Ind. Eng. Chem. Res.

1998, 37, 1917-1928 1917

SEPARATIONS

Measurement of Residue Curve Maps and Heterogeneous Kinetics in

Methyl Acetate Synthesis
Wei Song,† Ganesh Venimadhavan, Jason M. Manning, Michael F. Malone, and
Michael F. Doherty*
Department of Chemical Engineering, University of Massachusetts, Amherst, Massachusetts 01003

Kinetically controlled reactive distillation is a bridge between the two limiting cases of nonreactive
and equilibrium reactive distillation. In this paper, we study the influence of heterogeneous
catalysis on the transition from the nonreactive to the equilibrium reactive limits for the
esterification of acetic acid with methanol. A Langmuir-Hinshelwood/Hougen-Watson rate
model was developed to represent the reaction kinetics. Since reactive distillation is carried
out at the boiling temperature of the liquid, the pressure of the system plays an important role
in determining the product composition. Higher operating pressures imply higher temperatures
and faster rates of reaction but could also lower equilibrium conversions (for exothermic systems)
and trigger unwanted side reactions. To study the importance of side reactions and the effect
of pressure on product selectivity, we also include the reaction kinetics for methanol dehydration.
Isothermal batch kinetic experiments were performed using a heterogeneous (Amberlyst 15W)
catalyst at various temperatures and catalyst concentrations. Independent binary adsorption
experiments were also performed to estimate the adsorption equilibrium constants. As a test
of the kinetic model, independent equilibrium reactive open-evaporation experiments were
performed and the model prediction was found to be in good agreement with the experimental
residue curve measurements. The model was also used to predict the behavior of the system in
the kinetically controlled regime. Residue curves for the kinetically controlled cases are
qualitatively similar to that of the equilibrium case, showing that the production of methyl acetate
can be carried out using reactive distillation in both the equilibrium and the kinetically controlled
regimes.

Introduction stand the transition from the nonreactive to the equi-

Reactive distillation is an important hybrid separation
process (e.g., Agreda and Partin, 1984; Agreda et al.,
1990; DeGarmo et al., 1992; Doherty and Buzad, 1992;
Smith, 1981, 1984, 1990). A useful tool for the synthesis
and analysis of both nonreactive and reactive distillation
systems is the simple distillation residue curve map
(RCM) (e.g., Fidkowski et al., 1993; Foucher et al., 1991;
Wahnschafft et al., 1992; Venimadhavan et al., 1994).
The structure of the residue curve map is determined
by the number of singular points in the mixture together
with their temperature and composition. For a non-
reactive mixture, these singular points are the pure
components and azeotropes; however, their number,
temperature, and composition may change with the
introduction of chemical reaction. Reactive distillation
systems are bounded by two limiting cases: (1) the
equilibrium reactive case where there is simultaneous
vapor-liquid and reaction equilibrium (Barbosa and
Doherty, 1988; Ung and Doherty, 1995a-d) and (2) the
nonreactive case where no reaction occurs. To under-
* To whom correspondence should be addressed.
† Present address: Pennzoil Products Company, 1520 Lake
Front Circle (77380), P.O. Box 7569, The Woodlands, TX
77387.
S0888-5885(97)00879-8 CCC: $15.00 © 1998 American Chemical Society
Published on Web 04/01/1998
librium reactive distillation system, we need to know
the kinetics of the reaction (Venimadhavan et al., 1994;
Rev, 1994; Rehfinger and Hoffmann, 1990; Sundmacher
and Hoffmann, 1994). In this paper, we study the
influence of heterogeneous catalysis on the transition
from the nonreactive to the equilibrium reactive limits.
We report the related simple distillation experiments
for the reactive mixture.
Methyl acetate can be made by the liquid-phase
reaction of acetic acid (HOAc) and methanol (MeOH)
catalyzed by sulfuric acid or a sulfonic acid ion-exchange
resin in the temperature range of 310-325 K and at a
pressure of 1 atm. The reaction is
acetic acid + methanol S methyl acetate + water
(HOAc) (MeOH) (MeOAc) (H2O)
(1)
This is a classic example in reactive distillation (Agreda
et al., 1984, 1990; Siirola, 1995).
The simple distillation experiment is an easy way of
studying the feasibility of continuous and batch distil-
lation processes (Bernot et al., 1991; Fidkowski et al.,
1993; Wahnschafft et al., 1992). For reactive systems,
the limiting case of simultaneous vapor-liquid and
1918 Ind. Eng. Chem. Res., Vol. 37, No. 5, 1998
reaction equilibrium is now well understood theoreti-
cally (Barbosa and Doherty, 1988; Ung and Doherty,
1995a-d, Espinosa et al., 1995). However, in many
applications, conditions of reaction equilibrium may not
be approached because of limited rates of reaction and
residence times. Furthermore, in systems where the
main product is an intermediate that reacts further with
the reactants or with other products, it is undesirable
to let the system reach reaction equilibrium. The
behavior of a system near reaction equilibrium may be
quite different from conditions where the reaction is
kinetically controlled, and we must have a good under-
standing of the reaction kinetics to examine the behav-
ior.
Kinetic rate expressions used in reactive distillation
models are best written in terms of activities as opposed
to the more familiar concentration-based rate expres-
sions (e.g., Venimadhavan et al., 1994; Rehfinger and
Hoffmann, 1990; Sundmacher and Hoffmann, 1994). For
the methyl acetate system the rate expression in terms
of activities is strongly preferred because the high
polarity of water and methanol compared to methyl
acetate leads to strongly nonideal solution behavior.
Earlier works on the kinetics of this system have
reported preexponentials and the activation energies for
the concentration-based rate expressions for the esteri-
fication kinetics of different alcohols (Smith, 1939) or
have not addressed the range of species and catalyst
concentrations of interest for reactive distillation space
(Neumann and Sasson, 1984; Xu and Chuang, 1996).
In this paper we report the results of batch kinetic
experiments for the methyl acetate system over a range
of molar feed ratios more typical of reactive distillation
conditions.
A macroreticular ion-exchange resin such as Am-
berlyst 15W is an ensemble of microspheres. More than
95% of all functional groups (the protons) are inside the
microspheres and are only accessible to substances
which are able to penetrate the network of cross-linked
polymer chains. Consequently, adsorption effects must
be taken into account in order to describe reactions
catalyzed by ion-exchange resins, e.g., Oost and Hoff-
mann (1996). Therefore, we developed a heterogeneous
Langmuir-Hinshelwood/Hougen-Watson (LHHW) type
rate expression. The LHHW model has three types of
parameters, the forward reaction rate constant, the
reaction equilibrium constant, and the individual com-
ponent adsorption equilibrium constants. To decouple
the reaction and adsorption phenomena, we performed
independent isothermal binary adsorption experiments
for the nonreactive binary pairs.
Since reactive distillation is carried out at the boiling
temperature of the liquid, the pressure of the system
plays an important role in determining the product
composition. Higher operating pressures imply higher
temperatures and faster rates of reaction. Faster reac-
tion rates give higher conversions and/or smaller resi-
dence times and hence smaller equipment. However,
higher temperatures could also lead to triggering of
unwanted side reactions with higher activation energies
and, in the case of exothermic reactions, lower equilib-
rium conversions. Higher temperatures also require
more expensive materials of construction since acetic
acid/water mixtures are corrosive at elevated temper-
atures. To study the importance of side reactions and
the effect of pressure on product selectivity, we also
include the reaction kinetics of the methanol dehydra-
Figure 1. Experimental setup for the measurement of residue
curve maps.
tion reaction at different temperatures. This reaction
is
2MeOH S DME + H2O (2)
We developed a LHHW model for this reaction also. In
the next section, we describe the details of the ap-
paratus, the experimental conditions, and the data
acquisition for the kinetic and adsorption experiments.
Experiments
Materials. Methanol (purity > 99.9 wt %), acetic
acid (purity > 99.7 wt %), methyl acetate (purity > 99.5
wt %), and ethylene glycol dimethyl ether (anhydrous,
water < 0.005 wt %) were purchased from Aldrich. The
catalyst was a strongly acidic macroporous resin (Am-
berlyst 15 wet, moisture content 53 wt %) purchased
from Rohm & Haas Co. The concentration of acid sites,
the average pore diameter, and the surface area of the
dry catalyst were 4.9 mmol/g, 250 Å, and 45 m2/g,
respectively, as reported by the manufacturer.
Apparatus. A 500-mL, three-neck glass flask was
used for kinetic and adsorption experiments. One neck
was connected to a thermometer and another to a
condenser with a pressure release on top, and the third
was sealed with a septum cap. The flask was immersed
in a stainless steel tank filled with a 1:1 mixture of
ethylene glycol and water as the heating fluid. The
contents were stirred by a magnetic stirrer (Thermolyne
SP18400) positioned underneath the bath. A desired
constant temperature in the bath was obtained by a
digital circulator (HAAKE, DC3) which ensures a tem-
perature constancy of (0.1 °C. The cooling water
circulation for the condenser was achieved by a circula-
tor (NESLAB RTE-111).
Figure 1 shows a schematic of the experimental setup
for the residue curve measurements. A 500-mL, three-
neck glass flask was connected to a thermometer, a
custom-made distillation head, and a septum cap. The
heating was controlled by a voltage controller (Ace Glass
12088) and heating mantles. A magnetic stirrer was
used to mix the reactants. The distillation head and
the reaction flask were insulated with glass wool to
minimize heat loss to the surroundings and to prevent
condensation of vapor and reflux back to the liquid
mixture.
 Ind. Eng. Chem. Res., Vol. 37, No. 5, 1998 1919

Composition Analysis. An HP 5890 series II gas

chromatograph (thermal conductivity detector) equipped
with 7673 Automatic Injector and 3365 Chemstation
Software was used to analyze the composition of samples
from the liquid phase of the reactive mixture. The
sample size for GC was 1 µL. Both injection port and
detector temperatures were set to be 230 °C. A 30 m ×
530 µm × 1 µm HP INNOWax column (HP 19095N-
123) was used to separate methanol, acetic acid, methyl
acetate, water, and ethylene glycol dimethyl ether
(solvent used to dilute the sample). The column tem-
perature was programmed to rise from an initial value
of 50 to 80 °C at 30 °C/min, followed by a 60 °C/min
ramp up to 130 °C, and then held constant at 130 °C
for an additional 1.5 min. High-purity helium gas
(Merriam Graves 1071-300) with a minimum purity of
99.997% was used as a carrier gas. The flow rate of
the carrier gas was 17 mL/min, and a complete GC run
took 3.33 min.
All four components were calibrated for their indi-
vidual GC responses, and the calibrations were verified
by mixtures of the components.
Procedure. For kinetic studies, the catalyst was air-
dried for roughly 2 weeks until the weight remained
constant (within 0.5 wt %). For the kinetic experiments,
two 500-mL flasks, one charged with a measured
amount of methanol and the other charged with meas-
ured amounts of acetic acid and the air-dried catalyst,
were first kept in the constant-temperature bath for
about 1 h to reach the desired temperature. Then the
reactants and catalyst were mixed together, and timing
was started. The total volume of liquid was 306 mL.
Periodically, a 0.1-mL sample was taken from the liquid
phase using a 1-mL syringe and immediately diluted
with 20 mL of anhydrous ethylene glycol dimethyl ether Figure 2. Adsorption equilibrium diagrams for the three non-
in a sample vial. Subsequently, 1 µL of the diluted reactive pairs at 45 °C.
sample was injected into the GC for analysis. At the Adsorption Experiments. Binary adsorption pa-
beginning of the experiment samples were taken at ∼10- rameters are needed for the kinetic models (described
min intervals; the sampling intervals were increased as in the next section). Among the four components in the
the experiment progressed. A kinetic experiment was methyl acetate reaction, it is possible to carry out three
stopped when the compositions leveled off, which was independent binary adsorption experiments. Of the four
judged to happen when the difference between three nonreactive binary pairs, we investigated (1) acetic acid
consecutive measurements taken at 1-h intervals were with water, (2) methanol with methyl acetate, and (3)
within instrument error (5%). Typically, about 20 methanol with water. These pairs were picked to
samples were taken for one run. maximize the expected adsorption strength difference
For residue curve measurements, the flask was in order to increase experimental accuracy.
charged with 306 mL of liquid mixture of desired initial The experimental setup for the adsorption experi-
compositions along with a measured amount of air-dried ments was similar to that for the kinetic experiments.
catalyst. While valve A of the distillation head was open The flask was immersed in a constant-temperature bath
and valve B was closed (see Figure 1), a constant heat maintained at 45 °C. The Amberlyst 15 catalyst was
input (117 W) was supplied and the liquid was totally dried under vacuum (500-635 mmHg) at 80 °C for 8 h
refluxed until temperatures of both liquid and vapor and then under vacuum at room temperature for
phases of the mixture were stabilized. Then valve A another 12 h. Thirty grams of the vacuum-dried
was closed and valve B was opened, and the vapor phase catalyst were used in all adsorption experiments.
was removed continuously and condensed into a sepa- A binary liquid mixture was prepared with a total
rate collection flask. During the distillation process, volume of ∼100 mL and a composition of 10 mol % of
liquid samples were taken periodically and measured the stronger adsorbing species. The mixture was heated
for their composition. Eventually, the amount of liquid in the constant-temperature bath for 40 min before the
residue in the reaction flask was small enough to vacuum-dried Amberlyst 15 catalyst was added. In
preclude sampling, and the experiment was stopped. A preliminary experiments, the composition of the mixture
typical experimental run took around 1 h to stabilize became constant within ca. 10 min after the addition of
and could be run for 2 and 3 h (depending on the initial the catalyst. To ensure a close approach to adsorption
conditions) to collect the equilibrium RCM data before equilibrium, a liquid sample was taken 20 min after the
the still ran dry. Subsequent runs, beginning at com- addition of the catalyst. The composition of the sample
positions as close as possible to the measured end point was then determined by GC.
of the previous experiment, were necessary in most The relative adsorption strengths for the components
cases to get a significant portion of each residue curve. were determined from literature (Mazzotti et al., 1997).
1920 Ind. Eng. Chem. Res., Vol. 37, No. 5, 1998

Table 1. Summary of the Kinetic Studies for Methyl Model and Data Analysis
Acetate
The LHHW Model. The batch kinetic data were in
mol of H+ initial initial total
run temp catalyst (from catalyst/ moles of moles of time the form of data sets for mole fraction of the components
no. (°C) (g) mol of mixture HOAc MeOH (h) as a function of time. Since the reactions were carried
out in the presence of a heterogeneous catalyst, we used
1 40 24 0.009 86 1.87 3.74 23.16
2 40 48 0.019 72 1.87 3.74 23.00 a heterogeneous LHHW model. The assumptions are
3 40 48 0.029 58 1.87 1.87 23.50 as follows: (1) the adsorption sites are uniformly
4 45 48 0.019 72 1.87 3.74 23.00 energetic; (2) there is a monolayer coverage (typical of
5 45 24 0.009 86 1.87 3.74 23.50 chemisorption); (3) a molecule on site 1 does not influ-
6 45 48 0.029 58 1.87 1.87 23.00 ence what attaches onto a nearby site 2; (4) a dual-site
7 50 24 0.009 86 1.87 3.74 5.50 mechanism is used for the reaction; and (5) the surface
8 50 48 0.019 72 1.87 3.74 22.00
9 50 48 0.029 58 1.87 1.87 21.00 reaction is the rate-controlling step. A possible mech-
10 50 12 0.004 93 1.87 3.74 23.92 anism for the esterification reaction is as follows (Fro-
11 50 48 0.019 72 3.74 1.87 11.00 ment and Bischoff, 1990):
12 50 24 0.014 79 1.87 1.87 5.50
13 50 24 0.009 86 1.87 3.74 23.00 HOAc + S S HOAc-S
14 50 48 0.019 77 2.80 2.80 12.00
MeOH + S S MeOH-S
Table 2. Experimental Data for the Methyl Acetate
System Run No. 1: Measured Liquid-Phase Mole HOAc-S + MeOH-S S MeOAc-S + H2O-S
Fractions vs Time
time MeOAc-S S MeOAc + S
(min) MeOAc MeOH H2O HOAc
1.5 0.0053 0.6005 0.1063 0.2879 H2O-S S H2O + S (3)
20 0.0551 0.5402 0.1550 0.2497
40 0.0917 0.5074 0.1884 0.2125 The resulting LHHW model is
60 0.1163 0.4746 0.2258 0.1833
90 0.1477 0.4559 0.2371 0.1593 rMeOAc )

( )
120 0.1682 0.4356 0.2638 0.1323
150 0.1826 0.4189 0.2809 0.1176 aMeOAcaH2O
180 0.1958 0.4096 0.2889 0.1057 kS,1KHOAcKMeOH aHOAcaMeOH -
Keq1
240 0.2143 0.3893 0.3117 0.0848
300 0.2276 0.3794 0.3213 0.0716 (1 + KHOAcaHOAc + KMeOHaMeOH + KMeOAcaMeOAc + KH2OaH2O)2
360 0.2391 0.3749 0.3230 0.0631
420 0.2453 0.3680 0.3316 0.0551 (4)
450 0.2462 0.3647 0.3323 0.0568
540 0.2513 0.3583 0.3405 0.0499 where S represents an active site and kS,1 is the forward
600 0.2525 0.3534 0.3480 0.0461 reaction rate constant for the surface reaction defined
660 0.2523 0.3499 0.3512 0.0466 as follows:
720 0.2560 0.3513 0.3477 0.0450
810 0.2578 0.3489 0.3516 0.0418 kS,1 ) kS0,1WeE/RT (5)
900 0.2563 0.3484 0.3531 0.0421
1390 0.2572 0.3441 0.3582 0.0404
W is the catalyst concentration (mol of H+ ions/mol of
Water is adsorbed most strongly, followed in decreasing mixture) and E is the activation energy for the surface
order of adsorption strength by methanol, acetic acid, reaction (kcal/mol). Ki are adsorption equilibrium con-
and methyl acetate. The next data point was obtained stants, ai are the liquid-phase activities and Keq1 is the
by adding more of the stronger adsorbing component thermodynamic equilibrium constant for reaction 1.
to the previous mixture in order to study the adsorption Lumping some of the constants in the numerator, we
over the entire range of liquid compositions. To limit get
the accumulation of error, measurements were stopped rMeOAc )

( )
when the total volume of the liquid in the flask reached
aMeOAcaH2O
∼300 mL. A subsequent run was then started at a k′S,1 aHOAcaMeOH -
composition close to the last data point of the previous Keq1
run, and this process was continued until the entire
(1 + KHOAcaHOAc + KMeOHaMeOH + KMeOAcaMeOAc + KH2OaH2O)2
composition range was investigated. Figure 2 shows the
adsorption curves obtained for the three binary pairs. (6)

where k′S,1 can be written as

Results
Fourteen sets of kinetic experiments were performed
at different molar ratios of reactants, catalyst concen-
trations, and temperatures; Table 1 gives the conditions.
A typical data set for one of the kinetic experiments is
given in Table 2. These data were regressed as de-
scribed below. The model fit for the data in Table 2 is
given in Figure 5. The remaining data sets for the
methyl acetate kinetics are provided in the Supporting
Information (Tables S1-01-S1-13). The experimental
data and the model fits for the adsorption experiments
are given in Figure 2.
k′S,1 ) k′S0,1WeEAPP/RT (7)
k′S0,1 is the preexponential factor, and EAPP is the
apparent activation energy in kcal/mol. If we assume
that the adsorption equilibrium constants are independ-
ent of temperature (i.e., that their heats of adsorption
are small), then the apparent activation energy, EAPP,
will be equal to the activation energy of the reaction,
E. The model has seven parameters: the preexponen-
tial factor, the activation energy, the thermodynamic
equilibrium constant, and the four adsorption equilib-

rium constants. Regression of all the coefficients in the
LHHW model from the reaction kinetics experiments
alone is problematic due to the correlation of param-
eters, giving rise to convergence difficulties (e.g., Parra
et al., 1994). As an alternative, we need independent
binary nonreactive adsorption experiments to obtain the
adsorption equilibrium constants relative to a reference
component (methyl acetate). The next section describes
the development of the required adsorption model.
Modeling the Adsorption Experiments. For a
nonreactive binary adsorption experiment with two
components 1 and 2, an overall material balance gives
the composite isotherm (Kipling, 1965; p 28)
n0∆x
) nS1 x2 - nS2 x1 (8)
m
where n0 is the total initial number of moles in the liquid
phase, ∆x is the change in the mole fraction in the liquid
phase, m is the mass of the catalyst, and nS1 and nS2 are
the number of moles of 1 and 2 transferred onto the
surface of unit mass of catalyst. The quantities n0, x1,
x2, ∆x, and m can all be measured, leaving two un-
knowns in eq 8, nS1 and nS2 .
To get an expression relating the number of moles of
each species adsorbed (nSi ) and the activities of the
components in the two phases, we consider the chemi-
sorption process as a reaction of the following form:
1(l) + 2(s) S 1(s) + 2(l) (9)
We make the following assumptions about the nature
of the adsorbed layer: (1) The adsorbed layer is confined
to a single molecular layer, (2) the adsorption sites are
all equivalent, (3) the two components of the binary
mixture have the same molecular area in the adsorbed
phase, and (4) the fraction of sites occupied is constant
for all binary pairs at all compositions. If we also
assume that the liquid phase is nonideal and the solid
phase is ideal, the equilibrium constant for reaction 9
is
xS1 a2
) K2,1 (10)
xS2 a1
K2,1 can be thought of as a ratio of the equilibrium
constants for two independent adsorption processes of
the form
1(l) + s S 1(s) K1 (xS1 ) K1a1) (11a)
2(l) + s S 2(s) K2 (xS2 ) K2a2) (11b)
Equation 9 can be obtained by subtracting eq 11b from
eq 11a and, hence, K2,1 is the ratio of K2 to K1
K2,1 ) K2/K1 (12)
Since xS2 ) 1 - xS1 , it follows that
K2,1a1
xS1 ) (13)
K2,1a1 + a2
Because the total number of occupied sites is a constant
and all molecules occupy the same number of sites (have
the same molecular area), the total number of moles
Ind. Eng. Chem. Res., Vol. 37, No. 5, 1998 1921
adsorbed on the surface must be independent of surface
composition. Therefore,
nS1 + nS2 ) nS (14)
where nS is the constant total number of moles which
can be accommodated in the adsorbed phase by unit
mass of solid. Since xS1 ) nS1 /nS, eq 13 can be rewritten
as
K2,1nSa1
nS1 ) (15)
K2,1a1 + a2
with a similar expression for nS2 . Substituting these
expressions in eq 8 gives the composite isotherm
n0∆x nS(K2,1a1x2 - a2x1)
) (16)
m K2,1a1 + a2
There are two parameters in this model, K2,1 and nS,
which are found by nonlinear regression of the experi-
mental adsorption data.
There are four pairs of components for which adsorp-
tion experiments could be performed (the other pairs
are reactive). Only three of these pairs are independent
(the fourth ratio can be used as a consistency check).
Hence, we have three ratios of adsorption equilibrium
constants, and we can choose one of the Ki’s as a
reference component and relate all the others to it. We
chose the adsorption equilibrium constant of methyl
acetate as the reference and related the other adsorption
coefficients to it through these experimentally deter-
mined ratios:
KHOAc ) K1,3KMeOAc
KMeOH ) K2,3KMeOAc
KH2O ) K4,3KMeOAc (17)
The adsorption experiments were performed at 45 °C.
The denominator of the LHHW rate expression can be
written in terms of the reference component, and then
the kinetic model has only two adjustable parameters,
namely, the forward reaction rate constant k′S,1 and the
adsorption equilibrium constant for the reference com-
ponent KMeOAc. The ratios of the adsorption equilibrium
constants obtained from the adsorption experiments and
the value of KMeOAc obtained from the kinetic data fitting
at 45 °C were assumed to be independent of tempera-
ture.
The Equilibrium Constant. The reaction equilib-
rium constant Keq1 was obtained as follows. The kinetic
experiments were run to long times until the composi-
tion (mole fraction) vs time curves were essentially flat.
To determine whether the reaction had truly reached
equilibrium, we performed the following test. The
relative error of the GC was less than 5%. We per-
formed an error propagation analysis to get the error
in the measured mole fractions, and at long times we
checked the change in mole fractions between three
successive pairs of measurements. If the change in the
mole fraction was less than the error in the measure-
ment for these three successive pairs, we considered all
points after the third pair to be at equilibrium. These
data points were then used to get a value of Kx
1922 Ind. Eng. Chem. Res., Vol. 37, No. 5, 1998

Table 3. Thermodynamic Data for the Methyl Acetate/DME System

Antoine Coefficients
component A B C Vi (m3/mol)
acetic acid (1) 22.1001 -3654.62 -45.392 57.54
methanol (2) 22.4999 -3643.3136 -33.434 44.44
methyl acetate (3) 21.1520 -2662.78 -53.460 79.84
water (4) 23.2256 -3835.18 -45.343 18.07
DME (5) 21.2303 -2164.85 -25.344 69.07
Wilson Parameters
A11 ) 0.0 A12 ) 2535.2019 A13 ) 1123.1444 A14 ) 237.5248 A15 ) -96.6698
A21 ) -547.5248 A22 ) 0.0 A23 ) 813.1843 A24 ) 107.3832 A25 ) 900.9358
A31 ) -696.5031 A32 ) -31.1932 A33 ) 0.0 A34 ) 645.7225 A35 ) -17.2412
A41 ) 658.0266 A42 ) 469.5509 A43 ) 1918.232 A44 ) 0.0 A45 ) 703.3566
A51 ) 96.7797 A52 ) -418.6490 A53 ) -21.2317 A54 ) 522.2653 A55 ) 0.0

B
ln Psat ) A + Psat [Pa], T [K]
T+C

( )
C C xkΛki
ln γi ) 1 - ln( ∑ xjΛij) - ∑ C

∑x Λ
j)1 k)1
j kj
j)1

where

Λij )
Vj
Vi
exp ( )
-Aij
RT
Vj[m3/mol], Aij [cal/mol]

Aij ) 0 implies ideality

The dimerization constant in the vapor phase for acetic acid is
3166.0
log(KD) ) -12.5454 + KD [1/Pa], T [K]
T

Table 4. Minimum-Error Estimate of the Equilibrium
Constant for the Methyl Acetate Reaction
temp (°C) Keq temp (°C)
40 30.2 50
45 27.4
()xMeOAcxH2O/xHOAcxMeOH). The liquid-phase activity co-
efficients for each point were obtained using the Wilson
model with the parameters given in Table 3. Thether-
modynamic equilibrium constant for that point is found
from
aMeOAcaH2O
Keq1 ) ) KxKγ
aHOAcaMeOH
The thermodynamic equilibrium constant is only a
function of temperature. The value of Keq at a particular
temperature was obtained by adjusting Keq to minimize
the squared error between calculated and measured
equilibrium compositions of all the data points (with
different molar ratios and catalyst concentrations). A
detailed listing of the point values of Kx, Kγ, and Keq for
the equilibrium composition data points and the mini-
mum-error estimate of the equilibrium constant at the
three experimental temperatures is given in the Sup-
porting Information (Table S3). Table 4 gives the
minimum-error estimate of the equilibrium constant at
the three different temperatures.
An independent method for estimating Keq is from free
energies of formation (i.e., Keq ) e∆G°/RT). However, the
free energies of formation are large and their difference
(∆G°) is small. The result, therefore, has a large
uncertainty, and we did not find this method reliable.
Figure 3 shows a plot of the logarithm of the value of
the thermodynamic equilibrium constants of all the
Keq experimentally determined data points (at the three
24.0 different temperatures of 40, 45, and 50 °C (Table S3))
and one point at 154 °C from Menschutkin (1879) as a
function of reciprocal temperature. From the plot, the
following expression was obtained for the thermody-
namic equilibrium constant as a function of temperature
(T in K)
ln(Keq1) ) 0.839 83 + 782.98/T (19)
From this expression, we estimate the free energy of
(18) the reaction (∆G°) to be -1.55 kcal/mol. In the tem-
perature range of interest (40-120 °C), the value of Keq1
ranges from 28.2 to 17.0, which is slightly higher than
the value quoted by earlier workers (Agreda et al., 1990;
Barbosa and Doherty, 1988). They used a value of Kx
) 5.2 at 154 °C from Menschutkin (1879). Then using
a UNIFAC estimate for the liquid-phase activity coef-
ficients γι and the fact that Keq ) KxKγ, they estimated
the value for Keq1 to be 14.7.
If the Menschutkin data point is removed from Figure
3, the slope of the curve increases and the new expres-
sion for Keq1 is ln(Keq1) ) -0.8226 + 1309.8/T. In this
case, ∆G° ) -2.6 kcal/mol, and the value of Keq1 varies
from 28.8 to 12.3 over the temperature range of 40-
120 °C. This does not affect our results significantly
since the change in Keq1 over the 40-50 °C range (over
which the kinetic experiments were performed) is minor.
The value of Keq1 from these two correlations is signifi-
cantly different at the higher temperature end, but we
believe that inclusion of the Menchutkin data point (at
154 °C) would give a better estimate of the equilibrium

Figure 3. Temperature dependence of the reaction equilibrium
constant for the methyl acetate reaction: ln(Keq) vs 1/T. Open
symbols represent the individual data points; filled symbols are
the minimum-error estimates.
constant at higher temperatures in comparison to a
correlation that is purely based on equilibrium constant
values at much lower temperatures.
Regression of Kinetic Data. A summary of the
kinetic experiments performed is given in Table 1. At
45 °C, the LHHW model has two parameters that need
to be estimated from the kinetic data fit, namely, the
forward reaction rate constant k′S,1 and the adsorption
equilibrium constant of the reference component (meth-
yl acetate). These were obtained by minimizing the
following objective function:
total time 4
min f(x) ) ∑ ∑
time)0 j)1
(xj,expt - xj,model)2
where xj’s represent the mole fractions of the four
species, namely, acetic acid, methanol, methyl acetate,
and water. The minimization was done using a modi-
fied Levenberg-Marquardt algorithm (the IMSL rou-
tine DBCLSF (IMSL MATH/LIBRARY, 1987)) embed-
ded within the LSODES integrator (Hindmarsh, 1983).
Once the adsorption equilibrium constants are deter-
mined at 45 °C, only one parameter, namely, the
forward reaction rate constant k′S,1, remains to be
fitted using the kinetic experiments at the other two
temperatures. This is because we have assumed that
the value of the adsorption equilibrium constant for
methyl acetate and the ratios of the adsorption equi-
librium constants for the other components are inde-
pendent of temperature. The rate constants were
obtained by minimizing the objective function in eq 20.
The results are given in Table 5. Figure 4 shows the
logarithm of the forward reaction rate constant k′S,1 as
a function of reciprocal temperature for the methyl
acetate reaction. The slope of the curve gives an
apparent activation energy of 12.49 kcal/mol, and the
intercept gives a preexponential factor of 5.02 × 1010
(mol of mixture) (mol of H+ ions)-1 min-1. From the
plot, we get the following Arrhenius expression for the
forward reaction rate constant as a function of temper-
ature:
Ind. Eng. Chem. Res., Vol. 37, No. 5, 1998 1923
Table 5. Results of the Regression for the Methyl
Acetate/DME System
Reaction Equilibrium Constant for Methyl Acetate
Keq1 ) 2.32e782.98/T
Adsorption Equilibrium Constants
KH2O ) 10.50
KMeOH ) 4.95
KHOAc ) 3.18
KMeOAc ) 0.82
Forward Reaction Rate Constants
k′S,1 ) e(24.64-(6287.7/T))
k′S,2 ) e(27.4-(10654.0/T))
Figure 4. Logarithm of the forward reaction rate constant for
the MeOAc reaction as a function of reciprocal temperature.
6287.7
ln(k′S,1) ) 24.64 - (21)
(20) T (K)
Figure 5 shows a typical fit of the mole fraction for
each component as a function of time using the LHHW
model. As can be seen, the model does a very good job
of predicting the mole fraction profiles as a function of
time.
The DME Reaction. One of the side reactions in
the methyl acetate system is the dehydration of metha-
nol to dimethyl ether and water (eq 2). An increase in
pressure leads to an increase in the boiling points of
the components and hence the operating temperature
in reactive distillation. This leads to higher rates of
reaction and smaller equipment, leading to a savings
of investment costs. On the other hand, an increase in
temperature leads to a decrease in the equilibrium
constant (and hence the equilibrium conversion) and
could potentially trigger unwanted side reactions such
as the methanol dehydration reaction. Eleven sets of
high-pressure experiments were carried out with an
initial charge of pure methanol both with and without
the catalyst to measure the extent of the dehydration
reaction. A second apparatus similar to the one de-
scribed in Figure 1 was built out of stainless steel using
a Parr reactor (model 4521 constructed from T316
stainless steel with a volume of 1000 mL) with a
maximum working pressure of 700 psig. The details of
the high-pressure equipment are given in Venimadha-
van (1998).
1924 Ind. Eng. Chem. Res., Vol. 37, No. 5, 1998

Table 6. Summary of the Kinetic Studies for the DME

Reaction
mol of H+ initial initial total
run temp catalyst (from catalyst)/ moles of moles of time
no. (°C) (g) mol of mixture MeOH H2O (h)
1 100 25.0 0.009 65 9.88 0.280 12.0
2 100 49.0 0.018 60 9.88 0.659 12.5
3 100 71.0 0.028 31 9.88 0.610 12.0
4 100 0.0 0.000 00 9.84 0.140 12.0
5 100 72.0 0.028 29 9.88 0.688 12.0
6 100 72.0 0.028 55 9.88 0.590 12.0
7 100 130.0 0.015 26 9.88 9.880 12.0
8 100 82.4 0.027 21 9.88 1.190 12.6
9 100 72.9 0.028 27 9.88 0.660 12.0
10 115 71.0 0.028 61 9.88 0.570 12.0
11 85 72.0 0.028 56 9.88 0.590 12.0

Table 7. Experimental Data for the Kinetic Study of the

DME System (Run No. 10): Measured Liquid Mole
Fractions vs Time
time
(min) MeOH H2O DME
5 0.9361 0.0627 0.0012
120 0.8829 0.0856 0.0315
240 0.8213 0.1230 0.0557
360 0.7710 0.1534 0.0757
Figure 5. Methyl acetate system: isothermal batch kinetic data 480 0.7230 0.1739 0.1031
and model fit. The dots represent experimental data, and the solid 600 0.7020 0.1968 0.1012
line represents the heterogeneous (LHHW) model (T ) 40 °C, 720 0.6625 0.2272 0.1103
catalyst concentration ) 0.009 mol of H+/mol of mixture).
where ∆G° is in kcal/mol and R ) 0.001 987 kcal/mol‚K.
The reaction was not significant at low temperatures In the experimental temperature range (85-115 °C),
(pressures) even with high catalyst concentrations and the value for the thermodynamic equilibrium constant
large liquid holdups. However, at higher pressures and for the methanol dehydration reaction ranges from 68.4
catalyst concentrations (8.41-15.69 atm and 61 g of to 52.3. It was assumed that the amount of DME
catalyst for a 400-mL methanol charge), significant adsorbed was small and that the adsorption equilibrium
amounts of DME were formed. The LHHW model for constants for methanol and water had the same values
the methanol dehydration reaction is as those from the methyl acetate data fit. This leaves

( )
aDMEaH2O
kS,2KMeOH2 aMeOH2 -
Keq2
rDME )
(1 + KMeOHaMeOH + KDMEaDME + KH2OaH2O)2
(22)
where kS,2 is the forward reaction rate constant for the
surface reaction, ai’s are the liquid-phase activities
computed using the Wilson model with the parameters
given in Table 3, Ki’s are the adsorption equilibrium
constants, and Keq2 is the thermodynamic equilibrium
constant for reaction 2. DME is the lightest boiling
component in the mixture, with a boiling point of 44.68
°C at 10 atm pressure. Isothermal batch kinetic experi-
ments were performed at various temperatures in the
range 85-115 °C. If most of the DME is in the vapor
phase and if we lump the constants in the numerator
together, eq 22 can be simplified to
only one parameter, namely, the forward reaction rate
constant, to be estimated from the kinetic data for the
DME reaction.
The kinetic data from the methanol dehydration
reaction were regressed in a manner similar to that for
the methyl acetate reaction. Table 6 is a summary of
the kinetic experiments performed for the DME reac-
tion. Table 7 gives the measured data from one of the
experimental runs (at 85 °C and a catalyst concentration
of 72 g of catalyst in ∼400 mL of methanol). The data
for the remainder of the experimental runs are given
in the Supporting Information (Tables S2-01-S2-10).
Figure 6 shows a plot of the logarithm of the forward
reaction rate constant (k′S,2) as a function of the recip-
rocal temperature. From this graph, we find an appar-
ent activation energy of 21.17 kcal/mol and a preexpo-
nential factor of 7.9 × 1011 (mol of mixture) (mol of H+
ions)-1 min-1, giving the following Arrhenius rate
expression

rDME )
(
k′S,2 aMeOH2 -
aDMEaH2O
Keq2 ) (23)
ln(k′S,2) ) 27.40 -
10654.0
T (K)
Figure 7 shows a sample fit of the mole fraction for
(25)

(1 + KMeOHaMeOH + KH2OaH2O)2 each component as a function of time for the methanol

dehydration data given in Table 7. The solid line is the
The thermodynamic equilibrium constant for the computed value while the dots are the experimental
methanol dehydration reaction was taken from Nisoli data points. Our results indicated that the amount of
et al. (1997): DME formed was quite small at lower temperatures
(40-50 °C) but became significant at higher tempera-
∆G°
Keq2 ) exp -( RT
,) tures (85-115 °C).
Residue Curve Maps. As mentioned earlier, a
∆G° ) -2.4634 1.5167 × 10-3T (K) (24) useful tool for the synthesis and analysis of both

Figure 6. Logarithm of the forward reaction rate constant for
the DME reaction as a function of reciprocal temperature.
Figure 7. DME system: Isothermal batch kinetic data fit. The
dots represent experimental data, and the solid line represents
the heterogeneous (LHHW) model (T ) 85 °C, catalyst concentra-
tion ) 0.028 mol of H+/mol of mixture).
nonreactive and reactive distillation systems is the
residue curve map (e.g., Fidkowski et al., 1993; Foucher
et al., 1991; Wahnschafft et al., 1992; Venimadhavan
et al., 1994). An important parameter in the study of
the kinetically controlled reactive distillation system is
a Damkohler number defined by the ratio of a charac-
teristic residence time to a characteristic reaction time
(Venimadhavan et al., 1994). The Damkohler number
can be thought of as a dimensionless holdup in the
system or a dimensionless rate of reaction. For a
heterogeneous system, the Damkohler number can be
redefined to explicitly show its dependence on a normal-
ized catalyst concentration as follows:
H0/V0
Da ) (26)
1/k′S,1,refW
where H0 is the initial molar holdup in the still, k′S,1,ref
Ind. Eng. Chem. Res., Vol. 37, No. 5, 1998 1925
is the reference forward reaction rate constant (defined
at a convenient temperature such as the lowest boiling
temperature in the mixture), W is the normalized weight
of catalyst in moles of H+ ions per moles of mixture,
and V0 is the initial rate of the vapor leaving the still.
The model for a kinetically controlled reactive distil-
lation system is given below (for the detailed derivation
of the model; see Venimadhavan et al., 1994).
dxi H V0 N
dξ
) xi - yi + Da
H0 V j)1
∑
(νi,j - νT,jxi)Ri
(i ) 1, ..., (R + P - 1)) (27)
where xi and yi are the liquid and vapor phase mole
fractions, respectively, dξ is a “warped” time variable
defined by dξ ) (V/H) dt, V is the instantaneous vapor
rate, H is the instantaneous liquid holdup in the still, t
is the clock time, νi,j is the stoichiometric coefficient of
species i in reaction j, νT,j is the sum of the stoichiometric
coefficients in reaction j, and
Ri ) rj/k′S,1,ref (j ) 1, ..., N) (28)
where Ri is the normalized reaction vector, rj is the rate
of an individual reaction, and k′S,1,ref is the reference
surface reaction rate constant of the first reaction.
The i’s correspond to the five species, namely, acetic
acid, methanol, methyl acetate, water, and DME. The
rj’s are rMeOAc and rDME which were determined earlier
using the data from the kinetic and adsorption experi-
ments. The reference reaction rate constant is chosen
as the value for the methyl acetate reaction at the
boiling point of DME at 1 atm which is -24.72 °C (the
lowest point on the boiling surface). The matrix νi,j and
the vector νT,j in eq 27 are respectively
y) ( -1 -1 1 1 0
0 -2 0 1 1 ) (29)
and
yT ) ()
0
0
(30)
A limiting case that is well-understood is the case of
equilibrium reactive distillation where simultaneous
vapor-liquid and reaction equilibrium prevail. The
assumption of reaction equilibrium allows us to define
certain transformed composition variables which make
the analysis of the equilibrium reactive residue curve
maps easier (Barbosa and Doherty, 1988; Ung and
Doherty, 1995a-d).
As a test of our model at the equilibrium limit, we
performed independent equilibrium open-evaporation
experiments. One way of ensuring that the system
reaches equilibrium rapidly is to have a large amount
of catalyst present in the reactor. We ensured that
there was a sufficiently large amount of catalyst present
by performing several experiments starting with the
same number of moles of acetic acid and methanol but
with increasing amounts of catalyst on successive runs.
For each run, we plotted the data on a transformed mole
fraction diagram until a further increase in the amount
of catalyst did not result in any appreciable shift in the
RCM (Figure 8). We then concluded that, under the
given conditions, the reaction could not proceed any
faster and thus we had achieved almost instantaneous
reaction and phase equilibrium. Earlier calculations
1926 Ind. Eng. Chem. Res., Vol. 37, No. 5, 1998
Figure 8. Effect of the mass of catalyst for simultaneous reaction
and phase equilibrium.
(Figure 8) showed that, for all values of Da > 80, the
structure of the residue curve map was indistinguish-
able from that at simultaneous vapor-liquid and reac-
tion equilibrium (Da f ∞). The residue curves com-
puted from our model at Da ) 99 (chosen well above
the minimum required to model equilibrium behavior)
were compared to the experimentally obtained residue
curves (Figure 9a). Figure 9b gives the curves computed
by Barbosa and Doherty (1988). The qualitative agree-
ment between their diagram and the experimental data
is good considering the fact that they had obtained the
value of Kx ) 5.2 from Menschutkin (1879) and esti-
mated the value of Kγ ≈ 2.83 using the UNIFAC method
to get an overall value of Keq ≈ 14.7 (independent of
temperature). This value is somewhat lower than the
range of values that we obtained from the experimental
data in this work (Keq in the range of 20-30). The solid
lines in Figure 9a show the computed curves, while the
symbols show the measurements. The agreement is
good, especially considering that none of the parameters
in the model were adjusted to fit the measurements. The
good agreement appears to validate the modeling ap-
proach and provides confidence in applying our kinetic
and VLE models to reactive distillation systems of
commercial interest.
We used the model to predict residue curve maps at
lower values of Da in the kinetically controlled regime.
Figure 10 shows the results at Da ) 1, 10, and 50. The
model predicts that the lightest boiler is always the
methyl acetate-methanol azeotrope, that the heaviest
boiler is always pure acetic acid, and that methyl
acetate, methanol, and water are always intermediate
boilers for all values of Da. Since the structure of the
residue curve map is qualitatively the same for all the
values of Da, we predict that methyl acetate can be
successfully produced by reactive distillation in both the
equilibrium-controlled and the kinetically controlled
regimes.
Conclusions
Analysis of kinetically controlled reactive distillation
systems requires knowledge of the chemical kinetics.
Rate expressions for reactive distillation systems are
Figure 9. (a) Comparison of computed (solid line) and experi-
mentally measured equilibrium reactive RCM for the methyl
acetate system at P ) 1 atm. (b) RCM for the methyl acetate
system at vapor-liquid and reaction equilibrium computed by
Barbosa and Doherty (1988).
usually written in terms of the liquid-phase activities
of the components rather than the more common
concentration-based rate expressions used in reaction
engineering. The methyl acetate synthesis is a classic
problem for the application of reactive distillation, but
there is a lack of kinetic rate data/expressions in the
range of interest for this system. We performed kinetic
experiments on a solid sulfonic acid resin catalyst
(Amberlyst 15W) for the methyl acetate reaction as well
as for an unwanted side reactionsthe dehydration of
methanol to dimethyl ether and water. We developed
a heterogeneous (LHHW) model for the reaction kinetics
for these two reactions. To decouple the reaction and
the adsorption phenomena, we performed independent
nonreactive binary adsorption experiments. These ex-
periments gave estimates of the three independent
ratios of the adsorption equilibrium constants. The
remaining parameters of the LHHW model were fitted
from the kinetic data. The resulting kinetic models fit
the experimental data quite well. These rate expres-
sions are applicable over a wide range of catalyst
concentrations and molar ratios of reactants. To test
the equilibrium limit of the model, we performed
independent equilibrium reactive open-evaporation ex-

Figure 10. RCMs at Da ) 1, 10, and 50 on transformed
coordinates for the methyl acetate reaction.
periments. The experimental residue curves were
compared to the predictions generated by the model, and
the agreement was found to be very good considering
that none of the parameters in the model were adjusted
to fit the simple distillation data. The good agreement
appears to validate our vapor-liquid equilibrium and
kinetic models and gives us confidence in applying these
models to the reactive distillation of systems of com-
mercial interest.
Ind. Eng. Chem. Res., Vol. 37, No. 5, 1998 1927
Acknowledgment
We are grateful for the financial support provided by
the National Science Foundation (CTS-9613489) and the
National Environmental Technology Institute. We are
also grateful to Ms. Pamela Stephan for preparing the
illustrations.
Supporting Information Available: Tables of
experimental data for kinetic study of the methyl
acetate and the DME systems for several runs and
equilibrium constants for the methyl acetate reaction
(26 pages). Ordering information is given on any
current masthead page.
Notation
ai ) activity of component i
Da ) Damkohler number ()(H0/V0)/(1/kS,1,refW))
E ) activation energy (kcal/mol)
EAPP ) apparent activation energy (kcal/mol)
∆G° ) change in free energy (kcal/mol)
H ) liquid holdup (mol)
H0 ) initial liquid holdup (mol)
kf ) forward reaction rate constant for a homogeneous
reaction (1/time)
kS,j ) forward reaction rate constant for surface reaction j
(1/time)
k′S,j ) apparent forward reaction rate constant for surface
reaction j (1/time)
k′S,j,ref ) reference apparent reaction rate constant for the
surface reaction (1/time)
Keqj ) thermodynamic equilibrium constant for reaction j
Ki ) adsorption equilibrium constant for component i
Ki,j ) ratio of the adsorption equilibrium constants for
components i and j
Kx ) reaction equilibrium constant based on mole fractions
Kγ ) ratio of the activity coefficients of the products to those
of the reactants
m ) mass of catalyst for the adsorption experiments
mol ) gmol
nSi ) number of moles of species i transferred onto the
surface of unit mass of catalyst
n0 ) total initial number of moles in the liquid phase
rj ) rate of reaction for reaction j (1/time)
R ) universal gas constant (1.987 cal/mol‚K)
Rj ) normalized reaction vector defined as rj/k′S,1,ref
S ) active site on the catalyst
t ) time (min)
T ) temperature (K)
V ) vapor rate (mol/time)
V0 ) initial vapor rate (mol/time)
W ) normalized catalyst concentration (mol of H+ ions/
mol of mixture)
∆x ) change in the liquid-phase mole fraction for the
adsorption experiments
xi ) liquid-phase mole fraction for component i
xSi ) mole fraction on the catalyst for component i
yi ) vapor phase mole fraction for component i
Greek Symbols
ξ ) “warped” time
νi,j ) stoichiometric coefficient of component i in reaction j
νT,j ) sum of the stoichiometric coefficients for reaction j
1928 Ind. Eng. Chem. Res., Vol. 37, No. 5, 1998
Subscripts
i ) component i
0 ) initial value
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Received for review December 1, 1997
Revised manuscript received February 4, 1998
Accepted February 5, 1998
IE9708790