Energy 123 (2017) 326e339

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

A study on optimal composition of zeotropic working fluid in an

Organic Rankine Cycle (ORC) for low grade heat recovery
K. Satanphol, W. Pridasawas, B. Suphanit*
Department of Chemical Engineering, Faculty of Engineering, King Mongkut's University of Technology Thonburi, 126 Pracha Utit Rd., Tungkru, Bangkok
10140, Thailand

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

Article history: The Organic Rankine Cycle (ORC) is an interesting heat recovery alternative for low grade heat at the
Received 2 September 2016 present time. In an ORC, the irreversibility of heat transfer in the cycle could be reduced by the appli-
Received in revised form cation of zeotropic working fluid. In this work, the potential of zeotropic working fluid application in an
22 December 2016
ORC for low grade heat recovery was investigated. The types of fluid, the composition and the operating
Accepted 5 February 2017
Available online 6 February 2017
conditions that achieved the maximum net work output were determined through flowsheet modeling
and optimization in Aspen Plus v.8.4 simulation software. The working fluids considered in this study
were the components found in the 400-series refrigerant blends from REFPROP database. Among the
Keywords:
Low grade heat
group of pure working fluids in this study, the ORC using R-227ea provided the best performance in
Maximum net work output terms of net work output. In case of zeotropic working fluid, the optimum performance fluid was the
Zeotropic working fluid blend of R-218/227ea/C318/245fa (32.1/13.4/38.8/15.7). Besides, when including the environmental fac-
Organic Rankine Cycle tor into consideration, the optimum low-GWP blend consisting of R-290/152a/600a/601a (35.1/38.1/22.4/
4.4) was determined. The possible binary and ternary blends of the resulting constituents were also
investigated. In addition, the thermo-economic analysis of each working fluid was carried out and
discussed.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction transform it into power or electricity. The ORC is versatile to recover

In various kinds of processes such as fuel combustion in power
plants, chemical reactions in industrial, electronic or biological
processes, a large amount of waste heat is commonly lost to envi-
ronment, leading to low energy efficiency in the process. In addi-
tion, the waste heat release is also a contributing factor to the global
warming which is threatening the world at the present time. Any
measures to reduce or recover the waste heat are therefore
considered with high priority in all kinds of processes. A massive
amount of medium (230e650
C) and low grade (<230
C) waste
heat [1] is emitted from certain types of equipment such as gas
turbine, steam boiler, internal combustion engine (ICE), and
furnace. The recovery of the medium and low grade waste heat
could be carried out in numerous ways. It may be recovered as
thermal energy to be used directly in the process. In some cases, the
recovered energy usage may be rather limited if the waste heat
temperature level is too low. One of the interesting recovery ap-
proaches being focused on recently was the application of an
Organic Rankine Cycle (ORC) to recover waste heat and to
* Corresponding author.
E-mail address: bunyaphat.sup@kmutt.ac.th (B. Suphanit).
energy from various sources such as geothermal, solar or waste
heat from industrial processes [2,3]. In an ORC, low boiling com-
pounds (mostly organics) are used as the working fluid to recover
medium or low grade waste heat. In general, the critical tempera-
ture of a working fluid used in an ORC is much lower than that of
water in a typical steam cycle at the same operating pressure [4].
This is a clear advantage of the ORC over the conventional Rankine
especially in the low temperature region. Apart from the ORC, the
other interesting power cycles for waste heat recovery are
Maloney-Robertson cycle and Kalina cycle which use ammonia
solution as the working fluid. However, when compared them with
an ORC under similar size, it was found that the ORC could provide
approximately the same or better performance at a much lower
pressure [5,6]. Consequently, much larger attention was focused on
the ORC as shown by thousands of related journal articles pub-
lished in recent years. The overview of the ORC in various aspects,
e.g. cycle architectures, types of working fluids, thermodynamic
and economic performances or equipment hardware, can also be
found in some recent review articles [7e10]. In our work, however,
not every aspect involving the ORC was considered. Only the in-
fluence of zeotropic working fluid on the ORC performance was
focused on.

http://dx.doi.org/10.1016/j.energy.2017.02.024
0360-5442/© 2017 Elsevier Ltd. All rights reserved.
 K. Satanphol et al. / Energy 123 (2017) 326e339
Depending on the slope of vapor saturation line on the
temperature-entropy diagram, the working fluids used in an ORC
can typically be divided into three types; i.e. wet fluid (negative
slope), dry fluid (positive slope) and isentropic fluid (infinite slope)
[11]. For dry or isentropic working fluid under subcritical region,
the condition at the turbine inlet is only needed to be saturated or
low degree of superheated vapor, respectively. Under these cir-
cumstances, there will be no operating difficulty involving the
liquid droplet formation when these fluids expand across the tur-
bine. On the other hand, the turbine inlet condition of most wet
fluids in an ORC must be superheated to a certain degree otherwise
the liquid droplet formation during expansion may occur. The
damage on turbine blades could then follow as a consequence. The
results from several research works also suggested that dry and
isentropic fluids were the most favorable types of fluids for an ORC
[12e18].
The performance of an ORC can be affected by several factors. The
choice of working fluid is one of the key factors among others such as
the cycle operating region (subcritical or transcritical) and the cycle
configuration. Numerous works on working fluid selection for an
ORC have been studied to choose the right working fluid in various
aspects [11e13,19,20]. Several screening criteria for choosing a
suitable working fluid such as cost, cycle performance, environ-
mental impact, thermal stability, flammability or toxicity may be
applied. Basically, the cycle performance is the main objective used
to identify an appropriate working fluid. In general, this could be
accomplished by the optimization of either the net work output
[14,21] or the thermodynamic efficiencies [22e24]. Other economic
indicators such as the ratio of net work output to total cost [21], the
levelized cost of electricity (LCOE) [24], or the ratio of heat exchanger
area to net work output [25] might also be set as objectives. Many
researchers [14,16,18,20,26] tried to relate the cycle performance
with the critical temperature of the working fluid in order to
establish simple criteria for fluid selection. For instance, He et al. [16]
investigated 22 pure working fluids operating in subcritical region;
and found that the working fluids with the critical temperatures
close to the heat source temperature tend to perform better in terms
of net power output than those with higher or lower critical tem-
peratures. However, their investigation was only limited to the
subcritical ORCs. The deduction from their work might not be valid
for other working fluids operating in the transcritical region. Ayachi
et al. [18] showed that the working fluid with the best thermody-
namic performance operated in the transcritical region. The opti-
mum critical temperature could be identified. The fluids with the
critical temperatures lower than the optimum critical value tended
to operate optimally in the transcritical region but with lower cycle
performance. On the other hand, the fluids with the critical tem-
peratures higher than the optimum critical value tended to operate
optimally in the subcritical region. The optimum critical tempera-
ture from Ayachi et al. [18] was around 0.7e0.8 times the heat source
temperature. Others may suggest different criteria such as 0.5 times
[20] or 0.8 times [27] the heat source temperature. These criteria
may vary due to the differences in heat source temperature or the
objective function used in various studies.
As discussed above, an ORC operating in the transcritical region
was found to deliver better performance than the same ORC
operating in the subcritical region due to better temperature
driving force distribution in the evaporator. The temperature dif-
ferences between the heat source and the working fluid along the
heat transfer path were more uniform in case of the transcritical
ORC than those in the subcritical ORC. The temperature profile of
the working fluid in this situation may also be called temperature
glide [28]. In general, the larger the temperature glide, the better
the performance of an ORC. Although the efficiency could be
improved by operating an ORC in the transcritical region, the heat
327
transfer area requirement in an evaporator increases as a result of
decreasing in temperature driving force. In addition, the effect of
changes in some physical properties of fluid mixture, e.g. thermal
conductivity and viscosity in the evaporator could also degrade the
heat transfer characteristic, thereby leading to a larger area
requirement as above. The evaporator cost was therefore inevitably
higher in case of the transcritical ORC.
In a transcritical ORC, a good temperature glide can be achieved in
an evaporator. However, on the condenser side, a temperature glide
does not occur if the working fluid is pure. To improve the temper-
ature glide in both evaporator and condenser, the other possible
alternative, i.e. the application of a zeotropic mixture, may be used
instead. The number of research works on the application of zeo-
tropic working fluid in an ORC increased remarkably during the last
couple of years. Several researchers had already confirmed the
benefit of gliding improvement from zeotropic fluid in both evapo-
rator and condenser on the ORC performance [17,20,22,23,29e34].
Some of them found that the performance improvement was mainly
a consequence of the good gliding match in the condenser
[20,22,23,30]. The zeotropic mixtures mostly considered in the past
literature were binary mixtures of some preselected fluids. Hence,
the studies on optimal zeotropic composition in an ORC were pri-
marily carried out through sensitivity analysis over the whole
composition range [17,22,29e32]. The other optimization methods
such as the genetic algorithm [20], and a Generalized Reduced
Gradient (GRG) nonlinear multistart algorithm [23] were also used in
the determination of optimal binary composition. The multi-
objective optimization was also investigated by Clarke et al. [35]
and Feng et al. [36] in order to simultaneously optimize the ther-
modynamic and economic performances. The studies on optimal
composition of ternary or multicomponent working fluids were rare.
Chys et al. [29] investigated the effect of the third additional
component of several ternary working fluids on the ORC perfor-
mance. They found that the addition of the third component into a
binary fluid yielded insignificant improvement in terms of both po-
wer output and cycle efficiency when compared to the original bi-
nary fluid. Recently, Chaitanya et al. [37] used the sequential
quadratic programming (SQP) method to optimize composition of
several zeotropic mixtures which are mostly hydrocarbons in an
ORC. The results showed that several good performance ternary and
multicomponent fluids could be found. There was still no clear
conclusion on the suitable number of components to be used in a
zeotropic fluid. Therefore, the identification of high-performance
multicomponent zeotropic fluid should be considered further since
there may be some good combinations waiting to be discovered.
In this work, the potential of applying zeotropic working fluid in
an ORC for low grade heat was explored. Our approach was
different from those in some previous works. Rather than consid-
ering some preselected multicomponent mixtures then performing
the optimization [29,37], the working fluid selection and the opti-
mization of fluid compositions were carried out simultaneously.
The compositions of fluid species which were not suitable would be
reduced to zero during the optimization. The number of fluid
species in the zeoptropic fluids could then be reduced to optimum.
Our detail optimization approach was described in Section 3. The
objective function considered in this work was to maximize the net
work output. Both transcritical and subcritical conditions were
considered in this work to evaluate the maximum possible per-
formance of an ORC operating with each working fluid. All simu-
lations and optimizations of zeotropic fluid composition used in an
ORC were carried out by Aspen Plus V8.4 simulation software.
2. Working fluids
In this study, the selected working fluids were the components
328 K. Satanphol et al. / Energy 123 (2017) 326e339

found in the ASHRAE R400-series refrigerant blends and some
additional fluorocarbon components from REFPROP database [38].
As shown in Table 1, a total of 24 working fluids were investigated.
All of them were listed in order of their normal boiling points. The
other related thermodynamic properties such as critical tempera-
ture and pressure, the molecular weight, the type of fluid expansion
characteristic and the environmental, health and safety indices
were also shown on the same table.
In this work, the major criterion used to evaluate the zeotropic
working fluid was the net work output. Besides, the scenario in
which the environmental issue was considered as the first priority
was also investigated.
3. ORC modeling and optimization
To optimize the performance of an ORC operating with a pure or
zeotropic working fluid, a simulation model of a conventional ORC
is necessary. Aspen Plus V8.4 simulation software was applied for
this task. A conventional ORC model consists of 4 main pieces of
equipment; i.e. an evaporator, a turbine, a condenser and a pump
(cf. Fig. 1). In the evaporator (EVAP), the working fluid is heated up
from the subcooled liquid to the saturated or the superheated vapor
condition by recovering heat from a waste heat or geothermal heat
source. After leaving the evaporator, the hot working fluid vapor is
expanded across the turbine (TURBINE) to generate work. The
turbine exhaust vapor is then condensed into the saturated liquid
by heat rejection through the condenser (CONDENSE) using cooling
water as the cooling medium. Finally, the condensed liquid is
pumped back to the evaporator to continue cycle operation.
The thermodynamic properties of a working fluid at any
particular point in an ORC were calculated by REFPROP model [38]
in Aspen Plus software. All ORC optimizations were executed with
regard to a set of assumptions, specifications and constraints as
shown in Table 2. The objective function used in this work was the
maximization of net work output. The optimization variables
considered in case of pure and zeotropic working fluids were the
mass flow rate of each constituent, the evaporator pressure (or
pump discharge pressure), the condenser pressure (or turbine exit
pressure), and the degree of superheating of the working fluid at
the evaporator exit. Here, we have made an assumption on the
lower bound of the degree of superheating of the working fluid at
the evaporator exit. Instead of using 0 K to represent the saturated
vapor condition, a marginal value of 1 K was specified in order to
avoid any discontinuities which may arise at the vapor-liquid phase
boundary during optimization. If an optimum solution appears to
be at 1 K of superheating, it is considered to be an optimum at the
saturated vapor condition. For the optimization in the subcritical
region of a pure working fluid, the critical pressure was taken as the
upper bound value of the evaporator pressure. However, for some
working fluids, the evaporator pressure may approach the critical
region during the optimization. It is therefore possible that the
optimum condition in the evaporator may lie above the critical
point of that working fluid. The operating region considered in the
optimization will be switched from the subcritical to the tran-
scritical region. In such cases, the upper bound of the evaporator
pressure will be set arbitrarily to a value higher than the critical
value. The degree of superheating variable will also be replaced by
the working fluid temperature at the evaporator exit.
Due to the non-linear nature of this optimization problem, the
sequential quadratic programming (SQP) method was selected to
solve this problem. Here, the SQP was used as a black-box method
by converging tear stream variables and design specifications
separately in two nested loops. In this manner, the number of de-
rivative evaluations in any iteration could be reduced since tear
stream variables were converged separately. Moreover, this
convergence approach is more robust than the default approach by
Aspen Plus in which tear variables are converged simultaneously
with other optimization variables. In this problem, the flowsheet
convergence involves three separate loops. First, at any particular
values of optimization variables, the inner loop is used to achieve
tear variable convergence (pump inlet pressure) via the Wegstein
method. Next, the cooling water (CW) flow is adjusted to achieve
the specified CW return temperature via the Broyden method.
Finally, the optimization block is converged by the SQP method in
the outer loop. The optimization tolerance was set at the default
value of 0.001.
The optimal zeotropic composition was also determined via
optimization in which the flow rate of each constituent was varied
simultaneously with other operating variables. However, due to a
large number of pure components considered in this study, all

Table 1
Physical properties of selected pure working fluids [43].

Working fluid Chemical formula PC (MPa) TC (
C) TB (
C) Type MW ASHRAE 34 Safety Group ODP GWP 100 yrs Atm Life (years)

R-32 CH2F2 5.78 78.105 51.70 Wet 52.02 A2L 0 716 5.2
R-125 CHF2CF3 3.62 66.015 48.11 Wet 120.02 A1 0 3420 28.2
R-1270 CH3CH]CH2 4.6 91.7 47.7 Wet 42.08 A3 0 <20 0.001
R-143a CH3CF3 3.76 72.73 47.34 Dry 84.04 A2L 0 4180 47.1
R-290 CH3CH2CH3 4.25 96.68 42.08 Wet 44.10 A3 0 ~20 0.041
R-22 CHClF2 4.97 96.15 40.83 Wet 86.47 A1 0.04 1790 11.9
R-115 CClF2CF3 3.16 80 39.11 Dry 154.47 A1 0.57 7230 1020
R-218 CF3CF2CF3 2.68 71.9 36.70 Isentropic 188.02 A1 0 8830 2600
R-12 CCl2F2 4.13 111.8 29.79 Isentropic 120.91 A1 0.82 10900 100
R-134a CH2FCF3 4.06 101.03 26.07 Wet 102.03 A1 0 1370 13.4
R-E170 CH3OCH3 5.37 126.95 24.84 Wet 46.07 A3 0 e 0.015
R-152a CH3CHF2 4.52 113.29 24.02 Wet 66.05 A2 0 133 1.5
R-227ea CF3CHFCF3 2.91 101.68 16.36 Dry 170.03 A1 0 3580 38.9
R-124 CHClFCF3 3.66 122.5 12.10 Isentropic 136.48 A1 0.02 619 5.9
R-600a CH(CH3)2CH3 3.63 134.65 11.87 Isentropic 58.12 A3 0 ~20 0.016
R-C318 -(CF2)4- 2.78 115.22 5.98 Isentropic 200.03 A1 0 10300 3200
R-236fa CF3CH2CF3 3.22 124.92 1.45 Isentropic 152.04 A1 0 9820 242
R-600 CH3CH2CH2CH3 3.80 151.97 0.55 Dry 58.12 A3 0 ~20 0.018
R-245fa CHF2CH2CF3 3.64 154.05 15.30 Dry 134.05 B1 0 1050 7.7
R-245ca CH2FCF2CHF2 3.93 174.42 25.25 Dry 134.05 e 0 726 6.5
R-123 CHCl2CF3 3.66 183.79 27.83 Dry 152.93 B1 0.01 77 1.3
R-601a (CH3)2CHCH2CH3 3.38 187.25 27.84 Dry 72.15 A3 0 ~20 0.009
R-142b CH3CClF2 4.04 137.14 32.00 Isentropic 100.50 A2 0.06 2220 17.2
R-601 CH3CH2CH2CH2CH3 3.37 196.55 36.06 Dry 72.15 A3 0 ~20 0.009
 K. Satanphol et al. / Energy 123 (2017) 326e339 329

HW-OUT HW-IN some pure fluids. To solve this problem, a series of optimization were
then executed. Starting from choosing an arbitrarily low pressure
value as the upper bound of the evaporator pressure, the optimiza-
TUR-IN tion is performed repeatedly, each time with a small increase in the
upper bound value. Once reaching the value in which the flash
EVAP-IN EVAP
convergence in the evaporator can no longer be achieved at opti-
TURBINE
mum, the maximum evaporator pressure of an ORC is then deter-
PUMP mined. This situation generally occurs as the condition approaches
the critical region. For mixtures consisting of constituents with a
wide range of volatilities as shown by a critical temperature ratio
CW-IN CW-OUT greater than 2, the property calculation at saturation generally fails
[38]. The optimization region of the wide-boiling zeotropic fluids was
mostly limited in the subcritical region due to this limitation. The
PUMP-IN TUR-OUT
overall optimization procedures for optimal zeotropic composition in
an ORC were summarized as shown in Fig. 2.
CONDENSE

Fig. 1. Flow diagram of a conventional ORC. 4. Thermo-economic analysis

Apart from the optimization of net work output, the optimum

constituent flow values could not be varied simultaneously. The ORC using each working fluid was also analyzed in terms of both
total number of components in this study exceeded the allowable thermodynamic and economic performances. The thermodynamic
limit in REFPROP model which was 20 components [38]. Moreover, analysis was carried out by evaluating the exergy efficiency of each
the optimization of a large number of variables was time- piece of equipment and the overall cycle. All ORCs were also eval-
consuming. The initial guess which could produce a converged uated and compared on the economic point of view. The exergy and
flowsheet result was also very difficult to obtain. Hence, several economic analysis of an ORC are briefly described here.
optimization problems were carried out sequentially in this study.
Starting with only a small group of randomly chosen components
4.1. Exergy analysis
(around 6 components), the optimization was executed until
reaching convergence. Some constituent flow values were reduced
To evaluate the efficiency of energy conversion in a thermody-
to zero at optimum. These constituents were then replaced with
namic cycle, the analysis was generally considered in terms of the
the other unconsidered components. The optimization was then
converted quantity according to the first law of thermodynamics.
repeated until all pure components were considered in the prob-
However, the second law analysis was also applied as an additional
lem. Any solution obtained could not however be guaranteed as a
tool to analyze the quality of energy or the potential of thermal
global optimum due to the non-linearity of the system. The final
energy to produce work. According to the second law, the exergy
solution largely depended on the initial guess. Hence, several initial
efficiency was a good performance indicator for each piece of
guesses were tried to ensure the best possible solution from the
equipment in a cycle. By considering this value, inefficient pieces of
optimization.
equipment in the cycle can be identified and then investigated for
Yet, there is still another issue left to be resolved. Unlike the case of
any possible alternatives in order to improve the cycle perfor-
pure fluid in which the upper bound value of the evaporator pressure
mance. Here, the concise fundamentals of exergy analysis and
is generally set at the critical pressure of working fluid, the appro-
exergy efficiency calculation were described. Exergy of a process
priate upper bound value in case of a zeotropic fluid is undetermined
stream at a given temperature and pressure (T and P) is defined as
ahead of the optimization. The critical pressure of a zeotropic fluid
the maximum amount of work output which can be obtained as the
depends on the fluid composition, thereby varying during optimi-
stream changes reversibly from that given state to the state of
zation. Specifying the largest critical pressure value of the existing
equilibrium with the environment at T0 and P0, hence given by:
constituents in a zeotropic fluid as the upper bound sometimes leads
to an optimum which might be poorer than those obtained from

Table 2
Assumptions, specifications, and constraints in a conventional ORC model.

No. Assumptions, specifications, and constraints

1 The conditions of the hot water heat source were assumed to be at 140
C,
and 6 bar.
2 The hot water flow rate was 50,000 kg/h.
3 The isentropic efficiencies of pump and turbine were 85%.
4 The minimum temperature approaches in evaporator and condenser were
specified at 10 K.
5 The condition of working fluid at the turbine exit must be either saturated
or superheated vapor. This can be achieved by setting the vapor fraction of
working fluid at the turbine exit to one.
6 The minimum allowable pressure at turbine exit is 5 kPa [47].
7 The operating temperature range of the cooling water was set between 25
and 35
C.
8 The heat loss in all heat exchangers and pipelines was neglected.
9 There was no pressure drop in the evaporator and condenser.
10 There was no chemical loss from the system.
Fig. 2. Optimization procedure for optimal zeotropic composition in ORCs.
330 K. Satanphol et al. / Energy 123 (2017) 326e339

 
Ex ¼ H  T0 S (1) Exloss;cond ¼ DExWF;cond   DExCW (11)

where H and S are the stream enthalpy and entropy with reference Exloss;cond
to the ambient conditions T0 and P0. The typical values of reference hEx;cond ¼ 1    (12)
temperature and pressure are 25
C and 1 atm, respectively.
As a matter of fact, exergy of a stream is a direct function of its
enthalpy and entropy, which are both functions of state, the exergy
itself is therefore a state function. Thus, the exergy value of a given
stream can be calculated from the stream properties (composition,
temperature and pressure). If a stream changes from state 1 to state
2, the exergy change of the stream is given by:
DEx12 ¼ Ex2  Ex1 ¼ ðH2  H1 Þ  T0 ðS2  S1 Þ (2)
According to the second law of thermodynamics, all natural
DExWF;cond 
For an ORC, the overall exergy loss is the combination of all
exergy losses from all pieces of equipment. The same definition of
exergy efficiency as in Eq. (4) can be applied to the overall system as
shown in Eq. (14).
Exloss;overall ¼ Exloss;pump þ Exloss;evap þ Exloss;turb þ Exloss;cond
(13)
DExCW þWturb  Exloss;overall
processes are irreversible and therefore lead to the degradation of hEx;overall ¼ ¼1   (14)
energy. Whenever energy is transformed or transferred, its po-
tential to produce useful work or exergy is reduced forever. For that
reason, to accomplish a certain exergy output, a real process always
requires a higher exergy input. The difference between them is the
exergy lost due to irreversibility.
Exin  Exout ¼ Exirr ¼ Exloss
The exergy loss value provides a measure of thermodynamic
efficiency of a process. The maximum thermodynamic efficiency
may be achieved by a reversible process in which there is no exergy
loss. Reversible processes, however, have no driving forces and can
never be achieved in practice.
The exergy efficiency of a process can be defined as follows:
Exout Ex
hEx ¼ ¼ 1  loss
Exin Exin
The exergy efficiency used in this work was the rational [39] or
functional [2] exergy efficiency. This definition of exergy efficiency
was suitable for the system or equipment with good understanding
of purpose or behavior. In an ORC, the exergy input could be either
the heat or work flow into a unit, or the exergy provided by a
stream flowing through that unit. Similarly, the exergy output
could be either the exergy taken up by a stream flowing through a
unit, or the heat or work flow out of the unit. Applying Eqs. (3) and
(4) in an ORC, the exergy loss and the exergy efficiency of each piece
of equipment can be determined as follows:
Pump:
jDExHW j þ Wpump  jDExHW j þ Wpump 
4.2. Economic analysis
In addition to the thermodynamic performance of an ORC, the
(3) economic performance is also another essential factor to be
considered. The working fluid capable of yielding not only good
energy performance but also low cost of electricity production
would be very attractive for being used in an ORC. However, this
might not be the case in general. For example, in transcritical ORCs,
the systems could deliver good energy performance since they
operated with large pressure change across the turbine. On the
other hand, the capital investment was rather high in such cases
due to the high pressure condition in the evaporator and the tur-
(4) bine. This led to poor economy which was in contrast to the good
energy performance. Basically, the cost of electricity generated
from an ORC mainly depends on the capital investment of the ORC
itself. The operating costs such as cooling water cost, labor cost, or
maintenance cost are typically estimated in proportion to the
capital investment. In this study, however, these estimated oper-
ating costs were not considered in the analysis. The economic
performance of an ORC operating with each working fluid was
therefore evaluated on the basis of the estimated specific pur-
chased equipment cost (SPEC) in $/kWe. The detail of equipment
cost estimation was described in the Appendix. The electricity
production capacity was calculated from the net electricity pro-
duced from an ORC. The electricity conversion efficiencies were
assumed to be 100% and 96% for pump and turbine, respectively.
 
Exloss;pump ¼ Wpump   DExWF;pump (5)
5. Results and discussion
Exloss;pump
hEx;pump ¼ 1    (6) 5.1. Optimization of ORC using pure fluid
Wpump 

Evaporator: Although the optimizations of ORCs using numerous pure fluids

had been done extensively in the past, the assumptions used in
Exloss;evap ¼ jDExHW j  DExWF;evap (7) previous studies were different from those used in this work. The
comparison of performance between pure and zeotropic fluids
Exloss;evap would therefore be inconsistent if the results from some previous
hEx;evap ¼ 1  (8) works were used. The optimizations of ORCs using pure fluids were
jDExHW j
then carried out under the assumptions used in this study. The re-
Turbine: sults were evaluated and employed as bases for comparison with the
  performance of ORCs using optimal zeotropic working fluids. For
Exloss;turb ¼ DExWF;turb   Wturb (9) each considered working fluid, all variables affecting the net work
output as described in Section 3 were optimized simultaneously.
Exloss;turb The subcritical region was considered at the beginning. However, for
hEx;turb ¼ 1    (10)
DExWF;turb  some cases in which the optimization results approached the critical
region, the optimization problems were then relocated to the
Condenser: transcritical region instead. From Table 3, it was found that the ORCs
 K. Satanphol et al. / Energy 123 (2017) 326e339 331

Table 3
Optimization results of ORCs operating with pure working fluids.

Rank Refrigerant Wnet (kW) Eff (%) QEvap (kW) MWF (kg/h) THW,out (
C) TEvap,in (
C) TT,in (
C) DSPH (
C) TT,out (
C) PT,in (MPa) PT,out (MPa) Cycle type

1 R-227ea 426.56 9.12 4677 143,221 60.2 46.5 111.3 e 51.6 3.37 0.79 Trans-
2 R-115 413.35 9.17 4506 152,383 63.2 48.8 124.6 e 60.2 5.94 1.42 Trans-
3 R-143a 411.96 9.59 4297 83,729 66.8 49.0 127.8 e 66.5 6.38 1.96 Trans-
4 R-125 402.26 8.78 4584 120,753 61.8 48.7 125.4 e 72.3 6.75 2.11 Trans-
5 R-32 398.19 9.73 4092 52,993 70.3 49.2 128.8 e 57.3 7.35 2.73 Trans-
6 R-218 397.40 8.37 4750 160,795 59.0 47.3 125.6 e 74.5 5.93 1.32 Trans-
7 R-C318 382.16 9.37 4078 116,947 70.5 44.6 104.7 1.0 64.2 2.21 0.54 Sub-
8 R-1270 381.64 9.37 4074 45,570 70.6 49.3 114.3 e 45.1 5.53 1.84 Trans-
9 R-290 379.46 9.15 4148 45,792 69.4 48.3 108.4 e 45.0 4.56 1.53 Trans-
10 R-134a 379.24 9.66 3925 81,015 73.2 47.6 111.8 e 45.0 4.29 1.16 Trans-
11 R-22 364.82 10.30 3541 67,081 79.8 48.1 125.1 e 53.6 5.30 1.71 Trans-
12 R-236fa 335.23 9.05 3703 83,069 77.0 44.9 94.8 1.0 57.0 1.70 0.49 Sub-
13 R-124 327.17 9.06 3610 84,433 78.6 45.6 94.5 1.0 51.0 2.09 0.67 Sub-
14 R-12 321.79 8.74 3680 95,747 77.4 46.7 96.3 4.7 45.0 2.86 1.08 Sub-
15 R-600a 318.38 9.08 3505 34,706 80.4 45.1 93.4 1.2 56.6 1.71 0.59 Sub-
16 R-152a 313.66 8.79 3568 46,329 79.3 46.5 98.1 8.0 45.0 2.88 1.04 Sub-
17 R-245fa 307.57 9.16 3357 55,660 82.9 44.4 96.5 5.7 62.4 1.02 0.29 Sub-
18 R-E170 307.22 9.54 3220 23,929 85.3 44.6 126.9 37.3 80.3 2.70 0.97 Sub-
19 R-600 306.39 9.16 3344 29,330 83.2 44.7 94.6 3.7 60.5 1.27 0.42 Sub-
20 R-142b 306.04 9.38 3263 53,617 84.6 45.3 98.3 5.9 54.8 1.79 0.59 Sub-
21 R-245ca 303.15 8.85 3425 53,561 81.3 44.4 90.4 2.2 61.2 0.70 0.20 Sub-
22 R-601a 302.20 8.97 3370 30,187 82.7 44.2 89.9 1.0 63.3 0.56 0.17 Sub-
23 R-601 296.68 8.99 3300 27,158 83.9 44.0 95.9 7.3 69.1 0.46 0.13 Sub-
24 R-123 294.61 8.98 3281 60,322 84.2 44.3 97.1 9.4 64.6 0.59 0.18 Sub-

using pure working fluids with the critical temperatures approxi-
mately below 100
C tended to operate optimally in the transcritical
condition. The optimum critical temperature was found to be
around 0.7 times the heat source temperature. This coincided with
the results from some previous works [18,27]. There were 10
working fluids of this kind which ranked top on the list as shown in
Table 3. The remaining fluids which operated optimally in the
subcritical region then followed in subsequent order except R-C318
which had an outstanding performance above others in the
subcritical group. From Table 3, R-227ea was the best performance
fluid in terms of the net work output while R-123 was the worst
performance fluid under the assumptions in this study. The best
pure fluid obtained (R-227ea) was similar to the result at the same
heat source temperature from Chagnon-Lessard et al. [40]. The
ranking of the top 5 pure fluids was also in close agreement with the
results obtained by Walraven [41] for simple ORCs. The first law or
thermal efficiencies of all pure working fluids were in range of
8.37e10.30%. The results showed that there was no distinct linkage
between the net work output and the thermal efficiency obtained by
these working fluids. On the other hand, the net work output was
largely affected by the amount of heat recovery in the evaporator.
The ORC operating with high heat recovery level in the evaporator
tended to produce a large net work output.
The amount of heat recovery in the evaporator depended on the
temperature profiles of both hot and cold streams. Effective heat
recovery could be achieved in the evaporator having appropriate
temperature glide or rather uniform temperature difference along
the heat transfer path such as those found in the evaporators
operating at the supercritical condition. On the contrary, the heat
recovery in the evaporator operating at the subcritical condition
was less effective due to the pinch limitation generated by the
phase-change location. From Fig. 3, the ORCs operating in the
transcritical region, e.g. R-227ea, R-115, R-143a, R-125, or R-218,
exhibited relatively uniform temperature differences in the evap-
orators. The temperature differences in these evaporators were also
very close to the given minimum temperature approach (10
C).
Hence, the heat recovery of the evaporator operating at the su-
percritical condition was more effective than those operating at the
subcritical condition. For working fluids in the subcritical group, dry
and isentropic fluids, e.g. R-236fa, R-124, R-12, R-600a, operated
optimally near the saturated vapor condition while wet fluids such
as R-E170 operated optimally at a significant degree of superheating
at the evaporator outlet as shown in Fig. 3. Considered in terms of
the optimum operating pressure in the evaporator or the turbine
inlet pressure (PT,in), it was found that the transcritical ORCs oper-
ated at a much higher pressure than the subcritical ORCs did. The
potential to generate work through the turbine was therefore high
in case of the transcritical ORCs. In condenser, the temperature
profiles of the heat-exchanged streams were rather similar in both
transcritical and subcritical ORCs. The phase change occurred at
constant temperature hence there was no temperature gliding on
the working fluid side. For some working fluids such as R-227ea or
R-143a, the internal pinch which limited the condensing temper-
ature could be found. For others such as R-290 or R-134a, the pinch
may occur at the hot end of the condenser. For all pure working
fluids, the condensing temperature in the condenser were found to
be in range of 40e45
C. Since the condensing temperature and
pressure were directly related, the condensing pressure was limited
by this temperature range. Hence, the potential to generate more
work through the turbine was reduced.
5.2. Optimization of ORC using zeotropic working fluid
After evaluating the ORC performance of each pure fluid, the
ORC using zeotropic working fluid was further explored to identify
any possible improvement on the net work output. By applying the
optimization procedure outlined in Section 3, it was found that
from the total of 24 fluid species considered, the optimum blend of
zeotropic working fluid consisted of R-218, R-227ea, R-C318, and R-
245fa with the composition of 32.1, 13.4, 38.8, and 15.7 wt%,
respectively. The number of fluid species was reduced from 24 to
only 4 at optimum by using the proposed methodology. Both fluid
selection and optimal compositions were obtained from the opti-
mization. The boiling range of this optimum blend was quite wide.
The critical temperature ratio of the heaviest (R-245fa) to the
lightest constituents (R-218) in the blend was around 2.14 which
was higher than the limitation of property calculation around
critical region in REFPROP model [38]. Hence, the optimum
332 K. Satanphol et al. / Energy 123 (2017) 326e339

160 160
R-227ea R-115
140 140

120 120 Hot water

Hot water

100 100
Temperature (°C)

Temperature (°C)
R-227ea (Evaporating) R-115 (Evaporating)
80 80

60 60
R-227ea (Condensing) R-115 (Condensing)
40 40

Cooling water Cooling water

20 20

0 0
0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000 0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000
Heat duty (kW) Heat duty (kW)
160 160
R-143a R-125
140 140

120 120
Hot water

100 100 Hot water

Temperature (°C)
Temperature (°C)

R-143a (Evaporating)
80 80
R-125 (Evaporating)

60 60
R-143a (Condensing) R-125 (Condensing)
40 40

Cooling water Cooling water

20 20

0 0
0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000 0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000
Heat duty (kW) Heat duty (kW)

160 160
R-32 R-218
140 140

120 Hot water 120

Hot water
100 100
Temperature (°C)

Temperature (°C)

R-32 (Evaporating)
80 80 R-218 (Evaporating)

60 60
R-32 (Condensing) R-218 (Condensing)
40 40

Cooling water Cooling water

20 20

0 0
0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000 0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000
Heat duty (kW) Heat duty (kW)

160 160
R-C318 R-1270
140 140

120 120
Hot water Hot water

100 100
Temperature (°C)
Temperature (°C)

R-C318 (Evaporating) R-1270 (Evaporating)

80 80

60 60
R-C318 (Condensing) R-1270 (Condensing)
40 40

Cooling water Cooling water

20 20

0 0
0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000 0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000
Heat duty (kW) Heat duty (kW)

Fig. 3. Temperature profiles in the evaporator and condenser of optimal ORCs operating with various pure fluids. Solid lines represent the temperature profiles of hot water and
cooling water. Dash lines represent the temperature profiles of working fluids.
 K. Satanphol et al. / Energy 123 (2017) 326e339 333

160 160
R-290 R-134a
140 140

120 Hot water 120

Hot water

100 100
Temperature (°C)

Temperature (°C)
R-290 (Evaporating)
R-134a (Evaporating)
80 80

60 60
R-290 (Condensing) R-134a (Condensing)
40 40

Cooling water Cooling water

20 20

0 0
0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000 0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000
Heat duty (kW) Heat duty (kW)

160 160
R-22 R-236fa
140 140

120 Hot water 120 Hot water

100 100
Temperature (°C)

Temperature (°C)
R-22 (Evaporating) R-236fa (Evaporating)
80 80

60 60
R-22 (Condensing) R-236fa (Condensing)
40 40

Cooling water Cooling water

20 20

0 0
0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000 0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000
Heat duty (kW) Heat duty (kW)

160 160
R-124 R-12
140 140

120 Hot water 120 Hot water

100 100
Temperature (°C)
Temperature (°C)

R-12 (Evaporating)
80 R-124 (Evaporating) 80

60 60
R-124 (Condensing) R-12 (Condensing)
40 40

Cooling water Cooling water

20 20

0 0
0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000 0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000
Heat duty (kW) Heat duty (kW)
160 160
R-600a R-152a
140 140

120 Hot water 120 Hot water

100 100
Temperature (°C)

Temperature (°C)

R-600a (Evaporating) R-152a (Evaporating)

80 80

60 60
R-600a (Condensing) R-152a (Condensing)
40 40

Cooling water Cooling water

20 20

0 0
0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000 0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000
Heat duty (kW) Heat duty (kW)

Fig. 3. (continued).
334 K. Satanphol et al. / Energy 123 (2017) 326e339

160 160
R-245fa R-E170
140 140

120 Hot water 120 Hot water

100 100
Temperature (°C)

Temperature (°C)
R-245fa (Evaporating)
80 80 R-E170 (Evaporating)

60 60
R-245fa (Condensing) R-E170 (Condensing)
40 40

Cooling water Cooling water

20 20

0 0
0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000 0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000
Heat duty (kW) Heat duty (kW)
160 160
R-600 R-142b
140 140

120 Hot water 120 Hot water

100 100

Temperature (°C)
Temperature (°C)

R-600 (Evaporating) R-142b (Evaporating)

80 80

60 60
R-600 (Condensing) R-142b (Condensing)
40 40

Cooling water Cooling water

20 20

0 0
0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000 0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000
Heat duty (kW) Heat duty (kW)
160 160
R-245ca R-601a
140 140

120 Hot water 120 Hot water

100 100
Temperature (°C)

Temperature (°C)

R-245ca (Evaporating) R-601a (Evaporating)

80 80

60 60
R-245ca (Condensing) R-601a (Condensing)
40 40

Cooling water Cooling water

20 20

0 0
0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000 0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000
Heat duty (kW) Heat duty (kW)
160 160
R-601 R-123
140 140

120 Hot water 120 Hot water

100 100
Temperature (°C)

Temperature (°C)

R-601 (Evaporating) R-123 (Evaporating)

80 80

60 60
R-601 (Condensing) R-123 (Condensing)
40 40

Cooling water Cooling water

20 20

0 0
0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000 0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000
Heat duty (kW) Heat duty (kW)

Fig. 3. (continued).
 K. Satanphol et al. / Energy 123 (2017) 326e339 335

Table 4
Optimization results of ORCs operating with zeotropic working fluids.

Refrigerant blend Wnet Eff QEvap MWF (kg/ THW,out TEvap,in TT,in DSPH TT,out PT,in PT,out Cycle
(kW) (%) (kW) h) (
C) (
C) (
C) (K) (
C) (MPa) (MPa) type

R-218/227ea/C318/245fa (32.1/13.4/38.8/ 461.61 8.90 5188 145,775 51.4 36.5 102.3 1.0 53.9 2.73 0.68 Sub-
15.7)
R-290/152a/600a/601a (35.1/38.1/22.4/4.4) 403.88 9.59 4212 47,987 68.2 39.7 105.2 6.3 46.5 3.65 1.14 Sub-

zeotropic fluid was found to operate under the subcritical region.
The evaporator pressure of this blend was 2.73 MPa which was
significantly lower than that of the best pure fluid in the blend
(3.37 MPa for R-227ea). This blend also operated near vapor satu-
ration at the evaporator outlet. When comparing the performance
of this blend with R-227ea, the maximum net work output of the
ORC using this blend was 461.61 kW (cf. Table 4) which was around
8.2% higher than that of the ORC using R-227ea. The thermal effi-
ciency was however lowered by around 0.22% points. The
improvement in the net work output resulting in this case was
largely due to high heat recovery in the evaporator. The amount of
heat recovery in the evaporator in this case was 5188 kW which was
around 10.9% higher than that in case of R-227ea.
When this optimum zeotropic blend was considered in terms of
health and safety issues, it was found that three constituents
namely R-218, R-227ea, and R-C318 were classified in A1 group
while R-245fa was in B1 group according to ASHRAE standard 34-
2013 [42]. All constituents in this blend were in the non-flame
propagation group (group 1). Therefore, this blend was safe in
terms of flammability. However, the toxicity of this blend must be
evaluated before assigning the safety classification to the blend
since it contains R-245fa which is toxic (group B).
On the environmental issue, this blend has zero Ozone
Depletion Potential (ODP), but the weight-average Global Warm-
ing Potential (GWP) is very high at 7475. This blend does not
correspond to the GWP criteria of the fourth generation re-
frigerants which delimited the acceptability of the working fluid
with GWP below 150 [43]. If the environmental concern is on the
top priority when selecting a working fluid for an ORC, only low-
GWP components should be allowed in the consideration. In this
study, there were only 9 low-GWP components, i.e. R-1270, R-290,
R-E170, R-152a, R-600a, R-600, R-123, R-601a, and R-601. The
optimization of the ORC using zeotropic working fluids in this
low-GWP group could be carried out in the same manner as
earlier. It was found that the optimum blend of the low-GWP
working fluids consisted of R-290, R-152a, R-600a, and R-601a
with the composition of 35.1, 38.1, 22.4, and 4.4 wt%, respectively.
When compared to the performance of the best pure fluid in this
blend (R-290), the maximum net work output of the ORC using
this low-GWP blend was 403.88 kW (cf. Table 4) which was
around 6.4% higher than that of the ORC using R-290. The thermal
efficiency was also higher by 0.44% points. The amount of heat
recovery in the evaporator in this case was 4212 kW which was
only 1.5% higher than that in case of R-290. The improvement in
the net work output resulting in this case was to a lesser extent
affected by a marginal increase in heat recovery in the evaporator
but rather by the improvement in the cycle efficiency. This opti-
mum blend operated at the subcritical condition and a low degree
of superheat at the evaporator outlet. The maximum and the
minimum pressures (the turbine inlet and outlet pressures) in the
ORC using this blend were also lower than those in case of R-290.
This low-GWP blend has zero ODP. The weight-average GWP is 63
which is below the environmental criteria. Also, this low-GWP
blend has low toxicity (group A). The only concern for this low-
GWP blend is on the flammability issue since most of the con-
stituents are highly flammable (A3 group) [42].
5.3. Optimization of ORC using binary and ternary zeotropic fluids
From the results in the previous section, the optimal number of
constituents in both optimal blends was four. However, the optimal
zeotropic fluids obtained may not be the global optimal results due
to the non-linearity of the system. It is therefore worth considering
the possible binary and ternary fluids containing the constituents
presented in the optimal fluids. Some equivalent or even better
performance fluids may be found. The optimization results of all
possible binary and ternary fluids for both optimal zeotropic fluids
were shown in Table 5. The results of some possible ternary or

Table 5
Optimization results of ORCs operating with binary and ternary zeotropic working fluids.

Refrigerant blend Wnet (kW) Eff (%) QEvap (kW) MWF (kg/h) THW,out (
C) TEvap,in (
C) TT,in (
C) DSPH (K) TT,out (
C) PT,in (MPa) PT,out (MPa) Cycle type

R-218/C318/245fa (35.9/50.5/13.6) 463.01 8.87 5221 149,933 50.9 36.5 103.1 1.0 54.5 2.74 0.67 Sub-
R-218/227ea/245fa (24.3/55.1/20.6) 461.31 9.13 5055 134,345 53.7 36.9 103.4 1.0 51.3 2.87 0.70 Sub-
R-218/227ea (0.4/99.6) 397.03 8.27 4800 145,960 58.1 45.5 95.7 1.2 53.2 2.53 0.79 Sub-
R-227ea/C318 (33.5/66.5) 426.25 9.13 4669 140,851 60.4 44.1 105.3 1.0 57.1 2.63 0.65 Sub-
R-218/C318 (22.7/77.3) 446.41 8.74 5107 156,903 52.8 39.5 103.5 1.0 57.1 2.63 0.66 Sub-
R-218/245fa (68.2/31.8) 426.80 8.10 5271 146,112 50.0 36.6 100.9 1.0 54.8 2.90 0.84 Sub-
R-227ea/245fa (89.8/10.2) 419.99 9.15 4588 127,853 61.8 44.1 103.2 1.0 52.8 2.74 0.71 Sub-

R-290/152a/600a (34.03/30.35/ 404.06 9.73 4154 47,067 69.2 40.6 106.5 5.3 45.3 3.69 1.11 Sub-
35.62)
R-290/152a/601a (74.1/12/13.9) 379.17 8.69 4364 43,869 65.6 38.4 98.5 4.8 50.7 3.22 1.19 Sub-
R-290/600a/601a (62.4/32.8/4.8) 385.33 9.57 4025 39,247 71.5 38.3 99.5 1.0 45.9 3.08 0.98 Sub-
R-152a/600a/601a (47.1/46.6/6.3) 378.52 9.56 3961 46,045 72.6 38.9 98.9 1.0 46.7 2.67 0.82 Sub-
R-290/152a (24.3/75.7) 378.72 8.77 4317 56,324 66.4 43.3 102.0 10.7 46.0 3.83 1.38 Sub-
R-152a/600a (40.9/59.1) 373.80 9.78 3822 45,260 74.9 41.0 102.1 1.0 45.0 2.95 0.87 Sub-
R-600a/601a (66.1/33.9) 357.91 9.27 3863 34,187 74.2 36.1 94.2 1.0 60.7 1.19 0.37 Sub-
R-290/600a (76.2/23.8) 389.67 9.58 4067 41,735 70.7 42.8 105.0 4.3 45.0 3.76 1.20 Sub-
R-290/601a (91.1/8.9) 398.14 9.44 4219 41,829 68.1 41.0 103.7 6.2 47.2 3.75 1.25 Sub-
R-152a/601a (73.8/26.2) 361.19 9.34 3866 43,497 74.2 37.4 98.6 2.0 50.4 2.16 0.69 Sub-
336 K. Satanphol et al. / Energy 123 (2017) 326e339

binary fluids, e.g. R-218/227ea/C318 or R-C318/245fa, may be 5.4. Thermo-economic analysis

missing since they were reduced to binary or pure fluids at optimal.
For the group of R-218, R-227ea, R-C318 and R-245fa, it was
found that the ternary zeotropic R-218/C318/245fa and R-218/
227ea/245fa could deliver the equivalent or slightly better perfor-
mance in terms of the net power output than the optimal quater-
nary zeotropic R-218/227ea/C318/245fa. For optimal ternary
zeotropic fluids, R-218 and R-245fa are important constituents
together with either R-C318 or R-227ea.
For the group of R-290, R-152a, R-600a, and R-601a, it was found
that the ternary zeotropic R-290/152a/600a could perform slightly
better in terms of net power output than the optimal R-290/152a/
600a/601a. It could be seen that the presence of R-601a in the
optimal R-290/152a/600a/601a was only 4.4%. When R-601a was
removed from the blend, it did not show any detrimental effect on
the ORC performance. The other ternary and binary fluids did not
perform better than the optimal R-290/152a/600a/601a and R-290/
152a/600a.
All optimized ORCs using pure fluids and zeotropic working
fluids were further analyzed in terms of exergy efficiency and the
ORC investment cost as described in Section 4. The exergy effi-
ciencies of all pieces of equipment and the ORC system using each
working fluid were determined. Their results were shown in Table 6.
In case of the optimum ORCs using pure working fluids, it can be
seen that the exergy efficiencies of pump, turbine, and condenser in
all cases were 85.37, 86.25, and 26.09%, respectively on average
with only a small variation. On the other hand, a much larger
variation in the exergy efficiencies of the evaporator can be
observed. Therefore, it was obvious that the evaporator was the
efficiency dominating equipment in the ORC system using pure
fluid. The exergy efficiencies of the evaporator in the transcritical
ORCs (82e87%) were in a higher range than those in the subcritical
ORCs (72e76% excluding R-C318). The overall exergy efficiencies of
the ORCs using pure working fluids also followed relatively the

Table 6
Results from thermo-economic analysis of ORCs operating with various working fluids.

Refrigerant Wnet (kW) Exergy efficiency Estimated SPEC ($/kWe)

Pump Evaporator Turbine Condenser Overall

Pure
R-227ea 426.56 85.40% 84.65% 86.02% 26.66% 57.67% 5979
R-115 413.35 84.40% 86.99% 86.32% 26.54% 60.95% 8207
R-143a 411.96 84.27% 86.63% 86.53% 25.93% 60.18% 7342
R-125 402.26 83.77% 86.35% 86.74% 24.91% 58.91% 8183
R-32 398.19 85.12% 83.59% 86.20% 26.63% 57.91% 6303
R-218 397.40 83.58% 87.28% 86.82% 24.09% 58.83% 8911
R-C318 382.16 85.54% 80.24% 86.46% 26.11% 54.06% 5092
R-1270 381.64 85.23% 83.27% 85.81% 26.13% 57.44% 6826
R-290 379.46 85.36% 81.94% 85.81% 26.10% 55.96% 6410
R-134a 379.24 85.44% 82.22% 85.81% 26.11% 56.15% 5825
R-22 364.82 85.47% 82.36% 86.05% 26.64% 57.37% 5903
R-236fa 335.23 85.76% 75.17% 86.20% 26.55% 50.11% 4898
R-124 327.17 85.70% 75.06% 85.98% 26.55% 50.14% 5078
R-12 321.79 85.74% 74.88% 85.81% 26.12% 49.87% 5531
R-600a 318.38 85.74% 74.12% 86.18% 26.51% 49.45% 4964
R-152a 313.66 85.72% 74.01% 85.81% 26.10% 48.96% 5296
R-245fa 307.57 85.95% 73.22% 86.38% 26.28% 48.36% 4628
R-E170 307.22 85.71% 75.78% 86.96% 24.88% 50.23% 5001
R-600 306.39 85.83% 73.28% 86.32% 26.35% 48.60% 4767
R-142b 306.04 85.77% 74.08% 86.10% 26.55% 49.60% 4907
R-245ca 303.15 85.77% 71.95% 86.34% 26.29% 46.99% 4547
R-601a 302.20 85.83% 72.23% 86.41% 26.26% 47.30% 4531
R-601 296.68 85.93% 72.14% 86.61% 25.74% 46.99% 4499
R-123 294.61 85.91% 71.77% 86.45% 26.20% 46.97% 4548

Zeotropic Blend
R-218/227ea/C318/245fa 461.61 85.15% 80.87% 86.09% 33.68% 58.31% 5493
R-218/C318/245fa 463.01 85.13% 81.26% 86.12% 33.32% 58.42% 5525
R-218/227ea/245fa 461.31 85.17% 81.01% 86.00% 33.96% 58.72% 5438
R-218/227ea 397.03 85.55% 79.76% 86.07% 26.75% 53.04% 5647
R-227ea/C318 426.25 85.47% 82.87% 86.21% 27.39% 56.55% 5395
R-218/C318 446.41 85.24% 82.02% 86.22% 29.93% 57.11% 5529
R-218/245fa 426.80 85.11% 79.99% 86.13% 29.70% 54.95% 5794
R-227ea/245fa 419.99 85.50% 81.93% 86.06% 27.91% 56.23% 5385

Low-GWP Blend
R-290/152a/600a/601a 403.88 85.23% 77.98% 85.85% 32.80% 56.67% 5499
R-290/152a/600a 404.06 85.24% 79.26% 85.81% 31.71% 57.20% 5533
R-290/152a/601a 379.17 85.28% 74.19% 86.01% 32.02% 52.74% 5497
R-290/600a/601a 385.33 85.30% 75.81% 85.84% 33.39% 55.17% 5298
R-152a/600a/601a 378.52 85.35% 75.30% 85.85% 32.85% 54.35% 5114
R-290/152a 378.72 85.35% 76.98% 85.81% 29.16% 53.38% 5707
R-152a/600a 373.80 85.41% 77.20% 85.80% 30.91% 55.13% 5239
R-600a/601a 357.91 85.44% 72.17% 86.32% 32.35% 51.15% 4627
R-290/600a 389.67 85.35% 79.41% 85.81% 29.77% 56.29% 5643
R-290/601a 398.14 85.29% 77.88% 85.87% 31.97% 56.17% 5592
R-152a/601a 361.19 85.42% 73.37% 85.99% 32.14% 52.15% 4852

same trend as the net work outputs. In most of the transcritical
ORCs, the overall exergy efficiencies were higher than those of the
subcritical ones (cf. Table 6).
In case of the optimal ORCs using zeotropic working fluids, it can
be seen that the exergy efficiencies of pump and turbine of the
ORCs using both optimum zeotropic fluids were very close to those
using pure fluids. For the ORC using the optimum R-128/227ea/
C318/245fa blend, the exergy efficiency of the condenser was
improved by 7% points when compared to that in case of R-227ea.
This was the result of a significant gliding improvement in the
condenser as shown in Fig. 4a). The temperature difference along
the temperature profiles in the condenser was rather uniform at
the minimum allowable value (10 K). On the contrary, the exergy
efficiency of the evaporator was deteriorated by 3.8% points due to
the subcritical operation in the zeotropic fluid case when compared
to the transcritical operation in case of R-227ea. However, the
temperature gliding in the evaporator was better than those using
pure fluids operating under the subcritical region. A large propor-
tion of uniform temperature difference could be observed along the
temperature profiles in the evaporator. The suitable gliding
matches found in both evaporator and condenser were as a result of
the optimal fluid composition. In this case, the gliding improve-
ment in the condenser was the dominating side since the best
possible gliding match had been achieved on this side with almost
uniform temperature difference along the profiles. These findings
a)
160
R-290/152a/600a/601a
140
(35.1/38.1/22.4/4.4)
120
100 Hot water
Temperature (°C)
80
R-290/152a/600a/601a (Evaporating)
60
R-290/152a/600a/601a (Condensing)
40
20 Cooling water
0
0 500 1000 1500 2000 2500 3000 3500
Heat duty (kW)
b)
Fig. 4. Temperature profiles in the evaporator and condenser of the ORCs operating
with (a) the optimum zeotropic fluid and (b) the optimum low-GWP zeotropic fluid.
Solid lines represent the temperature profiles of hot water and cooling water. Dash
lines represent the temperature profiles of working fluids.
K. Satanphol et al. / Energy 123 (2017) 326e339 337
were consistent with those found in some previous literature
[20,22,23,30]. The overall exergy efficiency of the ORC using this
optimum blend was also higher than that in case of R-227ea.
For the ORC using the optimum low-GWP blend (R-290/152a/
600a/601a), a similar observation could be found in both condenser
and evaporator as shown in Fig. 4b). The exergy efficiency of the
condenser was improved by 6.7% points while the exergy efficiency
of the evaporator was deteriorated by 4% points when compared to
that in case of R-290 (cf. Table 6). The overall exergy efficiency of
the ORC using this optimum low-GWP blend was a little higher
than that in case of R-290.
The economic performance of the optimum ORC using each
working fluid was represented in terms of the estimated SPEC as
shown in Table 6. For the ORCs using pure working fluids, the esti-
mated SPECs of the transcritical ORCs ($5825-8911/kWe) were in a
higher range than those of the subcritical ORCs ($4499-5531/kWe).
Therefore, the high-capacity ORCs operating in the transcritical re-
gion typically led to poor economy. However, that was not the case
when using the optimum zeotropic working fluid, the economic
performance was also better when compared to the best pure fluid
in the blend. The estimated SPEC of the ORC using the optimum R-
128/227ea/C318/245fa blend was $5493/kWe which was lower than
that in case of R-227ea. Similarly, the estimated SPEC of the ORC
using the optimum low-GWP (R-290/152a/600a/601a) blend was
lower than that in case of R-290. It was clearly seen that the optimum
zeotropic fluid was better than its best pure constituent in terms of
both thermodynamic and economic performance.
6. Concluding remarks
In our contribution, the potential of applying zeotropic working
fluid in an ORC for low grade waste heat was thoroughly explored
via optimization. The proposed optimization strategy has shown to
be sufficiently effective in finding suitable constituents of a zeo-
tropic fluid, their optimal compositions and operating conditions
for an ORC. By maximizing the net work output, the optimum
zeotropic fluid found in this work was a quaternary blend con-
sisting of R-218/227ea/C318/245fa (32.1/13.4/38.8/15.7). Both
thermodynamic and economic performances of this optimum
zeotropic blend were better than those of the best pure fluid in the
blend (R-227ea). This was mainly as a result of thermodynamic
improvement in the ORC condenser and higher heat recovery in the
evaporator when compared to that of the best pure fluid. The major
advantages of the optimum zeotropic blend over the best pure fluid
were lower operating pressure range and lower capital investment.
In addition, when the other criterion such as environmental issue
was considered in high priority, only the fluids passing the criterion
were considered. The optimum low-GWP blend, i.e. R-290/152a/
600a/601a (35.1/38.1/22.4/4.4), could also be obtained. Similarly,
both thermodynamic and economic performances of this optimum
low-GWP blend were better than those of the best pure fluid in this
blend (R-290). However, the improvement in this case was pri-
marily due to better thermodynamic efficiency in the ORC
condenser since the increase in heat recovery in the evaporator was
only marginal when compared to that of R-290.
The optimum zeotropic fluids obtained from the proposed
optimization strategy could not be guaranteed as the global opti-
4000 4500 5000 5500
mum due to the highly non-linear nature of the system. There could
be other zeotropic fluids which may perform better. When
considering the other possible ternary and binary fluids consisting
of the similar constituents as in the optimal fluids, it was found that
some ternary fluids, i.e. R-218/C318/245fa, R-218/227ea/245fa, or R-
290/152a/600a, could deliver equivalent or slightly better perfor-
mance than the optimal fluids in the same group of components. It
can be concluded that the optimal number of constituents in the
338 K. Satanphol et al. / Energy 123 (2017) 326e339

zeotropic fluid was either 3 or 4 under the conditions and com- In the heat exchanger area estimation, the overall heat transfer
ponents used in this study. coefficients were assumed constant as shown in Table A3 [46].
For future work, other optimization approaches such as sto-
chastic methods or genetic algorithm may be considered. The other
limitation in this work was the property calculation problem of Table A3
wide-boiling zeotropic fluids in REFPROP model when approaching Overall heat transfer coefficients used in the heat transfer area estimation.
the critical region. Future improvement in the property calculation Overall heat transfer coefficient (W/m2.K) Evaporator Condenser
of zeotropic fluids around the critical region could help unveiling
Uliquid-Supercritical 850 e
new high-performance zeotropic ORCs. Uliquid-Liquid 600 764
Uliquid-Boiling 600 e
Uliquid-Condensing e 764
Appendix. Capital cost estimation Uliquid-Vapor 428 484

The cost of each piece of major equipment in an ORC was esti-

mated by the cost models as outlined by Turton et al. [44]. The For turbine, the bare module factor (FBM) was fixed at 3.5.
purchased costs of equipment were based on the cost survey in The pressure factor (FP) in Eq. (3) can be determined as follows:
2001 (CEPCI ¼ 394.3). The costs calculated from the models were
then adjusted to the present costs when accounting for inflation.
The CEPCI value in 2012 (584.6) was used in this study [45]. The log10 FP ð2001Þ ¼ C1 þ C2 log10 ðPÞ þ C3 ½log10 ðPÞ2 (A-4)
purchased cost of the equipment, at ambient operating pressure
and using carbon steel in construction, could be estimated by the where
following equation:
P is pressure in barg;
log10 C0P ð2001Þ ¼ K1 þ K2 log10 ðAÞ þ K3 ½log10 ðAÞ2 (A-1) Fp (2001) is pressure factor in 2001; and
C1, C2, and C3 are constant parameters which depend on oper-
where ating pressure as shown in Table A4.

C0P ð2001Þ is the purchased cost of the equipment in 2001.

Table A4
A is the capacity or size parameter for the equipment. Constant parameters used in pressure factor Eq. (A-4).
K1, K2, and K3 are parameters for various kinds of equipment and
Equipment C1 C2 C3 Pressure
capacity. The values used in this study were given in Table A1.
(barg)

Table A1 Evaporator 0.00164 0.00627 0.0123 5 < P < 140

Constant parameters used in cost model Eq. (A-1). - Floating Head (Tube only)
Condenser 0 0 0 P<5
Equipment K1 K2 K3 A Min. Max. - Floating Head (Both shell &
Size Size tube)
Evaporator and condenser 4.8306 0.8509 0.3187 Area 10 1000 Turbine 0 0 0 e
(Floating Head type) (m2) - Axial gas
Turbine (Axial type) 2.7051 1.4398 0.1776 Power 100 4000 Pump 0.245382 0.259016 0.01363 10 < P < 100
(kW) - Reciprocating
Pump (Reciprocating type) 3.8696 0.3161 0.1220 Power 0.1 200
(kW)

The purchased equipment cost must be corrected with the bare Nomenclature
module factor (FBM) which accounted for the material (FM) and
pressure (FP) factors in construction. The corrected value, now Atm Atmospheric
called the bare module cost (CBM), is therefore used as the esti- CW Cooling water
mated capital cost in the economic analysis. Ex Exergy
Flow Mass flow rate
GWP Global warming potential
CBM ¼ Cp0 FBM (A-2)
H Enthalpy
For heat exchanger and pump, the bare module factor (FBM) can MW Molecular weight
be calculated as follows: ODP Ozone depletion potential
P Pressure
FBM ¼ B1 þ Bþ FP FM (A-3) Q Heat load
S Entropy
where B1 and B2 are constant parameters which depend on type of SPEC Specific purchased equipment cost
equipment as shown in Table A2. T Temperature
W Work
Table A2
WF Working fluid
Constant parameters used in bare module factor Eq. (A-3). h Efficiency
D Change, or difference
Equipment B1 B2 FM

Floating Head exchanger 1.63 1.66 1 Subscripts

Reciprocating pump 1.89 1.35 1.5
B Boiling point
 K. Satanphol et al. / Energy 123 (2017) 326e339
C Critical state
CW Cooling water
cond Condenser
evap Evaporator
Ex Exergy
HW Hot water
in Input
irr Irreversible
net Net output
out Output
turb Turbine
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