Energy Conversion and Management: X 12 (2021) 100123

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Energy Conversion and Management: X

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Performance analysis for binary mixtures based on R245fa using in high

temperature heat pumps
Chang Xu b, Hua Yang a, Xiaohui Yu a, *, Hongting Ma b, Mo Chen b, Mingchang Yang b
a
Tianjin Key Laboratory of Clean Energy and Pollution Control, School of Energy and Environment Engineering, Hebei University of Technology, Tianjin 300401, PR
China
b
School of Environmental Science and Engineering, Tianjin University, Tianjin 300072, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: As a reliable waste heat recovery device, the high-temperature heat pump (HTHP) is increasingly used in in­
High temperature heat pump dustrial enterprises. The selection of refrigerant is one of the most important factors to determine the safe,
Binary mixture reliability and economic operation of the HTHP. Starting from this perspective, a simple new method based on
Performance comparison
the characteristics of the extrema of volumetric heat capacity and coefficient of performance was developed to
Exergoeconomic analysis
obtain the appropriate composition of the binary mixtures. Then, the working fluids including four binary
mixtures with appropriate composition and R245fa were investigated experimentally in different high-
temperature conditions. The heating temperature of the HTHP system is 80–100 ◦ C and the temperature lift
between the heat source and the heat sink was kept at 35 ◦ C in the experiment. Experimental results showed that
the working fluids HG-1 had good COP due to the low power consumption of compressor, when the heat sink
temperature was 100 ◦ C, the COP of HG-1was higher than 4.9, and the comprehensive performance was better
than that of R245fa. In addition, the exergoeconomic performance of different working fluids was calculated
based on experimental data. The results showed that HG-1 has the lowest exergy destruction and extra cost rate
of overall system compared with other binary mixtures, which were 909.5 W and 0.117 $/hr, respectively at the
heat output temperature of 100 ◦ C. All the results demonstrated the feasibility and reliability of HG-1 as a new
high-temperature refrigerant to produce heat at the temperature of 80–100 ◦ C.

Moreover, the HTHP producing heat at the temperature of 60–140 ◦ C is

also widely needed in many industrial processes including paper, food
Introduction
processing, pharmaceutical, chemical and other industrial fields [5].
Therefore, it is expected to play a significant role in recovering the waste
With the development of science and technology and the improve­
heat and improving energy efficiency in industrial processes and has
ment of living standards, the energy demand is also increasing all over
attracted more and more attention.
the world. Due to the extensive use of fossil fuels, the environmental
The selection of refrigerant is a key element to determine the effi­
pollution and greenhouse benefits have threatened the future survival of
ciency, performance and safe operation of the HTHP. Hence, one area of
mankind. Environmental protection and energy saving have been paid
research emphasis on the HTHP is to seek suitable high temperature
more and more attention by various industries [1]. According to the “BP
refrigerants. HTHP’s refrigerants research mainly covers natural re­
Energy Outlook 2019 edition”, the energy demand will increase by one-
frigerants (such as R744 [6], R717 [7], R718 [8], R600 [9]) and syn­
third in the next two decades, and three-quarters of the increase will
thetic refrigerants such as HCFC (such as R142b [10]), HFC (such as
come from industry and construction [2]. High-temperature heat pump
R245fa [11], R161 [12]), HFO (such as R1233zd(E) [13], R1224yd(Z)
(HTHP) is an effective way to save energy and improve energy efficiency
[14]) and their mixtures. Many researchers have studied the application
by recovering waste heat and producing heat at high-level temperature
potential of different refrigerants by evaluating their safety, economy,
in the industrial processes [3]. As a reliable waste heat utilization
environmental and thermodynamic parameters. Based on the analysis of
technology, HTHP has an interesting perspective for application in many
some basic or derived heat pump parameters, Devotta et al. [15],
industrial processes. The temperature of industrial waste heat is about
selected some working substances from about 30 kinds of
30–70 ◦ C, which is very suitable for the heat source of HTHP [4].

* Corresponding author.
E-mail address: 2018133@hebut.edu.cn (X. Yu).

https://doi.org/10.1016/j.ecmx.2021.100123
Received 10 August 2021; Received in revised form 9 October 2021; Accepted 21 October 2021
Available online 26 October 2021
2590-1745/© 2021 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
C. Xu et al. Energy Conversion and Management: X 12 (2021) 100123

Nomenclature τ annual operating time (hr)

η efficiency
A weight or area (m2) α, β, γ parameter
C balance coefficient
Subscripts
Ċ cost rate ($/s)
1,2,3,… state point
c average cost per unit exergy ($/kJ)
ci capital investment
CEPCI chemical equipment cost index
com compressor
COP coefficient of performance
con condenser
CRF capital recovery factor
d destruction
Ė exergy flow (kW)
e entrance
e specific exergy (kJ/kg)
eev electric expansion valve
f exergoeconomic factor
ele electric
h enthalpy (kJ/kg)
eva evaporator
HC heat capacity (kW)
exc exchanger
HTHP high temperature heat pump
f fuel
k total amount
i interest
m/ ṁ mass flow rate (kg/s)
in inlet
ODP ozone depletion potential
k each component
Q heat (kW)
l leave or loss
r relative cost difference
max maximum
RPI relative performance index
n different composition or total operating time (year)
s entropy (kJ/kg-K)
om operation and maintenance
T temperature (◦ C)
ori original
ΔT temperature lift (◦ C)
out outlet
VHC volumetric heat capacity (kJ/m3)
p product
w work (kW)
R reference value
Ż levelized investment rate ($/hr) r refrigerant
Greek letters t target
ρ density (kg/m3) w water
φ maintenance factor

Fig. 2. The variations of COP and VHC with condensing temperature under
Fig. 1. The T-s diagram of theoretical heat pump cycle. different temperature lift.

hydrofluorocarbon and fluorate ether as substitutes for R114 using in
the HTHP. Bamigbetan et al. [16] proposed that R600 and R1233zd(E)
showed the highest potential for the immediate future implementation
in HTHPs. In addition to the study of pure refrigerant, the research on
mixed refrigerants has also become active. Yu et al. [17] proposed a
binary near-azeotropic mixture named BY- 4 which was suitable for
single-stage HTHPs. Zhang et al. [18] tested a mixture named BY-5 using
in HTHP and the COP of the system is 2.2 when the inlet and outlet water
temperature is 80 ◦ C and 130 ◦ C, respectively. Deng et al. [19] proposed
a new high temperature heat pump refrigerant mixture named NBY-1
and NBY-1 could achieve a COP of 2.74 when the outlet water tem­
perature is 130 ◦ C at a temperature lift of 50 ◦ C. Guo et al. [20] evalu­
ated a modified and potential zeotropic mixture recuperative heat pump
cycle. It can be drawn that the operating pressure and zeotropic mixture
composition greatly affect the COPs of modified subcritical recuperative
heat pump. Jahar et al. [21] considered that R744/R600a may be the
best alternative refrigerant to R114 due to superior COP and eliminating
the requirement of extremely high side pressure of R744 systems. In

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C. Xu et al.
Fig. 3. The energy flow diagram of simplified high-temperature heat pump
system model.
Table 1
The exergy cost equation of main components of HTHP.
Name Exergy cost equation Auxiliary term
Evaporator c1 Ė1 + c6 Ė6 + Żeva = c5 Ė5 + c2 Ė2 c5 = c6 = cwaste
Compressor c2 Ė2 + c7 Ė7 + Żcom = c3 Ė3 c7 = cele
Condenser c3 Ė3 + c9 Ė9 + Żcon = c4 Ė4 + c8 Ė8 c9 = c8
EEV c4 Ė4 + Żeev = c1 Ė1 / azeotropic mixture. The bubble point is set as the temperature
short, refrigerant is an important research content, especially for the
HTHP. However, to date, researchers have not found an ideal refrigerant
that can satisfy all the requirements including thermal suitability,
environmental compatibility, safety, efficiency, availability [22–24].
Therefore, developing new high-temperature refrigerants with good
performance are significant to HTHP.
R245fa is widely used in the HTHP field as a kind of environment
friendly and good performance refrigerant. However, with the growth of
demand and the imperfection of R245fa like low volumetric heat ca­
pacity, worldwide researchers have make great effort to find new re­
frigerants with better performance than R245fa to provide a variety of
choices and meet the different needs. At present, some researches have
been done to find some superior alternatives. Carlos et al. [25] proposed
that R1233zd(E) and R1224yd(Z) can be appropriate alternatives for the
R245fa replacement because of the improvement of COP. Li et al. [26]
tested the refrigerant BY3A/R245fa, BY3B/R245fa in a high tempera­
ture water source cascade heat pump with heat temperature in the range
100–140 ◦ C, but a suitable refrigerant is still been explored. Since
R245fa has the advantages of high COP, non-flammable, ODP = 0, and
good thermal conductivity, etc. when used in high-temperature heat
pumps, we decided to consider it as one of the components of our binary
mixtures. Some binary mixtures have been selected by theoretical
calculation and investigated by the HTHP test bench in our work to find
working fluids suitable for HTHP with a heat output range of 80–100 ◦ C.
The main work of this paper is to propose a simple method to obtain
the suitable components and compositions of the binary mixed working
fluids. Subsequently, the cycle performance of the selected mixed
working fluids is calculated and analyzed for its suitability for HTHP.
Then a single-stage HTHP test bench was designed and built to estimate
the practical performance of the some proposed working fluids. Exper­
imental investigation was carried out at temperature level of 45–65 ◦ C
on evaporator and 80–100 ◦ C on condenser. Finally the exergoeconomic
performance of four binary mixed working fluids were compared and
analyzed based on the experimental data. Thus, this paper is structured
as follows: the details of the performance calculation method and the
3
Energy Conversion and Management: X 12 (2021) 100123
working fluid screening plan are presented in section 2. Section 3
introduced the experimental system. The results of theoretical calcula­
tion and experimental investigation were discussed and analyzed in the
section 4. Conclusions are summarized in the last section.
Methods
Thermodynamic analysis
Fig. 1 is a heat pump theoretical cycle T-s (Temperature-entropy)
diagram of R245fa as a template, which includes the following main
processes: the evaporation process of working fluid (6–1), compression
process (1–2), condensation process (2–5) ,and throttling process (5–6).
In order to simplify the theoretical calculation, the following assump­
tions are made as follows.
All components of the system are operated under steady-states and
steady- flow conditions.
The temperature loss and pressure loss of the working fluid during
circulation are ignored.
The changes in kinetic energy and potential energy of the working
fluid are ignored.
In the theoretical cycle calculation, the degree of superheating is set
to 5 ◦ C and the degree of subcooling is 0 ◦ C. The isentropic efficiency
of compressor is assumed to be 75%. The heat transfer efficiency of
the heat exchanger is assumed to be 100%.
There is temperature slip during the phase change of the non-
reference point, which means that the evaporation temperature of
the mixed working fluid is assumed to be equal to T7, the condensing
temperature is equal to T3. The migration phenomenon of working
fluid components is not considered.
According to the first law of thermodynamic, the following energy
equation can be obtained.
High-temperature and high-pressure refrigerant vapor exchanges
heat with medium water in the condenser. The HC (heat capacity) can be
calculated as follows:
HC = mr (h2 − h4 ) = mhw Cp,hw (Tcon,out − Tcon,in ) (1)
The compressor provides power for the working fluid cycle, and its
theoretical power consumption is calculated as follows:
wcom = mr (h2 − h1 ) (2)
The heat capacity of the working fluid vapor per unit volume can be
reflected by the VHC (volumetric heat capacity). Under the same heat
capacity demand, the larger this parameter, the smaller the size of the
compressor. The parameter VHC can be calculated as follows:
h2 − h4
VHC = = (h2 − h4 )ρ1 (3)
ν1
The continuous operating efficiency of HTHP is related to the coef­
ficient of performance (COP), and the calculation formula is as follows:
HC h2 − h4
COP = = (4)
wcom h2 − h1
Working fluid screening plan
As the carrier and transporter of heat energy in high-temperature
heat pumps, the working fluid has an important influence on the sta­
bility and efficiency of this thermodynamic system. The selection of
working fluid should consider not only the thermodynamic perfor­
mance, but also the environmental and safety performance. In addition,
the respect of cost, source and related supporting etc. also need to be
considered. There have been many studies involving the selection basis
C. Xu et al. Energy Conversion and Management: X 12 (2021) 100123

Fig. 4. Schematic diagram of the HTHP test bench.

of high-temperature heat pump working fluids [1,27,39], so it won’t go discharge temperature/pressure, COP and VHC of different working
into details here. fluids are calculated, then the results are compared and suitable com­
According to the source, it can be divided into natural working fluid ponents are selected.
and synthetic working fluid. Natural working fluid usually has the ad­ After determining the component of the mixtures, it is necessary to
vantages of easy access, low price, and good environmental perfor­ find out the mixture composition which also has vital impact on the
mance, but shortcomings are safety problems such as toxicity and thermodynamic performance. This paper try to propose a parameter
flammability [28]. Synthetic working fluids usually have superior RPI, the RPI comprehensively reflects the closeness of COP and VHC to
thermodynamic properties and strong safety, but some of them are their extreme values. The smaller the value of RPI, the shorter the gap
prone to environmental problems [29]. After determining that one of the between the two indicators and their extreme values, the better the
binary mixture components is R245fa, the other component will be overall performance. Thereby the performance of binary mixtures with
selected from several common high-temperature heat pump pure different compositions can be compared, and it can be described as
working fluids, including 8 kinds of synthetic working fluids and 2 kinds follows:
of natural working fluids.
COPn,max − COPn VHCn,max − VHCn
Then the theoretical performance of R245fa and other 10 kinds of RPI n = A1 C + A2 (5)
COPn,max VHCn,max
pure working fluids were calculated by using REFPROP 9.1 [30]. The
temperature difference between the heat source and heat sink is 35 ◦ C. ∑k VHCn,max − VHCn
n=1 ( )
Considering that the temperature lift between the evaporation and C = ∑k
VHCn,max
(6)
condensing temperature is greater than that of the heat source and the
COPn,max − COPn
n=1 ( COPn,max
)
heat sink, the temperature lift of evaporation and condensing is set to
40 ◦ C. By changing the condensing temperature, the compressor where n is the different composition of the mixture, for example, R245fa

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C. Xu et al. Energy Conversion and Management: X 12 (2021) 100123

Table 2 were analyzed through the exergoeconomic method, the source of large
The main equipment parameters of the HTHP test bench. exergy destruction is found from the component level, and the perfor­
Equipment Type Specification mance variation in the exergy cost when using different binary mixtures
is compared. The main contents of the method are as follows:
Evaporator EB12P3832 double-pipe heat exchanger
Steel tube: Φ38 × 2 × 6000 mm The cost rate of exergy is related to each exergy flow, it can be
corrugated pipe: Φ32 × 0.8 × 6000 expressed as:
mm
Condenser CB12P3832 double-pipe heat exchanger Ċ = cĖ = c(ṁe) (7)
Steel tube: Φ42 × 2 × 5000 mm
corrugated pipe: Φ36 × 0.8 × 5200 The specific physical exergy of each component can be expressed as:
mm
Electronic expansion DPF(Q01)2.4 Diameter: 2.4 mm
e = h − h0 − T0 (s − s0 ) (8)
valve
Scroll compressor HRH049U4LP6 Rated power: 4.04 kW where the 0 represents the reference state which is considered as 298.15
Nominal refrigeration capacity: K and 101.325 kPa.
12.11 kW The sum of all cost rates related to exergy leaving the system is equal
Capacity: 8.24 m3/h
to the sum of all cost rates entering the system plus the cost incurred by
Water pump (heat source PUM200 Rated flow: 2.5 m3/s;
side) Pump head: 12 m; component investment. The exergy cost equation of the k-th component
Power: 0.25 kW. can be expressed as follows:
Water pump (heat sink PUM200L Rated flow: 2.5 m3/s; ∑ ∑
side) Pump head: 15 m; cl,k Ėl,k = ce,k Ėe,k + Ż k (9)
Power: 0.37 kW.
Water tank FX304 Volume: 1 m3 The component investment includes capital investment cost rate Żci
Material: 304 stainless steel
and operation and maintenance investment cost rate Żom . After time
Fan coil MDV-D71T2 Rated heat exchange capacity:
7100 W averaging treatment, the investment cost rate of a equipment can be
Circulating air volume: 1120 m3/h calculated as fallows [32]:
(1 + φ)Zci,k CRF
Ż k = Ż ci,k + Ż om,k = (10)
τyear
Table 3
The information of measuring instruments. where φ is the ratio of annual operation and maintenance investment to
Name Type Accuracy grade
the capital investment, which is 0.05; τyear is the annual operating time
of the equipment, which is 8000 h; CRF (capital recovery factor) is the
Digital power meter RK9900N ±0.5% FS
Turbine flow meter LWY-25 ±1.0 L/s
investment recovery coefficient based on compound interest, which can
Pressure gauge YTZ-150 ±1.5% FS be calculated as follows:
Resistance Temperature Detector PT1000 ±(0.15 + 0.002*|t|)
Electronic scale BBA231-3A15A II i(1 + i)n
CRF = (11)
(1 + i)n − 1

= 10 wt%, 20 wt%, … , 90 wt%; A1, A2 represent the weight of COP and where n is the total operating years of the equipment, which is set as10
VHC respectively, which means the importance of COP and VHC in a years; i is the interest rate, which is 15%.
system, and A1 = A2 = 0.5 in this paper means their effect are equal; C is The capital investment of each equipment in the HTHP system can be
the balance coefficient, since the relative difference of COP to its estimated using the following empirical formula [33]:
extreme value is much smaller than that of VHC, it is expanded by C
A
times so that the two terms can be at the same level of influence; k is the Zexc = ZR,exc ( )α (12)
AR
total amount of mixture composition.
The background of RPI is based on the theoretical performance
Ẇc β 1 − ηc γ
calculation results of the working fluids, which can be seen that the COP Zcom = ZR,com ( )( ) (13)
Ẇ R,c ηc
and VHC of different mixtures will have only one global extrema during
one condition when the temperature lift ΔT is fixed. Taking the working
where Zexc is the cost of the heat exchanger and Zcom is the cost of the
fluid R245fa(70%)/R600 as an example, which can be shown from
compressor; R represents the reference value, which ZR,exc is 8024 $ and
Fig. 2. As the condensation temperature increases, different temperature
ZR,com is 2620 $ , AR is 100 m2, ẆR,c is 10 kW; ηc is the efficiency of
lift will correspond to different variation in COP and VHC, but there is
compressor, which is considered as 0.85; The parameter α, β and γ are
always a unique global extrema of each indicator. Then, the perfor­
0.6, 0.87 and 1.0, respectively[34]; The cost of the EEV is relatively
mance of a certain working fluid close to its optimal solution can be
small and the investment can be ignored [35–37].
obtained under different working conditions. In addition, it is worth
The relevant recommended value from formula (12) and (13) comes
noting that the temperature lift can affect the extreme point of COP, but
from the year 2000, and CEPCI (chemical equipment cost index) is
do not affect the extreme point of VHC.
needed to convert the cost price of the reference year into the cost price
of the target year, which can be described as follows:
Exergoeconomic analysis
CEPCI t
Zt = Zori (14)
Exergoeconomic analysis, which includes exergy analysis and eco­ CEPCI ori
nomic principles, can provide information that cannot be obtained
In summary, referring to the energy flow diagram of the simplified
through traditional energy analysis method during system design or
HTHP shown in Fig. 3, the exergy cost equations of several equipments
operation [31]. This type of information is very important for a cost-
are listed in Table 1, the costs of waste heat and the input electric power
effective system, because it is often need to know the cost sources of
are set as 15.24 $/GJ and 32 $/GJ, respectively [38]. In addition, the
inefficient part in a system, then the economic performance of the sys­
exergy destruction and some exergy economic parameters such as the
tem can be improved specifically.
exergoeconomic factor f, cost rate of exergy destruction Ċd the relative
In this paper, the experimental results of different working fluids

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Fig. 5. The variation of (a) condensing pressure, (b) discharge temperature, (c) COP, (d) VHC with condensing temperature for the 11 pure working fluids.

cost difference r, can be calculated as follows: sight glasses and valves) together with the main equipment constitute
∑ ∑ the whole HTHP system. The hot water serving as heat source is supplied
Ėd = Ėin − Ėout + ΔĖQ,W (15) by a an automatic electric heat water tank with the full capacity of 15
kW. The inlet water temperature on the evaporator is controlled by a PID
Ċd,k = cf ,k Ėd,k (16) control system connected with an electric heater and the flow rate is
controlled by slide valves in the water loop of heat source (blue line).
fk =
Ż k
(17) The heat sink side (red line) of the system uses a fan-coil unit to
Ż k + cf ,k (Ėd,k + Ėl,k ) discharge heat into environment to maintain the heat balance of the
system. The water flow rate is controlled by slide valves, too. The main
cp,k − cf ,k
rk = (18) equipment parameters of HTHP system are listed in Table 2.
cf ,k Parameters measured in this experiment include temperature, pres­
sure, flow rate, electric power. Table 3 indicates the detailed informa­
where d represents the exergy destruction, f represents fuel, p represents
tion about the temperature sensor, pressure sensor and flow-meter. The
product.
data were recorded by an Aglient-34970A type data acquisition. Then,
gathered data were transferred to a personal computer through a RJ45
Experimental system description
transmission interface.

The HTHP system adopted in this study is shown in Fig. 4. The main
Results and discussion
equipment of the system is an evaporator, a scroll compressor, a
condenser, an electronic expansion valve. A vapor–liquid separator is
Results of working fluids selection
installed between the evaporator and the compressor to prevent the
refrigerant liquid entering the compressor and causing liquid hammer.
Firstly, the theoretical cycle performance of R245fa and 10 pure
Dry filter and refrigerant receiver are equipped between the electronic
working fluids are calculated, and the temperature difference between
expansion valve and the condenser. Some other accessories (such as
evaporation and condensation is set to 40 ◦ C. From the condensing

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temperature of 55 ◦ C to the respective critical temperature, some main

parameters are obtained and shown in Fig. 5.
Fig. 5(a) reflects the variation of condensing pressure with
condensing temperature. For working fluid with a relatively low critical
temperature, such as R161, R152a, R1234ze(E) and R227ea, when the
condensing temperature is 100 ◦ C the condensing pressure reaches
4.815 MPa, 3.505 MPa, 3.026 MPa, 2.822 MPa , respectively. These
working fluids are susceptible to pressure limitation. R245fa has a
relatively low condensing pressure, which is 1.265 MPa at a condensing
temperature of 100 ◦ C. The working fluids with lower condensing
pressure are R1233zd(E) and R365mfc. The condensing pressure is
average 82.6% and 46.1% of R245fa in the condensing temperature
range of 85–105 ◦ C, the two low-pressure working fluids have the po­
tential for lower compressor power consumption.
The compressor discharge temperature of the working fluid is closely
related to the slope (dt/ds) of the saturated vapor line in the T-s diagram.
According to different slopes, heat pump working fluids can be divided
into: dry working fluid (dt/ds < 0), neutral working fluid (dt/ds ≈ 0)
and wet working fluid (dt/ds > 0). The wet working fluid refers to the
working fluid that may enter the vapor–liquid zone during the isentropic
compression process. , The wet compression usually does not occur for
dry working fluid such as R161 and R152a . Therefore, the 5 ◦ C super­
heating uniformly adopted will increase their discharge temperature,
which can be seen from Fig. 5(b). Neutral working fluids , like R142b
and R1234ze(E), the discharge temperature is about 4.8 ◦ C and 5.8 ◦ C
higher than the condensing temperature respectively at the condensing
temperature range of 85 ~ 105 ◦ C. The rest of the working fluid belongs
to the wet working fluid and the discharge temperature is close to the
condensing temperature.
The COP and VHC usually show a negative correlation and it can be
seen from Fig. 5(c) and (d). This is because when the saturated vapor
pressure of some kinds of working fluids is relatively high (such as R161
and R152a), it will make the compressor suction vapor density larger
and lead to the higher VHC. At the same time, this kind of working fluids
usually correspond to higher compressor power consumption and will
cause the COP to decline, vice versa for low-pressure working fluids. It is
difficult for the two parameters to meet a high level at the same time,
instead we need a trade-off between them. In the condensing tempera­
ture range of 85 ~ 105 ◦ C, R227ea has low COP and VHC, which is not
suitable for the condition. Although R365mfc has a high COP, its VHC is
Fig. 6. The variation of RPI of different binary mixtures with the mass fraction too low, which restricts the selection of compressors and is therefore
of R245fa under the condensing temperature at (a) 85 ◦ C and (b) 105 ◦ C. abandoned. The VHC of R1234ze(E) is relatively high , but the COP,
condensing pressure and discharge temperature are not good enough, so
R1234ze(E) is also excluded. The remaining 7 kinds of working fluids
Table 4 become candidates for another component and enter the next step.
The appropriate composition of different binary mixtures and some related The relationship between the RPI and different composition is shown
properties. in Fig. 6. The working conditions corresponding to the upper (105 ◦ C)
and lower (85 ◦ C) temperature limits are selected as references to
Substance Mass Critical Critical Type ODP
name fraction of pressure temperature determine the appropriate composition of binary mixtures. RPI is a
R245fa (MPa) (℃) parameter under the common influence of COP and VHC. Generally, the
(%) smaller the value is, the better the overall performance of the working
R245fa/ 50 3.5819 154.95 Near- 0 fluid. As shown in Fig. 6, the optimal composition of R245fa/R161 at the
R1233zd azeotropic condensation temperature of 85 ◦ C is R245fa = 60 wt%, and the optimal
(E) composition at the condensation temperature of 105 ◦ C is R245fa =
R245fa/ 70 3.8227 148.31 Non-
40wt.%. Considering that a higher ratio of R161 will make the
<0.043
R142b azeotropic
R245fa/ 60 4.2781 131.42 0 condensing pressure higher, so the optimal composition is determined to
R152a be R245fa(60%)/R161. Another example is R245fa/R600, the RPI is
R245fa/ 60 4.8779 125.47 0 high in the middle and low on both sides. The composition R245fa =
R161
20 30wt.% and R245fa = 70wt.% may be better. Considering the flam­
R245fa/ 60 3.5072 142.30 0
R236fa
mability of R600, the appropriate composition is determined as R245fa
R245fa/ 70 3.5573 132.74 0 (70%)/R600. After referring to the RPI and considering some other as­
R600 pects, the appropriate components of the different binary mixtures were
R245fa/ 70 3.5498 129.90 0 determined and the results are listed in Table 4.
R600a
After obtaining the appropriate composition, the cycle performance
for different mixtures is performed under the same calculation condi­
tions as pure working fluids and the results are shown in Fig. 7. After

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Fig. 7. The variation of (a) condensing pressure, (b) discharge temperature, (c) COP, (d) VHC with condensing temperature for the 7 mixed working fluids.
forming the mixture, the critical temperature range shrinks to
125–155 ◦ C, and it becomes possible for some high-pressure working
fluids (such as R161, R152a) to be used in higher temperature regions. It
can be seen from Fig. 7(a) that the mixtures containing R161 and
R1233zd(E) still have the highest and lowest condensing pressures
respectively, and the difference between the two pressures can reach to
1.64 MPa when the condensing temperature is 105 ◦ C. If the condensing
pressure is limited to 2.8 MPa [35], the corresponding limitations of the
condensing temperature will be 102 ◦ C, 112 ◦ C, 117 ◦ C, 120 ◦ C, 131 ◦ C,
132 ◦ C, 141 ◦ C, corresponding to R245fa(60%)/R161, R245fa(60%)/
R152a, R245fa(70%)/R600a, R245fa(70%)/R600, R245fa(60%)/
R236fa, R245fa(70%)/R142b, R245fa(50%)/R1233zd(E), respectively.
The variation of compressor discharge temperature with condensing
temperature is shown in Fig. 7(b). The quantity relationship is similar to
that of pure working fluid. Except for R245fa(60%)/R161 and R245fa
(60%)/R152a, the other binary mixtures are wet working fluids.
Compared with pure R161, the difference between condensing tem­
perature and discharge temperature of R245fa(60%)/R161 are reduced
about 53% on average in the condensing temperature range of 85 ~
105 ◦ C. The corresponding value of is R245fa(60%)/R152a is 37%
compared with pure R152a.
The result of COP is shown in Fig. 7(c). The working fluid with the
highest COP is R245fa(50%)/R1233zd(E), which is average 5.76 under
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Energy Conversion and Management: X 12 (2021) 100123
the condensing temperature range of 85 ◦ C–105 ◦ C. The average COP of
the remaining working fluids is 98.3%, 95.8%, 95.6%, 91.7%, 90.0%,
88.3% of R245fa(50%)/R1233zd(E), corresponding to R245fa(70%)/
R142b, R245fa(60%)/R236fa, 245fa(60%)/R152a , R245fa(60%)/
R161, R245fa(70%)/R600, R245fa(70%)/R600a, respectively. The
result of VHC is shown in Fig. 7(d). Under the condensing temperature
range of 85 ~ 105 ◦ C, the working fluid R245fa(50%)/R1233zd(E) with
the highest COP but has the lowest VHC, with only an average of 3103
kJ/m3. The VHC of remaining working fluids are 118.6%, 113.7%,
167.6%, 202.2%, 135.5%, and 138.8% of R245fa(50%)/R1233zd(E) in
the order above.
Results of experimental test
After the completing the screening of binary mixtures and the per­
formance analysis, four mixed working fluids R245fa(70%)/R142b,
R245fa(70%)/R600, R245fa(70%)/R600a, HG-1 and R245fa are inves­
tigated by the HTHP test bench. The range of heat output temperature is
80–100 ◦ C and the temperature interval is 5 ◦ C, the temperature lift is
fixed at 35 ◦ C. The degree of superheating is controlled at about 3–5 ◦ C,
and the charge amount of working fluid is about 2.2 kg. The experi­
mental results are mainly used in the thermodynamic performance
analysis in Section 4.2 and the exergoeconomic analysis in Section 4.3.
C. Xu et al.
Fig. 8. The variation of (a) temperature parameters of compressor and (b) pressure parameters of compressor with heat output temperature for R245fa and four
binary mixtures.
The parameters of compressor greatly affect the operating efficiency
and the stability of the system. Excessive discharge temperature will
carbonize the lubricating oil and affect the lubrication effect, even
damage the insulation layer of enameled wire and break the compressor.
Excessive discharge pressure will put a test on the pressure resistance of
condenser and may increase the power consumption of the compressor.
The actual operating parameters of the compressor with different
working fluids are summarized in Fig. 8. It can be seen from Fig. 8(a)
that the working fluid with the highest discharge temperature is R245fa
(70%) R142b, followed by R245fa (70%)/R600a. The two kinds of
9
Energy Conversion and Management: X 12 (2021) 100123
working fluids are higher than the heat output temperature by an
average of 9.5 ◦ C and 8.2 ◦ C, respectively. The other three kinds of
working fluids have a relatively low discharge temperature. HG-1 has
the lowest discharge temperature, which is only about 4.2 ◦ C higher
than the heat output temperature on average. R245fa (70%)/R142b has
the largest temperature difference between suction and discharge with
average value of 47.0 ◦ C. It is related to R142b being a neutral working
fluid. HG-1 has the lowest temperature difference with average value of
41.4 ◦ C, and it is mainly due to the low discharge temperature of HG-1.
According to the content shown in Fig. 8(b), descending order of the
C. Xu et al.
Fig. 9. The variation of COP with heat output temperature for R245fa and four
binary mixtures and their error bands.
Fig. 10. The variation of VHC with heat output temperature for R245fa and
four binary mixture.
discharge pressure is R245fa(70%)/R600a, R245fa(70%)/R600, R245fa
(70%)/R142b, R245fa, HG- 1. The result is consistent with the theo­
retical analysis. When the heat output temperature is 100 ◦ C, the
discharge pressure of R245fa(70%)/R600a is 2.15 MPa, and the
remaining four kinds of working fluids are 90.9%, 79.5%, 63.3% , 62.6%
of R245fa(70%)/R600a in sequence. The suction temperature of R245fa
(70%)/R600a is gradually lower than R245fa(70%)/R600 after the heat
output temperature of 85 ◦ C. This is because the pressure loss of R245fa
(70%)/R600a in the evaporator increases with the higher heat source
temperature, and the pressure loss is accompanied by the temperature
loss.
Fig. 9 shows the results of COP with the five working fluids under
different working conditions. The experimental COP and theoretical
COP are relatively close. The main difference is that the experimental
COP decreases faster with the increase of heat output temperature. This
is because the actual compressor efficiency will decrease with the in­
crease of the heat output temperature, and the compressor efficiency is
always assumed at the same in the theory. When the heat output tem­
perature is 80 ◦ C, the experimental COP in the descending order are
5.64, 5.29, 5.15, 5.02 and 4.44, corresponding to the working fluid HG-
1, R245fa(70%)/R142b, R245, R245fa(70%)/R600 and R245fa(70%)/
R600a, respectively. Compared with the theoretical value, the difference
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Energy Conversion and Management: X 12 (2021) 100123
between the two is 1.53%, 6.60%, 9.64%, 4.18%, and 13.71% at 85 ◦ C
condensing temperature, respectively. As the heat output temperature
increases to 100 ◦ C, the difference increases to 10.22%, 18.20%,
15.37%, 11.19%, and 17.24% due to changes in compressor efficiency in
the actual process.
The result of VHC is shown in Fig. 10. The VHC of R245fa(70%)/
R600a is gradually lower than R245fa(70%)/R600 starting from the
heat output temperature of 85 ◦ C. This is due to the gradual drop in the
compressor suction pressure of R245fa(70%)/R600a, which make the
density of the suction vapor decrease then cause lower VHC. The dif­
ference between theoretical VHC and experimental VHC is average
2.92%, 1.98% , 5.13%, 6.90%, 3.51% for working fluid R245fa(70%)/
R142b, R245fa(70%)/R600, R245fa(70%)/R600a, HG-1, R245fa,
respectively. The experimental results show that HG-1 has higher COP
and VHC than R245fa, low discharge temperature and pressure. So it is
considered to be a binary mixed working fluid with optimal compre­
hensive performance, which has good potential for the heat output of 80
~ 100 ◦ C.
Analysis of exergoeconomic performance
The differences in exergoeconomic performance of four kinds of bi­
nary mixtures are investigated based on the experimental data by using
the the exergoeconomic method. Fig. 11 shows the exergy destruction of
each component and overall system under different working conditions.
The exergy destruction of overall system from low to high is HG-1,
R245fa(70%)/R142b, R245fa(70%)/R600, R245fa(70%)/R600a,
which is 909.5 W, 1085.3 W, 1277.3 W, 1465.6 W, respectively, at the
100 ◦ C heat output temperature. The difference in exergy destruction of
overall system mainly comes from the compressor. R245fa(70%)/R600a
shows the highest average compressor exergy dextruction of 448.6 W,
which is related to its higher compressor discharge temperature and
pressure. While the average compressor exergy destruction of R245fa
(70%)/R600, R245fa(70%)/R142b, HG-1 is only 55.3%, 35.1%, and
31.2% of R245fa(70%)/R600a.
Figs. 12–15 show the results of the extra cost rate Ċd +Ż , the exer­
goeconomic factor f, and the relative cost difference r. The compre­
hensive exergoeconomic performance can be obtained by analyzing the
combination of the three parameters.The sum Ċd +Ż is an important
parameter to measure the cost increase of a component. Due to the same
test bench, the equipment cost rate Ż remains unchanged, the difference
is mainly in Ċd . Therefore, Ċd +Ż of the overall system for the four kinds
of working fluids is closely related to the exergy destruction. The
ascending order is HG-1, R245fa(70%)/R142b, R245fa(70%)/R600,
R245fa(70%)/R600a, and the variation of Ċd +Ż of the overall system
with the heat output temperatures and their linear fit are shown in
Fig. 13. From the perspective of components, Ċd +Ż of four kinds of
working fluids are mainly concentrated in the condenser, accounting for
43.0%–59.2% of the overall system. In addition, R245fa(70%)/R600a
has a higher extra cost rate of compressor, accounting for about 34.3% of
the overall system, which is related to its higher exergy destruction of
the compressor.
Improving equipment performance can usually reduce the cost rate
of exergy destruction, but it will increase the investment. It is often need
a trade-off between the two kinds of cost rate to find a suitable solution.
The exergoeconomic factor f represents the ratio of the cost increase that
has no connection with exergy to the total cost increase [30]. If this
value is low, it can be considered to increase the investment of equip­
ment. It can be seen from Fig. 14 that the f of evaporator is high and
condenser is lower, it is due to the higher cost rate of exergy destruction
in the condenser based on the closeness of the investment cost of the two
components. HG-1and R245fa(70%)/R142b have a higher overall sys­
tem f, with an average of 39.7% and 36.9%. And the value for R245fa
(70%)/R600 and R245fa(70%)/R600a are lower, with an average of
29.0% and 22.9%, respectively. It shows that the cost rate of exergy
C. Xu et al.
Fig. 11. The exergy destruction of the main components and overall system in HTHP for four binary mixed working fluids under different working conditions.
destruction of the latter two mixtures accounts for a larger proportion of
the total cost increase, which means that the exergy efficiency may be
lower when using in HTHP.
The variable r can express the relative increase in average cost per
unit exergy between the fuel and the product of a component [36]. It can
be seen from Fig. 15 that the r of evaporator is very high. On the one
hand, it is related to the lower setting of the average cost per unit exergy
of the low-temperature waste heat. On the other hand, it also reflects
that the evaporator has the most optimization potential among the
equipment in the HTHP under the investigation working conditions. The
range of r of evaporator for HG-1 and R245fa(70%)/R142 is about
58.6%~134.3%, while R245fa(70%)/R600 and R245fa(70%)/R600a
can reach 69.9%~225.3%. This indicates that the exergy efficiency of
the evaporator may be lower when using R245fa(70%)/R600 and
R245fa(70%)/R600a as working fluid compared with the other two. In
addition, the r of the evaporator and overall system shows a downward
trend as the temperature of the heat source increases, which also shows
that the low-temperature heat is more difficult to use by HTHP.
11
Energy Conversion and Management: X 12 (2021) 100123
Conclusion
This paper proposes a screening method for binary mixed working
fluid using in HTHPs. The theoretical and experimental performance
analysis of the selected working fluids is carried out in the range of heat
output temperature of 80 ~ 100 ◦ C. Then the exergoeconomic perfor­
mance of different working fluids was explored based on the experi­
mental data. Some main conclusions are obtained as follows:
1. The calculation results of pure working fluid show that R227ea,
R365mfc, and R1234ze(E) are not suitable to participate in the for­
mation of a binary mixture for the heat output temperature range of
80–100 ◦ C.
2. By combining the variable RPI that COP and VHC affect together, the
performance of different mixture compositions is analyzed, and 7
kinds of suitable combinations are obtained: R245fa(60%)/R161,
R245fa(60%)/R152a, R245fa(70%)/ R600a, R245fa(70%)/R600,
R245fa(60%)/R236fa, R245fa(70%)/R142b, R245fa(50%)/
R1233zd(E).
3. The experimental results show that HG-1 has a higher COP, which
can reach 4.9 under condition 65/100 ◦ C, which is related to its
C. Xu et al. Energy Conversion and Management: X 12 (2021) 100123

Fig. 12. The cost rate sum Ċd +Ż of the main components and overall system in HTHP for four binary mixed working fluids under different working conditions.

Fig. 13. The variation of overall system sum Ċd +Ż with heat output temperature and their liner fit for four binary mixed working fluids.

12
C. Xu et al. Energy Conversion and Management: X 12 (2021) 100123

Fig. 14. The exergoeconomic factor f of the main components and overall system in HTHP for four binary mixed working fluids.

Fig. 15. The relative cost difference r of the main components and overall system in HTHP for four binary mixed working fluids.

lower power consumption of compressor. It is considered to be a 4. The exergoeconomic analysis shows that when HG-1 is used for
binary mixed working fluid with optimal comprehensive perfor­ HTHP, the overall system has a lower exergy destruction and extra
mance, which has good potential for the heat output of 80 ~ 100 ◦ C. cost rate, which is 909.5 W and 0.117 $/h at a heat output temper­
ature of 100 ◦ C. At this time, the same parameters of R245fa(70%)/

13
C. Xu et al.
R600a are 1465.6 W and 0.190$/h, respectively. Therefore, HG-1
has relatively optimal exergoeconomic performance.
CRediT authorship contribution statement
Chang Xu: Writing – original draft, Investigation, Methodology,
Formal analysis. Hua Yang: Supervision. Xiaohui Yu: Writing – review
& editing, Methodology, Conceptualization. Hongting Ma: Supervision,
Funding acquisition. Mo Chen: Investigation, Formal analysis. Min­
gchang Yang: Investigation, Formal analysis.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This research was supported by Technology Innovation Guidance
Special Foundation of Tianjin [grant number 20YDTPJC00190]; the
Science and Technology Youth Top-notch Project in Hebei Colleges and
Universities [grant number BJ2021021] and the National Natural Sci­
ence Foundation of China [grant numbers 51876137].
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