INTERNATIONAL JOURNAL OF ENERGY RESEARCH, VOL.

20,359-370 (1996)

THERMODYNAMIC ANALYSIS, PARAMETRIC STUDY AND

OPTIMUM OPERATION OF THE KALINA CYCLE
E. D. ROGDAKIS

National Technical Uniwrsity of Athens, Mechanical Engineering Department, Thermal Section, 42 Patission Street, Athens
I06 82, Greece

SUMMARY
The work described here has as major objectives the complete thermodynamic analysis and the parametric study of
the Kalina Power Unit. The device layout optimization is based on the presentation of the unit on the T-h and
h / T - s thermodynamic charts. The operation of the power unit is simulated by the use of equations describing the
thermodynamic behaviour of the NH,/H,O mixture. The important parameters of the unit, i.e. high, medium and
low pressures/rich, weak, working solution and boiler vapour mass fraction are discussed and related. Correlations
are developed which describe the optimum operation of the Kalina cycle. The maximum thermal efficiency, the heat
required to drive the unit and the work produced may be directly calculated from analytical functions in terms of the
ambient temperature and the low pressure of the units. The maximum theoretical efficiency ranges from 42.7% to
466%.

KEY WORDS: Kalina cycle; thermodynamic charts; ammonia-water mixture; parametric study; optimum operation of the Kalina cycle

INTRODUCTION
It is well known that the use of mixtures instead of one-component fluids improves the thermodynamic
efficiency of power cycles because the match between the heat source and the working medium is better.
The Kalina cycle was developed some years ago (Kalina, 1984, 1991; Kalina and Liebowitz, 1987). It uses
NH,/H,O as the working medium and shows a thermodynamic efficiency considerably higher than that
of the Rankine cycle.
In previous work (Kouremenos and Rogdakis, 1990) a method for the presentation of the complete
complex Kalina cycle on different thermodynamic charts was proposed. An analogous study for a high
efficiency aqua-ammonia power unit may be found in Rogdakis and Antonopoulos (1991).
The related computational task has been performed by fast algorithms based on the Schulz equation
as extended by Ziegler. Analytical functions have been developed to simulate the behaviour of the Kalina
cycle under conditions of optimum operation;

THERMODYNAMICS OF THE KALJNA CYCLE

The method of defining, calculating and representing the Kalina cycle was developed and explained some
years ago (Kouromenos and Rogdakis 1990). Figure 1 shows the Kalina power generation unit assumed in
this study and Figures 2 and 3 the corresponding graphical representation on the entropy-temperature
and entropy-enthalpy charts under conditions X, = 34%, X , = 42%, X , = 70%, X , = 96.7%, PL = 1.7
bar, PM = 4-7 bar, PH = 110 bar and superheating/reheating temperature Tuph = 510°C. All enthalpies
and entropies in these figures are expressed per 1 kg of vapour produced by the boiler. The characteristic
states of the working fluid are represented by the same numbers as those in the schematic representation
of the unit in Figure 1.

CCC 0363-907X/96/040359-12 Received 26 Jub1994

0 1996 by John Wiley & Sons, Ltd. Re vised 16 September 1994
 360 E.D. ROGDAKIS

15
Temperature (Not in scale)
b
Figure 1. A simplified Kalina cycle

The pressures of the reheaters are determined assuming at each stage of the turbine that the local
expansion ratio is given by the well-known equation:

So we find p R H -I = 274 bar and P R H - I I = 6.8 bar.

To 1 kg vapour mixture produced from the boiler (point 8) corresponds f kg rich solution incoming to
the generator (point 3) and g kg weak solution rejected from the generator (point 4w). The mass balance
of the ammonia into the generator and the counter-current absorber respectively gives

ENTROPY -b Kj/Kg OC
Figure 2. Thermodynamic cycle of the Kalina power unit in the entropy-temperature plane
 KALINA CYCLE 361

ENTROPY -b Kj/Kg OC
Figure 3. Thermodynamic cycle of the Kalina power unit in the entropy-enthalpy plane

and

For our example the evaluated values of g and f are:

- f = 4.012 kg rich solution/l kg boiler vapour (RS/1 kg BV)

- g = 3.500 kg weak solution/l kg boiler vapour (WS/1 kg BV).

The thermodynamics of the NH,/H,O mixture has been calculated by the Schulz equation (Schulz,
1971), which has been extended by Ziegler (1982) for pressures up to 50 bar. For pressures greater than
50 bar the phase envelope is obtained from the experimental values of Macriss and co-workers (Macriss
et af., 1964; Macriss and Zawacki, 1984) and Gillepsie and Wilson (1983). The enthalpy and entropy of the
NH,/H,O liquid mixture have been calculated by the equation for the specific heat taken from El Sayed
and Tribus (1985). Table 1 gives NH, and H,O reference enthalpy and entropy used in the present study
for a clear schematic form of the Kalina thermodynamic diagrams.

THERMAL PERFORMANCE OF THE KALINA POWER UNIT

The feasibility checking of all heat exchange temperature profiles as functions of the exchanged energies
of a reversible Kalina cycle can be achieved using the h-T diagram by a simple comparison of the slopes
of the heat-accepting and the heat-donating lines (the heating and the cooling processes respectively). In

Table 1. Reference enthalpy and entropy for NH, and H 2 0

Temperature Pressure Enthalpy (kJ/kgl Entropy (kJ/kg K)

(K) (bar) Liquid Gas Liquid Gas

NH3 32252 20 12500 2303.4 6.4171 96848

H2O 50705 30 995.8 2802.2 6.0379 9.6005
 362 E. D. ROGDAKIS

this way, with reference to Figure 4, the heat needed to drive a reversible Kalina unit is evaluated as
follows. For temperature levels below the low temperature of the generator, the heat quantities required
for the operation of the heat exchanger and the preheater are given by the co-current absorber and the
condenser respectively. So an external heat source up to this level is not required.
For temperature levels between the low temperature of the generator and the high temperature of the
condenser, the required heat is given to the preheater by the condenser. The remaining heat from the
condenser plus the heat taken from the vapour coming from the generator (change 45 in Figures 1, 2, 3
and 4) is given plus the heat taken from the vapour coming from the generator (Figures 1, 2 , 3 and 4) is
given to the generator. Because this heat quantity is not sufficient, the rest of the heat needed, i.e.
qR = 92-6 kJ/kg may be given by an external source.
For temperature levels above the high temperature of the condenser the required heat quantities are:

- Heat for the preheater, the boiler and the superheater q M A I N = 2620.8 kJ/kg
- Heat for the first reheater q R H - I = 496.7 kJ/kg
- Heat for the second reheater q R H - I=I 473.7 kJ/kg
- Heat may be taken from the hot vapour coming from the turbine, i.e. q v A p = 600.2 kJ/kg.
According to the above, the heat needed to drive the power unit is
4 =qMAIN +qRH-I +qRH-11 +q R -qVAP (4)
or
q = 2620.8 + 496.7 + 473.7 + 92.6 - 600.2
or
q = 3083.6 kJ/kg BV
With reference to Figure 3, the work produced by the Kalina unit can be calculated as:

or

or

The required work for the operation of the two pumps is Wt,pump
= 18.1 kJ/kg BV. So the net work

ENTHALW -b Ki IKg
Figure 4. Thermodynamic representation of the condensing system of a Kalina unit
 KALINA CYCLE 363

produced is:
w,= w,,T - w , , p u r n p (7)
or
W, = 1372.1 - 18.1 = 1354.0 kJ/kg BV
Thus the theoretical thermal efficiency of the cycle is
wt 1354-0
v=-=-q 3083.6
or q=43*91%

PARAMETRIC STUDY OF THE KALINA CYCLE

Under the conditions imposed in the preceding section a computer code calculating the whole cycle and
its efficiency has been developed.
Figure 5 shows how the overall theoretical efficiency of the unit changes with the working solution
mass fraction X, (55% to 80%) and the rich solution mass fraction XD (30% to 50%, step 4%) for fixed
values of the other main parameters, i.e. p H= 110 bar, pv = 4-7 bar. The optimum thermal efficiency is
45.6% when the mass fraction of the working and rich solution is 71.4% and 50% respectively. For the
other values of the rich solution the optimum value of the working solution mass fraction is given by the
relationship:
XiP' = 32.03 + O*7875XiPt (9)
The results shown in Figure 5 have been correlated as
17 - 42
--
10-4~
- (X, - 55)(X, + 1)(X, - F) (10)

G=g,+glX,+...+g4Xi (11)

F = -f2 2XR +f3xR (12)

where
go = 1093.9933, g, = - 109.66078, g2 = 4.089 1025 , g, = - 0.067 305 76,
g4 = 4.121 738 4E - 4,

fl = 54.418 908, f2 = - 29.286 785, f3 = 1.600 704 2

The maximum error is less than 4.3%.
The dependence of the work produced by the Kalina unit Wt (kJ/kg of the working solution mass
fraction) is shown in Figure 6 and has been approximated as
tt; = 1*48XD 1250-6 +
The heat required to drive the power unit is obtained as q = %/q.
Figure 7 shows the calculated efficiency q in terms of the low pressure p L (1 to 3 bar) with the medium
pressure p M as parameter (2 to 6 bar, step 2) with p H= 110 bar, quph = 510°C, X, = 42%, Ax =X, -
X, = 8%, XD= 70% and Xu= 96.70%.
The optimum efficiency of the unit is predicted for pM= 6 bar and p L = 1 bar and it is 54%. Further
the optimum relationship between the low and medium pressure is
PiPt = 1 + 3.3 p;pt (14)
The efficiency of the unit in terms of the two pressures pM and p L may be calculated as
 364 E. D. ROGDAKIS

WORKING SOLUTION PUSS FMCTION %(%)

Figure 5. Theoretical efficiency, 1) of a Kalina unit in terms of the working solution mass fraction, X,, for various values of the rich
solution mass fraction, X,

WORKING SOLUTION MASS FRACTION %(%)

Figure 6. Work produced, F,of a Kalina unit as a function of the working solution mass fraction, X ,

where
A = - 0.944 70085 p i + 8.870568 2 PM - 22.047349 (16)
B= - 0.381 323 89 p i + 4.048 1463 pM- 11.702681 (17)
C = 1.2152930 p i - 13.127963 + 81.367228 (18)
The influence of the work produced by the Kalina unit (kl/kg) on the low pressure p L (bar) is shown
in Figure 8 and has been approximated as
W, = - 287.34 ln(pL) + 1506 (19)
The maximum error is less than 0.2%. The heat required to drive the power unit is obtained as q = K / q .
Figure 9 shows the predicted influence of the high pressure p H (80 to 130 bar) on the theoretical
efficiency q of the Kalina cycle for various values of the superheating temperature Tsuph(450 to 550°C,
step 50°C) and for fixed values of the other parameters, i.e. pM = 4.7 bar, p L = 1 bar, X, =42%,
 KALINA CYCLE 365

Low PRESSURE pL(bar)

Figure 7. Theoretical efficiency,7 , of a Kalina unit in terms of the low pressure, p L , for various values of the medium pressure, p~

AX =X, - X, = 8%, X, = 70%, X, = 96.7%. The efficiency may be expressed in terms of the super-
heating temperature quph
(“C)and the high pressure P h (bar) by the following function.
D
v=-+E (20)
PH
where
D = -0.50856 Cup),- 185.819 (21)
E = 0.042 29 q u p h 26.382 (22)

Figure 10 shows the dependence of the work produced by the Kalina W, (kJ/kS, on the high pressure pH
(bar) and the superheating temperature Tsuph(OC)
and can be expressed by the following relation:
W, = 390 + 1*32T,,,, -k 0*2pH(o*3TsUph
- 25) (23)
The heat required to drive the power unit is obtained as q = W,/q.

LOW PRESSURE pL (bar)

Figure 8. Work produced, W;,of a Kalina unit as a function of the low pressure, p L
366 E. D. ROGDAKIS

H I G H PRESSURE pH (bar1

Figure 9. Theoretical efficiency, 7, of a Kalina unit in terms of the high pressure, p H , for various values of the superheating
temperature, Tsuph

7%
1588

1426

H I G H PRESSURE pH (bar)

Figure 10. Work produced, W,, of a Kalina unit as a function of the high pressure, p H , with the superheating temperature as
parameter

RESULTS FOR THE OPTIMUM OPERATION OF THE UNIT

The objective here is to derive correlations linking the main parameters of the unit ( r ) and W,)with the
ambient temperature (Tamb) under optimum operation of the Kalina cycle. Figure 11 shows the influence
of the temperature ambient Tomb(oC)on the rich and the working solution mass fraction X, and X, (%)
for various values of the low pressure p L (1.0 to 1.5 bar) and the medium pressure pw (4.30 to 5-95 bar)
respectively. The values for the optimum medium pressure are obtained from equation (14).
The results shown in Figure 11 have been correlated as

432-5674 44.6959
-~
L ( p ) = In ( p + 5.253) P
 KALINA CYCLE 367

1
5 'ie 15 2e 25 3e
AMBIENT TEMPERATURE TaJRb(OC)

Figure 11. Variation of (a) rich solution mass fraction, X,, and (b) working solution mass fraction, X,, in terms of the ambient
temperature, Tomb,for various values of the low pressure, p L ,for optimum operation of a Kalina unit

where X + X, when p +pL and X + X, when p +pM.

Figure 12 shows the predicted influence of the temperature ambient Tam,(")on the boiler vapour mass
fraction Xu(%)for various values of the low pressure pL(l.O to 1.5 bar).
The efficiency v(%) and the work produced by the unit W,(kJ/kg) are calculated for a great number of
combinations of the ambient temperature Tamb(7*5 to 27.5"C) and low pressure ~ ~ ( 1to
. 01.5 bar) under
the conditions imposed by the equations (9) and (14) for optimum operation of the Kalina cycle. The
values of the high pressure and the superheating temperature are fixed ( p H= 110 bar, Tsuph= 510°C).
The results are given in Figures 13(a), 13(b) and 13(c).
In Figure 13(c) it is seen that the maximum efficiency of the unit ranges from 42-7 to 46.6%. The
efficiency decreases with increasing Tamband p L for ambient temperature up to 20°C. Owing to the heat
rcquired to drive the unit the efficiency decreases more rapidly with increasing Tambfrom 20 to 27.5"C
for the low values of PL (1.0 to 1.3 bar).
According to the above the heat required to drive the unit, q, may be expressed as
+
q = 6.1 Tomb 3634 - 428 PL - Aq (27)

-
-
P

x
,96
B
B
v)
94

2 92 1.4
1.3
1.2

88

AMBIENT T E P I P E R A W T- ( OC )

Figure 12. Variation of boiler vapour mass fraction, X u , in terms of the ambient temperature, Tomb,
for various values of the low
pressure, p L , for optimum operation of a Kalina unit
368 E. D. ROGDAKIS

3588 I I
1.1

- ' 1.2

.-u"
2
3388

t- 1.3

~ 3288 * 1.4
i .
p =1 Sbar
E 3188 l
d t
z i
3888 I
5 18 15 28 25 38
AMBIENT TEMPERATURE Tamb(OC)

B
I

1388 1
5 18 15 28 25 38
AMBIENT TEMPBRATURE Tamb (OC)

46 ,

- 45 ,----- 0=45.

-
P

E 1.4bar
1. 5bar
E 4' I 1.3bar

\
pL=l. Obar

I
5 18 15 20 25 38
AMBIENT TEMPERATURE T-('Cl

Figure 13. Variation of (a) the heat input, q, (b) the work produced, 6 , and (c) the theoretical efficiency, 7 , in terms of the
ambient temperature, Tomb,for various values of the low pressure, p L ,for optimum operation of a Kalina unit
 KALINA CYCLE 369

where A q =0 when Tamb< 20°C and

1.5
A q = ( T - 20) ( 140-100pL) In - when Tamb> 20°C
PL
With reference to Figure 13(b) the work produced may be calculated from the equation:
W, = - 0.8Tamb+ 1738 - 216pL (28)
Thus, for example, using equations (27) and (281, for Tamb= 20°C the heat required and the work
produced will be respectively q = 3242.4 kJ/kg and W, = 1462.8 kJ. The accurate values (Figures 13(a)
and (b)) are 3232.2 kJ/kg and 1458.4 kJ/kg respectively.
The efficiency of the cycle in this example is

CONCLUSION
A method has been proposed which allows a complete thermodynamic analysis of the Kalina cycle. The
characteristics of the Kalina power unit has been clarified through the graphical representation of the
cycle on the typical thermodynamic diagrams. The efficiency and the work produced by the unit have
been calculated by fast algorithms based on Schulz and El Sayed equations for NH,/H,O mixtures and
have been shown on diagrams for the following values of the main parameters:
pH= 80 to 130 bar
pw= 2 to 6 bar
pL= 1 to 3 bar
Tsuph= 450 to 550°C

X R = 3 0 %to50%(X,=XR-8%)
X, = 55% to 80%

The results have been given too in the form of correlations, simulating the behaviour of the Kalina unit.
Simple equations have been derived, which link the main parameters of the unit under the condition
of optimum operation.
The parametric study conducted showed that the optimum theoretical efficiency of the Kalina power
unit for the above-referred values of the main parameters ranges from 42.7% to 46.6%

NOMENCLATURE
q = efficiency
h = specific enthalpy
p = pressure
q = specific heat
‘P = expansion ratio
S = specific entropy
W = specific work
X = mass fraction
370 E. D. ROGDAKIS

Subscripts
D = basic working solution
H = high pressure
L = low pressure
M = medium pressure
R = rich solution
T = turbine
Y = boiler vapour
W = weak solution

REFERENCES
El Sayed, Y. M. and Tribus, M. (1985). ‘Thermodynamic properties of water-ammonia mixtures: theoretical implementation for use
of power cycles analysis, ASME publication AES-Vol. 1.
Gillespie, P. and Wilson, G. (1983). ‘Ammonia-water vapour-liquid equilibrium measurements at high temperature and pressures’,
Wiltec Research Co., Inc., personal communication.
Kalina, A. I. (1984). ‘Combined cycle system with novel bottoming cycle’, ASME Journal of Engineeringfor Power, H4), 734-742.
Kalina, A. I. (1991). ‘Kalina cycles and system for direct-fired power plants’, ASME Winter Annual Meeting, AES-Vol.
25/HTD-Vol. 191, Atlanta, GA, pp. 41-47.
Kalina, A. I. and Leibowitz, H. M. (1987). ‘Kalina cycle promises improved efficiency’, Modem Power Systems ReUew (incorporating
Energy Intern.), 7, 19-23.
Kouremenos, D. A. and Rogdakis, E. D. (1990). ‘The temperature-entropy (or enthalpy) diagram of the Kalina cycle’, ASME
Winter Annual Meeting, AES-Vol. 19, Dallas, TX, pp. 13-19.
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report prepared by Institute of Gas Technology, Chicago IL.
Macriss, R. A,, Eakin, B. E., Ellington, R. T. and Huebler, J. (1964). ‘Physical and thermodynamic properties of ammonia-water
mixtures’, Research Bulletin No. 34, Institute of Gas Technology, Chicago, IL.
Rorrdakis. E. D. and Antonopoulos, K. A. (1991). ‘A high - efficiency
. NH,/H,O
- - absorption
- power
. cycle’, Heat Recowry System and
CHP, 11,263-275.
I - Refig.
Schulz. S. G. (1971). ‘Eauations of state for the svstem ammonia-water for use with computers’. Prom. . - Sc. Techno/.Proc. 13th
lntem. Congr. of Re&geration, Vol. 2, 431.
Ziegler, B. (1982). ‘Waerrr.etransformation durch einstufige Sorptionsprozess mit dem Stoffpaar Ammoniak-Wasser, Ph.D. thesis,
ETH Zurich. No. 7070.