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Chemical Engineering Journal 168 (2011) 293302

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Chemical Engineering Journal
j our nal homepage: www. el sevi er . com/ l ocat e/ cej
Kinetic study of catalytic esterication of butyric acid and n-butanol over Dowex
50Wx8-400
In Bum Ju
a
, Hye-Won Lim
b
, Wonjin Jeon
a
, Dong Jin Suh
a
, Myung-June Park
b,
, Young-Woong Suh
a,c,
a
Clean Energy Center, Korea Institute of Science and Technology, Seoul 136-791, Republic of Korea
b
Department of Chemical Engineering, Ajou University, Woncheon-dong, Yeongtong-gu, Suwon 443-749, Republic of Korea
c
Department of Chemical Engineering, Hanyang University, Haengdang-dong, Seongdong-gu, Seoul 133-791, Republic of Korea
a r t i c l e i n f o
Article history:
Received 4 March 2010
Received in revised form 24 August 2010
Accepted 31 December 2010
Keywords:
Esterication
Reactive distillation
n-Butanol
Butyric acid
Ion-exchange resin (Dowex 50Wx8-400)
Kinetic model
a b s t r a c t
A kinetic investigation for the esterication of butyric acid with n-butanol over Dowex 50Wx8-
400 was conducted. The catalytic experiments were performed in a reactive distillation mode, in
which the byproduct (water) is eliminated to prevent the reverse reaction from taking place. The
experimental parameters are reaction temperatures (100110

C), molar ratios of reactants (butyric


acid/n-butanol =0.254) and catalyst loading (1040g/L), and their effect on the reaction rate was found
that the conversion increased with temperature and catalyst loading whereas it decreased as the molar
ratio of reactants increased. The rate equations were derived on the basis of the pseudo-homogeneous
(PH) model, LangmuirHinshelwood (LH) model and EleyRideal (ER) model. From the best t models
showing good correlation between experimental and simulation results, the surface reaction was deter-
mined to be the rate determining step, while competitive adsorption on a catalyst surface and weak
interaction between resin and water by-product were conrmed in the esterication reaction of butyric
acid with n-butanol.
2011 Elsevier B.V. All rights reserved.
1. Introduction
Estericationis a chemically reversible reactionproducing ester
and water from two reactants of acid and alcohol. The desired
product, ester, provides useful applications in chemical indus-
try, such as solvents, plasticizers, medicinal agents, avors and
fragrances [1]. However, esterication shows limited conversion
due to low reaction rate and reversibility [2]. Although the reac-
tion rate and the conversion in esterication reactions can be
enhancedbyvaryingseveral reactionparameters, includingtheele-
vation of temperatures, the increase in alcohol-to-acid ratios and
the utilization of more catalytically active sites (e.g., higher con-
centration in the case of mineral acids), these can cause several
drawbacks in industrial applications such as corrosion, energy-
consuming product separation, and difcult and costly recovery
of the product. Therefore, it is desired in the industrial eld to
developanefcient estericationprocess for highyieldof ester pro-
duction, under mild reaction conditions. For example, the amount
of water, which is considered as a byproduct, needs to be con-
trolled since it causes unfavorable effect on chemical equilibrium
to inhibit the production of esters. The reactive distillation method

Corresponding author. Tel.: +82 31 219 2383; fax: +82 31 219 1612.

Corresponding author. Tel.: +82 2 958 5193; fax: +82 2 959 5209.
E-mail addresses: mjpark@ajou.ac.kr (M.-J. Park), ywsuh@kist.re.kr (Y.-W. Suh).
is known as a pertinent reacting system to solve the limitations
resulting from the existence of unfavorable byproducts. This sys-
tem is a combination of a reversible reaction and distillation, and
provides the conversion of reactants higher than equilibrium con-
version via the removal of water during esterication [39]. In
addition, the reactive distillation has a merit in the sense that,
since the distillation separates the undesirable products (water
in the case of esterication reaction) from the products in the
course of reaction, the need for additional separation unit is obvi-
ated.
The problem with low reaction rate can be resolved by the
employment of suitable catalysts. There are two catalysts to accel-
erate the rate of esterication reaction, that is, homogeneous and
heterogeneous catalyst. Mineral acid (H
2
SO
4
, HCl, and so on) and
only organic acid including HCOOH are typical acids for homoge-
neous acid catalysts [10]. Although homogeneous catalysts provide
distinguished performance in terms of reaction rate, the benet of
those catalysts is diminished since separation and recovery of cata-
lyst are difcult due to the miscibility between liquid acid catalyst
and reaction medium [1,10]. In addition, the homogeneous acid
catalysts cause the corrosion of equipment, more side reactions
and additional neutralization cost to treat waste containing acids
[1,2,10,11].
The ion-exchange resin is a promising material for the replace-
ment of the homogeneous acid catalysts. The solid type of
material has good physical and chemical properties, and shows
1385-8947/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2010.12.086
294 I.B. Ju et al. / Chemical Engineering Journal 168 (2011) 293302
Nomenclature
a
i
activity of component i
A pre-exponential factor in the Arrhenius equation
(mol/g
cat
s)
C
A
reactant concentration (mol/cm
3
)
C
Ab
bulk concentration (mol/cm
3
)
C
li
bulk concentration of the limiting reactant
(mol/cm
3
)
C
M
Mears parameter
C
WP
WeiszPrater parameter
D
AB
diffusivity of solute A (cm
2
/s)
D
Aj
dilute binary diffusion coefcient of solute A in j
(cm
2
/s)
D
Am
dilute diffusion coefcient of solute A through the
mixture (cm
2
/s)
D
eff
effective diffusivity (cm
2
/s)
D
lm
diffusivity of limiting reactant in the mixture
(cm
2
/s)
d
p
diameter of the catalyst particle (cm)
E
A
activation energy (J/mol)
F vaporization rate (mol/s)
g gravitational acceleration (cm/s
2
)
k
C
mass transfer coefcient (cm/s)
k
f
forward reaction rate constant (mol/g
cat
s)
K
a
overall reaction equilibrium constant
K
acid
acid (n-butanoic acid) adsorption equilibrium con-
stants
K
alc
alcohol (n-butanol) adsorption equilibrium con-
stants
K
ester
ester (n-butyl butyrate) adsorption equilibrium
constants
K
i
adsorption equilibrium constants of component i
K
s
equilibrium constant
K
water
water adsorption equilibrium constants
n reaction order
n
i
molar amount of component i (mol)
n
vap
total amount of vaporized molecules (mol)
N
Sc
Schmidt number
P
sat
i
saturated pressure of component i (kPa)
r
A,obs
observed reaction rate (mol/g
cat
s)
R
c
catalyst particle radius (cm)
STDEV standard deviation of errors (%)
t reaction time (s)
T
error
total average error in Eq. (21) (%)
x
j
mole fraction of liquid component i
y
i
molar fraction of component i
Greek letters
resin afnity for water
activity coefcient

c
viscosity of the solution (g/cms)

j
viscosity of component j (g/cms)

m
mixture viscosity (g/cms)
v
i
the stoichiometric coefcient of component i

v
the void fraction

b
bulk density of catalyst bed (g/cm
3
)

c
catalyst density (g/cm
3
)

l
density of the solution (g/cm
3
)
excellent performance as a heterogeneous catalyst in esterica-
tion reaction. The mechanical separation by ltering is possible,
and the ion exchange resin is reusable, guaranteeing the continu-
ous operation [1,12]. Besides, catalysts in the solid type preclude
corrosion as well as pollution, and show both high selectivity and
thermal stability [3,13,14]. Several works onestericationwiththis
heterogeneous catalyst have been studied with various reactants.
Bochner and Gerber [15] studied the esterication of salicylic acid
with methanol by utilizing the ion exchange resin as a catalyst and
investigated the effect of catalyst size, stirring speed, initial water
concentration and reverse reaction on the production rate of ester.
Meanwhile, the research on the esterication of acetic acid with
propyl alcohol over heterogeneous catalyst, Dowex MONOSPHERE
650 C, has been reported [16], where the reaction mechanism was
presented, and kinetic and thermodynamic parameters were cal-
culated.
The investigation of the kinetics for the esterication reaction
on the basis of experimental data obtained in the reactive distilla-
tion system has been widely reported in the literature [49], and
many illustrative research works can be referred to Schmitt and
coworkers work [6]. In spite of many reports on the esterica-
tion with heterogeneous catalysts, however, a few kinetic studies
consider the steps between ion exchange resins and liquid reac-
tants/products. In other words, many steps such as adsorption,
desorption, reaction and diffusion should be taken into account in
the heterogeneous system, unlikely to homogeneous catalytic sys-
tem[17]. Therefore, the reaction mechanisms and rate expressions
are more complex than those in the case of homogeneous sys-
tem. The typical kinetic models in heterogeneous catalytic systems
are the pseudo-homogeneous (PH) model, LangmuirHinshelwood
(LH) model and EleyRideal (ER) model. The rst model is similar
to the power law model for homogeneous reactions [18]. The LH
model represents the rate-determining step being the reaction of
both reactants (e.g., acid and alcohol in the esterication reaction)
adsorbed on the catalyst surface, whereas the ER model indicates
that the rate-determining step is the reaction between one reac-
tant adsorbed on the catalyst surface and its counterpart reactant
in the bulk region. Lee and coworkers [18,19] conducted the kinetic
study for the esterication over ion exchange resins, where the
kinetic behavior of heterogeneous estericationandthe correlation
of experimental data with the PH, LH, ER and modied LH models
were investigated.
The kinetics of ion exchange resin-catalyzed esterication, with
butyric acid and n-butanol as reactants to produce butyl butyrate,
was studied in this work since no investigation in heterogeneous
estericationhas beenreportedfor the reactionof butyric acidwith
n-butanol. For this reaction, Dowex 50Wx8-400, which contains
sulfonic acid groups, was selected as an ion exchange resin and it
shows both high catalytic activity and fewside reactions compared
to sulfuric acid [1]. The effects of temperature, catalyst loading and
reactant ratio were evaluated experimentally as well as kinetically.
In the kinetics model, strong resin water afnity was considered,
and the non-ideality of the systemwas augmented by applying the
no-random two liquid (NRTL) model. The experimental data were
correlated with the PH, LH, ER and modied models, in such a way
that the most reasonable kinetic model was presented.
2. Experimental
Among various cation-exchange resins, Dowex 50Wx8-400
witha particle size range of 0.040.07mm, a cross-linking extent of
8%andamaximumoperatingtemperatureof 150

Cwas selectedas
a catalyst for the esterication of butyric acid with n-butanol, and
purchased from SigmaAldrich. This resin exists in gel-type and
includes sulfonic acid as a catalytic functionality, where its matrix
type is styrene-divinyl-benzene (DVB), total exchange capacity is
1.7mequiv/mL, and water retention capacity of the resin is 5058%
in mass. Before being applied to the esterication experiment, the
catalyst was dried in a vacuum oven at 70

C for 48h. If they are


I.B. Ju et al. / Chemical Engineering Journal 168 (2011) 293302 295
Table 1
Reaction conditions.
Run # Temperature (

C) Ratio of BA/BuOH Catalyst loading (g/L)


1 110 1 20
2 110 0.5 20
3 110 2 20
4 110 0.25 20
5 110 4 20
6 110 1 10
7 110 1 40
8 105 1 20
9 100 1 20
bakedat higher temperature than70

C, it causes the loss of sulfonic


groups of the catalysts.
The DeanStark apparatus was employed in this study. The
round-bottomed ask with three necks was used in a reaction
part and it has the capacity of 1000mL. The reactant mixture of n-
butanol and butyric acid was heated on the heating mantle purged
by inert gas and stirred on the hot-plate stirrer. The reaction tem-
perature was measured using type-K thermocouple located in the
middle of the reaction mixture and controlled with a tempera-
ture controller (Korea Furnace Development Co.) connected to the
heating mantle. As discussed earlier, the esterication reaction is
reversible and produces water as a byproduct, indicating that the
removal of water is essential in this process. The water product is
subjectedtobeseparatedfromthereactor byDeanStarktrap. After
n-butanol and butyric acid were injected in the reactor which con-
tainedn-decane as aninternal standard, the heater andstirrer were
immediately turned on. It is well known that the internal standard
is usedfor the purpose of the precise quanticationof reactants and
products, and n-decane was selected as the internal standard since
it satises most of requirements for the standard such as no chem-
ical reaction with reactants and products, a higher boiling point
(i.e. non-volatility), a relatively similar density to those of reac-
tants and products. When the temperature of mixture reached to
desired temperature, the catalyst was added into the reactor (t =0).
The catalytic loading was varied from 10 to 40g/L in a tempera-
ture range of 100110

C and the ratio of butyric acid to n-butanol


were varied in a range of 0.54. At a certain time, 0.1mL of liquid
product sample was extracted through a syringe lter and ana-
lyzed with a gas chromatograph (GC, Young Lin Acme 6000 series)
equipped with a ame ionization detector (FID) and HP-INNOWAX
column (30m, 0.053mm, 1.00m). Here, the amount of sample
extracted was negligible as compared to total amount of reactants
(41.4mL) [11]. For reproducibility, the experiment at each set of
operating conditions was repeated at least 35 times, and the mea-
sured experimental errors were determined to be within ca. 1%.
The experimental conditions used in this study are summarized in
Table 1.
From GC data, the conversion and reaction rate were calculated
as follows:
Conversion of butyric acid =
moles of butyric acid consumed
initial moles of butyric acid
(1)
r
A,obs
=
moles of limiting reactant (A) consumed in reaction time (mol)
catalyst loading (g
cat
) reaction time (s)
(2)
Note that Eq. (2) tends to make errors in the values of reaction rate.
Nevertheless, the degree of the errors by this calculation method
was assumed to be negligible for determining the reaction rate,
since mass transfer limitations would be minimized (cf. Section
3.1).
3. Mathematical modeling
3.1. Kinetic mechanism and reaction rates
The esterication reaction in the present study is the formation
of ester (butyl butyrate) and water by the reaction of a carboxylic
acid (butyric acid) with an alcohol (n-butanol) as follows [1,10]:
CH
3
CH
2
CH
2
COOH + C
4
H
9
OH C
8
H
16
O
2
+H
2
O (3)
Depending on the assumptions about the reaction mechanism
and rate determining step, different models could be developed.
Reaction mechanism differs in terms of the component which
adsorbed onto the catalyst; (i) the EleyRideal (ER) model where
the adsorbed butyric acid reacts with n-butanol in the uid or the
adsorbed n-butanol is reacting with butyric acid in the uid, and
(ii) the LangmuirHinshelwood (LH) model where both reactants
are adsorbed. Rate determining steps can be adsorption, surface
reaction or desorption of any products. Since the water afnity for
the cation-exchange resins is reported to be strong [13,14,18,19],
the correction factor () was added in the calculation of the activ-
ity for water, and thus total 39 different rate equations have been
developed in this study. Table 2 shows these equations along with
the pseudo-homogeneous rate equation. The rst part of the model
name, given in the second column of Table 2, corresponds to the
reaction mechanism; EleyRideal (ER) or LangmuirHinshelwood
(LH), while the second part of the name represents the reactants
being adsorbed; acid (Acid) or alcohol (Alc). The third part indi-
cates the rate determining step (RDS); adsorption (Ad), desorption
(De) and surface reaction (Surf), and the last part is the value
of correction factor (), which is included in the calculation of
the resin afnities for water, i.e. a
water
=(x
water

water
)

. For exam-
ple, the model #3 corresponds to ER Acid Surf 2, which adopts
the ER mechanism with butyric acid as adsorbent and the sur-
face reaction is the RDS, while the resin afnity is calculated as
a
water
=(x
water

water
)
2
.
3.2. Diffusion
To consider the effect of external mass transfer resistance on
the rate of reaction, the Mears criterion for external diffusion was
examined and the dimensionless Mears parameter (C
M
) was calcu-
lated as follows:
C
M
=
r
A,obs

b
R
c
n
k
C
C
Ab
< 0.15 (4)
where n is the reaction order, R
c
is the catalyst particle radius,
b
is
the bulk density of catalyst bed, C
Ab
is the bulk concentration and
k
C
is the mass transfer coefcient. To estimate the mass transfer
coefcient (k
C
), the following equation was employed [20]:
k
C
=
2D
AB
d
p
+0.31N
2/3
Sc
_

c
g

2
c
_
1/3
(5)
here D
AB
is the diffusivity of the solute A in solution, d
p
is the diam-
eter of the catalyst particle,
c
is the viscosity of the solution, g is
the gravitational acceleration, N
Sc
is the Schmidt number (dened
as
c
/
c
D
AB
) and =|
l

c
| where
l
and
c
are the density of
the solution and the density of the catalyst, respectively. Note that
k
C
is dependent on the limiting reactant; as the limiting reactant
is butyric acid in all the cases except runs 3 and 5, the value of k
C
in Table 3 is for butyric acid (runs 1, 2, 4, 6, 7, 8 and 9) or butanol
(runs 3 and 5).
296 I.B. Ju et al. / Chemical Engineering Journal 168 (2011) 293302
Table 2
Reaction rate equations for different reaction mechanisms and rate determining steps.
Model name
a
RDS Rate equation
1 PH 1/2/3 Surface reaction r
i
= Mcat k
f
_
a
alc
a
acid

1
Ks
aester awater
_
2/3/4 ER Acid Surf 1/2/3 1/2/3 Surface reaction r
i
=
M
cat
k
f
K
acid
(a
acid
a
alc
(a
ester
a
water
/Ka))
1+K
acid
a
acid
+K
water
a
water
5/6/7 ER Acid Ad Acid 1/2/3 1/2/3 Adsorption of acid r
i
=
M
cat
k
acid
(a
acid
(a
ester
a
water
/(Kaa
alc
)))
1+(K
acid
/Ka)(a
ester
a
water
/a
alc
)+K
water
a
water
8/9/10 ER Acid De Ester 1/2/3 1/2/3 Desorption of ester r
i
=
M
cat
k
ester
Ka(a
alc
a
acid
/a
water
)(a
ester
/Ka)
1+K
acid
a
acid
+KaK
ester
(a
alc
a
acid
/a
water
)
11/12/13 ER Acid De Water 1/2/3 1/2/3 Desorption of ester r
i
=
M
cat
k
water
Ka(a
alc
a
acid
/a
ester
)(a
water
/Ka)
1+K
acid
a
acid
+KaK
water
(a
alc
a
acid
/a
ester
)
14/15/16 ER Alc Surf 1/2/3 1/2/3 Surface reaction r
i
=
M
cat
k
f
K
alc
(a
acid
a
alc
(a
ester
a
water
/Ka))
1+K
alc
a
alc
+K
water
a
water
17/18/19 ER Alc Ad Acid 1/2/3 1/2/3 Adsorption of acid r
i
=
M
cat
k
alc
(a
alc
(a
ester
a
water
/(Kaa
acid
)))
1+(K
alc
/Ka)((a
ester
a
water
)/a
acid
)+K
water
a
water
20/21/22 ER Alc De Ester 1/2/3 1/2/3 Desorption of ester r
i
=
M
cat
k
ester
Ka((a
alc
a
acid
/a
water
)(a
ester
/Ka))
1+K
alc
a
alc
+KaK
ester
(a
alc
a
acid
/a
water
)
23/24/25 ER Alc De Water 1/2/3 1/2/3 Desorption of ester r
i
=
M
cat
k
water
Ka((a
alc
a
acid
/a
ester
)(a
water
/Ka))
1+K
alc
a
alc
+KaK
water
(a
alc
a
acid
/a
ester
)
26/27/28 LH Surf 1/2/3 1/2/3 Surface reaction r
i
=
M
cat
k
f
K
acid
K
alc
(a
acid
a
alc
(a
ester
a
water
/Ka))
(1+K
acid
a
acid
+K
alc
a
alc
+K
ester
a
ester
+K
water
a
water
)
2
29/30/31 LH Ad Acid 1/2/3 1/2/3 Adsorption of acid r
i
=
M
cat
k
acid
(a
acid
(a
ester
a
water
/(Kaa
alc
)))
1+(K
acid
/Ka)((a
ester
a
water
)/a
alc
)+K
alc
a
alc
+K
ester
a
ester
+K
water
a
water
32/33/34 LH Ad Alc 1/2/3 1/2/3 Adsorption of acid r
i
=
M
cat
k
alc
(a
alc
(a
ester
a
water
/(Kaa
acid
)))
1+K
alc
/Ka(a
ester
a
water
/a
acid
)+K
acid
a
acid
+K
ester
a
ester
+K
water
a
water
35/36/37 LH De Ester 1/2/3 1/2/3 Desorption of ester r
i
=
M
cat
k
ester
Ka(a
alc
a
acid
/a
water
(a
ester
/Ka))
1+K
acid
a
acid
+K
alc
a
alc
+KaK
ester
(a
alc
a
acid
/a
water
)+K
water
a
water
38/39/40 LH De Water 1/2/3 1/2/3 Desorption of ester r
i
=
M
cat
k
water
Ka(a
alc
a
acid
/a
ester
(a
water
/Ka))
1+K
acid
a
acid
+K
alc
a
alc
+K
ester
a
ester
+KaK
water
(a
alc
a
acid
/a
ester
)
a
awater =(xwaterwater)

.
The diffusivity (D
AB
) was obtained from the multi-component
diffusivity correlation, Perkin and Geankoplis method, as shown
below [21]:
D
Am

0.8
m
=
n

j = 1
j / = A
x
j
D
Aj

0.8
j
(6)
whereD
Aj
is thedilutebinarydiffusioncoefcient of Ainj, D
Am
is the
dilute diffusion coefcient of A through the mixture, x
j
is the mole
fraction,
j
is the viscosity of component j,
m
is the mixture vis-
cosity. The D
Aj
can be obtained from the WilkeChang correlation
[21].
If the value of left-hand side in Eq. (4) is lower than 0.15, the
external mass diffusion can be negligible in the kinetic study [17]
and Table 3 shows that the calculated Mears parameters (C
M
) are
less than 0.15.
The occurrence of any internal pore diffusion limitation is
determined on the basis of the WeiszPrater criterion, where the
dimensionless WeiszPrater parameter (C
WP
) is calculated as fol-
lows:
C
WP
=
r
A,obs

c
R
2
c
D
eff
C
A
(7)
where r
A,obs
is the rate of the reaction in mol/g of catalyst/s and

c
is the catalyst density in g/cm
3
. The symbols R
c
, D
eff
, and C
A
represent the effective radius of the catalyst (the ratio of catalyst
pellet volume to the surface area of catalyst) in cm, the effective
diffusivity in cm
2
/s and the limiting reactant concentration in the
mixture in mol/cm
3
, respectively. If the C
WP
is much greater than
one, a strong resistance to internal pore diffusion exists, resulting
in a concentration gradient from the catalyst surface to its pores
[17,22]. The effective diffusivity (D
eff
) can be expressed as:
D
eff
=
2

D
lm
(8)
where
v
is the void fraction and D
lm
is the diffusivity of limiting
reactant in the mixture. The diffusivity of limiting reactant can be
calculated by the PerkinsGeankoplis method and WilkeChang
correlation.
As listed in Table 3, the calculated WeiszPrater parameters
were less than 1, implying that the resistance to internal pore diffu-
sion is sufciently small and the internal diffusion can be negligible
in the kinetic study.
3.3. Activity coefcient
The activity coefcient () was calculated using the multi-
component NRTL equation, and the parameters required in the
Table 3
The criteria for external and internal diffusion.
Run # C
li
a
at 30min (mol/cm
3
) r
A,obs
at 30min (mol/gcat s) Mears parameter WeiszPrater parameter
kc
b
(cm/s) CM D
eff
(cm
2
/s) CWP
1 0.0060 9.29e5 1.93e2 1.77e3 3.83e6 2.45e2
2 0.0018 6.39e5 1.87e2 4.19e3 3.87e6 5.55e2
3 0.0014 5.87e5 1.97e2 4.67e3 3.80e6 6.68e2
4 0.0009 3.86e5 1.79e2 5.27e3 3.90e6 6.65e2
5 0.0006 4.18e5 2.01e2 7.62e3 3.79e6 1.11e1
6 0.0040 9.25e5 1.93e2 2.64e3 3.83e6 3.65e2
7 0.0027 4.12e5 1.93e2 1.74e3 3.83e6 2.41e2
8 0.0034 6.81e5 1.75e2 2.52e3 3.47e6 3.50e2
9 0.0036 6.38e5 1.63e2 2.40e3 3.22e6 3.33e2
a
C
li
denotes a concentration of the limiting reactant in bulk phase.
b
k
C
is for butanol (runs 1, 2, 4, 6, 7, 8 and 9) or butanol (runs 3 and 5).
I.B. Ju et al. / Chemical Engineering Journal 168 (2011) 293302 297
Table 4
NRTL parameters used in the present study.
i B
ij

ij
BuOH
a, b
BA
a, b
BB
a, b
Water
b
BuOH
a, b
BA
a, b
BB
a, b
Water
b
BuOH
a
0 107.92 116.247 1345.784 0 0.3 0.3 0.3
BA
a
120.345 0 263.466 1241.582 0.3 0 0.3 0.3
BB
a
251.472 19.49 0 2794.991 0.3 0.3 0 0.3
Water 48.399 78.809 737.926 0 0.3 0.3 0.3 0
a
BuOH: n-butanol; BA: n-butyric acid; BB: n-butyl butyrate.
b
j: BuOH; BA; BB; water.
Table 5
Parameters for Antoine equation.
a
n-Butanol n-Butyric acid n-Butyl butyrate Water
T
min
(

C) 1.850 88.65 92 1.850


Tmax (

C) 289.9 353.9 342.9 374.1


Coeff A 1.088e2 1.295e2 6.861e1 6.593e1
Coeff B 1.007e4 1.150e4 8.259e3 7.228e3
Coeff C 0 0 0 0
Coeff D 1.326e1 1.651e1 7.431e0 7.177e0
Coeff E 4.380e6 9.336e6 6.730e18 4.031e6
Coeff F 2.00e0 2.00e0 6.00e0 2.00e0
a
lnP
sat
= A +
B
C+T
+DlnT +E T
F
.
equation are available in the UniSim Design Suite (Honeywell Inc.)
software (cf. Table 4):
ln
i
=

n
j=1

ji
G
ji
x
j

n
k=1
G
ki
x
k
+
n

j=1
_
x
j
G
ij

n
k=1
G
kj
x
k
_

ij

n
k=1
x
k

kj
G
ki

n
k=1
G
kj
x
k
__
(9)

ij
=
B
ij
T
(
ij
/ =
ji
) (10)
G
ij
= exp(
ij

ij
) (11)

ij
=
ji
(12)
where
i
and x
i
represent activity coefcient and component frac-
tion in the liquid phase (n
i
/n), respectively. The saturated pressure
(P
sat
i
) was calculated by the Antoine equation, whose parameters
are listed in Table 5.
3.4. Reactor model
Since the reaction temperature is higher than 100

C, the reac-
tor is a reactive distillation system. Therefore, accumulation term
includes both the catalytic reaction rate and the effect of vapor-
ization. It is also observed from the experimental results that the
reaction also takes place in the absence of the catalysts, and thus,
the non-catalytic reaction is considered in the model.
dn
i
dt
= r
i,cat
+r
i,noncat
y
i
F (13)
where n
i
, r
i,cat
and r
i,noncat
denote the amount of component i in
mole, rate of the catalytic reaction and the non-catalytic reaction,
respectively. The symbol F represents the vaporization rate and y
i
is the molar fraction of component i in the vapor phase.
For the vapor/liquid phase equilibrium, it is assumed that the
vapor phase follows the ideal behavior since the pressure in the
reactor is relatively low. In order to calculate the activity coef-
cient (), multi-component NRTL equation and parameters in the
previous section are used.
Onthebasis of overall reactionmechanism, thenet changeinthe
number of total molecules is unchanged by the reaction (

v
i
= 0
wherev
i
is thestoichiometric coefcient of component i), but bythe
vaporization. Therefore, the total amount of vaporized molecules
(n
vap
) is calculated by subtracting the amount of molecules in the
liquid phase from the initial amount in the reactor, and then, the
values for eachreactionconditionarettedtothefollowingexpres-
sion as a function of time in s:
n
vap
= c
1
exp(c
2
t) +c
3
exp(c
4
t) (14)
Table 6 shows the values of parameters for each reaction con-
dition, determined by the curve tting, and the corresponding
coefcients of determination (R
2
). Fig. 1 shows the comparison of
curve tting results withthe experimental data, for the experimen-
tal run2. As showninbothTable6andFig. 1, thecurvettingresults
are satisfactory.
Since the vaporization rate (F) is the derivative formof the total
amount of vaporization, it can be determined from Eq. (14) as fol-
lows:
F(t) =
n
vap
dt
= c
1
c
2
exp(c
2
t) +c
3
c
4
exp(c
4
t) (15)
It is worthnoting that, althoughthe vaporizationrates are calcu-
lated for each condition in order to consider the effects of reaction
rate and experimental condition, the expressions are empirical and
thus, they wouldbe usedina limitedmanner. Inother words, under
more general situations such as reactor design and optimization,
where experimental conditions are vigorously changing, the vapor-
ization rate should be calculated using a more detailed kinetics
model [17].
The fraction of products by non-catalytic reaction is 13% and
the maximum amount is about 0.5mL under the experimental
Table 6
Curve tting results for total amount of vaporized molecules as a function time.
a
Run no. c
1
c
2
c
3
c
4
Coefcient of
determination (R
2
)
1 2.04e01 3.43e06 2.08e01 3.40e04 0.997
2 1.50e01 2.57e06 1.50e01 5.56e04 0.999
3 1.10e01 1.76e05 1.10e01 7.71e04 0.994
4 1.11e01 1.48e06 1.11e01 5.91e04 0.999
5 7.52e02 4.18e06 7.51e02 9.24e04 0.998
6 1.48e01 1.51e05 1.47e01 3.76e04 0.993
7 1.94e01 8.08e06 1.94e01 6.19e04 0.998
8 1.33e01 1.34e05 1.33e01 6.07e04 0.997
9 1.31e01 1.20e05 1.30e01 5.11e04 0.999
a
nvap = c
1
exp(c
2
t) +c
3
exp(c
4
t).
298 I.B. Ju et al. / Chemical Engineering Journal 168 (2011) 293302
0.04
0.05
0.06
V
a
p
o
r
i
z
e
d

a
m
o
u
n
t

[
m
o
l
]
0.01
0.02
0.03
Time [hr]
6 5 4 3 2 1 0
0.00
Fig. 1. The amount of vaporized molecules for non-catalytic reaction under the
reaction condition No. 2 in Table 1.
conditions inthis study. Thenon-catalytic reactionrateis expressed
using the following reaction rate and the kinetic parameters are
determined by tting the experimental data.
r
noncat
= k
f,noncat
_
a
acid
a
alc

a
ester
a
water
K
s,noncat
_
(16)
Reaction equilibrium constant, K
s,noncat
, is dened as
k
f,noncat
/k
f,noncat
(backward reaction rate constant divided by
forward reaction rate constant) and they are determined as
k
f,noncat
=1.218e5 and K
s,noncat
=1.058, respectively. The value of
relative errors for these kinetic parameters is calculated as 3.03%.
It is worth noting that the rate constants for non-catalytic reaction
are xed as a constant since the effect of temperature on the rates
is assumed to be negligible.
3.5. Parameter estimation
To estimate kinetic parameters, conversions of acid and alcohol
at thepre-speciedsamplingtimes aretakenintoaccount andthen,
the optimization is performed to minimize the following objective
function:
F
obj
=
1
2

all sampling points


_
n
i,calc
n
i,exp
n
i,exp
_
2
(17)
where ndenotes the mol of component i, where i =butyric acid(BA),
n-butanol (BuOH), butyl-butyrate (BB) and water, at a sampling
time under a certain condition, and subscripts calc and exp mean
the calculated and experimental values, respectively.
The temperature dependence of kinetic parameters is consid-
ered by using the Arrhenius-type for reaction rate constants while
the equilibriumconstants are assumedtobe xeddue totheir weak
temperature dependency:
k
i
(T) = k
i,0
exp
_
E
i
RT
_
(18)
The pre-exponential factors, activation energies, and equilib-
rium constants are scaled in the form of y
scaled
=y
actual
/y
scaling-factor
in order to reduce the statistical correlation and to prevent the ill-
conditioning problems resulting from the differences of the orders
of magnitude between parameters.
Under the experimental conditions presented in Table 1, the
catalytic experiments were carried out using Dowex 50Wx8-400
catalyst. Duringthe reaction, samplingwas conductedevery30min
and the reaction time was specied between 5 and 6h, and thus,
total of 63 points were used in the nonlinear data-tting proce-
dure. The objective function, Eq. (17), was minimized using the
lsqcurvet subroutine in the MATLAB (The MathWorks, Inc.) where
the LevenbergMarquardt method is applied. In order to guaran-
tee the physico-chemical meanings of the kinetic parameters, the
following constraints for the estimates of parameters have been
applied to the optimization step [2224]:
Reaction rate constant, k =Aexp( E
A
/RT):
Rule 1 : k > 0 (19)
Rule 2 : E
A
> 0 (20)
Thenumerical integrationof Eq. (13), whichwas requiredduring
each iterative step in the nonlinear regression, was performed by
the ODE solver, ode23s implemented in the MATLAB.
4. Results and discussion
4.1. Determination of kinetic parameters
In order to determine kinetic parameters (A
f
, E
A
and equilibrium
constants) of eachreactionrates inTable 2, the following steps have
been repeatedly applied to the parameter estimation step for each
model, andthus, total of 41 parameter estimations (1 PHmodel and
40 heterogeneous models) have been conducted:
(1) Step 1: Data under the conditions of 17 (constant temper-
ature, T =110

C) were used to estimate the kinetic


parameters k
f
(110

C) and equilibrium constants K


i
s.
(2) Step 2: k
f
(105

C) and k
f
(100

C) were estimated using the data


under the conditions of 8 and 9, respectively, while the
equilibrium constants K
i
s are xed at the values from
Step 1.
(3) Step 3: Pre-exponential factor (A
f
) and activation (E
A
) are cal-
culated using the values of k
f
at 100, 105 and 110

C.
Table 7 shows the estimated values of kinetic parameters and it
is observed that the activation energy (E
A
) ranges between 30 and
60kJ/mol as reported in the literature [1]. In order to determine the
best t model, the total average errors (T
error
), dened as Eq. (21),
are calculated for each model using the corresponding estimated
kinetic parameters, and the values are listed in Table 7.
Total average error (%) =

(y
exp,i
y
calc,i
)/y
exp,i

N
100 (21)
where N is the total number of data points. The symbols y
exp
and
y
calc
denote the experimental data and the simulation results using
the estimated kinetic parameters in each model, respectively.
With multi-parameter models and particularly with the rather
mathematically related models in Table 2, model discrimination is
complicated and difcult. The number of parameters to be tted
is also of importance and thus, the Akaikes information criteria
(AIC) [25], where a function that measures some complexity of the
model structure is included, is calculated and the values are listed
in Table 7.
The models whose T
error
s are lower than the value of PH
model are #2 (ER Acid Surf 1), #14 (ER Alc Surf 1) and #26
(LH Surf 1), among which #14 has a little bit smaller value than
the others, but the standard deviation dened as Eq. (22) is the
smallest for #2.
STDEV =
_
(Individual error T
error
)
2
N 1
(22)
Thespecic equations, inwhichthegeneral formof K
a
is reduced
to the corresponding expression for the models #2, #14 and #26,
are provided for the purpose of comparison between them, as
I
.
B
.
J
u
e
t
a
l
.
/
C
h
e
m
i
c
a
l
E
n
g
i
n
e
e
r
i
n
g
J
o
u
r
n
a
l
1
6
8

(
2
0
1
1
)

2
9
3

3
0
2
2
9
9
Table 7
Values of estimated parameters.
No. Model name A
f
E
A
k
f
(110

C) k
f
(105

C) k
f
(100

C) Ks K
acid
K
alc
Kester Kwater Terror AIC STDEV
1 PH 1.44e2 3.82e4 1.16e3 8.00e4 4.90e4 1.03e3 12.81 13.08 61.15
2 ER Acid Surf 1 6.09e2 4.26e4 1.17e3 8.00e4 5.13e4 9.90e0 1.25e0 5.36e10 12.52 12.95 59.55
3 ER Acid Surf 2 1.10e6 5.55e4 3.50e2 2.49e2 1.52e2 9.20e1 3.35e2 1.44e7 13.94 14.42 63.51
4 ER Acid Surf 3 1.13e6 5.57e4 3.31e2 2.43e2 1.46e2 8.26e1 3.58e2 1.49e8 14.85 15.37 65.81
5 ER Acid Ad Acid 1 3.44e1 3.56e4 6.99e4 4.19e4 2.36e4 7.07e1 9.89e0 1.97e1 15.16 15.69 75.18
6 ER Acid Ad Acid 2 1.30e4 5.30e4 1.22e3 7.30e4 2.95e4 8.48e1 1.50e1 6.89e1 16.27 16.83 81.61
7 ER Acid Ad Acid 3 2.05e3 4.50e4 2.13e3 2.79e3 3.60e4 4.67e1 8.42e0 2.84e1 17.43 18.04 84.18
8 ER Acid De Ester 1 1.29e7 5.44e4 3.95e0 2.26e0 7.20e3 1.65e1 9.97e1 9.92e1 16.68 17.26 85.80
9 ER Acid De Ester 2 1.32e8 5.91e4 1.72e1 5.99e0 7.94e3 1.36e1 9.93e1 9.94e1 17.30 17.90 85.84
10 ER Acid De Ester 3 2.70e1 1.54e8 1.11e1 3.86e2 4.57e2 2.59e0 1.01e2 9.98e1 24.52 25.37 110.63
11 ER Acid De Water 1 1.81e7 5.59e4 1.17e1 1.93e1 1.77e2 6.49e0 1.01e2 6.54e1 19.80 20.49 98.55
12 ER Acid De Water 2 1.02e8 6.90e4 1.23e1 3.79e1 5.90e4 9.11e0 1.03e1 7.24e0 17.44 18.05 86.46
13 ER Acid De Water 3 7.24e7 6.52e4 1.19e1 1.05e0 2.99e3 1.01e1 1.03e1 9.67e0 17.85 18.47 87.34
14 ER Alc Surf 1 9.84e2 4.44e4 1.08e3 7.35e4 4.68e4 7.36e0 1.43e0 4.10e10 12.38 12.81 59.68
15 ER Alc Surf 2 2.13e4 4.85e4 6.35e3 4.52e3 2.76e3 1.00e1 1.92e1 1.27e8 13.90 14.38 63.41
16 ER Alc Surf 3 2.45e4 4.56e4 7.05e3 9.63e2 3.12e3 1.01e1 1.74e1 6.69e5 14.78 15.29 65.76
17 ER Alc Ad Alc 1 3.60e2 4.04e4 1.46e3 9.78e4 6.15e4 2.06e1 9.12e0 3.82e0 14.87 15.39 71.21
18 ER Alc Ad Alc 2 6.40e2 4.05e4 2.35e3 1.80e3 1.10e3 9.19e1 6.59e0 9.86e0 15.67 16.21 72.39
19 ER Alc Ad Alc 3 4.52e1 3.64e4 6.32e4 4.58e4 2.71e4 9.96e1 3.25e1 1.08e0 16.99 17.58 77.56
20 ER Alc De Ester 1 1.83e7 7.01e4 1.35e2 6.92e3 6.90e4 1.87e1 1.02e1 9.80e0 16.14 16.70 82.79
21 ER Alc De Ester 2 3.00e8 6.11e4 3.26e1 5.77e0 7.81e3 1.36e1 1.02e2 9.86e1 17.21 17.81 85.45
22 ER Alc De Ester 3 6.35e7 5.63e4 4.67e0 8.62e0 3.08e2 6.41e0 1.15e2 8.51e1 18.31 18.95 89.79
23 ER Alc De Water 1 1.06e8 6.10e4 5.74e0 1.84e0 6.12e3 1.33e1 1.15e2 9.20e1 16.69 17.27 85.82
24 ER Alc De Water 2 4.36e7 5.61e4 6.01e1 4.71e1 1.79e2 7.71e0 1.04e2 7.30e1 17.93 18.55 88.94
25 ER Alc De Water 3 2.77e7 5.31e4 1.34e1 5.84e0 2.93e2 1.08e1 9.99e1 9.94e1 17.82 18.44 87.22
26 LH Surf 1 4.50e5 5.37e4 2.55e2 1.76e2 1.11e2 8.36e0 2.90e1 1.94e1 1.17e2 6.18e3 12.52 13.13 59.99
27 LH Surf 2 3.41e4 4.94e4 7.46e3 5.59e3 3.29e3 1.03e2 1.15e0 6.50e1 2.26e1 8.49e1 15.50 16.25 69.18
28 LH Surf 3 5.25e3 4.40e4 6.37e3 4.93e3 2.76e3 7.21e1 1.49e0 8.22e1 9.88e1 9.00e1 16.66 17.47 73.97
29 LH Ad Acid 1 9.02e3 5.12e4 1.42e3 7.78e4 4.43e4 1.04e2 1.40e0 4.61e1 1.58e0 1.36e0 15.35 16.10 76.35
30 LH Ad Acid 2 1.41e7 7.03e4 1.19e2 4.97e3 4.14e4 3.93e0 1.16e0 9.16e1 8.22e1 3.64e1 17.11 17.94 85.36
31 LH Ad Acid 3 3.45e7 7.24e4 1.64e2 5.95e3 4.52e4 1.59e0 1.47e0 8.87e1 2.70e1 6.48e1 17.66 18.52 86.24
32 LH Ad Alc 1 5.86e2 4.34e4 9.48e4 5.89e4 3.77e4 9.95e1 9.45e1 5.43e1 1.01e0 1.19e0 15.28 16.02 72.32
33 LH Ad Alc 2 1.18e2 3.83e4 9.61e4 6.18e4 3.78e4 9.68e1 1.26e0 2.70e1 1.04e0 1.01e0 16.31 17.10 76.36
34 LH Ad Alc 3 7.13e7 6.85e4 1.93e1 2.89e2 2.71e3 6.58e0 1.24e1 1.04e1 9.56e0 7.73e0 17.72 18.58 86.62
35 LH De Ester 1 1.08e1 3.56e4 1.95e4 1.40e4 7.87e5 9.01e1 9.30e1 1.77e0 5.12e1 5.32e0 15.19 15.93 72.20
36 LH De Ester 2 6.23e7 7.12e4 6.92e2 9.31e3 1.19e3 8.88e0 1.06e1 1.10e1 8.80e0 8.53e0 17.21 18.05 85.61
37 LH De Ester 3 3.86e7 7.47e4 4.46e2 9.88e4 1.49e4 1.66e0 1.63e0 1.47e0 7.06e1 4.82e1 17.68 18.54 86.48
38 LH De Water 1 5.89e8 7.77e4 2.10e1 1.02e2 6.23e4 1.10e1 1.10e1 1.01e1 8.90e0 8.17e0 16.66 17.47 85.70
39 LH De Water 2 4.69e6 5.50e4 1.85e1 1.21e1 7.84e2 4.21e2 3.96e2 4.15e2 1.66e3 1.41e3 17.41 18.26 77.58
40 LH De Water 3 5.18e7 5.36e4 1.84e2 3.79e0 1.32e2 5.01e1 6.15e1 7.61e1 1.67e2 1.23e2 17.78 18.64 86.78
300 I.B. Ju et al. / Chemical Engineering Journal 168 (2011) 293302
follows:
#2(ER Acid Surf 1) : r
i
=
M
cat
k
f
_
(K
acid
a
acid
)a
alc
a
ester
(K
water
a
water
)/K
s
_
1 +K
acid
a
acid
+K
water
a
water
(23)
#14(ER Alc Surf 1) : r
i
=
M
cat
k
f
_
a
acid
(K
alc
a
alc
) a
ester
(K
water
a
water
)/K
s
_
1 +K
alc
a
alc
+K
water
a
water
(24)
#26(LH Surf 1) : r
i
=
M
cat
k
f
_
(K
acid
a
acid
)(K
alc
a
alc
) (K
ester
a
ester
)(K
water
a
water
)/K
s
_
(1 +K
acid
a
acid
+K
alc
a
alc
+K
ester
a
ester
+K
water
a
water
)
2
(25)
here K
s
is the surface reactionequilibriumconstant, while K
acid
, K
alc
,
K
ester
and K
water
are the adsorption equilibrium constants for acid,
alcohol, ester andwater, respectively. The activities for acid, alcohol
and ester are dened as a
i
=x
i

i
(i =acid, alc, ester). The activity for
water is a
water
=x
water

water
for the models #2 and #14, while the
value of 2 for the resin afnity of water () in the model #26 results
in the denition of a
water
=(x
water

water
)
2
.
In the sense of AIC values, where the complexity of multi-
parameter model is taken into account, the models #2 and #14
show better performance than the PH model, while the model #26
has a little bit higher value than the PH model. It is worth noting
that the models #2 and #14 are based on the ER mechanism, while
the model #26 adopts the LH mechanism. This feature indicates
that one of two types of reactants (n-butanol and butyric acid) may
adsorb more dominantly than the other one.
Although it is hard to decide the best t model, several common
features areobservedinmodels #2, #14and#26. Therst is therate
determining step, which is the surface reaction. Since the adsorp-
tion of reactants may be less considerable compared to the surface
reaction, both ER and LH models show good tting performances
as long as the RDS is specied with the surface reaction, and the
adsorption equilibriumconstants of acid and alcohol are estimated
to be similar (see that K
acid
for #2, K
alc
for #14, and both for #26
have similar values). The second is the behavior of water molecule.
In the case of the esterication of propionic acid with propanol, the
resin water afnity is observed to be strong, that is, the value of
is determined to be 2 in Ali and coworkers study [1]. However,
in all models selected in this study have the value of one, which
means that the water afnity in the case of the esterication of
butyric acid with n-butanol is not as strong as that in the propanol
case. This feature is also supported in the values of adsorption equi-
librium constants. The equilibrium constants for the adsorption of
water (K
water
) are very low for the models #2 and #14, indicating
that most of water molecules are desorbed from the catalyst the
moment they are formed from the reaction. As for #26, the value
of K
water
is relatively low compared to the other kinetic parame-
ters. This feature may be contributed to the fact that the reaction
temperature in this work is specied relatively high (above 100

C)
for the reactive distillation, compared to the case reported in the
literature (below 60

C) [1]. It is worth noting that, the order of


the adsorption equilibrium constants for species other than water
is same as in the propanol case (cf. K
alc
>K
acid
>K
ester
>K
water
in this
studyandK
water
>K
alc
>K
acid
>K
ester
inthe estericationof propionic
acid [1]), since their temperature dependency under 120

C is not
signicant.
It should be noted that the performance of the PHmodel is com-
parabletothoseof theselectedmodels. However, thePHmodel fails
to provide the information on the detailed kinetic mechanism. In
0.4
0.6
0.8
1.0 (a)
6 5 4 3 2 1 0
C
o
n
v
e
r
s
i
o
n
0.0
0.2
0.8
1.0
(b)
C
o
n
v
e
r
s
i
o
n
0.0
0.2
0.4
0.6
6 5 4 3 2 1 0
0.6
0.8
1.0
(c)
6 5 4 3 2 1 0
C
o
n
v
e
r
s
i
o
n
0.0
0.2
0.4
Time [hr]
Fig. 2. Comparison of BA conversion between experimental data and simulation
results using the model #2 with estimated parameters for the change of (a) the ratio
of BA/BuOH (: 0.25, : 0.5, : 1.0, : 2.0, : 4.0), (b) catalytic loading (: 10g, :
20g, : 40g), and (c) temperature (: 100

C, : 105

C, : 110

C).
addition, the PH model is not intrinsic, but it ts the data available
fromthe lab-scale reactor used in the present study within the lim-
ited range of operating conditions. In other words, since the kinetic
parameters of the PH model is apparent (effective for the specic
reactor), it cannot be utilized to predict the behavior of the reactor
for the entire range of operating condition, and its application to
the design of large-scale reactor is signicantly limited.
It should be also noted that, although three data points, that is,
the values at 100, 105 and 110

C, were used for the calculation


of activation energies of the parameter k
f
, the temperature range
is limited and thus, the accuracy of the calculated values may be
insufcient. However, since the purpose of the present study is to
ndthe plausible kinetic mechanismfor catalytic esterication, not
todetermine the activationenergies, this feature does not inuence
the conclusion that the mechanismin the models #2 and #14 plays
important role in the esterication of n-butanol and butyric acid
using Dowex 50Wx8-400.
4.2. Effect of operating conditions
Figs. 24 show the comparison of experimental data and simu-
lation results for the models #2, #14, and #26, respectively. Each
gure is composed of three diagrams with respect to the varia-
tion of operating conditions. Diagrams (a), (b), and (c) describe the
effect of the ratio of BA/BuOH, the catalytic loading, and tempera-
ture, respectively. As showningures, simulationresults of models
#2, #14, and #26 are in good agreement with experimental data.
I.B. Ju et al. / Chemical Engineering Journal 168 (2011) 293302 301
0.4
0.6
0.8
1.0 (a)
6 5 4 3 2 1 0
C
o
n
v
e
r
s
i
o
n
0.0
0.2
0.8
1.0
(b)
C
o
n
v
e
r
s
i
o
n
0.0
0.2
0.4
0.6
6 5 4 3 2 1 0
0.6
0.8
1.0
(c)
6 5 4 3 2 1 0
C
o
n
v
e
r
s
i
o
n
0.0
0.2
0.4
Time [hr]
Fig. 3. Comparison of BA conversion between experimental data and simulation
results using the model #14 with estimated parameters for the change of (a) the
ratio of BA/BuOH(: 0.25, : 0.5, : 1.0, : 2.0, : 4.0), (b) catalytic loading (: 10g,
: 20g, : 40g), and (c) temperature (: 100

C, : 105

C, : 110

C).
As the ratio of BA/BuOH is increased, the conversion of butyric
acid is decreased since the amount of BuOH is decreased. For the
equimolar case, the conversion is about 90%. When the ratio is
decreased to 0.25, most BA is consumed and thus, the product (BB)
and the excess reactant (BuOH) remain in the reactor. When n-
butanol is limiting reactant (the ratio of BA/BuOH is higher than
1), the conversion of BA is lower than 0.4 while the conversion of
BuOH is close to 100% resulting in the two components (BB and
BA) remaining in the reactor. Although the yield of BB is decreased
for non-equimolar case, this ratio may be preferable in the sense
of separation (the number of separating components is decreased
from 3 to 2). It is worth noting, however, that the actual cost and
revenue for each case should be evaluated carefully to determine
the best BA/BuOH molar ratio.
It is shown in diagrams (b) and (c) of Figs. 24 that the increased
amount of catalyst and high temperature increase the conversion,
since the increase of catalyst loading corresponds to more avail-
able active sites for the reaction, resulting in higher reaction rate.
In the model, the term M
cat
represents the catalyst loading, and,
as shown in the comparison between experimental and simulation
results, the order of one is enough to consider its contribution to
the reaction rate. The effect of temperature is taken into account
in the forward reaction rate constant, meaning that high tempera-
ture gives rise to more frequent and successful collision for higher
conversion of reactants to ester products. However, if the reaction
0.4
0.6
0.8
1.0 (a)
6 5 4 3 2 1 0
C
o
n
v
e
r
s
i
o
n
0.0
0.2
0.8
1.0
(b)
C
o
n
v
e
r
s
i
o
n
0.2
0.4
0.6
6 5 4 3 2 1 0
0.0
0.6
0.8
1.0
(c)
6 5 4 3 2 1 0
C
o
n
v
e
r
s
i
o
n
0.0
0.2
0.4
Time [hr]
Fig. 4. Comparison of BA conversion between experimental data and simulation
results using the model #26 with estimated parameters for the change of (a) the
ratio of BA/BuOH(: 0.25, : 0.5, : 1.0, : 2.0, : 4.0), (b) catalytic loading (: 10g,
: 20g, : 40g), and (c) temperature (: 100

C, : 105

C, : 110

C).
takes place at too high temperature, the reactants are also vapor-
ized to alleviate the efciency of reactive distillation system, that
is, there exists a tradeoff between high reaction rate due to the
increased temperature and the decrease of reaction rate resulting
fromthe vaporization of reactants. Therefore, it might be necessary
to determine the optimal reaction temperature or the optimal tra-
jectory of temperature, considering the production rate as well as
the vaporizing rate of reactants.
5. Conclusions
The kinetic study for the esterication of butyric acid with n-
butanol over ion-exchange resin, Dowex 50 Wx8-400, was carried
out in this study. The experiment was conducted in a reactive
distillation mode, and several experimental conditions, such as
the reactant molar ratio, catalyst loading and reaction tempera-
ture were varied. Prior to the mathematical modeling, absence of
resistance to internal and external diffusion was veried with the-
oretical criteria, the Mears and WeiszPrater parameters. Then, 40
reaction rate equations were derived based on theoretical kinetic
models, and the resin afnity for water due to strong interaction
between resin and water by-product. Three models (#2, #14 and
#26) showing better performance than the others were deter-
mined in terms of the mathematical tting of kinetic models
with experimental data. Although the best t model could not be
302 I.B. Ju et al. / Chemical Engineering Journal 168 (2011) 293302
determined, it is evident that the surface reaction is the rate deter-
mining step, while the adsorption of two reactants on the catalyst
surface are competitive in the esterication reaction and the inter-
action between Dowex 50Wx8-400 and water byproduct is not
relatively strong. In addition, both experimental results obtained
under various reaction conditions and the corresponding simula-
tion data inform that the conversion of butyric acid increases as
catalyst loading and reaction temperature increase, or the molar
ratio of butyric acid/n-butanol decreases. It should be kept in mind,
however, that the reaction rate and the separation efciency need
to be taken into account simultaneously to determine the opti-
mal reaction condition for industrial scale reactors. In conclusion,
the kinetic information presented in this study is expected to pro-
vide valuable insight into the design of large-scale butyl butyrate
production processes.
Acknowledgements
The authors acknowledge the nancial support of Korea
Ministry of Environment as Converging Technology Project
(202101006) and Basic Science Research Program through the
National Research Foundation of Korea (NRF) funded by the Min-
istry of Education, Science and Technology (No. 2010-0003380).
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