Applied Thermal Engineering 94 (2016) 754–762

Contents lists available at ScienceDirect

Applied Thermal Engineering

j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / a p t h e r m e n g

Research Paper

Optimization of mixed working fluids for a novel trigeneration system

based on organic Rankine cycle installed with heat pumps
Zishen Li a, Weiyi Li a,*, Borui Xu b
a Key Laboratory of Efficient Utilization of Low and Medium Grade Energy, MOE, Tianjin University, No.92 Weijin Road, Tianjin 300072, China
b
China Aviation Planning and Construction Development Co,. LTD, Beijing 100120, China

H I G H L I G H T S

• Investigation of a novel CCHP–ORC system built-in heat pumps.

• Ejector coefficient and evaporation temperature are considered for dual variables.
• To find an optimized zeotropic mixture and component concentration to the system.
• Thermodynamic, systematic and economic assessment methodology for mixtures selected.

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

Article history: A novel combined cooling, heating and powerorganic Rankine cycle (CCHP–ORC) system installed with
Received 25 June 2015 heat pumps is presented in this paper. The CCHP–ORC system using zeotropic mixtures is first dis-
Accepted 28 October 2015 cussed, and this work is focused on selecting optimal zeotropic mixtures and determining the component
Available online 11 November 2015
concentration that gives a better performance. A system model under an idealized operating condition
was built. The heat source is geothermal water whose temperature is 95 °C, and the mass flow is 40 t/h.
Keywords:
The heat transfer fluid is heated to 45 °C for heating with the ambient temperature of −5 °C, and the re-
CCHP–ORC system
frigerating fluid is cooled to 0 °C with the ambient temperature of 35 °C. In this paper, 20 zeotropic mixtures
Heat pumps
Zeotropic mixtures were analyzed. The evaluation index net output power, heating capacity, refrigerating capacity, coeffi-
Evaluation index cient of performance (COP), economic thermal efficiency and exergy efficiency were calculated with the
Component concentration changing evaporation temperature under the condition of ejector coefficient 0.2. The ejector coefficient
Ejector coefficient and evaporation temperature had been analyzed as independent variables. The results showed that R141b/
R134a, R141b/R152a and R123/152a have a higher COP and exergy efficiency than others. By analyzing
the component concentration of the optimized three kinds of zeotropic mixtures, it can be inferred that
a mixture of dry and wet working fluids is more suitable for the system. The system gives rise to higher
energy output if zeotropic mixtures are made of a higher proportion of wet working fluid and a lower
proportion of dry working fluid.
© 2015 Published by Elsevier Ltd.

1. Introduction an important solution to solve the problem of global energy short-

Over the past quarter-century, because of the increasingly serious
problem such as shortage of global energy, climate variation and
environmental pollution, energy and environment have gradually
attracted people’s attention. Energy saving and renewable energy
have now been promoted in many parts of the world via various
measures, like incentives and legislations. The world energy demand
is expected to increase by around 40% between 2006 and 2030 [1].
To improve energy utilization efficiency, increasing the use of re-
newable energy and developing new and clean energy have become
* Corresponding author. Tel.: +86 36 0213 5402.
E-mail address: liwy@tju.edu.cn (W. Li).
age and environmental pollution.
CCHP systems may be promising to increase utilization efficien-
cy of energy. The main characteristic of this technology is that the
production of energy is dispersedly close to the consumption of
energy, and based on the principle of energy cascade utilization, it
is beneficial to meet the demand of user’s energy consumption. Most
of the studies on CHP (combined heating and power) or CCHP over
the past few decades have shown that they have enormous advan-
tages in comparison with the traditional way of energy consumption
[2–4].
The overall thermal efficiency of a conventional power plant that
produces electricity and heat separately reaches about 60% [5]. On
the other hand, the efficiency of a power plant where the waste heat
from the prime mover is utilized could reach up to 80% [5,6].

http://dx.doi.org/10.1016/j.applthermaleng.2015.10.145
1359-4311/© 2015 Published by Elsevier Ltd.
 Z. Li et al./Applied Thermal Engineering 94 (2016) 754–762 755

Table 1
Some cycle parameters of selected mixtures.

Components Component Critical Critical Initial Pressure Initial Pressure

concentration temperature pressure temperature (H-T-E) (H-T-E) temperature (L-T-E) (L-T-E)
% °C MPa °C MPa °C MPa

R245ca/R141b 50:50 190.4 4.05 84.26 0.53 −10.16 0.018

R245ca/R123 50:50 178.75 4.13 84.83 0.66 −10.01 0.024
R245ca/R142b 50:50 153.1 4.01 78.89 1.01 −21.74 0.040
R245ca/R236ea 50:50 157.96 3.78 82.35 0.85 −13.88 0.031
R141b/R123 50:50 195.39 4.03 84.78 0.52 −10.13 0.019
R141b/R142b 50:50 170.49 4.40 72.81 0.80 −25.04 0.032
R141b/R236ea 50:50 176.06 3.79 79.05 0.62 −14.74 0.023
R123/R142b 50:50 155.58 4.00 76.70 0.97 −22.141 0.041
R123/R236ea 50:50 161.42 3.51 80.85 0.75 −13.90 0.028
R142b/R236ea 50:50 137.98 3.75 84.27 1.35 −12.40 0.071
R245ca/R152a 70:30 145.97 4.29 68.56 1.07 −33.57 0.037
R245ca/R134a 50:50 132.77 4.19 61.70 1.15 −34.12 0.045
R141b/R152a 80:20 176.40 4.67 57.49 0.67 −39.88 0.025
R141b/R134a 70:30 174.61 4.93 54.15 0.70 −40.67 0.026
R123/R152a 85:15 163.25 4.10 64.06 0.76 −35.60 0.028
R123/R134a 70:30 155.82 4.40 60.22 0.87 −37.03 0.032
R142b/R152a 95:5 135.15 4.10 84.18 1.59 −10.96 0.10
R142b/R134a 85:15 131.47 4.12 82.83 1.68 −12.25 0.11
R236ea/R152a 65:35 124.88 4.02 80.05 1.74 −18.19 0.088
R236ea/R134a 55:45 188.29 3.88 78.72 1.85 −20.45 0.091

Note: Terminal temperature of low temperature evaporation is −10 °C.

“H-T-E” means high temperature evaporation, “L-T-E” means low temperature evaporation.

Trigeneration plants appear to be more efficient because of utiliz-
ing the waste heat from prime movers.
Huang et al. studied a biomass fuelled trigeneration system in-
tegrated with organic Rankine cycle, and the results showed that
for a wide range of commercial buildings, biomass trigeneration
offers an economical solution of providing power, heating and cooling
which is more environment friendly than conventional methods [7].
Al-Sulaiman et al. also got similar conclusions through the exper-
iment research of CCHP–ORC system driven by biomass [8].
Ahmadi et al. proposed a new multi-generation system based
on an ORC system; besides the CCHP structure, it also included a
proton exchange membrane electrolyzer to produce hydrogen. A
parametric study was performed to investigate the effects of several
important design parameters on the energy and exergy efficien-
cies of the system [9].
Khaliq conducted a performance analysis of an industrial waste
heat-based trigeneration system. They analyzed the system from
the aspect of exergy to calculate the source of irreversibility [10].
Al-Sulaiman made an energy and exergy analysis of a novel
trigeneration system using parabolic trough solar collectors for com-
bined cooling, heating, and power production [11]. Cardona also
carried out a research on the CCHP or/and CHP system from the per-
spective of energy management and environmental benefits, and
the results indicated that polygeneration was considered to have
a large potential for residential and commercial buildings district
network [12].
ORC refers to the traditional Rankine cycle using organic sub-
stance. The ORC has become a hot research topic in the field of
utilizing low grade thermal energy in recent years [13–16]. Zhao
investigated an ORC system using zeotropic mixtures, and the results
showed that the generator temperature, condenser temperature and
evaporator temperature have a strong effect on the cycle perfor-
mance [17,18]. Researchers also studied the ORC system with
zeotropic mixtures from the perspective of first law thermal effi-
ciency [19], exergy [20] and composition shift [21]. It was
demonstrated that the use of zeotropic mixtures leads to an effi-
ciency increase compared to the ORC system using pure fluids.
Hong replaced the heat pump compressor with an ejector and
combined heat pumps with ORC to increase energy utilization ef-
ficiency [22]. In another study, Hong has completed a variety of heat
pumps and ORC cogeneration system, and by the optimization of
working fluids, finding that R600 has highest comprehensive eval-
uation [23]. Guo et al. proposed a novel cogeneration system driven
by low-temperature geothermal sources. It consists of a low-
temperature geothermally-powered ORC subsystem, an intermediate
heat exchanger and a commercial R134a-based heat pump subsys-
tem, with main purpose of identifying appropriate fluids for a better
performance [24]. The thermodynamic properties are obtained by
the software REFPROP 8.0 [25], which was developed by the Na-
tional Institute of Standards and Technology of the United States.
Refer to previous studies on working fluids of ORC system [26–29],
selecting typical dry and wet working fluids to mix. The proper-
ties of zeotropic mixtures are listed in Table 1.
In this paper, a novel CCHP–ORC system built-in heat pumps is
put forward. It consists of an ORC subsystem using zeotropic mix-
tures and a heat pump subsystem. The system is simple and more
efficient compared to general trigeneration systems.
This work is focused on identifying an optimized zeotropic
mixture for the CCHP–ORC system and understanding the effects
on component concentration to the system. Firstly, we make a re-
search about the dual variables ejector coefficient and evaporation
temperature. And then, on the condition of the fixed ejector coef-
ficient, we select some optimized pure working fluids which give
a better performance in pure substance system, make a series of
combinations of two together and then select the best zeotropic
mixture. Thirdly, we determine the best component concentra-
tion according to the system requirements. Finally, through the
changing evaporation temperature, performance indicators using
different working fluids with different component concentrations
are compared so as to select the most suitable one. Meanwhile,
besides the CCHP, the system is also able to achieve only CCP or CHP
by adjusting the four-way valve.
2. Structure and model
2.1. System description
The schematic of the CCHP–ORC system using zeotropic mix-
tures is shown in Fig. 1. In the system, condensing process in pure
working fluids is transformed as partial condensation–gas–liquid
756 Z. Li et al./Applied Thermal Engineering 94 (2016) 754–762

condenser after separation, d-a is adiabatic throttle process, a-b is

to absorb heat to evaporate in the low temperature evaporator.
By adjusting the four-way valve, the function of the low tem-
perature evaporator and condenser swaps, so that the system can
be transformed from CCHP mode to CHP or CCP mode. The working
fluid in the low temperature evaporator is at low temperature and
low pressure and is to absorb heat so as to realize refrigeration. At
the moment, high temperature condenser can still produce heating
to realize trigeneration providing cooling, heating and electricity at
the same time.

2.2. Initial parameters setting

Table 2 depicts the initial parameters that show how the heat
source temperature and flow rate are established.

2.3. Mathematical modeling

Fig. 1. Structure of CCHP–ORC system installed with heat pumps using zeotropic Ejector coefficient of the system [30] is defined as
mixtures.
u = q y qg (1)

where q means mass flow rate of working fluids, subscripts g and

separation–recondensation process. It can make the concentra-
y represent mass flow of working fluids through the high-
tion of working fluids in subsequent high-temperature evaporation
temperature evaporator and low-temperature evaporator.
and low-temperature evaporation change so as to respectively meet
Heat input of system, also the heat absorption of high-
the demand of thermal properties of two different circulations for
temperature evaporator is defined as
improving the overall efficiency. The key components of the system
are the high temperature evaporator, injector, expander, genera- Q 1 = q g ( h5 − h4 ) (2)
tor, high temperature condenser, separator, working fluid pump, low
temperature condenser, throttle valve, low temperature evapora- where h means enthalpy of working medium, subscripts 5 and 4
tor and four-way valve, etc. represent the outlet of high-temperature evaporator and working
Under the CCHP operational mode, as shown in Fig. 2, the low fluid pump.
temperature and low pressure steam (point b, concentration III) pro- The working fluids through the expander include two parts: one
duced by low temperature evaporator is ejected by high temperature is from high-temperature evaporator, it is defined as qg, and the other
and high pressure steam (point 5, concentration II), the state of su- defined as qy is from low-temperature evaporator driven by the
perheated steam after mixing is point 1 (concentration I). The process ejector. Considering that the efficiency of the generator is ηe, the
1–2 in Fig. 1 is adiabatic expansion process in expander. Similarly, output power of the expander is defined as
point 2-e is condensation process in high temperature condenser,
e-3 and e-c are separation process of liquid working fluid (concen- We = q g (1 + u ) ( h1 − h2 )ηe (3)
tration II) and gaseous fluid (concentration III) in separator, 3–4 is
where the subscripts 1 and 2 represent inlet and outlet of the
compression process of liquid working fluid by working fluid pump,
expander.
4–5 is evaporation process in the high temperature evaporator, c-d
is condensation process of gaseous fluid in low temperature

Table 2
Initial parameters.

Initial parameters Value/type

Heat source Geothermal

Temperature of geothermal water (°C) 95
Mass flow rate of geothermal water (t/h) 40
Evaporation temperature of high-temperature evaporation (°C) 85
Pinch point temperature (°C) 5
Interval of superheating temperature (°C) 0~5
CHP-Initial condensing temperature of high-temperature 50
condenser (°C) −10
CHP-Terminal evaporating temperature of low-temperature
evaporator (°C)
CHP-Environment temperature (°C) −5
CCHP-Terminal evaporating temperature of low-temperature −5
evaporator (°C)
CCHP-Initial condensing temperature of high-temperature 50
condenser (°C)
CCHP-Initial condensing temperature of low-temperature 40
condenser (°C)
Expander efficiency-ηe (%) 75
Working medium pump efficiency-ηp (%) 68
Fig. 2. T-s diagram of CCHP–ORC system installed with heat pump using zeotropic
Ejector coefficient 0.2
mixtures. (For interpretation of the references to color in this figure, the reader is
Specific heat capacity of water-c (J/kg/K) 4200
referred to the web version of this article.)
 Z. Li et al./Applied Thermal Engineering 94 (2016) 754–762
Taking that the efficiency of the pump is ηp, the power con-
sumption of the working fluid pump is defined as
Wp = q g ( h4 − h3 ) η p (4)
where the subscripts 3 and 4 represent inlet and outlet of the
working fluid pump.
The total output power is defined as
Wnet = We − Wp (5)
For the CCHP–ORC system using zeotropic mixtures, heating ca-
pacity of the high-temperature condenser is defined as
Q h2h = q g (1 + u ) ( h2 − he ) (6)
When the system is switched to the CHP mode, heating capac-
ity of the low-temperature condenser is defined as
Q h2l = uq g ( hc − hd ) (7)
where the subscripts c and d represent inlet and outlet of the low-
temperature condenser.
Total heating capacity of the CCHP–ORC system is defined as
Q h 2 = Q h 2h + Q h 2l (8)
Refrigerating capacity of the CCHP–ORC system using zeotropic
mixtures is defined as
Q c 2 = uq g ( hb − ha ) (9)
where the subscripts a and b represent inlet and outlet of the low-
temperature evaporator.
2.4. Evaluation index
The energy utilization rate of the system can be measured by
heat utilization efficiency. In an ORC system, thermal efficiency is
generally used to represent the heat utilizing efficiency, while in
heat pumps or refrigeration system, performance coefficient is often
used to describe its thermal performance. Because the heat utiliz-
ing efficiency may be higher than 1 in the CCHP–ORC system
installed with heat pump, in this paper, the ratio of output energy
and input heat is defined as the coefficient of performance (COP)
to represent its heat utilization efficiency. COP of the CCHP–ORC can
be defined as
ηT = ( Wnet + Q c 2 + Q h 2 ) Q 1 (10)
Although COP analyses the degree of effective utilization of
thermal energy in number through the first law of thermody-
namics, it cannot indicate the differences in quality among cool-
ing, heating and electricity. As a result, we also need to use the
second law of thermodynamics to make an exergy analysis on
the system. Exergy efficiency of the CCHP–ORC can be defined
as
ηex = ( Wnet + Ec + Eh ) E1 (11)
where E 1 , E c and E h represent absorbed heat exergy in high-
temperature evaporator, cold exergy and heat exergy of the overall
system [31], respectively. They are defined as
E1 = (1 − T0 Ts ) Q 1 (12)
Ec = ( T0 Tc − 1) Q c 2 (13)
Eh = (1 − T0 Th ) Q h2h + (1 − T0 Tl ) Q h2l (14)
757
where T0 is environment temperature, Ts is the temperature of geo-
thermal water, Tc is the temperature of cold fluid, Th and Tl are the
temperature of heat transport fluids in high temperature condens-
er and low temperature condenser. In the process of heat transfer,
when fluids temperature change, the average temperature of inlet
and outlet in heat exchanger is used as the calculating temperature.
Because of the differences of economy among cooling, heat and
electricity, the economic efficiency used to evaluate the system can
be defined as
ηec = ( Wnet + α Q c 2 + β Q h 2 ) Q 1 (15)
where α represents the ratio of cooling and electricity price, and β
represents the ratio of heat and electricity price under the same mea-
surement units. Here, we assume that α = 0.8, β = 0.5 [31].
Under the refrigeration mode, we still need to measure the re-
frigeration capacity of the system. The refrigeration efficiency can
be defined as the ratio of refrigerating capacity to absorbed heat
of the system:
ηTc = Q c 2 Q 1 (16)
The above evaluation indexes of the system are all on the basis
of heat absorbed by the system, but to the heat source with a fixed
temperature and a constant mass flow rate, the heat recovery ef-
ficiency of the heat exergy (the temperature is higher than the
ambient temperature) is not evaluated. Assuming that the heat
source temperature changes in a range and within the scope of this
temperature, under the condition of that the change of specific heat
capacity can be ignored, heat recovery efficiency can be defined as
ηhs = ( Ts1 − Ts 2 ) ( Ts1 − T0 ) (17)
where s1 and s2 represent inlet and outlet of the heat source,
respectively.
3. Results and discussion
3.1. Properties of mixed working fluids
Unlike pure working fluids, the phase transition of compo-
nents of zeotropic mixtures is not uniform in the process of
evaporation and condensation. CCHP–ORC system installed with heat
pumps realizes thermal performance changes with different com-
ponents concentration and has “adaptivity” with system circulation
process. Through the method of separation after part of the zeotropic
mixtures phase changes, different circulation process has different
components concentration, the thermodynamic properties of the
zeotropic mixtures can match each cycle process well so as to further
improve the system efficiency.
In this part, based on the existing studies on systems using pure
working fluids, we choose some working fluids from the aspect of
different evaluation index and make two combinations of them. In
addition, the component concentration is also optimized so as to
make the thermal properties better meet the requirements of the
cycle.
When choosing the working fluids, first of all, we should make
sure it is dry working fluid in the expansion process, and give full
consideration to the proportion of dry and wet working fluids to
balance the output efficiency of cooling, heat and electricity. The
dry working fluids such as R245ca, R141b, R123, R142b and R236ea
are selected, and there are 10 combinations of two dry working
fluids. Furthermore, the above 5 dry working fluids separately
combine with wet working fluids R152a and R134a, and there are
also 10 combinations of dry and wet working fluids.
Some basic parameters of 20 mixed working fluids are given in
Table 1.
758 Z. Li et al./Applied Thermal Engineering 94 (2016) 754–762

Table 1 shows that under the CCHP–ORC mode, the low tem-
perature evaporation pressure of the system using vast majority of
mixed working fluids is negative pressure, and the high tempera-
ture evaporation pressure of all working fluids are less than 2 MPa.
In addition, dry and wet working fluids when mixed have a signif-
icant influence in the temperature glide than the mixtures of two
dry working fluids.

3.2. Ejector coefficient

Ejector coefficient is an important parameter for this CCHP–

ORC system installed with heat pumps. For a trigeneration system,
net output power and COP are relatively important. The ejector co-
efficient will affect other performance index. In this part of the
analysis, ejector coefficient and evaporation temperature will be con-
sidered for independent variables to analyze net output power, COP
and heat recovery efficiency of the system under CCHP mode.
Calculation model such as heat source temperature and flow rate
has been established just as shown in Table 2. In view of the influ-
ence of temperature glide, we can raise the evaporation temperature
appropriately. Making the terminal temperature of evaporation
process change within a range of 65~90 °C (minimum pinch point
temperature is 3 °C), calculation step is 0.5 °C; Ejector coefficient
is from 0 to 1, calculation step is 0.01. Under all evaporation tem-
peratures, when net output power is negative, the calculation process
stops. Using a mixture of R245fa and R134a, setting concentration
I (concentration after mixed) as a standard, R245fa and R134a have
a mass concentration of 75% and 25%, respectively.
Fig. 3 shows the effect of ejector coefficient and evaporation tem-
perature on the net output power under the CCHP mode. With the
increasing ejector coefficient, net output power keeps narrowing
down. While with the increasing evaporation temperature, the net
output power first increases and then decreases. There exists a best
evaporation temperature to maximize it. The best evaporation tem-
perature also rises as the ejector coefficient increases. When ejector
coefficient is 0, the best evaporating temperature is 75.5 °C, and the
net output power is 72.18 kW. With the increase of ejector coeffi-
cient and evaporation temperature, net output power first shows
negative when the ejector coefficient is 0.3 and evaporation tem-
perature is 65 °C. Fig. 3 shows when the ejector coefficient is 0.3 the
best evaporating temperature is 82.5 °C, corresponding to the largest
Fig. 4. Effect of ejector coefficient and evaporation temperature to the COP under
the CCHP mode. (For interpretation of the references to color in this figure, the reader
is referred to the web version of this article.)
net output power of 31.13 kW. The biggest ejector coefficient is 0.71,
and only when the evaporation temperature is higher than 91.5 °C,
can the ejector coefficient be achieved.
Fig. 4 shows the effect of ejector coefficient and evaporation tem-
perature to the COP under the CCHP mode. As shown in Fig. 4, with
the rising ejector coefficient, the COP of the system increases. And
under the condition of each fixed ejector coefficient from 0 to 0.7,
the COP increases slightly with the rising evaporation tempera-
ture. The optimal performance coefficient is 1.41, which can de
achieved when ejector coefficient and evaporation temperature both
reach their highest values.
Fig. 5 shows the trends of heat recovery efficiency with chang-
ing ejector coefficient and evaporation temperature. When the
ejector coefficient and evaporation temperature rise, the heat re-
covery efficiency decreases. Under the condition of maximum net
output power, heat recovery efficiency is 0.32, while when achieving

Fig. 3. Effect of ejector coefficient and evaporation temperature to the net output Fig. 5. Effect of ejector coefficient and evaporation temperature to the heat recov-
power under the CCHP mode. (For interpretation of the references to color in this ery efficiency under the CCHP mode. (For interpretation of the references to color
figure, the reader is referred to the web version of this article.) in this figure, the reader is referred to the web version of this article.)
 Z. Li et al./Applied Thermal Engineering 94 (2016) 754–762 759

the maximum heat recovery efficiency, the net output power is rel- R245ca/R141b
atively low, so the energy output cannot increase by reducing R245ca/R123
100 R245ca/R142b
evaporation temperature to reduce the outlet temperature of heat R245ca/R236ea
source. R141b/R123
R141b/R142b
The net output power or COP is best under the condition of 80 R141b/R236ea

Net output power/kW

ejector coefficient or/and evaporation temperature takes peak values, R123/R142b
R123/R236ea
but when the corresponding COP is high, the output energy may R142b/R236ea
60
be very low. Higher ejector coefficient or evaporation tempera- R245ca/R152a
R245ca/R134a
ture is unfavorable not only to net output power but also to cooling R141b/R152a
and heating output. When achieving the maximum heat recovery 40 R141b/R134a
R123/R152a
efficiency, the net output power is relatively low. Therefore, for a
R123/R134a
further study on the selection of system parameters, we should con- R142b/R152a
sider both the efficiency and actual output energy at the same time. 20 R142b/R134a
R236ea/R152a
R236ea/R134a
3.3. Selection of mixed working fluids 0

Considering that the heat source is geothermal water, what this 70 75 80 85 90

CCHP–ORC system aims to do is to produce more electricity and Evaporation temperature/ °C
achieve higher heat recovery efficiency. It is shown in Figs. 3 and
5 that the lower the ejector coefficient is, the higher these two eval-
(a)
uation indices are. In order to avoid the boundary conditions of R245ca/R141b
extreme factors, the ejector coefficient is defined as 0.2. Perhaps there R245ca/R123
R245ca/R142b
are different standards for different working fluids, but through the 3000 R245ca/R236ea
analysis, they have a similar trend. When we study the CCHP–ORC R141b/R123
R141b/R142b
system using specific mixed working fluids, the ejector coefficient 2500 R141b/R236ea
can be changed according to the actual demand. When the ejector Heating capacity/kW R123/R142b
R123/R236ea
coefficient is 0.2 and the terminal temperature of high tempera- 2000 R142b/R236ea
ture evaporator changes within 70 °C~90 °C, the net output power, R245ca/R152a
R245ca/R134a
heating capacity, refrigerating capacity, COP, economic efficiency and 1500 R141b/R152a
exergy efficiency of CCHP–ORC system using 20 mixed working fluids R141b/R134a
R123/R152a
are calculated. By contrast, we can choose the optimal zeotropic mix- 1000 R123/R134a
tures more properly for the system. R142b/R152a
R142b/R134a
Fig. 6(a) shows that net output power of the system using all 500 R236ea/R152a
working fluids first increases and then decreases with the increas- R236ea/R134a
ing evaporation temperature in the range of 70 °C~90 °C. There is 0
a best evaporation temperature to make the net output power
maximal. The best evaporation temperature of each mixed working 70 75 80 85 90
fluid is different, about 80 °C~85 °C. Under the CCHP mode, the Evaporation temperature/ °C
system using R141b/R134a (70:30 wt%), R123/R134a (70:30 wt%),
R141b/R152a (80:20 wt%) and R245ca/R134a (50:50 wt%) has a
(b)
higher net output power than others. Corresponding to the best evap-
R245ca/R141b
oration temperature and maximum output power respectively are 500 R245ca/R123
86 °C/97.01 kW, 85 °C/80.62 kW, 85 °C/79.30 kW and 83 °C/67.46 kW. R245ca/R142b
450 R245ca/R236ea
The main cause of this result is the changing working condition of R141b/R123
evaporation and condensation of the system at low temperature. 400 R141b/R142b
Refrigerating capacity/kW

R141b/R236ea
Fig. 6(b) shows that heating capacity of the system decreases with 350 R123/R142b
the increasing evaporation temperature from 70 °C~90 °C. The system R123/R236ea
300 R142b/R236ea
using zeotropic refrigerants R141b/R134a (70:30 wt%), R123/ R245ca/R152a
R134a (70:30 wt%), R141b/R152a (80:20 wt%) and R245ca/R134a 250 R245ca/R134a
R141b/R152a
(50:50 wt%) still has a higher heating capacity. It is mainly because 200 R141b/R134a
when the evaporation temperature increases, the mass flow of R123/R152a
150 R123/R134a
working fluids decreases. Although the enthalpy-drop through high- R142b/R152a
temperature condenser increases, it cannot compensate for the 100 R142b/R134a
R236ea/R152a
decreasing mass flow. The overall trend is to make the heating ca- 50 R236ea/R134a
pacity decrease. 0
Fig. 6(c) shows that refrigerating capacity of the system also de-
-50
creases with the increasing evaporation temperature from
70 75 80 85 90
70 °C~90 °C. The system using R123/152a (85:15 wt%), R141b/
R152a (80:20 wt%) and R141b/R134a (70:30 wt%) could provide a Evaporation temperature/ °C
larger refrigerating capacity than any other working fluid. When the (c)
ejector coefficient is constant, the mass flow through low-
temperature evaporation shrinks to make the refrigerating capacity Fig. 6. Trends of net power output (a), heating capacity (b) and refrigerating ca-
pacity (c) with the change of the evaporation temperature under the CCHP mode.
decrease. (For interpretation of the references to color in this figure, the reader is referred to
Fig. 7(a) shows that the COP using all mixed working fluids slowly the web version of this article.)
decreases with the increasing evaporation temperature under the
CCHP mode. Because of the higher high-temperature-evaporation
760 Z. Li et al./Applied Thermal Engineering 94 (2016) 754–762

R245ca/R141b conclusions, the net output power shows a nearly parabolic rela-
1.30 R245ca/R123
R245ca/R142b
tionship, but heating capacity and refrigerating capacity have a
R245ca/R236ea negative correlation with the evaporation temperature. Consider-
R141b/R123
1.25 R141b/ R142b ing the influence of the working fluids mass flow, the COP shows
R141b/R236ea the tendency of decrease. Due to the existence of heat pumps, the
R123/ R142b
R123/R236ea COP of the system is larger than 1.
1.20 R142b/R236ea
R245ca/R152a
Fig. 7(b) shows that the economic efficiency using all mixed
working fluids improves slightly with the changing evaporation tem-
COP

R245ca/R134a
R141b/ R152a
R141b/R134a perature under the CCHP mode. The system using R142b/R152a (95:5
1.15 R123/ R152a wt%) and R123/152a (85:15 wt%) has a higher economic efficien-
R123/R134a
R142b/ R152a cy than others. Considering the differences of three kinds of energy
R142b/R134a in the economy, the economic efficiency shows the same trend as
1.10 R236ea/ R152a
R236ea/R134a the COP.
Fig. 7(c) shows that the exergy efficiency using all mixed working
1.05 fluids improves with the change of the evaporation temperature
70 75 80 85 90 under the CCHP mode. Because when the evaporation tempera-
Evaporation temperature/ °C ture increases, the energy grade rises, the exergy of the energy
(a) increases so the exergy efficiency shows a gradually increasing trend.
Besides the three mixtures R141b/R134a (70:30 wt%), R141b/
R245ca/R141b
R245ca/R123 R152a (80:20 wt%) and R245ca/R134a (50:50 wt%), R123/R152a
R245ca/R142b
0.72 R245ca/R236ea
(85:15 wt%) also has a high exergy efficiency.
R141b/R123 Summarized, under the CCHP mode, the CCHP–ORC system using
R141b/ R142b
0.70 R141b/R236ea R141b/R134a (70:30 wt%), R123/134a (70:30 wt%) and R141b/
R123/ R142b R152a (80:20 wt%) produces high net output power, cooling and
Economic efficiency

R123/R236ea
0.68 R142b/R236ea heating output at the same time, and R123/152a (85:15 wt%) has
R245ca/R152a
R245ca/R134a
a better performance in the aspect of refrigeration. The above 4
R141b/ R152a working fluids also have a higher exergy efficiency than others.
0.66 R141b/R134a
R123/ R152a Although the system using R142b/R152a (95:5 wt%) has high COP
R123/R134a and economic performance coefficient, it has no obvious advan-
0.64 R142b/ R152a
R142b/R134a tage in the net output power, heating capacity and refrigerating
R236ea/ R152a capacity.
0.62 R236ea/R134a
The main cause of the above results is that the 3 zeotropic mix-
tures have a higher evaporation pressure and a lower condensing
0.60 pressure to make the COP higher. The systems using a combina-
70 75 80 85 90
tion of dry and wet working fluids all have a higher COP than two
Evaporation temperature/°C
dry working fluids. Therefore to some extent, it indicates that mix-
(b) tures of dry and wet working fluids is more suitable for this novel
R245ca/R141b CCHP–ORC system.
R245ca/R123
0.64 R245ca/R142b
R245ca/R236ea
0.62
R141b/R123
0.60 R141b/ R142b 3.4. Component concentration
0.58 R141b/R236ea
R123/ R142b
0.56 R123/R236ea In the above analysis, through the contrast of various perfor-
Exergy efficiency

0.54 R142b/R236ea mance indicators to the 20 mixed working fluids, we selected three
R245ca/R152a
0.52 R245ca/R134a zeotropic mixtures that have a better performance in a number of
0.50 R141b/ R152a indicators, including R141b/R134a (70:30 wt%), R141b/R152a (80:20
R141b/R134a
0.48 R123/ R152a wt%) and R123/152a (85:15 wt%). In this part, we will study the in-
0.46 R123/R134a
fluence of concentration on performance indicators of the system
0.44 R142b/ R152a
R142b/R134a using above zeotropic mixtures.
0.42 R236ea/ R152a
Under the condition of the ejector coefficient of 0.2 and the ter-
0.40 R236ea/R134a
minal temperature of high temperature evaporator of 85 °C, the
0.38
0.36
performance index of this system is calculated using the
abovementioned three zeotropic mixtures which have different con-
70 75 80 85 90 centrations of dry and wet working fluids. The initial concentrations
Evaporation temperature/ °C of these three mixed working fluids are shown in Table 1. We make
(c) a gradual increase in concentration of dry working fluid and a gradual
decrease in concentration of wet working fluid until the concen-
Fig. 7. Trends of COP (a), economic efficiency (b) and exergy efficiency (c) with the
tration of wet working fluid is 0. The step size is 0.025.
change of the evaporation temperature under the CCHP mode. (For interpretation
of the references to color in this figure, the reader is referred to the web version of Our main objective is that for the specific mixed working fluid,
this article.) through changing concentration, we can find the effects on net
output power, COP, exergy efficiency and so on. We should know
the best concentration that can make the system have an optimal
and higher low-temperature-evaporation, it is obvious that the performance index.
system using R142b/R152a (95:5 wt%) and R123/152a (85:15 wt%) Fig. 8(a) shows that the net output power decreases with the in-
has a higher COP than others, with the corresponding COP to be creasing component concentration of dry working fluid. The
1.25~1.27 and 1.2~1.22, respectively. Combined with the above maximum net output power is 96.90 kW to the system using
 Z. Li et al./Applied Thermal Engineering 94 (2016) 754–762 761

100 R141b/R134a, 79.30 kW to the R141b/R152a and 55.43 kW to the

R123/152a.
80 Fig. 8(b) shows that the heating capacity decreases with the in-
creasing component concentration of dry working fluid. The
Net output power/kW

maximum heating capacity is 1713.54 kW to the system using

60
R141b/R134a, 1467.32 kW to the R141b/R152a and 1297.95 kW to
the R123/152a.
40 Fig. 8(c,d) shows that the refrigerating capacity decreases with
R141b/R134a
R141b/R152a the increasing component concentration of dry working fluid, while
R123/R152a
20 the refrigeration efficiency shows different trends: the refrigera-
tion efficiency of the system using R141b/R134a will decrease with
0 the increasing component concentration of dry working fluid, but
R141b/R152a and R123/152a have the opposite trends. The
0.70 0.75 0.80 0.85 0.90 0.95 1.00 maximum refrigerating capacity of the three kinds of mixed working
Component concentration(Dry) fluids are 287.40 kW, 283.31 kW and 281.61 kW, respectively.
(a) Fig. 9(a,b) shows that COP and economic thermal efficiency almost
1800 have the same trends. In the changing range of component con-
1600 centration, the COP and economic thermal efficiency of the system
using R141b/R134a decreases with the increasing component con-
1400
centration of dry working fluid, while the systems using R141b/
Heating capacity/kW

1200 R152a and R123/152a have the opposite trends.

1000
Fig. 9(c) shows the effect of component concentration to the
exergy efficiency under the CCHP mode. As shown in the figure,
800
with the increasing component concentration of dry working fluid,
600 R141b/R134a the exergy efficiency of the system using R141b/R134a first de-
R141b/R152a
400 R123/R152a
creases, and then increases, and finally decreases, while in R141b/
R152a and R123/152a, the exergy efficiency decreases gradually. The
200
varying trend of the exergy efficiency is because we reduce the heat
0.70 0.75 0.80 0.85 0.90 0.95 1.00 exergy of low-temperature condenser and add cold exergy in the
Component concentration(Dry) calculation.
(b)
300 4. Conclusions

250 In this paper, we made a research of a novel CCHP–ORC

Refrigerating capacity/kW

system installed with heat pumps using zeotropic mixtures from

200
the perspective of the optimization of ejector coefficient and 20
zeotropic mixtures, and through the 3 optimized mixed working
150
fluids, the effects of components concentration to the system is
100
first taken into account in this paper. The following conclusions are
R141b/R134a made:
R141b/R152a
50 R123/R152a
1. The net output power or COP is best under the condition of
0 ejector coefficient or/and evaporation temperature is of extreme
0.70 0.75 0.80 0.85 0.90 0.95 1.00 value, but when the corresponding COP is high, the output energy
Component concentration(Dry)
may be very low, while when the maximum heat recovery ef-
(c) ficiency is achieved, the net output power is relatively low, so
0.30 the output energy cannot increase by reducing evaporation tem-
0.28
perature to reduce the outlet temperature of heat source. Higher
R141b/R134a
ejector coefficient or evaporation temperature is unfavorable not
0.26
R141b/R152a only to net output power but also to cooling and heating capac-
Refrigeration efficiency

0.24 R123/R152a ity output.

0.22 2. For the CCHP–ORC system using zeotropic mixtures, we can select
optimal working fluids that have high net output power, cooling
0.20
and heating capacity output at the same time, such as R141b/
0.18 R134a and R141b/R152a.
0.16 3. Under the CCHP mode, R123/152a has a better performance in
the aspect of refrigeration. It also has a higher COP and exergy
0.14
efficiency.
0.12
4. The systems using combinations of dry and wet working fluids
0.70 0.75 0.80 0.85 0.90 0.95 1.00 all have higher performance index; therefore to some extent, it
Component concentration(Dry) indicates that mixtures of dry and wet working fluids are more
(d) suitable for the system.
5 The above three kinds of zeotropic mixtures have similar trends
Fig. 8. Effect of component concentration to the net output power (a), heating ca- of net output power, heating capacity, COP and economic thermal
pacity (b), refrigerating capacity (c) and refrigeration efficiency (d) under the CCHP efficiency with changing component concentration, while their
mode.
respective exergy efficiencies are different.
762 Z. Li et al./Applied Thermal Engineering 94 (2016) 754–762

1.40 References

1.35 [1] Energy Information Administration, International Energy Outlook, USA, 2009.
R141b/R134a
R141b/R152a [2] D. Maraver, A. Sin, J. Royo, F. Sebastian, Assessment of CCHP systems based on
1.30 R123/R152a biomass combustion for small-scale applications through a review of the
technology and analysis of energy efficiency parameters, Appl. Energy 102
1.25 (2013) 1303–1313.
[3] S. Cao, A. Mohamed, A. Hasan, K. Siren, Energy matching analysis of on-site
micro-cogeneration for a single-family house with thermal and electrical
COP

1.20
tracking strategies, Energy Build. 68 (Pt A) (2014) 351–363.
[4] A. Mohamed, H. Mohamed, A. Hasan, et al., The performance of small scale
1.15 multi-generation technologies in achieving cost-optimal and zero-energy office
building solutions, Appl. Energy 152 (2015) 94–108.
1.10 [5] T. Kerr, Combined Heating and Power and Emissions Trading: Options for Policy
Makers, International Energy Agency, France, 2008.
1.05 [6] International Energy Agency, Combined heat and power: evaluating the benefits
of greater global investment, France 2008.
0.70 0.75 0.80 0.85 0.90 0.95 1.00 [7] Y. Huang, Y.D. Wang, S. Rezvani, et al., A techno-economic assessment of biomass
fuelled trigeneration system integrated with organic Rankine cycle, Appl. Therm.
Component concentration(Dry) Eng. 53 (2013) 325–331.
(a) [8] F.A. Al-Sulaiman, I. Dincer, F. Hamdullahpur, Energy and exergy analyses of a
biomass trigeneration system using an organic Rankine cycle, Energy 45 (2012)
0.80 975–985.
[9] P. Ahmadi, I. Dincer, M.A. Rosen, Development and assessment of an integrated
Economic thermal efficiency

biomass-based multi-generation energy system, Energy 56 (2013) 155–166.

0.76 R141b/R134a
[10] A. Khaliq, R. Kumar, I. Dincer, Performance analysis of an industrial waste heat
R141b/R152a
based tri-generation system, Int. J. Energy Res. 33 (2009) 737–744.
R123/R152a
[11] F.A. Al-Sulaiman, F. Hamdullahpur, I. Dincer, Performance assessment of a novel
0.72 system using parabolic trough solar collectors for combined cooling, heating
and power production, Renew. Energy 48 (2012) 161–172.
[12] E. Cardona, A. Piacentino, F. Cardona, Matching economical, energetic and
0.68 environmental benefits: an analysis for hybrid CHCP-heat pump systems, Energy
Convers. Manag. 47 (2006) 3530–3542.
[13] J. Wang, et al., Multi-objective optimization of an organic Rankine cycle (ORC)
0.64 for low grade waste heat recovery using evolutionary algorithm, Energy Convers.
Manag. 71 (2013) 146–158.
[14] M. Habka, S. Ajib, Studying effect of heating plant parameters on performances
0.60 of a geothermal-fuelled series cogeneration plant based on Organic Rankine
Cycle, Energy Convers. Manag. 78 (2014) 324–337.
[15] T.C. Hung, S.K. Wang, C.H. Kuo, B.S. Pei, K.F. Tsai, A study of organic working
0.56 fluids on system efficiency of an ORC using low-grade energy sources, Energy
0.70 0.75 0.80 0.85 0.90 0.95 1.00 35 (2010) 1403–1411.
Component concentration(Dry) [16] H.D. Madhawa Hettiarachchi, M. Golubovic, W.M. Worek, et al., Optimum design
criteria for an organic Rankine cycle using low-temperature geothermal heat
(b) sources, Energy 32 (2007) 1698–1706.
[17] X.Y. Yang, L. Zhao, H.L. Li, et al., Theoretical analysis of a combined power and
ejector refrigeration cycle using zeotropic mixture, Appl. Energy 160 (2015)
0.58 912–919.
[18] L. Zhao, J.J. Bao, Thermodynamic analysis of organic Rankine cycle using
zeotropic mixtures, Appl. Energy 130 (2014) 748–756.
0.56
[19] B.S. Dong, G.Q. Xu, Y. Cai, et al., Analysis of zeotropic mixtures used in high-
temperature organic Rankine cycle, Energy Convers. Manag. 84 (2014) 253–260.
Exergy efficiency

0.54 [20] S. Lecompte, B. Ameel, D. Ziviani, et al., Exergy analysis of zeotropic mixtures
as working fluids in organic Rankine cycles, Energy Convers. Manag. 85 (2014)
727–739.
0.52 R141b/R134a [21] L. Zhao, J.J. Bao, The influence of composition shift on organic Rankine cycle
R141b/R152a (ORC) with zeotropic mixtures, Energy Convers. Manag. 83 (2014) 203–211.
R123/R152a [22] G. Hong, X.M. Zhang, J.J. Li, Thermodynamic analysis combined cooling heat
0.50 and power-organic Rankine cycle system installed with heat pump, J. Hefei Univ.
Technol. 35 (2012) 1297–1301.
0.48 [23] G. Hong. Evaluate and optimize to combined heating and power-organic Rankine
cycle system with low grade heat source. Chongqing University. 2012.
[24] T. Guo, H.X. Wang, S.J. Zhang, Selection of working fluids for a novel low-
0.46 temperature geothermally-powered ORC based cogeneration system, Energy
0.70 0.75 0.80 0.85 0.90 0.95 1.00 Convers. Manag. 52 (2011) 2384–2491.
Component concentration(Dry) [25] E.W. Lemmon, M.L. Huber, M.O. McLinden, REFPROP version 8.0. NIST standard
reference database 23. The US Secretary of Commerce, America; 2007.
(c) [26] M.Z. Stijepovic, P. Linke, A.I. Papadopoulos, A.S. Grujic, On the role of working
fluid properties in organic Rankine cycle performance, Appl. Therm. Eng. 36
Fig. 9. Effect of component concentration to the COP (a), economic thermal effi- (2012) 406.
ciency (b) and exergy efficiency (c) under the CCHP mode. [27] J. Wang, J. Zhang, Z. Chen, Molecular entropy, thermal efficiency, and designing
of working fluids for organic Rankine cycles, Int. J. Thermophys. 33 (6) (2012)
970.
[28] Q. Liu, Y. Duan, Z. Yang, Effect of condensation temperature glide on the
performance of organic Rankine cycles with zeotropic mixture working fluids,
6 To the selected 3 optimal working fluids, from the aspect of Appl. Energy 115 (2014) 394.
[29] F. Heberle, M. Preissinger, D. Brugerman, Zeotropic mixtures as working fluids
output energy and exergy efficiency, when the component con-
in organic Rankine cycles for low-enthalpy geothermal resources, Renew. Energy
centration of dry working fluid is low and wet working fluid is 37 (1) (2012) 364.
high, the system has good performance, while from the aspect [30] J. Godefroy, R. Boukhanouf, S. Riffat, Design, testing and mathematical modelling
of COP and economic thermal efficiency, we should choose of a small-scale CHP and cooling system (small CHP-ejector trigeneration), Appl.
Therm. Eng. 27 (2007) 68–77.
optimal component concentration of different zeotropic mix- [31] C. Yang, Z.L. Yang, R.X. Cai, Comparison of CCHP efficiencies based on off-design
tures to meet the actual requirement. characteristics, Proc. CSEE 28 (2008) 8–13.