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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


energy from various sources such as geothermal, solar or waste
In various kinds of processes such as fuel combustion in power heat from industrial processes [2,3]. In an ORC, low boiling com-
plants, chemical reactions in industrial, electronic or biological pounds (mostly organics) are used as the working fluid to recover
processes, a large amount of waste heat is commonly lost to envi- medium or low grade waste heat. In general, the critical tempera-
ronment, leading to low energy efficiency in the process. In addi- ture of a working fluid used in an ORC is much lower than that of
tion, the waste heat release is also a contributing factor to the global water in a typical steam cycle at the same operating pressure [4].
warming which is threatening the world at the present time. Any This is a clear advantage of the ORC over the conventional Rankine
measures to reduce or recover the waste heat are therefore especially in the low temperature region. Apart from the ORC, the
considered with high priority in all kinds of processes. A massive other interesting power cycles for waste heat recovery are
amount of medium (230e650  C) and low grade (<230  C) waste Maloney-Robertson cycle and Kalina cycle which use ammonia
heat [1] is emitted from certain types of equipment such as gas solution as the working fluid. However, when compared them with
turbine, steam boiler, internal combustion engine (ICE), and an ORC under similar size, it was found that the ORC could provide
furnace. The recovery of the medium and low grade waste heat approximately the same or better performance at a much lower
could be carried out in numerous ways. It may be recovered as pressure [5,6]. Consequently, much larger attention was focused on
thermal energy to be used directly in the process. In some cases, the the ORC as shown by thousands of related journal articles pub-
recovered energy usage may be rather limited if the waste heat lished in recent years. The overview of the ORC in various aspects,
temperature level is too low. One of the interesting recovery ap- e.g. cycle architectures, types of working fluids, thermodynamic
proaches being focused on recently was the application of an and economic performances or equipment hardware, can also be
Organic Rankine Cycle (ORC) to recover waste heat and to found in some recent review articles [7e10]. In our work, however,
not every aspect involving the ORC was considered. Only the in-
* Corresponding author.
fluence of zeotropic working fluid on the ORC performance was
E-mail address: bunyaphat.sup@kmutt.ac.th (B. Suphanit). 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 327

Depending on the slope of vapor saturation line on the transfer area requirement in an evaporator increases as a result of
temperature-entropy diagram, the working fluids used in an ORC decreasing in temperature driving force. In addition, the effect of
can typically be divided into three types; i.e. wet fluid (negative changes in some physical properties of fluid mixture, e.g. thermal
slope), dry fluid (positive slope) and isentropic fluid (infinite slope) conductivity and viscosity in the evaporator could also degrade the
[11]. For dry or isentropic working fluid under subcritical region, heat transfer characteristic, thereby leading to a larger area
the condition at the turbine inlet is only needed to be saturated or requirement as above. The evaporator cost was therefore inevitably
low degree of superheated vapor, respectively. Under these cir- higher in case of the transcritical ORC.
cumstances, there will be no operating difficulty involving the In a transcritical ORC, a good temperature glide can be achieved in
liquid droplet formation when these fluids expand across the tur- an evaporator. However, on the condenser side, a temperature glide
bine. On the other hand, the turbine inlet condition of most wet does not occur if the working fluid is pure. To improve the temper-
fluids in an ORC must be superheated to a certain degree otherwise ature glide in both evaporator and condenser, the other possible
the liquid droplet formation during expansion may occur. The alternative, i.e. the application of a zeotropic mixture, may be used
damage on turbine blades could then follow as a consequence. The instead. The number of research works on the application of zeo-
results from several research works also suggested that dry and tropic working fluid in an ORC increased remarkably during the last
isentropic fluids were the most favorable types of fluids for an ORC couple of years. Several researchers had already confirmed the
[12e18]. benefit of gliding improvement from zeotropic fluid in both evapo-
The performance of an ORC can be affected by several factors. The rator and condenser on the ORC performance [17,20,22,23,29e34].
choice of working fluid is one of the key factors among others such as Some of them found that the performance improvement was mainly
the cycle operating region (subcritical or transcritical) and the cycle a consequence of the good gliding match in the condenser
configuration. Numerous works on working fluid selection for an [20,22,23,30]. The zeotropic mixtures mostly considered in the past
ORC have been studied to choose the right working fluid in various literature were binary mixtures of some preselected fluids. Hence,
aspects [11e13,19,20]. Several screening criteria for choosing a the studies on optimal zeotropic composition in an ORC were pri-
suitable working fluid such as cost, cycle performance, environ- marily carried out through sensitivity analysis over the whole
mental impact, thermal stability, flammability or toxicity may be composition range [17,22,29e32]. The other optimization methods
applied. Basically, the cycle performance is the main objective used such as the genetic algorithm [20], and a Generalized Reduced
to identify an appropriate working fluid. In general, this could be Gradient (GRG) nonlinear multistart algorithm [23] were also used in
accomplished by the optimization of either the net work output the determination of optimal binary composition. The multi-
[14,21] or the thermodynamic efficiencies [22e24]. Other economic objective optimization was also investigated by Clarke et al. [35]
indicators such as the ratio of net work output to total cost [21], the and Feng et al. [36] in order to simultaneously optimize the ther-
levelized cost of electricity (LCOE) [24], or the ratio of heat exchanger modynamic and economic performances. The studies on optimal
area to net work output [25] might also be set as objectives. Many composition of ternary or multicomponent working fluids were rare.
researchers [14,16,18,20,26] tried to relate the cycle performance Chys et al. [29] investigated the effect of the third additional
with the critical temperature of the working fluid in order to component of several ternary working fluids on the ORC perfor-
establish simple criteria for fluid selection. For instance, He et al. [16] mance. They found that the addition of the third component into a
investigated 22 pure working fluids operating in subcritical region; binary fluid yielded insignificant improvement in terms of both po-
and found that the working fluids with the critical temperatures wer output and cycle efficiency when compared to the original bi-
close to the heat source temperature tend to perform better in terms nary fluid. Recently, Chaitanya et al. [37] used the sequential
of net power output than those with higher or lower critical tem- quadratic programming (SQP) method to optimize composition of
peratures. However, their investigation was only limited to the several zeotropic mixtures which are mostly hydrocarbons in an
subcritical ORCs. The deduction from their work might not be valid ORC. The results showed that several good performance ternary and
for other working fluids operating in the transcritical region. Ayachi multicomponent fluids could be found. There was still no clear
et al. [18] showed that the working fluid with the best thermody- conclusion on the suitable number of components to be used in a
namic performance operated in the transcritical region. The opti- zeotropic fluid. Therefore, the identification of high-performance
mum critical temperature could be identified. The fluids with the multicomponent zeotropic fluid should be considered further since
critical temperatures lower than the optimum critical value tended there may be some good combinations waiting to be discovered.
to operate optimally in the transcritical region but with lower cycle In this work, the potential of applying zeotropic working fluid in
performance. On the other hand, the fluids with the critical tem- an ORC for low grade heat was explored. Our approach was
peratures higher than the optimum critical value tended to operate different from those in some previous works. Rather than consid-
optimally in the subcritical region. The optimum critical tempera- ering some preselected multicomponent mixtures then performing
ture from Ayachi et al. [18] was around 0.7e0.8 times the heat source the optimization [29,37], the working fluid selection and the opti-
temperature. Others may suggest different criteria such as 0.5 times mization of fluid compositions were carried out simultaneously.
[20] or 0.8 times [27] the heat source temperature. These criteria The compositions of fluid species which were not suitable would be
may vary due to the differences in heat source temperature or the reduced to zero during the optimization. The number of fluid
objective function used in various studies. species in the zeoptropic fluids could then be reduced to optimum.
As discussed above, an ORC operating in the transcritical region Our detail optimization approach was described in Section 3. The
was found to deliver better performance than the same ORC objective function considered in this work was to maximize the net
operating in the subcritical region due to better temperature work output. Both transcritical and subcritical conditions were
driving force distribution in the evaporator. The temperature dif- considered in this work to evaluate the maximum possible per-
ferences between the heat source and the working fluid along the formance of an ORC operating with each working fluid. All simu-
heat transfer path were more uniform in case of the transcritical lations and optimizations of zeotropic fluid composition used in an
ORC than those in the subcritical ORC. The temperature profile of ORC were carried out by Aspen Plus V8.4 simulation software.
the working fluid in this situation may also be called temperature
glide [28]. In general, the larger the temperature glide, the better 2. Working fluids
the performance of an ORC. Although the efficiency could be
improved by operating an ORC in the transcritical region, the heat 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 lower bound of the degree of superheating of the working fluid at
additional fluorocarbon components from REFPROP database [38]. the evaporator exit. Instead of using 0 K to represent the saturated
As shown in Table 1, a total of 24 working fluids were investigated. vapor condition, a marginal value of 1 K was specified in order to
All of them were listed in order of their normal boiling points. The avoid any discontinuities which may arise at the vapor-liquid phase
other related thermodynamic properties such as critical tempera- boundary during optimization. If an optimum solution appears to
ture and pressure, the molecular weight, the type of fluid expansion be at 1 K of superheating, it is considered to be an optimum at the
characteristic and the environmental, health and safety indices saturated vapor condition. For the optimization in the subcritical
were also shown on the same table. region of a pure working fluid, the critical pressure was taken as the
In this work, the major criterion used to evaluate the zeotropic upper bound value of the evaporator pressure. However, for some
working fluid was the net work output. Besides, the scenario in working fluids, the evaporator pressure may approach the critical
which the environmental issue was considered as the first priority region during the optimization. It is therefore possible that the
was also investigated. optimum condition in the evaporator may lie above the critical
point of that working fluid. The operating region considered in the
3. ORC modeling and optimization optimization will be switched from the subcritical to the tran-
scritical region. In such cases, the upper bound of the evaporator
To optimize the performance of an ORC operating with a pure or pressure will be set arbitrarily to a value higher than the critical
zeotropic working fluid, a simulation model of a conventional ORC value. The degree of superheating variable will also be replaced by
is necessary. Aspen Plus V8.4 simulation software was applied for the working fluid temperature at the evaporator exit.
this task. A conventional ORC model consists of 4 main pieces of Due to the non-linear nature of this optimization problem, the
equipment; i.e. an evaporator, a turbine, a condenser and a pump sequential quadratic programming (SQP) method was selected to
(cf. Fig. 1). In the evaporator (EVAP), the working fluid is heated up solve this problem. Here, the SQP was used as a black-box method
from the subcooled liquid to the saturated or the superheated vapor by converging tear stream variables and design specifications
condition by recovering heat from a waste heat or geothermal heat separately in two nested loops. In this manner, the number of de-
source. After leaving the evaporator, the hot working fluid vapor is rivative evaluations in any iteration could be reduced since tear
expanded across the turbine (TURBINE) to generate work. The stream variables were converged separately. Moreover, this
turbine exhaust vapor is then condensed into the saturated liquid convergence approach is more robust than the default approach by
by heat rejection through the condenser (CONDENSE) using cooling Aspen Plus in which tear variables are converged simultaneously
water as the cooling medium. Finally, the condensed liquid is with other optimization variables. In this problem, the flowsheet
pumped back to the evaporator to continue cycle operation. convergence involves three separate loops. First, at any particular
The thermodynamic properties of a working fluid at any values of optimization variables, the inner loop is used to achieve
particular point in an ORC were calculated by REFPROP model [38] tear variable convergence (pump inlet pressure) via the Wegstein
in Aspen Plus software. All ORC optimizations were executed with method. Next, the cooling water (CW) flow is adjusted to achieve
regard to a set of assumptions, specifications and constraints as the specified CW return temperature via the Broyden method.
shown in Table 2. The objective function used in this work was the Finally, the optimization block is converged by the SQP method in
maximization of net work output. The optimization variables the outer loop. The optimization tolerance was set at the default
considered in case of pure and zeotropic working fluids were the value of 0.001.
mass flow rate of each constituent, the evaporator pressure (or The optimal zeotropic composition was also determined via
pump discharge pressure), the condenser pressure (or turbine exit optimization in which the flow rate of each constituent was varied
pressure), and the degree of superheating of the working fluid at simultaneously with other operating variables. However, due to a
the evaporator exit. Here, we have made an assumption on the 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.
DExWF;cond
As a matter of fact, exergy of a stream is a direct function of its For an ORC, the overall exergy loss is the combination of all
enthalpy and entropy, which are both functions of state, the exergy exergy losses from all pieces of equipment. The same definition of
itself is therefore a state function. Thus, the exergy value of a given exergy efficiency as in Eq. (4) can be applied to the overall system as
stream can be calculated from the stream properties (composition, shown in Eq. (14).
temperature and pressure). If a stream changes from state 1 to state
2, the exergy change of the stream is given by: Exloss;overall ¼ Exloss;pump þ Exloss;evap þ Exloss;turb þ Exloss;cond
(13)
DEx12 ¼ Ex2  Ex1 ¼ ðH2  H1 Þ  T0 ðS2  S1 Þ (2)
According to the second law of thermodynamics, all natural
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- jDExHW j þ Wpump jDExHW j þ Wpump
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 4.2. Economic analysis
exergy lost due to irreversibility.
In addition to the thermodynamic performance of an ORC, the
Exin  Exout ¼ Exirr ¼ Exloss (3) economic performance is also another essential factor to be
considered. The working fluid capable of yielding not only good
The exergy loss value provides a measure of thermodynamic energy performance but also low cost of electricity production
efficiency of a process. The maximum thermodynamic efficiency would be very attractive for being used in an ORC. However, this
may be achieved by a reversible process in which there is no exergy might not be the case in general. For example, in transcritical ORCs,
loss. Reversible processes, however, have no driving forces and can the systems could deliver good energy performance since they
never be achieved in practice. operated with large pressure change across the turbine. On the
The exergy efficiency of a process can be defined as follows: other hand, the capital investment was rather high in such cases
due to the high pressure condition in the evaporator and the tur-
Exout Ex
hEx ¼ ¼ 1  loss (4) bine. This led to poor economy which was in contrast to the good
Exin Exin energy performance. Basically, the cost of electricity generated
The exergy efficiency used in this work was the rational [39] or from an ORC mainly depends on the capital investment of the ORC
functional [2] exergy efficiency. This definition of exergy efficiency itself. The operating costs such as cooling water cost, labor cost, or
was suitable for the system or equipment with good understanding maintenance cost are typically estimated in proportion to the
of purpose or behavior. In an ORC, the exergy input could be either capital investment. In this study, however, these estimated oper-
the heat or work flow into a unit, or the exergy provided by a ating costs were not considered in the analysis. The economic
stream flowing through that unit. Similarly, the exergy output performance of an ORC operating with each working fluid was
could be either the exergy taken up by a stream flowing through a therefore evaluated on the basis of the estimated specific pur-
unit, or the heat or work flow out of the unit. Applying Eqs. (3) and chased equipment cost (SPEC) in $/kWe. The detail of equipment
(4) in an ORC, the exergy loss and the exergy efficiency of each piece cost estimation was described in the Appendix. The electricity
of equipment can be determined as follows: production capacity was calculated from the net electricity pro-
Pump: 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- and isentropic fluids, e.g. R-236fa, R-124, R-12, R-600a, operated
mately below 100  C tended to operate optimally in the transcritical optimally near the saturated vapor condition while wet fluids such
condition. The optimum critical temperature was found to be as R-E170 operated optimally at a significant degree of superheating
around 0.7 times the heat source temperature. This coincided with at the evaporator outlet as shown in Fig. 3. Considered in terms of
the results from some previous works [18,27]. There were 10 the optimum operating pressure in the evaporator or the turbine
working fluids of this kind which ranked top on the list as shown in inlet pressure (PT,in), it was found that the transcritical ORCs oper-
Table 3. The remaining fluids which operated optimally in the ated at a much higher pressure than the subcritical ORCs did. The
subcritical region then followed in subsequent order except R-C318 potential to generate work through the turbine was therefore high
which had an outstanding performance above others in the in case of the transcritical ORCs. In condenser, the temperature
subcritical group. From Table 3, R-227ea was the best performance profiles of the heat-exchanged streams were rather similar in both
fluid in terms of the net work output while R-123 was the worst transcritical and subcritical ORCs. The phase change occurred at
performance fluid under the assumptions in this study. The best constant temperature hence there was no temperature gliding on
pure fluid obtained (R-227ea) was similar to the result at the same the working fluid side. For some working fluids such as R-227ea or
heat source temperature from Chagnon-Lessard et al. [40]. The R-143a, the internal pinch which limited the condensing temper-
ranking of the top 5 pure fluids was also in close agreement with the ature could be found. For others such as R-290 or R-134a, the pinch
results obtained by Walraven [41] for simple ORCs. The first law or may occur at the hot end of the condenser. For all pure working
thermal efficiencies of all pure working fluids were in range of fluids, the condensing temperature in the condenser were found to
8.37e10.30%. The results showed that there was no distinct linkage be in range of 40e45  C. Since the condensing temperature and
between the net work output and the thermal efficiency obtained by pressure were directly related, the condensing pressure was limited
these working fluids. On the other hand, the net work output was by this temperature range. Hence, the potential to generate more
largely affected by the amount of heat recovery in the evaporator. work through the turbine was reduced.
The ORC operating with high heat recovery level in the evaporator
tended to produce a large net work output. 5.2. Optimization of ORC using zeotropic working fluid
The amount of heat recovery in the evaporator depended on the
temperature profiles of both hot and cold streams. Effective heat After evaluating the ORC performance of each pure fluid, the
recovery could be achieved in the evaporator having appropriate ORC using zeotropic working fluid was further explored to identify
temperature glide or rather uniform temperature difference along any possible improvement on the net work output. By applying the
the heat transfer path such as those found in the evaporators optimization procedure outlined in Section 3, it was found that
operating at the supercritical condition. On the contrary, the heat from the total of 24 fluid species considered, the optimum blend of
recovery in the evaporator operating at the subcritical condition zeotropic working fluid consisted of R-218, R-227ea, R-C318, and R-
was less effective due to the pinch limitation generated by the 245fa with the composition of 32.1, 13.4, 38.8, and 15.7 wt%,
phase-change location. From Fig. 3, the ORCs operating in the respectively. The number of fluid species was reduced from 24 to
transcritical region, e.g. R-227ea, R-115, R-143a, R-125, or R-218, only 4 at optimum by using the proposed methodology. Both fluid
exhibited relatively uniform temperature differences in the evap- selection and optimal compositions were obtained from the opti-
orators. The temperature differences in these evaporators were also mization. The boiling range of this optimum blend was quite wide.
very close to the given minimum temperature approach (10  C). The critical temperature ratio of the heaviest (R-245fa) to the
Hence, the heat recovery of the evaporator operating at the su- lightest constituents (R-218) in the blend was around 2.14 which
percritical condition was more effective than those operating at the was higher than the limitation of property calculation around
subcritical condition. For working fluids in the subcritical group, dry 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. earlier. It was found that the optimum blend of the low-GWP
The evaporator pressure of this blend was 2.73 MPa which was working fluids consisted of R-290, R-152a, R-600a, and R-601a
significantly lower than that of the best pure fluid in the blend with the composition of 35.1, 38.1, 22.4, and 4.4 wt%, respectively.
(3.37 MPa for R-227ea). This blend also operated near vapor satu- When compared to the performance of the best pure fluid in this
ration at the evaporator outlet. When comparing the performance blend (R-290), the maximum net work output of the ORC using
of this blend with R-227ea, the maximum net work output of the this low-GWP blend was 403.88 kW (cf. Table 4) which was
ORC using this blend was 461.61 kW (cf. Table 4) which was around around 6.4% higher than that of the ORC using R-290. The thermal
8.2% higher than that of the ORC using R-227ea. The thermal effi- efficiency was also higher by 0.44% points. The amount of heat
ciency was however lowered by around 0.22% points. The recovery in the evaporator in this case was 4212 kW which was
improvement in the net work output resulting in this case was only 1.5% higher than that in case of R-290. The improvement in
largely due to high heat recovery in the evaporator. The amount of the net work output resulting in this case was to a lesser extent
heat recovery in the evaporator in this case was 5188 kW which was affected by a marginal increase in heat recovery in the evaporator
around 10.9% higher than that in case of R-227ea. but rather by the improvement in the cycle efficiency. This opti-
When this optimum zeotropic blend was considered in terms of mum blend operated at the subcritical condition and a low degree
health and safety issues, it was found that three constituents of superheat at the evaporator outlet. The maximum and the
namely R-218, R-227ea, and R-C318 were classified in A1 group minimum pressures (the turbine inlet and outlet pressures) in the
while R-245fa was in B1 group according to ASHRAE standard 34- ORC using this blend were also lower than those in case of R-290.
2013 [42]. All constituents in this blend were in the non-flame This low-GWP blend has zero ODP. The weight-average GWP is 63
propagation group (group 1). Therefore, this blend was safe in which is below the environmental criteria. Also, this low-GWP
terms of flammability. However, the toxicity of this blend must be blend has low toxicity (group A). The only concern for this low-
evaluated before assigning the safety classification to the blend GWP blend is on the flammability issue since most of the con-
since it contains R-245fa which is toxic (group B). stituents are highly flammable (A3 group) [42].
On the environmental issue, this blend has zero Ozone
Depletion Potential (ODP), but the weight-average Global Warm- 5.3. Optimization of ORC using binary and ternary zeotropic fluids
ing Potential (GWP) is very high at 7475. This blend does not
correspond to the GWP criteria of the fourth generation re- From the results in the previous section, the optimal number of
frigerants which delimited the acceptability of the working fluid constituents in both optimal blends was four. However, the optimal
with GWP below 150 [43]. If the environmental concern is on the zeotropic fluids obtained may not be the global optimal results due
top priority when selecting a working fluid for an ORC, only low- to the non-linearity of the system. It is therefore worth considering
GWP components should be allowed in the consideration. In this the possible binary and ternary fluids containing the constituents
study, there were only 9 low-GWP components, i.e. R-1270, R-290, presented in the optimal fluids. Some equivalent or even better
R-E170, R-152a, R-600a, R-600, R-123, R-601a, and R-601. The performance fluids may be found. The optimization results of all
optimization of the ORC using zeotropic working fluids in this possible binary and ternary fluids for both optimal zeotropic fluids
low-GWP group could be carried out in the same manner as 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 All optimized ORCs using pure fluids and zeotropic working
found that the ternary zeotropic R-218/C318/245fa and R-218/ fluids were further analyzed in terms of exergy efficiency and the
227ea/245fa could deliver the equivalent or slightly better perfor- ORC investment cost as described in Section 4. The exergy effi-
mance in terms of the net power output than the optimal quater- ciencies of all pieces of equipment and the ORC system using each
nary zeotropic R-218/227ea/C318/245fa. For optimal ternary working fluid were determined. Their results were shown in Table 6.
zeotropic fluids, R-218 and R-245fa are important constituents In case of the optimum ORCs using pure working fluids, it can be
together with either R-C318 or R-227ea. seen that the exergy efficiencies of pump, turbine, and condenser in
For the group of R-290, R-152a, R-600a, and R-601a, it was found all cases were 85.37, 86.25, and 26.09%, respectively on average
that the ternary zeotropic R-290/152a/600a could perform slightly with only a small variation. On the other hand, a much larger
better in terms of net power output than the optimal R-290/152a/ variation in the exergy efficiencies of the evaporator can be
600a/601a. It could be seen that the presence of R-601a in the observed. Therefore, it was obvious that the evaporator was the
optimal R-290/152a/600a/601a was only 4.4%. When R-601a was efficiency dominating equipment in the ORC system using pure
removed from the blend, it did not show any detrimental effect on fluid. The exergy efficiencies of the evaporator in the transcritical
the ORC performance. The other ternary and binary fluids did not ORCs (82e87%) were in a higher range than those in the subcritical
perform better than the optimal R-290/152a/600a/601a and R-290/ ORCs (72e76% excluding R-C318). The overall exergy efficiencies of
152a/600a. 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
K. Satanphol et al. / Energy 123 (2017) 326e339 337

same trend as the net work outputs. In most of the transcritical were consistent with those found in some previous literature
ORCs, the overall exergy efficiencies were higher than those of the [20,22,23,30]. The overall exergy efficiency of the ORC using this
subcritical ones (cf. Table 6). optimum blend was also higher than that in case of R-227ea.
In case of the optimal ORCs using zeotropic working fluids, it can For the ORC using the optimum low-GWP blend (R-290/152a/
be seen that the exergy efficiencies of pump and turbine of the 600a/601a), a similar observation could be found in both condenser
ORCs using both optimum zeotropic fluids were very close to those and evaporator as shown in Fig. 4b). The exergy efficiency of the
using pure fluids. For the ORC using the optimum R-128/227ea/ condenser was improved by 6.7% points while the exergy efficiency
C318/245fa blend, the exergy efficiency of the condenser was of the evaporator was deteriorated by 4% points when compared to
improved by 7% points when compared to that in case of R-227ea. that in case of R-290 (cf. Table 6). The overall exergy efficiency of
This was the result of a significant gliding improvement in the the ORC using this optimum low-GWP blend was a little higher
condenser as shown in Fig. 4a). The temperature difference along than that in case of R-290.
the temperature profiles in the condenser was rather uniform at The economic performance of the optimum ORC using each
the minimum allowable value (10 K). On the contrary, the exergy working fluid was represented in terms of the estimated SPEC as
efficiency of the evaporator was deteriorated by 3.8% points due to shown in Table 6. For the ORCs using pure working fluids, the esti-
the subcritical operation in the zeotropic fluid case when compared mated SPECs of the transcritical ORCs ($5825-8911/kWe) were in a
to the transcritical operation in case of R-227ea. However, the higher range than those of the subcritical ORCs ($4499-5531/kWe).
temperature gliding in the evaporator was better than those using Therefore, the high-capacity ORCs operating in the transcritical re-
pure fluids operating under the subcritical region. A large propor- gion typically led to poor economy. However, that was not the case
tion of uniform temperature difference could be observed along the when using the optimum zeotropic working fluid, the economic
temperature profiles in the evaporator. The suitable gliding performance was also better when compared to the best pure fluid
matches found in both evaporator and condenser were as a result of in the blend. The estimated SPEC of the ORC using the optimum R-
the optimal fluid composition. In this case, the gliding improve- 128/227ea/C318/245fa blend was $5493/kWe which was lower than
ment in the condenser was the dominating side since the best that in case of R-227ea. Similarly, the estimated SPEC of the ORC
possible gliding match had been achieved on this side with almost using the optimum low-GWP (R-290/152a/600a/601a) blend was
uniform temperature difference along the profiles. These findings 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
a) advantages of the optimum zeotropic blend over the best pure fluid
160 were lower operating pressure range and lower capital investment.
R-290/152a/600a/601a
In addition, when the other criterion such as environmental issue
140
(35.1/38.1/22.4/4.4)
was considered in high priority, only the fluids passing the criterion
120
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,
100 Hot water both thermodynamic and economic performances of this optimum
Temperature (°C)

low-GWP blend were better than those of the best pure fluid in this
80
blend (R-290). However, the improvement in this case was pri-
R-290/152a/600a/601a (Evaporating)
60 marily due to better thermodynamic efficiency in the ORC
R-290/152a/600a/601a (Condensing) condenser since the increase in heat recovery in the evaporator was
40
only marginal when compared to that of R-290.
20 Cooling water The optimum zeotropic fluids obtained from the proposed
optimization strategy could not be guaranteed as the global opti-
0
0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000 5500
mum due to the highly non-linear nature of the system. There could
Heat duty (kW) be other zeotropic fluids which may perform better. When
considering the other possible ternary and binary fluids consisting
b) 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-
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.
290/152a/600a, could deliver equivalent or slightly better perfor-
Solid lines represent the temperature profiles of hot water and cooling water. Dash mance than the optimal fluids in the same group of components. It
lines represent the temperature profiles of working fluids. 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 339

C Critical state grade waste heat recovery with subcritical and supercritical Organic Rankine
Cycle based on natural refrigerants and their binary mixtures. Energy
CW Cooling water
2015;88:80e92.
cond Condenser [23] Lecompte S, Ameel B, Ziviani D, van den Broek M, De Paepe M. Exergy analysis
evap Evaporator of zeotropic mixtures as working fluids in Organic Rankine Cycles. Energy
Ex Exergy Convers Manag 2014;85:727e39.
[24] Le VL, Kheiri A, Feidt M, Pelloux-Prayer S. Thermodynamic and economic
HW Hot water optimizations of a waste heat to power plant driven by a subcritical ORC
in Input (Organic Rankine Cycle) using pure or zeotropic working fluid. Energy
irr Irreversible 2014;78:622e38.
[25] Madhawa Hettiarachchi HD, Golubovic M, Worek WM, Ikegami Y. Optimum
net Net output design criteria for an Organic Rankine cycle using low-temperature
out Output geothermal heat sources. Energy 2007;32(9):1698e706.
turb Turbine [26] Borsukiewiczgozdur A, Nowak W. Comparative analysis of natural and syn-
thetic refrigerants in application to low temperature ClausiuseRankine cycle.
Energy 2007;32(4):344e52.
References [27] Vetter C, Wiemer H-J, Kuhn D. Comparison of sub- and supercritical Organic
Rankine Cycles for power generation from low-temperature/low-enthalpy
[1] Waste heat recovery. Energy efficiency guide for industry in Asia. UNEP; 2006. geothermal wells, considering specific net power output and efficiency.
[2] DiPippo R. Geothermal power plants: principles, applications, case studies and Appl Therm Eng 2013;51(1e2):871e9.
environmental impact. second ed. Great Britain: Butterworth-Heinemann; [28] Radermacher R. Thermodynamic and heat transfer implications of working
2008. fluid mixtures in Rankine cycles. Int J Heat Fluid Flow 1989;10(2):90e102.
[3] Vescovo R. ORC recovering industrial heat. Cogeneration and on-site power [29] Chys M, van den Broek M, Vanslambrouck B, De Paepe M. Potential of zeo-
production: decentralized energy. 2009. p. 53e7. tropic mixtures as working fluids in organic Rankine cycles. Energy
[4] Karellas S, Schuster A. Supercritical fluid parameters in organic rankine cycle 2012;44(1):623e32.
applications. Int J Thermodyn 2008;11(3):101e8. [30] Heberle F, Preißinger M, Brüggemann D. Zeotropic mixtures as working fluids
[5] Bombarda P, Invernizzi CM, Pietra C. Heat recovery from Diesel engines: a in Organic Rankine Cycles for low-enthalpy geothermal resources. Renew
thermodynamic comparison between Kalina and ORC cycles. Appl Therm Eng Energy 2012;37(1):364e70.
2010;30(2e3):212e9. [31] Liu Q, Shen A, Duan Y. Parametric optimization and performance analyses of
[6] Little AB, Garimella S. Comparative assessment of alternative cycles for waste geothermal organic Rankine cycles using R600a/R601a mixtures as working
heat recovery and upgrade. Energy 2011;36(7):4492e504. fluids. Appl Energy 2015;148:410e20.
[7] Tchanche BF, Lambrinos G, Frangoudakis A, Papadakis G. Low-grade heat [32] Kang Z, Zhu J, Lu X, Li T, Wu X. Parametric optimization and performance
conversion into power using organic Rankine cycles e a review of various analysis of zeotropic mixtures for an organic Rankine cycle driven by low-
applications. Renew Sustain Energy Rev 2011;15(8):3963e79. medium temperature geothermal fluids. Appl Therm Eng 2015;89:323e31.
[8] Velez F, Segovia JJ, Martín MC, Antolín G, Chejne F, Quijano A. A technical, [33] Habka M, Ajib S. Evaluation of mixtures performances in Organic Rankine
economical and market review of organic Rankine cycles for the conversion of Cycle when utilizing the geothermal water with and without cogeneration.
low-grade heat for power generation. Renew Sustain Energy Rev 2012;16(6): Appl Energy 2015;154:567e76.
4175e89. [34] Chen H, Goswami DY, Rahman MM, Stefanakos EK. A supercritical Rankine
[9] Bao J, Zhao L. A review of working fluid and expander selections for organic cycle using zeotropic mixture working fluids for the conversion of low-grade
Rankine cycle. Renew Sustain Energy Rev 2013;24:325e42. heat into power. Energy 2011;36(1):549e55.
[10] Lecompte S, Huisseune H, van den Broek M, Vanslambrouck B, De Paepe M. [35] Clarke J, McLeskey JT. Multi-objective particle swarm optimization of binary
Review of organic Rankine cycle (ORC) architectures for waste heat recovery. geothermal power plants. Appl Energy 2015;138:302e14.
Renew Sustain Energy Rev 2015;47:448e61. [36] Feng Y, Hung T, Greg K, Zhang Y, Li B, Yang J. Thermoeconomic comparison
[11] Mikielewicz D, Mikielewicz J. A thermodynamic criterion for selection of between pure and mixture working fluids of organic Rankine cycles (ORCs) for
working fluid for subcritical and supercritical domestic micro CHP. Appl low temperature waste heat recovery. Energy Convers Manag 2015;106:
Therm Eng 2010;30(16):2357e62. 859e72.
[12] Hung TC, Wang SK, Kuo CH, Pei BS, Tsai KF. A study of organic working fluids [37] Chaitanya Prasad GS, Suresh Kumar C, Srinivasa Murthy S, Venkatarathnam G.
on system efficiency of an ORC using low-grade energy sources. Energy Performance of an organic Rankine cycle with multicomponent mixtures.
2010;35(3):1403e11. Energy 2015;88:690e6.
[13] Rayegan R, Tao YX. A procedure to select working fluids for Solar Organic [38] NIST. NIST standard reference database 23. Reference fluid thermodynamic
Rankine Cycles (ORCs). Renew Energy 2011;36(2):659e70. and transport properties-REFPROP, version 80. Gaithersburg. 2007.
[14] Yu HS, Feng X, Wang YF. A new pinch based method for simultaneous se- [39] Kotas TJ. The exergy method of thermal plant analysis. first ed. Great Britain:
lection of working fluid and operating conditions in an ORC (Organic Rankine Butterworths; 1985.
Cycle) recovering waste heat. Energy 2015;90:36e46. [40] Chagnon-Lessard N, Mathieu-Potvin F, Gosselin L. Geothermal power plants
[15] Vaja I, Gambarotta A. Internal combustion engine (ICE) bottoming with with maximized specific power output: optimal working fluid and operating
organic Rankine cycles (ORCs). Energy 2010;35(2):1084e93. conditions of subcritical and transcritical Organic Rankine Cycles. Geo-
[16] He C, Liu C, Gao H, Xie H, Li Y, Wu S, et al. The optimal evaporation tem- thermics 2016;64:111e24.
perature and working fluids for subcritical organic Rankine cycle. Energy [41] Walraven D, Laenen B, D’haeseleer W. Comparison of thermodynamic cycles
2012;38(1):136e43. for power production from low-temperature geothermal heat sources. Energy
[17] Zhao L, Bao J. Thermodynamic analysis of organic Rankine cycle using zeo- Convers Manag 2013;66:220e33.
tropic mixtures. Appl Energy 2014;130:748e56. [42] ANSI/ASHRAE. ANSI/ASHRAE Standard 34e2013. Designation and safety
[18] Ayachi F, Boulawz Ksayer E, Zoughaib A, Neveu P. ORC optimization for me- classification of refrigerants. USA: Safety Group Classifications; 2013.
dium grade heat recovery. Energy 2014;68:47e56. [43] Calm JM, Hourahan GC. Physical, safety, and environmental data for current
[19] Tchanche BF, Papadakis G, Lambrinos G, Frangoudakis A. Fluid selection for a and alternative refrigerants. In: The 23rd International Congress of Refriger-
low-temperature solar organic Rankine cycle. Appl Therm Eng ation. Prague, Czech Republic; 2011.
2009;29(11e12):2468e76. [44] Turton R, Bailie RC, Whiting WB, Shaeiwitz JA. Analysis, synthesis, and design
[20] Andreasen JG, Larsen U, Knudsen T, Pierobon L, Haglind F. Selection and of chemical processes. third ed. Upper Saddle River, N.J: Prentice Hall; 2009.
optimization of pure and mixed working fluids for low grade heat utilization [45] Lozowski D. Economic indicators. Chemical engineering. USA: Access Intelli-
using organic Rankine cycles. Energy 2014;73:204e13. gence; 2014. p. 72.
[21] Yang M-H, Yeh R-H. Economic performances optimization of the transcritical [46] Hewitt GF, Shires GL, Bott TR. Process heat transfer. Boca Raton, FL: CRC Press;
Rankine cycle systems in geothermal application. Energy Convers Manag 1994.
2015;95:20e31. [47] Drescher U, Brüggemann D. Fluid selection for the Organic Rankine Cycle
[22] Braimakis K, Preissinger M, Bruggemann D, Karellas S, Panopoulos K. Low (ORC) in biomass power and heat plants. Appl Therm Eng 2007;27(1):223e8.