Chemical Engineering and Processing 81 (2014) 41–47

Contents lists available at ScienceDirect

Chemical Engineering and Processing:

Process Intensification
journal homepage: www.elsevier.com/locate/cep

n-Butyl acrylate production by esterification of acrylic acid with

n-butanol combined with pervaporation
Emine Sert ∗ , Ferhan S. Atalay
Ege University, Chemical Engineering Department, Bornova, Izmir, Turkey

a r t i c l e i n f o a b s t r a c t

Article history: In this study, the esterification reaction of acrylic acid and n-butanol to produce n-butyl acrylate and water
Received 9 January 2014 was studied using the pervaporation–esterification hybrid process to perform the separation and reaction
Received in revised form 24 February 2014 simultaneously to increase the conversion of limiting reactant. A Pervap 2201 polymeric membrane
Accepted 22 April 2014
was used to separate water and also to shift the equilibrium. The Pervap 2201 membrane showed high
Available online 30 April 2014
selectivity to water in the n-butanol, acrylic acid, n-butyl acrylate, and water reaction system. The effects
of temperature, the initial molar ratio of n-butanol to acrylic acid, catalyst loading, and the ratio of
Keywords:
membrane area to reaction volume (S/V) were studied. The maximum conversion of acrylic acid was
Pervaporation
Esterification
calculated as 96.3% at a temperature of 358 K, a molar ratio of 8, with a catalyst loading of 10 g/L and an
Membrane S/V ratio of 70 m−1 .
n-Butyl acrylate © 2014 Elsevier B.V. All rights reserved.

1. Introduction distillation. They concluded that the process intensification can

decrease the equipment needed, thereby reducing the investment
The coupling of reaction and separation has become a current and operating costs. Due to high risk of polymerization of acrylic
trend in the chemical industry in order to obtain more efficient acid and butyl acrylate, Niesbach et al. [5] present an experimental
processes and lower energy consumption. A classic example is the investigation of inhibition period of acrylic acid and n-butyl acrylate
production of esters, which are traditionally obtained by reacting polymerization. In their study, hydroquinone and phenothiazine
an organic acid and an alcohol in the presence of suitable cata- were used as inhibitors. The pilot plant reactive distillation exper-
lysts. A major difficulty in such reactions is the limitation by the iments were conducted to show proper concept of polymerization
thermodynamic equilibrium, which requires a separation step with inhibition successfully in the industrial application.
a subsequent reactant reflux allows to shift the chemical equilib- The integration of a pervaporation process into a conven-
rium toward the ester production [1]. According to the Le Chatelier tional esterification process is attractive because it provides the
principle, the yield and selectivity of the targeted compound are opportunity to continuously shift the conversion beyond the ther-
increased by the removal of the byproducts of the reaction. Ester- modynamic equilibrium by removing water from the chemical
ification reactions produce water as byproduct that reduces both reactor [6,7]. Pervaporation has been proven to be a successful
catalytic activity and forward reaction rate. Studies by Kusdiana technique for selectively removing a certain component from a
and Saka [2] on the esterification and transesterification reactions liquid mixture because of its low energy requirements and its abil-
reveal that the presence of water deactivates the catalyst activity, ity to separate azeotropic mixtures [8]. Pervaporation solely relies
which decreases the reaction rate. on the solubility and transport rate of each component. Pervapor-
Among the hybrid processes, reactive distillation which com- ation also demonstrates incomparable advantages in separating
bines reaction and separation processes in a single unit was applied heat sensitive, close-boiling, and azeotropic mixtures due to its
for n-butyl acrylate synthesis. Zeng et al. [3] studied the design mild operating conditions, no emission to the environment, and
and control of a reactive distillation column for the production of no involvement of additional species into the feed stream [9].
n-butyl acrylate. Also, Niesbach et al. [4] studied an experimen- The application of pervaporation to reversible reactions such
tal and theoretical investigation of butyl acrylate using reactive as esterification has been studied in recent studies. Figueiredo
et al. [10] studied the pervaporation-assisted esterification of oleic
acid with ethanol using hydrophilic Pervap 1000 membrane. The
hydrophilic membrane was able to remove water from the reaction
∗ Corresponding author. Tel.: +90 232 3111493; fax: +90 232 388 7776. mixture, thus increasing the ester yield. In another study, Delgado
E-mail address: [email protected] (E. Sert). et al. [11] studied the synthesis of ethyl lactate from ethanol and

http://dx.doi.org/10.1016/j.cep.2014.04.010
0255-2701/© 2014 Elsevier B.V. All rights reserved.
42 E. Sert, F.S. Atalay / Chemical Engineering and Processing 81 (2014) 41–47

lactic acid in a batch reactor combined with a pervaporation unit. Table 1

The properties of Amberlyst 131 (as reported by the manufacturer).
A hydrophilic membrane Pervap 2201 was used and almost total
use of lactic acid was achieved. Korkmaz et al. [12] studied the Amberlyst 131
esterification reaction between acetic acid and iso-butanol by using
Manufacturer Rohm and Haas
polydimethylsloxane (PDMS) membrane. The experiments indicate Polymer type Macroreticular
that the PDMS membrane can be used to remove iso-butyl acetate Matrix type Styrene divinyl benzene
selectively by the pervaporation process. Functional group Sulfonic acid
Ionic form H+
Polyvinyl alcohol (PVA) is a polyhydroxy polymer, which is very
Exchange capacity, meq/mL 1.35
common in practical applications because of its easy preparation Maximum operating temperature, ◦ C 120
and biodegradability. It has been selected as polymer matrix in Particle size, mm 0.7–0.8
view of its film-forming capacities, hydrophilic properties and high
density of reactive chemical functions favorable for cross-linking
by irradiation, chemical or thermal treatments [13]. In general,
Table 2
polyvinyl alcohol (PVA) membranes when applied to the pervapor- The properties of Pervap 2201 (as reported by the manufacturer).
ation aided esterification processes must be cross linked to avoid
the esterification of the alcoholic groups of the membrane and its Pervap 2201

consequent loss of its separative properties. The polymeric material Manufacturer Sulzer ChemTech.
presents high hydrophilicity and stability under acidic conditions Maximum temperature ( C) ◦
105
when undergoing the cross linking treatment. Maximum water content in feed (%) <50
Butyl acrylate is a clear colorless liquid with a characteris- Organic acids <50
tic fruity odor. It is readily miscible with most organic solvents. pH 2–7

It is readily polymerized and shows a wide range of properties

dependent on the selection of the monomer and reaction condi-
tions. n-Butyl acrylate is used in the production of homopolymers
and co-polymers [3]. n-Butyl acrylate was synthesized from the cat- 2.2. Procedure
alytic esterification of acrylic acid with n-butanol catalyzed with
acidic catalysts. In esterification reactions, homogeneous catalysts To explore the pervaporation aided esterification process,
such as H2 SO4 , p-toluene sulphonic acid [14–16], and heteroge- experiments were done in a batch reactor given in Fig. 1. The mem-
neous catalysts [17–19] can be used to accelerate the reaction. brane was placed in the stainless steel reactor with a volume of
Catalysis with cation exchange resins offers several advantages 2 L. The effective membrane area is about 179 cm2 . n-Butanol, cat-
over homogeneous acid catalysis. Resins are easily separated from alyst, and inhibitor were put in the reactor together and heated
the reaction medium and they can be reused without handling up to the reaction temperature. The preheated acrylic acid was
and storage concerns [20]. Moreover, ion exchange resins elimi- added to the reactor and the temperature was kept constant at the
nate corrosion and environmental problems. However, they have reaction temperature. The pressure at the permeate side was kept
low thermal, stability and possibility of diffusion and deactivation constant at 4 mbar using a Vacuubrand RZ 2.5 vacuum pump and
problems [21]. permeates were collected using two cold traps. During the exper-
In the literature, several studies of pervaporation coupled ester- iments, samples were taken from both the reaction mixture and
ification of some acids with alcohols have been stated, while permeate and analyzed by gas chromatograph (GC). The condi-
esterification of acrylic acid with n-butanol was not investigated. In tions of the GC analysis were reported in our previous study [22].
this study, pervaporation assisted esterification reaction of acrylic The amount of water in each sample was measured with a Mettler
acid and n-butanol, yielding n-butyl acrylate and water was stud- Toledo v20 Karl Fisher titrator during the experiment. The repro-
ied. Also, the effect of membrane process on the shift of the chemical ducibility of GC and Karl fisher analysis were found to be ±1.41 and
equilibrium was considered. The influences of catalyst loading, ±3.12, respectively. The operational conditions are summarized
temperature, the initial molar ratio of reactants, and ratio of mem- in Table 3.
brane area to volume of the reaction mixture were investigated by
using the polymeric membrane, Pervap 2201.

2. Materials and methods

2.1. Chemicals

The membrane used in the esterification of acrylic acid with n-

butanol was the commercial hydrophilic membrane Pervap 2201
(Sulzer ChemTech). Acrylic acid (Merck, purity >99) and n-butanol
(Merck, purity >99) were used as reactants and phenothiazine
was used as inhibitor to prevent any polymerization reaction.
Amberlyst 131 is a macro porous resin made of styrene divinyl ben-
zene copolymer functionalized with sulfonic groups that ensure
strong acidity of the catalyst. Some characteristics and physi-
cal properties of Amberlyst 131 and Pervap 2201 are given in
Tables 1 and 2, respectively. The catalyst reusability was discussed
in previous study [22] and Amberlyst 131 was found to be reusable
Fig. 1. Diagram of the esterification coupling with pervaporation ((1) condenser,
four times without deactivation and can be regenerated after (2) heater, (3) mixer, (4) catalyst basket, (5) membrane, (6) stainless steel sheet, (7)
deactivation. traps, (8) valve, (9) pump).
 E. Sert, F.S. Atalay / Chemical Engineering and Processing 81 (2014) 41–47 43

Table 3
The operational conditions for pervaporation-assisted esterification experiments.

T (K) Butanol/acrylic acid CL (g/L) S/V (m−1 )

Effect of temperature 338 4 10 70

348 4 10 70
358 4 10 70
Effect of catalyst loading 358 4 10 70
358 4 15 70
358 4 20 70
Effect of molar ratio of hexanol to acrylic acid 358 4 10 70
358 6 10 70
358 8 10 70
Effect of S/V 348 4 10 35
348 4 10 52.5
348 4 10 70

3. Theory The total flux was determined from the weight of the permeate
and the area of the membrane;
3.1. Reaction kinetics
W
J= (5)
St
The esterification reaction between acrylic acid and n-butanol
is given below: where W, S and t denote the permeate amount, effective membrane
area, and reaction time, respectively.
C3 H4 O2 + C4 H9 OH ↔ C7 H12 O2 +H2 O (1) The partial fluxes of components (Ji ) are the function of total flux
The kinetic study was studied in our pervious study and the and weight fraction of the component in permeate.
details of determination of reaction kinetics were given [22]. The
Ji = Jyi (6)
Langmuir–Hinshelwood–Haugen–Watson (LHHW) model which
takes into account the adsorption of reactants and desorption of As for the esterification–pervaporation coupling process, the
products fits the experimental data; ratio (F) of rates of water removal to water production rate is
 1
 decided to be key factor defined as:
Ccat kf Kacid Kalchohol aacid aalchohol − a a
K ester water
ri = JD S/V
(1 + Kacid aacid + Kalchohol aalchohol + Kester aester + Kwater awater )2 F= (7)
(2) dCD /dt

where Ki is the adsorption constant of components, kf is the for- where F is a dimensionless parameter that refers for the relation
ward reaction rate constant, Ccat is the catalyst loading, ai are the between water removal rate and water production rate during the
activities of the species (ai =  i xi ),  i are the activity coefficients of esterification–pervaporation hybrid process, and when
the components which were determined by UNIQUAC method to
consider the non-ideality of the reaction mixture. • F < 1, the rate of water removal is less than the water production
The temperature dependency of forward reaction rate constant, rate, showing that the conversion can be increased a little over the
equilibrium constant and adsorption constants of compounds were equilibrium conversion, and it is controlled by the water removal
determined in our specified work. These results illustrate that the due to the pervaporation.
reaction is exothermic, and because of exothermicity equilibrium • F > 1, the rate of water removal is larger than the water produc-
constants decreased as the temperature was raised. The equilib- tion rate, showing that the conversion of limiting reactant can
rium constants were found to decrease in agreement with Ali et al. reach 100%, and it is controlled by the water production rate by
[23] who found the same trend while studying the esterification of chemical reaction [24].
2-propanol with acetic acid.
3.3. Pervaporation in terms of the Hansen solubility parameters
3.2. Reaction and pervaporation
In the separation of organic-liquid mixtures by pervaporation,
The stoichiometry of the esterification of acrylic acid with n- selectivity is caused by the differences in solubility and/or diffu-
butanol was defined in Eq. (1). This is reversible reaction which sivity in a membrane among feed components. The increase of the
proceeds with the formation of the products, n-butyl acrylate and solubility difference leads to further swelling of the membrane by
water. its plasticization and results in reduction of the selectivity [25].
From the GC analysis, the conversion of limiting reactant was The Hansen solubility parameters (ıd , ıp , ıh ) have been defined
calculated as follows: as follows:
Conversion of limiting reactant ı2t = (ı2d + ı2p + ı2h ) (8)
moles of limiting reactant consumed
= (3) where ıd , ıp , and ıh are contributions from the non-polar interac-
initial moles of limiting reactant tion, dipole interaction and hydrogen bonding, respectively.
Table 4 shows the solubility parameters of n-butanol, acrylic
By applying a material balance, the variation in the number of acid, n-butyl acrylate, water and polyvinyl alcohol (PVA). The dif-
mole of species i can be expressed as ference in the solubility parameter  was calculated from the
dNi differences between the compounds and PVA;
= ri VCcat − Ji S (4)      
dt
 = ınBUOH − ıPVA  ,  = ıAcAc − ıPVA  ,  = ıwater − ıPVA  ,
where Ji is the flux (mol/m2 h) of component i, and S is the mem-  
brane area (m2 ).  = ınBuAc − ıPVA  (9)
44 E. Sert, F.S. Atalay / Chemical Engineering and Processing 81 (2014) 41–47

Table 4 without PV, 338 K without PV , 348 K without PV, 358 K

The solubility parameters of n-butanol, acrylic acid, n-butyl acrylate, water and PVA.
with PV, 338 K with PV, 3 48 K with PV, 358 K
100
ıd (cal1/2 cm−3/2 ) ıp (cal1/2 cm−3/2 ) ıh (cal1/2 cm−3/2 )

Conversion of acrylic acid (%)

n-Butanol 8.7 3.0 7.7 80
Acrylic acid 9 3.2 7.5
n-Butyl acrylate 8.6 3.9 2.45
Water 7.6 7.8 20.7 60
PVA 7.8 6.9 11.7

40

As shown in Table 4, the differences in the solubility parameters 20

were calculated from Eqs. (8) and (9). The water–PVA interaction
gives the maximum solubility difference, , so the highest coupling
is achieved between water and PVA.

4. Results and discussion Fig. 2. Effect of pervaporation on the conversion of acrylic acid.

In an esterification–pervaporation hybrid process there are Fig. 3. It can be seen that partial fluxes of components were found in
mainly four operating variables: temperature, initial reactant molar the following order Jwater > JBuOH ∼ Jacid ∼ Jester ∼ 0. The Pervap 2201
ratio, ratio of membrane area to initial volume of reaction mix- membrane showed good selectivity for water when exposed to the
ture, and catalyst loading. David et al. [26] divided these important reaction mixture. Water is clearly the dominant component in the
variables into different groups: (1) factors which affect directly the total flux because of the high selectivity of the membrane for water
esterification kinetics: catalyst loading and initial reactant molar [29]. The flux of water increases rapidly with time especially during
ratio, (2) factors that affect directly pervaporation: ratio of effective the first five hours and then decreases because of a decreasing driv-
membrane area to initial volume of reaction mixture, (3) factors ing force. As the temperature increased, the flux of water increased.
that affect simultaneously the esterification and pervaporation: An increase in temperature enhances the esterification reaction
temperature. because of the higher temperature and water removal by perva-
Internal mass transfer resistance was eliminated according to poration.
the Weisz Prater criterion for the esterification of acrylic acid with Fig. 4 shows the Arrhenius plot of water flux versus tempera-
n-butanol in our previous study [22]. Also external mass trans- ture. The activation energy of water permeation across the Pervap
fer resistance can affect the heterogeneous catalytic esterification 2201 is 36.52 kJ/mol. These values show that high energy is needed
reaction negatively. It was proven in our previous study [22] that for water permeation through the Pervap 2201; this is compatible
the external mass transfer resistance can be eliminated at 800 rpm. with the strong temperature effect shown in Fig. 2. According to
So, the experiments were performed at a stirring speed of 800 rpm. the Arrhenius relationship, an increase in temperature causes to an
The polymerization tendency of acrylic acid and n-butyl acrylate increase in the permeation flux of water.
is well-known. In this work, phenothiazine was used as inhibitor
and polymerization was not observed during the experiments and 4.1.2. Molar ratio of n-butanol to acrylic acid
analysis. The effect of molar ratio on the conversion of acrylic acid was
Pervaporation assisted esterification experiments were per- studied at a temperature of 358 K and a catalyst loading of 10 g/L.
formed at different operating parameters to study the effects of The initial molar ratio of n-butanol to acrylic acid varied between
temperature, the initial reactant molar ratio, the ratio of membrane 4, 6 and 8 because of the pH limitation of the Pervap 2201 mem-
area to the initial volume of reaction mixture, and catalyst loading. brane. As shown in Fig. 5, the conversion of acrylic acid increased
slightly due to an increased excess of n-butanol, as the mole ratio
4.1. Effect of operating parameters of n-butanol to acrylic acid was increased. It is well known that
an excess amount of one reactant generally alcohol causes the
4.1.1. Temperature increased conversions [30]. Fig. 6 shows the partial fluxes of each
The esterification of acrylic acid with n-butanol was studied component through the membrane for different molar ratios of n-
both with and without a membrane at a molar ratio of n-butanol butanol to acrylic acid. As can be seen, the fluxes of water through
to acrylic acid of 4 and a catalyst loading of 10 g/L. The experi- membrane are much higher than those of n-butanol, acrylic acid,
ments were performed at three different temperatures (338, 348, and n-butyl acrylate. This is not unexpected because the solubility
and 358 K) catalyzed by Amberlyst 131. Fig. 2 shows the conversion parameter of Pervap 2201 is closer to water than other components.
of acrylic acid versus time for all temperatures. As given in Fig. 2, The difference in the solubility parameter between each pair is in
the batch pervaporation process increases the conversion of acrylic the order of butyl acrylate-membrane > acrylic acid-membrane > n-
acid significantly. Conversions of acrylic acid increased from 36% to butanol-membrane > water-membrane, indicating that water and
69%, from 53% to 84% and from 70% to 92% at temperatures of 338, the membrane pair has the strongest interaction since they have the
348, and 358 K, respectively. Due to the water removal from the closest solubility parameter compared to the other pairs. As shown
reaction mixture, the conversion of acrylic acid obtained with the in Fig. 6, there is a change in the total flux of water as the molar
pervaporation–esterification hybrid process is significantly higher. ratio is increased; this result is confirmed with the conversion of
The operating temperature has a dual effect on both the reaction acrylic acid at different molar ratios of n-butanol to acrylic acid. At
kinetics and membrane structure [27]. The production rates of the the end of 6 h, 91.95%, 94.52%, and 96.3% of acrylic acid conversion
products, water and n-butyl acrylate, are higher at a higher tem- was achieved at a molar ratio of 4, 6, and 8, respectively.
perature. The diffusion of the permeats is facilitated, as the thermal
motion of the polymer chains increases with an increase in the tem- 4.1.3. Catalyst loading
perature [28]. The partial fluxes of components were calculated by Experiments were carried out at a temperature of 358 K, with
using Eq (6) versus reaction time for Pervap 2201 and presented in an initial molar ratio of 4. The effect of catalyst loading was
 E. Sert, F.S. Atalay / Chemical Engineering and Processing 81 (2014) 41–47 45

Acrylic acid Butanol Butyl acrylate Water 4 6 8

0.18 100

Conversion of acrylic acid (%)

0.16 338 K
0.14 80

0.12
J (mol/hm2)

60
0.10
0.08
40
0.06
0.04
20
0.02
0.00
0
0 60 120 180 240 300 360
Time (min)

Acrylic acid Butanol Butyl acrylate Water Fig. 5. Effect of molar ratio of n-butanol to acrylic acid on the conversion of acrylic
0.18
acid.
0.16 348 K
0.14
0.12
J (mol/hm2)

0.10
0.08
0.06
0.04
0.02
0.00
0 60 120 180 240 300 360
Time (min)

Acrylic acid Butanol Butyl acrylate Water

0.18
358 K
0.16
0.14
0.12
J (mol/hm2)

0.10 Fig. 6. Effect of molar ratio on the partial fluxes of components.

0.08
0.06 10 g/L 15 g/L 20 g/L
0.04 100
Conversion of acrylic acid (%)

0.02
80
0.00

60

Fig. 3. Effect of temperature on the partial fluxes of components.

40

20

2.5 0

2
Fig. 7. The effect of catalyst loading on the conversion of acrylic acid.
ln (water lux)

1.5

investigated by changing the catalyst loading to 10, 15, and 20 g/L.

1
In this study, the catalyst loading is defined as the ratio of mass of
ln(water lux) =14.223 -4393.6 (1/T) catalyst to the initial volume of the reaction mixture. The conver-
0.5 R² = 0.9329 sion of acrylic acid (Fig. 7) and also the water production rate was
proportional to the catalyst loading. As expected increasing the cat-
0 alyst loading favors the formation and removal of water. But, above
15 g/L of catalyst loading, there was no change in the flux of water
(Fig. 8) because of the maximum permeability of water. As the cata-
lyst loading was increased, the conversion of acrylic acid increased
Fig. 4. Arrhenius plot of water flux vs. temperature.
slightly due to the increase in active sites and about 94% of the
acrylic acid conversion was obtained at a catalyst loading of 15 g/L.
46 E. Sert, F.S. Atalay / Chemical Engineering and Processing 81 (2014) 41–47

12 338 K 348 K 358 K 4 6 8 10 g/L 15 g/L 20 g/L

10

F
4

Fig. 8. Effect of catalyst loading on the partial fluxes of components.

Fig. 11. The variation of F with time.

35 m⁻¹ 52.5 m⁻¹ 70 m⁻¹

100 permeability can be compensated by using a larger membrane area
[31].
Conversion of acrylic acid (%)

80
4.2. Pervaporation performance
60
To evaluate the performance of pervaporation, the F factor
40 should be calculated. The variations of F versus time at different
temperatures (338, 348, and 358 K), catalyst loadings (10, 15, and
20 g/L) and molar ratios of n-butanol to acrylic acid (4, 6, and 8) are
20
given in Fig. 11. The F factor increased with increasing temperature
due to the acceleration of the water removal rate. As expected, the
0 water production and permeability are higher at a higher temper-
ature. As stated earlier, the Pervap 2201 membrane showed high
water selectivity. The water selection of the membrane increased
Fig. 9. Effect of S/V on the conversion of acrylic acid. as the reaction time increased. So, as time increased, the perme-
ation of the flux of water exceeds the water production rate so F
becomes greater than 1 after 4 h.
As shown in Fig. 11, the highest value of F is obtained from exper-
iments which are performed at a molar ratio of 8. This result is
consistent with the conversion of acrylic acid. Maximum conver-
sion of acrylic acid was found to be 96.3% at a temperature of 358 K,
a molar ratio of 8, a catalyst loading of 10 g/L and a S/V ratio of
70 m−1 . F was obtained as 10.43 at these conditions.
The equilibrium constants were calculated as 88.8%, 87.4% and
87.1% at temperatures of 338, 348 and 358 K in our previous work
[22]. By pervaporation-assisted esterification, equilibrium conver-
sions were achieved in a 6 h of operation time.

5. Conclusion

In reversible reactions such as esterification, chemical equilib-

rium limits the conversion and so, additional process is required
Fig. 10. Effect of S/V on the partial fluxes of components. to shift the chemical equilibrium toward the side of products.
Removing of the one of the products usually water increases the
forward reaction rate. The different technologies are developed to
4.1.4. S/V ratio remove water from a reaction mixture such as reactive distillation,
The ratio of membrane area to reactor volume (S/V) is one of adsorption, pervaporation, or vapor permeation. Among of them,
the most important parameters for the pervaporation process. The pervaporation–esterification is one of the promising processes, as
effect of the ratio of membrane area to reactor volume on the it combines reaction and product separation to reduce cost and
conversion of acrylic acid is given in Fig. 9. Experiments were per- enhance performance.
formed at a temperature of 348 K, a catalyst loading of 10 g/L, and In this study, a pervaporation–esterification hybrid process for
the S/V ratio varied as 35, 52.5, and 70 m−1 . As shown in Fig. 9, the n-butyl acrylate production by the esterification of n-butanol and
conversion of acrylic acid decreased with the decrease of the S/V. acrylic acid was performed by using the Pervap 2201 polymeric
The conversion of acrylic acid was obtained as 72.58%, 79.30%, and membrane.
83.67% at S/V ratios of 35, 52.5, and 70 m−1 , respectively. Also, the The Pervap 2201 membrane showed high selectivity to water
rate of water removal increased with the increase of S/V (Fig. 10). in the n-butanol/acrylic acid/n-butyl acrylate/water system. The
In the esterification–pervaporation process, low membrane coupling of pervaporation with the esterification reaction was an
 E. Sert, F.S. Atalay / Chemical Engineering and Processing 81 (2014) 41–47 47

efficient method for shifting the equilibrium toward n-butyl acry- References
late production.
The effects of some operating conditions on the esterification– [1] F. Lipnizki, R.W. Field, P.K. Ten, J. Membr. Sci. 153 (1999) 183–210.
[2] D. Kusdiana, S. Saka, Bioresour. Technol. 91 (2004) 289–295.
pervaporation performance have been studied. The most impor- [3] K. Zeng, C. Kuo, I. Chien, Chem. Eng. Sci. 61 (13) (2006) 4417–4431.
tant parameter found was temperature due to the dual effect. Both [4] A. Niesbach, R. Fuhrmeister, T. Keller, P. Lutze, A. Górak, Ind. Eng. Chem. Res. 51
the pervaporation and reaction rate increased with the operating (50) (2012) 16444–16456.
[5] A. Niesbach, J. Daniels, B. Schroeter, P. Lutze, A. Gorak, Chem. Eng. Sci. 88 (2012)
temperature. There are no significant effects of catalyst loading and 95–107.
molar ratio of n-butanol to acrylic acid for the water removal. [6] T.M. Aminabhavi, R.S. Khinnavar, S.B. Harogoppad, U.S. Aithal, Q.T. Nguyen, K.C.
Hansen, J. Macromol. Sci. Rev. Macromol. Chem. Phys. C34 (1994) 139–204.
[7] R. Rautenbach, R. Albrect, J. Membr. Sci. 25 (1985) 1–23.
Nomenclature [8] R. Rautenbach, R. Albrect, J. Membr. Sci. 25 (1985) 25–54.
[9] P. Shao, R.Y.M. Huang, J. Membr. Sci. 287 (2007) 162–179.
[10] K.C.S. Figueiredo, V.M.M. Salim, C.P. Borges, Catal. Today 133–135 (2008)
809–814.
Ccat concentration of catalyst (gcat /m3 ) [11] P. Delgado, M.T. Sanz, S. Beltran, L.A. Nunez, Chem. Eng. J. 165 (2010)
J total flux (mol/m2 h) 693–700.
[12] S. Korkmaz, Y. Salt, S. Dinçer, Ind. Eng. Chem. Res. 50 (2011) 11657–11666.
Ji flux of component i (mol/m2 h) [13] D.L. Zugic, I.M. Perovic, V.M. Nikolic, S.L. Maslovara, M.P.M. Kaninski, Int. J.
Ni number of moles of component i (mol) Electrochem. Sci. 8 (2013) 949–957.
ri reaction rate (mol/gcat h) [14] M.D. Bernal, J.D. Quintero-Arias, W. Osorio-Viana, I. Dobrosz-Gomez, J.
Fontalvo, M.A. Gomez-Garciea, Int. J. Chem. Kin. 45 (2012) 10–18.
S membrane area (m2 ) [15] H. Bart, J. Reidetschlagerj, K. Schatkaj, A. Lehmannt, Ind. Eng. Chem. Res. 33
t time (h) (1994) 21–25.
V volume of reaction mixture (m3 ) [16] R. Rönnback, T. Salmi, A. Vuori, H. Haario, J. Lehtonen, A. Sundqvist, E. Tirronen,
Chem. Eng. Sci. 52 (1997) 3369–3381.
W permeate amount (mol)
[17] S. Ali, S.Q. Merchant, Ind. Eng. Chem. Res. 48 (5) (2009) 2519–2532.
[18] P. Delgado, M.T. Sanz, S. Beltran, Chem. Eng. J. 126 (2007) 111–118.
Greek letter [19] S.H. Ali, S.Q. Merchant, Int. J. Chem. Kinet. 38 (2006) 593–612.
[20] E. El-Zanati, E. Abdel-Hakim, O. El-Ardi, M. Fahmy, J. Membr. Sci. 280 (1-2)
ı Hansen solubility parameters (2006) 278–283.
[21] Y. Peng, X. Cui, Y. Zhang, T. Feng, Z. Tian, L. Xue, Int. J. Chem. Kinet. 46 (2) (2014)
Subscripts 116–125.
[22] E. Sert, A.D. Buluklu, S. Karakus, F.S. Atalay, Chem. Eng. Proc. 73 (2013)
d non-polar interaction 23–28.
p dipole interaction [23] S.H. Ali, A. Tarakmah, S.Q. Merchant, T. Al-Sahhaf, Chem. Eng. Sci. 62 (2007)
h hydrogen bonding 3197–3217.
[24] Q. Liu, Z. Zhang, H. Chen, J. Membr., Sci. 182 (2001) 173–181.
[25] T. Yamaguchi, Y. Miyazaki, S. Nakao, T. Tsuru, S. Kimura, Ind. Eng. Chem. Res.
Acknowledgements 37 (1998) 177–184.
[26] M.O. David, T.Q. Nyugen, J. Neel, Chem. Eng. Res. Des. 69 (1991) 341–346.
[27] I.F.J. Vankelecom, Chem. Rev. 102 (2002) 3779–3810.
The authors acknowledge the financial supports from TUBITAK [28] S. Korkmaz, Y. Salt, A. Hasanoğlu, S. Özkan, İ. Salt, S. Dinçer, Appl. Catal. 366
(The Scientific and Technological Research Council of Turkey) under (2009) 102–107.
[29] Y. Zou, Z. Tong, K. Liu, X. Feng, Chin. J. Catal. 31 (2010) 999–1005.
grant no. 110M 462, from EBILTEM (Research and Application Cen- [30] A. Hasanoğlu, Y. Salt, S. Keleşer, S. Dinçer, Desalination 245 (2010) 662–669.
ter of Science and Technology) under grant no. 2012 BIL 022. [31] X. Feng, R.Y.M. Huang, Chem. Eng. Sci. 51 (1996) 4673–4679.