Chemical Engineering and Processing 41 (2002) 413 418

www.elsevier.com/locate/cep

Comparison of computer simulation of reactive distillation using

ASPEN PLUS and HYSYS software

Q. Smejkal a,*, M. S& oos b,1

a
ICT Prague, Technicka 5, CZ-166 28, Prague,Czech Republic
b
Department of Chemical Engineering, STU Bratisla6a, Radlinskeho 9, SK-812 37, Bratisla6a, Czech Republic

Received 5 June 2001; received in revised form 25 July 2001; accepted 25 July 2001

Abstract

A comparison of computer simulation results of reactive distillation obtained by ASPEN PLUS and HYSYS software was done.
Esterification of acetic acid and 1-butanol was chosen as the model reaction proceeding in a reactor and reactive distillation
column (RD) system. A nearly equimolar reaction mixture was fed into the equilibrium fixed bed reactor and the liquid product
was continuously fed into reaction zone of the reactive distillation column. The same mass balance in the reactor and reactive
distillation column was used to compare the adequacy of chosen simulation systems. The results of computer simulation have been
consequently compared with pilot plant experimental data. A good agreement was reached. 2002 Elsevier Science B.V. All
rights reserved.

Keywords: Butylacetate; Reactive distillation; Simulation; ASPEN PLUS; HYSYS

1. Introduction enables a simplification of the butylacetate technology.

Butylacetate is a common solvent, used in the chemi-
cal industry, e.g. as a paint solvent. The production of
butylacetate has been growing in the last decade due to
a continual demand for solvents not containing
aromatics.
Esterification has been traditionally catalyzed by
acidic agents, e.g. sulphuric acid, p-toluenesulfonic
acid, etc. Recently, heterogeneous catalysts, like ion
exchange resins, have also been applied. Using liquid
acidic catalysts, several problems occur like corrosion
and difficulties with waste disposal. Furthermore, to
increase conversion, either an excess of reactants must
be used, or at least one of the products must be
constantly removed from the reaction system because
esterification reactions are in general reversible reac-
tions. A reactive distillation system consisting in a solid
acidic catalyst in the reaction zone of the column
* Corresponding author. Tel.: + 36-420-2-24354188; fax: +36-
420-2-3119657.
E-mail addresses: quido.smejkal@vscht.cz (Q. Smejkal),
soos@cvt.stuba.sk (M. S& oos).
1
Tel.: + 36-421-7-59325208; fax: + 36-421-7-52496743.
The utilisation of a homogeneous catalyst and associ-
ated problems with product-catalyst separation and
with waste disposal in traditional technologies are dis-
advantageous in comparison with ecologically friendly
catalytic active packing used in butylacetate synthesis
by reactive distillation technique.
The reactive distillation processes have become im-
portant in industrial scale in the last decade. The stud-
ies of reaction and separation operations are usually
divided into experimental and simulation parts. The
topic of this paper is focused on the relevance of the
commercial software ASPEN PLUS and HYSYS for the
simulation of RD problems. The modern trends in scale
up and process design are oriented to the technology
aided engineering software. The most important ques-
tion is then the adequacy of the chosen software, which
very often reduces the precision of chemical and phases
equilibrium.
In the present paper, the simulation packages ASPEN
PLUS and HYSYS were used to predict the behaviour of
the esterification reactor and the RD column in the
esterification system containing acetic acid and 1-bu-
tanol. The attention has been paid to the composition
of product streams and mass and heat balances.

0255-2701/02/$ - see front matter 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 2 5 5 - 2 7 0 1 ( 0 1 ) 0 0 1 6 0 - X
414 Q. Smejkal, M. S& oos / Chemical Engineering and Processing 41 (2002) 413418
The simulation results of butylacetate synthesis were
compared with pilot plant experimental data. The pilot
plant system of butylacetate consists of an equilibrium
reactor and a reactive distillation column. The equi-
librium reactor affords a mixture of reaction products
near its equilibrium composition. Considering the fact
that conversion of this equilibrium reaction is near 67%
[1], a reaction distillation column for increasing the
conversion and separation was used. The advantage of
esterification pre-reactor is based on the fact that the
greatest part of reaction component can react before
RD column and the throughput of reaction system
increases [2].
Two commercially program packages were employed
in this study, the software ASPEN PLUS 10.1 provided by
Aspen Technology Ltd. and the software HYSYS 2.1
made by AEA Technology Ltd. Both programs have
been frequently used in chemical engineering studies.
The detailed study and behaviour of the programs as
well as practical examples of simulation calculations are
available in the literature [3,4].
2. Computer simulation
2.1. Simulation assumption
A computer simulation was applied to the description
of the reactive distillation and the esterification pre-re-
actor. A model of a continuous isothermal equilibrium
reactor was used. Therefore, a set of assumptions was
applied to simplify the calculation. The most important
assumption for the RD simulation was based on the
fact that the mathematical model supposed both va-
pour liquid and chemical equilibrium in all theoretical
stages (TS) of the reaction zone and the phase equi-
librium in separation sections. Pressure drop was ne-
glected along the column (5 kPa in 45 TS), the column
was run under atmospheric pressure and liquid and
vapour phases were ideally mixed. The basic parame-
ters of the apparatus are summarised in Table 1.
Table 1
Process simulation parameters
Mathematical model Parameter
Equilibrium reactor Feed rate
Molar ratio NBA/AA in the feed
Reactive distillation column Reflux flow in the RD column (OP)
Precision of calculation
Numerical method
Maximum number of iterations
2.2. Phase and chemical data
The phase equilibrium data play an important role in
the whole engineering design of the esterification distil-
lation process. In this study, activity coefficients were
calculated by the NRTL equation. The case system
chosen in this study is typical by a non-ideal behaviour
of the liquid phase (the existence of a ternary
azeotropic mixture with 1-butanol and waterb.p.
90 C, [5] and two partial mixed liquids). Because the
program module RadFrac of the software ASPEN PLUS
was not able to describe the VL equilibrium properly,
for some binary systems, data of binary coefficients
(NBA-BAC and Water-AA) [6,7] available in the litera-
ture were used. In the ASPEN PLUS database there are
several sets of binary parameters available for VL
phase equilibrium, and for unification of binary coeffi-
cients the data from the HYSYS database (BAC-AA,
water-AA, AA-BAC) were used.
In case of the binary system water-NBA and -BAC,
the existence of two liquid phases for the computation
of binary coefficients of the VLL equilibrium was
supposed for the simulation of both the equilibrium
reactor and the reactive distillation column.
3. Pilot plant experiments
A nearly equimolar mixture of acetic acid and 1-bu-
tanol was fed to an equilibrium reactor (operation
temperature 75 C) packed with an acidic ion exchange
resin catalyst. A reaction mixture with an almost equi-
librium composition was fed into the middle position
(22 TS from the top) of the reaction zone in the RD
column (Fig. 1).
The esterification of acetic acid with 1-butanol pro-
ceeded in a stainless steel column with a 80 mm ID
operating continually under atmospheric pressure (F-
factor 0, 12). The experiments were done in a pilot-
plant unit in Chemopetrol Ltd. Co, Litvinov, CZ. The
apparatus consisted of a rectification column with re-
Dimension Value
kg/h 2,8117
1,096
kg/h 11,1
9106
Newton
100
 Q. Smejkal, M. S& oos / Chemical Engineering and Processing 41 (2002) 413418 415

mental data for accurate calculation of chemical equi-

Fig. 1. Flow sheet of the equilibrium reactor and the reactive distilla-
tion column for production of butylacetate.
boiler, condenser and a phase separator. The reaction
zone of the reactive distillation column was filled with the
structural packing KATAPAK S with a efficiency of 3
TS, containing an acidic ion exchange resin in H+ form
(5 eq/kg). Both the lower and upper separation zones
were packed by high effective CY structural packing.
The efficiency of each zone was equivalent to 20 TS.
The water formed by the reaction was taken off from
the phase separator and the major part of the organic
phase was refluxed back to the column. Another smaller
part of the organic phase was withdrawn as distillate.
Crude butylacetate (bottom product) was withdrawn at
a rate assuring constant liquid holdup from the reboiler.
There is no side reaction in the RD system. The
detailed description of pilot plant column and experi-
mental work as well as the sensitivity study (operating
conditions versus selectivity of the process) have been
discussed in our previous papers [8].
librium. Concerning minimal temperature dependence of
equilibrium constant for production of butylacetate with
no specific information about temperature dependence
of Kr, the experimental measured value (at 75 C) of the
equilibrium constant Kr= 4,27, was used. This value is
in a good agreement with data available in the literature
[1]. A comparison of computer simulation and pilot plant
experimental data is summarised in Table 2. For both
programs a chemical equilibrium was supposed to be the
parameter of the chemical reactor in the calculation
model. The conditions and feed composition remained
the same.
The results in Table 2 show the adequacy of both
chosen programs. Also calculated conversions of esterifi-
cation are in good agreement with published values [1].
Therefore, it is possible to note that the product from the
esterification reactor with a composition of butylacetate
close to 58 mass % will be fed to the RD column. On
the other hand, the composition and progress of the
reactive distillation column will be influenced by the
reaction conversion in the esterification pre-reactor.
The presented results are valid only in a narrow
interval of the reaction temperature (9 5%) in the
esterification reactor. For the reactor with reaction in
both vapour and liquid phases or reaction with vapour
liquid separation, one should first check the build-in data
for the NRTL equation.
The calculation of reaction composition in the equi-
librium reactor by minimisation of Gibbs free energy
depends on temperature and leads to important changes
of product composition with increasing system tempera-
ture (ASPEN PLUS) [9]. The chemical reaction should be
defined at constant temperature. On the other hand, the
software HYSYS allows defining the equilibrium constant
independently on temperature [10].
Table 2
Comparison of experimental product composition in the esterification
reactor with results obtained by simulation using ASPEN PLUS and
HYSYS software

Composition Program
4. Results and discussion (wt.%)
Feed stream Product stream

4.1. Simulation of equilibrium reactor Exp+ASPEN Experiment ASPEN HYSYS

+ HYSYS
In this study the esterification reactor was calculated
with the aid of build-in equilibrium models. The software AA 39,533 12,71 11,96 13,46
NBA 53,462 21,54 19,43 21,27
ASPEN PLUS allows the description of chemical equi-
BAC 4,337 56,27 57,67 54,78
librium in a reactor by the minimisation of Gibbs free Water 2,668 9,48 10,94 10,49
energy. The HYSYS program is able to define the equi-
Conversion of 0,678 0,697 0,66
librium reaction using minimisation of Gibbs free en- AA
ergy, as equilibrium constant, which is independent or
dependent of temperature and the regression of experi- feed composition was the same for all simulations.
416 Q. Smejkal, M. S& oos / Chemical Engineering and Processing 41 (2002) 413418

Table 3 the experimental measured mass balance, and conse-

RD Column comparison of pilot plant experiments and simulation
quently the temperature profile. The results are listed in
data
Table 3.
Parameter Experiment ASPEN PLUS HYSYS Table 3 shows a comparison of pilot plant experi-
ments and simulation data. Some differences appeared
Feed flow (kg/h) 2,811 2,811 2,811 in the flow rate of bottoms product streams, reaction
Reflux (kg/h) 11,08 11,1 11,1
water and the organic phase. These differences were
Reboiler duty (kW) 3 2,4 2,73
T boiler (C) 127 128 128 caused by experimental errors (910%) of the flow rate
measurements. Differences of experimental and simula-
Product (kg/h) 2,6 2,2 2,19
Product composition
tion compositions for product stream and reflux can be
(wt.%) explained by the phase and reaction equilibrium for
Acetic acid 0,178 0 0 theoretical and reaction stages. In the case of pilot
Butanol 0,323 0,314 0,2 plant experiment the chemical and phase equilibrium
Butylacetate 99,5 99,69 99,8 were not reached. Another reason is temperature de-
Water phase (kg/h) 0,325 0,3977 0,39 pendence of equilibrium constant for esterification reac-
Organic phase (kg/h) 0,123 0,214 0,236 tion and simulation. For simulation the equilibrium
Reflux composition constant Kr=4,27 was used. This value of Kr was
(wt.%) obtained from experiments performed at temperature
Water 10,5 12,06 14,42 75 C. On the other hand, the temperature on the feed
Acetic acid 0,356 0 0,08
Butanol 53,37 51,74 48,79
stage of the RD column is between 115 and 120 C, so,
Butylacetate 35,77 36,20 36,77 this fact influence the reaction equilibrium.
By comparing both programs, the mass balance
along the equilibrium reactor is not absolutely relevant,
The simulation error in chemical equilibrium calcula- (see Table 3), and thus, small differences between calcu-
tion in the RD column is minimised by the definition of lated results can occur. These differences are observed
a proper equilibrium constant in the module of the in the amount of NBA and BAC in the rectifying
reaction zone in the RD system, which is in both section and consequently in the temperature and con-
programs allowed. centration profiles drawn in Figs. 2 and 3. Following
these explanations, the results and comparison of simu-
4.2. Simulation of the reacti6e distillation column lations show, that both computer simulations are in a
good agreement with experiments.
The computer simulation parameters were the same The difference in the composition of reflux could be
in both programs. The operation conditions: reflux flow caused by a different definition of equilibrium reaction
and butylacetate production, were chosen to describe or different description of VLL equilibrium in the
the mass and enthalpy balances along the column. The simulation software used in this study. The influence of
reboiler duty determined the temperature in the bottom phase equilibrium and its description in the rectifying
part of the column and thus, the temperature profile part of the column can play an important role in the
could be compared. The feedback of the simulation was discussions concerning both simulation programs.

Fig. 2. Temperature profile along the RD column conditions for simulation are given in Table 3, , HYSYS; , ASPEN PLUS; , Pilot plant
experiment.
 Q. Smejkal, M. S& oos / Chemical Engineering and Processing 41 (2002) 413418 417

Fig. 3. Concentration profile in the liquid phase along the RD column ", NBA; , BAC; , water (simulation by ASPEN); , NBA; , BAC;
, water; (simulation by HYSYS).

The temperature profile along the RD column for
both simulations is illustrated in Fig. 2. The composi-
tion profile for the liquid phase composition is shown in
Fig. 3. The relation between HYSYS and ASPEN PLUS
calculations is good, only the measured temperature
below the reaction zone is higher than that obtained by
calculation. This inaccuracy may be explained by lower
boiler duty used in the calculation.
The temperature profile edge is dropped during the
calculations to the top column stages and the course of
the temperature curve is similar for experiments and
calculations (see the temperature profile on the temper-
ature curve for the experiment on the 23rd stage and
for simulation on the 23rd and the 35th stages). The
break on the feed stage is typical for the reactive
distillation process and represents the feed point loca-
tion on the column in the reaction zone.
The comparison between ASPEN PLUS and HYSYS
software in the concentration profile is relevant, both
programs calculated very close concentration profiles
along the column.
5. Conclusion
Commercial simulation programs HYSYS and ASPEN
PLUS have been used in this study. A reactive distilla-
tion system was chosen to compare the adequacy of
these program packages. An excellent agreement be-
tween experimental data and simulation results was
obtained. Thus the equilibrium model can be used to
describe chemical reaction and simulate the process. If
chemical and phase equilibrium data are very close,
both programs describe the reactive distillation of acetic
acid and 1-butanol properly. Simulation program pack-
ages HYSYS and ASPEN PLUS were applied to fit the pilot
plant experimental data. A good agreement was
obtained.
Concerning economical aspect, both programs
needed the same computation time for the same type of
computer for RD simulations. Therefore, the program
package prices should also play an important role in
the presented discussion. The software HYSYS is ap-
proximately two times cheaper in comparison with the
software ASPEN PLUS.
Appendix A: Nomenclature
AA acetic acid
BAC butylacetate
Kr equilibrium constant
NBA 1-butanol
Acknowledgements
One author (Q.S.) was supported by the Grant
Agency of the Czech Republic (grant No. 104/00/P004).
Other author (M.S& .) was partly supported by the Grant
Agency of the Slovak Republic (Grant VEGA 1/8112/
01).
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