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1996
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P.A. PILAVACHI
European Commission, DGXII-Science, Research and Development, 1049 Brussels, Belgium
Abstract -Various aspects related to simulation, design and operation of reactive distillation
processes are presented through a systematic analysis of the model parameters and the important
design/operational variables. The need for reliable, versatile and consistent simulation tools that
allow the analysis of design/operation of reactive distillation processes are highlighted through
two well known examples. The model parameters for the estimation of the properties related to
physical and chemical equilibrium have been found to be highly sensitive to the design and
operation of the two systems studied. The reactive phase diagrams and the existence of reactive
azeotropes have been found to influence the choice of the condition of operation and the existence
of multiple solutions.
INTRODUCTION
In recent years, reactive distillation has received increased attention since it has the potential of separating liquid
mixtures involving azeotropes or isomers. Separation of these mixtures by conventional distillation requires high
energy costs while separation with solvent based distillation requires a suitable solvent, which in some cases, may
not be available. Another important advantage of reactive distillation is that, by allowing separation of the reaction
products from the reactants in the same unit operation, it is able to increase the product yield. Examples of
application of reactive distillation can be found in esterification processes (Agreda et al, 1990, Sawistowski and
Pilavachi, 1988), separation of isomers (Saito et al., 1971), and, in the manufacture of "anti-knock" enhances such
as MTBE and TAME (e.g., DeGarmo et al. 1992, Ignatius et al. 1995).
Although the use of reactive distillation as a separation technique has been known for a long time, it has
only been shown recently to be able to solve separation problems which were previously considered difficult or
unsolvable. Despite the recent advances by Doherty and co-workers (Barbosa and Doherty, 1988, Ung and
Doherty, 1995), it can be claimed that there are still no generally accepted design methods for these processes.
One important reason is the difficulty associated with the modelling of these processes. As a result, reliable and
consistent models (for properties prediction, reaction kinetics and process simulation) are not available, and, the
dependence of the model parameters are unknown. It is obvious that without appropriate "tools", the design and
operation of any new process would be subject to unacceptable uncertainties.
The objective of this paper is to present a systematic approach to the analysis of design and operation of
reactive distillation processes. First, appropriate models and their parameters are validated. Second, the validated
models are employed to generate relationships between variables that have a large impact on the design and
operation of the process. Finally, the generated relationships are employed to analyse the reliability and efficiency
of design and operation of the reactive distillation columns.
liquid phase activity coefficients (because the reactions are assumed to occur only in the liquid phase which
represents a non-ideal mixture). In addition, for the esterification process, the effect of dimerization in the vapor
phase fugacity coefficients has also been found to have importance.
Selection/validation of models: The MTBE process simulations have been performed with ASPEN-PLUS
(1995) using various model combinations. With the combination of the UNIQUAC model for the liquid phase
activity coefficients, the Redlich-Kwong EOS for the vapour phase, the Rehfinger-Hoffmann expression (1990) for
the temperature dependent equilibrium constant term, and, the non-ideal expression for the stoichiometry based
equilibrium constant term, it was possible to match the results reported by Jacobs and Krishna (1993) and those of
Hauan et al. (1995). Figure 1 shows the variation of fractional conversion of iso-butene as a function of the
methanol feed location. With the UNIFAC model (for the liquid phase activity coefficient), although the high
conversion solutions were found to be approximately similar, the low conversion solutions (between feed stages 8
to 10) were found to be somewhat different (not shown in Fig. 1). Figure I also shows that using the Colombo et
al. (1983) expression for the temperature dependent equilibrium constant term, multiple solutions are not obtained
and the fractional conversion of iso-butene is different for methanol feed stages 11 to 14 (Curve B in Fig. 1). The
phase diagrams shown in Fig. 2 (Rehfinger-Hoffmann expression used) confirm the existence of reactive
azeotropes for inert compositions (1-butene mole fraction) greater than 0.0155. Using the Colombo expression,
however, the reactive azeotrope could not be found. Therefore, for the MTBE process, the choice of the
temperature dependent equilibrium constant expression is very important
The esterification simulations have been performed with ASPEN-PLUS and READYS (Ruiz et al., 1995)
using various model combinations. The simulation results obtained with ASPEN-PLUS are shown in Figures 3a-
3c, and, the corresponding steady states obtained through dynamic simulations with READYS are shown in Fig. 4.
From these figures, an important point to note is that the experimental data of Suzuki et al. (1971) are quite
difficult to match unless the "fitted" activity coefficient model (modified Margules in Figure 4) proposed by Suzuki
et al. is employed together with the expressions for the reaction kinetics. With ASPEN PLUS, the best match of
the Suzuki et al. data could be achieved with the combination of UNIFAC for the liquid phase, the Virial equation
for the vapour phase (taking into account, association and dimerization) and the Venkataraman et al. (1990) rate
of reaction expression. The CPE program package did not find any reactive azeotrope for this system.
Level 2 : Relationships
Model/parameter Sensitivities: For the MTBE process, the activity coefficient model parameters have been found
to be sensitive to the low conversion solution. It was possible even to obtain UNIQUAC model parameters which
gave only the high conversion solutions (for the reactive zone). The choice of the temperature dependent
expression (or the parameters for this expression) also appears to be important for the low conversion region. Note
that the low conversion corresponds to higher temperatures and that the deviation between the Rehfinger-
Hoffmann and the Colombo et al expressions increase as the temperature increases. For this reason, only the low
conversion solutions are affected by use of the Colombo et al. expression. Neglecting the non-ideal term (not
recommended in this paper) of the stoichiometry based equilibrium constant expression, also produces the high
and low conversion solutions (which are different from the reported solutions of Hauan et al.).
For the esterification process, the sensitivity of the model parameters is also very high. If the reaction is
described by a correlated reaction kinetic expression, then the corresponding activity coefficient model parameters
used together with this correlation must be employed in the simulations. That is, activity coefficient model
parameters estimated from purely vapour-liquid equilibrium data, when employed in process simulations will not
produce acceptable results. The ASPEN-PLUS results show that the physical equilibrium based activity coefficient
model parameters can be used, when the association and dimerization of acetic acid in the vapour phase are also
considered. It can be noted from Fig. 3b, that the rate of generation of ethyl acetate is approximately zero.
Therefore, it is likely that these stages are in chemical equilibrium. Subsequent computations of the rate of change
of Gibbs energy (from the known liquid phase compositions) also show that equilibrium has indeed been attained.
Influence of Phase Diagrams: The phase diagrams of the type shown in Fig. 2 (temperature-composition
diagrams) provides information related to the location of the feed and the influence of the inert composition (e.g.,
for the MTBE process). The existence of reactive azeotropes increases the importance of these phase diagrams.
Figure 5a shows the location of the stage compositions (elemental mass fractions calculated with Eq. 2) for the
high and low conversion solutions when the methanol feed stage is 10. It can be noted that the high conversion
solution stage compositions are located in one end of the phase diagram while the low conversion solution is
located at the other end. A magnification of the diagram between 0.4 and 0.6 would show that at stage 10, the
composition is exactly on the reactive azeotrope point.
The location of the reactive azeotrope is closely related to multiple solutions. For the MTBE process, Fig.
5b shows the distribution of the calculated reactive relative volatilities (using Eq. 4) for reactive stage 10 as a
function of methanol feed location. It can be noted that for methanol feed at stage 10 or above, the conditions for
reactive azeotrope is satisfied on reactive stage 10. From the phase diagrams in Fig. 2 and considering the 1-
butene stage compositions (for the low conversion solution), it can also be noted that the value of Xa for stage 4 lie
after the corresponding reactive azeotrope, and, outside the zone corresponding to the high conversion solution.
$270 European Symposium on Computer Aided Process Engineering~6. Part A
Therefore, in this case, the higher conversion solution is not obtained (implying that a relationship exists between
the two multiple solutions, the location of the reactive azeotrope and the choice of the initial condition).
CONCLUSIONS
Through two well known reactive distillation processes, we have highlighted the results from a systematic analysis
related to design and operation of these processes. Because the reactive systems are highly system specific, it is not
feasible to propose a generalized methodology. The analysis, however, show that there exists a set of sensitive
properties and that the selected models for their predictions play an important role in the design/operation of the
distillation columns. The analysis also illustrate how design decisions related to feed location, product
specification and initial conditions can be made, and, points out the dangers related to design/operation of the
reactive distillation columns due to incorrect choices of the models/parameters. Therefore, the basic steps of the
proposed analysis approach are also valid for other reactive systems. Multiple solutions appear to be related to the
existence of reactive azeotropes, and, the design/operation of the reactive distillation columns are closely related to
the phase diagrams of the reactive system. Current and future work is focussing on the development of a general
reactive distillation model and the development of an algorithm which combines design and operation through the
elemental mass fraction based phase diagrams. Finally, compared to the transformation variables based approach,
the elemental mass balance based approach to simulation, design and analysis provides a promising alternative
that deserves further attention.
REFERENCES
Agreda, V.H., Partin, L.R., and Heise, W.H., 1990, High-purity Methyl Acetate via Reactive Distillation, Chem.
Eng. Prog., 86, 40.
Aspen Technology Inc., 1995, The ASPEN PLUS User "s Manual. Ver.8.5-6.
Barbosa, D., and Doherty, M.F., 1988, Design of Multicomponent Reactive Distillation Columns, IChem. Eng.
Symposium Series No. 194, B369.
Colombo, F., Cori, L., Dalloro, L., and Delogu, P., 1983, Equilibrium Constant for the Methyl tert-butyl ether
Liquid Phase Synthesis by use UNIFAC, Ind. Eng. Chem. Fundam., 22, 219.
De Garmo, J.L., Parulekar, V.N., and Pinjala, V.,1992, Consider Reactive Distillation, Chem. Eng. Prog. 88,43.
Hauan, S., Hertzberg, T., and Lien, K.M., 1995, Why methyl tert-butyl ether Production by Reactive Distillation
May Yield Multiple Solutions, Ind. Eng. Chem. Res., 34, 987.
Ignatius, J., J~irvelin, H., and Lindquist, P., 1995, Use TAME and Heavier Ethers to improve Gasoline Properties,
Hydrocarbon Processing, 2, 51.
EuropeanSymposiumon ComputerAidedProcessEngineering--6.Part A $271
Jacobs, R., and Krishna, R., 1993, Multiple Solutions in ReactiveDistillation for Methyl tert-butylether Synthesis,
Ind. Eng. Chem. Res., 32, 1706.
Ptrez-Cisneros, E. S., Gani, R., and Michelsen,M.L., 1995, Reactive Separation Systems. Part I: Computationof
Physical and ChemicalEquilibrium,SEP 9547, IVC-SEP Report, DTU, Denmark.
Rehfinger, A., and Hoffmann,U., 1990, Kineticsof the Methyltertiarybutyl ether Liquid Phase Synthesis
Catalysed by Ion ExchangeResin-I. IntrinsicRate Expression in the Liquid Phase Activities, Chem. Eng.
Sci., 45, 1605.
Ruiz, C.A., Basuaido, M S., and Scenna,N.J., 1995, Reactive Distillation DynamicSimulator, Trans IChem.
Engrs., Part A, 73, 363.
Saito, S., Michishta, T., and Maeda, S., 1971, Separationof Meta- and Para-xyleneMixture by Distillation
accompaniedby ChemicalReactions,J. Chem. Eng. Japan, 4, 37.
Sawistowski, H., and Pilavachi, P., 1988, Performanceof Esterificationin a Reaction-DistillationColumn, Chem.
Eng. Sci., 43, 355.
Suzuki, I., Yagi, H., Komatsu,H., and Hirata, M., 1971, Calculation of MulticomponentDistillation accompanied
by a ChemicalReaction,J. Chem. Eng. Japan, 4, 26.
Ung, S., and Doherty M.F., 1995, Vapour-liquidPhase Equilibrium in Systemwith Multiple ChemicalReactions,
Chem. Eng. Sci., 50, 23.
Venkataraman,S., Chan, W.K., and Boston, J.F., 1990, ReactiveDistillation using ASPEN PLUS, Chem. Eng.
Prog., 86 (8), 45.
ABBREVIATIONS
CPE: Chemical-PhysicalEquilibrium; MTBE:Methyl-tert-butylether; TAME:Tert-amylmethyl ether.
ACKNOWLEDGEMENT
The authors would like to acknowledgethe useful informationreceivedfrom ProfessorK. Lien and Mr. S.
Hauan with respect to the MTBE steady state results with ASPENPLUS.
"~0,3 0,3
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Fig 1. Fractionalconversionof isobuteneas a functionof the Fig 2. ReactivePhasediagramscorresponding
methanol feedlocationusing two differentexpressionsfor K(T). to the MTBEprocess.MethanolFeedat stage10.
$272 European Symposiumon ComputerAided Process Engineering---& Part A
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using different thermodynamic models, different thermodynamic models.
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Fig. 3c. Activity Coefficients of Ethyl Acetate Fig.4. Computed profiles of Temperature
at each stage, with READYS.
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mass fractions for two inert compositions, a function of Methanol feed location.