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Chemical Engineering Science 56 (2001) 403}410

A reactive distillation process for a cascade and azeotropic reaction


system: Carbonylation of ethanol with dimethyl carbonate
Hu-Ping Luo, Wen-De Xiao*
UNILAB Research Center of Chemical Reaction Engineering, East China University of Science and Technology, Shanghai, 200237,
People's Republic of China

Abstract

Modelling and simulation of the reactive distillation column have been carried out for the carbonylation process of ethanol with
dimethyl carbonate (DMC) producing diethyl carbonate (DEC). As it includes three azeotropes and two cascade reversible reactions
with an undesired intermediate, methyl-and-ethyl carbonate (MEC), the reactive distillation is ideally appropriate. Calculations via
a robust transient method reveal that a complete DMC conversion, a sound DEC selectivity over 99.5%, a perfect overcoming of
azeotropic limitation, as well as a thorough separation of the alcohols from carbonates can be accomplished in the studied column.
The model reliability is analyzed by assuming several values of Murphree tray e$ciency, showing no considerable di!erence between
the equilibrium and non-equilibrium models for this system. Moreover, e!ects of the feed locations of the two reactants and the re#ux
ratio on the performance of the column are discussed, too.  2001 Elsevier Science Ltd. All rights reserved.

Keywords: Reactive distillation; Equilibrium model; Dimethyl carbonate; Carbonylation; Diethyl carbonate

1. Introduction Generally, DMC may be taken as the carbonylated


product of methanol, and used as a building block for
Concerns of environment, safety and health (ESH) producing carbonate esters of higher alcohols through
have been spurring forward R&D of environmentally transesteri"cation processes. Diethyl carbonate (DEC),
benign chemicals and processes. Dimethyl carbonate an important solvent and intermediate for preparing
(DMC), hardly toxic and nicely biodegradable, and in- nor#oxacin, a broad-spectrum antibiotic, is previously
cluding both the carbonyl and the methyl groups, is just manufactured by using phosgene (Zhang, 1996). Luo
a chemical of this kind. DMC has been used as an (1999) investigated the routine for DEC by using DMC
e!ective carbonylation agent to substitute the virulent as the carbonylation agent, and proposed a modi"ed
phosgene for manufacturing plastics polycarbonate and K CO catalyst. It is found that the reaction is limited by
 
urethane polymers, and as a useful methylation agent to the chemical equilibrium, and an intermediate, methyl-
replace the hazardous dimethyl sulfate (Ono, 1996). and-ethyl carbonate (MEC), also appears. Moreover, the
Moreover, DMC has been successfully manufactured by reaction system includes "ve compounds and three bi-
using CO , the greenhouse gas, and methanol as the raw nary azeotropes, implying a challenge in the separation.

materials according to a zero-discharge process co-pro- A multifunctional reactor integrating a fractionating
ducing ethylene or propylene glycol (Knifton, 1993; Xiao separation and a chemical reaction, often referred to as
& Jin, 1994; Pachelco & Marshall, 1997). As a result, in the reactive distillation column, is becoming more and
respect of the carbonylation usage of DMC, phosgene more prominent in the chemical industry. The expected
is simply substituted by carbon dioxide, which may be bene"ts from such a synergetic interaction of two unit
one of the most signi"cant dedications to the chemical operations in one column are an enhanced conversion in
industry. excess of the chemical equilibrium, an improved selectiv-
ity, and the overcoming of azeotropic limitations. In
recent years, quite a number of contributions were pub-
lished on design principles, modeling and operation of
* Corresponding author. Tel. & fax: #86-21-64252814. the reactive distillation columns (Sundmacher &
E-mail address: sane@npc.haplink.com.cn (W.-D. Xiao). Ho!mann, 1996; Lee & Dudukovic, 1998; Subawalla

0009-2509/01/$ - see front matter  2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 9 - 2 5 0 9 ( 0 0 ) 0 0 2 4 2 - 6
404 H.-P. Luo, W.-D. Xiao / Chemical Engineering Science 56 (2001) 403}410

& Fair, 1999). However, most of them either considered


only a single reaction, i.e., the formation of ethyl acetate
(Higler, Taylor & Krishna, 1998; Kreul, Gorak & Barton,
1999), or considered a parallel reaction system, i.e., the
production of MTBE or TAME (Sneesby, Tade, Datta
& Smith, 1997; Sundmacher and Ho!mann, 1999).
This paper presents a unique reactive distillation sys-
tem of the transesteri"cation of DMC with ethanol to
form DEC and methanol, which includes two cascade
reversible reactions with the intermediate MEC being the
undesired byproduct, and "ve components with three
binary azeotropes. Based on the chemical kinetic models
and the phase equilibria data developed by Luo (1999),
and an equilibrium MESH model, simulation and theor- Fig. 1. Experimental kinetic data: DMC conversion and DEC selectiv-
etical analysis have been done. ity changing with time.

 
12210.2
k "3.076;10 exp ! , (5)
2. Chemical reaction characteristics  R¹

 
!628.44
The transesteri"cation of DMC and ethanol consists k "145.95 exp ! ,
A R¹
of two cascade reversible reactions with an intermediate,
MEC
 
!593.87
k "33.222 exp ! , (6)
A R¹
O O
"" cat ""
where C (i"1,5) represent the molar concentrations of
H COCOCH #C H OH& H COCOC H #CH OH,
        G
(DMC) (MEC) ethanol, DMC, MEC, methanol and DEC.
In the range of 45}1003C, the experimental results
(1)
show that: (a) the generated heat of the two reactions is so
small as to be less than 1 kJ/mol; (b) the reaction equilib-
O O
"" cat "" rium constants are 1.9}2.0 and 0.44}0.46, respectively; (c)
C H OCOCH #C H OH& C H OCOC H #CH OH the reactions proceed with a DMC conversion of about
         
(MEC) (DEC) 90% and a DEC selectivity of about 50%.
(2)

It has been found by Luo (1999) that hydrates of alkali 3. Phase equilibrium characteristics
metals can catalyze the reactions, but solid byproducts of
carbonates of the used alkali metals usually appear. Then As can be seen from Eqs. (1) and (2), the system in-
potassium carbonates are tested with the promotion of cludes "ve components: methanol, ethanol, DMC, MEC,
a proprietary phase transferring agent, and thus, the and DEC, their atmospheric boiling points being 64.5,
reaction can homogeneously take place in the liquid 78.5, 90.0, 109.2 and 1263C, respectively. The correspond-
phase. The kinetics measured is shown in Fig. 1 at a feed ing Antoine coe$cients can be found in Luo (1999). As
ratio of ethanol to DMC of 6. It can be noticed that for the vapor}liquid equilibrium of the involved mix-
reaction (1) reaches equilibrium state in about 10 min, tures, Luo (1999) has conducted experimental measure-
and reaction (2) in about 30 min, with the equilibrium ments in detail, and correlated the data by using the
DMC conversion and DEC selectivity changing little Wilson model, with the resulting parameters shown in
with increasing the reaction temperature. Table 1.
Luo (1999) proposed the following expressions to rep- There exist three binary azeotropes methanol}DMC,
resent the kinetics of the reactions: ethanol}DMC, and ethanol}MEC amongst the "ve com-
ponents, and their corresponding atmospheric boiling
r "k ;[C C !C C /k ], (3) points together with compositions are displayed in Table
      A
2. As can be noticed, they all are possible reactive azeo-
r "k ;[C C !C C /k ], (4) tropes as their corresponding atmospheric boiling points
      A
are so close to the light components in the system;

 
12454.9 methanol and ethanol. This phenomenon poses much
k "2.148;10 exp ! ,
 R¹ di$culty for the separation of the involved species in
H.-P. Luo, W.-D. Xiao / Chemical Engineering Science 56 (2001) 403}410 405

Table 1
Parameters of Wilson equation estimated by Luo (1999)

System (j !j ) (j !j ) System (j !j ) (j !j )
       
Methanol}Ethanol 135.8113 !132.0576 Ethanol}MEC 709.523 164.462
Methanol}DMC 771.98 202.44 Ethanol}DEC 626.606 331.781
Methanol}MEC 684.591 203.922 DMC}MEC 323.814 !311.777
Methanol}DEC 364.177 411.055 DMC}DEC !474.659 1000.0
Ethanol}DMC 522.235 450.581 MEC}DEC 80.9023 !83.1232

Table 2 4. Modelling of reactive distillation column


Azeotropes in the discussed system at 101.3 kPa measured by Luo
(1999) The con"guration of a reactive distillation tower is
Binary system Composition (mol%) Temperature (3C) shown in Fig. 2 with two feeding inlets for the separate
charge of the two reactants. As the studied reactions are
Methanol}DMC 86.6% of methanol 63.7 homogeneous, the column is a kind of tray with the
Ethanol}MEC 95% of ethanol 78.9 advantage that the residence time or the liquid holdup
Ethanol}DMC 69% of ethanol 74.9 volume in each stage can be easily regulated to meet the
needs of the chemical reactions. Usually, the objective of
the chemical reactions can be guaranteed by increasing
a conventional process in which reactions and distillation the liquid holdup of the tower, and that of the phase
are carried out in separate vessels. separation by the stage number. In the packed tower,
In order to assure the complete conversion of DMC, contradiction may arise between the two objectives, as
and to avoid the occurrence of methanol}DMC azeo- the liquid holdup is relatively small as compared with the
trope in the top distillate of the reactive distillation tray column.
column, excess of stoichiometric ethanol is applied. Two types of models have been proposed for the
Therefore, two objectives for the design and operation of conventional distillation columns, equilibrium and non-
the column are: (1) the top product is the mixture of equilibrium, which are also suitable for the reactive
methanol and ethanol; (2) the bottom product is a nearly distillation columns. Generally, the equilibrium model
pure DEC, implying a complete conversion of DMC to consists of MESH (Material balance, vapor}liquid Equi-
DEC and a thorough separation of the alcohols from the librium equations, mole fraction Summations, and Heat
carbonates in the one-pass multifunctional reactor. balance) equations, and the non-equilibrium model

Fig. 2. The reactive distillation column con"guration for carbonylation of ethanol with DMC.
406 H.-P. Luo, W.-D. Xiao / Chemical Engineering Science 56 (2001) 403}410

consists of the so-called MERQ (Material balance, En- In addition, several assumptions are suggested: (a) the
ergy balance, Rate equations for mass transfer, and phase operation reaches steady state; (b) the reactions take
equilibrium at vapor}liquid interface) equations. Re- place entirely in the liquid bulk; (c) the fugacity coe$-
cently, the non-equilibrium models are more preferred by cients of the vapor phase are unity because of the low
some researchers (Higler, Taylor & Krishna, 1999; Kreul, pressure; (d) the stage-to-stage pressure drop is constant.
Gorak & Barton, 1999), as the Murphree tray e$ciencies The steady-state solution of the model equations is
of the multiple component system are generally di$cult obtained by a procedure referred to as the relaxation or
to estimate a priori (Sundmacher and Ho!mann, 1996). transient method (Luo, 1999). The procedure arranged
However, the non-equilibrium model is much more com- the MESH equations and the reaction kinetic equations
plex (Kreul et al., 1996; Yu, Zhou & Tan, 1997), and the to three loops: the inner loop, including Eqs. (10)}(12), is
mass and heat transfer rates are also estimated empiric- solved for > and ¹ ; the middle loop, including Eq. (7)
GH G
ally from considerable experiments, and to some extent, and Eqs. (3) and (4), is integrated for X ; and the outer
GH
are hardly accurate due to the strong interaction between loop, including Eq. (9), is solved for < and ¸ . It is
H H
reaction and mixing. However, from a thorough com- certainly robust as the accurate solution can be con-
parison of the equilibrium model (plus Murphree e$cien- verged to regardless of the initial estimation of the un-
cy) with the non-equilibrium model for the esteri"cation known variables. In addition, the multiple steady-state
reaction system between ethanol and acetic acid, Lee solutions, if any, can be achieved only if multiple initial
and Dudukovic (1998) concluded that the latter can be estimation is employed.
imitated by the former when a reasonable value of
Murphree tray e$ciency (about 0.6) is assigned to each
stage and component. 5. Simulated results and discussions
The transesteri"cation of DMC with ethanol is to
some extent similar to the esteri"cation of ethanol and In the considered reactive distillation column, the cata-
acetic acid with respect to the thermodynamic and mass- lyst K CO and the promoter are introduced at the top
 
transfer properties. Therefore, equilibrium models plus of the column, thus, the reactions occur in each tray
Murphree tray e$ciency is used in this work. In fact, as except for the condenser. The overhead pressure is as-
the equilibrium model has less empirical parameters to sumed to be 101.3 kPa, and the pressure drop through
be estimated than the non-equilibrium one, it is more each stage is "xed at 0.6 kPa. The simulated column is
convenient to use. supposed to be operated in the laboratory, with an inner
The MESH equations are described as follows: diameter of 50 mm. The holdup on each tray, an essential
Material balance is de"ned as factor for the chemical reactions, can be adjusted by
designing di!erent weir height, a necessary con"guration
 parameter for the tray column.
< > #¸ X #F Z # (e Re )
H> G H> H\ G H\ H G H I H I H Initially, a proper holdup is determined by a primary
I
simulation. The results are shown in Fig. 3. As can be
!< > !¸ X "0, (7)
H G H H G H seen, on the conditions that: the equilibrium tray number
where the reaction rate in the jth stage is given by is 30; the re#ux ratio is 6.0; the feed ratio of ethanol to
DMC is 6.0 and the feed rate of DMC is 5.5 mol/h, an
Re "Holdup ;r . (8) approximately complete conversion of DMC can be ob-
I H H I H
tained at a holdup of 3 ml, and a DEC selectivity more
The energy balance is de"ned as
< H #¸ H #F H !< H
H> 4 H> H\ * H\ H $ H H 4 H
!¸ H #Q "0. (9)
H * H H
The vapor}liquid equilibrium equations are
> P"X c PQ . (10)
G H G H G G
Summations of the liquid and vapor phases are given by
+
X "0 (11)
G H
G
and
+ Fig. 3. The e!ects of holdup on DMC conversion, DEC selectivity and
> "0. (12)
G H residence time.
G
H.-P. Luo, W.-D. Xiao / Chemical Engineering Science 56 (2001) 403}410 407

than 99% is possibly achieved at a holdup of about


10 ml. These two values of holdup correspond to weir
heights of about 3.3 and 10.5 mm, respectively. Therefore,
the following calculations are based upon a holdup of
10 ml.

5.1. A typical operation mode

Figs. 4}7 demonstrate a typical operation mode for the


two cascade reactions of transesteri"cation of DMC with
ethanol in the reactive distillation column. The condi-
tions are the same as those in Fig. 3 but the stage number
is 50. Ethanol and DMC are fed at Stage 25.
The composition pro"les in the liquid and vapor Fig. 5. Vapor composition pro"le along the column.
phases are displayed in Figs. 4 and 5, respectively. It is
assumed that the reactions take place in the liquid phase
from the 1st to the Nth stage due to the fact that the
catalyst is introduced at the 1st stage resolved in the
re#ux #ow containing almost all the alcohols. It can be
noticed that three abrupt changes occur in the composi-
tions around the 1st stage, the 25th stage, and the Nth
stage. The top product (see Fig. 5), contains no carbon-
ates but the two alcohols, and the bottom DEC product
(see Fig. 4), does not include any of DMC and MEC. This
means that the expected objectives of a complete conver-
sion of DMC, and a thorough separation of alcohols
from carbonates have been accomplished.
It can be further noticed that, the molar compositions
in the top product are 66.59% of ethanol, 33.36% of
methanol, and 0.048% of DEC, and those in the bottom Fig. 6. Vapor and liquid #ow rate pro"les along the column.
product are 0.81% of ethanol, and 99.19% of DEC.
A perfect separation of methanol from ethanol, and that
of ethanol from DEC, is then not di$cult to "nish. the vicinity of 803C in the internal stages except for those
The inter-stage liquid and vapor molar #ow rates are near the reboiler where temperature is 132.33C. The top
shown in Fig. 6. The considerable increase in the liquid temperature is 75.53C.
#ow from Stages 24 to 25 is due to the saturated liquid The DMC conversion pro"le shows that the "rst reac-
feed on Stage 25. The pro"le of the vapor #ow rate is tion of the transesteri"cation, as expressed in Eq. (1),
approximately constant throughout the column. Fig. rapidly proceeds with only about eight stages required. It
7 depicts the pro"les of temperature, DMC conversion can be estimated that the real residence time for the "rst
and DEC selectivity. The temperatures change a little in reaction is nearly 2 min, "ve times less than its equilib-
rium time (see Fig. 1). This reaction acceleration is
certainly due to the removal of the products from the
reaction region by the fractionating separation. Never-
theless, the DEC selectivity pro"le is much smoother
than the DMC conversion pro"le. As MEC can form an
azeotrope with ethanol, it is liable to be stripped upward
to the top by the large amount of the distillated ethanol.
Therefore, MEC is also distributed above the feed stage,
and the re#ux #ow contributes much to the further con-
version of MEC into DEC in the trays over the feed tray
25, implying a large re#ux ratio to be employed.

5.2. Ewect of feed locations

In principle, feed locations of the raw materials should


Fig. 4. Liquid composition pro"le along the column. provide enough contact time for the reactions. The lower
408 H.-P. Luo, W.-D. Xiao / Chemical Engineering Science 56 (2001) 403}410

Fig. 7. DMC conversion, DEC selectivity and temperature pro"les Fig. 8. E!ect of relux ratio on DMC conversion and DEC selectivity.
along the column.

boiling point reactant, ethanol in this system, is usually the unconverted reactants to the reaction zone. However,
introduced from the bottom section of the column, and several negative e!ects can be endowed by increasing the
the higher boiling point component, DMC here, from the re#ux ratio: (a) increase in concentration of a product,
top. But this general rule is not suitable for this system here methanol, in the reaction zone which may decrease
due to the occurrence of azeotropes. As presented in the forward reaction rate: (b) decrease in the total reac-
Table 3, a higher ethanol feed position but a lower DMC tion residence time: (c) reduction in the temperatures of
position results in a DMC conversion of up to 100%, but each tray: (d) increase in the heat duty of the reboiler.
a lower DEC selectivity. The reason is that a large For the transesteri"cation reaction system of DMC
amount of both ethanol and MEC may escape from the and ethanol with an intermediate byproduct MEC, the
top, then the residence times of ethanol and especially e!ect of the re#ux ratio is much complicated, as shown in
MEC are too short. On the other hand, a higher DMC Fig. 8. If the re#ux ratio is less than 3.8, a complete DMC
feed location but a lower ethanol location produce both conversion cannot be obtained, and if it is lower than 5.2,
lower DMC conversion and DEC selectivity, as DMC a DEC selectivity over 99% is impossible. This phenom-
can escape from the top due to a lower DMC residence enon is mainly attributed to the tendency forming the
time. As a result, both the higher DMC conversion and ethanol-MEC azeotrope. Thereby, the operating re#ux
DEC selectivity can only be guaranteed by both the ratio is determined as 6.
lower ethanol and DMC feed stages in the lower section
of the column. For the given operating conditions and 5.4. Ewect of Murphree tray ezciency
the column con"guration parameters, the calculated op-
timal locations both for ethanol and DMC are the 20th To compensate for the di!erence between the real tray
stage with a 100% DMC conversion and 99.681% DEC and the equilibrium, or theoretical one, the model modi"-
selectivity. cation with the Murphree tray e$ciency is employed in
this work, as done by Lee and Dudukovic (1998). Table 4
5.3. Ewect of reyux ratio depicts the e!ect of the Murphree tray e$ciency. It can
be seen that, when the e$ciency is reduced from unity,
In a reactive distillation column, re#ux not only en- corresponding to the theoretical tray, through 0.75, cal-
hances the separation but also the reaction by recycling culated by the empirical correlation of Macfarland,
Table 3
E!ect of feed locations of ethanol and DMC

Feed stage DMC conversion DEC selectivity DEC yield


Ethanol DMC (%) (%) (%)

6 24 100.0 46.642 46.642


10 20 100.0 65.653 65.653
14 16 100.0 77.547 77.547
17 17 100.0 97.490 97.490
20 20 100.0 99.681 99.681
20 18 97.7 85.963 83.986
20 12 84.4 94.592 79.798
24 8 70.3 93.480 65.694
H.-P. Luo, W.-D. Xiao / Chemical Engineering Science 56 (2001) 403}410 409

Table 4
E!ect of Murphree tray coe$ciency

Murphree tray DMC DEC Top product composition (mol%) Bottom product
e$ciency conversion (%) selectivity (%) composition (mol%)
Methanol Ethanol DMC MEC DEC
Ethanol DEC

1.0 100.0 99.546 33.36 66.59 0.0 0.0 0.05 0.81 99.19
0.75 100.0 99.549 33.38 66.47 0.0 0.01 0.14 1.34 98.66
0.55 100.0 99.310 33.28 66.34 0.0 0.09 0.29 2.48 97.52

Sigmund and van Winkle (1972), to 0.55, estimated ac- clusion that the mass and heat transfer has little e!ect
cording to the results of the equilibrium and non-equilib- on the performance of the studied carbonylation system,
rium simulations by Lee and Dudukovic (1998), the for the reason that the performance is mainly determined
DMC conversion remains unchanged at a value of 100% by the chemical equilibirum limitation of the reaction of
and the DEC selectivity changes very little. In addition, MEC and ethanol, and by the azeotropic limitation of
changes in the compositions of both the top and the MEC and ethanol.
bottom products are also displayed in Table 4, showing In summary, the objectives of a complete conversion of
increases in the MEC and DEC concentrations in the DMC into DEC and a thorough separation of the alco-
top, and ethanol in the bottom. But the e!ect is so small hols from the carbonates can be achieved under the given
that the simulation based on the equilibrium model is conditions, and simulations based on the equilibrium
doubtlessly reliable. This means that the column perfor- model are reliable and can be useful.
mance is certainly de"ned by the chemical and phase
equilibrium limitations for the considered carbonylation
system of ethanol with DMC. Notation

C liquid concentration of component i, mol/L


G
6. Conclusions F feed #ow rate, mol/h
H
Holdup holdup on the jth tray, L
H
This paper demonstrates the feasibility of the reactive H feed enthalpy, J/mol
$ H
distillation process to the carbonylation reaction system H liquid enthalpy, J/mol
G H
of ethanol with dimethyl carbonate (DMC) with two H vapor enthalpy, J/mol
4 H
cascade and reversible reactions and three binary azeo- k forward kinetic rate constant of Eq. (3),

tropes. Simulations based on the equilibrium model and mol/(L h)
a robust transient method have been done for a laborat- k forward kinetic rate constant of Eq. (4),

ory column having a diameter of 50 mm. As the strong mol/(L h)
interaction of the chemical reaction and the phase equi- K chemical equilibrium constant of Eq. (1)
A
librium, this system shows some unexpected behaviors. K chemical equilibrium constant of Eq. (2)
A
Firstly, the holdup of the tray is an essential con"gura- ¸ liquid #ow rate, mol/h
H
tion parameter to the complete conversion of DMC into M number of components
diethyl carbonate (DEC). Secondly, the feed locations of N total number of stages
the raw materials a!ect the performance greatly. Both P pressure, atm
ethanol and DMC must be introduced into the column PQ saturated vapor pressure under the system
G
on trays closer to the bottom, in order to provide enough temperature, atm
residence time for the intermediate methyl-and-ethyl car- Q heat removed or added, J/h
H
bonate (MEC) to be completely converted into DEC and R universal gas constant, 8.314 J/(mol K)
overcome the ethanol}MEC azeotropic limitation. Re extent of reaction, mol/h
I H
Thirdly, the relux ratio is important not only for the r reaction rate de"ned by Eq. (3), mol/(L h)

phase separation, but also for the carbonylation reac- r reaction rate de"ned by Eq. (4), mol/(L h)

tions of ethanol with DMC, owing to the presence of the ¹ temperature, K
undesired intermediate MEC, which is liable to form an < vapor #ow rate, mol/h
G
azeotrope with ethanol. Therefore, a large value of the X molar fraction of component i in liquid phase
G H
re#ux ratio over 6.0 is necessary. Fourthly, the reliability of stage j
of the used equilibrium model has also been judged by > molar fraction of component i in vapor phase
G H
introducing the Murphree tray e$ciency, with a con- of stage j
410 H.-P. Luo, W.-D. Xiao / Chemical Engineering Science 56 (2001) 403}410

Z molar composition of component i in the feed Kreul, L. U., Gorak, A., & Barton, P. I. (1999). Modeling of homogene-
G H ous reactive separation processes in packed column. Chemical En-
stage j.
e stoichiometric coe$cient in the kth reaction for gineering Science, 54, 19}34.
I H Lee, J. H., & Dudukovic, M. P. (1998). A comparison of the equilibrium
the jth component and nonequilibrium models for a multicomponent reactive distilla-
c activity coe$cient of liquid
G tion column. Computer & Chemical Engineering, 23, 159}172.
Luo, H. P. (1999). Studies on the diethyl carbonate synthesis by transes-
terixcation of DMC with ethanol. Master thesis, East China Univer-
Subscripts sity of Science & Technology.
Macfarland, S. A., Sigmund, P. M., & van Winkle, M. (1972). Predict
distillation e$ciency. Hydrocarbon Process, 51, 111.
i component number, i!1,2,2,M Ono, Y. (1996). Dimethyl carbonate for environmentally benign reac-
j stage number, j!1,2,2,N tions. Pure and Applied Chemistry, 68, 367}375.
F feeds Pachelco, M. A., & Marshall, C. L. (1997). Review of dimethyl carbon-
< vapor phase ate (DMC) manufacture and its characteristics as a fuel additive.
Energy & Fuels, 11(1), 2}29.
¸ liquid phase Sneesby, M. G., Tade, M. O., Datta, R., & Smith, T. N. (1997). ETBE
synthesis via reactive distillation. 1. Steady-state simulation and
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Subawalla, H., & Fair, J. R. (1999). Design guideline for solid-catalyzed
reactive distillation systems. Industrial and Engineering Chemistry
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