10th International Symposium on Process Systems Engineering - PSE2009

Rita Maria de Brito Alves, Claudio Augusto Oller do Nascimento and Evaristo
Chalbaud Biscaia Jr. (Editors)
© 2009 Elsevier B.V. All rights reserved. 1005

A Software for the Calculation of the Exergetic

Efficiency in Distillation Columns
Cauê T. O. G. Costa1,*, Eduardo M. Queiroz1 and Fernando L. P. Pessoa1
1
Escola de Química – Universidade Federal do Rio de Janeiro, Av. Athos da Silveira
Ramos, n. 149, Edifício Centro de Tecnologia, Bloco E, Sala 209,CEP 21941-909, Rio
de Janeiro - RJ, Brazil.
*
E-mail address: caue.costa@gmail.com

Abstract
Many processes in chemical industries consume a lot of energy and often operate
inefficiently. This implies high operation costs, which can be reduced through
improvements in the use of energy in the process.
Distillation is an important unit operation that is widely used in industry and requires an
excessive energy demand.
The exergetic analysis, which is based on the second law of thermodynamics, is an
alternative to minimize this demand. Exergy or availability is the measure of the
maximum amount of stream energy that can be converted into shaft work if the stream
is taken to the reference state. This property may be applied to measure the quality of
energy employed in a process. Therefore, the purpose of this study is to develop a
program to calculate the exergetic efficiency and suggest, if necessary, possible
operational changes that lead to the reduction of energy losses by irreversibilities in
distillation columns.
The preliminary conclusion is that exergy analysis is vital for evaluating inefficiencies
in industrial processes and thus the exergetic analysis can be used as an important tool
not only for process synthesis but also for process optimization activities.

Keywords: exergy, distillation column, exergetic efficiency.

1. Introduction
Among the common utilized in industry processes, most attention was given to
distillation, an important unit operation that is widely used and requires an excessive
energy demand (Pessoa 2005). To evaluate the energy consumption, efficiencies based
in the produced work-supplied energy ratio are often used. But not all energy can be
turned into work, according to the second law of thermodynamics (Szargut et al 1988).
Thus, it is important measure the availability in industrial plants. The exergetic or
availability analysis can be used as alternative to minimize the irreversibility, resulting
in a better consume of energy. Exergy is defined as the amount of work obtainable when
some matter is brought to a state of thermodynamic equilibrium with the common
components of the natural surroundings by means of reversible process, involving
interactions only with the above-mentioned components of nature. This state property
may be applied to measure the quality of energy employed in a process (Szargut et al
1988).
The purpose of this work is to develop a software capable of calculate the exergetic
efficiency in distillation columns, working with a simulator process, and to suggests
improvements for a better exergetic utilization.
1006 C.T.O.G. Costa et al.

2. Bibliographic Review
The exergetic analysis has been largely applied in processes of power generation,
although not much applied in distillation processes (Maia 2001). This concept was
introduced by Rant and is directly related with the second law of thermodynamic.
Smith et al, presenting at chapter 5 a detailed description about the second law and
entropic balance. The generated entropy is proportional to the destructed exergy in a
process, as shown in the law of Gouy-Stodola:

δB = T0 S p

where δB is the exergy losses, T0 is the reference state temperature and S P is the
entropy produced.
Szargut et al defined the concept of exergy as in the preview section and deduces the
law of Gouy-Stodola abovementioned. They also show various forms of exergy
calculation to different thermal, chemical and metallurgic processes; the physical,
chemical and radioactive flow exergy calculation. Beyond, they show a data base for the
standard exergy to dry air and sea water components, and reference reactions for
calculation of the standard exergy to these reference environments.
Røsjorde et al studied the entropy production in diabatic and adiabatic separations of
propylene/propane, optimizing lower entropy production, and evaluating and discussing
the effects of changing operational conditions and the geometry of the column. The
main conclusions are that for less generation of entropy it was necessary increase the
areas of heat exchange in the reboiler and condenser and the number of trays.
Araujo et al studied the case of purification of EDC. In his work, showed ways of
calculating the exergetic efficiency in different approaches and identified that most of
the exergtic lost in the proposed separations occurs in the condenser.
Koeijer et al evaluted the production of entropy and exergetic losses on the
experimental column and identified that the column loses less exergy when there is heat
exchange in the trays.
Maia explained the concept of the reversible column and quasi-reversible column
proposed by Zemp (1994). And also optimizing separations networks through the
exergetic analysis for 3, 4 and 5 components systems.
Rivero et al simulated and evaluated the exergy losses in Tertiary Amyl Methyl Esther
production comparing the system with the adiabatic and diabatic and measuring the
Exergy Improvement Potential.

3. Algorithm development
Exergy is not conservative, opposed to energy (Szargut 1988). This thermodynamic
property flows through the system boundaries by three different ways: mass flows, heat
and shaft work (Rivero 2001). As previously described, to the system availability
balance evaluation of the studied system, it is necessary computing the exergetic inputs
and outputs of the system, the holdup factor and also the exergetic losses.
Figure 1 shows a separation system in the process simulator UniSim® Design from
Honeywell. It describes a system made by a simple distillation column operating in
steady-state; the exergetic inputs are given by the feed (F), and the heat added in the
reboiler (E-200). The exergetic outputs are the products (D and B), and also the heat
removed in the condenser (E-100). Since the described system is in steady-state, the
A Software for the Calculation of the Exergetic Efficiency in Distillation Columns 1007

holdup term is null. For a more rigorous approach, it is also necessary to consider the
heat lost by the column for the surroundings, which can be calculated in a system
energy balance.

Figure 1 – Distillation column in HYSYS

To measure the exergy of stream, the procedure described by Maia, physical exergy is
calculated by H – T0*S, where H is the flow enthalpy, S is the entropy and T0 is the
reference temperature. The chemical exergy was neglected.
The calorific contribution is given by the involved heat multiplied by the efficiency of
Carnot engine for the system. It is easily justified by the fact that the efficiency of this
engine is the maximum thermodynamically allowed.
Thus, the exergetic balance is given by the equation:

§ T0 ·  § T ·  § T ·
δB = B feed − Bdist − Bbot + Q reb ¨¨1 − ¸¸ − Qcond ¨¨1 − 0 ¸¸ − Qcol ¨¨1 − 0 ¸¸
© Treb ¹ © Tcond ¹ © Tcol ¹

where δB  is the heat of

is the lost work, B is the exergy of a stream in kJ/h, Q
equipment or column, Q  col is the heat lost to environment and Tcol is the mean
temperature of the column.
The minimum work of separation Wmin was computed and is given for the equation:

Wmin = (Bdist + Bbot ) − (B feed )

For the calculated the exergetic efficiency, used the following equation:

Wmin
η=
Wmin + δB
1008 C.T.O.G. Costa et al.

The algorithm was developed in MATLAB® from The MathWorks, for use with the
UniSim® Design process simulator. The flow rate, temperature, pressure, composition,
enthalpy and entropy of each flow are the data input, and also the involved heat in the
process heat exchangers.

4. Results and Discussion

The model was tested initially with a quaternary separation proposed by Yeomans et al.
The column was feed by a current saturated liquid at 12 bar discharge of 100kmol/h
with 30% propane, 30% n-butane, 20% n-pentane and 20% n-hexane.
The separation target was to recovery 98% of light and heavy key component of the
feed in the top and bottom product, respectively. The model chosen was the
thermodynamic equation of state of Peng-Robinson.
Columns were tested, 25 and 13 stages, with food in the trays 11 and 6. In both
simulations, the values of the exergetic balance were very close to the law of Gouy-
Stodola, resulting in an absolute difference in the order of 10-9 and relative difference of
10-14. Table 1 shows the results for these simulations:

Trays/Feed Exergy Losses Minimum Work Exergetic efficiency

25/11/ 53120 KJ/h 140930 KJ/h 72.63%
13/6/ 55623 KJ/h 139800 KJ/h 71.54%
Table 1: Results of first simulation of system with propane, n-butane, n-pentane and n-
hexane.

It is important to point out that the lost exergy in both cases has a little difference when
they are compared to the total exergy, but the difference is significative on the period of
one year.
With the validated model, focuses on another system of separation, the distillation of the
isomers n-butane and i-butane. The column was fed with a flow of saturated liquid
100kmol / h. The pressure was 12bar and target was 95% purity of the products. Two
columns were simulated, which varied was the number of stages, 60/30 and 50/25. The
results follow below:

Trays/Feed Exergy Losses Minimum Work Exergetic efficiency

60/30 111500 KJ/h 123350 KJ/h 52.52%
50/20 147520 KJ/h 123570 KJ/h 45.58%
Table 2: Results of simulation of system with n-butane and i-butane.

Observe that in these simulations, the differences were significant. Due to difficulty of
separation of these compounds, there is the need greater height of columns to hold it. In
a difference of 10 stages of the reduction efficiency is almost 7%.
As the third simulation to evaluate the software, used a system with 50% propane and
50% n-butane. The pressure and flow of the supply current was the same also with
previous simulations of saturated liquid, and a target was used for purity of 98%. To
evaluated, it was tested columns with 18, 16 and 10 trays, and the feed stage, 7, 6 and 4.
The results follow in the table 3:
A Software for the Calculation of the Exergetic Efficiency in Distillation Columns 1009

Trays/Feed Exergy Losses Minimum Work Exergetic efficiency

18/7/ 122470 KJ/h 170710 KJ/h 58.23%
16/6/ 147660 KJ/h 170670 KJ/h 53.61%
10/4/ 512320 KJ/h 170730 KJ/h 24.99%
Table 3: Results of simulation of system with propane and n-butane.

Similarly to the previous example, reducing the number of stages results in higher
exergy losses. The system in question has a minimum theoretical stages equal to 6.5.
When approaching this value, simulating with 10 stages, occurs a high exergy
destruction
The results obtained using the computational program were excellent. One can seen that
it is necessary more exergy for components which are more difficult to separate, which
can be compensated using more trays. When the number of stages is close to the
minimum number of stages there is a big reduction of efficiency.

5. Conclusions
A software was developed and the results demonstrated that it can be used as a powerful
tool for process engineer in the evaluation of energetic efficiency of distillation column.
Neverthe less it is necessary to use a process simulator to obtain the column data. The
software was capable to identify the better process operational conditions and to
decrease the exergy lost and the energy consume.
Using this program together an economic evaluation software it is possible to select the
best operational conditions, optimizing in all aspects (efficiency and economic).

References
A. B. Araujo, R. P. Brito, L. S. Vasconcelos, 2007, Exergetic analysis of distillation processes—
A case study, Energy Journal, 29, 1185-1193.
G. de Koeijer, R. Rivero, 2003, Entropy production and exergy loss in experimental distillation
columns, Chemical Engineering Science 58,1587–1597
A. Hepbasli, 2008, A key revew on exergetic analysis and assessment of renewable energy
resources for a sustainable future, Renewable and Sustainable Energy Reviews, 12, 593-661
A. P. Hinderink,F. P. J. M. Kerkhof, A. B. K. Lie, J. De Swaan Arons,H. J. Van Der Kooi, 1996,
Exergy analysis with a flowsheeting simulator—I. Theory: calculating exergies of material
streams. Chem Eng Sci,51,4693–700.
M. L. O. Maia, 2001, Síntese e otimização de Sistemas de Destilação utilizando a Análise
Exergética, UNICAMP, doctoral thesis.
L. S. Moussa, 2001, Análise Termodinâmica de Colunas de Destilação Visando à Otimização
Exergética, UNICAMP, masther thesis.
F. L. P. Pessoa, 2005, O uso eficiente de energia em colunas de destilação, UFRJ
R. Rivero, 2001, Exergy Simulations and optimization of adiabatic and diabatic binary
destillation, Energy Journal, 26, 561-593.
R. Rivero, M. Garcia, J. Urquiza, 2004, Simulation, exergy analysis and application of diabatic
distillation to a tertiary amyl methyl ether production unit of a crude oil refinery, Energy
Journal, 29, 467-489.
A. Røsjorde, S. Kjelstrup, 2005, The second law optimal state of a diabatic binary tray distillation
column, Chemical Engineering Science 60, 1199 – 1210
J. M. Smith,H. C. Van Ness, M. M. Abbott,2000, Introdução á Termodinâmica da Engenharia
Química. Rio de Janeiro, LTV Editora.
J. Szargut, D. R. Morris, F. R. Steward, 1988, Exergy analysis of Thermal, Chemical and
metallurgic Process.
1010 C.T.O.G. Costa et al.

H. Yeomans, I. E. Grossmann, 1999, Nonlinear disjunctive programming models for the synthesis
of heat integrated distillation sequences, Computers and Chemical Engineering 23, 1135–1151
R. J. Zemp, 1994, Thermodynamic Analysis of Separation Systems. Inglaterra, UMIST, doctoral
thesis