAE were found to be distinctly higher than the NIE. The highest conversion of acrylic acid
was obtained as 83.3% at Tr =60 oC, MR =3 : 1, CC =2% and S/Vo =14.1 m−1. Equilibrium conversion of acrylic acid in
NIE was obtained as 55.1% at 60 oC, 1 : 1 in 7 h, while using IPAE conversion enhances to 67.6%. Esterification of
acrylic acid and ethanol with presently studied operating parameters provides a new approach to existing literature
reported esterification-pervaporation system.

m
er as
Keywords: Pervaporation, Acrylic Acid, Esterification, Kinetics, Equilibrium

co
eH w
INTRODUCTION vaporation unit to esterification reactor could overcome the ther-
modynamic equilibrium barrier due to the simultaneous removal

o.
Merging a reactor with a separation unit has become a recent of side-product (water) continuously with a subsequent reactant
rs e
trend in the chemical industry in order to increase the process effi- reflux to shift the chemical equilibrium towards the greater pro-
ou urc
ciency and lower the energy consumption [1]. Combining a chem- duction of desired product (ester).
ical reactor, executing equilibrium limited reaction, with a mem- Esters of acrylic acid have many industrial uses and hence the
brane based pervaporation unit could result in achieving higher esterification of acrylic acid with different alcohols (methanol, eth-
conversion due to selective removal of the product from the react- anol, n-butanol) has been widely investigated [6,7]. Out of these,
o

ing mixture. In addition, the integration leads to lower production ethyl acrylate is a useful ester that is used as a reactive building block
aC s

cost (product concentration is achieved by-product removal). Per- to produce coatings and inks, adhesives, sealants, textiles, plastics
v i y re

vaporation membrane separation technology has gotten a global and elastomers. Integration of pervaporation with esterification has
reorganization in application for dehydrating organic mixtures [2- been explored in the last few decades for its possibility to intensify
5]. Esterification reactions are reversible with the products being conversion of esterification reactor. In this regard, pervaporation
ester and water. The dehydrating potential of hydrophilic mem- membrane reactors assisted with esterification have been studied
ed d

branes employed in pervaporation units could provide a solution for acetic acid and iso-propanol [8], acetic acid and iso-butanol
to lower yield of the esterification reaction. The integration of per- [9], acetic acid and ethanol [10], lactic acid and ethanol [11,12],
ar stu

Table 1. A few literature studies on effect of process parameters for the esterification-pervaporation process of carboxylic acids with alcohol
System (acid and alcohol) Catalyst Membrane Parameter studied Reference
sh is

Acetic acid and isopropanol p-Toluenesulfonic acid Hydrophilic membrane PERVAP 1005 (GFT) Tr, S/Vo, MR, CC 0[8]
Th

Acrylic acid and n-butanol Amberlyst 131 Hydrophilic membrane, PERVAP 2201 Tr, S/Vo, MR, CC 0[7]
Lactic acid and n-butanol Sulphuric acid Hydrophilic Polyvinyl alcohol-polyether sul- Tr, S/Vo, MR, CC [15]
fone (PVA-PES) composite type membrane
Lactic acid and ethanol Amberlyst 15 CS-TEOS hybrid membranes Membrane casting [16]
solution recipe,
Tr, MR, CC
Acetic acid and ethanol and H2SO4 Acid-stable mordenite membrane Tr, MR, CC [17]
n-butanol
Propionic acid and ethanol Strong-acid ion T-type zeolite membrane Tr, S/Vo, MR [18]
exchange resin 002CR

†
To whom correspondence should be addressed.
E-mail: [email protected]
Copyright by The Korean Institute of Chemical Engineers.

1
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 2 G. Jyoti et al.

lactic acid and iso-propanol [13], acrylic acid and n-butanol [7],
oleic acid and ethanol [14] and many more studies. Table 1 sum-
marizes some studies performed with the parameters and condi-
tions investigated. The studies have focused on the effect of operating
conditions, membrane types and membrane dynamics. Polymeric
and ceramic membranes have shown to have potential in the selec-
tive separation of water from the product of esterification reaction.
Out of these hydrophilic polymeric based membranes (such as
PVA, polyethersulfone, polyetherimide) have been more commer-
cially a success owing to having high hydrophilicity and stable under
acidic conditions. A very few works related to pervaporation-cum-
esterification reactors for esterification of acrylic acid with ethanol
have been available on literature. Truong et al. [2] used both poly-
mer and zeolite based membrane to improve the synthesis of acrylic
esters. They observed that polymeric base membrane performed
better than the zeolite membrane. Additionally, chemical stability
of these membranes was also investigated.
In the present work, we investigated esterification of acrylic acid

m
and ethanol in esterification reactor integrated pervaporation in-

er as
situ unit (IPAE) and compared the non-integrated esterification
Fig. 1. Schematic diagram of the pervaporation-esterification inte-

co
unit (NIE). PVA membrane was used in the pervaporation unit. grated system.

eH w
Employing an in-situ membrane unit could result in reduction of 1. Condenser 06. Sampling point
material cost and time to recycle the reaction and hence prove to 2. Stirrer 07. Membrane

o.
be better against the loop assemblies. Effects of different operating 3. Temperature sensor 08. Chiller/cold trap
rs e
parameters such as reaction and pervaporation temperature (Tr), 4. Heater 09. Valve
ou urc
ratio of membrane area to initial reaction liquid (S/Vo), catalyst con- 5. Reactor 10. Vacuum pump
centration (CC) and initial molar ratio of reactants (MR) on the esteri-
fication pervaporation aided process were investigated. During the experiment, samples were withdrawn from the reactor
at regular intervals. The permeate flux was obtained from the mass
o

MATERIALS AND METHODS of permeate collected, which in turn was obtained gravimetrically.
aC s

3. Sample Analysis
v i y re

1. Materials Samples collected from the reactor and the permeate were ana-
Hydrophilic PVA membrane was supplied by Permionics Mem- lyzed by NUCON series gas chromatography with oven tempera-
branes Pvt. Ltd., India. For the esterification reaction sulfuric acid ture programmed as 180 oC equipped with a thermal conductivity
(homogeneous catalyst) was used as catalyst. Reactants, acrylic acid, detector (TCD). The GC column was a porapak column (id 2 mm,
ed d

ethanol and catalyst were of analytical grade with purity higher od 1/8'', length 2 m) and hydrogen gas taken as carrier gas with
than 99% and obtained from Merck India and were used without flow rate 60 ml/min.
ar stu

further purification.
2. Experimental Procedure THEORETICAL DEVELOPMENT
The IPAE experimental set-up used for the experiments is shown
in Fig. 1. The operation was in-situ batch mode. The membrane The esterification of acrylic acid (A) with ethyl alcohol (B) to
sh is

was placed just below the reactor in a particularly designed stain- produce ethyl acrylate (E) and water (W) can be represented as an
Th

less steel permeation cell, which provided an effective membrane elementary second-order reversible reaction as well as first-order
area (78.5 cm2) in contact with the feed mixture. One reactant was reaction with respect to each reagent and is presented as [19]:
added to the reactor together with catalyst and heated to the de-
C3 H4 O2 + C2 H6 O ↔ C5 H6 O2 + H2 O (1)
sired reaction temperature. Other reactant was heated separately,
and after reaching the reaction temperature was added to the reac- The rate expression for second-order reversible reaction in the pres-
tor. At the same time, the stirrer was started at 300 rpm speed for ence of catalyst can be written by considering the catalyst concen-
the proper mixing of reaction mixture, and the time was taken as tration as CC:
the initial time for the experiment. A thermostat was used to
− dC
maintain the temperature within an accuracy of ±1 oC during the − rA = -------------A- = k1CACBCC − k−1CECWCC (2)
dt
reaction. With the help of hydrophilic membrane (PVA), water
was separated from the feed mixture simultaneously. The pressure where CA, CB, CE, CW and CC represent the concentration (mol/m3)
on the permeate side was held constant at 5 mbar using a vacuum of acrylic acid, ethanol, ethyl acrylate, water and catalyst, respec-
pump and permeates (water rich vapor stream) were condensed and tively. k1 and k−1 are the rate constants of forward and backward
collected using a chiller with temperature maintained at −5 oC. reaction and ‘t’ is the reaction time.

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 Esterification of acrylic acid with ethanol using pervaporation membrane reactor 3

From material balance, the change in concentration of acrylic

acid, ethyl alcohol, ester and water can be represented as
− dC − dC dC dCW
ri = -------------A- = -------------B = --------E- = ----------
- = k1CACBCC − k−1CECWCC (3)
dt dt dt dt

Eq. (3) can be written as

d( C ) C E C W⎞
− ri = -----------i- = k1CC⎛⎝CACB − -------------
- (4)
dt Keq ⎠

where, the equilibrium constant (Keq) can be calculated by the fol-

lowing equation:
k CE C W
Keq = ------1- = -------------
- (5)
k−1 CACB

By combining pervaporation with esterification, the change of con-

centration can be written as follows: Fig. 2. Comparison of conversion of acrylic acid with time in esteri-
d(Ci ) S
fication of acrylic acid with ethanol in IPAE and NIE system
------------ = ri − ------ Ji (6) (Tr=60 oC, MR=1 : 1, CC=2%, S/Vo=14.1 m−1).
dt Vo

m
er as
The effective surface area of the membrane (S) and total flux of the

co
membranes is determined by:

eH w
J=W/(S·t) (7)

o.
where W, S and t denotes the permeate amount, effective mem-
rs e
brane area and reaction time, respectively. The partial flux of com-
ou urc
ponents (Ji) is the function of total flux and weight fraction of the
component in permeate (xi).
Ji=Jxi (8)
o

In the present work, a hydrophilic PVA membrane was used and

aC s

thus the partial fluxes of acrylic acid, ethanol and ethyl acrylate were
v i y re

neglected (JEthanol~JAcid~Jester~0) [7,20].

RESULTS AND DISCUSSION

ed d

In this study, experiments involved a laboratory-scale reactor with Fig. 3. Comparison of concentration of water with time in esterifi-
and without pervaporation unit. The effect sof the various operat- cation of acrylic acid with ethanol in IPAE and NIE system
ar stu

(Tr=60 oC, MR=1 : 1, CC=2%, S/Vo=14.1 m−1).

ing parameters such as reaction temperature, molar ratio of the
reactant, catalyst concentration, ratio of effective membrane area
and unit volume of reaction mixture on reaction as well as separa- centration profile of water in the reaction mixture for the per-
tion were studied. The results obtained in this study are discussed vaporation-esterification process, which shows that at the begin-
sh is

in the following sections. ning the content of water increases until a maximum value has been
Th

1. Comparison of Esterification with Pervaporation and With- reached. After this, the water concentration in the reactor decreases
out Pervaporation continuously due to the water removal by pervaporation from the
Conversion of acrylic acid in the esterification process of acrylic reaction mixture, which in turn is much faster than its formation
acid and ethanol mixture was studied using NIE and IPAE sys- rate by esterification [8]. At t=0, there is no water present. At the
tem. The obtained results are shown in Fig. 2 and 3. Fig. 2 pres- start of reaction when t is slightly greater than 0, water starts form-
ents the conversion of acrylic acid at a Tr of 60 oC, CC of 2% and ing but the concentration is not large so in both IPAE and NIE,
with MR of 1. The conversion in IPAE is distinctly higher than in the water is produced at the same rate till it attains a peak (maxi-
NIE. This is attributed to the continuous water removal from the mum value). Thereafter in NIE, it continues to increase as the
reaction mixture by the IPAE, which increased the yield of ethyl water starts building up. As the reaction is reversible, this leads to
acrylate. Conversion of acrylic acid in the NIE was obtained to be more or less stabilization of the conversion of acrylic acid as seen
54.8% which increased to 67.6% with IPAE in 7 h time. for time 180 min onwards in without pervaporation unit. Water
Since IPAE is responsible for the increase in conversion, a better concentration increases from 3.8 to 4.7 mol/m3 in time 180 to 420
view of the obtained results can be presented if water concentra- min. On the other hand, in IPAE, water concentration in the reac-
tion is monitored with respect to time. Fig. 3 represents the con- tor falls from 3.1to 2.4 kmol/m3 which leads to the shoot.

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 4 G. Jyoti et al.

Hasanoglu et al. [10] observed that by using pervaporation mem- m−1). Fig. 4 shows the variation of conversion of acrylic acid ver-
brane system the conversion of acid increased from 57.5% to 65.8%, sus time at different temperatures. Both reaction rate and perme-
Han et al. [1] found from 56.3 to 70.0% increase, Ameri et al. [21] ation rate are influenced by the reaction temperature. It can be
obtained from 49.0 to 59.0% increase and Zhang et al. [18] ob- seen from Fig. 4 that while increasing reaction temperature from
served from 82.6% to 90.8% increase on other acids. The obtained 50 to 70 oC th conversion also increases from 57.2 to 72.9% and
results agree with literature in pervaporation aided system of vari- the IPAE unit significantly increases the conversion of acrylic acid
ous acid and alcohol. from 45.0% to 57.2%, from 55.1% to 67.6% and from 63.2% to
2. Effect of Reaction Temperature 72.9% at temperatures of 50, 60, and 70 oC, respectively. Higher tem-
Esterification of acrylic acid+ethanol mixture was studied at var- perature is appropriate for the increase in rate of the forward reac-
ious reaction temperatures in an in-situ membrane reactor of IPAE tion compared to backward reaction [22-24].
and NIE system with constant MR (1.0), CC (2%) and S/Vo (14.13 With increasing temperature, the permeation rate through the

m
er as
co
eH w
o.
rs e
ou urc
Fig. 4. Effect of the reaction temperature on the conversion of acrylic Fig. 5. Effect of the reaction temperature on water concentration in
o

acid in the esterification of acrylic acid and ethanol mixture the esterification of acrylic acid and ethanol mixture using
aC s

(MR=1 : 1, CC=2%, S/Vo=14.1 m−1). IPAE system (MR=1 : 1, CC=2%, S/Vo=14.1 m−1).
v i y re

Table 2. Overview of effect of temperature on the conversion of acrylic acid of the pervaporation-aided esterification process and Compari-
son of results of esterification reaction with and without pervaporation process
Operating conditions Conversion of acid (%)
Intensification
ed d

System Tr Without With Reference

Constant parameters (%)
ar stu

(oC) pervaporation pervaporation

50 44.9 57.2 27.3
Acrylic acid MR =1 : 1, Cc =2%, S/Vo=14.1 m−1,
60 55.1 67.6 22.6 Present work
and ethanol t=420 min
70 63.2 72.9 13.3
sh is

70 79.9 83.4 04.2

Propionic acid MR =2 : 1, S/Vo=0.1059 m2 ·kg−1,
Th

80 83.3 92.0 09.4 [18]

and ethanol t=420 min
90 85.3 97.4 12.4
50 47.8 51.7 07.5
Acetic acid and MR =1 : 1, CC=5 g, Amberlyst 15/100 g
60 51.0 65.1 21.7 [10]
ethanol acetic acid, t=360 min
70 66.0 71.3 07.4
Acetic acid and MR =1 : 1, CC=1 g sulfuric acid/100 g ace-
60 65.3 70.6 08.1 [10]
ethanol tic acid, S/Vo =13.3 m−1, t=360 min
65 36.5 68.8 46.9
Acrylic acid
MR =4, CC 10 g/L, t=360 min 75 54.3 86.0 36.9 [7]
and n-butanol
85 71.5 93.5 23.5
Oleic acid and MR =15 : 1, t=420 min 80 56.3 70.0 19.6
[1]
ethanol MR =15 : 1, t=1440 min 80 84.2 87.2 03.4

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 Esterification of acrylic acid with ethanol using pervaporation membrane reactor 5

membrane as well as the water production rate by esterification

increases. As a result, water concentration has a higher maximum
value for a higher reaction temperature (Fig. 5). At earlier stage of
the reaction the water content went through its maximum value,
due to a slower backward reaction rate; after water content reached
the maximum value, it decreased faster due to a higher backward
reaction rate.
Vapor pressure of permeating components in the upstream side
of the membrane was increased, when operating temperature in-
creased. Due to vapor pressure difference between the upstream
and downstream side of the membrane the transport driving force
was enhanced. As a result, with increasing temperature attained
higher molecular diffusivity; so, the mass transport was faster. More-
over, polymer chains became more flexible and accommodated
larger available free volume of the polymer matrix for diffusion, as
temperature was increased, which allowed easier water transfer
across membrane [16]. Fig. 7. Effect of the catalyst loading on the conversion of esterifica-
Comparative statement of different literature reported esterifica- tion of acrylic acid and ethanol in IPAE (Tr=60 oC, MR=1 : 1,

m
tion reaction system using IPAE and NIE unit is given in Table 2. S/Vo=14.1 m−1).

er as
Conversion and percentage intensification in the reported systems

co
do vary from the present work due to many changes in the esteri- varying the catalyst amount to 1, 1.5 and 2 (vol) % of initial reac-

eH w
fication-pervaporation operating conditions in those systems. How- tion mixture (Fig. 7). Increasing catalyst amount obviously increases
ever, our results are comparable and better than many literatures’ the reaction rate because reaction rate is proportional to catalyst

o.
reported work. concentration and water production rate. Consequently, an increase
rs e
The Arrhenius plot of water flux versus temperature for esterifi- in the amount of catalyst leads to an increase in the water produc-
ou urc
cation of acrylic acid+ethanol system is illustrated in Fig. 6. An tion rate and thus increases in water permeation flux. Less amount
increase in temperature increases the flux of water. Activation energy of catalyst (up to 2%) was considered for experiments because of
of water permeation across the PVA membrane is 17.5 kJ/mol, which its corrosive nature. Conversions of acrylic acid were obtained as
reveals high energy requirement for water permeation through the 50.4% and 67.6% after 7 h for the lowest and highest values of cat-
o

PVA membrane. Sert and Atalay, [7] reported the need of 36.5 kJ/ alyst concentration, respectively, which indicates that catalyst con-
aC s

mol activation energy for Pervap 2201 membrane for acrylic acid+ centration had significant effect on the reaction. Both forward and
v i y re

n-butanol system. Similarly, Yun et al. [25] also reported the Arrhe- backward reaction rate was varied with the change of catalyst con-
nius relationship between temperature and water flux for water/ centration, and thus increasing the catalyst loading favors the for-
organic separation. Activation energies for water permeation in mation and removal of water. The concentration of water in the
binary water/organic systems were reported to be 9.1, 13.5, and reactor was higher for a higher catalyst loading, and it increased at
ed d

4.4 kJ/mol for water/n-butanol, water/n-butyl acetate and water/ initial stage during the reaction and reached a maximum value
acetic acid, respectively.
ar stu

3. Effect of Catalyst Concentration

For this study, experiments were performed at a constant Tr of
60 oC and with an MR of 1. The effect of CC was investigated by
sh is
Th

Fig. 8. Effect of the catalyst loading on the concentration of the water

of esterification of acrylic acid and ethanol in IPAE (Tr=
Fig. 6. Arrhenius plot of water flux vs. temperature. 60 oC, MR=1 : 1, S/Vo=14.1 m−1).

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 6 G. Jyoti et al.

Table 3. Overview of effect of catalyst concentration on the conversion of acrylic acid of the pervaporation-aided esterification process
Operating conditions Conversion
System Reference
Constant parameters CC of acid (%)
1 50.4
Acrylic acid and Tr =60 oC, MR =1 : 1,
1.5 60.4 Present work
ethanol S/Vo=14.1 m−1, t=420 min
2 vol% 67.6
10 89.0
Acrylic acid and
Tr=85 oC, MR =4 : 1, t=360 min 15 92.1 0[7]
n-butanol
20 g/L 95.5
0.1 68.5
0.2 77.7
Lactic acid and Tr=90 oC; MR =1.4; S/Vo=15.2 m−1,
0.3 82.7 [13]
iso-propanol t=8 h
0.4 85.8
0.5 kmol/m3 87.6
0.1 75.1
0.2 80.3
Lactic acid with Tr=90 oC; MR =1.4; S/Vo =15.2 m−1,

m
0.3 84.9 [15]
n-butanol t=480 min

er as
0.4 87.6
0.5 kmol/m3 88.9

co
eH w
0 18.0
Acetic acid and o 2.1 33.0

o.
Tr=80 C; MR =0.66, t=180 min [26]
benzyl alcohol 4.1 46.0
rs e 11 mol/m3 49.0
ou urc
and beyond that it decreased with time (Fig. 8). In case of 1% cat-
alyst concentration the water removal rate was much less in com-
o

parison to production rate; therefore, water concentration tended

aC s

to increase with time. But at higher catalyst concentration, water

v i y re

concentration in the reactor dropped beyond 180 min. Higher par-

tial pressure of water was created in the vapor phase due to in-
crease in water production rate in reactor while passing through
the membrane, which resulted in increase in water permeation
ed d

[21]. Table 3 reviews the results in terms of conversion obtained

by researchers by using various IPAE. Similar kinds of results have
ar stu

been reported as obtained by experiments and showed that con-

version of acid increased with increasing amount of catalyst.
4. Effect of Molar Ratio of Ethanol to Acrylic Acid
The effect of initial MR of ethanol to acrylic acid (EOH : AA)
sh is

was investigated over a range of 1 : 1 to 3 : 1. All the experiments

were in an IPAE reactor at 60 oC and 2% catalyst loading of initial
Th

Fig. 9. Effect of the initial alcohol/acid molar ratio on the conver-

reaction mixture. Using excess amount of one reactant (generally sion of the esterification of acrylic acid and ethanol in IPAE
alcohol) did ensure higher conversions. It is evidence from Fig. 9 (Tr=60 oC, CC=2%, S/Vo=14.1 m−1).
that the initial rate of increase of conversion of acrylic acid was
more for high MR 3 : 1 as compared to other MR (2 : 1 and 1 : 1).
The conversion of acrylic acid increased from 67.6% to 83.3% at EOH : AA ratio increased, the water production rate decreased,
7 h when the initial molar ratio of ethanol to acrylic acid increased which led to decrease in maximum water content. Initial molar
from 1 : 1 to 3 : 1 due to increased excess ethanol. Table 4 summa- ratio of reactant had an effective role in reaction rate, but exerted
rizes related studies to the effect of MR on the IPAE and shows no effect on pervaporation kinetics [16]. In the study of esterifica-
that acid conversion increased with the increase MR. tion pervaporation coupled process, similar behavior has been de-
Fig. 10 represents the water concentration profile in reacting picted in the literature [8,27].
mixture during the reaction. Similar kind of trend line was observed 5. Effect of the Membrane Area to Initial Solution Volume
for all three molar ratios of reactants. However, water concentra- Ratio (S/Vo)
tion was max for low MR and it was low for high MR. When the S/Vo ratio has significant impact on pervaporation process due

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 Esterification of acrylic acid with ethanol using pervaporation membrane reactor 7

Table 4. Overview of effect of initial molar ratio (MR) on the conversion of acrylic acid of the pervaporation-aided esterification process
Operating conditions Conversion
System Reference
Constant parameters MR (alcohol : acid) of acid (%)
1:1 67.6
Acrylic acid Tr =60 oC, CC=2 vol%,
2:1 74.2 Present work
and ethanol S/Vo=14.1 m−1, t=420 min
3:1 83.3
1:1 84.4
Propionic acid Tr =90 oC, S/Vo=1059 cm2 ·kg−1, 1.5 : 1 93.6
[18]
and ethanol t=420 min 2:1 96.3
3:1 97.5
4:1 90.7
Acrylic acid
Tr =85 oC, CC=10 g/L, t=360 min 6:1 93.6 0[7]
and n-butanol
8:1 95.6
Acetic acid and Tr =60 oC, CC=1 g sulfuric acid/ 1:1 70.7
[10]
ethanol 100 g acetic acid, t=360 min 1.5 : 1 79.7
Acetic acid and Tr =60 oC, CC=5 g Amberlyst 15/ 1:1 64.0

m
[10]

er as
ethanol 100 g acetic acid, t=360 min 1.5 : 1 70.0
1:1 68.2

co
Lactic acid and
Tr =75 oC, S/Vo=23 m−1, CC =2 wt%

eH w
2:1 86.5 [11]
ethanol
3:1 89.6

o.
rs e
ou urc
o
aC s
v i y re
ed d
ar stu
sh is

Fig. 10. Effect of the initial alcohol/acid molar ratio on the concen- Fig. 11. Effect of the ratio of membrane area to initial volume on
tration of the water esterification of acrylic acid and etha- the concentration of the water of the esterification of acrylic
Th

nol in IPAE (Tr=60 oC, CC=2%, S/Vo=14.1 m−1). acid and ethanol in IPAE (Tr=60 oC, CC=2%, MR=14.1 m−1).

to its influence on water extraction rate. In the present work, ester- 79.1 and 83.0% by varying the S/Vo as 35, 52.5 and 70 m−1. Zhang
ification experiments were carried out using constant membrane et al. [18] also reported the increase of conversion from 90.0% to
area (78.5 cm2) by changing the initial reaction volume and em- 99.8% with membrane area to initial reaction liquid (S/m), rang-
ploying S/Vo as 14.1, 17.6 and 25.4 m−1. The obtained results for ing from 158.9 to 1,059 cm2·kg−1.
various S/Vo ratios on acrylic acid conversion and concentration of When membrane area per unit reaction volume was increased
water in esterification reaction are shown in the Fig. 11 and Fig. 12 from 14.1 to 25.4 m−1, the concentration of water in the reactor
while keeping the other operating parameters as constant (MR dropped drastically from 2.4 to 1.8 kmol/m3. The water removal
(1 : 1), CC (2%) and Tr (60 oC)). The conversion of acrylic acid in- rate decreased with the decrease of S/Vo; however, water produc-
creased from 67.6 to 76.1% with increase of S/Vo ratio from 14.1 tion rate was similar for various S/Vo. In this study, ratio of the
to 25.4 m−1, respectively with equilibrium time period of 7 h (Fig. membrane area and the reaction volume was selected based on
11). Similarly, Sert and Atalay [7] obtained the conversion as 71.8, economical point of view [28].

Korean J. Chem. Eng.

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 8 G. Jyoti et al.

MR : initial molar ratio of alcohol to acid

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June, 2017
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