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478 Research Article

Shiwei Guo
Esterification of Acetic Acid and Ethanol in a
Benqiao He
Jianxin Li Flow-Through Membrane Reactor Coupled
Quan Zhao
with Pervaporation
Yu Cheng

Tianjin Polytechnic University, The esterification of acetic acid is an important industrial process for the
School of Materials Science and synthesis of ethyl acetate. A membrane reactor with a sulfonated polyethersul-
Engineering, State Key fone/polyethersulfone/non-woven fabrics composite catalytic coupled with a
Laboratory of Hollow Fiber poly(vinyl alcohol) pervaporation membrane was applied in continuous esterifi-
Membrane Materials and cation of ethanol with acetic acid in a flow-through mode. High equilibrium con-
Processes, Tianjin, China. version was obtained for esterification in a closed-loop mode. For the pervapora-
tion-assisted esterification in this mode, the experimental conversion was very
close to the theoretical value.

Keywords: Composite catalytic membrane, Esterification, Ethyl acetate, Pervaporation


Received: July 13, 2013; revised: October 29, 2013; accepted: December 13, 2013
DOI: 10.1002/ceat.201300467

1 Introduction (PVA) blend catalytic membrane as a heterogeneous catalyst to


produce biodiesel from long-chain fatty acids with methanol
Ethyl acetate is widely applied as solvent in paints, inks, adhe- in batch mode. Shah and Ritchie [14] introduced sulfonic acid
sives, and coatings. In many chemical processes, it can replace onto the pore surface of polyethersulfone (PES) nanofiltration
aromatic compounds which are potentially dangerous for the membranes to catalyze esterification of acetic acid with etha-
environment and human beings. Four methods are employed nol in a flow-through mode. A conversion of 16 % within 20 s
to produce ethyl acetate, namely, esterification of acetic acid was achieved [15]. In our previous study [16], a composite
with ethanol [1], addition of ethylene to acetic acid [2], dimer- catalytic membrane (CCM) was prepared from sulfonated
ization of acetaldehyde [3], and one-pot synthesis from etha- polyethersulfone (SPES) and PES blend supported by non-wo-
nol [4]. ven fabrics (NWF) as a heterogeneous catalyst to continuously
Among these methods, esterification is industrially impor- produce biodiesel from esterification of oleic acid with metha-
tant because of the simple processing. An appropriate catalyst nol in a flow-through mode. The conversion of oleic acid was
in esterification is vital to achieve high esterification efficiency. over 98.0 % in a residence time of 162 s and remained stable
The catalysts used can be homogeneous, such as H2SO4 and for over 500 h. The catalytic membrane might have a potential
HCl [5, 6], or heterogeneous, e.g., solid acids [7, 8]. Homo- prospect for application in the esterification of acetic acid with
geneous catalysts often show high catalytic efficiency due to ethanol.
excellent contact between reactants and catalyst molecules. Esterification of acetic acid with ethanol, as a typical reversi-
However, they are difficult to be separated from the products. ble equilibrium reaction, is inhibited by thermodynamic lim-
In addition, they cannot be reused and sometimes cause severe itation. It is an effective method to overcome the limitation
corrosion. Heterogeneous catalysts could overcome the short- through separating the by-product water from the product by
comings of the homogeneous types resulting from their better pervaporation under mild reaction conditions [17, 18]. For in-
reactant-product separation, catalyst recovery, and the ability stance, Benedict et al. [19] prepared a PVA/polyacrylonitrile
to conduct continuous esterification [9–12]. pervaporation membrane to promote the esterification of
As one form of solid catalysts, functional membranes with lactic and succinic acids with ethanol under solid catalysts.
catalytically active groups recently attracted considerable atten- Conversion in excess of the equilibrium conversion was at-
tion due to their high and stable catalytic activity. Zhu et al. tained by selective removal of water from the reaction mixture
[13] prepared a poly(styrene sulfonic acid)/poly(vinyl alcohol) by pervaporation. Some inorganic pervaporation membranes,
such as zeolite T [18] or hydroxyl sodalite (SOD) tubular [20],
were also applied for esterification of acetic acid and ethanol
by means of Amberlyst-15 resin as catalyst. Conversions of
– esterifications were markedly improved. Although a number of
Correspondence: Prof. Benqiao He (hebenqiao@tjpu.edu.cn), Tianjin
studies on pervaporation-assisted esterification have been
Polytechnic University, School of Materials Science and Engineering, conducted, a CCM as a heterogeneous catalyst to produce
State Key Laboratory of Hollow Fiber Membrane Materials and ethyl acetate in a membrane reactor coupled with pervapora-
Processes, Tianjin 300387, China. tion membrane has been rarely reported.

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Research Article 479

A membrane reactor with the SPES/PES/NWF CCM as a and ethanol was carried out in a single flow-through mode,
heterogeneous catalyst coupled with a PVA pervaporation closed-loop flow-through mode, and pervaporation-assisted
membrane is employed to produce ethyl acetate from acetic esterification in the closed-loop flow-through mode, respec-
acid and ethanol in a flow-through mode. In order to investi- tively. The process setup is illustrated in Fig. 1.
gate the process parameters and equilibrium conversion, con- In a single flow-through mode in order to investigate the
tinuous esterification of acetic acid and ethanol is carried out process parameters, the reactants with initial molar ratios of
in a single flow-through mode, closed-loop flow-through ethanol/acetic acid in the range from 1.3:1 to 6.5:1 were
mode, and pervaporation-assisted esterification in the closed- pumped into the membrane reactor from the upper inlet at a
loop flow-through mode, respectively. defined flow rate (0.85 mL min–1) and flowed through the
CCM with different inner volumes (935.34–15 589 mm3) and
reacted in the CCM at various reaction temperatures (328–
2 Methods 348 K). Then the effluent was collected at the bottom outlet.
The reactants passed the CCM only once in the single flow-
2.1 Materials through mode.
In a closed-loop flow-through mode in order to achieve an
PES (Ultrason® E3010P) was purchased from BASF (Ger- equilibrium conversion, the reactants flowed through the
many). SPES with a degree of sulfonation (DS) of 48.3 % was CCM into the product tank. Then, the reaction mixture in the
self-synthesized according to the literature [21] and used as a product tank was continuously transported back to the feed
main catalytic component. The PVA pervaporation membrane tank to be further catalyzed in the membrane reactor. The
was from Beijing Hongzhi Jiahe Technology Co. (China). Poly- process was carried out till an equilibrium conversion was
ethylene glycol (PEG) (analytic reagent, molecular weight reached. In this mode, the initial molar ratio of ethanol/acetic
600), glacial acetic acid, and ethanol were from Tianjin Kermel acid was 3.9:1 (total mass of 200 g), the flow rate was
Chemical Reagents Co. (China) and used as received. The 8.5 mL min–1, the inner volume of the membranes was
other chemicals were AR grade and employed without further 9353.4 mm3, and the reaction temperature was 348 K.
purification. The NWF from Tianjin Xinfu Spinning Co. In order to overcome the thermodynamic equilibrium lim-
(China) was pretreated with PEG. The SPES/PES/NWF CCM itation of esterification, pervaporation-assisted esterification
was prepared according to the reported method [16]. The was carried out as indicated in Fig. 1. Esterification of ethanol
CCM has an ionic exchange capacity of 3.16 mmol g–1 and a and acetic acid took place when the reactants circularly passed
mean pore size of 2–4 lm with a porosity of 68.0 %. through the CCM, and then the produced water was removed
by a pervaporation membrane as illustrated in the frame in
Fig. 1. The esterification conditions were the same as those in
2.2 Esterification Reaction in the Membrane Reactor the closed-loop process mentioned above. The pervaporation
conditions were as follows: effective surface area in the perva-
The membrane reactor was made from titanium alloy for acid poration cell of 60 cm2, temperature of 348 K in the pervapora-
resistance, equipped with a water-bath jacket to heat the reac- tion cell controlled by an electro-heater, pressure of 0.1 MP at
tants. The CCM was cut into round sheets with a diameter of the permeate side, and cold trap temperature of 253 K con-
68 mm and fixed into the reactor. Esterification of acetic acid trolled by a salt-water bath.

Figure 1. Process setup of esterification in flow-through mode. Dashed frame: pervaporation setup.

Chem. Eng. Technol. 2014, 37, No. 3, 478–482 © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
480 Research Article

2.3 Analysis of Esterification Process

The samples were withdrawn from the product tank at regular


intervals. The running time at which the product started to
flow out of the outlet of the reactor was considered as zero-
time of the experiment. The content of components (except
for water) of the samples from the product tank was immedi-
ately analyzed by GC (HP 6890, column HP-FFAP). At the
same time, the water content of the samples from the product
tank was tested by Karl Fischer Water Tester with a sensitivity
of 500 ppm (KF-1A, Shanghai Precision and Scientific Instru-
ment Co. Ltd., Shanghai, China).
The residence time of reactants in the CCM was controlled
by the flow rate of reactants and the inner volume of mem-
branes. It can be calculated by the following equation [22]:

Residencetime…s† ˆ
Figure 2. Effect of reaction temperature on acetic acid conver-
Inner volume of membranes …mm3 † × 60 sion at ethanol/acetic acid molar ratio of 1.3:1 and residence
(1)
Volumetric flow rate of reactant …ml=min† × 1000 time of 66 s in single flow-through mode.

The esterification reaction of acetic acid with ethanol for


producing ethyl acetate and water in the membrane reactor is 3.1.2 Effect of Ethanol/Acetic Acid Molar Ratio
given as follows:
The relationship between acetic acid conversion and ethanol/
CH3 COOH…A† ‡ CH3 CH2 OH…B† acetic acid molar ratio (from 1.3:1 to 6.5:1) at a reaction tem-
$ CH3 COOCH2 CH3 …C† ‡ H2 O…D† (2) perature of 348 K and residence time of 66 s is illustrated in
Fig. 3. The conversion of acetic acid kept stable within the run-
The equilibrium constant Keq can be written as: ning time and rose from about 10.0 % to 24.6 % with the in-
crease of the ethanol/acetic acid molar ratio from 1.3:1 to
‰CŠeq ‰DŠeq 3.9:1. The reason is that a high molar rate of ethanol and acetic
Keq ˆ (3)
‰AŠeq ‰BŠeq acid could provide excellent contact between ethanol and
acetic acid to promote esterification. Upon further increasing
where [C]eq, [D]eq, [A]eq,and [B]eq are the concentrations of the molar ratio from 3.9:1 to 6.5:1, the conversion decreased.
ethyl acetate, water, ethanol, and acetic acid when the reaction This is the reason that a high concentration of ethanol would
reaches equilibrium state. prevent acetic acid from being adsorbed in catalytic sites [1].
Hence, the ethanol/acetic acid molar ratio of 3.9:1 was suitable
for the high conversion.
3 Results and Discussion
3.1 Esterification in Single Flow-Through Mode

3.1.1 Effect of Reaction Temperature

The process parameters, such as reaction temperature, etha-


nol/acetic acid molar ratio, and residence time, significantly
affected esterification. Fig. 2 demonstrates the varying conver-
sion in the temperature range of 328–348 K (below the boiling
point of ethanol). The ethanol/acetic acid molar ratio was
1.3:1 and the residence time 66 s. The conversion of acetic acid
kept stable within the continuous running time of 300 min
and was up to 10.0 % at a residence time of 66 s when the
reaction temperature reached 348 K. A high temperature is
apparently favorable for the acceleration of the reaction. The
higher the reaction temperature, the higher the conversion
was.
Figure 3. Effect of ethanol/acetic acid molar ratio on acid con-
version at reaction temperature of 348 K and residence time of
66 s in single flow-through mode.

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Research Article 481

3.1.3 Effect of Residence Time although the flow rate was different. This is because of the low-
er external mass transfer in a higher flow rate in looping mode
In order to underline the role of residence time, the reaction compared with a single-pass experiment [16]. With longer
was performed at different residence times (0–1100 s) with the running time, the acid conversion increased in esterification in
same reaction temperature of 348 K and initial ethanol/acetic the closed-loop mode and then reached a maximum conver-
acid molar ratio of 3.9:1. As demonstrated in Fig. 4, the con- sion of 91.0 %. It can be inferred from Fig. 5 that the maxi-
version increased considerably with longer residence time. For mum conversion should be close to the equilibrium conver-
example, the conversion quickly rose from 24.6 % to 75.5 % sion. Therefore, an experimental equilibrium constant Keq
with prolonging the residence time from 66 s to 330 s at the obtained according to Eq. (3) was 3.065 at 348 K. This data is
first stage. For a residence time of 1100 s, the conversion slowly consistent with literature data [20]. The similar trend could
increased to 85.5 %. In order to prolong the residence time, a also be observed in the process of pervaporation-assisted ester-
lower flow rate of reactant or a thicker membrane was pre- ification. But the acid conversion obtained in this process was
ferred. However, a low flow rate led to a high external mass higher than that in esterification. A maximum conversion
transfer of reactants on the catalytic membrane surface. reached to 95.4 %. This is because the selective removal of
Furthermore, a thick membrane often leads to a high inner water is able to accelerate the reaction rate and overcomes the
mass transfer resistance [16]. It is implied that it was difficult thermodynamic equilibrium limitation of the reversible reac-
to further increase the conversion only by prolonging the resi- tion during pervaporation-assisted esterification.
dence time in a single flow-through mode. Therefore, esterifi-
cation in a closed-loop mode was carried out in order to
achieve a higher conversion. In addition, a higher flow rate of
the reactant is important in industrial production.

Figure 5. Acetic acid conversion in esterification and pervapora-


tion-assisted esterification in closed-loop mode. Initial molar
ratio of ethanol/acetic acid: 3.9:1 (total mass 200 g); flow rate:
8.5 mL min–1; inner volume of membranes: 9353.4 mm3; reaction
temperature: 348 K; pressure of permeate side: 0.1 MP; cold trap
Figure 4. Effect of residence time on acetic acid conversion at re- temperature: 253 K in the pervaporation unit.
action temperature of 348 K and ethanol/acetic acid molar ratio
of 3.9:1 in single flow-through mode. Furthermore, the changes of water content in the product
tank with the running time in esterification and pervapora-
tion-assisted esterification processes were measured as indi-
3.2 Esterification and Pervaporation-Assisted cated in Fig. 6. The experimental contents of water were deter-
Esterification in Closed-Loop Mode mined by Karl Fischer water tester. The theoretical value was
calculated from the acid conversion obtained (in Fig. 5).
The looping pattern is highly important for industrial pro- For the esterification process, the experimental and theoreti-
cesses to obtain a high conversion because of the effectiveness cal values of water content quickly rose at the beginning and
of membranes and energy efficiency of this reaction pattern then almost kept stable. There was the same trend as the con-
[23]. The relationship between acid conversion and running version change (Fig. 5). Fig. 6 illustrates that the experimental
time in a closed-loop mode as well as pervaporation-assisted value of water content was lower than the theoretical one, and
esterification in closed-loop mode were investigated. the difference kept approximately 1.2 wt %. The reason was
The relationship between acid conversion and running time that a part of water was absorbed by the SPES/PES/NWF CCM
is displayed in Fig. 5. At the initial running time, there was no as a result of the existence of hydrophilic groups, such as sulfo-
pervaporation when the effluent just flowed out of the outlet. nic groups in SPES chains.
Thus, the same conversion of 31.2 % was achieved in esterifica- Further, the theoretical water content calculated from the
tion and pervaporation-aided esterification processes. The acid conversion in the pervaporation-assisted esterification process
conversion of 31.2 % in looping mode was higher than the was higher than that in the esterification process. The reason
24.6 % in the single mode at the same residence time of 66 s was that the pervaporation-assisted esterification had a higher

Chem. Eng. Technol. 2014, 37, No. 3, 478–482 © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
482 Research Article

Scholars and Innovative Research Team in University


(PCSIRT), and Tianjin Natural Science Foundation of China
(Grant No. 13JCZDJC32700).

The authors have declared no conflict of interest.

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