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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$ciency, showing no considerable di!erence between
the equilibrium and non-equilibrium models for this system. Moreover, e!ects of the feed locations of the two reactants and the re#ux
ratio on the performance of the column are discussed, too. 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Reactive distillation; Equilibrium model; Dimethyl carbonate; Carbonylation; Diethyl carbonate
0009-2509/01/$ - 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
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
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> GH> H\ GH\ H GH IH IH 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 GH H GH 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-
IH H IH
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> 4H> H\ *H\ H $H H 4H
!¸ H #Q "0. (9)
H *H H
The vapor}liquid equilibrium equations are
> P"X c PQ . (10)
GH GH G G
Summations of the liquid and vapor phases are given by
+
X "0 (11)
GH
G
and
+ Fig. 3. The e!ects of holdup on DMC conversion, DEC selectivity and
> "0. (12)
GH residence time.
G
H.-P. Luo, W.-D. Xiao / Chemical Engineering Science 56 (2001) 403}410 407
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
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
Z molar composition of component i in the feed Kreul, L. U., Gorak, A., & Barton, P. I. (1999). Modeling of homogene-
GH ous reactive separation processes in packed column. Chemical En-
stage j.
e stoichiometric coe$cient in the kth reaction for gineering Science, 54, 19}34.
IH Lee, J. H., & Dudukovic, M. P. (1998). A comparison of the equilibrium
the jth component and nonequilibrium models for a multicomponent reactive distilla-
c activity coe$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
design aspects. Industrial and Engineering Chemistry Research, 36(5),
Acknowledgements 1855}1869.
Subawalla, H., & Fair, J. R. (1999). Design guideline for solid-catalyzed
reactive distillation systems. Industrial and Engineering Chemistry
Financial support of this work by China Petrochemi- Research, 38(10), 3696}3709.
cal Inc. (SINOPEC) is gratefully acknowledged. Sundmacher, K., & Ho!mann, U. (1996). Development of a new cata-
lytic distillation process for fuel ethers via a detailed nonequilibrium
model. Chemical Engineering Science, 51, 2359}2368.
References Sundmacher, K., & Ho!mann, U. (1999). Multiple reactions in catalytic
distillation processes for the production of the fuel oxygenates
MTBE and TAME: Analysis by rigorous model and experimental
Higler, A., Taylor, R., & Krishna, R. (1998). Modeling of a reactive
validation. Chemical Engineering Science, 54, 2839}2847.
separation process using a nonequilibrium stage model. Computers Xiao, W. D., & Jin, Y. H. (1994). An improved process for manufactur-
& Chemical Engineering, 22, s111}s118. ing di-alkyl carbonate. Chinese Patent No. 94,112,211,5.
Higler, A. P., Taylor, R., & Krishna, R. (1999). The in#uence of mass
Yu, S. B., Zhou, A. Y., & Tan, Q. (1997). Simulation of multistage
transfer and mixing on the performance of a tray column for catalytic stripping with a nonequilibrium stage model. Computer
reactive distillation. Chemical Engineering Science, 54, 2837}2881. & Chemical Engineering, 21(4), 409}415.
Knifton, J. F. (1993). Process for cogeneraton of ethylene glycol and
Zhang, S. (1996). Handbook of the xne chemicals: organic components (p.
dimethyl carbonate. US Patent No. 5,214,182. 945). Beijing: Chemical Industry Press.
Kreul, L. U., Gorak, A., & Barton, P. I. (1996). Modeling of reactive
distillation processes in a packed column. Proceedings of the second
Nordic symposium of reactive separation systems, Helsinki, Finland.