Ind. Eng. Chem. Res.

2008, 47, 1453-1463 1453

Thermodynamic Equilibrium and Reaction Kinetics for the Esterification of

Lactic Acid with Ethanol Catalyzed by Acid Ion-Exchange Resin
Carla S. M. Pereira,† Simão P. Pinho,‡ Viviana M. T. M. Silva,§ and Alı́rio E. Rodrigues*,†
Laboratory of Separation and Reaction Engineering (LSRE), Faculdade de Engenharia, UniVersidade do Porto,
Rua Dr. Roberto Frias s/n, 4200-465 Porto, Portugal, Laboratory of Separation and Reaction Engineering
(LSRE), Departamento de Tecnologia Quı́mica e Biológica, Instituto Politécnico de Bragança, Campus de
Santa Apolónia, 5301-857 Bragança, Portugal, and FluidinoVa, Engenharia de Fluidos S.A., TecMaiasRua
Engenheiro Frederico Ulrich, 2650, 4470-605 Moreira da Maia, Portugal

The heterogeneous catalysis of lactic acid (88 wt %) esterification with ethanol in the presence of Amberlyst
15-wet was studied for catalyst loading of 1.2-3.9 wt %, initial molar ratio of reactants of 1.1-2.8, and
temperature from 50 to 90 °C. In this work a methodology based on the UNIQUAC model was developed to
determine the thermodynamic equilibrium constant since in the literature there is inconsistency concerning
the temperature dependence of the thermodynamic equilibrium constant. A simplified Langmuir-Hinshelwood
kinetic model was used to predict the experimental data. The proposed rate law is r ) kc(aEthaLa - aELaW/
K)/(1 + KEthaEth + KWaW)2; the kinetic parameters are the preexponential factor, kc,0 ) 2.70 × 107
mol‚g-1‚min-1, and the activation energy, Ea ) 49.98 kJ/mol. The equilibrium reaction constant is K )
19.35 exp(-515.13/T (K)) with reaction enthalpy 4.28 kJ/mol. The model reasonably predicts the kinetic
experimental data, and it will be very useful to apply to the design and optimization of industrial hybrid
reactive separation processes.

1. Introduction
Petroleum (“black gold”) is at the heart of today’s economics
and political problems. It is a finite resource, and the use of petro-
chemical solvents has several implications for the environment.
Therefore, the replacement of traditional petroleum-derived solvents
is one of the major challenges that the industry has been facing.
The lactate esters derived from bio-based organic acids fall into
the category of green solvents and are promising replacements The use of lactic acid as reactant is then complicated, since
for halogenated petroleum-based solvents in a wide range of the extent of self-esterification increases with the increase of
applications. Ethyl lactate is a green solvent derived, for example, the acid concentration. A method to purify lactic acid is through
from processing corn or sugar crops, and it is so benign that the esterification with lower alcohols, such as methanol, ethanol, or
U.S. Food and Drug Administration approved its use in food prod- butanol; then the produced ester is separated and hydrolyzed
ucts. It is biodegradable and it could replace a range of environ- back into pure lactic acid and the alcohol is recovered and
ment-damaging halogenated and toxic solvents, including carcino- reused.4
genic methylene chloride, and toxic ethylene glycol ethers and Ethyl lactate synthesis comprises a liquid-phase reversible
chloroform,1 which will result in a much safer workplace. reaction between ethanol and lactic acid, wherein water is a
Lactic acid has a wide range of applications in the food subproduct:
(preservative and flavor), cosmetic, pharmaceutical, textile, and
leather industries, but for that it must be highly pure.2 Lactic H+
acid contains a hydroxyl group adjacent to the carboxylic acid
ethanol (Eth) + lactic acid (La) 798
and because of its bifunctional nature undergoes intermolecular ethyl lactate (EL) + water (W)
esterification in aqueous solutions above 20 wt % to form linear
dimer and higher oligomer acids:2,3 All esterification reactions occur in acid medium; they are
self-catalyzed by the acid involved in the reaction. However,
2La1 S La2 + W (lactic acid dimer formation) the kinetics of the self-catalyzed reaction is too slow and the
use of a homogeneous or heterogeneous catalyst is advanta-
La1 + La2 S La3 + W (lactic acid trimer formation) geous. For the process of ethyl lactate production it will be
desirable to use a high lactic acid concentration, with lower
l water content, in order to increase the yield of the reaction
and the concentration of the ethyl lactate. However, this will
La1 + Lan-1 S Lan + W (lactic acid oligomer formation)
imply the presence of lactic acid oligomers during the
esterification, which will be converted into the corresponding
with n g2, where
esters:
* To whom correspondence should be addressed. Tel.: +351 22
La1 + Eth S EL1 + W (ethyl lactate formation)
5081671. Fax: +351 22 5081674. E-mail: arodrig@fe.up.pt.
†
Universidade do Porto.
‡
Instituto Politécnico de Bragança.
§ La2 + Eth S EL2 + W (ethyl lactate dimer formation)
Fluidinova.

10.1021/ie071220p CCC: $40.75 © 2008 American Chemical Society

Published on Web 01/30/2008
1454 Ind. Eng. Chem. Res., Vol. 47, No. 5, 2008
La3 + Eth S EL3 + W (ethyl lactate trimer formation)
l
Lan + Eth S ELn + W (ethyl lactate oligomer formation)
where
For an aqueous solution with 88 wt % lactic acid, the molar
percentages of the monomer (La1), dimer (La2), and trimer (La3)
are about 43.5, 9.2, and 1.8 mol %, respectively, with about 45
mol % water. A 20 wt % aqueous solution of lactic acid is
constituted only by monomer and water, with the monomer
molar percentage being about 5.6 mol %.5 However, the
percentage of lactic acid and ethyl lactate oligomers is less than
5% at equilibrium,5,6 and the use of an aqueous solution with a
high lactic acid concentration is desirable to produce ethyl lactate
on an industrial scale by means of a continuous hybrid process
such as reactive pervaporation, reactive chromatographic pro-
cesses, and others.
The kinetics of ethyl lactate production has been studied since
1957,4 but lately has deserved more attention since it is a green
solvent and an alternative to the traditional petroleum-derived
solvents. Troupe and Dimilla4 studied the esterification reaction
between lactic acid and ethanol using sulfuric acid as catalyst.
However, this kind of homogeneous catalyst may be the origin
of a lot of problems, because of their miscibility with the
reaction medium, which causes separation problems; in addition,
strong acid catalysts lead to corrosion of the equipment. The
replacement of homogeneous catalysts by heterogeneous cata-
lysts is gaining importance due to their ecofriendly nature.
Besides being noncorrosive and easy to separate from the
reaction mixture, the heterogeneous catalyst can be used
repeatedly over a prolonged period without any difficulty in
handling and storage. Many solid-acid catalysts have been used,
such as acid-treated clays,7 heteropolyacids,7-10 iodine,11 MCM-
41,12 zeolite-T membrane,6 Smopex-101,13,14 HY zeolite,15-17
zeolite beta,17 and ZSM-5.7,16-18 However, ion-exchange resins
are the most commonly used solid catalysts and they have been
proved to be effective in liquid-phase esterification.19-24 Since
heterogeneous catalysis is clearly advantageous, some studies
have been already performed for the esterification of lactic acid
with ethanol. Zhang and co-workers24 studied the kinetics of
esterification of lactic acid (20 wt %) with ethanol catalyzed
by five different cation-exchange resins. They proposed a
simplified mechanism based on the Langmuir-Hinshelwood
model to describe the kinetics behavior. Delgado et al.25 also
investigated the esterification of lactic acid with ethanol and
the hydrolysis of the ethyl lactate in the presence of a
commercial cation-exchange resin; an aqueous lactic acid
solution of 20 wt % and a mechanism based on the Langmuir-
Hinshelwood model to describe the kinetics was used. This
esterification with/without a solid catalyst (Amberlyst XN-1010)
was also investigated by Benedict and collaborators.23 A kinetic
model based on concentrations to describe the behavior of the
reaction between an 88 wt % lactic acid solution with ethanol
was used. The presence of oligomers was not mentioned in their
Figure 1. Representation of experimental values of ln K as function of
1/T. Data collected from Delgado et al.26
work. In Tanaka and co-workers6 studies about this esterifica-
tion, the presence of oligomers was considered and the reactions
were described by simple nth-order reversible rate expressions
based on the species concentration. Three different solutions
of lactic acid (20, 50, 88 wt %) were used in the esterification
reaction with ethanol in Asthana and collaborators’ work.5 The
presence of oligomers was also taken into account, and a similar
model based on the species concentration was used to describe
the reaction kinetics.
In spite of the number of kinetic studies available in the
literature, the thermodynamic equilibrium of the reaction in the
liquid phase has not been clearly studied, and some of the
authors do not report the values of the equilibrium constant.24
In some works4,25 different equilibrium constants based on
concentration (Kx) at the same temperature are reported. The
authors of those studies have concluded that the equilibrium
constant Kx varies significantly with the initial molar ratio of
the reactants, being less sensitive to the temperature. However,
the thermodynamic equilibrium constant defined as a function
of the species liquid activities, which is only temperature
dependent, is not presented in their works. In order to overcome
the lack of thermodynamic data, Delgado and coauthors26 have
studied the vapor-liquid reactive equilibria for ethyl lactate
synthesis, and they have proposed the following expression to
describe the reaction equilibrium constant:
2431.2
ln(K) ) 7.893 - (1)
T (K)
Nevertheless, they have found some difficulties in measuring
the vapor-phase composition, which significantly affects the
experimental values of the experimental equilibrium constant,
leading to high deviations between experimental values and
those predicted by eq 1, as shown in Figure 1.
This work was undertaken to obtain the reaction equilibrium
and kinetic data for the synthesis of ethyl lactate in the liquid
phase, avoiding the vaporization of all species by working at 6
bar (helium pressurization). The pressure influence on the value
of the equilibrium constant is negligible for this system for the
temperature and pressure operating range, as it can estimated
by the correction factor KP.27 Therefore, the thermodynamic
equilibrium constant was estimated by the UNIQUAC method
and the esterification reaction catalyzed by the ion-exchange
resin Amberlyst 15-wet was described by a simple activity based
kinetic model, which will be applied in the modeling of some
reactive separation processes, such as membrane reactors. In
this work a high lactic acid concentration was used with the

Figure 2. Experimental setup for kinetic studies. BR, batch reactor; FV,
feed vessel; M, motor; TT, temperature sensor; PT, pressure sensor; PM,
manometer; BV, blow-off valve; V1, sampling valve; V2, injection valve;
NV, needle valve; GC, gas chromatograph; TB, thermostatic bath.
objective of maximizing the ethyl lactate productivity for an
industrial process. The presence of oligomers was neglected,
since at equilibrium the total amount of lactic acid and ethyl
lactate oligomers represents less than 5% according to the
Tanaka et al.6 and Asthana et al.5 studies. However, in the final
section of this paper the presence of oligomers will be addressed.
2. Experimental Section
2.1. Chemicals and Catalyst. The chemicals used were
ethanol (>99.9% in water), lactic acid (>85% in water), and
ethyl lactate (>98% in water) from Sigma-Aldrich (U.K.). A
commercial strong-acid ion-exchange resin named Amberlyst
15-wet (Rohm & Haas) was used as catalyst and adsorbent.
This resin is a bead-form macroreticular polymer of styrene and
divinylbenzene, with particle diameters varying between 0.3 and
1.2 mm, an ion-exchange capacity of 4.7 mequiv of H+/g of
dry resin, and an inner surface area of 53 m2/g. According to
Ihm et al.28 only 4% of the active sites are located at the
macropores (surface of the microspheres) and the other 96%
are inside gel polymer microspheres. Since the water adsorbed
on the catalyst surface decreases the reaction kinetics, because
it is one of the reaction products, it was necessary to guarantee
anhydrous resin. For that, the resin was washed several times
with deionized water and dried at 90 °C until the mass remained
constant. This method is of value for the reuse experiments,
since water is abundantly present due to the lactic acid solution.
2.2. Experimental Setup. The experiments were carried out
in a glass-jacketed 1 dm3 autoclave (Büchi, Switzerland),
operating in a batch mode, mechanically stirred at 600 rpm,
equipped with pressure and temperature sensors and with a
blow-off valve (Figure 2). The temperature was controlled by
a thermostated ethylene glycol/water solution (Lauda, Germany)
that flows through the jacket of the reactor and feed vessel. To
maintain the reacting mixture in liquid phase over the whole
temperature range, the pressure was set at 0.6 MPa with helium.
The lactic acid solution was charged into the reactor and heated
to the desired reaction temperature. The dry catalyst was placed
in a basket at the top of the stirrer shaft. Ethanol was heated to
the desired temperature in the feed vessel and then charged to
the reactor by opening the on/off valve. The agitation was
immediately turned on and the basket of catalyst fell down in
Ind. Eng. Chem. Res., Vol. 47, No. 5, 2008 1455
the reactant solution. This time is considered to be the starting
time of the esterification reaction. One of the outlets of the
reactor was connected directly to a liquid sampling valve (Valco,
USA), which injects 0.2 µL of pressurized liquid to a gas
chromatograph.
2.3 Analytical Method. All the samples were analyzed in a
gas chromatograph (Chrompack 9100, Netherlands) using a
fused silica capillary column (Chrompack CP-Wax 57 CB, 25
m × 0.53 mm i.d., df ) 2.0 µm) to separate the compounds
and a thermal conductivity detector (TCD 903 A) to quantify
it. The column temperature was programmed with a 1.5 min
initial hold at 110 °C, followed by a 50 °C/min ramp up to 190
°C and holding for 8.5 min. The injector and detector temper-
atures were maintained at 280 and 300 °C, respectively. Helium
N50 was used as the carrier gas with a flow rate 10.50 mL/
min. In order to analyze the lactic acid and ethyl lactate
oligomers at equilibrium, a HPLC system from Gilson (France)
using an ICSep ION-300 column held at 20 °C was used. A
0.0085 N H2SO4 solution was used as mobile phase (0.4 mL/
min), and species were quantified by a refractive index detector.
3. Thermodynamic Equilibrium Results
The experiments to measure the equilibrium constant were
done in a temperature range of 323-363 K. At each temperature
different experiments were performed using different initial
molar ratios (REth/La ) 1.0 to REth/La ) 2.8) and different masses
of catalyst (2.3-6.0 wt %) (see Table 1). All the experiments
lasted long enough to ensure that the equilibrium was reached.
3.1. Thermodynamic Equilibrium Constant. In its most
general form the chemical equilibrium constant (K) for a reaction
is given by
( )
∆G°
K ) exp -
RT
) ∏i aνi i
(2)
where ∆G° is the reaction standard free Gibbs energy, R is the
ideal gas constant, T is the absolute temperature, ai is the activity
of species i, and νi is its stoichiometric coefficient in the reaction.
For the esterification reaction, occurring in the liquid phase
at low pressure
aELaW xELxW γELγW
K) ) ) KxKγ (3)
aEthaLa xEthxLa γEthγLa
x and γ are the mole fraction and the activity coefficient of
each species, respectively.
The chemical equilibrium constant is only temperature
dependent. From the experimental point of view, however,
changing isothermically the initial mass of each reactant will
give, most probably, different values for the equilibrium
constant. Naturally, that is a consequence of experimental errors
as well as deficiencies in the thermodynamic models used to
calculate the activity coefficients. For example, as can be
observed in Table 1 three different runs were carried out at
323.15 K. Estimating the activity coefficients by the UNIFAC
method,29 using the relative molecular volume, the surface area,
and the interaction parameters presented in Reid et al.,30 the
resulting equilibrium constants are quite different: 4.126, 3.813,
and 4.637, respectively, from top to bottom.
One possibility to get a single equilibrium constant value for
each temperature would be to fit all the equilibrium constants
using an equation of the type
ln K ) a + b/T (4)
1456 Ind. Eng. Chem. Res., Vol. 47, No. 5, 2008

Table 1. Conditions of the Experiments Performed To Measure the Thermodynamic Equilibrium Constant
initial number of moles equilibrium number of moles
T (K) catalyst loading (wt %) ethanol lactic acid water ethanol lactic acid ethyl lactate water
323.15 5.67 0.8154 0.4051 0.2968 0.5459 0.1356 0.2695 0.5662
323.15 5.95 0.7329 0.4051 0.2966 0.4786 0.1508 0.2543 0.5509
323.15 5.63 0.4033 0.4051 0.2957 0.1983 0.2000 0.2051 0.5008
333.15 5.67 0.8154 0.4051 0.2968 0.5403 0.1300 0.2751 0.5719
333.15 5.95 0.7329 0.4051 0.2966 0.4744 0.1465 0.2586 0.5551
333.15 5.63 0.4033 0.4051 0.2957 0.1963 0.1981 0.2070 0.5027
343.15 5.67 0.8154 0.4051 0.2968 0.5351 0.1249 0.2802 0.5770
343.15 5.95 0.7329 0.4051 0.2966 0.4730 0.1452 0.2599 0.5565
343.15 5.63 0.4033 0.4051 0.2957 0.1969 0.1986 0.2065 0.5022
343.41 2.82 5.6988 2.0197 1.4837 4.1506 0.4716 1.5481 3.0319
343.41 2.82 5.6988 2.0197 1.4837 4.1361 0.4570 1.5627 3.0464
353.15 2.37 3.9033 3.4444 2.5154 1.9555 1.4966 1.9477 4.4632
362.87 2.82 5.6988 2.0197 1.4837 4.1173 0.4382 1.5815 3.0652
362.87 2.82 5.6988 2.0197 1.4837 4.1029 0.4239 1.5958 3.0796

Table 2. UNIQUAC Interaction Parameters (K)

ethanol ethyl lactate water lactic acid
ethanol 0.0000 -152.319 -17.554 + 0.2797T (K)a -35.008
ethyl lactate 264.990 0.0000 207.789 -20.986
water -21.987 + 0.2276T (K)a -13.093 0.0000 -99.183
lactic acid 33.741 219.89 213.19 0.0000
a DECHEMA.32

This, however, presents a big deficiency. In fact, using a unique estimated using data from the quaternary system measured by
value for the equilibrium constant at a given temperature, the Delgado et al.26 The parameters were estimated minimizing the
equilibrium composition must be recalculated for each specific following objective function (Fob):

( )
initial condition, which will immediately introduce changes in
the magnitude of the activity coefficients. γexp - γcalc 2

Assuming a given value for the equilibrium constant at 323.15
K, solving eq 3 in order to the equilibrium composition involves
an iterative procedure. First, all the activity coefficients must
be assumed equal to 1, obtaining the equilibrium composition
of an ideal solution. Then the activity coefficients can be
determined using a model such as UNIQUAC or UNIFAC, and
a new equilibrium composition can now be calculated. The
procedure is repeated until convergence. It must be stressed that
this final equilibrium composition will certainly not be the same
as the one presented in Table 3, which was used to calculate
the equilibrium constant and to regress the coefficients in eq 4.
Therefore, this inconsistency must be avoided.
To overcome this problem, in this work it is suggested to
obtain the coefficients in eq 4 that allow the calculation of the
equilibrium composition as close as possible to that observed
experimentally. Therefore, the coefficients were estimated
minimizing the following objective function (Fob):
∑j ∑i
i i
Fob ) (6)
γexp
i j
where i is the species and j is the experimental data point. It
should be mentioned that the parameters between water and
ethanol were found in the DECHEMA books.33 The interaction
parameters are given in Table 2.
The average relative deviation found for the activity coef-
ficients was 12.9%, but special difficulties were found when
describing the behavior of diluted solutions, which was never
the case when the chemical equilibrium experimental studies
were carried out in this work.
3.2. Equilibrium Constant and Reaction Enthalpy for the
Synthesis of Ethyl Lactate. Using the data found experimen-
tally for the chemical equilibrium compositions in 14 different
runs, at four different temperatures in the range between 323.15
and 362.87 K, the following relation for the equilibrium constant

( )
was found:
Xexp calc
k - Xk
2

Fob ) ∑k (5) ln K ) 2.9625 - 515.13/T (K) (7)

Xexp
k
where Xexp k and Xcalc
k are the experimental and the calculated
equilibrium conversions for experiment k, respectively.
3.1.1. Activity Coefficients Estimation. In this work, instead
of using the UNIFAC method, it was preferred to apply the
UNIQUAC model. Indeed, there are some available experi-
mental vapor-liquid equilibrium data involving mixtures of
species involved in the reaction under study, which makes it
preferable to use a correlation model instead of a pure predictive
method.
Initially the parameters between ethanol and ethyl lactate were
estimated based on the data published by Peña-Tejedor et al.31
and Vu et al.32 Then the parameters between water and ethyl
lactate were obtained based on the data by Vu et al.32 Finally
the parameters between lactic acid and all other species were
Using this result and the iterative procedure described before,
the deviations found between the experimental and calculated
equilibrium compositions for all experiments are given in Table
3. It can be seen that the higher deviation found between the
experimental and calculated equilibrium compositions is about
5.6%.
In Table 4 the activity coefficients for the equilibrium
composition and the thermodynamic equilibrium constant are
presented.
In terms of equilibrium conversion the average relative
deviation found was 2.60%; it was possible to find an average
reaction enthalpy of 4.28 kJ‚mol-1 in that temperature interval.
Some authors24 have also indicated that the reaction is slightly
endothermic, but the uncertainty is high. In fact, using the values
found for the standard state enthalpy of formation in the DIPPR
 Ind. Eng. Chem. Res., Vol. 47, No. 5, 2008 1457

Table 3. Experimental and Calculated Equilibrium Compositions for All Experiments Performed and Corresponding Deviation Percent
equilibrium composition
experimental calculated
T (K) ethanol ethyl lactate water lactic acid ethanol ethyl lactate water lactic acid av dev (%)
323.15 0.3598 0.1776 0.3732 0.0894 0.3561 0.1813 0.3769 0.0857 2.06
323.15 0.3336 0.1773 0.384 0.1051 0.3264 0.1845 0.3913 0.0978 3.77
323.15 0.1812 0.1854 0.4527 0.1808 0.1931 0.1734 0.4407 0.1928 5.58
333.15 0.3561 0.1813 0.3769 0.0857 0.3528 0.1846 0.3802 0.0824 1.87
333.15 0.3307 0.1802 0.3869 0.1021 0.3228 0.1881 0.3948 0.0943 4.11
333.15 0.1794 0.1871 0.4544 0.179 0.1881 0.1784 0.4457 0.1878 4.08
343.15 0.3527 0.1847 0.3803 0.0823 0.3498 0.1876 0.3832 0.0794 1.67
343.15 0.3297 0.1812 0.3879 0.1012 0.3194 0.1915 0.3982 0.0909 5.41
343.15 0.1799 0.1866 0.4539 0.1796 0.1835 0.1831 0.4504 0.183 1.64
343.41 0.451 0.1682 0.3295 0.0512 0.451 0.1683 0.3295 0.0512 0.01
343.41 0.4495 0.1698 0.3311 0.0497 0.451 0.1683 0.3295 0.0512 1.18
353.40 0.1983 0.1975 0.4525 0.1517 0.202 0.1937 0.4488 0.1555 1.78
362.87 0.4474 0.1719 0.3331 0.0476 0.4474 0.1718 0.3331 0.0477 0.07
362.87 0.4459 0.1734 0.3347 0.0461 0.4474 0.1718 0.3331 0.0477 1.30

Table 4. Activity Coefficients for the Equilibrium Composition and Thermodynamic Equilibrium Constant
activity coefficient
T (K) ethanol lactic acid ethyl lactate water K
323.15 1.0563 1.2391 1.3557 1.6928 3.9291
323.15 1.0563 1.2632 1.3941 1.6629 3.9291
323.15 1.0263 1.3238 1.7011 1.5288 3.9291
333.15 1.0652 1.2397 1.3386 1.6847 4.1217
333.15 1.0660 1.2643 1.3749 1.6547 4.1217
333.15 1.0398 1.3285 1.6644 1.5200 4.1217
343.15 1.0737 1.2396 1.3222 1.6771 4.3116
343.15 1.0755 1.2649 1.3564 1.6467 4.3116
343.15 1.0531 1.3325 1.6300 1.5117 4.3116
343.41 1.0607 1.1543 1.2338 1.7832 4.3165
343.41 1.0607 1.1543 1.2338 1.7832 4.3165
353.40 1.0749 1.3350 1.5295 1.5267 4.5035
362.87 1.0707 1.1511 1.2125 1.7715 4.6781
362.87 1.0707 1.1511 1.2125 1.7715 4.6781

Table 5. Standard State Enthalpy of Formation of Different Species34

ethanol lactic acid ethyl lactate water
∆H°f (kJ‚mol-1) -234.950 -682.960 -695.084 -241.814
error (%) <1 <10 <25 <0.2

801 database34 (see Table 5), it is possible to calculate -20.97
( 186.7 kJ‚mol-1 for the reaction enthalpy at 298.15 K. This
considerably high error ((186.7 kJ‚mol-1) is mainly due to the
high uncertainty in the ethyl lactate standard state enthalpy of
formation. Nevertheless, the value found is in good agreement
to values given in the literature.23,24
3.3. Application of this Methodology to Other Works. The
equilibrium compositions and equilibrium conversions of other
studies4,23,25 were predicted by the UNIQUAC model and the
equilibrium constant proposed in this work. It should be noted
that those equilibrium compositions were not used in the
estimation of the UNIQUAC parameters nor in the estimation
of the chemical equilibrium constant presented by eq 7. The
comparison between the experimental and calculated equilibrium
compositions is shown in Figure 3a for ethanol and water and
in Figure 3b for lactic acid and ethyl lactate. The equilibrium
compositions are very well predicted for ethanol and water,
while for the ethyl lactate and lactic acid the deviations are
higher, but even so are satisfactory. The larger deviations may
be due to the fact that the interaction parameters used in the
UNIQUAC model for those particular species are not based on
a large and consistent set of experimental vapor-liquid equi-
librium (VLE) data as is the case for water and ethanol species.
Furthermore, the composition range is now much more restricted
(maximum mole fraction around 0.20), which for the model
presents more difficulties to calculate accurately the activity
coefficients, and the analytical method for these species is not
as precise as it is for water and ethanol compounds.
In terms of the deviation of experimental and calculated
equilibrium conversion (Figure 4), it can be seen that, when 85
wt % lactic acid feed is used, the model prediction is quite good.
In the remaining cases, for 44 wt % lactic acid and mainly for
20 wt % lactic acid solution, the deviations are more significant.
This may be due to the fact that diluted solutions in lactic acid
and, obviously, in ethyl lactate are used, and as mentioned before
the UNIQUAC model does not describe with the desired
accuracy the behavior of that kind of solution. If possible, it
would be preferable to use activity coefficients at infinite
dilution.
4. Kinetic Studies
The experimental results of the reaction kinetics of the
esterification of lactic acid and ethanol catalyzed by the
Amberlyst 15-wet resin are presented in this section. The effect
of various conditions, such as catalyst loading, initial molar ratio
between ethanol and lactic acid, and reaction temperature, on
lactic acid conversion as a function of time is studied. This study
was performed varying the condition under evaluation and
keeping constant the remaining conditions, in the absence of
mass transfer limitations and catalyst deactivation as shown by
the preliminary studies performed.
1458 Ind. Eng. Chem. Res., Vol. 47, No. 5, 2008
Figure 3. (a) Experimental and calculated equilibrium molar fractions of
ethanol and water species. (b) Experimental and calculated equilibrium molar
fractions of ethyl lactate and lactic acid species.
Figure 4. Experimental and calculated equilibrium conversion. Data
collected from Troupe and Dimilla,4 Benedict et al.,23 Delgado et al.,25 and
this work.
4.1. Preliminary Studies. 4.1.1. Evaluation of External
Mass Transfer Limitations (Effect of Stirring Speed). To
quantify the influence of external mass transfer resistance,
preliminary experiments at different stirring speeds were run.
It was concluded that with a stirring speed of 600 rpm there is
no limitation due to external resistance, so all further experi-
ments were done at 600 rpm.
Figure 5. Effect of the Amberlyst 15-wet reusability on conversion of
lactic acid history at 344.05 K for a molar ratio of ethanol to lactic acid of
1.82 using 2.4 wt % Amberlyst 15-wet catalyst with an average particle
diameter of 0.685 mm and stirrer speed of 600 rpm.
4.1.2. Evaluation of Internal Mass Transfer Limitations
(Effect of Particle Size). Amberlyst 15-wet was separated by
particle size, and three classes with different diameters were
obtained: 0.425 mm < dp < 0.5 mm, 0.5 mm < dp < 0.6 mm,
and 0.6 mm < dp < 0.85 mm. Kinetic experiments were
performed using the three classes obtained and, also, unsieved
resin. No significant internal diffusion limitations were found;
therefore, the unsieved resin was used for the following kinetic
experiments performed in this work. This is in agreement with
several works performed with this kind of resin and type of
reaction.20,24,25,35
4.1.3. Evaluation of Catalyst Deactivation (Effect of
Catalyst Reusability). The Amberlyst 15-wet catalyst reus-
ability was studied at 344.05 K. The resin was reused up to
three times. First, a reaction was carried out using fresh catalyst.
Then the catalyst used was separated from the reaction mixture
by filtration, washed several times with deionized water, and
dried at 90 °C until the mass remained constant, and the catalyst
was charged again to the reactor. A new esterification reaction
was performed using the same conditions that the first one used,
and so on. The lactic acid conversion as a function of time was
analyzed, and the three conversion histories are presented in
Figure 5. As can be seen, no significant changes were observed.
The resin activity was kept the same in the three runs. However,
each experiment was performed using fresh Amberlyst 15-wet
catalyst. Dixit and Yadav36 studied the reusability of Amberlyst
15-wet in the alkylation reaction of o-xylene with styrene, and
they observed a drastic reduction in the conversion of styrene
due to the direct deposition of the byproducts on the active sites
and the loss of accessibility of the active sites due to pore
blockage. Thus, it can be concluded that the catalytic activity
of the resins depends on its interaction with the reaction
medium.
4.2. Kinetic Model. The esterification reactions have been
described using different models, such as pseudohomogeneous,
Eley-Rideal, and Langmuir-Hinshelwood (L-H).21,35,37-39
However, the L-H model has been considered the most
appropriate model for the reaction between lactic acid and
ethanol.24,25 Therefore, the model developed is based on an L-H
mechanism and it considers the following steps:
ethanol and lactic acid adsorption:
Ks,Eth
Eth + S 798 Eth‚S
Ks,La
La + S 798 La‚S
 Ind. Eng. Chem. Res., Vol. 47, No. 5, 2008 1459

surface reaction between the adsorbed species of 4.2.1. Parameter Estimation from Experimental Data. The
ethanol and lactic acid: mass balance in the batch reactor for a component i, in liquid
K1 phase, at constant temperature is given by
Eth‚S + La‚S 798 EL‚S + W‚S
dni
desorption of ethyl lactate and water: ) Viwcatr (12)
dt
K/s,EL
EL‚S 798 EL + S where ni is the number of moles of component i, t is the time,
wcat is the mass of catalyst, and r is the reaction rate expressed
Ks,W
/

W‚S 798 W + S in moles of i/(mass of catalyst ‚min).

The number of moles of component i (ni) as a function of
The surface reaction is assumed to be the controlling step, the conversion X of the limiting reactant (l) is

( )
with the other steps remaining in equilibrium. Multicomponent
Langmuir adsorption isotherms, written in terms of activities, X
ni ) nl,0 Ri/l + νi (13)
are assumed to describe the adsorption behavior of the com- |νl|
pounds of the reaction mixture in the surface of the resin. Taking
into account the above considerations, the following rate where nl,0 and νl are, respectively, the initial number of moles
expression, written in terms of activities of components, due to and the stoichiometric coefficient of the limiting reactant and
the nonideality of the reaction mixture, is obtained: ri/l is given by

ni,0
aELaW ri/l ) (14)
aEthaLa - nl,0
K
r ) kc (8) where ni,0 is the initial number of moles of component i.
W
(1 + ∑
i)Eth
Ks,iai) 2 Introducing eq 13 into eq 12, we get

where kc is the kinetic constant, Ks,i is the adsorption
constant for species i, and K is the equilibrium reaction con-
stant.
In order to reduce the number of optimization parameters,
only those components that had the strongest adsorption were
taken into account. It was considered that the most polar
molecules, water and ethanol, have the strongest adsorption
strengths on the Amberlyst 15-wet surface, so the adsorption
of lactic acid and that of ethyl lactate were therefore neglected.
This consideration is corroborated by several works on adsorp-
tion in similar resins.24,37,40,41 Thus, the simplified rate expression
used to describe the experimental data is
aELaW
aEthaLa -
K
r ) kc (9)
(1 + Ks,EthaEth + Ks,WaW)2
dX |νl|wcatr
) (15)
dt nl,0
with the initial condition: t ) 0; X ) 0.
The differential equation (15) combined with the suggested
rate expression, eq 9, was solved numerically with the DASOLV
integrator implemented in gPROMS (general PROcess Model-
ling System), version 3.0.3, which is a commercial package from
Process Systems Enterprise. For all simulations a tolerance equal
to 10-5 was fixed. The estimation of the unknown parameters
(Ea, k0,c, K0,Eth, K0,W, ∆HEth, and ∆HW) was carried out using
the “Parameter estimation in gPROMS” that attempts to
determine the values for the parameters, in order to maximize
the probability that the mathematical model will predict the
values obtained from experiments. Assuming independent,
normally distributed measurement errors, ǫik, with zero means
and standard deviations, σik, this maximum likelihood goal can
be captured through the following objective function:

{ [ ]}
In this kinetic model (eq 9) there are three parameters to be NE NMi X′ik - Xik
N 1
estimated, the kinetic constant (kc) and the two adsorption Φ)
2
ln(2π) + min
2 θ
∑ ∑ ln(σik2) +
parameters (Ks,Eth and Ks,W), instead of five if the rate equation i)1 k)1 σik2
(8) was used to describe the experimental data. (16)
The temperature dependence of the kinetic constant was fitted where N is the total number of measurements taken during the
with the Arrhenius equation: experiments (N ) 290), θ is the set of model parameters to be

( )
estimated (θ ) 6), NE is the number of experiments performed
Ea
kc ) k0,c exp - (10) (NE ) 15), NMi is the number of measurements of the
RT conversion in the ith experiment, σik2 is the variance of the kth
measurement of the conversion in experiment i (σ j 2 ) 1.83 ×
where Ea is the reaction activation energy, k0,c is the preexpo- 10-3), X′ik is the kth measured value of conversion in experi-
nential constant, R is the gas constant, and T is the temperature. ment i, and, finally, Xik is the kth (model-) predicted value of
The temperature dependence of the adsorption equilibrium conversion in experiment i. The quality of the model fit was
constants were fitted with tested through the mean relative deviation (MRD) between the

( )
calculated conversion values (Xcalc) and the experimental ones
∆Hs (Xexp) (see eq 17).
Ks ) K0,s exp - (11)

( |)
RT
1 Xcalc - Xexp
where K0,s is the constant for eq 11 and ∆Hs is the adsorption MRD ) ∑|
N N Xexp
× 100% (17)
enthalpy.
1460 Ind. Eng. Chem. Res., Vol. 47, No. 5, 2008
Figure 6. Representation of experimental values of ln kc as function of
1/T and linear fitting.
Figure 7. Effect of catalyst loading on conversion of lactic acid history
for a molar ratio of ethanol to lactic acid of 1.82 at 353.49 K and using an
average particle diameter of 0.685 mm and stirrer speed of 600 rpm.
4.3. Modeling and Discussion of Results. The simplified
L-H model (eq 9) was used to describe the kinetic behavior of
the esterification of lactic acid with ethanol using Amberlyst
15-wet as catalyst. In order to obtain the unknown parameters,
at least two different experiments (different initial molar ratios)
were performed for each temperature, which varied from 323.15
to 363.15 K. The values of the optimized parameters along with
the MRD value are presented in Table 6. A value of MRD
between experimental and calculated conversions of 6.8% was
obtained.
As mentioned before in section 4.2, the Arrhenius equation
was used to fit the kinetic (kc) constant (Figure 6) and eq 11
was used to fit the adsorption constants (Ks,Eth and Ks,W), which
are given by KW ) 15.19 exp(12.01/T (K)) and KEth ) 1.22
exp(359.63/T (K)). From the temperature dependence of the
kinetic constant with temperature the apparent activation energy
was calculated; the correspondent value was 49.98 kJ/mol.
4.3.1. Effect of Catalyst Loading. The catalyst loading was
varied from 1.2 to 3.9 wt % (weight of catalyst/total weight of
reaction mixture), keeping the rest of the experimental conditions
similar. The effect of the catalyst loading on the esterification
reaction between lactic acid and water is shown in Figure 7.
As may be observed, the reaction rate increases with the
percentage of Amberlyst 15-wet. This was expected since the
increase of catalyst implies an increase in the number of active
sites available for the reaction.
Table 6. Parameters of the Kinetic Model Expressed in Terms of Activities (eq 9) and Mean Relative Deviation (MRD)
k0,c (mol‚g-1‚min-1) Ea (kJ‚mol-1) K0,W
2.70 × 107 49.98 15.19
Figure 8. Effect of initial molar ratio of ethanol to lactic acid on conversion
of lactic acid history at 353.40 K and using 2.4 wt % Amberlyst 15-wet
catalyst with an average particle diameter of 0.685 mm and stirrer speed of
600 rpm.
Figure 9. Effect of reaction temperature on conversion of lactic acid history
for a molar ratio of ethanol to lactic acid of 1.82 and using 2.4 wt %
Amberlyst 15-wet catalyst.
4.3.2. Effect of Initial Molar Ratio of Reactants. To study
the effect of the initial molar ratio of reactants (REth/La) on the
conversion of lactic acid, this condition was varied from 1.1 to
2.8, as presented in Figure 8. It can be seen that the equilibrium
conversion increases with the increase of the initial molar ratio
of ethanol to lactic acid and that the equilibrium is achieved
faster for upper initial molar ratio values.
It may be observed from Figure 8 that the experiments are
initially well predicted by the model (until about 120 min), and
due to the methodology developed in this work, the equilibrium
is also well described. However, there is a transient state
(between 120 min and the equilibrium) where the model fails
to describe the experiments, being more significant for higher
values of the initial molar ratio between ethanol and lactic acid.
4.3.3. Effect of Reaction Temperature. The effect of
reaction temperature is shown in Figure 9. The reaction rate
increases with the reaction temperature. The same effect is
noticed on the equilibrium conversion. Once again, it can be
noticed that, in the transient state, the model predicts higher
conversion of lactic acid values than those obtained experimen-
tally.
4.3.4. Effect of Lactic Acid and Ethyl Lactate Oligomers.
The proposed model shows a kinetic behavior with two limiting
∆HW (J‚mol-1) K0,Eth ∆HEth (J‚mol-1) MRD (%)
-99.85 1.22 -29.95 × 102 6.84

Figure 10. (a) Molar fraction histories of the compounds: ethyl lactate
monomer, ethanol, lactic acid monomer, and water. T ) 363.15 K and REth/La
) 3. The kinetic model and the parameters used were taken from Tanaka
et al.6 (b) Molar fraction histories of the oligomers: ethyl lactate dimer,
ethyl lactate trimer, lactic acid dimer, and lactic acid trimer. T ) 363.15 K
and REth/La ) 3. The kinetic model and the parameters used were taken
from Tanaka et al.6
situations: (a) first slope at the beginning of the experiment,
corresponding to the initial reaction rate; (b) final plateau,
corresponding to the reaction equilibrium.
However, experimentally, it seems that there are three limiting
situations, where the first and third are the same as the ones
described by the proposed model, but the transient state is
represented by a line with a very small slope. This could be
due to the presence of the lactic acid oligomers and, conse-
quently, ethyl lactate oligomers that where formed. To confirm
this assumption, an evaluative modeling study was made
considering the presence of oligomers using the kinetic model
and the corresponding parameters reported by Tanaka et al.6 In
Figure 10a the molar fractions of ethyl lactate, lactic acid,
ethanol, and water as a function of time are presented, and those
of the corresponding oligomers are presented in Figure 10b.
Analyzing the simulated kinetic curve for the ethyl lactate
monomer, here denominated just as ethyl lactate, one can
conclude a behavior similar to the experimental results shown
in this work, where there are three limiting steps:
(a) The first limiting step is the initial conversion of lactic
acid oligomers in ethyl lactate oligomers, but the kinetic rate is
much higher for the monomers than for the dimers and trimers.
Therefore the experiments are initially well predicted.
(b) The second step is the transient state, where the ethyl
lactate monomer concentration increases slowly, since several
Ind. Eng. Chem. Res., Vol. 47, No. 5, 2008 1461
Figure 11. (a) Molar fraction histories of ethyl lactate and lactic acid for
different initial molar ratios. T ) 353.15 K. The kinetic model and the
parameters used were taken from Tanaka et al.6 (b) Molar fraction histories
of ethyl lactate dimer for different initial molar ratios. T ) 353.15 K. The
kinetic model and the parameters used were taken from Tanaka et al.6
reversible reactions are occurring and the equilibrium is shifted
toward lactic acid monomer formation and consequently ethyl
lactate monomer. In this transient step, first the dimer concen-
trations of lactic acid and ethyl lactate decrease due to their
hydrolysis, and then the same happens to the trimers that are
converted into dimers and finally again into monomers, until
the equilibrium is reached.
(c) Last is the reaction equilibrium: when all the reversible
reactions are in equilibrium, the total amounts of lactic acid
and ethyl lactate oligomers are less than 0.4%. Therefore, the
experiments are well predicted at the equilibrium since the
oligomer presence is neglectable.
The transient behavior, where the hydrolyses of dimers and
trimers of lactic acid and ethyl lactate are dominant to produce
the ethyl lactate monomer, is even more noticeable for higher
values of initial molar ratio of ethanol/lactic acid, as is shown
in Figure 11a. This is due to the fact that the excess of ethanol
benefits more the ethyl lactate dimer formation as shown in
Figure 11b, which will be further hydrolyzed, and the lactic
acid dimer formed will be converted into lactic acid monomer,
which will be finally converted into ethyl lactate monomer.
Nevertheless, in the equilibrium composition the excess of
ethanol leads to smaller amounts of oligomers (2.4 mol % in
the case of REth/La ) 1 and 0.4 mol % in the case of REth/La )
3).
4.3.5. Effect of Polar Species. The activity of the resin varies
with the polarity of the reaction medium, since it influences
1462 Ind. Eng. Chem. Res., Vol. 47, No. 5, 2008
the number of available sulfonic groups and their acidity.42 The
polarity of the medium, mainly due to the water and alcohol
concentrations, can affect the reaction rate in two ways:
(i) The more adsorbed species (water and alcohol) inhibit
the others to adsorb onto the active sites.
(ii) Water can ionize, solvate, and dissociate the acidic protons
of the sulfonic groups, depending on their concentration; when
the sulfonic sites are completely dissociated, the reaction occurs
in the liquid phase as in the case of homogeneous catalysis.43
In this case, the reaction medium has a high water concentra-
tion: besides the water initially present in the reaction due to
the lactic acid solution, more water is being formed during the
course of the esterification of lactic acid with ethanol. Although
the kinetic model proposed in this work has taken into account
the inhibitory effect caused by adsorption, it does not consider
the remaining effects that could be due to the presence of water
or ethanol. Therefore, this could also be a reason for the
deviations between the experimental results and those predicted
by the kinetic model in the transient stage. Françoisse and
Thyrion44 studied the ETBE synthesis catalyzed by Amberlyst
15. In that study the influence of ethanol on the reaction rate
was taken into account. A kinetic model to describe the behavior
of the reaction for low and high ethanol concentrations was
developed. However, this case is different from the one
presented in this work, since the most adsorbed component was
ethanol and there was no water as reaction product. They used
a nonpolar solvent (n-pentane), and the other reactant (isobutene)
was also nonpolar. In the case under study, besides ethanol there
is also lactic acid concentrated solution that has a high water
content. Therefore, at the beginning of the reaction there are
three polar species competing for the acid sites; it was observed
that the initial kinetic rate increases with the ethanol concentra-
tion until a plateau, which was not the behavior observed in
the ETBE kinetics. Most works about the esterification reaction
of ethanol and lactic acid consider that water and ethanol are
the most adsorbed species, which supports our kinetic model
assumptions.24,25 Moreover, in a later work from Dassy et al.45
for the esterification of lactic acid with butanol catalyzed by
Amberlyst 15, the authors did not observe different mechanisms
for high and low alcohol concentrations, and similar to our
model, they neglected the presence of oligomers and only
considered the water adsorption.
The proposed model describes quite well the experimental
data up to 80% of the equilibrium conversion as well as the
equilibrium stage, which are the most important to apply to a
hybrid reactive separation technology.
5. Conclusions
The equilibrium composition for the liquid-phase reaction of
ethyl lactate synthesis catalyzed by the acid ion-exchange resin
Amberlyst 15-wet was measured in the temperature range 50-
90 °C, at 6 bar. The thermodynamic equilibrium constant
estimated by the UNIQUAC method was ln K ) 2.9625 -
515.13/T (K) and the average reaction enthalpy was 4.28
kJ‚mol-1 in that temperature interval. This relation was also
successfully applied to describe the equilibrium compositions
of other published studies; better prediction was found for
systems where high concentrations of lactic acid were used.
Because of the strong nonideality of the liquid reaction
mixture, the reaction rate model was formulated in terms of
activities. The rate-controlling step for the esterification reaction
between lactic acid and ethanol, heterogeneously catalyzed by
Amberlyst 15-wet was the surface reaction, since external and
internal mass resistances were insignificant for the temperature
range 50-90 °C. The catalyst reusability was also studied, and
catalyst deactivation was not verified until three usages of the
same resin sample.
A three-parameter model based on a Langmuir-Hinshelwood
rate expression was proposed to describe the experimental
kinetic results: r ) kc(aEthaLa - aELaW/K)/(1 + KEthaEth +
KWaW)2; the model parameters are kc ) 2.70 × 107 exp(-
6011.55/T (K)), KW ) 15.19 exp(12.01/T (K)), and KEth ) 1.22
exp(359.63/T (K)). The agreement between experimental and
simulated results was good for the following operating condi-
tions: catalyst loading from 1.2 to 3.9 wt %, initial molar ratio
of reactants from 1.1 to 2.8, and temperature from 50 to 90 °C.
Acknowledgment
C.S.M.P. gratefully acknowledges the Fundação para a
Ciência e a Tecnologia (FCT, Portugal) for the Ph.D. Research
Fellowships SFRH/BD/23724/2005. This work was also sup-
ported by the project POCI/EQU/61580/2004 (FCT, Portugal).
Notation
a ) liquid phase activity
dp ) pellet diameter (mm)
df ) film thickness (µm)
Ea ) apparent reaction activation energy (J mol-1)
K ) equilibrium reaction constant
Kx ) equilibrium constant based on molar fractions
Kγ ) equilibrium constant based on activity coefficients
Ks ) equilibrium adsorption constant
kc ) kinetic constant (mol g-1 min-1)
k0,c ) preexponential factor (mol g-1 min-1)
K0,s ) constant for eq 17
MRD ) mean residual deviation
n ) number of moles (mol)
N ) total number of measurements taken during the experiments
NE ) number of experiments performed
NMi ) number of measurements of the conversion in experi-
ment i
∆Hs ) enthalpy of adsorption (J mol-1)
∆H°f ) standard enthalpy of formation (J mol-1)
∆G° ) standard Gibs energy of reaction (J mol-1)
R ) gas constant (J mol-1 K-1)
r ) reaction rate (mol g-1 min-1)
REth/La ) initial molar ratio of ethanol to lactic acid
t ) time coordinate (min)
T ) temperature (K)
X ) conversion of the limiting reactant x molar fraction
wcat ) mass of dry catalyst (g)
Xik ) kth (model-) predicted value of conversion in experiment
i
X′ik ) kth measured value of conversion in experiment i
Greek Symbols
ν ) stoichiometric coefficient
γ ) activity coefficient
θ ) set of model parameters to be estimated
σik2 ) variance of the kth measurement of conversion in
experiment i
j 2 ) average of variance
σ
Subscripts
0 ) initial value
Eth ) ethanol
La ) lactic acid
EL ) ethyl lactate

W ) water
exp ) experimental
calc ) calculated
i ) relative to component i
l ) relative to limiting reactant
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ReceiVed for reView September 11, 2007
ReVised manuscript receiVed November 22, 2007
Accepted November 30, 2007
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