12/11/2018 AspenTech: Knowledge Base

Why is rate-based distillation better than using

equilibrium stages with ef ciencies?
Products: Aspen Plus
Last Updated: 20-Jan-2017
Versions: Multiple, V7.0, V7.1, V7.2, V7.3, V7.3.2, V8.0, V8.2, V8.4, V8.6, V8.8, V9.0
Article ID: 000025980
Primary Subject: Columns

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Problem Statement
Why is Aspen Rate Based Distillation (RateSep) better than using equilibrium stages with ef ciencies? There seem to be a
lot of fudge factors in rate-based distillation also?

Solution
Equilibrium stage ef ciencies are a function of all column conditions ( ow, temperature, pressure). This means that they
generally do not extrapolate well to other conditions. A rate-based distillation model has more basis in reality using mass-
and heat transfer correlations based on transfer properties and tray/packing geometry to predict column performance,
without the need of ef ciency factors and the fudge factors have more physical meaning. Once the column is calibrated to
one set of conditions, it does generally extrapolate to other conditions. We have customers who have had success using
RateSep and being able to predict new scenarios after tuning the column to an initial set of conditions. This added degree of
rigor is especially critical for modeling gas scrubbers, sour water strippers, azeotropic systems, reactive distillations, nitric
acid absorption columns, narrow-boiling separations, and other highly non-ideal separation processes.

The rate-based modeling approach has many advantages over the equilibrium-stage modeling approach. The rate-based
models represent a higher delity, more realistic modeling approach and the simulation results are more accurate than
those attainable from the equilibrium-stage models. The rate-based modeling approach can reduce the risk of inadequate
designs or off-spec operation because the rate-based models explicitly account for the actual column con guration which
affects column performance.

Designed to model reactive multistage separation problems rigorously and accurately, Aspen RateSep balances gas and
liquid phase separately and considers mass and heat transfer resistances according to the lm theory by explicit calculation
of interfacial uxes and lm discretization. The lm model equations are combined with relevant diffusion and reaction
kinetics and include the speci c features of electrolyte solution chemistry, electrolyte thermodynamics, and
electroneutrality where appropriate. The hydrodynamics of the column is accounted for via correlations for interfacial area,
hold-up, pressure drop, and mass transfer coef cients.

Fast reactions for processes such as CO2 removal with MEA do need to use the discretization lm model available in the
current rate-based distillation model not available previously in the older RateFrac.

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RateSep uses a rate-based modeling approach, which is much more rigorous than the equilibrium stage modeling approach
employed by the original RadFrac module. The rate-based model assumes that the separation is caused by mass transfer
between the contacting phases, and uses the Maxwell-Stefan theory to calculate the mass transfer rates[1]. The equilibrium
modeling approach assumes that the contacting phases are in equilibrium with each other, which is inherently awed
because the contacting phases are never in equilibrium in a real column.

The rate-based (or nonequilibrium) modeling approach has a lot of advantages over the equilibrium modeling approach, and
is becoming more and more popular in both the academia and the industry. The rate-based model is more reliable and
accurate than the equilibrium model, and therefore can reduce the risk of inadequate designs or off-spec operation. The
rate-based model gives more realistic simulation results than the equilibrium model, because the column con guration is
included in the rate-based model and will affect the simulation results as it should. Engineers can use the rate-based model
to do more realistic what-if studies and improve the operations of existing columns. The rate-based model can also predicts
the behavior of a column more accurately, and can help the process control engineers develop better control strategies.

It is generally accepted in the literature that the rate-based model is more accurate than the equilibrium model. In some
cases the rate-based model gives accurate results while the equilibrium model gives wrong results.

Taylor et al. [2] reviewed the modeling of distillation and concluded that the rate-based simulations "are not only feasible,
but in some circumstances they should be regarded as mandatory". For a bubble cap distillation column used to separate
water, ethanol and acetone, the composition trajectory predicted by the rate-based model agrees with the experimental
data very well, while the equilibrium model gives very different results. The rate-based model also accurately predicts that
the distillation boundary is crossed, while the equilibrium model wrongly predicts that the distillation boundary can never
be crossed. Taylor et al.[2] also used experimental data from Springer et al.[3] for the water-cyclohexane-ethanol system to
demonstrate that the rate-based model can predict the composition trajectory accurately, while the equilibrium model
cannot.

Kucka et al.[4] used the rate-based model to simulate the sour gas absorption by aqueous amine solutions. They compared
the simulation results with experimental data from a pilot plant column and an industrial scale column and found that the
rate-based model can accurately predict the temperature and composition pro les.

Springer et al.[5] used the rate-based model to simulate ternary azeotropic distillation and compare the simulation results
with experimental data from a bubble cap distillation column with the water-ethanol-methylacetate system. They found
that the rate-based model ?is in excellent agreement with a series of experiments carried out in different composition
regions. In sharp contrast, an equilibrium (EQ) stage model fails even at the qualitative level to model the experiments.? They
concluded that "for reliable simulation of distillation of azeotropic systems exhibiting a distillation boundary, we must adopt
a rigorous NEQ (or rate-based) stage model."

Eckert and Vanek[6] studied three-phase distillation columns with the rate-based modeling approach. Extensive
experimental work for the ethanol-water-cyclohexane system[7-9] was used to compare the rate-based approach and the
equilibrium approach. They found that the rate-based model can predict the composition pro les much better than the
equilibrium model, especially in the middle of the column. The rate-based model also predicts the disappearance and
reappearance of the second liquid phase very well.

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Kreul et al.[10] studied the modeling of reactive separation processes in packed columns and found that the concentration
pro les calculated by the rate-based and equilibrium models can be very different, and the rate-based model should be
preferred for reactive separation processes.

Kenig et al.[11] studied reactive absorption using models with different complexities. Both the steady state and dynamic
models were used. They found that for a H2S scrubber, the rate-based modeling approach can predict the concentration
pro les very well, while the equilibrium model may yield results completely inconsistent with the experimental studies.

Sundmacher and Hoffmann[12] used a rate-based model to simulate reactive distillation of the MTBE system in a packed
column. The simulation results were validated with experimental data from a laboratory scale column with excellent
agreement.

Frey and Stichlmair[13] mentioned in their review paper on reactive distillation that rate-based model has been used to
accurately predict the performance of commercial reactive distillation processes in Germany and Texas, and that the model
has been validated for the design of TAME, ETBE and TAEE units with data from semi-commercial operations.

Pinjala et al.[14] used a rate-based model for reactive distillation of the MTBE and TAME processes in columns lled with
Koch Katamax? packing. The simulation results were compared to some pilot-plant data with good agreement.

Most recently, Kloker et al.[15] compared the rate-based model with the equilibrium model for two reactive separation
processes, the synthesis of ethyl acetate from ethanol and acetic acid via reactive distillation and the synthesis of octyle
hexanoate from octanol and hexanoic acid via reactive stripping. They found that the rate-based model with a ne
discretization is able to match the column temperature pro le and the bottom concentration better than the equilibrium
stage model.

The rate-based modeling approach has been used successfully to model many industrial separation processes. It has been
adopted by many researchers to model reactive distillation of MTBE[12, 14, 16], TAME[13, 14], ETBE[13], TAEE[13], ethyl
acetate[15], propylene glycol[17], ethylene glycol[17], propyl acetate[18], diacetone alcohol[19, 20] etc. It is also used to
model other reactive separation processes such as reactive absorption[4, 11, 15, 21] and reactive stripping[15]. The rate-
based model has also found successful application in azeotropic distillation[5] and three-phase distillation[6, 22, 23].

The rate-based model is especially preferred over the equilibrium model in the following situations:

(1)   Packed columns. The rate-based model does not need the HETP (Height Equivalent to a Theoretical Plate) of
the packing, while the equilibrium model does. The HETP can vary widely from component to component and from
packing to packing, and cannot be estimated accurately in most cases.

(2)   Absorption and desorption. The absorption and desorption processes are normally operated in conditions far
away from phase equilibrium, and are mass transfer and heat transfer limited. The tray ef ciency for a
absorption/desorption column can be as low as 5%[2]. Therefore, the rate-based model is more appropriate than
the equilibrium model.

(3)   Reactive separation such as reactive distillation and reactive absorption. The rate-based model can model
reaction rates much more accurately than the equilibrium model. The ef ciencies are not meaningful for reactive
separation processes.

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(4)    Strongly nonideal systems. The ef ciencies are highly uncertain and can vary widely from tray to tray and
component to component. It is very dif cult to determine the ef ciencies for the equilibrium model. Therefore, the
rate-based model should be preferred.

(5)   Columns with a complicated con guration (pump-around, side streams). It is very dif cult to determine the
theoretical stage locations for pump-around and side streams, which are necessary for the equilibrium model. The
rate-based model does not need any information about theoretical stages, and should be preferred.

(6)   Columns with mixed trays and packing. It is very dif cult to determine the number of theoretical stages for
each tray/packing section. The rate-based model does not need any information about theoretical stages, and
should be preferred.

The major drawback of the rate-based model is that it is much more complicated than the equilibrium model. Previously, the
rate-based model was considered as impractical due to its complexity. Right now, the rate-based model can be solved readily
on any mainstream PC, thanks to the ever-increasing computing power.

There are some special advantages for RateSep:

(1)    RateSep is seamlessly embedded in RadFrac. It is very easy to con guration a RateSep simulation for someone
who does not know very much about the rate-based model. The complexity of the rate-based model is in the
background and not noticeable to the user.

(2)    RateSep has many built-in correlations for mass transfer and holdup. There are default correlations for each
tray/packing type. The user does not need to worry abut the correlation unless he/she wants to choose other
correlations.

(3)    RateSep has detailed examples for user subroutines. The user can easily modify the examples to create his/her
own user subroutines for mass transfer, heat transfer and holdup.

(4)    A continuation method has been implemented in RateSep to improve the convergence for problems that are
dif cult to converge. The user only needs to choose two continuation parameters to use the continuation method.

(5)    Several tuning parameters have been de ned to help the advanced users to model a column more accurately.
The user also has control on how he/she wants to calculate the uxes, how to average the diffusivities and mass
transfer coef cients.

(6)    It is very easy to switch between the equilibrium mode and the rate-based mode. For a large owsheet, if the
block with RateSep fails to converge, the user can easily switch back to the equilibrium mode and make the
owsheet converge. After that, he/she can switch to the rate-based mode and try to make the whole owsheet
converge.

(7)    RateSep supports lm reactions and lm discretization. Therefore, it is capable of solving reactive separation
problems accurately.

It is necessary to have accurate properties, kinetic and equilibrium constants if needed, and then tune the factors such as the
interfacial area factor and the heat transfer factor for the rate-based column. But, because the model has more physical
meaning, it can then be used to model new situations more accurately. A number of our customers have used the Rate Based
Distillation model successfully.

References

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[1] Taylor, R. and Krishna, R. (1993). Multicomponent mass transfer. New York: Wiley.

[2] Taylor, R. , Krishna, R. and Kooijman, H. (2003). Real-World modeling of distillation. Chemical Engineering Progress,
98(7), 28-39.

[3] Springer, P.A.M., et al. (2002). Crossing of the distillation boundary in homogeneous azeotropic distillation: in uence
of interphase mass transfer. Industrial and Engineering Chemistry Research, 41, 1621-1631.

[4] Kucka, L. et al. (2003). On the modeling and simulation of sour gas absorption by aqueous amine solutions. Chemical
Engineering Science, 58, 3571-3578.

[5] Springer, P.A.M., van der Molen, S. And Krishna, R. (2002). The need for using rigorous rate-based models for
simulations of ternary azeotropic distillation. Computers and Chemical Engineering, 26, 1265-1279.

[6] Eckert, E. and Vanek, T. (2001). Some aspects of rate-based modeling and simulation of three-phase distillation
columns. Computers and Chemical Engineering, 25, 603-612.

[7] Muller, D. et al. (1997). Experimental validation of an equilibrium stage model for three-phase distillation. IChemE
Symposium Series, 142, 149-159.

[8] Klein, W. (1996). Experimental investigation of the stationary and dynamic behavior of heteroazeotropic distillation.
Diploma project. RWTH Aachen (in German).

[9] Dux, A. (1996). Veri cation of an equilibrium model in dynamic simulation of three-phase distillation. Diploma
project. RWTH Aachen (in German).

[10] Kreul, L.U., Gorak, A. and Barton, P.I. (1999). Modeling of homogeneous reactive separation processes in packed
columns. Chemical Engineering Science, 54, 19-34.

[11] Kenig, E.Y., Schneider, R. and Gorak, A. (2001). Reactive absorption: optimal process design via optimal modeling.
Chemical Engineering Science, 56, 343-350.

[12] Sundmacher, K. and Foffmann, U. (1996). Development of a new catalytic distillation process for fuel ethers via a
detailed nonequilibrium model. Chemical Engineering Science, 51, 2359-2368.

[13] Frey, T. and Stichlmair, J. (1999). Thermodynamic fundamentals of reactive distillation, Chemical and Engineering
Technology, 22, 11-18.

[14] Pinjala, V. et al. (1992) Rate based modeling of reactive distillation operations, AIChE annual meeting, Session 3,
Distillation with reaction.

[15] Kloker, M. et al. (2004) Rate-based modeling and simulation of reactive separations in gas/vapor-liquid systems.
Chemical Engineering and Processing, to be published.

[16] Pyhalahti, A. and Jakobsson, K. (2003). Rate-based mixed-pool model for a reactive distillation column. Industrial
and Engineering Chemistry Research, 42, 6188-6195.

[17] Dhale, A.D. et al. (2004) Propylene glycol and ethylene glycol recovery from aqueous solution via reactive
distillation. Chemical Engineering Science, 59, 2881-2890.

[18] Bart, H.-J. and Landschutzer, H. (1996). Heterogene Reaktivdestillation mit axialer Ruckvermischung, Chem. Ing.
Tech., 68, 944-946.

[19] Huang, C.C. et al. (1998). A study of mass transfer behavior in a catalytic distillation column. Canadian Journal of
Chemical Engineering, 76, 323-330.

[20] Huang, C.C. et al. (1998). Application of catalytic distillation for the aldol condensation of acetone: a rate based
model in simulating the catalytic distillation performance under steady state conditions. Chemical Engineering Science,
53, 3489-3499.

[21] Bolhar-Nordenkampf, M. et al. (2004). Modeling selective H2S absorption and desorption in an aqueous MDEA-
solution using a rate-based non-equilibrium approach. Chemical Engineering and Processing, 43, 701-715.
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[22] Repke, J., Villain, O. and Wozny, G. (2004). A nonequilibrium model for three-phase distillation in a packed column:
modeling and experiments. Computers and Chemical Engineering, 28, 775-780.

[23] Higler, A. et al. (2004). Nonequilibrium modeling of three-phase distillation. Computers and Chemical Engineering,
28, 2021-2036.

 
 

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