7186 Ind. Eng. Chem. Res.

2009, 48, 7186–7204

Reactive Distillation for Esterification of an Alcohol Mixture Containing

n-Butanol and n-Amyl Alcohol
Hao-Yeh Lee,† Ling-Ting Yen,† I-Lung Chien,‡ and Hsiao-Ping Huang*,†
Department of Chemical Engineering, National Taiwan UniVersity Taipei, 10617, Taiwan, and Department of
Chemical Engineering, National Taiwan UniVersity of Science and Technology, Taipei 10607, Taiwan

Manufacturing processes in the semiconductor and pharmaceutical industries often produce alcohol mixture
byproducts. Therefore, the esterification of alcohol mixtures may be an important step in reusing wastes from
these industries. There are two alternative methods for using the alcohol mixtures as feed for reactive distillation
(RD). The first method separates this mixture into pure alcohols first and then follows with esterification
using the RD column. The second method uses direct esterification of the alcohol mixture in a RD column,
and then separates the mixed-ester products. This paper discusses the esterification of a n-butanol (BuOH)
and n-amyl alcohol (AmOH) mixture with acetic acid (HAc). This study presents two important results based
on optimizing the total annual cost (TAC). First, the mixed BuOH/AmOH system, with direct esterification
with RD followed by product separation, is more economical than the system that first separates the mixture.
Second, this study proposes a novel economical indirect-sequence design flowsheet with aqueous reflux. Another
important issue in this study is the choice of the relative feed location, because the boiling point of acid lies
between that of the two alcohols (i.e., BuOH < HAc < AmOH). Reaction kinetics is an important factor to
be considered in determining the feed location of the alcohol mixture.

1. Introduction ranging from C1 to C5 with process flowsheets classified into

Manufacturing processes in the semiconductor and pharma-
ceutical industries often produce alcohol mixture byproducts.
Therefore, the esterification of alcohol mixtures may be an
important step in reusing wastes from these industries. This
paper proposes that an alcohol mixture of BuOH and AmOH
can be used as a feed stream for further processing. Manufactur-
ing plants often use BuOH and AmOH alcohols as organic
solvents for paint, in adhesives, in creating artificial leather, and
processing textiles and spices. However, existing literature on
this topic focuses on the single esterification of either BuOH
or AmOH with acid (e.g., acetic acid) to obtain buytl acetate
(BuAc) or amyl acetate (AmAc) in a RD system. Discussion
on the esterification of an alcohol mixture as a feed stream is
relatively scarce.
Several papers in the literature discuss RD in the esterificaton
of a single alcohol. Steinigeweg and Gmehling1 used RD
experiments and simulations to explore the effects of steady
state design variables for a BuOH esterification system. Gan-
gadwala et al.2,3 and Singh et al.4 developed a steady-state
column model with reaction kinetics and compared it with
experimental data from the literature. Specifically, their model
compares three different column configurations for the produc-
tion of BuAc, preventing the formation of dibutyl ether
byproduct and achieving a high purity product. Furthermore,
Gangadwala and Kienle5 applied a mixed integer nonlinear
programming optimization method to the BuAc RD system.
Their optimized designs offer significant economic improve-
ments in production. Chiang et al.6 explored RD system design
for a steady state AmOH esterification system and compared it
with a coupled reactor/column structure. Their RD system is
more efficient with a reduced total annual cost. Tang et al.7
studied the esterification of HAc with five different alcohols,
* To whom correspondence should be addressed. Tel.: 886-2-2363-
8999. Fax: 886-2-2362-3935. E-mail: huanghpc@ntu.edu.tw.
†
National Taiwan University Taipei.
‡
National Taiwan University of Science and Technology.
10.1021/ie801891q CCC: $40.75  2009 American Chemical Society
Published on Web 07/06/2009
types I, II, and III for these five systems. Their results show
that BuOH and AmOH esterification systems have similar
thermodynamic properties and are classified as type III systems.
On the basis of reaction types, RD systems can be classified
as single reversible reactions, series reactions, or parallel
reactions. In the case of parallel reactions, such mixtures as
mixed isopropyl alcohol and BuOH and mixed ethanol and
BuOH react with HAc in the esterification process. These
esterification processes with mixed alcohols are only mentioned
in several patents.8-11 The mixed BuOH and AmOH feeds of
this paper also fall into the case of parallel reactions.
In this study, the esterification reactions of BuOH and AmOH
demonstrate the use of an alcohol mixture as a feed stream in
the RD process. Based on thermodynamic properties and
reaction kinetics, this study presents two alternative process
designs with three kinds of configurations for the overall RD
system.
2. Thermodynamic and Kinetic Models
Chiang et al.6 and Venimadhavan et al.12 used the NRTL
and UNIQUAC thermodynamic models for the BuOH and
AmOH esterification processes, respectively. To simulate a
mixed alcohols system, it is first necessary to merge these
thermodynamic models into a single model, and then regress
the additional three binary pairing parameters. This paper
chooses the NRTL model to describe the liquid phase and the
Hayden-O’Connell model13 to describe vapor phase. This
approach corrects fugacity due to association as dimer in acetic
acid at the atmospheric pressure. This system contains six
components and 15 binary parameters. The HAc/AmAc, HAc/
H2O, AmOH/AmAc, and AmAc/H2O binary parameters are
from Chiang et al.6 The BuOH/AmOH, BuOH/AmAc, BuAc/
AmAc are obtained from the Aspen data bank, and the
remaining binary parameters are regressed from experimental
data.14-23 These binary parameters are regressed by maximum-
likelihood method which can be found in the Aspen Properties
 Ind. Eng. Chem. Res., Vol. 48, No. 15, 2009 7187
software. Table 1 shows all NRTL binary parameters used in

Chiang et al.6
AmAc
the simulation. The calculation of the vapor pressure of all pure

254.47
2221.5
H2O
components can be found in Appendix A of the supplemental

0.2
0
0
file.
On the basis of the thermodynamic model, Figure 1 displays

BuAc
all results of 15 binary pairings. In Figure 1, T-xy plot is placed

H2O

regression
-5.519
-6.472
2428.1
3774.4
0.3116
on left-hand side and the x-y plot is placed on the right-hand
side. Furthermore, the liquid-liquid equilibrium results of
ternary systems are shown in Figure 2. In Figure 2, the gray

AmAc
BuAc
with dot area is two liquid regions and the straight line connected

-113.6
Aspen

128.17
between two hollow circles is the tie line. Available experi-

0.3
mental data are also displayed in Figure 1a-g and Figure 2

0
0
with square and diamond symbols. Figures 1 and 2 show that

AmOH

regression
the model results agree quite well with binary and ternary

57.328
1424.8
0.2869
H2O
experimental data. Table 2 displays the boiling points rankings

0
0
for pure components and the azeotropic temperatures of all the
azeotropes from experimental data and predictive results.

AmOH

Chiang et al.6
AmAc
Esterification is a reversible reaction catalyzed by an acidic

-144.8
320.65
0.3009
catalyst. The system described in this paper uses Amberlyst 15
as a solid catalyst. Amberlyst 15 is an acid ion exchanged resin

0
0
that has the benefit of no environmental problems than

AmOH
homogeneous catalysts. The parallel and competing esterification

BuAc

regression
reactions in this system occur as the following equations.

-0.039

-391.9
0.0734
793.01

0.2662
k1

[ ]
HAc + BuOH y\z BuAc + H2O

mj
BuOH

∑x τ G
kj
k2

∑x G
m mj
H2O

regression
(1)

k
161.48
1186.4
0.3962
k3
HAc + AmOH y\z AmAc + H2O

k
m
k4

0
0

τij-
AmAc
BuOH
Table 3 shows the reaction kinetics equations from Gangad-

kj
203.57
138.54
Aspen

∑x G
wala et al.2 and Lee et al.24 The BuOH esterification rate

xjGij

k
0.3
equation is expressed as a pseudo-homogeneous model by 0
0

k
activity, and the AmAc system is expressed as a quasi-

∑
BuOH

regression
BuAc

j
homogeneous system by concentration. BuOH esterification is
-2.861
-442.3
1.2268

1264.2
0.3112

+
an exothermic reaction, and AmOH esterification is an endo-

ji

ki
∑xτ G
thermic reaction.

∑x G
j ji

k
In all the design studies followed, the software package of
AmOH

-110.6
BuOH

Aspen

125.45

k
Aspen Plus was used to conduct the rigorous simulation.

j
0.3

Equilibrium stages were assumed in the column simulation.

ln γ )
0
0

i
Total material, component, and energy balances were calculated
Chiang et al.6

in each column tray via RadFrac module in Aspen Plus. The

HAc
H2O

-110.6

modified Newton’s method of Broyden is chosen to obtain the

424.02
0.2987
Table 1. NRTL Model Parameters for BuOH/AmOH Mixture Systema

steady-state solution for the system of algebraic equations. As

0
0

for the reactive section of the column, catalyst volume in each where Gij ) exp(-Rijτij), τij ) aij + bij/T, Rij ) cij, τii ) 0, and Gii ) 1.
tray is assumed to occupy half of the total holdup. Catalyst cost
AmAc
HAc

Chiang et al.6

is assumed to be $3.5/lb with its density assumed to be 800

-37.94

kg/m3.
214.55
0.2
0
0
BuAc

3. Conceptual Design of the Process Flowsheet

HAc

To compare the minimum TAC, this section discusses two

regression
-2.909

-1000
3.0379
1194.7

types of process design for a mixed alcohols system. The first

0.301

is “separation first,” which first separates the mixed alcohols

AmOH
HAc

from the upstream, and then feeds the BuOH and AmOH into
different RD columns for HAc esterification. The second is
regression

41.866
150.87

“reaction first” which feeds the mixed alcohols stream directly

0.3

into a RD column, and then separates the two ester products

BuOH

0
0
HAc

and water. All the conceptual design of the alternative process

Aspen Plus NRTL:

flowsheets are shown in Figure 3.

regression

-8.415
-4129

3.1. “Separation First” Design. The “separation first”

13.513

2580.4
0.18

process flowsheet includes one traditional distillation column

component i
component j

and two RD columns. The first column separates the BuOH

and AmOH from the feed stream as shown in Figure 3a. Then
source

bij (K)
bji (K)

the BuOH and AmOH are fed into their own RD columns and
a
Rij
aij
aji

react with HAc. The final products of AmAc and BuAc are
7188 Ind. Eng. Chem. Res., Vol. 48, No. 15, 2009
Ind. Eng. Chem. Res., Vol. 48, No. 15, 2009 7189
7190 Ind. Eng. Chem. Res., Vol. 48, No. 15, 2009
Ind. Eng. Chem. Res., Vol. 48, No. 15, 2009 7191
7192 Ind. Eng. Chem. Res., Vol. 48, No. 15, 2009

Figure 1. T-xy and x-y experiment and predicted diagrams under 1 atm. (a) Gmehling et al.,15 Part 2b, p 138; (b) Gmehling et al.,17 Part 5, pp 147-151;
(c) Gmehling et al.,15 Part 2b, pp 194-197; (d) Koichi and Hitoshi;19 (e) Cho et al.;20 (f) Gmehling et al.,16 Part 2d, p 432; (g) Gmehling et al.,14 Part 1a,
p 383.
 Ind. Eng. Chem. Res., Vol. 48, No. 15, 2009 7193

Figure 2. LLE experiment and predicted diagram for the ternary system under 1 atm: (a,b) Ruiz Bevia et al.,21 (c) Tan and Aravinth,22 (d) Esquı́el and
Bernardo-Gil.23

Table 2. Boiling Points and Azeotropes of BuOH/AmOH Mixture System under 1 atm
experimental data computed data
component mole fraction temp °C mole fraction temp °C
a b
BuOH/BuAc/H2O (0.0726, 0.224, 0.7034) 90.38 (0.0912, 0.2142, 0.6946) 90.44
BuAc/H2Oa (0.299, 0.701)c 91 (0.2871, 0.7129) 90.98
BuOH/AmAc/H2Oa (0.1882, 0.0823, 0.7295) 91.82
BuOH/H2Oa (0.247, 0.753)d 92.8 (0.2458,0.7542) 92.85
AmOH/AmAc/H2Oa (0.046, 0.107, 0.847)e 94.9 (0.0418, 0.1352, 0.823) 94.76
AmAc/H2Oa (0.166,0.834)f 95.2 (0.1696, 0.8304) 94.9
AmOH/H2Oa (0.146,0.854)g 95.8 (0.1471, 0.8529) 96
H2O 1 100.02 1 100.02
BuOH/BuAc (0.773, 0.227)h 117 (0.7614, 0.2386) 117.01
BuOH 1 117.68 1 117.68
HAc 1 118.01 1 118.01
HAc/BuOH/BuAc (0.4283, 0.4754, 0.0963) 122.43
HAc/BuOH (0.404, 0.596)I 122.6 (0.4174, 0.5826) 122.48
BuAc 1 126.01 1 126.01
AmOH 1 137.68 1 137.68
AmAc 1 147.71 1 147.71
a
Heterogeneous azeotrope. b Gmehling et al.18 part II, p 863. c Gmehling et al.18 part I, p 96. d Gmehling et al.18 part I, p 80-81. e Gmehling et al.18
part II, p 867. f Gmehling et al.18 part I, p 102. g Gmehling et al.18 part I, p 91. h Gmehling et al.18 part I, p 531-532. I Gmehling et al.18 part I, p
291-292.
obtained at the bottoms of the two RD columns and H2O is not be economical due to the requirement of more columns. The
emitted from the outlet at the top of the decanter. results of Tang et al.7 provide an optimal design of BuAc and
According to the boiling point and azeotrope information AmAc RD processes for pure BuOH and AmOH. Therefore,
presented in Table 2, the BuOH and AmOH mixed alcohols feed determining the optimal design of the first distillation column is
stream does not contain any azeotropes. This means that this the only additional finding required.
“separation first” process flowsheet can be used because the BuOH This study makes several assumptions in the following simula-
and AmOH can be easily separated by a distillation column. Notice tion: The mixed alcohols feed stream (BuOH/AmOH) is set to
that if the mixed reactants contain an azeotrope, this design would equal molar, and the total flow rate is 100 kmol/h. The feed stream
7194 Ind. Eng. Chem. Res., Vol. 48, No. 15, 2009

of pure reactant HAc is also set at a 100 kmol/h flow rate. The
decanter temperature is set at 40 °C. Product specifications are set
as follows: xBuAc ) 99 mol %; xAmAc ) 99 mol %; and the xHAc in
the BuAc product stream must be less than 50 ppm. The tray weir
height of the distillation column is set to be 0.0508 m.
TAC calculations for optimal system design are based on
information provided by Douglas:25
Table 3. Reaction Kinetics of BuOH/AmOH Mixture Systema
(1) BuAc (Pseudo-homogeneous Model)
TAC ) operating cost + (capital cost/payback period)
(2)
The operating cost includes the costs of heating and cooling
water, and the capital cost includes the costs of the columns,
trays, reboilers, and condensers. The payback period is assumed
to be three years, and the wastewater treatment cost is assumed
to be negligible in the overall TAC.
forward reaction rate
constant (T ) 402 K) Keq (T ) 402 K)

r ) mcat(k1aHAcaBuOH - k2aBuAcaH2O) k1 ) 2.23 × 10-3 [kmol/(kgcat · s)] 9.75

k1 ) 3.3856 × 106 exp(-70660/RT),

k2 ) 1.0135 × 106 exp(-74241.7/RT)
(2) AmAc (Quasi-homogeneous Model)

r ) mcat(k3CHAcCBuOH - k4CBuAcCH2O) k3 ) 5.9 × 10-6 [m3/(kmol · kgcat · s)] 2

k3 ) 31.1667 exp(-51740/RT)
k4 ) 2.2533 exp(-45280/RT)
a
R ) 8.314 (kJ/kmol/K), T (K), r (kmol/s), mcat (kgcat), Ci (kmol/m3cat). (1) Gangadwala et al.2; (2) Lee et al.24

Figure 3. (a) “Separation first” flowsheet; (b1) “direct-sequence”; and (b2) “indirect-sequence” of “reaction first” flowsheet.

There are two design variables for the distillation column:
total number of stages and feed tray location. The reflux ratio
and reboiler duty serve as manipulation variables to meet the
BuOH and AmOH specifications at the top and bottom of the
RD columns, respectively. High-purity BuOH and AmOH are
required to use the optimal design proposed by Tang et al.7 for
the remaining two RD columns. Therefore, the BuOH and
AmOH purity levels must be 99.98 mol % at the top and bottom
of the RD columns, respectively. The optimization procedure
for the distillation column can be described as follows:
1. Guess a total number of stages (NT).
2. Guess the feed tray location (NF).
3. Change the reboiler duty and the reflux ratio until the two
product specifications are met.
4. Go back to step 2 and change the NF until TAC is
minimized.
5. Go back to step 1 and change the NT until TAC is
minimized.
Based on this procedure, the result of NT is 56 stages, and
the minimum TAC point occurs at the NF ) 28th stage (counts
from top to bottom). The values of the reflux ratio and reboiler
duty are 2.63 and 1938.5 kW, respectively. The minimum TAC
of this distillation is $588.1 ($1000/year). Upon combining the
results of the other two RD columns from Tang et al.,7 the
energy consumption of the overall “separation first” process is
6677.7 kW and the minimum TAC of the overall process is
$1971.1 ($1000/year).
The “separation first” design contains three columns, includ-
ing one distillation column and two RD columns with decanters.
Therefore, the TAC of the “separation first” design may be
greater than that in the “reaction first” design, which uses only
one RD column with a decanter for process esterification and
one distillation column for product separation. The following
section investigates the “reaction first” design.
3.2. “Reaction First” Design. Before the simulation of the
“reaction first” design can be conducted, two important condi-
tions must be considered. The first consideration is the location
of the feed tray for the mixed alcohols stream in relation to the
HAc feed stream. To increase contact between the reactants in
the reaction zone, the feed tray should generally be located in
such a way that reactants feeding to create counter-current flow
inside the column determined by the boiling points. According
to Table 2, the reactant boiling point is BuOH < HAc < AmOH.
As described by Tang et al.,7 the BuOH and AmOH also have
different feed tray locations in relation to HAc. To reduce the
number of simulations, the “reaction first” design assumes that
the feed tray location of the mixed alcohols is higher than the
HAc. This is because the difference between the AmOH and
HAc boiling points is greater than that between BuOH and HAc.
Under equal molar feed conditions, the boiling point of the
alcohol mixture should be higher than that of HAc.
The second consideration is that there are two types of
configurations in the “reaction first” process flowsheet: “direct-
sequence” and “indirect-sequence”. The RD columns of these
flowsheets are shown in Figure 3, panels b1 and b2. Table 2
clearly shows that the heaviest product, AmAc, can easily be
obtained at the bottom of the RD column, and according to
Figure 4 the lightest product, H2O, can be obtained from the
top of decanter’s aqueous outlet. However the middle-boiling
product, BuAc, has two possible directions to go. In the “direct-
sequence” design, the BuAc is obtained together with the AmAc
at the bottom of the RD column and then an additional
distillation column is used to separate the two esters. In the
“indirect-sequence” design, the organic stream at the top of
Ind. Eng. Chem. Res., Vol. 48, No. 15, 2009 7195
Figure 4. RCM and LLE of BuOH-BuAc-H2O ternary system under 1
atm.
the RD decanter is fed to a subsequent distillation column, and
the BuAc is obtained at the bottom of this distillation column.
3.2.1. “Direct-Sequence” Configuration. Figure 3b1 shows
the configuration of the “direct-sequence” design. Since the RD
column of system characteristics is similar to the type III in
Tang et al.,7 the major concept of this type III system is extended
with an additional distillation column. In this system, both esters
are easily obtained at the bottom of the RD columns. Further-
more, Figure 4 displays a minimum boiling BuOH/BuAc/H2O
azeotrope in the large two-liquid region. In this liquid-liquid
region, one end of the tie-line is directed to the pure water. The
overhead stream of the RD column enters the decanter, and the
organic rich stream is totally refluxed back to the RD column.
The bottom stream enters another distillation column to separate
the two esters. The heaviest component, AmAc, is thus easily
obtained at the bottom of the distillation column and the BuAc
product is obtained at the top of this column.
This study makes several assumptions in the following
simulation: The mixed alcohols feed stream is set to equal molar.
As with the HAc feed stream, the total flow rate of mixed
alcohols feed stream is set at 100 kmol/h. The decanter
temperature is again set at 40 °C. The BuAc and AmAc product
specifications are the same as in the “separation first” design.
However, the constraint of the xHAc content in the BuAc product
being less than 50 ppm is lifted to simplify process design. The
tray weir heights of the RD and distillation columns are set to
be 0.1016 and 0.0508 m, respectively. In this system, the feed
location of the alcohol mixture is assumed to be higher than
that of the HAc feed stream in the reaction zone because the
boiling point of the BuOH-AmOH mixture is greater than that
for HAc.
The seven design variables of this case are the stage numbers
of the reactive zone (Nrxn), the rectifying stage numbers of RD
(NR), the stripping stage numbers of RD (NS), the HAc feed
location (NFHAc), the mixed alcohols feed location (NFOH), the
total stage numbers of the distillation column (NT), and the
feed location (NF) in the distillation column. Three manipulating
variables, which include reboiler duty of both columns and the
reflux ratio of the distillation column, can be used to meet
product specifications.
Note that there are two product specifications, but three
manipulation variables. The additional manipulation variable
7196 Ind. Eng. Chem. Res., Vol. 48, No. 15, 2009
Figure 5. Optimal results of “direct-sequence” configuration.
is usually used for optimization. However, if the HAc composi-
tion of the RD bottom stream is greater than 0.3 mol %, the
reactant residue affects product purity levels, and product
specifications cannot be met in the following distillation column.
Therefore, the RD reboiler duty is used to meet the HAc
composition requirement of 0.3 mol % at the bottom of the RD
columns. Then the reflux ratio and reboiler duty of the
distillation column are used to meet the BuAc and AmAc
specifications, respectively. The catalyst cost is added to the
TAC objective function:
TAC ) catalyst cost + operating cost +
(capital cost/payback period) (3)
The detailed calculation of individual terms in the TAC can
be found in Appendix B of the Supporting Information.
The optimization procedure is described in the following
steps:
1. Guess Nrxn.
2. Guess NR and NS.
3. Guess NFHAc and NFOH.
4. Guess NT and NF.
5. Change the RD reboiler duty to meet the RD bottom HAc
requirement of less than 0.3 mol % and change the reflux
ratio and reboiler duty of the distillation column until the
product specifications are met.
6. Go back to step 4 and change NT and NF until the TAC
is minimized.
7. Go back to step 3 and change NFHAc and NFOH until the
TAC is minimized.
8. Go back to step 2 and change NR and NS until the TAC is
minimized.
9. Go back to step 1 and vary Nrxn until the TAC is
minimized.
Figure 5 and Table 4 show the optimal results of the direct-
sequence configuration after completing the steps above. Figure
5 shows that the Nrxn is 27 stages, the NS is 90 stages in the RD
column, and the reactant feed tray locations NFOH and NFHAc
are on the first and fifth stages in the upper section of the RD
column. These results are very similar to the results for the single
Table 4. Optimal TAC and Overall Reboiler Duties of Each Case
reaction first
separation direct-sequence indirect-sequence:
case first (ignore HAc spec.) aqueous reflux
Qr (kW) 6677.7 6010.4 4616.5
Qr saving 10% 31%
capital cost ($1000/year) 1244.0 1505.5 945.8
operating cost ($1000/year) 727.1 781.2 597.9
TAC ($1000/year) 1971.1 2286.7 1543.7
TAC saving -16% 22%
BuAc or AmAc RD system. The total number of stages and
the feed tray location in the distillation column are 43 stages
and the 24th stage.
There is no need for NR in the RD column because of the
large liquid-liquid envelop (LLE) region at the top of the de-
canter, and further, because the organic phase stream of the
decanter is totally refluxed. The overhead composition can easily
fall into the LLE region, and almost pure H2O is obtained from
the aqueous phase stream of the decanter because one end of
the tie line is near the pure water corner. One problem with
this design flowsheet is that it requires a very large NS, as Figure
5 indicates. According to Figure 6, the temperature and
composition profiles display only slight changes in the stripping
section. Figure 6b clearly shows that more NS is required because
the HAc composition decreases very slowly. This can be
explained by the closeness of the boiling point temperature
between HAc and BuAc in Table 2. Figure 7 displays the
reaction rate profiles in the RD column, showing that the
reaction rate profile for BuAc is sharper and narrower than for
AmAc. This means that the BuAc reaction is faster in these
two competing reactions.
Table 4 shows that the overall reboiler duty is 6010.4 kW,
which represents an energy savings of almost 10% compared
with the “separation first” design. However, the total TAC is
$2286.7 ($1000/yr), which is 16% more than the “separation
first” design. This is because there are too many stages in the
RD column, which effectively negates the advantage of reduced
energy consumption. This design has another weak point in that
the HAc specifications for the BuAc product stream are not
included. Figure 6(b) shows that the BuAc composition in the
 Ind. Eng. Chem. Res., Vol. 48, No. 15, 2009 7197

Figure 6. RD (a) temperature and (b) composition profiles of “direct-sequence” configuration.

stripping section of the RD column initially increases, but then

decreases when approaching the bottom of the RD columns.
This unwanted remixing effect at the bottom of the RD columns
also makes the “direct-sequence” configuration not competitive
with other design alternatives. The following section considers
another type of configuration, the “indirect-sequence” design.
3.2.2. “Indirect-Sequence” Configuration with Aqueous
Reflux. Figure 3b2 shows another possible configuration, the
“indirect-sequence” design. Unlike the “direct-sequence” con-
figuration, where two esters accumulate at the bottom of the
RD columns, the “indirect-sequence” configuration only collects
the heaviest product, AmAc, at this location. The other product,
BuAc, is obtained at the bottom of another distillation column,
which is fed by the organic stream from the top of the first RD
decanter.
The configuration of partial organic reflux can be found in
the design of the esterification RD process7,26 where both
organic and aqueous products are drawn out from the RD
system. The purpose of the organic reflux is to put ester back
Figure 7. BuAc and AmAc reaction rate of “direct-sequence” configura- into the RD column, forcing water to the top by forming the
tion. ternary minimum boiling azeotrope of alcohol-ester-water.
7198 Ind. Eng. Chem. Res., Vol. 48, No. 15, 2009
Figure 8. Distillation column mass balance line of “indirect-sequence” configuration.
Typical applications include the ethyl acetate and isopropyl
acetate RD processes, which comprise type II RD systems in
Tang et al.7
In this paper, we demonstrate a similar column configuration
but with different reflux policy of the RD system with a
decanter. In this proposed design, we need to force BuAc to go
out from the top of the RD column. Thus, putting this
component back into the RD column (as organic reflux) does
not make any sense. Instead, this study proposes a novel design
configuration shown in Figure 3b2. In this design configuration,
the role of water (considered to be a light component) is to
extract the heavy component, BuAc, to the top of the RD column
by forming a ternary BuOH-BuAc-H2O minimum-boiling
azeotrope. In other words, this study proposes a design
configuration of aqueous reflux with no organic reflux. Figure
8 shows that pure BuAc can be obtained from the bottom of
the second distillation column. The top composition of this
distillation column does not fall into the LLE region. Thus, an
obvious choice for the overhead recycle stream is to put it back
to the RD column, and not the decanter. Figure 3b2 depicts the
overall design concept.
For a fair comparison with the “separation first” design, the
optimal design of this proposed “aqueous reflux” design must
also require the impurity specification of acetic acid to be less
than 50 ppm. However, this specification cannot be met at the
bottom of the distillation column with an equal molar mixed
alcohols feed. This is because from Figure 1b the HAc and
BuAc, although form no azeotrope, are hard to separate due to
the xy line very close to the 45° line at the pure BuAc end.
Therefore, to make the bottom of the distillation column meet
the HAc purity requirement of 50 ppm, the HAc in the RD
column must be almost entirely reacted. This means that the
decanter’s organic phase should contain only very small amounts
of HAc when entering the distillation column. To achieve this
purpose, a tiny feeding excess of alcohol must be added.
Additional tiny amounts of BuOH can increase the HAc
conversion rate and meet the HAc specifications. Figure 9
displays different excess BuOH feed flow rates under the
preliminary results of the simulation. Results show that a small
excess of BuOH in the feed stream (50.3 kmol/h) produces the
minimum TAC which also meets all product specifications. Even
with this feed condition, however, there are still 10 design
variables which need to be optimized. Compared with the
“direct-sequence” design, additional design variables include
the recycle stream feed location from the overhead of the
distillation column (NFRecycle), the aqueous reflux split ratio (SR),
and the distillation column reflux ratio (RR). These 10 design
variables include two continuous variables of SR and RR. To
simplify the optimization step, SR and RR intervals of 0.01 and
0.5, respectively, are used to find the optimization results. The
AmAc purity requirement is set to 99 mol % at the bottom of
the RD columns by varying the RD reboiler duty. The
specifications for the bottoms of the distillation columns are
set at BuAc g 99 mol % and HAc ) 50 ppm. This is because
simply varying the distillation bottom flow rate can produce a
BuAc composition greater than 99 mol %, with a HAc
composition of 50 ppm. Notice that the reboiler duty of this
column was not used as a manipulation variable to avoid the
convergence problem in the simulation.
The optimization procedure of indirect-sequence is shown
in the following steps:
1. Guess NR.
2. Guess SR.
3. Guess NFRecycle.
4. Guess NFHAc and NFOH.
5. Guess Nrxn and NS.
6. Guess NT and NF.
7. Guess RR.
8. Change the RD reboiler duty to meet the RD bottom
AmAc requirement of 99 mol %. Change the bottom flow
rate of the distillation column until the HAc specification
and BuAc product purity requirements are met.
9. Go back to (7) and change RR until the TAC is
minimized.
10. Go back to (6) and change NT and NF until the TAC is
minimized.

Figure 9. Optimal feed stream amount of BuOH excess.
Figure 10. Optimal results of “indirect-sequence” with aqueous reflux configuration.
11. Go back to (5) and change Nrxn and NS until the TAC is
minimized.
12. Go back to (4) and change NFHAc and NFOH until the
TAC is minimized.
13. Go back to (3) and change NFRecycle until the TAC is
minimized.
14. Go back to (2) and change SR until the TAC is
minimized.
15. Go back to (1) and change NR until the TAC is
minimized.
Figure 10 shows the optimal results of the indirect-sequence
design after running the optimization procedure. This figure
shows that the minimum TAC occurs when NR is equal to 26
stages. Clearly, the rectifying section stages in the direct- and
indirect-sequence configurations are very different. For the
Ind. Eng. Chem. Res., Vol. 48, No. 15, 2009 7199
direct-sequence configuration, only water needs to be separated
out at the top of the RD column. This can easily be achieved
by a decanter due to a larger LLE region, thus fewer rectifying
section stages are required. In the indirect-sequence design, both
water and BuAc must be drawn out from the top of the RD
column. The HAc impurity in the organic phase of the decanter
would accumulate at the bottom of the distillation columns, thus
messing up the HAc specification in the BuAc product stream.
As a result, more rectifying section stages would be required
to force HAc back into the RD column.
Figure 10 also shows that the total number of stages in the
distillation column is much less than in the direct-sequence
configuration. This is because the distillation column in the
indirect-sequence configuration does not separate esters with
similar boiling points. As a result, only 21 stages are required
7200 Ind. Eng. Chem. Res., Vol. 48, No. 15, 2009
Figure 11. RD (a) temperature and (b) composition profiles of “indirect-sequence” with aqueous reflux configuration.
for the feed location at the sixth stage. The conceptual design
of the second column in Figure 8 shows that it is better to bring
the top composition of the distillation column close to the
distillation boundary so that less BuAc component will be
recycled back to the RD column. However, as this composition
approaches the distillation boundary by increasing the reflux
ratio, the reboiler duty increases also. As a result, the best reflux
ratio is 2.5 to achieve the minimum TAC.
Figure 11 shows the temperature and composition profiles
of the RD column. Compared with Figure 6a, these shape and
temperature range profiles are quite different. For the indirect-
sequence configuration, there is an obvious temperature break
at the 26th stage, and the temperature range is wider than the
direct-sequence configuration. Composition profiles reveal two
phenomena in the RD column. Compared with direct-sequence
configuration, the remixing effect disappears toward the bottom
of the RD column in this design. The other phenomenon is that
double peaks of HAc composition appear at the 25th and 47th
stages. The high HAc peak at the 25th stage is caused by larger
stages of the rectifying section suppressing the HAc composition
in the top of the RD column, which forces the heavier HAc
down to the end of this section. Below this 25th stage, the HAc
reacts with the recycle stream, which contains rich BuOH
component. As a result, the HAc composition decreases after
this stage. The reaction rate profiles in Figure 12 also show
that BuAc esterification exhibits two higher peaks near the
recycle stream and the mixed alcohols feed locations.
Table 4 shows that the indirect-sequence of the “reaction first”
design is better than the “separation first” design. The overall
savings of the reboiler duty and TAC are 31% and 22%,
respectively, in comparison with the “separation first” design.
For the mixed BuOH and AmOH esterification system, the
“indirect-sequence” with aqueous reflux is a better process
configuration than the “direct-sequence” configuration.
4. Effects of Reaction Kinetics on Relative Feed Tray
Location
Another interesting issue is the relative feed location of the
reactants. The mixed alcohols esterification system can be

Figure 12. BuAc and AmAc reaction rate of “indirect-sequence” with
aqueous reflux configuration.
classified into two categories based on a ranking of the reactant
boiling points. One is called “in series,” which means that the
boiling points of both alcohols are higher or lower than HAc.
The feed locations for this design are easy to determine by
feeding heavier reactants at higher stages and lighter reactants
at lower stages. This forms a counter-current flow that increases
contact between the reactants. However, this heuristic method
Table 5. Reaction Kinetics of BuOH/AmOH Mixture System with Equilibrium Constant Exchangea
(1) BuAc (Pseudo-homogeneous Model)
Ind. Eng. Chem. Res., Vol. 48, No. 15, 2009 7201
experiences difficulty when the HAc boiling point lies between
that of the two alcohol reactants. This condition is always
advantageous to one alcohol but disadvantageous to the other
alcohol, no matter which relative feed location is chosen.
Furthermore, there are still two competitive reactions in the
system. Reaction kinetic effects should be considered in
determining the relative feed location of the system. One
conjecture is that the relative feed location should be determined
by the esterification reaction with the lower reaction rate to
promote this weaker reaction. Another conjecture is to calculate
the boiling point of the mixed alcohols to determine the relative
feed location of reactants. However, the boiling point of the
mixed alcohols is always influenced by the ratio of the mixed
alcohols. If we can understand which factors have the greatest
effect on the relative feed locations of the reactants in alternating
system, the half of the optimization steps can be saved.
The previous section uses the boiling point of mixed alcohols
to determine the relative feed location of the two reactants.
Because the BuOH boiling point is very close to the HAc boiling
point in the BuOH/AmOH mixing system, the feed location of
the mixed alcohols was placed above HAc at equal molar
BuOH/AmOH ratio. If the other conjecture was used, the feed
location of the mixed alcohols should be determined by the
weaker reaction. Table 3 shows that the reaction rate constant
cannot be compared due to different units. However, the reaction
equilibrium constant of AmOH esterification is smaller than that
for BuOH (4.875 times smaller at 402 K). Because AmOH has
a higher boiling point than HAc, the mixed alcohols feed
location should be advantageously placed above the HAc feed
forward reaction rate
constant (T ) 402 K) Keq (T ) 402 K)

r ) mcat(k1aHAcaBuOH - k2aBuAcaH2O) k1 ) 2.23 × 10-3 [kmol/(kgcat · s)] 2

k1 ) 3.3856 × 106 exp(-70660/RT),

k2 ) 4.9432 × 106 exp(-74241.7/RT)
(2) AmAc (Quasi-homogeneous Model)

r ) mcat(k3CHAcCBuOH - k4CBuAcCH2O) k3 ) 5.9 × 10-6 [m3/(kmol · kgcat · s)] 9.75

k3 ) 31.1667 exp(-51740/RT)
k4 ) 0.46267 exp(-45280/RT)
a
R ) 8.314 (kJ/kmol/K), T (K), r (kmol/s), mcat (kgcat), Ci (kmol/m3cat).

Table 6. Reaction Kinetics of BuOH/AmOH Mixture System with Reaction Rate Constant Changea
forward reaction rate
constant (T ) 402 K) Keq (T ) 402 K)
(1) BuAc (Pseudo-homogeneous Model)

r ) mcat(k1aHAcaBuOH - k2aBuAcaH2O) k1 ) 2.23 × 10-4 [kmol/(kgcat · s)] 9.75

k1 ) 3.3856 × 105 exp(-70660/RT),

k2 ) 1.0135 × 105 exp(-74241.7/RT)
(2) AmAc (Quasi-homogeneous Model)

r ) mcat(k3CHAcCBuOH - k4CBuAcCH2O) k3 ) 5.9 × 10-5 [m3/(kmol · kgcat · s)] 2

k3 ) 311.667 exp(-51740/RT)
k4 ) 22.533 exp(-45280/RT)
a
R ) 8.314 (kJ/kmol/K), T (K), r (kmol/s), mcat (kgcat), Ci (kmol/m3cat)
7202 Ind. Eng. Chem. Res., Vol. 48, No. 15, 2009
Table 7. Results of Relative Feed Locations Comparison at Each Reaction Kinetic Condition
location. It is hard to determine whether or not reaction kinetics
will affect the relative feed location or the ranking of the mixed
alcohols versus HAc. For this reason, the equilibrium constants
and reaction rate constants are modified to observe the effects
of relative feed location under the optimal condition of minimum
TAC.
The following simulations are based on the “indirect-
sequence” configuration with aqueous reflux. The HAc
specification is released in the BuAc product stream to make
the product specifications of AmAc and BuAc the same (both
are set at 99 mol %). Three cases are simulated using original
kinetics, a hypothetical case with the equilibrium constant
Keq changed and another hypothetical case with the reaction
rate constant k changed. Table 5 shows how to change Keq
by adjusting the pre-exponential factor. Table 6 displays a
new k under the fixing Keq by a decreasing of 10 times of
the k1 and k2 pre-exponential factors of the BuAc reaction
and also bu an increasing of 10 times of the k3 and k4 pre-
exponential factors of the AmAc reaction. Based on the
optimization procedure of the “indirect-sequence” configu-
ration with aqueous reflux, Table 7 shows the overall results
with different kinetics. Figure 13 displays the reaction rate
profiles of these three cases. Under original kinetic conditions,
the mixed alcohols feed location is more advantageously
placed above the HAc regardless of the reason of boiling
point ranking or equilibrium constant. The first row of Table
7 also reflects the results. If the correct relative feed location
is given, the TAC and Qr can decrease 12% and 15%,
respectively. The second row of Table 7 displays the
condition of Keq changed. Basing the relative feed location
on a comparison of the equilibrium constants increases the
TAC and Qr. This result shows that a comparison of the
equilibrium constants should not be used as the judgment of
the relative feed location. The third row of Table 7 shows
that the decision of the relative feed location should be altered
when the k1 and k2 pre-exponential factors of the BuAc
reaction decrease 10 times and the k3 and k4 pre-exponential
factors of the AmAc reaction increase 10 times. However,
the TAC and Qr are almost the same even if the relative
feed location is set wrong.
Comparing the reaction rate profiles of the best relative
feed location in these three cases clearly reveals that the
reaction rate profiles of BuAc and AmAc are similar for the
original kinetics and Keq changed cases. However, Figure 13c
shows that the reaction rate profiles are quite different than
the profiles in Figure 13 panels a and b. This reflects that
the relative reaction rates of the two BuAc and AmAc
reactions are changed in comparison with the original kinetic
case. The above observations of Figure 13 and Table 7 imply
that the equilibrium constant is not a major factor affecting
the relative feed location. The relative feed location is more
significantly affected by the reaction rate constant k than the
equilibrium constant Keq.
Another result shown in Table 7 is that the saving of the
TAC or Qr depends on both the reason of boiling point ranking
and the relative reaction rates of the two reactions. When the
two reasons all indicate the same relative feed location as in
the original kinetic case, if the relative feed location is guessed
wrong, the TAC and Qr will increase significantly. However,
 Ind. Eng. Chem. Res., Vol. 48, No. 15, 2009 7203
5. Conclusion
This study presents a feasible design for the esterification of
BuOH and AmOH mixtures with HAc, and also finds the rules
of relative feed location for an alternating system. Three design
configurations are explored in this work: one “separation first”
design and two “reaction-first” designs. The best choice between
these different configurations is based on TAC savings and
energy consumption. Comparing these three cases shows that
esterification by RD column directly in conjunction with the
“indirect-sequence” design with aqueous reflux is the best
configuration. Compared with “separation first” design, this
configuration can eliminate one RD column. This configuration
can also avoid the remixing effect toward the bottom of the
RD columns compared with “direct-sequence” configuration.
The heaviest product, AmAc, is obtained at the bottom of the
RD columns and the RD overhead is fed to a decanter for water
separation. Part of the aqueous phase is refluxed back to the
RD column for extracting more BuAc to the top of this column.
Organic phase material is fed to another distillation column to
further purify the BuAc product at the bottom of this column.
This proposed design can save 31% reboiler duty and reduce
the TAC by 22% compared with the “separation first” design.
Because the boiling point of the acid in this system lies
between the two mixed alcohols (BuOH < HAc < AmOH), the
relative feed location of this alternating system is also an
important issue in this study. Reaction kinetics and equilibrium
constants are changed to verify some conjectures. Results show
that the boiling point of mixed alcohols and a comparison of
the two reaction rate constants are the most important factors
to be considered in determining the relative feed location of
this alternating system.

Acknowledgment
This work is supported by the National Science Council of
ROC under Grant No. NSC 95-2221-E-002-379-MY3.

Supporting Information Available: Vapor pressure model;

TAC calculation. This material is available free of charge via
the Internet at http://pubs.acs.org.

Nomenclature
AmAc ) amyl acetate
AmOH ) n-amyl alcohol
BuAc ) butyl acetate
BuOH ) n-butanol
HAc ) acetic acid
Keq ) equilibrium constant
ki ) reaction rate constant (i ) 1, 2, 3, 4)
LLE ) liquid-liquid envelope
NT ) total number of stages
NF ) feed tray location
NFHAc ) the HAc feed location
NFOH ) the mixed alcohols feed location
NFRecycle ) recycle stream feed location
Nrxn ) stage numbers of the reactive zone
Figure 13. BuAc and AmAc reaction rate of (a) original kinetics, (b) NR ) rectifying stage numbers of RD
equilibrium constant exchanged, and (c) changing of the reaction rate NS ) stripping stage numbers of RD
constant. Qr ) reboiler duty (kW)
r ) reaction rate (kmol/s)
RCM ) residual curve map
if the boiling point ranking and the reaction kinetics contrarily RD ) reactive distillation
indicate the relative feed location, either locations offer similar RR ) distillation column reflux ratio
TAC or Qr. SR ) aqueous reflux split ratio
7204 Ind. Eng. Chem. Res., Vol. 48, No. 15, 2009
TAC ) total annual cost
xi ) component i mole fraction (i ) HAc, BuOH, AmOH, BuAc,
AmAc, H2O)
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ReceiVed for reView December 9, 2008
ReVised manuscript receiVed June 1, 2009
Accepted June 12, 2009
IE801891Q