ICASTOR Journal of Engineering

Vol. 7, No. 3 (2014) 135 – 147

Exergy Analysis of Cryogenic Air Separation Unit with Flash Separator

Zeinab A. M. Khalel , Ali A. Rabah & Taj Alasfia M. Barakat
Department of Chemical Engineering,
Faculty of Engineering,
University of Khartoum,
Khartoum, Sudan.

ABSTRACT
The objective of this work is to provide exergy analysis of the newly developed cryogenic air
separation unit with flash separator. As a reference, exergy analysis to the conventional double column air
separation process is made. The system of equations of heat and work exergy, material exergy and exergy
destruction are solved numerically. Aspen Plus simulation package is used to obtain thermodynamics data
(enthalpy, entropy, etc…). The result revealed that the exergy loss of modified process is lower by 17.2 % than
that of the conventional one. The rational efficiency for the modified process is 16 % while that for the
conventional process is 12 %; an enhancement of 33.3 %. Similarly the energy consumption is less by 8.2 % in
the modified process. The exergy analysis of the modified process will bring in more confidence in the newly
developed design of Cryogenic Air Separation Unit with Flash Separator. Low exergy loss is an additional
advantage besides production of more pure N2 and O2 relative to the conventional design.

Keywords: cryogenic, flash separator, exergy analysis, Aspen Plus.

INTRODUCTION
Figure 1 shows the main unit in Cryogenic Air Separation Unit (CASU). It
consists mainly of compressor, heat exchangers and distillation columns. CASU is an
energy intensive process. In order to develop energy conservation measures for CASU, the
source of energy loss and level and potential energy savings need to be identified and
quantified. Exergy analysis has been considered as a vital tool in identification of the source
and level of energy loss and potential savings in different cryogenic air separation processes.
Cornelissen and Hirr (1998) performed an exergy analysis to study the potential
energy saving in the cryogenic distillation process. They found that more than 50% of the
exergy loss takes place in the liquefaction unit, and about 30% in the air compression unit,
while exergy losses are minimum in the distillation and the main heat exchangers. Van der

____________________________________________________________________________________________
Correspondence: Ali A. Rabah, Department of Chemical Engineering, Faculty of Engineering, University of
Khartoum, P.O. Box 321, Khartoum, Sudan. E-mail: rabahss@hotmail.com
 Zeinab A. M. Khalel , Ali A. Rabah & Taj Alasfia M. Barakat

Ham and Kjelstrup (2010) have evaluated two cryogenic processes; one with two
distillation columns and another with three distillation columns, using exergy analysis.
They found that the three column design is superior to two column design in term of exergy
destruction by 12%. Yan et al. (2010) have simulated a large -scale air separation unit.
According to the simulation results, exergy efficiency of major equipment is analyzed and
an optimization problem is solved by a new algorithm. Accordingly a modified air
separation process is proposed. The energy consumption is 7.55MW lower than the original
process and the total energy efficiency is raised by 27.21%.
Khalel et al. (2013) have recently developed a modified CASU, in which a flash
separator is introduced. The flash separator is used to replace the expansion turbine in the
conventional CASU. The flash separator has significantly enhanced energy consumption
and pure O2 produced. The objective of this work is to provide exergy analysis of the newly
developed CASU

Figure 1: Unit operations for a cryogenic air separation process (Querol et al., 2011).

1. Exergy Analysis
There are several modes of exergy transfer such as work and heat exergy, material
stream exergy and exergy destruction.
1.1 Work and heat exergy
The exergy transfer with work interaction is equivalent to work, i.e work is
considered as pure exergy as
(1)
Where Ework is exergy transferred due to work interaction and W is work. The work value is
given by Aspen Plus and is taken as positive (+) when is added to the equipment and
negative (-) when is generated. The exergy of heat flow is
1 (2)

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 Exergy Analysis of Cryogenic Air Separation Unit with Flash Separator

Where:
Eheat = exergy transfer rate due to heat interaction.
Q = heat transfer rate.
T0 = ambient temperature.
T = temperature at which the heat transfer takes place.
1.2 Material stream exergy
The exergy associated with material stream Ematerial is given by the sum of physical
exergy (Eph), chemical exergy (Ech), kinetic exergy (Eke), and potential exergy (Epe) as
, (3)
The kinetic and potential exergies are neglected in this study because of their small
values compared with the physical and chemical exergy.
Physical exergy is the work obtainable by taking the substance through reversible
processes from its initial state temperature T and pressure P, to the reference or standard
state of To = 298 K and pressure of Po = 1 atm at which the free enthalpy and entropy of
formation are calculated (Van der Ham and Kjelstrup, 2010). The physical exergy is
calculated as
(4)
The values of enthalpy entropy of different stream are obtained from Aspen Plus.
The chemical exergy of a mixture is calculated from the standard chemical exergies of the
components ( 0,i) and their mole fractions (xi) (Van der Ham and Kjelstrup, 2010).
∑ " !" # ," $ ∑" !" ln !" (5)
In case of no chemical reaction as in the cryogenic air separation process, the first
term in the right hand side of Equation. 5 vanishes. Hence chemical exergy is only due to
mixing.

1.3 Exergy Destruction

The exergy destruction, also called irreversibility or exergy loss, is calculated by
setting up the exergy balance as:
' ( ) " * ∑"* " ∑ ) " (6)
1.4 Process Flow diagram structure
Material, energy and exergy balances are algebraically solved using matrix
calculations as (Querol et al., 2011):
+, - (7)
Where A is an incidence matrix, in which the process structure is stored. The rows
of the matrix represent equipment and the columns represent stream. The elements of the

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 Zeinab A. M. Khalel , Ali A. Rabah & Taj Alasfia M. Barakat

matrix are 0 if the stream has no relation with the piece of equipment, +1 if the stream is an
input or -1 if the stream is an output
7
* 1 1 0 89:; <:9= >?@; 9< A@>;?8 B9 1 0
+./ 03 4 35 . 0 3 5 005 (8)
6 1 1 1 89:; <:9= >?@; 9< A@>;?8 B9 8 0
1 1 0 ;C@D?:EF 9< A@>;?8 B9 1 0
+. 03 4 35 . 0 3 5 0 05 (9)
1 1 1 ;C@D?:EF 9< A@>;?8 B9 8 0
1 1 0 ;!;>GF 9< A@>;?8 B9 1
+. 03 4 35 . 0 3 5
1 1 1 ;!;>GF 9< A@>;?8 B9 8
;!;>GF H;A@>IJ@K9C 9< ;LIKE8;C@ B9 1
0 3 5 (10)
;!;>GF H;A@>IJ@K9C 9< ;LIKE8;C@ B9 C

The exergy destruction should be positive for any real (irreversible) process where
the total exergy flowing into any unit operation is greater than the total exergy flowing out,
and zero for reversible process as there is no exergy losses during process in unit operation
but it cannot be negative (Querol et al., 2011). For “n” number of equipments and “m”
number of streams the incidence matrix is defined as [n × m] matrix. The required
information to build the incidence matrix is extracted from Figures 2 and 3 as shown in
Table 1 and 2.
X is the vector for mole flow rate, enthalpy or exergy balance of each stream
considered in the incidence matrix. B is zero for material and energy and is exergy
destruction for exergy balance. Equations (8 - 10) represent the mass, energy and exergy
matrix. (impossible operation). The summation of the exergy destruction of all equipments
equals the total exergy destruction of the process as shown in Equation 10.
∑*MNO M (11)
1.5 Exergy Efficiency
The exergy efficiency is generally described by what so called rational efficiency.
The rational efficiency is defined as a ratio of the desired exergy output to the exergy used
as (Cornelissen, 1997).
QRSTUVSR WXYZXY
P
QXTSR
(12)

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 Exergy Analysis of Cryogenic Air Separation Unit with Flash Separator

2. Case Study
The exergy analysis is made for the modified CASU and the conventional CASU.
Comprehensive description of the two processes is found in Khalel et al. (2013). Figure 2
shows schematic presentation of the conventional double-column cryogenic air separation
process. It consists of two compressors (C1 and C2), a turbine (T), two thermally linked
distillation columns [low pressure column (LPC) and high pressure column (HPC)] and two
sets of heat exchangers (HX1, HX2). The air is compressed form atmospheric pressure to 6
atm in C1. The compressed air is then split into two streams; one stream for HPC (hereafter
is called HPC split) and the other stream for LPC (hereafter is called LPC split). The LPC
split is compressed in C2 further to 7.5 atm, cooled in HX1 and throttled in T to 1.3 atm and
finally fed to the LPC. The HPC split is cooled in HX1 and then fed to the HPC. The
products of the LPC are pure N2 (top), pure O2 (bottom) and waste N2 (side stream). The
products of the HPC are pure N2 (top) and air-rich oxygen (bottom). The pure N2 of HPC is
working as reflux to the LPC and the air-rich oxygen of HPC is an extra feed to the LPC.
The two columns are thus thermally linked by exchanging the latent heat of vaporization via
condenser of the HPC and reboiler of the LPC. The products of the LPC are liquid pure O2
from the bottom, gas pure N2 from the top, and side product of waste N2, all these products
are heated in the two sets of heat exchangers before storage (Khalel et al., 2013).
Figure 3 shows schematic presentation of the modified CASU with flash separator.
The air is compressed in C3 from atmospheric pressure to 4 atm instead to 6 atm as in the
conventional process then split into two streams. The HPC split is compressed in C4 further
to 6 atm and subsequently cooled in HX1 and then injected to HPC. Hence this stream is
maintained at the same conditions as in the conventional process. The LPC split is cooled in
HX1 and then throttle in a flash separator (F) to 1.3 atm. The bottom product of the flash
separator is air-rich O2 and the top product is a waste N2. The waste N2 is a final product
(mixed with the waste N2 from the LPC). The bottom product of the flash (air-rich O2) is fed
to the LPC. The rest of the process remains the same as in the conventional process. The
turbine is used in the conventional process to produce cold energy, while the flash separator
does the dual job of cold energy production and separation.
The conventional and modified processes are simulated using Aspen plus. Table 3
shows the operation conditions for both processes. The isentropic efficiency of compressors
in both processes and the turbine in the conventional process are taken as 72%. This is a
default value in Aspen plus program. The pressure drop across the heat exchangers and
along the HPC and the LPC is assumed as 0.1 atm, The minimum temperature approach is

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 Zeinab A. M. Khalel , Ali A. Rabah & Taj Alasfia M. Barakat

1.5K for the HX1 and 2.5 K for HX2. A 5 kW energy loss is the thermal integration
between the two columns.

Table 1: Structure of the Conventional Process as Stored in its Incidence Matrix

Table 2: Structure of the Modified Process as Stored in its Incidence Matrix

The reference state is taken as (To=298 K) and (Po=1atm) at which the physical
exergy of all material streams is zero. The feed air is assumed to gain 5 K more than the
ambient temperature (298 K) in the processes of drying and cleaning prior to the inlet of the
main compressor.
The feed air in both processes is a binary mixture composed of 79.1% N2 & 20.9%
N2. Argon (Ar), which is about 1% of the air is neglected as the base case of the
conventional one. Ar removal requires extra treatment as it is mainly produced with pure O2.

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 Exergy Analysis of Cryogenic Air Separation Unit with Flash Separator

Parameter Conventional Process Modified Process

1st Compressor discharge pressure 6.0 atm 3.9 atm
2nd Compressor discharge pressure 7.5 atm 6.0 atm
LPC Pressure 1.2 atm 1.2 atm
HPC Pressure 5.8 atm 5.8 atm
No. of stages in LPC column 20 20
No. of stages in HPC column 15 15
Table 3: Simulation Parameters of the Conventional & Modified Processes

Figure 2: Conventional Double-Column Cryogenic Air Separation Process

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 Zeinab A. M. Khalel , Ali A. Rabah & Taj Alasfia M. Barakat

Figure 3: Modified Cryogenic Air Separation Process

3. Results and Discussion
3.1 Streams Specifications
Tables 4 and 5 show the mass flow, composition, enthalpy and exergy of each
stream in both conventional and flash air
3.2 Exergy Destruction
Based on the unit function, the process is divided into three units as feed pre-
processing unit, main heat exchanger unit and distillation unit. The post product - processing
equipments such as pumps, cooler, compressors or mixers as well as auxiliary units such as
splitters, mixers, and valves are excluded from the analysis. The work or heat duty and the
destroyed exergy of each unit are shown in Table 6.
3.2.1 Exergy Destruction in Feed Pre-processing Unit
The external work needed in the two processes exists only in feed pre-processing
unit. The units C1, C2, C3 and C4 consume electrical energy, and the unit T in the
conventional process recovers some of consumed electrical energy, while the unit F in the
modified process works adiabatically.
The total work needed in the modified CASU is lower than that in the conventional
process. This is due to the fact that in the modified CASU the total air is compressed to 3.9
atm while in the conventional is compressed to 6 atm. Clearly, the modified CASU is
superior to conventional CASU despite that fact that a portion of energy is recovered by the

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turbine in the conventional process. Similar to total energy, exergy destruction in the
modified CASU is lower than that in the conventional process. What to be remembered is
that energy integrated between the units is excluded. For example the net energy of
compressor is difference between the compressor consumption and the energy recovered by
the turbine in the conventional process. It is worth to be mentioning that, the outlet streams
of the flash separator have higher chemical exergy than the input stream; reduced exergy
losses. This is due to the change of chemical composition of stream (separation process).
(Material Vector) (Energy Vector) (ExergyVector)
stream O 2 ( mole %) N 2 (mole %) Mole Flow Rate Enthalpy Flow Exergy Flow
(k mol/s) Rate (kW) Rate (kW)
101 20.9 79.1 0.62003973 82.84980359 80.84573063
102 20.9 79.1 0.62003973 -5.393410135 2828.658028
103 20.9 79.1 0.09920639 -0.86294591 452.585436
104 20.9 79.1 0.09953972 -2.049580866 508.9458296
105 20.9 79.1 0.09953972 -595.6893824 877.465516
106 20.9 79.1 0.09953972 -676.7805003 683.7221233
107 20.9 79.1 0.52083333 -4.530464138 2376.072547
108 20.9 79.1 0.52083333 -3664.442424 5419.335293
201 0.3987 99.6013 0.19087849 -2049.502417 3680.717534
202 0.3987 99.6013 0.19087849 -2224.485324 3978.172781
203 0.3987 99.6013 0.19087849 -2224.485324 3961.546234
301 32.76 67.24 0.32995485 -3716.83349 6173.102653
302 32.76 67.24 0.32995485 -3849.605672 6450.377534
303 32.76 67.24 0.32995485 -3849.605672 6392.021319
401 0.1274 99.8726 0.1314736 -848.3207431 839.1113226
402 0.1274 99.8726 0.1314736 -776.6892585 640.0075947
403 0.1274 99.8726 0.1314736 -1.591642672 92.00809985
501 99.9987 0.0013 0.09967723 -1270.427164 2360.323322
502 99.9987 0.0013 0.09967723 -86.9260672 400.1533997
601 7.6487 92.3513 0.38888889 -2488.857202 2285.687604
602 7.6487 92.3513 0.38888889 -2297.733479 1737.375663
603 7.6487 92.3513 0.38888889 -4.768333125 116.3782329
Wc1 -88.2432 4389.9304
Wc2 -1.179771 78.844122
Wtr1 80.819573 -80.819573
QDC -2141 4470.585492
Table 4: Material, Energy, Exergy Vectors of the Conventional Process

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 Zeinab A. M. Khalel , Ali A. Rabah & Taj Alasfia M. Barakat

(Material Vector) (Energy Vector) (ExergyVector)

stream O2 ( mole %) N 2 (mole %) Mole Flow Rate Enthalpy Flow Exergy Flow
(k mol/s) Rate (kW) Rate (kW)
101 20.9 79.1 0.62003973 82.84980359 80.84573063
102 20.9 79.1 0.62003973 4.983403258 2168.572816
103 20.9 79.1 0.52083333 4.18605839 1821.601015
104 20.9 79.1 0.52083333 -4.530464138 2376.072547
105 20.9 79.1 0.52083333 -3664.442424 5419.335293
107 20.9 79.1 0.099206 0.797341658 346.9704027
108 20.9 79.1 0.099206 -852.0108898 1290.452819
201 0.3987 99.6013 0.1909 -2094.7457 3681.095746
202 0.3987 99.6013 0.1909 -2168.8149 3844.421005
203 0.3987 99.6013 0.1909 -2168.8149 3809.150321
301 32.76 67.24 0.33 -3717.45 6173.85907
302 32.76 67.24 0.33 -3827.01 6400.62187
303 32.76 67.24 0.33 -3825.01 6332.17723
304 34.49 65.51 0.037291 -458.30639 782.234291
401 0.13 99.87 0.1382 -891.72168 882.0488995
402 0.13 99.87 0.1382 -816.43032 672.7615835
403 0.13 99.87 0.1382 -1.6730492 96.71650965
501 99.96 0.04 0.1144 -1458.028 2707.621567
502 99.96 0.04 0.1144 -3.4723832 452.5640547
601 2.49 97.51 0.3675 -1966.16928 1893.645193
602 4.1 95.9 0.3675 -2248.18125 1808.540066
603 4.21 95.79 0.3675 -4.47909 157.5543605
604 12.71 87.29 0.061915 -393.680336 359.3497214
605 4.21 95.79 0.3675 -2359.46025 2175.195154
Wc1 -77.86643 3229.9
Wc2 -8.716523 796.7
QDC -2146.9 4487.758442
Table 5: Material, Energy, Exergy Vectors of the Modified Process

3.2.2 Exergy Destruction in Main Heat Exchanger Unit

In heat exchangers, work and loss to surrounding are neglected. Hence the exergy
loss is due to temperature difference between the hot and cold streams and friction pressure
drop. In heat exchangers, the exergy destruction in the modified CASU is lower than that in
the conventional CASU. This is due to change in the stream specification cause by the flash
separator. The flash separator produce waste N2 and reduce the load to distillation unit and
heat exchanger. In the conventional unit the waste N2 is removed after distillation.

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Conventional Process Modified Process

Unit Work or Destroyed Work or Destroyed
Unit Unit
Heat Duty Exergy (kW) Heat Duty Exergy (kW)
Feed Pre- C1 4390 1642 C3 3230 1142
Processing C2 79 22 C4 797 242
T -81 275 F - 149
Total 4388 1939 4027 1533
Main Heat
HX1 - 717 HX1 - 547
Exchanger
Distillation LCP 2141 1082 LPC 2141 952
HCP -2146 36 HPC -2146 52
HX2 - 173 HX2 - 186
Total
-5 1291 -5 1190
Total
4383 3947 4022 3270
process
Table 6: Work/Heat Duty and Destroyed Exergy

3.2.3 Exergy Destruction in Distillation Unit

The two distillation columns are thermally integrated; hence the exergy loss is due
to temperature difference between the reboiler of LPC and the condenser of HPC. It should
also be remembered that the reboiler and the condenser assumed to lose 5 kJ to the
surrounding. There is no significant difference in exergy losses of modified and
conventional CASU. This is attributed to the fact that the columns of both processes have
the same design specification (no of trays, reflux ration, etc…) and no significant difference
between the specification and quantity of streams.
3.2.4 Overall Exergy Destruction of the Processes
It is clear that (cf. Table 6), the total exergy loss of modified CASU is lower that of
conventional CASU by 17.2%. So it can be concluded that introduction of flash separator to
the conventional CASU enhanced the exergy loss in addition to its merits of less energy
consumption and production of more pure O2 and pure N2.
3.2.5 Rational Efficiency
Tables (7 and 8) present the exergy of feed and product streams (the physical exergy
is neglected in the streams that near to the ambient condition), total exergy used and the
calculated rational efficiency for both the modified and conventional CASU. The analysis
revealed that the rational efficiency of the modified CASU is higher by 33.3% than that of
the conventional CASU. This is attributed to the followings:

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 Zeinab A. M. Khalel , Ali A. Rabah & Taj Alasfia M. Barakat

1. The modified CASU has higher exergy product than the conventional CASU. This
is due to high flow rates of pure O2 and pure N2 produced.
2. The lower energy consumption in the compressors of the modified CASU relative to
that of the conventional CASU. In the conventional CASU the air is compressed to
6 atm while in the modified process is compressed to 3.9 atm in the first compressor
and in the second compressed of the conventional CASU, the air further
compressed to 7.5 atm while in the modified CASU is compressed to 6 atm as
shown in Table 3.

Physical Chemical
Stream Temperature Pressure Exergy Exergy Total
kPa kJ/kmol kJ/kmol Exergy kW
Feed air 303 101.33 1.21 129.18 81
O2 269 101.33 45 3970 400
N2 298 101.33 zero 700 92
Waste N2 298 101.33 zero 299 116
Total Used = EC1 + EC2 + ET = 4390 + 79 - 81 = 4388
Exergy (kW)
Rational = (EO2 + EN2 + Ewaste N2 - Eair) / total exergy used
Efficiency = (400 + 92 + 116 -81) / 4388 = 0.12
Table 7: Physical & Chemical Exergies and Plant Rational Efficiency of the Conventional Process

Physical Chemical
Stream Temperature Pressure Exergy Exergy Total
kPa kJ/kmol kJ/kmol Exergy kW
Feed air 303 101.33 1.21 129.18 81
O2 297 101.33 zero 3956 453
N2 298 101.33 zero 700 97
Waste N2 298 101.33 zero 429 158
Total Used = EC1 + EC2 =3230+797 = 4027
Exergy (kW)
Rational = (EO2 + EN2 + Ewaste N2 - Eair) / total exergy used
Efficiency = (453 + 97 + 158 -81) / 4027 = 0.16

Table 8: Physical & Chemical Exergies and Plant Rational Efficiency of the Modified Process

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CONCLUSIONS
The exergy analysis emphasized the advantages of the modified CASU over the
conventional CASU in terms of energy consumption and exergy loss in addition to production of more
pure N2 and O 2. This paves the way for the development of energy conservation measures of CASU.
The exergy analysis will enhance the maturity of the modified design and bring in more confidence in
the design. This will make an enroute to the wide acknowledgement and acceptance of the new trend
in the design of CASU.
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