SEPARATION SCIENCE AND ENGINEERING

Chinese Journal of Chemical Engineering, 18(5) 755ü760 (2010)

Coupled Reaction/Distillation Process for Hydrolysis of Methyl Acetate*

ZHAO Suying (䎫㍖㤧)1,**, HUANG Jingzhao (哺䮒䫀)1, WANG Liang’en (⧁㢥᚟)1 and
HUANG Guoqiang (哺ളᕰ)2
1
College of Chemistry and Chemical Engineering, Fuzhou University, Fuzhou 350002, China
2
National Engineering Research Center for Distillation Technology (NERCDT), Tianjin 300072, China

Abstract A process composed of a fixed-bed and a distillation column with a side withdraw, mainly methanol, is
developed to hydrolyze methyl acetate (MA) as a typical byproduct in polyvinyl alcohol (PVA) and pure
terephthalic acid (PTA) factory. The process is simulated by employing the equilibrium stage model RadFrac and
plug flow model Rplug in Aspen Plus. Experiments are also carried out in a lab-scale to evaluate the process. The
results show that at the molar ratio of water to methyl acetate about 4.05.0 in the feed stream and the volume ratio
of distillate to feed MA above a critical value, the side product contains more than 80% (by mass) (MeOH) and less
than 2% (by mass) MA, while the bottom contains more than 46% (by mass) acetic acid (HAc) and less than 0.5%
(by mass) methanol with almost complete conversion of MA. Compared with the old catalytic distillation process
we proposed before, this process can cut down 47.6% energy consumption and a distillation column.
Keywords methyl acetate, hydrolysis, simulation

1 INTRODUCTION twice that of fixed-bed reactor technology. Wang et al.

Methyl acetate (MA) is a byproduct in the indus-
try of polyvinyl alcohol (PVA) and purified
terephthalic acid (PTA). In order to obtain more valu-
able compound, MA is usually hydrolyzed to metha-
nol (MeOH) and acetic acid (HAc), which are recy-
cled to the production process of PVA or PTA. The
conventional hydrolysis process contains a fix-bed re-
actor and four separation columns [1]. The hydrolysis
reaction is carried out in the fixed-bed reactor catalyzed
by ion exchange resin. Limited with a equilibrium con-
stant ~0.14 at 25°C, the hydrolysis ratio is relatively
low (~23%), resulting in a large amount of recircula-
tion [2]. Furthermore, in order to deal with the azeotropes
of methyl acetate-methanol and methyl acetate-water
existing in the system, a complex separation process
required 4 columns is introduced. A number of improved
processes have been developed to overcome the dis-
advantages mentioned above [36]. Reactive distilla-
tion, a process that combines reaction and separation
together, is an attractive alternative process and it
gives clear advantages for systems with small equilib-
rium constant. Fuchigami [7] proposed a reactive dis-
tillation configuration with total reflux on the top and
bottom product withdrawal for the hydrolysis process.
The reactive zone placed in the mid-section is packed
with catalyst which consists of ion exchange resin and
polyethylene powder. With a molar ratio of water to
methyl acetate (RW/MA) more than 8, a nearly complete
conversion (~99%) can be achieved. However, owing
to the large amount of excess water, the concentration
of acetic acid in the hydrolysate is so low that it can-
not be accepted by PVA and PTA factory. Xiao et al. [8]
proposed replacing the fixed-bed reactor by a catalytic
distillation column to achieve 56% MA conversion as
[9] reported an industrial application of catalytic dis-
tillation for MA hydrolysis with 56% conversion. The
mixture of MA and water was fed in the top of cata-
lytic distillation column, and the hydrolysate was
withdrawn from the bottom. MA recycle ratio was
reduced with the raise of hydrolysis ratio in the two
process mentioned above, yet the separation problem
of the azeotrope MA-MeOH still cannot be solved.
Moreover, due to the use of heterogeneous cata-
lyst, typically strong acidic cation ion exchanger resin
in the hydrolysis process, there must be some internal
equipments to place catalyst in the reactive distillation
column [1013]. Three additional distillation columns
are still needed in order to separate the hydrolysate. A
new process which consists of a fixed-bed reactor for
hydrolysis and a conventional distillation column for
separation was developed in this paper. In this process,
MeOH is withdrawn from the side of the column and
HAc from the bottom of the column. Feasibility of the
process was evaluated and the optimal technology con-
ditions were obtained through experiment and simulation.
2 EXPERIMENTAL
A lab-scale experiment was carried out to study
the coupled process. The experimental schematic dia-
gram is shown in Fig. 1.
Methyl acetate and SK-1A ion exchanger resin
catalyst used in the experiment were supplied by the
Fujian Spinning and Chemical Fiber Group Company
and the Mo-Ti stainless steel ș shape packing by Tian-
jin University.
The concentration of acetic acid in samples was
measured by acid-base titration while those of MA
and methanol were measured by a VARIAN CP-3800

Received 2010-01-08, accepted 2010-07-17.

* Supported by the National Torch Program of China (2007HG560031).
** To whom correspondence should be addressed. E-mail: zhaosuying@fzu.edu.cn
756 Chin. J. Chem. Eng., Vol. 18, No. 5, October 2010

uses the equilibrium stage model, also called the

MESH model, and consists of a set of nonlinear equa-
tions to represent material balance, vapor-liquid equi-
librium, mole fraction summation, and heat balance.
The RPlug model, based on plug flow model, was
used to model the fixed-bed reactor. The reactions in
the reactor were based on power-law kinetics.

3.1 Physical equilibrium

An important consideration in distillation simula-

Figure 1 The schematic diagram of experimental setup
1üdeionized water container; 2üconstant flow pump; 3ü
laminar current pump; 4ümethyl acetate container; 5üflask;
6üthermometer; 7üstandby mouth; 8übottom outlet; 9ü
outlet pump; 10übottom product container; 11üfixed-bed
reactor; 12üflowmeter; 13ücondenser; 14üpacked distilla-
tion column; 15üside product container
GC equipped with a 30 m×0.25 mm XP-1701 capil-
lary column and hydrogen flame ionization detector.
The GC conditions were: injector temperature 200°C,
detector temperature 250 °C and a stepwise column
temperature. The initial column temperature was 50
°C for 3 min, heated up to 120 °C at 15 °C·min–1, and
then held for 1 min.
3 SIMULATION MODELING
Simulations were performed using the Aspen
Plus® (Aspen Technology Inc., Aspen Plus®, Version
10.1) software package. The distillation unit was
modeled using the RadFrac model in Aspen Plus®. It
tion is the choice of physical equilibrium model and
the ability to reliably predict multicomponent vapor-
liquid equilibrium (VLE) and liquid-liquid equilib-
rium (LLE). Reliable VLE and LLE are needed to
establish distillation boundaries and to determine if
and where azeotropes and phase separation occur.
Several equations can be used to model methyl ace-
tate-methanol-water-acetic acid system such as Van
Laar, NRTL, UNIQUAC. Dirk-Faitakis [14] recom-
mended NRTL model. Taking the non-ideality of the
vapor phase caused by dimerization of acetic acid into
account, Hayden-O’Connell(HOC) method was cho-
sen. Therefore, the NRTL-HOC property method was
used in this work because of the presence of high
concentration of acetic acid.
Binary interaction parameters were taken from As-
pen Plus® data banks. Table 1 summarizes the interactive
parameters used in vapor-liquid equilibrium calculation.
It was reported that methyl acetate-methanol sys-
tem exhibits an azeotrope with minimum boiling point
at 53.5 °C and 0.6618 mole fraction methyl acetate in
the vapor at 101.32 kPa [15]. Methyl acetate-water
exhibits a homogeneous azeotrope and also displays a
miscibility gap in the region at ambient pressure.
Bessling et al. [16] reported a minimum boiling azeotrope
at 0.92 mole fraction methyl acetate at temperature of
56.1 °C. Azeotropes predicted by NRTL-HOC model
at P 101.3 kPa are shown in Table 2.

Table 1 Summary of NRTL binary interaction parameters used in the prediction of equilibrium data
Component i Component j Temperature units aij aji bij bji cij
MA MeOH K –1.14353 0.509837 536.8947 31.74408 0.3
MA H2 O K –2.43297 –0.12096 1311.373 805.9797 0.419742
MeOH H2 O K –2.626 4.8241 828.3871 –1329.54 0.3
MeOH HAc K –3.8591 7.4858 975.377 –2151.88 0.3
MA HAc K 0 0 415.2702 –239.246 0.3
H2O HAc K 3.3293 –1.9763 –723.888 609.8886 0.3

Table 2 Azeotropes predicted by Aspen Plus® using NRTL-HOC model

Azeotrope P/kPa Taz/°C Component Mole fraction Mass fraction
MA-MeOH(homogeneous) 101.32 53.57 MA 0.6644 0.8207
MeOH 0.3356 0.1793
MA-H2O(homogeneous) 101.32 56.66 MA 0.9154 0.9780
H2O 0.0846 0.0220
 Chin. J. Chem. Eng., Vol. 18, No. 5, October 2010 757

3.2 Reaction kinetics the column, thus the stage is 11. In order to meet de-
mands of MeOH mass concentration of less than 0.5%
The hydrolysis of methyl acetate is a reversible in bottom product in the PTA and PVA plants, we set a
reaction with the following expression: design value of 0.4%. RL/F of 4.5 and RW/MA of 5.0 are
ZZX HAc  MeOH
MA  H 2 O YZZ (1) feasible parameters obtained by several simulations.
Other parameters are the same as the experimental
The equilibrium constant of this reaction is 0.15 at data. All the parameters for the base case simulation
55°C. According to the reaction mechanism the pseudo- are given in Table 3. All feed streams enter at 25°C.
homogeneous reaction kinetics can be expressed as: The mass basis distribution in the hydrolysate

c k  CMA CH 2 O  k  CMEOH CHAC
r Ccat (2)  distillation column is shown in Figs. 2 and 3. Fig. 2
indicates the methanol concentrations in vapor phase
A detailed study of this reaction has been done in at 6th14th stages are more than 0.8 with less than 0.15
our previous work [17] and the forward and reverse water, 0.03HAc and rare MA. That means 6th14th
reaction rate constant ( k  and k  , respectively ) can stages are the feasible locations for side withdrawal
be expressed by following equations. and the side product is readily to be refined by simple
Forward:
k0 3.181 u 104 m6·mol–1·s–1·g–1,

Ea 59.4 kJ·mol–1 (3)

Reverse:
k0 4.556 u 104 m6·mol–1·s–1·g–1,
Ea 55.3 kJ·mol–1 (4)
5 –3
c in Eq. (2) was 7.8×10 g·m (catalyst
The Ccat
mass/reaction liquid) in this experiment. And this ki-
netics equation was verified by experiments. Figure 2 Vapor profiles in the hydrolysate separation
column
4 RESULTS AND DISCUSSION MEOH; HAc; MA; Water

4.1 Simulation of coupled reactor/column process

After confirmed the physical equilibrium and re-

action kinetics, the continuous reaction and distillation
process shown in Fig. 1 can be simulated. The hydro-
lysate distillation column consists of a 20 stages col-
umn with none condenser and a partial reboiler. The
height of packed section of the experimental column is
1.6 m. According to the manufacturer, one meter ș shape
packing equals 12 theoretical stages, so the theoretical
stages of packed section is 20 including reboiler.
Compared the results of simulation with experimental Figure 3 Liquid profiles in the hydrolysate separation
data in the next part, 20 theoretical stages is suitable. column
The side product location is 0.9 m from the bottom of MEOH; HAc; MA; Water

Table 3 Parameters used in the simulations

Parameter Value
column pressure/MPa 0.1
total number of stages 20
distillate to feed MA volume ratio(RL/F) 4.5
feed stage location(above stage) 1
side product(vapor) stage location 11
fixed-bed reaction temperature/°C 55
loading capacity of fixed-bed/g·g–1·h–1 0.32
water to feed MA molar ratio (RW/MA) 5.0
Adjusted automatically by simulation model to control the MeOH mass concentration of
side product to feed MA volume ratio(RSP/F) bottom product less than 0.4%
758 Chin. J. Chem. Eng., Vol. 18, No. 5, October 2010

Table 4 The results of experiment and simulation (mass fraction)

xW-HAc xW-MeOH xSP-MeOH xSP-MA xSP-HAc
RW/MA RL/F RSP/F
Exp. Calc. Exp. Calc. Exp. Calc. Exp. Calc. Exp. Calc.
3.00 4.50 0.56 0.5366 0.5344 0.0611 0.0541 0.5687 0.5590 0.3744 0.3736 0.0156 0.0084
3.81 5.00 0.58 0.5404 0.5378 0.0017 0.0039 0.7432 0.8016 0.0419 0.0993 0.0207 0.0124
3.91 6.70 0.59 0.5226 0.5360 0.0052 0.0001 0.8040 0.8025 0.0401 0.0853 0.0193 0.0117
4.41 4.85 0.58 0.4963 0.5112 0.0149 0.0005 0.8479 0.8588 0.018 0.0006 0.0174 0.0170
4.41 6.90 0.58 0.5096 0.5118 0 0.0001 0.8548 0.8600 0.0072 0.0013 0.0163 0.0142
4.86 3.61 0.56 0.4659 0.4734 0.0031 0.0135 0.7982 0.8346 0.0196 0.0002 0.0252 0.0218
4.86 4.66 0.57 0.4749 0.4769 0 0.0032 0.8589 0.8569 0.0080 0.0001 0.0197 0.0169
4.86 6.70 0.58 0.4820 0.4801 0 0.0001 0.8427 0.8505 0.0057 0.0001 0.0225 0.0151
5.00 3.00 0.58 0.4664 0.4671 0.0024 0.0097 0.8146 0.8208 0.0073 0.0002 0.0276 0.0241

distillation to attain high purity methanol. In this way

the separation problem of the azeotrope MA-MeOH
has been solved. The bottom product only composes
of acetate acid and water. The mass concentration of
acetic acid is higher than 40% and meets the require-
ment of PTA plant.

4.2 Experimental verification

The results of the experiment and simulation are

compared in Table 4. Here, the experimental value of
RSP/F were adopted by simulation. As shown in the table, Figure 4 Effect of RL/F on MeOH concentration in side
most of the side product is composed of more than 80% product
(by mass) methanol(xSP-MeOH) and less than 2% (by mass) RW/MA:Ƶ3;ƽ4;Ʒ5
MA(xSP-MA), which is readily to get >96% (by mass)
methanol in the following distillation. At the same
time, the mass concentration of the HAc in the bottom
(xW-HAc) is more than 46%, which satisfied the re-
quirement in the PVA manufacture. The experimental
results agree with those predicted by simulation. Thus,
the simulation model can be used to discuss the influ-
ence of different parameters on the process.

4.3 Feasible technology conditions

RW/MA and RL/F are the most important parameters

in this process. Their value decide whether MA can be
hydrolyzed completely or not. Simulation work has
been done to study the effect of RL/F on the side prod-
uct, while RW/MA is kept constant. As shown in Figs. 4
and 5, the increase of RL/F will raise MeOH concentra-
tion in the side product and reduce MA impurity when
RW/MA is 4 and 5. Fig. 5 shows that there is a critical
value of RL/F. Below it, MA in the side product is quite
high, which means that MA is not hydrolyzed com-
pletely. Above it, MA is near zero, indicating about
100% conversion of MA. The critical value is 3 at
RW/MA = 5.0 and about 4.5 at RW/MA 4.0. Attentions
must be paid that at RW/MA 3.0 there always contains
a large amount of MA in the side product no matter
how much RL/F is. It can be predicted that the critical
value will further decrease if a larger RW/MA is pro-
vided. But the acid concentration in the bottom will
Figure 5 Effect of RL/F on MA concentration in side product
RW/MA:Ƶ3;ƽ4;Ʒ5
decrease. Proper operation conditions can be chosen
with the specification of the manufacturer. Under con-
ditions that RW/MA 4.05.0 and RL/F above critical
value, more than 80% (by mass) MeOH in the side
product and more than 46% (by mass) HAc in the
bottom can be obtained (Fig. 6).
In the simulation mentioned above, a Design
specs-Vary was set, which varied the amount of side
product to keep MeOH mass concentration <0.4% in
the bottom. At the same RW/MA, the volume of side
product decreases with the increase of RL/F. Taking
RW/MA 4.0 for example, the RSP/F changes from 0.68
to 0.57, while RL/F changes from 2 to 9. Because of the
 Chin. J. Chem. Eng., Vol. 18, No. 5, October 2010 759

simple distillation column was added to purify metha-

Figure 6 Effect of RL/F on HAc concentration in bottom
product
RW/MA:Ƶ3;ƽ4;Ʒ5
decrease of RSP/F, the quantity of water in the side
product reduces. On consequence, the concentration of
HAc in the bottom product decreases with the increase
of RL/F when the MA is totally hydrolyzed.
5 SUPERIORITIES OF THIS PROCESS
A further simulation was carried out to examine
the energy consumption of the proposed process. A
nol. As shown in Fig. 7, the side product is distillated
to get methanol with high purity and the bottom
product is sent back to fixed-bed reactor. Process flow
diagram (PFD) of the catalytic distillation process is
shown in Fig. 8. This technology [18, 19] has industri-
alized in several PTA and PVA plants. Ref. [19] de-
scribes the process in details.
Based on data given by a certain petrochemical
corporation, energy consumption was compared be-
tween this process and the catalytic distillation one
(the old process). The mass compositions of the feed
MA stream are as follows: MA 94.625%, MeOH 0.625%,
and water 3.75%. The purity specifications that the
HAc in the bottom equals to 46% (by mass) and prod-
uct MeOH amounts to 96% (by mass) are required.
The two processes were both simulated by Aspen
plus based on the thermodynamics and kinetics which
have been discussed earlier. The operation conditions
for catalytic column are: the volume ratio of reflux to
MA feed, 3.0, and the molar ratio of H2O to MA feed,
4.0. The catalytic column can be simulated using these
data by the model introduced by Wu et al. [20]. The
energy consumption of other distillation columns can
be calculated easily according to separation require-
ments. The energy consumptions of the main equipments

Figure 7 PFD of the coupled reactor/column process

Figure 8 PFD of the catalytic distillation process

Table 5 The energy consumptions of the main equipments of the old process (kW)
Catalytic distillation Hydrolysate distillation MA-MeOH separation MeOH distillation Total energy
column (CD) column (HD) column (MMSD) column (MD) consumption
675.70 546.61 100.02 262.84 1585.17

Table 6 The energy consumptions of the main equipments of the new process (kW)
Fixed-bed(F-BED) Hydrolysate distillation column (C1) MeOH distillation column(C2) Total energy consumption
25.59 722.22 87.23 835.03
760 Chin. J. Chem. Eng., Vol. 18, No. 5, October 2010
of the two processes are summarized in Tables 5 and 6,
respectively.
Obviously the new process have saved a main
equipment by comparing Figs. 7 and 8. The MA-MeOH
separation column is not needed in which the
side-withdraw of the hydrolysate distillation column
can solve the separation problem of the azeotrope
MA-MeOH. Table 5 shows that the sum of energy
consumptions of fixed-bed and hydrolysate distillation
column in the new process is 747.81 kW. It is much
smaller than that of CD column and hydrolysate dis-
tillation column of 1222.31 kW in the old process. As
known, MA hydrolyzes with water in liquid phase [21].
But MA is vaporized in the reactive distillation zone
of the CD column. Thus, the reflux quantity on the top
of the CD column needs to be increased to promote
reaction. More reflux quantity, more energy consump-
tion. The energy consumption of MeOH distillation
column are also reduced greatly as shown in Table 6.
In the old process, extra water enters on the top of the
MA-MeOH distillation column to extract MeOH from
MA, so methanol concentration is much lower than
that of the side product in the new process. The vapor
feeding used in the new process also saves a lot of
energy. The energy consumption gap between the new
and the old is up to 47.6%. Therefore, no matter in the
capital investment or in the operation cost, the new
process takes every superiority.
6 CONCLUSIONS
Both simulation and experiment have proven that
MA can be hydrolyzed completely in the coupled sys-
tem of fix-bed reactor and distillation column with
vapor side product. However, RW/MA should be greater
than 3.0 and RL/F above the critical value at every
RW/MA. Under the conditions that RW/MA 4.05.0 and
RL/F above the critical value the side product will con-
tain more than 80% (by mass) MeOH and less than
2% (by mass) MA, while the bottom will contain
more than 46% (by mass) HAc. Only a simple column
is needed to attain MeOH with high purity. Compared
with the catalytic distillation process we proposed
before, this process can save 47.6% of energy con-
sumption and a distillation column.
NOMENCLATURE
Cccat density of the catalyst, g·m–3
–3
Ci concentration of component i, mol·m
Ea apparent activation energy, kJ·mol–1
k rate constant, m6·mol–1·s–1·g–1
k0 pre-exponential factor, m6·mol–1·s–1·g–1
R universal gas constant, J·mol–1·K–1
RL/F distillate to feed MA volume ratio, m3·m–3
RSP/F volume ratio of side product to feed MA, m3·m–3
RW/MA molar feed ratio of water to methyl acetate, mol·mol–1
r reaction rate, mol·s–1·m–3
xSP-HAc mass concentration of acetate acid in the side product
xSP-MA mass concentration of methyl acetate in the side product
xSP-MeOH mass concentration of methanol in the side product
xW-HAc mass concentration of acetate acid in the bottom product
xW-MeOH mass concentration of methanol in the bottom product
Superscripts
+ forward reaction
– reverse reaction
Subscripts
az azeotrope
cat catalyst
REFERENCES
1 Ma, Y.G., Mou, C.G., Wu, S.H., Technology of PVA Production, Tex-
tile Industry Press, Beijing (1986). (in Chinese)
2 Wang, C.X., “Study on hydrolysis of methyl acetate in a catalytic
distillation column”, Chin. J. Chem. Eng., 9, 382387 (2001).
3 Pan, Y.B., Li, W.X., Shen, P.D., Wan, H., Han, M.J., Guan, G.F.,
“Study on hydrolysis of methyl acetate from production of purified
terephthalic acid by catalytic distillation”, Chem. Reac. Eng. & Tech.,
25, 132136 (2009). (in Chinese)
4 Wang, J.F., Ge, X.D., Wang, Z.W, Jin, Y., “Experimental studies on
the catalytic distillation for hydrolysis of methyl acetate”, Chem.
Eng. Technol., 24, 155159 (2001).
5 Sander, S., Flisch, C., “Methyl acetate hydrolysis in a reactive di-
vided wall column”, Chem. Eng. Res. Des., 85,149154 (2007).
6 Yuan, P.Q., Chen, Z.M., Liu, T., Yuan, W.K., “Hydrolysis of methyl
acetate under near or supercritical condition”, Chem. J. Chinese U.,
24, 12411245 (2003). (in Chinese)
7 Fuchigami, Y., “Hydrolysis of methyl acetate in distillation column
packed with reactive packing of ion exchange resin”, J. Chem. Eng.
Jpn., 23, 354359 (1990).
8 Xiao, J., Liu, J.Q., Li, J.T., Jiang, X.H., Zhang, Z.B., “Increase MeOAc
conversion in PVA production by replacing the fixed bed reactor with a
catalytic distillation column”, Chem. Eng. Sci., 56, 65536562 (2001).
9 Wang, L.E., Su, W.R., Zhao, Z.S., Liu, J.Q., Wu, Y.X., Shen, J.N., Qiu, T.,
“Industrial application of the catalytic distillation technique in hydrolysis
of methyl acetate”, Viny. Commu., 21, 1012 (2001). (in Chinese)
10 Wu, Y.X., Wang, L.E., Zhao, Z.S., Tan, T.E., “Mass transfer model
for catalyst capsule in catalyst distillation (I) mathematical model”,
CIESC J., 53, 503507 (2002). (in Chinese)
11 Wu, Y.X., Wang, L.E., Zhao, Z.S., Tan, T.E., “Mass transfer model for
catalyst capsule in catalyst distillation (II) measurement and calculation
of effectiveness factor”, CIESC J., 53, 508512 (2002). (in Chinese)
12 Kim, K., Roh, H.D., “Reactive distillation process and equipment for
the production of acetic acid and methanol from methyl acetate hy-
drolysis”, U.S. Pat., .5970770 (1998).
13 Moritz, P., Hasse, H., “Fluid dynamics in reactive distillation pack-
ing Katapak®-S”, Chem. Eng. Sci., 54, 136713741 (1999).
14 Dirk-Faitakis, C.B., An, W.Z., Lin, T.B., Chuang, K.T., “Catalytic
distillation for simultaneous hydrolysis of methyl acetate and etheri-
fication of methanol”, Chem. Eng. Process., 48, 10801087 (2009).
15 Gmehling, J., Bölts, R., “Azeotropic data for binary and ternary sys-
tems at moderate pressures”, J. Chem. Eng. Data., 41, 202209 (1996).
16 Bessling, B., Löning, J.M., Ohligschläger, A., Schembecker, G.,
Sundmacher, K., “Investigations on the synthesis of methyl acetate
in a heterogeneous reactive distillation process”, Chem. Eng. Technol.,
21, 393400 (1998).
17 Wu, Y.X., Zhao, Z.S., Wang, L.E., Zhao, S.Y., “Kinetics of hydroly-
sis of methyl acetate and the effectiveness factor of catalyst capsule”,
Eng. Chem. Meta., 20, 241246 (1999). (in Chinese)
18 Wang, L.E., Liu, J.Q., Su, W.R., Zhao, Z.S., Zheng, W.H., Zhang,
J.L., “Catalytic distillation process for methyl acetate hydrolysis and
its equipments”, China Pat., 97101306.3 (1997).
19 Wang, L.E., Zhao, Z.S., Qiu, T., Zhao, S.Y., Zheng, H.D., Qiu, T.R.,
Su, W.R., Xie, Y.H., Luo, D.H., “Byproduct methyl acetate hydroly-
sis process and its equipments in the industry of PTA”, China Pat.,
200610124556.7 (2006).
20 Wu, Y.X., Tan, T.E., Wang, L.E., Zhao. Z.S., “Simulation of the
catalytic distillation process for hydrolysis of methyl acetate”, Eng.
Chem. Meta., 21, 2429 (2000). (in Chinese)
21 Pöpken, T., Götze, L., Gmehling, J., “Reaction kinetics and chemical
equilibrium of homogeneously and heterogeneously catalyzed acetic
acid esterification with methanol and methyl acetate hydrolysis”, Ind.
Eng. Chem. Res., 39, 26012611 (2000).