Applied Thermal Engineering 21 (2001) 381390

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Technical note

Unconventional working uids in organic Rankine-cycles

for waste energy recovery systems
V. Maizza*, A. Maizza
Faculty of Engineering, Polytechnic of Bari, 200 Via Re David, 70125 Bari, Italy
Received 15 June 1999; accepted 11 March 2000

Abstract
This paper investigates the thermodynamic and physical properties of some unconventional uids for
use in organic Rankine-cycles supplied by waste energy sources. Energy requirement and recovery
system performances are analyzed using realistic design operating conditions. Thermodynamic
eciencies and other useful results have been calculated by varying some recovery system operating
parameters at various reference temperatures. With reference to proposed application, equations and
graphs are presented which interrelate the recovery system operational parameters for some possible
working uids with computation results. 7 2000 Elsevier Science Ltd. All rights reserved.
Keywords: Energy recovery systems; Unconventional uids; Power plants; Organic Rankine-cycles; Parametric
analysis

1. Introduction
Rankine-cycle engines employing organic uids as the working media have exhibited good
performance for many systems where the heat source temperature is low as in waste energy
available sources.
The selection of suitable organic uids for use in organic Rankine-cycles (ORC) still deserves
intensive thermodynamic and physical study of the following desirable characteristics:
* Corresponding author. Tel.: +390-80-242-411.
1359-4311/01/$ - see front matter 7 2000 Elsevier Science Ltd. All rights reserved.
PII: S 1 3 5 9 - 4 3 1 1 ( 0 0 ) 0 0 0 4 4 - 2

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Nomenclature
h
p
T
W
Z

specic enthalpy
pressure
temperature
molecular weight
eciency

Subscripts
c
condensing conditions
ca
relative to the Carnot cycle
cy
relative to the cycle
heat transfer eectiveness
ht
k
critical point conditions
p
cycle pumps
t
cycle turbine
v
vapor conditions
R
relative to the theoretical Rankine-cycle
1, 2,. . . relative to cycle points
appropriate low critical temperature and pressure, small specic volume, low viscosity and
surface tension, high thermal conductivity, suitable thermal stability, be non-corrosive, nontoxic and compatible with engine material and lubricating oil.
Previous research [1] examines the aforesaid questions and identies some possible
environmentally acceptable working uids. The desirable thermodynamic properties of the
uids are: high latent heat and low liquid specie heat or a near vertical saturated liquid
line so that most of the heat is added during change of phase without the need for the
complexity of regenerative feed heating to ``carnotize the cycle'' to realize high eciency.
Besides, a near-vertical saturated vapor line is desirable so that, on the one hand, little
moisture results during expansion and, on the other, it is unnecessary to condense a
superheated vapour.
Finally, it is convenient if a moderate vapor pressure, in the range of 0.12.5 MPa , occurs
in the heat-exchange units.
Table 1 shows the thermodynamic characteristics and calculation parameters of some
potential working uids for an ideal ORC system.

2. Thermodynamic analysis for the choice of working uids

Section 1 summarizes the major thermodynamic parameters aecting the performance of an
ORC recovery system. Seeking a single uid with the aforesaid better features we attempt to
determine rational criteria which could help us to select the more protable working media.

Table 1
Thermodynamic characteristic and calculation parameters of some potential working uids for an ideal ORC system
Chemical
formula

HCF-22
HC-40
Methyl
chloride
HCFC-123
HCFC-124a
HFC-125
HFC-134a
HCFC-142b
HFC-152a
HC-170
Ethane
HC-290
Propane
HC-600a
Iso-butane
R-401A
R-401B
R-401C
R-402A
R-402B
HFC-404A
HFC-407C
HFC-410A
R-508B

CHClF2
CH3C1
C2HCl2F3
C2HClF4
C2HF5
C2H2F4
C2H3ClF2
C2H4F2
C2H6
C3H8
(CH3)3CH
(a)
(a)
(a)
(b)
(b)
(b)
(c)
(d)
(e)

Molecular
weight W

Boiling
point (8C)

Critical pressure
pk (MPa)

Critical
temperature Tk
(K)

Sonic velocity at
298 K (m/s)

Latent heat at boiling point

(kJ/kg mol)

86.47

40.5

4.98

369.24

184.189

20,207

50.48

24

6.681

416.1

242.386

21,644

152.91
136.5
120.02
102.03
100.5
66.05

27.75
12.03
48.3
26.1
36
24.2

3.606
3.616
3.595
4.064
4.123
4.52

457.15
395.57
339.2
374.3
410
386.44

128.5
137.75
148.75
161.5
165.168
203.16

26,005
22,654
19,276
22,160
21,624
21,039

30.07

88.6

4.82

305.5

312.605

14,645

44.1

42.1

4.26

369.9

251.407

18,669

11.7
32.97
34.67
28.4
49.19
47.4
46.45
43.56
51.533
88.27

3.65
4.604
4.682
4.366
4.135
4.445
3.732
4.619
4.926
3.926

408
381.16
379.25
386.15
348.65
355.75
345.22
359.89
345.13
287.15

217.53
173.546
175.247
166.862
166.042
173.298
168.241

199.503

21,174
21,476
21,288
21,906
19,700
19,889
19,725

58.12
94.44
92.8
101
101.55
94.71
97.6
86.2
72.584
95.39

V. Maizza, A. Maizza / Applied Thermal Engineering 21 (2001) 381390

Fluid

(a) Azeotrope mixture of HCFC-22, HCFC-124, HFC-152a, (b) azeotrope mixture of HCFC-22, HFC-125, HC-290, (c) azeotrope mixture of
HFC-32, HFC-125, HFC-134a (22/25/52% by weight), (d) azeotrope mixture of HFC-32, HFC-125 (50/50% by weight), (e) azeotrope mixture of
HCFC-23, FC-116 (46/54% by weight) [7].
383

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V. Maizza, A. Maizza / Applied Thermal Engineering 21 (2001) 381390

The uid thermodynamic characteristics give rise to thermodynamic limitations to the amount
of energy that can be extracted from the heat source.
This boundary depends on the waste stream temperature and on the temperature of the
cooling medium, i.e. air, river water, etc. The amount of energy which can be recovered is
greater if the waste source temperature is higher and if the cooling source temperature is lower.
A rst survey can be carried out by a direct comparison of some working uid parameters in
the log ph chart.
Fig. 1 shows the liquid and vapour saturation lines of some uids in the log ph chart over a
wide operating range.
The conclusions and suggestions resulting from previous research [l4] are that a critical
temperature Tk lower than 385 K (average value) is not suitable.
For the condensing pressure the reference value is pc = 0.7 MPa and the lower acceptable
condensing temperature is Tc = 308 K [6]. In view of proposed working uid use and
regarding the low waste heat temperature a uid vaporization temperature above 383 K does
not appear feasible.
Fig. 2 shows the location of critical points of some working uids in relation to a feasible
vaporization and condensing range.
Fig. 3 shows the reference Rankine-cycle of a typical uid (R-142b) for lower condensing
temperature.

Fig. 1. Comparison of the uid saturated lines in the log ph chart.

V. Maizza, A. Maizza / Applied Thermal Engineering 21 (2001) 381390

385

Fig. 2. Location of the working uid critical points in relation to selected vaporization values (TV = 801108C) and
the condensing reference value (TC = 358C).

Fig. 3. The Rankine-cycle in the log ph chart of R-142b uid for lower condensing temperature (Tc = 308 K).

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V. Maizza, A. Maizza / Applied Thermal Engineering 21 (2001) 381390

3. Conguration description
The fundamental components of a Rankine ``bottoming'' plant are: heat recovery vapor
generator, turbine, condenser, feed pump, feed liquid heaters and circulating uid system.
Fig. 4 illustrates all of the above components plus other minor components required to
complete an operable system included in the ORC ``bottoming plant''.
The circled numbers in Fig. 4 correspond to Rankine-cycle points in Fig. 3 and to the
subscripted parameters later utilized for the calculations.

4. The system performances

In the studies previously related [1,3] eorts have been made to establish the inuence of
working uids properties on the power plant design and performance. It is not the purpose of
this paper to duplicate this type of work but rather to present some practical reference values
useful to the choice of working uids for the present application.
A computer program has been utilized for the calculation of ORC system realistic
performance in the case of use of some of the working uids shown in Table 1. Performance
evaluation of the ORC recovery system has been carried out by setting the variation of the
operating parameters to be in the following ranges:

Fig. 4. ORC bottoming plant schematic. (1) Vaporizer, (2) superheater, (3) turbine inlet, (4) turbine outlet, (5)
regenerator, (6) condenser, (7) vapor separator-storage tank, (8) main feed pump, (9) regenerator return inlet, (10)
regenerator return outlet, (11) vaporizer inlet, (12) pump, (13) feed liquid heater, (14) available power (electrical
generator), (15) ow control valve, (16) cooling tower, (17) waste heat source.

V. Maizza, A. Maizza / Applied Thermal Engineering 21 (2001) 381390

387

. vaporizer or superheater temperature T1, 2 = 353383 K (801108C);

. cycle condenser temperature T6 = 308333 K (35608C).
For the component performance, values suggested in similar application have been assumed
[4,5].
. cycle pumps eciency: Zp 80% adiabatic;
. turbine eciency: Zt 88% adiabatic;
. heat transfer eectiveness (all components): Zht 80%:
The ORC eciencies Zcy have been calculated by using the enthalpy values with reference to
the points and notations in Figs. 3 and 4.
The enthalpy of vaporization is
h3 h11 h2 h11
because the vapour superheat is low. Accordingly the point (1) (see Fig. 3) is laid on the point
(3) and the expansion line is near the vapour saturation line.
For the same reason the enthalpy drop in the turbine is
h3 h4 h2 h4
and, if the enthalpy drop of the turbine outlet is small, the point (4) (see Fig. 3) is laid on the
point (5).
Besides, if the preheating of the liquid supplied to the vaporizer is low the point (9) is laid
on the point (10). Finally, for simplicity of calculation it is assumed that the enthalpy at the
vaporizer inlet is the same as the enthalpy at the regenerator outlet. This means that the point
(11) is laid on the point (10).
With the aforesaid assumptions the cycle eciency becomes
Zcy

h2 h4
h2 h11

The overall system eciency Z was obtained using the component eciencies values Zp , Zt , Zht ,
previously indicated.
Fig. 5 shows the overall system eciency for some uids in a realistic waste vaporization
temperature range (Tv = 801108C) at dierent possible condensing temperature Tc (Tc = 35,
40, 50, 608C).

5. The uid basic performances

Independent of the numerical values of the system eciency the working uid basic
thermodynamic behaviour has been investigated in a waste heat utilization cycle where the
available temperatures are low.
In order to evaluate the thermodynamic characteristics suitability of the working uid to the

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V. Maizza, A. Maizza / Applied Thermal Engineering 21 (2001) 381390

peculiar operative conditions the theoretical Rankine-cycle eciencies ZR bave been compared
with the Carnot eciency values over the same temperature range. The uid behaviour and the
consequent ZR value depends only on such basic thermodynamic characteristics as the critical
point location, the shape and slope of liquid and vapour saturation lines, etc., which can lead
to high waste heat recovery eciency.
For the aforesaid reasons in the vaporization and condensing temperature range previously
investigated have been calculated the Carnot eciencies
Zca

Tv Tc
Tv

The dierence between the Rankine-cycle and the Carnot eciency is a measure of the
working uid behaviour in the specic application and can be a guide to the choice of the best
working uid in a preliminary design.

Fig. 5. Overall system eciency Z for some selected uids in the vaporization temperature range Tv = 801108C at
dierent condensing temperature. (a) Tc = 358C; (b) Tc = 408C; (c) Tc = 508C; (d) TC = 608C.

V. Maizza, A. Maizza / Applied Thermal Engineering 21 (2001) 381390

389

Fig. 6 shows this dierence in the same vaporization range as Fig. 5 (Tv = 801108C) at
dierent possible condensing temperatures Tc = 35, 40, 50, 608C.

6. Conclusions
Preliminary consideration of the thermophysical and thermodynamic characteristics of a
variety of uids allows a rational selection of the working uids suitable for an ORC system
utilizing waste heat.
Based on a performance model for energy recovery, criteria for optimal working uid choice
with respect to its thermodynamic characteristics and available vaporization and condensing
temperature, have been derived analytically .
Figures and tables provide a speedy solution to the choice of some optimal system

Fig. 6. Shifting the Rankine-cycle eciency ZR from the Carnot eciency in the vaporization range Tv = 801008C
for dierent condensing temperature. Tc = 35, 40, 50, 608C.

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V. Maizza, A. Maizza / Applied Thermal Engineering 21 (2001) 381390

parameters at the stage of system design study and/or turbomachinery preliminary design of
closed cycle gas turbines.
The system and cycle eciencies were calculated down to a minimum realistic condensing
temperature of 358C. Obviously the system eciency below this temperature improves and
other uids become suitable.
Of the uids analyzed in this study R-123 and R-124 couple good system performance with
high operative elasticity as found in previous research [l].
The small recovery system performance of the working uid blend R-401C is due to the
strict thermal operative conditions imposed. However present industrial interest in blended
uids [79] suggests that R-401C or similar blended uids, may be the most suitable uid for
an ORC recovery system.

References
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[3] V. Maizza, Organic Rankine-cycle turbine power plant utilizing low-temperature heat sources, ASME Paper 80GT-153 (1980) 110.
[4] S.C. Kaushic, et al., Thermal modelling and energy conservation studies on freon Rankine-cycle cooling system
with regenerative heat exchanger, Heat Recovery System & CHP 14 (1994) 6677.
[5] T.S. Nemec, W.E. Lear, Thermodynamic design point study of a semi-closed recuperated intercooled gas turbine
combined with a Rankine bottoming cycle, ASME Paper 96-GT-434 (1996) 17.
[6] M.J. Lee, D.L. Tien, C.T. Shao, Thermophysical capability of ozono safe working uids for an organic
Rankine-cycle system, Heat Recovery System & CHP 13 (1993) 409418.
[7] A. Robledo, Du Pont Fluoroproducts lberica Personal communication, 1999.
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Biennal European Seminar on Latest Technologies in Refrigeration and Air Conditioning, Milano (I), 1997, pp.
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