PII:

Applied Thermal Engineering Vol. 18, No. 6, pp. 427439, 1998

# 1998 Elsevier Science Ltd. All rights reserved
Printed in Great Britain
1359-4311/98 $19.00 + 0.00
S1359-4311(97)00047-1

EXERGY ANALYSIS OF THE KALINA CYCLE

P. K. Nag and A. V. S. S. K. S. Gupta
Department of Mechanical Engineering, Indian Institute of Technology, Kharagpur, 721302 India
(Received 7 May 1997)
AbstractTo reduce thermal irreversibility a thermodynamic cycle was conceptualized for the bottoming part of a combined cycle by Kalina, which uses NH3H2O mixture as the working substance. In
this paper, the Kalina cycle has been analysed thermodynamically for which a general code has been
developed for the calculation of thermodynamic properties of the mixture. The eect of key parameters
on the cycle performance has been studied. One of these parameters, mixture concentration at turbine
inlet, appears to have an optimum value with respect to second law eciency. The eects of these parameters on the exergy loss of each component have also been studied. # 1998 Elsevier Science Ltd.
KeywordsKalina cycle, NH3H2O mixture, exergy, phase equilibrium, Gibbs free energy, fugacity.

NOMENCLATURE
p
R
T
a
b
Z
F
f
f
x
y
Kij
g
v
h
s
m
I
E
o
cp

pressure, bar
gas constant, 8.314 kJ/kmol K
temperature, K
attractive parameter
Van der Waals covolume
compressibility factor
fraction to be converted into vapour at separator
fugacity, bar
fugacity coecient
ammonia mass fraction in liquid phase
ammonia mass fraction in vapour phase
PengRobinson's constant
Gibbs free energy, kJ/kmol
specic volume, m3/kg
specic enthalpy, kJ/kg
specic entropy, kJ/kg K
mass ow rate, kg/s
thermodynamic irreversibility, kJ
exergy, kJ
acentric factor
specic heat at constant pressure, kJ/kg K

Subscripts/superscripts
v
vapour phase
l
liquid phase
w
cooling water
o
reference state
R
reduced/dimensionless
c
critical condition
in
inlet
ex
exhaust
NH3 ammonia
H2O water

INTRODUCTION

Rankine cycle, with steam as the working uid, is usually the bottoming cycle of of a gasbased combined cycle power plant. In this cycle, boiling essentially takes place at constant pressure and temperature and does not have a good match with the temperature prole of the exiting
427

428

P. K. Nag and A. V. S. S. K. S. Gupta

ue gas from the topping cycle resulting in the large loss of availability. Kalina [1] developed a
new bottoming cycle which utilises a binary mixture (e.g., ammoniawater) as a working agent.
When a binary aquaammonia mixture changes its state from liquid to vapour, the more volatile ammonia vaporises rst and then the water starts vaporising. Hence, a better match with
the temperature prole of the ue gas ensues. The loss of exergy is less due to variable temperature boiling in the heat recovery steam generator (HRSG).
Figure 1 depicts the Ts diagram of the Kalina cycle in comparison with the Rankine cycle
working with the same temperature limits. The area between the line of heat source and the line
representing the working uid corresponds to the exergy loss in the process of heat transfer in
the HRSG. These losses are less in the Kalina cycle compared with the Rankine cycle. It is due
to the variation of temperature during evaporation. These losses can be minimised by the proper
selection of composition and the dierent parameters of the cycle.
The cycle was originally conceived by Kalina [1] for the usage of waste heat of the gas turbine
in a combined cycle power generation system. El-sayed and Tribus [2] made a theoretical comparison of the Kalina cycle with the Rankine cycle. The congurations developed by them were
very much complicated because several heat exchangers had more than two streams. Later,
Marston [3] modied the El-sayed and Tribus [2] conguration with simple two stream heat
exchangers and performed the thermodynamic analysis by using the property charts developed
by them. Rogdakis and Antonopoulos [4] proposed an absorption power cycle with NH3H2O
mixture as a working agent and observed 20% higher eciency in comparison with the Rankine
cycle. This cycle was also optimised by Rogdakis [5] who developed correlations describing the
optimum operation of the cycle.
The study of the Kalina cycle requires the thermodynamic properties of an ammoniawater
mixture. PengRobinson [6] developed a new two-constant equation of state which represents
the phase behaviour of the multicomponent system. Ziegler and Trepp [7] developed equations

Fig. 1. Comparison of the Rankine cycle with the Kalina cycle (Ts diagram with heat source).

Exergy analysis of the Kalina cycle

429

of state for NH3H2O mixture, which represent the Gibbs free energy of the mixture as a function of pressure, temperature and mixture composition.
In the present paper, thermodynamic analyses (both rst law and second law) of the Kalina
cycle have been carried out to nd the optimum ammonia concentration at turbine inlet (x9) on
the basis of exergy analysis. The PengRobinson's equation of state has been considered for the
phase behaviour of a multicomponent mixture. Gibbs free energy equations of mixture have
been used for the evaluation of thermodynamic properties. The eects of dierent variables on
the fractional exergy loss are also studied.

THERMODYNAMIC PROPERTY DATA OF AMMONIA WATER MIXTURE

In the two phase region, the vapourliquid compositions are always dierent and these
change continuously at constant pressure between the bubble point and the dew point with the
variation of mixture composition. To specify a pure substance, two degrees of freedom (i.e.
pressure and temperature) are sucient. But for a binary mixture a third degree of freedom (i.e.
concentration) is needed to specify the equilibrium state. However, at saturated state any of the
two degrees of freedom is sucient. To study the phase behaviour of NH3H2O binary mixture,
the PengRobinson's equation of state is used and the details are given in the Appendix. The
fugacity coecients of the mixture in both the liquid and the vapour phases have been estimated
by Equation (A13). In equilibrium state, the fugacities of each species of the mixture in both the
liquid phase and the vapour phase are equal [10].
f

l
i

f vi ,

px i fli pyi fvi :

The pressure can be calculated by the summation of the concentrations of all the components
of the mixture and is given as:
p
From Equation (2),

N
X
f

l
i
l
i1 fi

N
X
f

v
i
v
fi
i1

!
fli
x i:
yi
fvi

Vapour phase composition, yi, is estimated from the fugacity coecients of both the phases
and the liquid phase composition.
The thermodynamic property of a mixture is the sum of analogous properties of pure components weighted with their fractional composition and the property change on mixing. In
vapour phase, assuming it as an ideal mixture, the property change on mixing is neglected. The
properties of the mixture are estimated from the Gibbs free energy equations and in reduced
form are given as [7]:liquid phase:
glR 1 xglR,H2 O glR,NH3 x ln x 1 xln1 x gR,mix ;

gvR 1 ygvR,H2 O ygvR,NH3 y ln y 1 yln1 y:

vapour phase:

The thermodynamic properties are dened as [7]

molar enthalpy, hR T

2
R

@ gR =TR
@TR


PR

430

P. K. Nag and A. V. S. S. K. S. Gupta

Fig. 2. Schematic diagram of the Kalina cycle.


molar entropy, sR TR


@ gR
@TR

@gR
molar volume, vR
@ PR


PR


TR

The values of Gibbs free energy of the pure component in both liquid and vapour phases are
taken from Ziegler and Trepp [7].
Generalised subroutines are developed to estimate the enthalpy, the entropy and the specic
volume of NH3H2O mixture by using PengRobinson's equation of state and Gibbs free
energy equations for specied pressure, temperature and mixture composition.
KALINA CYCLE DESCRIPTION

The schematic diagram of the Kalina cycle, for which the analysis has been made, is shown in
Fig. 2. The turbine exhaust (10) is cooled in the distiller, then diluted with a weak solution (3)
and condensed in the absorber. The saturated liquid leaving the absorber is heated in a distiller
by the turbine exhaust. The working uid is separated into rich ammoniawater vapour (4) and
poor liquid mixture (2i) in the separator. The rich mixture vapour is mixed with the original
condensate to obtain the desired concentration. Then, it is cooled in a feedwater heater, condensed in a condenser, compressed, heated in a feedwater heater and sent to the boiler, where it
is superheated by the exhaust from the gas turbine. The superheated vapour is expanded in the
turbine.
To produce 1 kg of vapour mixture corresponds to m1 kg of working uid at the separator
and its estimation is the most important task for the given input parameters. These input parameters for the analysis are the turbine inlet condition and the separator temperature (T4). The
fraction of mass to be converted into vapour (F) at the separator for the given separator temperature is rst assumed. Then, the mass ow rate at separator (m1), the properties and mass

Exergy analysis of the Kalina cycle

431

ow rates around the loop (1, 2i, 2o, 3, 12i, 12o, 13, 15i, 15o and 16) are calculated by mass and
energy balance. This procedure is repeated by varying F, until the state 1 matches with the
state 16.
Figures 35 show the temperatureentropy, the temperatureenthalpy and the enthalpyentropy diagrams of the Kalina cycle operating under the conditions T4=708C, T9=5008C and
x9=0.7. The characteristic states of the working uid are represented by the same numbers as
those of the schematic diagram in Fig. 2. All enthalpies and entropies are expressed per kg of
vapour mixture at the turbine inlet condition.
ASSUMPTIONS USED IN THE ANALYSIS

1.
2.
3.
4.
5.
6.

Pressure drop and heat loss in pipe lines are neglected.

Turbine inlet pressure is assumed as 100 bar.
The gas turbine exhaust temperature is assumed as 5508C.
The isentropic eciency of the turbine is 85%.
The pump eciency is assumed to be 60%.
The pinch point temperature dierence for each of the heat exchangers (i.e., distiller, reheater, feedwater heater) is 58C.

THERMODYNAMIC ANALYSIS

The eciency of the cycle is dened on the basis of the rst law of thermodynamics as the
ratio of output energy of the cycle to the input energy.
Cycle efficency

Wt pw1 pw2
,
Heat addition

Fig. 3. Temperatureentropy diagram of the Kalina cycle.

10

432

P. K. Nag and A. V. S. S. K. S. Gupta

Fig. 4. Temperatureenthalpy diagram of the Kalina cycle.

Turbine work Wt m9 h9 h10 ,

11

Boiler pump work pw1 v6o p6o p7 ,

12

Condensate pump work pw2 v12o p12o P13 ,

13

Heat supplied in HRSG m9 h9 h8 :

14

EXERGY ANALYSIS

The exergy losses due to thermodynamic irreversibility in each of the components are calculated for the specied dead state. Let p0, T0 are the pressure and temperature of a system when
it is in the dead state. The exergy of ue gas at inlet to the HRSG is estimated from:
Ein

mf cp E TA T0
Mf

15

where cEp =mean, molar isobaric exergy capacity for evaluating physical exergy of the ue gas [8].
Mf=molecular weight of ue gas [8]
mf=mass of the ue gas owing through HRSG and is estimated by energy balance:
mf hA hB m9 h9 h8 :

16

The exergy loss in each of the components is estimated by the GouyStodola equation [9] and
compared with that obtained by exergy balance.
Estimation of exergy loss in each component of the Kalina cycle is given below:

Exergy analysis of the Kalina cycle

433

Fig. 5. Enthalpyentropy diagram of the Kalina cycle.

Hrsg

0
HRSG



mf  s
s
c lnTA =T0 cpB lnTB =T0 Rf Dp=pA :
T0 m9 s9 s8
Mf pA


17

where csp =mean, molar isobaric entropy capacity for evaluating physical exergy of the ue
gas [8].
Turbine
I 0TBN T0 m9 s9 s10 :

18

I 0ABS T0 m12i s12i s12o mwa cpw lnTG =TE :

19

I 0DST T0 m10 s10 s11 m16 s16 s15o :

20

Absorber

Distiller

434

P. K. Nag and A. V. S. S. K. S. Gupta

Second law efficiency

0.55

0.53

0.51

at T4 = 70C
T9 = 475C
T9 = 500C
T9 = 525C
0.49
0.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

x 9, kg of NH3/kg of mixture
Fig. 6. Eect of x9 on second law eciency for dierent values of T9, at T4=708C.

Condenser
I 0CND T0 m6i s6i s6o mwc cpw lnTF =TD :

21

I 0BFP T0 m7 s7 s6o :

22

I 0CDP T0 m13 s13 s12o :

23

I 0FWH T0 m7 s8 s7 m4 s4 s5 :

24

I 0RHT T0 s2i s2o m15 s15o s15i :

25

Boiler feed pump

Condensate feed pump

Feedwater heater

Reheater

Exhaust loss
Exergy loss through exhaust I 0ex

mf cp E TB T0
:
Mf

26

The second law eciency can be dened as the ratio of exergy output to the exergy input.
The exergy output depends on the degree of irreversibility of the cycle. Therefore,

Exergy analysis of the Kalina cycle

435

0.62

T4 =
T4 =
T4 =
T4 =

Second law efficiency

0.60

70C
80C
90C
100C

0.58

0.56

0.54

0.52

T9 = 500C
0.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

x9, kg of NH3/kg of mixture

Fig. 7. Eect of x9 on second law eciency for dierent values of T4, at T9=5008C.

Second law efficiency

Ein SI 0
Ein

27

where SI0, is the sum of the exergy losses in all the components and the exergy loss through
exhaust.

0.34

0.33

Cycle efficiency

0.32

0.31

at T4 = 70C

0.30

T9 = 475C
T9 = 500C
T9 = 525C

0.29

0.28
0.50

0.55

0.60

0.65

0.70

0.75

0.80

x 9, kg of NH3/kg of mixture
Fig. 8. Eect of x9 on cycle eciency for dierent values of T9, at T4=708C.

0.85

436

P. K. Nag and A. V. S. S. K. S. Gupta

0.38

Cycle efficiency

0.36

0.34

0.32

T 9 = 500C

0.30

0.28
0.50

T4 =
T4 =
T4 =
T4 =
0.55

70C
80C
90C
100C
0.60

0.65

0.70

0.75

0.80

0.85

x9, kg of NH3/kg of mixture

Fig. 9. Variation of cycle eciency with x9 for dierent values of T4, at T9=5008C.

FRACTIONAL EXERGY LOSS

Fractional exergy loss of the component is dened as the ratio of exergy loss of the corresponding component and total irreversibility of the cycle. It is estimated for each of the components (i.e. HRSG, distiller, absorber, turbine and stack loss) and its behaviour has been
studied with dierent operating variables. At low values of ammonia mass concentration at turbine inlet (x9), the turbine loss is high and decreases with increasing x9, whereas, the HRSG irreversibility is low for low values of x9 and increases with increase of x9. As a result, the second

Fractional exergy loss

0.60

T 9 = 500C
T 4 = 70C

0.40

HRSG
Turbine
Distiller
Absorber
Exhaust loss
0.20

0
0.50

0.55

0.60

0.65

0.70

0.75

0.80

x9, kg of NH3/kg of mixture

Fig. 10. Eect of x9 on fractional exergy loss of dierent components.

0.85

Exergy analysis of the Kalina cycle

437

0.50

Fractional exergy loss

0.40

0.30

HRSG
Turbine
Distiller
Absorber
Exhaust loss

T 9 = 70C
x9 = 0.700

0.20

0.10

0
460

470

480

490

500

510

520

530

Turbine inlet temperature (T9), C

Fig. 11. Eect of T9 on fractional exergy loss of dierent components.

law eciency increases rst and then decreases with x9. There is an optimum value of x9, where
the second law eciency is maximum and it is dierent for the dierent values of the turbine
inlet temperature (T9) and the separator temperature (T4).
RESULTS AND DISCUSSION

It is observed that the important parameters which aect both the rst law and the second
law eciencies are the turbine inlet condition (i.e. composition and temperature) and the separator temperature. Figure 6 shows the variation of second law eciency with the mixture composition at turbine inlet (x9) for dierent values of turbine inlet temperature (T9) at specied
separator temperature (T4). For the given values of T9, the second law eciency increases rst
and then decreases with x9. The optimum values of x9 for dierent values of T9 are identied.
These are found to be increasing with T9 to a small extent. The reason may be that for low
values of x9, the turbine irreversibility is high due to more entropy generation, resulting in low
second law eciency. For high values of x9, the HRSG irreversibility is high and it decreases
with the increase of x9. Figure 7 shows the variation of the second law eciency with x9 for
dierent values of separator temperature (T4). These curves are also showing similar trends, but
the optimum concentration is decreasing with the increase of separator temperature.
Figures 8 and 9 show the eect of ammonia mass concentration at turbine inlet on cycle eciency for various values of T9 and T4 respectively. The cycle eciency has been noticed to be
decreasing with the increase of x9 and it is found to be increasing with the increase of both the
turbine inlet temperature and the separator temperature.
The exergy balance with respect to the main key parameters is shown in Figs 10 and 11 and
Fig. 12. It is observed that nearly 50% of the exergy loss takes place in the HRSG and it is
increasing with the increase of x9, but decreasing with the increase of both T4 and T9. This may
be due to closer agreement between the temperature prole of the ue gas and the working uid
during boiling, thus, resulting in less thermodynamic irreversibility for low values of x9. The
eect of x9 on stack loss is insignicant. The stack loss increases slowly with T9, but it increases
more signicantly with T4. Exergy loss in turbine decreases with the increase of x9 and it does
not depend on turbine inlet temperature and is increasing with the increase of T4. Relatively,
the absorber and the distiller losses are low and both are increasing with x9. But with the

438

P. K. Nag and A. V. S. S. K. S. Gupta

0.50

Fractional exergy loss

0.40

HRSG
Turbine
Distiller
Absorber
Exhaust loss

0.30

x9 = 0.700
T9 = 500C
0.20

0.10

0
60

70

80

90

100

110

Separator temperature (T4), C

Fig. 12. Eect of separator temperature on fractional exergy loss of dierent components.

increase of T9, the absorber exergy loss increases to a small extent whereas the distiller exergy
loss decreases signicantly.

CONCLUSION

The present study analyses the Kalina cycle from both the rst and the second law point of
view providing a rational procedure for estimating the NH3H2O mixture properties. The key
parameters, which aect the cycle as a whole, have been identied as the turbine inlet condition
(i.e. x9, T9) and the separator temperature (T4). However, x9 has an optimum value for a set of
other operating parameters such that the exergy loss of the cycle is minimum.

REFERENCES
1. I. A. Kalina, Combined cycle system with novel bottoming cycle. ASME Journal of Engineering for Gas Turbine and
Power 106, 737742 (1984).
2. Y. M. El-sayed, and M. Tribus, A theoretical comparison of Rankine and Kalina cycles, ASME publication AES,
Vol. 1 (1995).
3. C. H. Marston, Parametric analysis of the Kalina cycle. ASME Journal of Engineering for Gas Turbine and Power
112, 107116 (1990).
4. E. D. Rogdakis and K. A. Antonopoulos, A high eciency NH3H2O absorption power cycle. Heat Recovery
Systems and CHP 11, 263275 (1991).
5. E. D. Rogdakis, Thermodynamic analysis, parametric study and optimum operation of the Kalina cycle.
International Journal of Energy Research 20, 359370 (1996).
6. D. Y. Peng and D. B. Robinson, A new two-constant equation of state. Ind. Eng. Chem. Fundam. 15(1), 59
64 (1976).
7. B. Ziegler and Ch. Trepp, Equation of state for ammoniawater mixture. International Journal of Refrigeration 7(2),
101106 (1984).
8. T. J. Kotas, The Exergy Method of Thermal Plant Analysis, Butterworths, London (1985).
9. P. K. Nag, Engineering Thermodynamics, Second Edition, Tata McGraw-Hill, New Delhi (1995).
10. S. Ohe, VapourLiquid Equilibria Data at High Pressure, Physical Sciences Data 42, pp. 311314, Elsevier,
Kondansha (1990).

Exergy analysis of the Kalina cycle

439

APPENDIX
The PengRobinson's equation of state [6] has been chosen for calculation of the thermodynamic properties of ammoniawater mixture. For a pure component, one needs pressure and temperature to specify the state of the substance. But
for a binary mixture, a third independent variable is needed to specify the equilibrium state.
The PengRobinson's equation of state is:
p

RT
aT

v b vv b bv b

A1

where the constants in terms of critical data are:

aTc 0:45724

R2 T 2c
,
Pc

A2

RTc
:
Pc

A3

bTc 0:07780

At any temperature other than critical conditions have been calculated by [6]:
aT aTc aTr ,o ,

A4

bT bTc ,

A5

where a 1 m 1 T

0:5
r

0:5

m 0:37464 1:54226o 0:26992o 2 :

A6
A7

The acentric factors (o) for ammonia and water have been taken from Ohe [10]. For determining the mixture properties,
an empirically determined binary mixture interaction constant kij characterising the mixture formed by component i and
component j is included in the mixing rule for calculation of constant a.
The mixing parameters were dened by mixing rules:
a

N X
N
X
x i x j aij ,

A8

i1 j1

N
X
x i bi ,

A9

i1
0:5
where aij 1 kij a0:5
i aj

A10

where kij is the PengRobinson's constant.

Equation (A1) has been shown to be a cubic polynomial in compressibility factor (Z):
Z 3 1 B Z 2 A 3B 2 2B Z AB B 2 B 3 0
where A

ap
bp
pv
,B
,Z
:
R2 T 2
RT
RT

A11
A12

In the two-phase region, the largest root of the equation is the compressibility factor of the vapour phase, whereas the
smallest positive root corresponds to the compressibility factor in liquid phase and the third one has no physical meaning.
The fugacity coecient (fk) of component k in a mixture can be calculated by:
 


bk
A
2Sx i aik bk
Z 2:414B

ln
lnfk Z 1 lnZ B p
:
A13
b
a
b
Z 0:414B
2 2B