Professional Documents
Culture Documents
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
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 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. The ion-exchanged NH
4
ZSM-5 was
calcined at 550
C. The
products were cooled to 5
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
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
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
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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