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Applied Catalysis A: General 257 (2004) 3342

An efcient two-phase reaction of ethyl acetate production in


modied ZSM-5 zeolites
Kuo-Ching Wu, Yu-Wen Chen

Department of Chemical Engineering, National Central University, Chungli 32504, Taiwan, ROC
Received 4 March 2003; received in revised form 3 July 2003; accepted 18 July 2003
Abstract
Most of the commercial processes for ethyl acetate (EAc) production are via liquid-phase esterication. Owing to the thermodynamic
limitations, the overall yields of EAc are conned to 67% with equimolar reactant feeds of acetic acid and ethanol. The reactions were
conducted at 363400 K, with molar ratio of ethanol/acetic acid = 1.5 and with LHSV = 1 h
1
. One of the critical parameters in this novel
EAc synthesis process is the reaction (esterication) temperature. It was kept between the liquid- and gas-phase operation regimes at which
some parts of the reacting composition were vaporized. The major consideration is based on the equilibrium constants in the gas-phase
reaction, which are higher than those in the liquid phase. The initial reaction stage in the liquid phase has the advantage of smaller reactor size
and more efcient contacting with the catalysts. As the equilibrium had been achieved in the nal gas phase, a higher conversion of ethanol
was obtained due to the equilibriumconstant constraints. Consequently, both the equilibriumconversion constraint for the liquid-phase regime
and the larger reactor volume requirement for the gas-phase reaction has been overcome. In this study, the one-pass ethanol conversion was
successfully improved from 67 to 85 mol%. In addition, the solid acid catalysts used in this novel process have low impact to the environment
and cause no corrosion to the reactor wall. These catalysts had continued performance for 2200 h. Evaluation also shows that half of the
process water and one-third of the consumption of purication steam can be saved.
2003 Elsevier B.V. All rights reserved.
Keywords: Ethyl acetate; Catalyst process; Thermodynamic simulation; Esterication
1. Introduction
Ethyl acetate (EAc) is an important raw material for many
applications in chemical industry including coatings, adhe-
sives, perfumes, and plasticizers. There are four major com-
mercial processes for EAc production [1]: (1) Tishchenko
process: EAc is synthesized from acetaldehydes by the con-
densation of an oxidation-reduction process, which is cat-
alyzed by aluminum alkoxide [2]. (2) Direct esterication:
ethanol and acetic acid are esteried by the catalysis of acids
(or solid acids) [3]. (3) Liquid-phase oxidation of n-butane,
EAc is produced as the by-products while Co/Mn salts are
used as the catalysts. (4) Copolymerization of polyvinyl
acetate and n-butyraldehyde [4,5]. Recently, two brand-new
EA processes have evolved: (1) direct esterication of ethy-
lene and acetic acid in the gas phase on heteropolyacids cat-
alyst [4,5]; (2) one-step liquid-phase esterication process

Corresponding author. Fax: +886-3-425-2296.


E-mail address: ywchen@cc.ncu.edu.tw (Y.-W. Chen).
over coppered-based catalysts, developed by Kvaermer
Technology Ltd. [6].
Traditional liquid-phase esterication processes were
challenged by two problems: (1) the severe corrosion caused
by sulfuric acid/4-methylbenzenesulfonic acid to the reactor
vessel; and (2) the difculty and pollutions in the separation
of products from spent acid catalysts. Moreover, in order to
improve the equilibrium conversion of acetic acid accord-
ing to the reversible reaction mechanism, an excess amount
of alcohol had to be added by simultaneous removal of the
esterication products. Although cationic exchange resins
can improve both of these problems, this catalyst has poor
heat resistance that deactivates a lot as the reaction pro-
ceeds [7,8]. Hence the overall activities of these catalysts
are far less than those of sulfuric acids. Besides, it is dif-
cult to remove the reacting products in the reactor to shift
equilibrium, the products have to be removed outside the
reactor and reux the unreacted feed to the system. There-
fore, it is still an inefcient way to increase the yield of
EAc.
0926-860X/$ see front matter 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2003.07.014
34 K.-C. Wu, Y.-W. Chen / Applied Catalysis A: General 257 (2004) 3342
Nomenclature
C
A
concentration of component A
EAc ethyl acetate
f
i
fugacity of component i
f
v
i
the vapor-phase fugacity of component i
f
l
i
the liquid-phase fugacity of component i
f
0l
i
the standard fugacity of component i
K
eq
equilibrium constant for chemical reaction
P pressure
R gas law constant
T absolute temperature
V volume
v
i
the stoichiometric number of component i
x
i
liquid mol fraction of component i
y
i
liquid mol fraction of component i

i
the liquid-phase activity coefcient of
component i

i
the chemical potential of component i.

v
i
the vapor-phase fugacity coefcient of
component i
Superscript
l liquid phase
v vapor phase
For gas-phase esterication processes, both the reactants
and the products are always kept in the gas phase [9]. While
the use of inorganic catalysts which have good heat resis-
tance and are easy for separation is common in such sys-
tems, they are still suffering from the bulky reactor volume
with costly capital investment. In addition, the elevated re-
action temperature of the gas-phase system is usually dete-
riorated by unexpected by-products. In some circumstances,
the overshot temperature will dehydrate the alcohol to ether.
Moreover, carbonaceous deposits will block the active sites
and deactivate the catalysts; these in turn inuence the op-
eration of the whole process.
Recently, topics of catalytic distillation of sulfuric acid for
the EAc production process has been discussed extensively
[10]. While the ethanol cannot be completely reacted in the
distillation tower, it still needs another two sets of distillation
towers for purication. Accordingly, the catalytic distillation
still cannot replace the traditional processes to decrease the
number of distillation tower and reduce the capital/operation
cost.
Studies of the clean production of esterication pro-
cess over solid catalysts are numerous, including silica gel
[1114], zirconium based materials [1517], metal oxides
[18,19], zeolites [2022], resins [9,23], and solid superacids
[24]. The high temperature limit of these systems is con-
ned to 85

C; they are apparently less active than their


homogeneous counterparts (sulfuric acid, etc.) and are from
being far to be commercialized.
For efcient esterication of EAc process over solid cat-
alysts, it is important to increase the reaction temperature
to over 100

C. Under such reaction conditions, parts of the


reaction system are vaporized. As revealed in some reports
[25,26], the authors have proved that, under certain circum-
stance, the one-pass yield in the gas phase is higher than
that in the liquid-phase system. A patent [25] reveals a novel
esterication process with xed-bed reactor and solid acid
catalysts, under conditions of (i) two-phase reaction system
and (ii) at least one reactant remaining in one phase while
at least one product remains in the alternative phase. In the
patent [26], novel catalytic distillation processes substan-
tially decreased the altitude of distillation tower and energy
consumption.
Here, a thorough study of the highly efcient esterication
of ethanol and acetic acid was conducted. The critical pa-
rameters were investigated by experiment are mathematical
simulation. The relationship of esterication efciency with
reaction parameters, such as reaction temperature, space ve-
locity, molar ratio of reaction feed, particle size of catalysts,
and water content of feedstock were elucidated. The results
shows that half of the process water and one-third of puri-
cation steam could be saved as compared to the traditional
esterication processes.
2. Experimental
Acetic acid, ethanol, and ethyl acetate (EP) with a claimed
purity of >99.5% were purchased from Merck. Industrial
feedstock of ethanol (92%, with 8% of water) and acetic
acid (>99%) were supplied by Lee Chenag Yung Chemical
Industry Corporation. Reactions were conducted in an auto-
clave (Parr 4564) and a xed-bed reactor, respectively, over
HZSM-5 zeolite modied with organic acids.
2.1. Catalyst preparation
The HZSM-5 zeolite was prepared according to the ref-
erence [27]. Preparation comprised the following steps:
20 g of aluminum sulfate, Al
2
(SO
4
)
3
18H
2
O were added
to water to form 500 ml aqueous solution. To this solution,
180 ml aqueous solution of 3 g ammonium bromide was
added dropwise. Four hundred and sixty grams of sodium
silicate (water glass) was added, in which the SiO
2
con-
tent is 20 wt.%. Drops of sulfuric acid were used to keep
the pH of these mixtures constant. The nal SiO
2
/Al
2
O
3
molar ratio was 30. The above mixtures were guided
into a 2-l autoclave, heated to 160180

C and reacted
for 24 h. After the reaction was complete, the products
were ltrated and washed, then dried at 120

C overnight
and nally, calcined under 500

C for 12 h. The prepared


product is white crystalline NaZSM-5. The NaZSM-5
thus prepared was further treated with 1 M ammonium
nitrate under 80

C. The ion-exchanged NH
4
ZSM-5 was
calcined at 550

C for 12 h to yield the HZSM-5. The


K.-C. Wu, Y.-W. Chen / Applied Catalysis A: General 257 (2004) 3342 35
products of HZSM-5 were crushed and sieved to the size
of <100 mesh.
2.2. Catalyst modication [28]
An aliquot of 100 ml tartaric acid (0.4 M) was added to
20 g of HZSM-5; this mixture stirred vigorously and aged
for 24 h. The aged products were ltered, then washed with
100 ml of de-ionized water three times. After drying under
120

C overnight, the HZSM-5 was sieved and pulverized


to different sizes as the catalysts for esterication.
2.3. Catalyst characterization
For catalyst characterizations, the specic surface area
was determined by nitrogen adsorption (BET). The sec-
ondary porosity was measured by mercury porosimetry. The
acidity was determined by a temperature-programmed des-
orption (TPD) of ammonia, the sample (0.5 g) was treated in
air at 723 K for 1 h and then cooled to 343 K. Ammonia was
adsorbed at 343 K for 1 h and then swept with helium as a
carrier gas at 40 ml/min until the chromatogram was stable.
The desorption was carried out at a heating rate of 10 K/min.
2.4. The xed-bed reactor
A stainless steel xed-bed reactor (i.d. = 3/8 in.) was
lled with 7 ml of catalyst. The reactants were premixed in
a vessel and then injected volumetrically by LDC analyt-
ical pump (Consta Metric 3200). The reactions were con-
ducted at 363400 K, at molar ratio of ethanol/acetic acid =
13 with LHSV = 0.52 h
1
. The reactor was heated by
an electric heater (West 2050-loop controller). The temper-
ature uctuation of the catalyst bed was within 0.5

C. The
products were cooled to 5

C and collected every hour.


Samples were injected with 0.1 l into a gas chromatograph
(HP-5890) for analysis with a HP-FFAP column (10 m
0.53 mm 1.0 m, sample amount = 0.1 l).
3. Results and discussion
3.1. Catalyst characterization
In this study, the HZSM-5 zeolites, as modied by tar-
taric acid to increase the secondary pore volume and surface
acidity, were used as the catalysts [28,29]. The effects of
tartaric acid on catalysts were characterized and compared
with the results for bare HZSM-5. As shown in Table 1, the
BET surface area of the modied catalyst increased upon
modication. Besides, the surface acidity, as measured by
NH
3
TPD in millimoles per gram, also indicates that the tar-
taric acid treatment has effectively increased the acidity of
HZSM-5. The overall acid amount has increased 30%, from
1.24 to 1.63 mmol/g. The secondary pore site distribution
shown in Fig. 1 was measured by mercury porosimetry. It
Table 1
The properties of HZSM-5 catalyst
Untreated Treated
N
2
physical adsorption
Specic surface area BET (m
2
/g) 378 389
NH
3
TPD
Acidity (mmol/g)
<473 K 0.54 0.54
473673 K 0.49 0.75
673873 K 0.21 0.34
Mercury porosimetry
Pore volume (ml/g)
0.00300.01 m 0.000 0.127
0.010.1 m 0.003 0.295
0.11 m 0.067 0.019
110 m 0.001 0.012
10360 m 0.129 0.238
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0.00 0.01 0.10 1.00 10.00 100.00 1000.00
mean diameter (m)
i
n
c
r
e
m
e
n
t
a
l

v
o
l
u
m
e
(

m
)
Fig. 1. The secondary pore size distribution of the HZSM-5. () Untreated
and () treated with tartaric acid.
shows that the tartaric acid treatment has greatly enlarged
the secondary pores by 10 nm.
The treated and untreated HZSM-5 were used to catalyze
the esterication of ethanol and acetic acid. The results are
compared in Table 2; they show that the conversion of acetic
acid catalyzed by treated HZSM-5 was as high as 95.8%,
while for the untreated catalyst the conversion was only
89.3%. As concluded in the previous discussion, the incre-
ment in surface acidity and cumulative pore volume is ben-
ecial to catalyze the esterication.
3.1.1. The vapor-liquid-phase esterication
The vapor-liquid system is dened as one conducted
at a pressure of 1 atm and a temperature between 393 K
(gas-phase operation) and 353 K (liquid-phase operation) in
Table 2
The effect of modication by tartaric acid
Catalyst HZSM-5 Experimental
Conversion (%) Selectivity (%)
Untreated 89.3 99.2
Treated with tartaric acid 95.8 100.0
Reaction conditions: catalyst, 7 ml; temperature, 383 K; LHSV = 1 h
1
;
ethanol/acetic acid molar ratio = 1.5.
36 K.-C. Wu, Y.-W. Chen / Applied Catalysis A: General 257 (2004) 3342
which two-phase operation is plausible and in equilibrium.
In this case, the condensed phases are not only the liquid
adsorbates (pseudo-liquid phase) over solid catalysts but
also some over-saturated condensates, under which the tra-
ditional equilibrium criteria are not valid. Therefore, a new
equilibrium model is necessary to gure out the real state
of this two-phase system.
Keyes [3] conducted research on simultaneous processes
of reaction and distillation. The combined processes pro-
vide an advantage in saving energy consumption and in-
vestment cost-down, since these two steps are processed
simultaneously in a single unit. In spite of the importance of
the vapor-liquid equilibrium in the design and synthesis of
chemicals, most recent works were restricted on the devel-
opment of algorithms for solving some distillation problems
toward chemical reaction. Hence most of the studies focused
on the inuence of chemical reaction on the vapor-liquid
equilibrium. Harata and Komatsu [30] had measured the
vapor-liquid equilibrium values for the esterication of qua-
ternary system of acetic acidethanolethyl acetatewater.
They showed that the vapor-liquid equilibrium constants
could be correlated to the reaction temperature and the com-
position in the liquid phase at hypothetical conversion form
0 to 100%. Kang et al. [31] studied the esterication sys-
tem of acetic acidethanolethyl acetatewater mixture and
pointed out that both chemical reaction and phase equilib-
rium should be taken into consideration if the liquid-phase
reaction was very fast in the presence of catalysts.
3.1.2. Phase equilibrium with chemical reaction
equilibrium
For vapor-phase (superscript v) and liquid-phase (super-
script l) system at the same temperature and pressure, the
equilibrium relationship for component i is expressed in
terms of the fugacity, f
i
, as:
f
v
i
= f
l
i
, i = 1, 2, . . . , n (1)
Using the fugacity coefcient,

v
i
, and the liquid-phase ac-
tivity coefcient,
i
, one can rewrite Eq. (1) into the follow-
ing relations:

v
i
y
i
P =
i
x
i
f
0l
i
, i = 1, 2, . . . , n (2)
where f
0l
i
is the standard fugacity of pure component i; it
is chosen to be that of the pure liquid of that component at
system temperature and pressure and can be calculated by:
f
0l
i
= P
s
i

s
i
exp

p
p
s
i
V
l
i
RT
dP

Also, in Eq. (2),


v
i
is the fugacity coefcient of i component
in vapor phase and can be calculated from the volumetric
property by:
ln

v
i
=
1
RT

P
0

V
n
i

T,P,n
j=i

RT
P

dP (4)
For a process involving a composition change and occurring
in a closed system, when the reaction reaches equilibrium
at constant temperature and pressure, the constraint will be:
n

i=1

i
= 0 (5)
where
i
and
i
are the stoichiometric number and chemical
potential of component i. One can derive the equation for
chemical potential of component i as:

i
= G
0
i
+ RTln a
i
(6)
By rewriting Eq. (5) becomes
n

i=1

i
=
n

i=1

i
G
0
i
+ RT
n

i=1

i
ln a
i
= 0 (7)
After mathematical manipulations, the chemical equilib-
rium constant, K
a
, can be expressed in term of standard
Gibbs free energy change of reaction as:

i=1

i
G
0
i
RT
=
(G
0
)
RT
=
n

i=1

i
ln a
i
= ln K
a
(8)
The chemical equilibrium constant, K
a
, can be further
expressed by the activity coefcients (
i
) and mole fraction
(x
i
) of reactants and products for a liquid-phase reaction at
a pressure of 1 atm.
a
i
= x
i

i
(9)
K
a
=
n

i
a

i
i
=
n

i
(x
i

i
)

i
(10)
The equilibrium constant for chemical reaction in the liq-
uid phase, K
x
, can be expressed by the mole fraction (x
i
) of
reactants and products for a liquid-phase reaction.
K
x
=
n

i
x

i
i
(11)
The activity coefcients (
i
) in liquid phase are calculated
by the excess Gibbs free energy model of NRTL developed
for consideration of local compositions of the components.
Owing to the existence of water, Non-Random To Liquid
(NRTL) was chosen for the simulation of activity coefcients
since it is the best-tted model for water containing system
[32]. The relationship is expressed as:
ln
1
= x
2
2

21

G
12
x
1
+ x
2
G
21

2
+

12
G
12
(x
2
+ x
1
G
12
)
2

(12)
ln
2
= x
2
1

12

G
12
x
2
+ x
1
G
12

2
+

21
G
21
(x
1
+ x
2
G
21
)
2

(13)
where:

12
=
(g
12
g
22
)
RT
=
A
12
RT
;
21
=
(g
21
g
11
)
RT
=
A
21
RT
K.-C. Wu, Y.-W. Chen / Applied Catalysis A: General 257 (2004) 3342 37
Table 3
The NRTL model parameters of waterethanolacetic acidethyl acetate
i,j
a
A
ij
b
A
ji
b

ij
1,2 306.4428 322.6191 0.2987
1,3 1285.9880 1606.0820 0.4393
1,4 844.2996 436.9443 0.3138
2,3 114.8438 1376.3536 0.2983
2,4 34.1971 190.7763 0.3050
3,4 801.8698 412.4783 1.4905
a
Ethyl acetate (1)ethanol (2)water (3)acetic acid (4).
b
The NRTL model parameters are from DECHEMA handbook.
G
12
= exp(
12

12
); G
21
= exp(
12

21
)
A
12
= g
12
g
22
, A
21
= g
21
g
11
In this study, the vapor-liquid equilibrium parameters in
NRTL model are obtained from DECHEMAs vapor-liquid
equilibrium data collection [33,34]. Some of the parameters,
such as A
ij
, A
ji
, and
ij
for the quaternary systems of acetic
acidethanolethyl acetatewater are listed in Table 3. The
NRTL-Hayden-OConnell was used to elucidate the inu-
ence of association on the vapor-liquid equilibrium and
chemical reaction equilibrium, respectively. Commercial
software Aspen Plus

10.2 was used to do the calculation.


3.1.3. Effect of molar ratio
In homogenous esterication, the variation in molar ratio
of reactants can just alter the equilibrium compositions of
the products and will have no effect in the equilibrium con-
stant. For the esterication conducting in multi-phase sys-
tem, however, the equilibrium compositions of the products
vary according to the variation of reactant compositions. The
equilibrium constants derived by experiments were consti-
tuted for compositions in either phase. Therefore, these val-
ues are quite different from those derived in single phase
theoretically. The extent to which these two values deviated
depends on the difference of activity coefcients of reaction
compositions constituted in each phase. For the esterica-
tion of ethyl acetate, the boiling point of ethanol is far lower
than that of acetic acid. The increment of ethanol molar ra-
tio, which in turn means decreasing the vapor pressure of
acetic acid, favors the gas phase reaction under identical re-
action temperature to obtain higher equilibrium constants.
After increasing the molar ratio of acetic acid, the esteri-
cation temperature must be elevated to sustain the gas phase
reaction. Fig. 2 depicts the gas phase compositions at dif-
ferent reaction temperatures. It shows that as the molar ra-
tio of ethanol/acetic acid increases, the temperature for gas
phase reaction decreases. This favors the gas phase esteri-
cation under identical conditions to obtain higher equilib-
rium constants as well as acetic acid conversion. The results
are shown in Table 4.
3.1.4. The effect of reaction temperature
The reaction temperature is the most important parame-
ter for the gas-liquid esterication. While the boiling point
0
0.2
0.4
0.6
0.8
1
1.2
340 360 380 400 420
Temperature (K)
M
o
l
e

f
r
a
c
t
i
o
n

o
f

v
a
p
o
r
-
p
h
a
s
e
M=1.5 M=1 M=0.67
Fig. 2. The molar fraction of vapor phase vs. molar ratio of EtOH/HOAc
(ethanol/acetic acid) molar ratio (M) = 1.5, 1.0, 0.67.
of acetic acid (391 K) greatly exceeds ethanol (351 K), the
esterication has shifted from liquid phase to gas phase
as the ethanol/acetic acid molar ratio is increased. Some
of the simulations show that the temperature at which the
reaction takes place totally in the gas phase is decreased
as the ethanol/acetic acid molar ratio is increased. For inlet
composition with ethanol/acetic acid = 1.5 in moles, this
temperature should be 353 K; here the largest equilibrium
constant is obtain and a maximum equilibrium conversion
of 97.4% is obtained under this reaction conditions. For the
temperature below 353 K with liquid hour space velocity
(LHSV) equal to 1 h
1
, however, the catalysts (HZSM-5)
used in this study cannot sufce to catalyze the whole
reaction. The equilibrium conversion obtained experimen-
tally declines to 85.3% as the temperature goes down to
367 K; such valves are far lower than those derived by
our simulation. After the reaction temperature is increased
closely to 383 K, the simulation results are coincident with
those obtained by experiments. As the reaction tempera-
ture is above 383 K, the experimental results are identical
to those obtained by simulation. Therefore, the key role
is played by the activity of catalysts. Were the catalysts
not active enough, the compositions at the exit would not
be in equilibrium thermodynamically. Methods to improve
these conditions include elevating the activity of the cat-
alysts and decreasing the inlet ow rate of reactants. The
reactions conducted within 363400 K are compared in
Fig. 3.
Table 4
The effect of molar ratio
Ethanol/acetic acid molar ratio Experimental
Conversion (%) Selectivity (%)
1.0 85.2 99.7
1.5 95.8 100.0
3.0 97.2 99.9
Reaction conditions: catalyst, HZSM-5 (7 ml); temperature, 383 K;
LHSV = 1 h
1
.
38 K.-C. Wu, Y.-W. Chen / Applied Catalysis A: General 257 (2004) 3342
80%
84%
88%
92%
96%
100%
340 360 380 400 420 440
Temperature (K)
C
o
n
v
e
r
s
i
o
n

o
f

a
c
e
t
i
c

a
c
i
d
simulation experiment
Fig. 3. The simulation compared with experiment in vapor-liquid esteri-
cation catalyst: HZSM-5 (7 ml); LHSV = 1 h
1
; ethanol/acetic acid molar
ratio = 1.5.
3.1.5. Effect of liquid hour space velocity
The meaning of liquid hour space velocity (LHSV) for a
xed-bed reactor is similar to that of the reaction time for
a batch reactor. In practice, the reciprocal of LHSV is iden-
tical to the reaction time for a specic chemical reaction.
Another aspect of LHSV is the yield of products per volume
of catalysts per hour. The larger the LHSV, the more prod-
ucts can be derived from a certain reaction. Accordingly,
the large LHSV is desired for the reactor design basis while
the contacting time had to be shortened, which would in
turn, decrease the conversion under certain circumstances.
Table 5 shows the relation of LHSV to the esterication con-
version. For LHSV = 1 h
1
, the conversion of acetic acid
is 95.8%, the yield per liter catalyst per hour is 6.6 mol.
While the LHSV doubled, the conversion of acetic acid is
declined to 90.4%. As the LHSV is decreased to 0.5 h
1
,
the conversion is as high as 96.7%, a value approaches the
theoretically equilibrium value of 96.7. Under this condi-
tion, the yield of products declined to 3.4 mol/l of catalyst
per hour. Therefore, the LHSV has to be optimized within
extremes of ease of separation and production yield. The
LHSV is an important parameter for the xed-bed esteri-
cation. An optimal LHSV is crucial and practical. Hence
we derive the relationship between the LHSV and conver-
sion by combining thermodynamics and experimental results
with a suitable regression approach from which the LHSV is
optimized.
Table 5
The effect of liquid hour space velocity
LHSV
(h
1
)
Space
time (h)
Experimental Productivity
(mol/l h)
Conversion (%) Selectivity (%)
0.5 2.0 96.7 100.0 3.34
0.7 1.5 96.6 100.0 4.47
1.0 1.0 95.8 100.0 6.62
1.4 0.7 93.9 100.0 9.33
2.0 0.5 90.4 100.0 12.66
Reaction conditions: catalyst, HZSM-5 (7 ml); temperature, 383 K;
ethanol/acetic acid molar ratio = 1.5; productivity: ethyl acetate produced
per liter of catalyst in 1 h.
In the above discussion, the reversible reaction mecha-
nisms with secondary order kinetics are assumed for the
esterication. The initial concentrations of acetic acid and
ethanol are designated as C
A0
and C
B0
, respectively, while
the concentration of ethyl acetate and water is zero, initially.
Accordingly, the overall reaction can be described as:
Acetic acid (A) + ethanol (B)
k
1

k
2
EAc (C) + H
2
O(D)
The rate of reaction (r
A
):
(r
A
) =
dC
A
dt
= k
1
C
A
C
B
k
2
C
C
C
D
(14)
Eq. (14) can be rewritten as the following relations:
C
A0
dX
a
dt
= k
1
C
2
A0
(1 X
a
)(M X
a
) k
2
C
2
A0
X
2
a
;
dX
a
dt
= k
1
C
A0

(1 X
a
)(M X
a
)
1
K
eq
X
2
a

(15)
where K
eq
(equilibriumconstant) = k
1
/k
2
M =
C
B0
C
A0
In case the molar ratio of C
A0
/C
B0
= 1.5, i.e. M = 1.5,
the equilibrium constant, K
eq
at 383 K calculated by Gibbs
free energy expression would be 53. To replace it with K
eq
in Eq. (15), we integrate the equation and rearrange it to the
simplied form as follows:
ln

1.581 X
a
0.9669 X
a

0.492 = 0.614k
1
C
A0
t (16)
After introducing the experimental values in Table 5 to
the Eq. (16), we can derive the forward rate expression for
the esterication, as shown in Table 6. The mean forward
reaction rate (k
1
C
A0
) is 6.2 h
1
. Based on this value, the
relation curves for the LHSV and conversion are depicted in
Fig. 4. It shows that, for the LHSV = 1 h
1
, the conversion
can be as high as 95.9% whose value is very close to the
theoretical value: 96.7%. The inuence on the conversion
for LHSV < 1 h
1
is vague, while for LHSV = 2 h
1
the
equilibrium conversion is declined to 90%. As a conclusion,
the optimal LHSV would be 1 under the reaction conditions
described in this study.
Table 6
The forward velocity of reaction
LHSV (h
1
) Space time (h) Conversion (%) k
1
C
A0
(1 h
1
)
0.5 2.0 96.7 6.26
0.7 1.5 96.6 6.19
1.0 1.0 95.8 6.27
1.4 0.7 93.9 6.24
2.0 0.5 90.4 6.23
Reaction conditions: catalyst, HZSM-5 (7 ml); temperature, 383 K;
ethanol/acetic acid molar ratio = 1.5.
K.-C. Wu, Y.-W. Chen / Applied Catalysis A: General 257 (2004) 3342 39
0.5
0.6
0.7
0.8
0.9
1.0
0 1 2 3 4
space velocity (LHSV, 1/hr)
c
o
n
v
e
r
s
i
o
Fig. 4. The effect of space velocity HZSM-5 (7 ml); temperature, 383 K;
ethanol/acetic acid molar ratio = 1.5.
3.1.6. Effect of water content
Since water is one of the major products in the esteri-
cation reaction, the content of water in the feedstock has a
detrimental effect in that it will decrease the conversion. For
the purity (99.5 wt.% or less) of industrial grade ethanol and
acetic acid, there will be 5 wt.% of water content. It will cost
a lot money and energy to increase the purity and simulta-
neously remove the water from the feedstock. Therefore, it
is benecial for one to conduct this reaction under certain
water-containing conditions without inuencing the original
activity. As shown in Table 7, the increase in water content
has a vague effect in lowering the equilibrium conversion.
Under the condition with 5 wt.% of water, the conversion
of acetic acid is as high as 93.4%. As the water content is
increased to 10 wt.%, the conversion of acetic acid is still
sustained to be 91.2%. These values could be taken into con-
sideration as the basis for process design. In fact, that the
industrial grade ethanol and acetic acid whose purities are
95 wt.% or so could be adopted as the feedstock without fur-
ther purication. This would in turn simplify the separation
stages and make the whole process more competitive.
3.1.7. Effect of particle size of catalyst
The contact of reactants with the catalysts in the xed-bed
reactor is important since the particle size of catalysts is cru-
cial for the mass transfer of reactants and nal products. The
smaller the catalyst particles, the smaller the mass transfer
resistance and the better the catalytic effect. As shown in
Table 8, the reactor with a diameter of 3/8 in. (D = 9.52 mm)
was used. The conversions for the reaction conducted over
catalysts with different particle sizes are compared. For
Table 7
The effect of water contained in feedstocks
Water content
(wt.%)
K
eq
(theorem)
Conversion
(simulated)
Experimental
Conversion
(%)
Selectivity
(%)
0.0 53 96.7 95.8 100.0
5.0 52 95.5 93.4 99.5
10.0 52 94.3 91.2 99.3
Reaction conditions: catalyst, HZSM-5 (7 ml); temperature, 383 K;
ethanol/acetic acid molar ratio = 1.5; LHSV = 1 h
1
.
Table 8
The effect of particle size of catalyst
Particle
size(mesh)
Particle
size(mm)
Experimental
Conversion (%) Selectivity (%)
1220 0.510.81 94.9 99.5
2030 0.390.51 95.6 99.5
3040 0.290.39 95.8 100.0
Reaction conditions: catalyst, HZSM-5 (7 ml); temperature, 383 K;
ethanol/acetic acid molar ratio = 1.5; LHSV = 1 h
1
.
catalysts with particle size of 1220 mesh, the conversion
is 94.9%, while for those with particle size of 3040 mesh,
the conversion is 95.8%. The similarity (only 0.9% deviated
from each other) in these two values has shown that there is
no mass transfer limitation in this system. It is noteworthy
that as the particle size of catalysts becomes too small, the
overall pressure drop across the reactor will soar. Besides,
there appears some channeling in the whole system that will
be detrimental to the conversion. Therefore, the optimal
particle size of catalysts should be within 1/101/20 of the
reactor diameter to avoid channeling and soaring of overall
pressure drop across the reactor bed.
3.1.8. Life test for acetic acid esterication in continuous
xed-bed reactor
As shown in the above section, the conversion of acetic
acid for esterication was over 95% when the reaction tem-
perature was 383 K with ethanol/acetic acid molar ratio of
1.5 and LHSV = 1 h
1
in a continuous xed-bed reactor.
After the preliminary investigation of the ZSM-5 catalysts
and process development, a series of bench scale experi-
ments were conducted in the scale-up reactor of 1000 ml
catalyst bed for further conrmation. For the rst 1200 h of
reaction, the feedstock was preheated in advance. The con-
version of acetic acid under this condition could be kept
around 95%. While for the next 1200 h of reaction, the feed-
stock at ambient temperature was directly introduced to the
catalyst bed without preheating. Under such circumstances,
part of the reaction zone functioned as the preheater for the
feedstock. Therefore, the conversion of acetic acid droped to
93%. After 2287 h of reaction, the conversion could be still
kept at 92%, during which the selectivity of ethyl acetate
was always as high as 99%, as shown in Fig. 5.
3.1.9. Process design
The commercial routes for the synthesis of ethyl ac-
etate nowadays are essentially based on the conventional
liquid-phase esterication catalyzed by sulfuric acids. For
these processes under optimal conditions, 2.1 tons of steam
and 1 ton of process water must be consumed per ton of
ethyl acetate produced. Moreover, the serious pollution due
to this waste acid has threatened the environment badly.
In this paper, our novel multi-phases esterication system
design has been described, while the process economics
evaluation has also been cited. All processes include one
40 K.-C. Wu, Y.-W. Chen / Applied Catalysis A: General 257 (2004) 3342
0
10
20
30
40
50
60
70
80
90
100
0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200
Time on stream (h)
C
o
n
v
e
r
s
i
o
n

o
f

a
c
e
t
i
c

a
c
i
d
(
%
)
Fig. 5. Life testing for acetic acid esterication with ethanol catalyst: HZSM-5 4.2 g (7 ml); temperature, 383 K; LHSV = 1 h
1
, ethanol/acetic acid molar
ratio = 1.5. The selectivity of ethyl acetate was always as high as 99%.
Fig. 6. The PFD of the continuous xed-bed reactor for the EAc esterication process. 1: HOAc feed from HOAc tank; 2: EtOH feed from EtOH tank; 3:
esterication product to block C-1; 4: block C-1 top organic phase to wash block C-2; 5: reux, 0.6 organic phase return; 6: block C-1 top water phase
to stripper block C-3; 7: block C-1 bottom HOAc back to reactor; 8: wash water feed from water tank; 9: block C-2 top organic phase to purication
block C-4; 10: block C-2 bottom water phase to stripper block C-3; 11: reux, 0.996 organic phase return; 12: block C-4 top water phase to stripper
block C-3; 13: block C-4 bottom EAc product; 14: block C-4 heavy [design]; 15: reux, molar ratio = 1.80399; 16: block C-3 top organic phase to
reactor; 17: block C-3 bottom water waste. Block C-1 is for acetic acid recycling: to recycle the unreacted acetic acid after esterication stage. Block
C-4 is for EAc purication: to purify distillates of EAc from the diazeotropic system of waterEAc. The product is EAc with 99.9% purity. Block C-3
is for recycling the organics: to recycle the ethanol and EAc in the hydrophilic (water) phase. Block C-2 is for extracting the ethanol from organics: to
destroy three-component azeotropy.
K.-C. Wu, Y.-W. Chen / Applied Catalysis A: General 257 (2004) 3342 41
Table 9
The comparison of commercial technique and this study
Processes Commercial This study
Catalyst Sulfuric acid HZSM-5
Operation unit reactor 1 1
Distillated column 2 2
Extractor 1 1
Stripper 1 1
Steam consumption (ton per ton EAc) 2.10 1.47
Process water consumption
(ton per ton EAc)
1.00 0.59
Waste water (ton per ton EAc) 1.23 0.82
xed-bed reactor, three distillation columns and one water
extraction tower. Some of the results have been discussed
in more detail in the following subsections (Table 9).
There is a three-component azeotropic system (ethanol
ethyl acetatewater) and three two-component azeotropic
systems (ethanolethyl acetate, ethanolwater, ethyl
acetatewater) in the reaction mixtures. Among these, the
three-component system has the lowest boiling point; next
is the ethyl acetatewater system. Since these two systems
has very similar boiling points, they are coexisting in the
top layer of the distillation column. Conventionally, they
are separated after the esterication stage by multi-stage
distillation. Since the ethyl acetate (EAc) in the azeotropic
systems is the major product while ethanol is the reac-
tant, in order to shift the azeotropic composition toward
EAc, the acetic acid has to be in great excess such that
the molar ratio of acetic acid/ethanol = 1.21.3. Accord-
ing to the model presumed in our study, the conversion
of ethanol would be as high as 90%. Besides, the ethanol
residues in the top layer of reactor can be easily removed
via single-stage column distillatory to a overall ethanol
content less than 4% which is far lower than those obtained
in the conventional processes by multi-stage distillation
(9%). The more efcient ethanol separation is benecial
for lowering the consumption of process water used in
the distillation process. Since the adiabatic reactors are
far more economical in energy consumption than those
of isothermal reaction mode in commercial scale, we also
evaluate the possibility of adiabatic operation. In our pre-
liminary study in bench scale reactor, the conversion of
ethanol is 90.6% with EAc selectivity of 99%, the reaction
conditions are: T = 383 K, treated HZSM-5 as catalyst,
loading = 950 g, reactant ow rate = 1032 ml/h, reactant
compositions: acetic acid:ethanol:water = 59.1:37.5:3.4
in wt.%.
The PFD of the continuous xed-bed reactor for the EAc
esterication process is depicted in Fig. 6. The overall pro-
cesses are simulated by commercially viable Aspen Plus

to evaluate the ideal plate numbers of distillation column,


to conduct the mass and energy balance and to calculate the
consumption of raw materials, steam and amount of waste
water per ton of EAc production. The design is based on a
plant that processes 50,000 tons of EAc per year (6250 kg/h)
plant.
1. Reboiler duty: 0.80 MMkcal per ton EAc (steam con-
sumption: 1.47 ton per ton EAc).
2. Process water: 0.59 ton per ton EAc.
3. Waste water: 0.80 ton per ton EAc.
4. Conclusion
Most of the conventional processes of acetic acid esteri-
cation have been conducted in the liquid-phase conditions.
While the limitation of thermodynamic equilibrium has con-
ned the maximum yield for ethyl acetate to not more than
67%, a novel process was developed in this study with
higher yield of ethyl acetate and more efciency in energy
harness.
In this study, the simulation software Aspen Plus

was
used with NRTL-HOC model to simulate the whole reac-
tion in details. Each composition in the reacting system was
allowed to exist in either phase according to the reaction
conditions. As the reaction temperature is lower than the
boiling point of ethyl acetate (351 K), the equilibrium con-
stant is almost constant and is independent of the reaction
temperature. The results are in accord with those experimen-
tal results in the liquid-phase conditions. As the temperature
is higher than the boiling point of acetic acid (391 K), the
experimental results are also in agreement with those obtain
by HK model. Interestingly, at reaction temperature within
351391 K, different phenomena were obtained. In this re-
gion, the highest yield of ethyl acetate was obtained in the
absence of the dilution of N
2
. The highest yield was con-
rmed by carrying out the reaction at a xed-bed reactor.
This new two-phase reaction system can improve the ef-
ciency of the reaction signicantly. When the coexistence
of gas and liquid phases was used, the esterication with
equimolar feeds has one-pass conversion increasing from
67 to 85% in moles while the ethanol concentration in the
products ow decreased from 14 to 6.5 wt.%. The reduction
of ethanol concentration is advantageous for further puri-
cation processes.
A detailed investigation about this two-phase process was
also conducted. It showed that the key role for the whole
process is the reaction temperature. The proper reaction
temperature is that within the temperature ranges for the
traditional gas and liquid-phase system. The liquid-phase
reactants are partially vaporized to the gas phase, in which
a higher conversion for ethanol is obtained. Owing to the
smaller reactor size and larger contacting time with the cat-
alysts, the initial reaction stage is still conducted in the liq-
uid phase, while the nal products exist in the gas phase.
Therefore, the disadvantages for the liquid phase (low equi-
librium yield) and gas phase (larger reactor volume) can
be overcome simultaneously. In addition, the HZSM-5 cata-
lysts have passed the 2200 h of life test. The process evalu-
ation shows that it can save up to 1/3 of steam consumption
for further purication and decrease half of the waste water
generation.
42 K.-C. Wu, Y.-W. Chen / Applied Catalysis A: General 257 (2004) 3342
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