Energy 74 (2014) 2e11

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Energy
journal homepage: www.elsevier.com/locate/energy

Inuence of working uid properties on system performance and

screen evaluation indicators for geothermal ORC (organic Rankine
cycle) system
Huixing Zhai a, Lin Shi a, Qingsong An b, *
a
Key Laboratory for Thermal Science and Power Engineering of Ministry of Education, Department of Thermal Engineering, Tsinghua University, Haidian
District, Beijing 100084, China
b
Key Laboratory of Efcient Utilization of Low and Medium Grade Energy of Ministry of Education, Tianjin University, Tianjin 300072, China

a r t i c l e i n f o a b s t r a c t

Article history: The ORC (organic Rankine cycle) system is one of the most effective approaches for recovering energy
Received 12 September 2013 from low grade heat sources like geothermal water. This paper describes the screen of uids for
Received in revised form geothermal ORC system. This study analyzed the inuence of the working uid properties of HC (hydro
3 December 2013
carbon) and HFC (hydro uorine carbon) working uids on the system performance and relates the
Accepted 12 December 2013
Available online 21 January 2014
properties to the molecular structures. HC and HFC working uids were adopted. A theoretical ORC
model was used to optimize the evaporating temperature to maximize the work output for each working
uid. The optimal working uids are given for heat sources at 383.15 K, 403.15 K and 423.15 K. The results
Keywords:
Organic Rankine cycle
show that for a specic source temperature, the optimized evaporating temperatures for all the working
Working uid screen uids are almost the same. Based on the inuence of working uid property on system performance, two
Geothermal system indicators are given for screening working uids. Fluids like R32, R134a and propylene with GWP (global
Indicator warming potential) value less than 1500 provide better performance than others, by extracting more
energy from the heat source.
2013 Elsevier Ltd. All rights reserved.

1. Introduction
Low temperature heat sources are abundant on the earth.
Turning low temperature energy into work effectively is one of the
most promising approaches for relieving the pressure of the energy
crisis. The ORC (organic Rankine cycle) is an effective way to
convert low temperature heat into work and has attracted the
attention of many researchers. Geothermal resources are renew-
able low temperature heat sources with geothermal water gener-
ally range between 353 K and 623 K [1]. High quality resources
produce dry vapor or a water-vapor mixture at temperatures of
more than 450 K. Medium and low quality sources with tempera-
tures below 450 K must use binary power plants such as ORC
systems to improve their efciency. Guzovic, Z., et al. [2] compared
the Kalina and ORC system to recover geothermal energy in Re-
public of Croatia. Results show that ORC has better performance
both in the thermal efciency and the exergetic efciency and gives
more net power. Raskovic, P [3].,who is in the same research group
* Corresponding author. Tel./fax: 86(0)22 27407617.
E-mail addresses: dihx11@mails.tsinghua.edu.cn (H. Zhai), rnxsl@tsinghua.edu.
cn (L. Shi), anqingsong@tju.edu.cn (Q. An).
with Guzovic, Z., made a more detailed Velika Ciglena medium
temperature (448.15 K) geothermal case study and indicated that
the plant design based on the ORC cycle has a higher thermody-
namic efciency and lower cost of equipment than Kalina cycle.
There are various opinions about the best working uids and
evaluation criteria for geothermal sources. Borsukiewicz-Gozdur
et al. [4] hold the view the best method to produce more work
was to increase the geothermal water ow rate to increase the work
output. Hettiarachchi et al. [5] set the heat transfer area per unit
work output as the optimum design criteria and recommended
PF5050, R123 and n-pentane. T. Guo et al. [6] found that R236ea
was the best working uid for maximizing the work output per unit
mass heat source ow rate while E170, R600 and R141b were the
best working uids when minimizing the heat transfer area per
work output. Besides the working uids, the turbine is also an
important part of ORC systems. When radial-inow turbines in an
ORC system, R134a provides the highest network output while n-
pentane provides the lowest network output among ve high-
density working uids [7].
Most working uid selection studies have compared all possible
working uids with a given criterion to screen suitable working
uids. Ghasemi, H., et al. [8] and Cheng, W.L., et al. [9] have made
detailed study on the modeling and optimization for geothermal

0360-5442/$ e see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.energy.2013.12.030
 H. Zhai et al. / Energy 74 (2014) 2e11
Fig. 1. Schematic diagram of a simple geothermal ORC system.
ORC system. However, the relationship between system perfor-
mance and working uids are not mentioned. Some researchers
have also begun to make a connection between the working uids
properties and system evaluation indicators [10] with CAMD
(computer aided molecular design) and process optimization [11].
These methods enable active working uid designs for different
ORC systems. However, these studies only consider universe ORC
system. In reality, each ORC system has its own working uid re-
quirements, especially for medium and low temperature
geothermal ORC systems.
This paper focuses on geothermal ORC systems. The study an-
alyses the inuence of the working uid properties on the system
performance and connects the properties and the molecular
structures. The results provide guidance for mixture working uid
design. Unlike waste gas or liquid discharged from industrial
sources, geothermal water is pumped from deep under the ground
which consumes work. The heat source utilization efciency is then
very important for geothermal ORC systems. The optimize objective
is to maximize the work output per unit mass of geothermal water.
Liu, B. T. et al. [12] referred that the maximum value of the total
heat-recovery efciency occurs at the appropriate evaporating
temperature between the inlet temperature of waste heat and the
condensing temperature. In this paper, a theoretical ORC model was
used to optimize the evaporating temperature to maximize the
work output per unit mass of geothermal water for each working
uid. HC (hydro carbon) and HFC (hydro uorine carbon) are cho-
sen as the working uids. The optimal working uids were found
for heat sources of 383.15 K, 403.15 K and 423.15 K.
Fig. 2. Tes diagram for geothermal ORC system.
3
Table 1
Simulation parameters and boundary conditions for the geothermal ORC model.
Parts Items Quantities
Heat source Inlet temperatures 383.15 K/403.15 K/423.15 K
Pipe pressure 0.5 MPa
Heat carrier mass ow rate 1 kg/s
Cycle Pinch evaporator 20 K
Condenser temperature 283.15 K/293.13 K/303.15 K
Isentropic pump efciency 1
Isentropic turbine efciency 0.8
2. Geothermal ORC system model
2.1. Description of geothermal ORC systems
The basic cycle without reheating or preheating includes a
pump, an evaporator, a turbine and a condenser. A pump pressur-
izes the organic working uids to the evaporating pressure. Then,
the working uid is injected into an evaporator and heated by the
geothermal hot water to produce vapor. The vapor is expanded in a
turbine to produce work. Finally, the exit vapor is condensed to
liquid in the condenser to start a new cycle as shown in Fig. 1.
The state points corresponding to the points in Fig. 1 are shown
in the Tes diagram in Fig 2. The organic working uid is heated
from point 2 to point 4 while the geothermal hot water is cooled
from point 6 to point 8. In addition, the heat absorbed by the latent
heat, Qel, is in the process from point 6 to point 7 while the heat
absorbed by the sensible heat, Qes, is from point 7 to point 8. The
pinch temperature difference is between point 3 and point 7.
2.2. Assumption and model
The simulation parameters and boundary conditions of the
geothermal ORC model are shown in Table 1. To simplify the
calculation, the pump isentropic efciency was set to 1 while the
turbine isentropic efciency was set to 0.8. The condensing tem-
perature was set to 293.15, 298.13 and 303.15 K. The condensing
temperature was xed to 303.15 K when compare of the various
working uids. And condensing temperature 283.15 and 293.13 are
calculated to analyses the condensing temperature inuence on the
cycle performance.
The evaporating temperature was varied in the analyses. One
restriction was that the evaporating pressure had to be lower than
0.9 times the critical pressure to guarantee a subcritical cycle. If the
critical temperature of the working uid is much higher than the
source inlet temperature (point 6 in Fig. 2), the other restriction is
that the evaporating pressure must be lower than the saturate
pressure of the evaporating temperature which is equal to the source
temperature minus the pinch temperature difference. The lower
limit of the evaporating temperature is the condensing temperature.
The working uid should operate at saturated conditions to
reduce the total irreversibility of the process [13]. The thermal ef-
ciency can be improved to some extent if the uid is superheated
at the turbine inlet. However, it increases the system cost as well
[14]. Thus, the simulation set the working uid to be saturated at
the turbine inlet. This paper was only subcritical cycles because
they are less expensive than supercritical cycles [15].
On the working uid side, the total cycle efciency is dened as:
wt  wp
h (1)
qe
where:
wt h4  h5 (2)
4 H. Zhai et al. / Energy 74 (2014) 2e11

Table 2
Simulation results comparison.

Working uids Simulation results Theoretical Theoretical Theoretical Simulation results The error (%)
of Ref. [16] (K) calculation 1 (K) calculation 2 (K) calculation 3 (K) of this paper (K)

R245fa 365 365.6 367.9 363.7 364.6 0.10959

R600 365.3 365.1 364.3 363.2 364.6 0.19162
R600a 366.2 368.4 367.3 364.8 369.8 0.983069
R601 362.4 362.8 362.8 362 361 0.38631
R601a 362.9 363.3 363 362.4 361.3 0.44089
cyclohexane 360.5 360.4 360.2 359.9 359.3 0.33287
hexane 362.3 361.8 363 361.6 359.7 0.71764
heptane 360.9 361.7 364.3 361.4 359.2 0.47104
toluene 362.1 359.4 359.8 359.1 357.8 1.18752
nonane 360.4 361.4 352.1 361.2 357.9 0.69367
decane 360.3 361.4 357.6 361.2 359.2 0.3053

wp h2  h1 (3) Qew Qe (10)

The total work output of the cycle, Wt, (per unit mass of
qe h4  h2 (4)
geothermal water):
On the heat source side, the total heat released from the
geothermal water is dened as Wt Qew $h (11)

Qe Qel Qes (5)

2.3. Model validation
where: Qel is energy heat absorbed from the heat source as latent
heat of the working uid and Qes is the energy absorbed as sensible The simulation results in this paper are compared with the
heat. simulation and three theoretical calculation results of Ref. [16] in
Where Qel is determined by the temperature decrease (relative the same working condition. The working uids chosen in both
to the pinch temperature) and the sensible heat of the geothermal paper are calculated to validate the model. The simulation result
hot water: differences are within 1% for most of the working uids and the
biggest error is 1.18% for toluene, however, whose result in this
ZT6 paper is much closer to the theoretical calculation results. The re-
Qel CPwa dT h6  h7 (6) sults are shown in Table 2.
T7

3. Fluids choice
and

Qes mwf $h3  h2 h7  h8 (7) 3.1. Working uids requirement

The mass ow rate of working uids, mwf, in the system is
determined by the partial heat of the geothermal hot water, Qel, and
the latent heat of the working uid, DHv:
mwf Qel =DHv
and,
DHv h4  h3
The energy balance assumes that the heat absorbed by the
working uid is the same as the heat released by the heat source
which ignores heat losses.
Previous studies [17e19] have indicated that good working
uids have the following characteristics:
- Dry or isentropic uids
(8) - Large latent heat (This is not suitable for the geothermal ORC
working uids used in this study. Even though a large latent
heat is good for the heat transfer, it is not good thermody-
namically for the heat source utilization.)
(9)
- High densities in both liquid and gas phase
- Moderate critical parameters
- High specic heat
- Moderate evaporating and condensing pressures

Table 3
Physical data for the HFC working uids (sorted by carbon number).

Substances Molecule M, kg/kmol Tb, K Tc, K Pc, MPa u GWP

R32 CH2F2 52.024 221.5 351.26 5.782 0.2769 716

R134a CF3CH2F 102.03 247.08 374.21 4.0593 0.32684 1370
R152a CHF2CH3 66.051 249.13 386.41 4.5168 0.27521 133
R161 C2H5F 48.06 235.6 375.3 5.091 0.217 12
R1234yf CF3CF]CH2 114.04 243.7 367.85 3.3822 0.276 <4.4
R1234ze(z) CHF]CHCF3 114.04 282.15 426.8 3.97 0.333 -but low
R1234ze(e) CHF]CHCF3(trans) 114.04 254.2 382.52 3.6363 0.313 6
R236ea CF3CHFCHF2 152.04 279.34 412.44 3.502 0.3794 1410
R245ca CHF2CF2CH2F 134.05 298.28 447.57 3.925 0.3536 726
R245fa CF3CH2CHF2 134.05 288.29 427.16 3.651 0.3776 1050
R365mfc CF3CH2CF2CH3 148.07 313.3 460 3.266 0.38 850
 H. Zhai et al. / Energy 74 (2014) 2e11 5

Table 4
Physical data for the HC working uids (sorted by carbon number).

Substances Molecule M, kg/kmol Tb, K Tc, K Pc, MPa u GWP

propyne CH3CCH 40.06 248 402.38 5.626 0.204 w20

cyclopropane cyclo-C3H6 42.081 241.67 398.3 5.5797 0.1306 w20
propylene CH2]CHeCH3 42.08 225.53 364.21 4.555 0.146 w20
propane CH3CH2CH3 44.096 231.04 369.89 4.2512 0.1521 w20
butane CH3-2(CH2)eCH3 58.122 272.66 425.13 3.796 0.201 w20
isobutane CH(CH3)3 58.122 261.4 407.81 3.629 0.184 w20
butene CH3eCH2eCH]CH2 56.106 266.84 419.29 4.0051 0.192 w20
cis-butene CH3eCH]CHeCH3 56.106 276.87 435.75 4.2255 0.202 w20
isobutene CH2eC(CH3)2 56.106 266.15 418.09 4.0098 0.193 w20
trans-butene CH3eCH]CHeCH3 56.106 274.03 428.61 4.0273 0.21 w20
cyclopentane cyclo-C5H10 70.133 322.4 511.69 4.515 0.195 w20
isopentane (CH3)2CHCH2CH3 72.149 300.98 460.35 3.378 0.2274 w20
neopentane C(CH3)4 72.149 282.65 433.74 3.196 0.1961 w20
pentane CH3-3(CH2)eCH3 72.149 309.21 469.7 3.37 0.251 w20
cyclohexane cyclo-C6H12 84.161 353.89 553.64 4.075 0.20926 w20
hexane CH3-4(CH2)eCH3 86.175 341.86 507.82 3.034 0.299 w20
isohexane (CH3)2CH(CH2)2CH3 86.175 333.36 497.7 3.04 0.2797 w20
benzene C6H6 78.112 353.22 562.02 4.9063 0.211 w20
methylcyclohexane C6H11(CH3) 98.186 374 572.2 3.47 0.23 w20
heptane CH3-5(CH2)eCH3 100.2 371.53 540.13 2.736 0.349 w20
toluene CH3eC6H5 92.138 383.75 591.75 4.1263 0.2657 w20
octane CH3-6(CH2)eCH3 114.23 398.77 569.32 2.497 0.393 w20
propylcyclohexane (C6H11)CH2CH2CH3 126.24 429.9 630.8 2.86 0.33 w20
nonane CH3-7(CH2)eCH3 128.26 423.91 594.55 2.281 0.4433 w20
decane CH3-8(CH2)eCH3 142.28 447.27 617.7 2.103 0.4884 w20

- Excellent heat transfer properties (low viscosity and high freedom energy equation to calculate the working uid properties.
thermal conductivity) The accuracy of the calculated density for pure uids is 0.1% in the
- Chemical stability regulated calculation range. GWP values are from Refs. [21] and
- Material capability and no corrosion [22]. The critical temperatures of the working uids are all higher
- High efciency than 303.15 K with ODP of 0 and GWP lower than 1500 [21,22]. The
- Safety (no toxicity, low ammability) physical data is listed in Tables 3 and 4.
- Environmentally beings (zero ODP (ozone depletion poten-
tial), low GWP (global warming potential))
- Market availability and cost
4. Results and discussion

4.1. Optimal evaporating temperature

3.2. Fluid choice
The simulations used HCs (hydro carbon) and HFCs (hydro
uorine carbon) as working uids. These working uids are widely
used, are not toxic and do not adversely affect the environment. The
working uid properties were taken from the NIST software
Refprop 9.0 [20]. This software uses the modied Helmholtz
The optimization objective was to maximize the work output,
Wt, per unit mass ow rate of the geothermal water. Wt can be
improved by increasing either the total heat absorbed from the
geothermal water, Qe, or the thermal efciency, h, according to Eq.
(11). The efciency and heat absorbed by the working uids in the
geothermal system are discussed in Part 5 to relate the working
uid properties to the system performance.

Fig. 3. Wt varies with Te for R32, R134a and propylene. Fig. 4. Efciency and Qe variations with Te for R32, R134a and propylene.
6 H. Zhai et al. / Energy 74 (2014) 2e11
Consider a 403.15 K heat source as an example, 303.15 K as
condensing temperature and propylene, R32 and R134a as repre-
sentative working uids. The relationships between Wt, Qe, h and
the evaporating temperature are shown in Figs. 3 and 4. In Fig. 3,
the work output for propylene and R32 continue to increase as the
evaporating temperatures increase, while R134a, whose Tc is rela-
tively high, has a maximum work output at just less than 0.9 times
Fig. 5. Optimized Te for various working uids with heat source temperatures: a)
383.15 K, b) 403.15 K, c) 423.15 K.
Fig. 6. Latent heat change with saturated temperature of R32.
Tc. This is because in Fig. 4 even though the efciency keeps
increasing with the evaporating temperature, Qe of R134a de-
creases as the evaporating temperatures increase while Qe of R32
and propylene have minimum value before 0.9 times Tc and then
increase as the evaporating temperature increases.
4.2. Substance selection results
The optimal evaporating temperatures for almost all the work-
ing uids were concentrated around 335 K for a 383.15 K heat
source (Fig. 5a), 345 K for a 403.15 K heat source (Fig. 5b) and 355 K
for a 423.15 K heat source (Fig. 5c).
Working uids with low Tc do not have a similar optimized Te
with other working uids.
The maximum evaporating temperature is the saturated tem-
perature of 0.9*Pc for working uids with a critical temperature
lower than the temperature of Ths minus 20 K, like R32 for 383.15 K
heat source. In the near-critical area, the latent heat is small and the
Qel which is determined by the temperature decrease is large. So, the
mass ow rate of the working uids is large and mwf is the dominate
factor for Wt. The mwf decreases rapidly, so as to Wt (detail seen in
part 4.4.2), as the Te decreases. So, optimized Te appears at the
limited pressure 0.9*Pc. Supercritical condition is more suitable for
low critical temperature working uids as they still have potential to
produce more work with increasing Te. However, Pan, L., et al. [23]
pointed out that near-critical conditions of ORC may have more
work output than supercritical conditions. So, results may vary from
different working conditions for different working uids.
For working uids with relatively high critical temperature, the
optimized Te is always lower than the saturated temperature of
0.9*Pc. This is because their maximum evaporating temperature is
lower than the saturated temperature of 0.9*Pc to satisfy the pinch
temperature difference requirement. Latent heat of the working
uids is large in far from critical area and mwf is small. In addition,
latent heat changes little with Te and mwf changes little. The latent
heat change is shown in Fig. 6. So, both the heat source temperature
decrease and mwf inuence on the Wt. So there is a peak value of Wt
as Te increases.
The work outputs of all the working uids for the optimal
evaporating temperature are shown in Fig. 7 for heat source tem-
peratures of 383.15 K, 403.15 K and 423.15 K.
The working uids that output the most work with these three
heat sources are shown on Table 5.
 H. Zhai et al. / Energy 74 (2014) 2e11 7

Working condition has the dominant inuence on the cycle Table 5

performance. So in Section 4.3, how the condensing temperature Working uids with the largest work output for the three heat source temperatures.

inuences the cycle performance are described. Wt is determined 383.15 K 403.15 K 423.15 K
by the efciency and Qe according to Eq. (11). In sections 4.4 and 4.5, Substances Wt, kJ Substances Wt, kJ Substances Wt, kJ
how the molecular structures inuence the cycle efciency and
R32 10.983 R32 24.049 R1234yf 46.4
how the physical properties inuence the heat absorption are
R1234yf 10.967 R1234yf 23.44 propane 42.788
described. propylene 10.644 propylene 23.035 R134a 42.607
propane 10.609 propane 20.803 propylene 41.86
R134a 10.578 R134a 20.143 R1234ze (e) 39.057

4.3. Inuence of Tcon on the cycle performance

The condensing temperature which is offered as the cycle

working condition is always decided by the environment temper-
ature and pinch temperature difference in the condenser. Consid-
ering the environment temperature is around 273.15e293.15 K
around the year with a 10 K pinch temperature difference. The
condensing temperature is around 283.15e303.15 K. Fig. 8 shows
the condensing temperature has a great inuence on the cycle
performance. From Ref. [17], the system efciency decreases as the
condenser-exit temperature increases. And for the geothermal ORC
system, both the efciency and Qe decreased dramatically as the
condensing temperature increase. So, more Wt can be gained by
using absorption chilling or other methods to decrease Tcon.

4.4. Molecular structures inuence on efciency

The cycle thermal efciency is inuenced by the working con-

ditions and the working uid properties. The three main factors are

Fig. 8. Efciency and Qe variations with Tcon for R32, R134a and propylene.

Fig. 7. Wt for various working uids with heat source temperatures: a) 383.15 K, b)
403.15 K, c) 423.15 K. Fig. 9. Molecular structures of typical working uids.
8 H. Zhai et al. / Energy 74 (2014) 2e11
Fig. 10. Efciencies of all the working uids at Te 345 K.
Fig. 11. Efciencies for three carbon-atom HFCs at Te 345 K.
Te, the presence of uorine and the molecular structure. Several
molecular structures are illustrated in Fig. 9.
For a given condensing temperature, the efciency increases
with the evaporating temperature for all the working uids. The
Fig. 12. Efciencies of HCs at Te 345 K.
efciencies for the average optimal evaporating temperature,
345 K, for the 403.15 K heat source are shown in Fig. 10. The ef-
ciencies do not vary much between the HFCs and the HCs. However,
the efciencies vary more with the molecular structure within the
HC and HFC groups.
Among the HFCs, R1234ze (Z) with a double-bond has higher
efciency than the other working uids. This observation is also
true for the HCs. Thus, the molecular structure has an important
inuence on the efciency.
The molecular structure and the interactions between mole-
cules differentiate one substance from another and determine all
the properties. However, the relationships between the molecular
structure and the substance properties can not be easily
determined.
The system efciency is a result of all the working uid prop-
erties with some properties having a large inuence while others
have little inuence. Again, the cycle performance can not be easily
related to the properties. This selection identies some connections
between the molecular structure and the cycle performance as a
reference to screen mixture working uids.
4.4.1. HFCs
Among HFCs, R1234ze (Z) with a double-bond structure has a
higher efciency than the other working uids. Consider the 3C-
molecular substances as an example. In Fig. 11, the efciencies for
both double-bond and single-bond working uids increase with
the critical temperature at an evaporating temperature of 343.15 K.
The double-bond working uid efciencies are all higher than the
single-bond working uid efciencies.
4.4.2. HCs
The HC structure can be divided into ve classes: cyclic structure
substances marked as cyclo (benzene is also a cyclic structure with
three double bonds), alkenes marked as double bonds, alkanes
with branch chains marked as iso and neo and other alkanes
marked as n. Calculations were also done for the 345 K evapo-
rating temperature.
The efciencies in Fig. 12 increase with the critical temperature.
The results show that double bonds/cyclo>n>iso>neo. Thus,
the cyclic and double bond structures are better for higher ef-
ciency while the branch chain structure has adverse impact.
Among the ve substances with double-bonds, propylene has
the highest efciency. Among the substances with cyclic structures,
benzene and toluene have relatively high efciencies. Because they
Fig. 13. Ratio of sensible heat to latent heat variation with Te for R32, R134a and
propylene.
 H. Zhai et al. / Energy 74 (2014) 2e11 9

Table 6
Wt and dmwf/dT for the substances that provide the largest Wt with a 403.15 K heat
source (sorted by Wt).

Substances Wt, kJ dmwf/Dt, kg/K

R32 24.049 0.066

R1234yf 23.44 0.037
Propylene 23.035 0.016
Propane 20.803 0.006

Z T6
4.5.1. Inuence of CP;wf dT=DHv variation with Te on Qe
T7

For the same evaporating temperature, Eq. (6) shows that the
energy absorbed by the latent heat, Qel, is the same for different
working uids. Thus, more energy absorbed by the sensible heat,
Qes, more heat absorbed into Qe.
On the heat source side:
Fig. 14. mwf variation with Te for R32, R134a and propylene.
ZT6 ZT6 ZT3
have three more double bonds than the other cyclo substances. Qe Qel Qes CP;wa dT CP;wa dT=DHv $ Cp;wf dT
Benzene is better than toluene and cyclohexane is better than T7 T7 T2
C1CC6 followed by C3CC6 because the branch chains reduce the 0 1
ZT6 ZT3
efciency. B C
HCs can be thought of as HFCs without F atoms. HCs have high CP;wa dT$@1 Cp;wf dT=DHv A
critical temperatures and relatively low molecular masses. HCs T7 T2
result in very low output work according to the simulations, even (15)
though they have higher efciencies and specic works than HFCs.
On contrary, some of the HFCs with the lowest efciencies and Z T6

specic work outputs have quite good work outputs because HFCs thus, since CP;wa dT is xed, for a specic heat source temper-
T7
make good use of the heat source with more heat absorbed from Z T3
the heat source. ature, a larger Cp;wf dT=DHv means that more heat is absorbed
T2
from the heat source. Therefore, larger Cp and lower DHv are
4.5. Physical properties inuence on the heat absorption Z T3
preferred. Fig. 13 shows how Cp;wf dT=DHv varies with the
The heat absorbed from the heat source, Qe, consists of Qel and T2

Qes, as dened in Eq. (14). Qe is determined by the mass ow rate of evaporating temperature. This quantity is higher for R32 than for
the working uid, mwf, and its latent heat, DHv, and its specic heat R134a and propylene at the same evaporating temperature, so R32
at constant pressure, Cp,wf. will absorb more from the heat source.

ZT3
4.5.2. Inuence of mwf variation with Te on Qe
Qe Qel Qes mwf $DHv mwf $ Cp;wf dT (14) Qe is largely decided by mwf according to Eq. (14). Comparison of
T2 Figs. 4 and 14 shows that the changes in Qe are the same as those of
mwf. Therefore, Qe and mwf increasing with Te is more preferable
since the cycle efciency increases with the evaporating
temperature.
From Eq. (8):
 
dQel dDHv
dmwf =dT $DHv  $Qel DHv2 (16)
dT dT
On the heat source side:

ZT6 ZT6
Qel CPwa dT CPwa dTzCPwa T6  T 20 (17)
T7 T20

since Cpwa is approximately constant for small temperature change.

dQel
CPwa (18)
dT
On the working uid side:
The latent heat can be approximated by the Pitzer correspond-
Fig. 15. dmwf/dT for all the working uids at the optimized Te with a 403.15 K heat ing states correlation [24].
source. If 0.6 < Tr  1.0 (where Tr T/Tc),
10 H. Zhai et al. / Energy 74 (2014) 2e11

Fig. 16. dmwf/dT for all the working uids at the optimized Te with the 423.15 K heat Fig. 17. dmwf/dT for all the working uids at the optimized Te with the 383.15 K heat
source. source.

5. Conclusion
DHv  
0:7081Tr 0:354 10:95u1Tr 0:456 where Rg R=M Geothermal water is pumped from deep in the earth to the
Rg Tc
ground to produce power in organic Rankine cycles which requires
(19) work input. The cycle optimization objective is to maximize the
work output Wt of the subcritical organic Rankine cycle per unit
thus, mass ow rate of the geothermal water. Wt is determined by the
cycle efciency and the heat absorption from the heat source. For a
dDHv h specied source temperature, the results show that the optimized
Rg 0:708  0:354  1  T=Tc 0:646 10:95 evaporating temperatures are almost the same for all the selected
dT
i working uids including HCs and HFCs.
 0:456u1  T=Tc 0:544 (20) The efciency is related to the molecular structure for a given
evaporating temperature. The results show that working uids
Equations (18) and (20) can be substituted into Eq. (16) to get a
with double bonds or cyclic structures provide higher efciencies.
general equation dmwf/dT for all for all the working uids. With a
At relatively low evaporating temperatures, the efciencies are
403.15 K heat source, the uids giving the maximum work output
all similar for the various uids. Thus, Qe, the energy absorption
are those working uids whose mwf increases with Te (dmwf/
from the heat source is the most important factor. Two key in-
dT > 0). Detail results are shown in Fig. 15 and Table 6. Thus, a
dicators are the ratio of the specic heat capacity to the latent heat
positive dmwf/dT reects greater use of the heat source which in-
of evaporation (Cpwf/DHv) and the mass variation with the system
uences the work output.
evaporating temperature (dmwf/dT). Working uids like R32 with
The working uids that provide the largest Wt for the 432.15 K
higher Cpwf/DHv and positive dmwf/dT make better use of the heat
heat source are shown in Fig. 16 and Table 7. For the 383.15 K heat
source to provide higher work output than the other uids.
source, the results in Fig. 17 show that only the value for R32 is
positive; thus, R32 is the best working uid as shown in Table 4
because the latent heat of vaporization is larger for lower temper- Acknowledgments
atures and its change with temperature is larger than Qel; So dmwf/
dT is negative for most working uids. The magnitudes of the This work was supported by the State Key Program of the Na-
negative dmwf/dT are very similar for all working uids. However, tional Natural Science Foundation of China (Grant No. 51236004,
working uids with a positive dmwf/dT provide much larger Wt No. 50976060), and the Science Fund for Creative Research Group
than the other uids. (No. 51321002).

Nomenclature
GWP global warming potential
Table 7
h enthalpy, kJ/kg
Wt and dmwf/dT for the substances that provide the largest Wt with the 423.15 K heat
source (sorted by Wt). m mass, kg
M molar mass, kg/kmol
Substances Wt, kJ dmwf/Dt, kg/K
ODP ozone depletion potential
R1234yf 46.4 0.1496 P pressure, MPa
propane 42.788 0.040
Q heat, kJ
R134a 42.607 0.101
propylene 41.86 0.050 q heat absorbed per unit mass of working uid, kJ/kg
R1234ze(e) 39.057 0.062 R molar gas constant, J/(mol K)
R161 37.89 0.044 Rg mass gas constant, J/(g K)
R32 37.238 0.123 T temperature, K
R152a 31.981 0.023
W work output (kW)
 H. Zhai et al. / Energy 74 (2014) 2e11 11

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