_________________________________________________________________________

www.paper.edu.cn

Journal of Membrane Science 196 (2002) 171–178

Modeling of esterification of acetic acid with n-butanol in the

presence of Zr(SO4 )2 ·4H2 O coupled pervaporation
Qing Lin Liu a,∗ , Hong Fang Chen b
a Department of Chemical Engineering, Xiamen University, Xiamen 361005, China
b Department of Chemical Engineering, Tianjin University, Tianjin 300072, China
Received 22 December 2000; received in revised form 6 June 2001; accepted 7 June 2001

Abstract
Modeling of esterification of acetic acid with n-butanol in the presence of Zr(SO4 )2 ·4H2 O coupled pervaporation was
studied in this paper. The influence of several process variables, such as process temperature, initial mole ratio of acetic
acid over n-butanol, the ratio of the effective membrane area over the volume of reacting mixture and catalyst content,
on the esterification was discussed. The calculated results for the conversion of n-butanol to water and permeation flux
were consistence with the experimental data. The permselectivity and water content can be roughly estimated by the model
equations. © 2002 Elsevier Science B.V. All rights reserved.
Keywords: Pervaporation; Esterification reaction; Poly(vinyl alcohol) membrane; Composite membranes

1. Introduction [2] or catalytic application [3]. It is clear that the sep-

The use of pervaporation separation has received
considerable attention during decade. Among the
applications most of them concern separating one
component from liquid feed mixture. For an example,
this technique has been applied to acetobutylic fer-
mentation so as to extract in situ the butanol produced
thereby obtaining a greater glucose consumption and
a greater higher production [1].
Combining a membrane with a chemical reaction,
has been shown to offer advantages in a number of
different instances. One way to classify the different
situations in which membrane reactors are advanta-
geous is by the type of reaction taking place, and us-
ing this scheme, most membrane reactor applications
would be classified as either biological application
∗ Corresponding author.
E-mail address: qlliu@xmu.edu.cn (Q.L. Liu).
aration of the products should be as fast and selective
as possible in order to obtain a high yield for the
reaction.
One of potentials application is the use of perva-
poration process to drive an equilibrated reaction. Re-
views of the literature concerning catalytic membrane
reactors reveal that a very large fraction of catalytic
membrane reactor applications involve reversible
reactions which reach a thermodynamically limited
conversion level in a conventional reactor [4–9]. By
conducting these reactions in a catalytic membrane
wherein one product can selectively permeate through
the membrane and out of the reaction zone, an over-
all conversion is attained which is much greater than
that realized in the conventional reactor. A number of
investigations have concerned on the application of
hydrogen separation membranes to reversible gaseous
reaction and will not be considered in the present
study. Other recent investigations have been made

0376-7388/02/$ – see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 3 7 6 - 7 3 8 8 ( 0 1 ) 0 0 5 4 3 - 9
 _________________________________________________________________________
中国科技论文在线 www.paper.edu.cn

172 Q.L. Liu, H.F. Chen / Journal of Membrane Science 196 (2002) 171–178

presented and their valid was verified by comparing

Nomenclature the prediction to the experimental results.
A, B, E, acetic acid, n-butanol, butyl
and W acetate and water, respectively
Ci concentration of component 2. Modeling of PV-aided esterification
i in reacting mixture (mol l−1 )
Ji permeation flux of component The esterification of acetic acid with n-butanol is in
i (mol m−2 h−1 ) the form of the following equation:
Mi molar molecular weight of A+B↔E+W (1)
component i (g mol−1 )
Ni molar number of component In the case of n-butanol, non-permeating through the
i (mol) membrane (the amount of n-butanol or n-butyl acetate
Ni 0 molar number of component in the permeate is very small and can be negligible
i at zero-time (mol) practically), the variation of n-butanol concentration
Pi permeation parameter of can be expressed by
component i (l m−2 h−1 ) dCB
PW , PA parameters as a function − = k1 CA CB Ccat − k2 CW CE Ccat (2)
dt
of process temperature
R universal gas constant Here,
(J mol−1 K−1 ) NA NB NE
CA = , CB = , CE = ,
R0 initial molar ratio of acetic V V V
acid to n-butanol NW Ncat
S effective area of the CW = , Ccat = (3)
V V
membrane (m2 )
So,
SA,B , SA,E parameter concerning influence

to acetic acid permeating by dCB 1 dV dNB
= 2 −NB +V (4)
existing of n-butanol and dt V dt dt
butyl acetate
Substituting Eq. (4) into Eq. (2) gives
SW,B , SW,E parameter concerning influence

to water permeating by existing dV dNB Ncat N W NE
NB −V = k1 N A NB − (5)
of n-butanol and butyl acetate dt dt V keq
V volume of reacting mixture (ml)
X conversion of n-butanol The conversion of n-butanol to n-butyl acetate is
written by
Greek letter NB0 − NB
X= (6)
ρi density of component i in the NB0
liquid mixture
The expression is valid for this study since acetic acid
is in excess, and the permeating of n-butanol through
on the application of water permeable membranes to the membrane is negligible.
liquid-phase reaction [10–21]. It is assumed that the permeation fluxes of com-
The objective of this study was an attempt to ponent i (i = A, B, W and E) can be estimated in a
investigate the effect of operating parameters on the binary liquid mixture of the water content less than
typical variable−water content in the reactor during of 10 wt.% by
the esterification of acetic acid with n-butanol in
Ji = Pi Ci (7)
the presence of Zr(SO4 )2 ·4H2 O coupled, the extrac-
tion of water by pervaporation. Model equations for Here, Pi is permeability coefficient and Ji is the per-
pervaporation-aided (PV-aided) esterification were meation flux of i that can be modified in the quarter
 _________________________________________________________________________
中国科技论文在线 www.paper.edu.cn

Q.L. Liu, H.F. Chen / Journal of Membrane Science 196 (2002) 171–178 173

mixture on the basis of the binary mixture, so the Isothermal operation is valid since the reaction heat
amount of i in the permeate in moles of Qi can be is small. Ideal mixing is assumed in the reactor since
obtained by the volume of reacting mixture is relatively large and
 t is nearly constant.
Qi = Ji S dt (8) Following equations can be obtained by substituting
0 Eq. (9) into Eqs. (13), (15) and (17)
Differentiating Eq. (6) with respect to t gives
dNA dNB
dX dNB + JA S − =0 (13A)
NB0 =− (9) dt dt
dt dt
dNW dNB
For acetic acid we have + JW S + =0 (15A)
dt dt
NA = NA0 − NB0 X − QA (10)
dNE dNB
dQA + =0 (17A)
= JA S (11) dt dt
dt
Differentiating Eq. (10) with respect to t gives In the end, the variables; NA , NB , NE , NW , V can
be solved simultaneously by the Eqs. (5), (13A),
dNA dX dQA (15A), (17A) and (18) as an initial problem using the
= −NB0 − (12)
dt dt dt Runge–Kutta–Gill fourth-order method.
Substituting Eq. (11) into Eq. (12) The reaction rate constants for the esterification are
shown in Eqs. (19) and (20), in which is demonstrated
dNA dX that forward reaction rate constant is larger than back-
+ JA S + NB0 =0 (13)
dt dt ward reaction in quantities:
Similarly, as for water and n-butyl acetate in the

event of n-butyl acetate non-permeating through the 53.13 × 103
k1 = 4.531 × 106 exp − (19)
membrane, we have RT
NW = NW0 + NB0 X − QW (14)

58.94 × 103
k2 = 4.376 × 106 exp − (20)
dNW dX RT
+ JW S − NB0 =0 (15)
dt dt
During PV separation of the quarter mixture
NE = NB0 X (16)
of water/acetic acid/n-butanol/butyl acetate by the
dNE dX poly(vinyl alcohol) (PVA)/ceramic composite mem-
− NB0 =0 (17)
dt dt branes, there was largely water and little acetic acid
The volume of the liquid in the reactor, V, is given by in the permeate while n-butanol or butyl acetate
Eq. (18) according to the additive of volume: could be neglected. Fluxes of water and acetic acid
permeation can be calculated when water concentra-
NA MA N B MB N E ME N W MW tion was less than 10 wt.%. The expressions of flux
V = + + + (18)
ρA ρB ρE ρW for water and acetic acid permeation are present in
Eqs. (21) and (22), for which the parameters obtained
The model used following assumptions:
from the PV separation of mixture of water/acetic
1. isothermal operation; acid/n-butanol/butyl acetate are displayed in [22]:
2. negligible permeating of n-butanol and butyl
acetate through the membrane, which resulted from JW = PW CW exp(SW,B CB + SW,E CE ) (21)
the PV separation of mixture of water/acetic acid/
n-butanol/butyl acetate; P A CW + M
JA = (22)
3. ideal mixing for reactants in the reactor. exp(SA,B CB + SA,E CE )
 _________________________________________________________________________
中国科技论文在线 www.paper.edu.cn

174 Q.L. Liu, H.F. Chen / Journal of Membrane Science 196 (2002) 171–178

3. Experimental

3.1. Materials

All reagents had purity better than 99% and were

used without further purification. The poly(vinyl alco-
hol)/porous ceramic composite membranes prepared
in our laboratory exhibited a good selectivity to water
in the organic mixtures used [21].

3.2. Esterification reaction with and without PV

The esterifications with and without PV were car-

ried out in a batch mode. The batch reactor for esterifi- Fig. 1. Conversion of n-butanol to water both with and without
cation studies was a thermostatic cell equipped with a pervaporation (T = 80◦ C; R0 = 1.60; C cat = 10.6 g l−1 ).
mechanic stirrer. The experiments of PV-aided esteri-
fication were conducted in a stirred cell that served at
the same time as a batch reactor and a PV cell. In the
cell, the membrane of effective surface area of 34 cm2
was installed at the bottom of the cell and supported
by a stainless steel plate. Each run was carried out
simultaneously in the reactor without the membrane
and in the PV cell using the same original mixture.
The time at which the catalyst was added to the alco-
hol/acid mixture was referred to zero-time. Samples
were withdrawn and analyzed by gas chromatography.

4. Results and discussion

Fig. 2. Water concentration in the reacting mixture for esterification
4.1. Esterification compared to PV-aided both with and without pervaporation (T = 80◦ C; R0 = 1.60;
esterification C cat = 10.6 g l−1 ).

Fig. 1 shows the variation of conversion of n-butanol

to water as a function of time for the esterification
both with and without PV, respectively. It was indi-
cated that PV enhanced the conversion and it was
higher for the PV-aided esterification than for the
reaction without PV. The variation of water concen-
tration in the reacting mixture as a function of time
for the reaction without PV and the PV-aided reac-
tion is displayed in Fig. 2. It reflected that the water
content for the reaction without PV was higher than
for the PV-aided reaction due to water removal by
PV. Figs. 3 and 4 show the permeation fluxes (both
overall and partial) and permselectivity coefficient as
a function time for the PV-aided process, the overall Fig. 3. Permeation fluxes as a function of time (T = 80◦ C;
flux of permeation, partial fluxes of permeation and R0 = 1.60; C cat = 10.6 g l−1 ).
 _________________________________________________________________________
中国科技论文在线 www.paper.edu.cn

Q.L. Liu, H.F. Chen / Journal of Membrane Science 196 (2002) 171–178 175

Fig. 4. Permselectivity coefficients as a function of time Fig. 6. Calculated curves compared to experimental points for
(T = 80◦ C; R0 = 1.60; C cat = 10.6 g l−1 ). permeation fluxes (T = 80◦ C; R0 = 2.34; C cat = 10.6 g l−1 ).

the permselectivity coefficient are obviously changed
during the process, and it is known that the quantities
of partial permeation flux of n-butanol is so small that
its permeation through the membrane can practically
be neglected during the process.
4.2. Model equations verification
The experimental points and the results of simu-
lation for the conversion is given in Fig. 5, which
reflected that both were in a good agreement. It was
shown that the calculated value for the conversion was
larger than the experimental one may probably due to
the negligence of n-butanol permeating through the
membrane by the model equations. Fig. 6 shows the
calculated results and the experimental data for the
overall flux of permeation, partial fluxes of water and
acetic acid permeation, respectively, and the agree-
ment between them was roughly good. The calculated
value for the overall permeation flux was less than the
experimental one also because of the same reason de-
scribed previous. Fig. 7 presents the permselectivity
coefficient of water to acetic acid for the experimental
points and the estimated results, which indicated that
the agreement between them was acceptable.
It is known from the model equations that the
influencing operating parameters for the PV-coupled
esterification was: process temperature (T); initial
molar ratio of acetic acid to n-butanol (R0 ); ratio of
the membrane area to the reacting mixture volume
(S/V); the catalyst content (Ccat ).

Fig. 7. Calculated curves compared to experimental points

Fig. 5. Calculated curve compared to experimental points for for permselectivity coefficients (T = 80◦ C; R0 = 2.34;
n-butanol conversion (T = 80◦ C; R0 = 2.34; C cat = 10.6 g l−1 ). C cat = 10.6 g l−1 ).
 _________________________________________________________________________
中国科技论文在线 www.paper.edu.cn
176 Q.L. Liu, H.F. Chen / Journal of Membrane Science 196 (2002) 171–178
So, simulation was carried out for various process
variables in the following section. The water contents
in the reacting mixture were measured and compared
with the calculated values in order to see if the model
equations were valid for the coupling process.
4.3. The effects of process variables on
PV-aided esterification
Water concentration in the reactor is a typical
variable to evaluate PV-aided esterification since its
variation are result from water production rate and
water removal rate. So process variables result in the
variation in water concentration were chosen as a
model to study the PV-esterification coupling.
4.3.1. The effect of temperature
The reaction rate constants for the esterification are
a function of process temperature, and were increased
with the increase of the temperature. The accelerating
of the reaction rate constant with the increase of the
temperature for the forward reaction was faster than
the backward process. So water production rate was
higher in a higher temperature than in a lower temper-
ature. Meanwhile, the permeation parameter for water
is also varied with the temperature and was increased
with the increase of the temperature. As a result, wa-
ter permeation flux was increased with the increase of
the process temperature.
The model predictions and the experimental data for
water content variation in the reacting mixture during
the coupling process at 90, 80 and 70◦ C are plotted in
Fig. 8, which indicated that simulation could predict
the experimental points. The estimated values for mass
fraction of water are larger than the experimental ones,
which can be explained by the fact that the calculated
values for the flux of water permeation are less than
the experimental data (which reflected in Fig. 6). It is
reflected in Fig. 8 that the difference in the values of
water content between the experimental and the simu-
lated become larger at a lower temperature. It may be
attributed to that (dk1 /dT )/(dk2 /dT ) = 0.935 < 1 in
the temperature range of 50–100◦ C, indicating the rate
constant for the backward reaction reduced faster than
for the forward reaction with the decrease of temper-
ature, as well as k1 > k2 , so the difference between
k1 and k2 is larger at a lower temperature. The water
content in the reacting mixture during the process had
Fig. 8. Calculated curves compared to experimental points for
water content in the reacting mixture over various temperature
(R0 = 1.60; C cat = 13.33 g l−1 ; S/V = 23 m−1 ).
maximum amplitude and increased at the beginning.
This may due to the fact that water production rate
was higher than the rate of water removal by PV at the
earlier stage during the process and was reverse when
water content reached the maximum value. Water con-
centration had a higher maximum value for a higher
process temperature. This may be explained by the fact
that the acceleration for water production rate had a
higher value at a higher temperature, so water content
increased faster during the earlier reaction stage due
to a slower backward reaction rate; while decreased
faster later due to a higher backward reaction rate.
4.3.2. The effect of R0
It can be concluded from the model equations that
R0 played a part in reaction rate but exerted no effect
on kinetics of PV. Fig. 9 shows that water contents in
the reactor between calculated results and experimen-
tal data are in good consistency. Water production
rate is decreased with the increase of R0 and caused
the maximum amplitude in water content lower at
a higher R0 . The water contents in the reactor were
lower for a higher R0 during the process, which was
for the most part attributed to that R0 played no role
in the kinetics of PV.
4.3.3. The effect of the catalyst content (Ccat )
The model fitting and experimental data for
water content in the reactor at various Ccat are shown
in Fig. 10, which again demonstrated that both are in
good consistency. The variation of both forward and
 _________________________________________________________________________
中国科技论文在线 www.paper.edu.cn
Q.L. Liu, H.F. Chen / Journal of Membrane Science 196 (2002) 171–178
Fig. 9. Calculated curves compared to experimental points for
water content in the reacting mixture over various R0 (T = 80◦ C;
C cat = 13.33 g l−1 ; S/V = 23 m−1 ).
backward reaction rate occurred during the change
of Ccat . The water production rate was higher for a
higher Ccat since the forward reaction rate constant
was higher than the backward one. Thus, the water
contents in the reactor had higher maximum ampli-
tude for a higher Ccat during the reaction. The water
contents in the reactor were higher for a higher Ccat
for a period at the beginning during the reaction and
than were lower later.
4.3.4. The effect of S/V
S/V exerted no influence on reactive kinetics but
caused the variation of the water extraction rate. The
effect of S/V on PV-aided esterification was similar to
that of R0 , which resulted from the variation of water
Fig. 10. Calculated curves compared to experimental points for
water content in the reacting mixture over various Ccat (T = 80◦ C;
R0 = 1.60; S/V = 23 m−1 ).
177
Fig. 11. Calculated curves compared to experimental points for
water content in the reacting mixture over various S/V (T = 80◦ C;
R0 = 2.34; C cat = 13.33 g l−1 ).
contents in the reactor during the process. As a result
of fitting between the experimental data and the calcu-
lated results for the water content in the reactor over
various S/V during the process are shown in Fig. 11.
5. Conclusions
The water contents in the reactor between numerical
simulation and experimental results in quantities were
roughly similar indicating that the model equations
were valid for the PV-aided esterification.
The process temperature and the catalyst concen-
tration had a similar effect on the variation of water
content during the process, so did the R0 and S/V.
Acknowledgements
The support of Fujian Natural Science Foundation
Grant no. F00022 in preparation of this article is grate-
fully acknowledged.
References
[1] M.A. Larrayoz, L. Puigjaner, Study of n-butanol extraction
through PV in acetobutylic fermentation, Biotechnol. Bioeng.
30 (1987) 692–696.
[2] R.A. Kemp, A.R. Macrae, Esterification process, European
Patent (EP) 506159 (1992).
[3] G.K. Pearce, Esterification process, European Patent (EP)
210055 (1987).
 _________________________________________________________________________
中国科技论文在线 www.paper.edu.cn
178 Q.L. Liu, H.F. Chen / Journal of Membrane Science 196 (2002) 171–178
[4] K. Mohan, R. Govind, Analysis of equilibrium shift in
isothermal reactors with a permselective wall, AIChE J. 34
(1988) 1493–1503.
[5] K. Mohan, R. Govind, Analysis of a current membrane
reactor, AIChE J. 32 (1986) 2083–2086.
[6] K. Mohan, R. Govind, Effect of temperature on equilibrium
shift in reactors with a permselective wall, Ind. Eng. Chem.
Res. 27 (1988) 2064–2070.
[7] N. Itoh, A membrane reactor using palladium, AIChE J. 33
(1987) 1576–1578.
[8] Y.M. Sun, S.J. Khang, A catalytic membrane reactor: its
performance in comparison with other types of reactors, Ind.
Eng. Chem. Res. 29 (1990) 232–238.
[9] S. Vemiya, N. Sato, H. Ando, E. Kikuchi, The water gas
shift reaction assisted by a palladium membrane reactor, Ind.
Eng. Chem. Res. 30 (1991) 585–589.
[10] I.K. Song, W.Y. Lee, Methyl t-butyl ether decomposition in
an inert membrane reactor composed of 12-tungstophosphoric
acid catalyst and polyphenylene oxide membrane, Appl. Catal.
A: Gen. 96 (1993) 53–63.
[11] H. Kita, K. Tanaka, K. Okamoto, M. Yamamoto, The
esterification of oleic acid with ethanol accompanied by
membrane separation, Chem. Lett. (1987) 2053–2056.
[12] M.O. David, Q.T. Nguyen, J. Neel, PV membranes endowed
with catalytic properties based on polymer blends, J. Membr.
Sci. 73 (1992) 129–141.
[13] K. Okamoto, M. Yamamoto, Y. Otoshi, T. Semoto, PV-aided
esterification of oleic acid, J. Chem. Eng. Jpn. 26 (5) (1993)
475–481.
[14] H. Kita, S. Sasaki, K. Tanaka, K.I. Okamoto, M. Yamoto,
Esterification of carboxylic acid with ethanol accompanied
by PV, Chem. Lett. (1988) 2025–2028.
[15] J.F.F. Keurentjes, G.H.R. Janssen, J.J. Gorissen, The
esterification of tartaric acid with ethanol; kinetics and shifting
the equilibrium by means of PV, Chem. Eng. Sci. 49 (1994)
4681–4689.
[16] X. Feng, R.Y.M. Huang, Studies of a membrane reactor:
esterification facilitated by PV, Chem. Eng. Sci. 51 (1996)
4673–4679.
[17] L. Bagnell, K. Cavell, A.M. Hodges, A.W.H. Mau, A.J. Seen,
The use of catalytically active PV membranes in esterification
reactions to simultaneously increase product yield, membrane
permselectivity and flux, J. Membr. Sci. 85 (1993) 291–300.
[18] Qinglin Liu, Peishi Jia, Hongfang Chen, Study on catalytic
membranes of H3 PW12 O40 entrapped in PVA, J. Membr. Sci.
159 (1999) 233–241.
[19] M.O. David, R. Gref, Q.T. Nguyen, J. Neel, PV-esterification
coupling. I. Basic kinetic model, Trans. Inst. Chem. Eng. 69
(1991) 335–340.
[20] M.O. David, R. Gref, Q.T. Nguyen, J. Neel, PV-esterification
coupling. II. Modeling of the influence of different operation
parameters, Trans. Inst. Chem. Eng. 69 (1991) 341–346.
[21] Q.L. Liu, Y.S. Zhu, H.F. Chen, Esterification accompanied by
PV using crosslinked PVA composite membrane, J. Chem.
Eng. Chin. Univ. 11 (2) (1997) 172–176.
[22] Q.L. Liu, Z.B. Zhang, H.F. Chen, Study on the coupling of
esterification with pervaporation, J. Membr. Sci. 182 (2001)
173–181.