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Performance of cascade cycles working with blends

of CO
2
D natural refrigerants
Giovanni Di Nicola
a,
*, Fabio Polonara
a
, Roman Stryjek
b
, Alessia Arteconi
c
a
Dipartimento di Energetica, Universita` Politecnica delle Marche, 60100 Ancona, Italy
b
Institute of Physical Chemistry, Polish Academy of Sciences, 01-224 Warsaw, Poland
c
Universita` degli Studi e-Campus, Via Isimbardi 10, 22060 Novedrate (CO), Italy
a r t i c l e i n f o
Article history:
Received 9 July 2010
Received in revised form
30 March 2011
Accepted 2 May 2011
Available online 11 May 2011
Keywords:
Carbon dioxide
Hydrocarbon
Cascade system
Low temperature
Modelling
Refrigerating system
a b s t r a c t
In this paper, an analysis on the performance of a cascade refrigeration cycle operated with
blends of carbon dioxide (or R744) plus hydrocarbons (ethane or R170, propane or R290,
ethylene or R1150, propylene or R1270) and dimethyl ether (or RE170) as the low-temper-
ature working uid was carried out. The properties of the investigated blends were used to
simulate the behaviour of a cascade cycle using ammonia (or R717) as the high-tempera-
ture-circuit working uid.
Theaimof this workwas tostudythepossibility of using carbondioxide mixtures inthose
applications where temperatures below its triple point (216.59 K) are needed. The analysis
was carried out by developing a software based on the CarnahaneStarlingeDeSantis (CSD)
Equation of State (EoS) using binary interaction parameters derived from the experimental
data in the literature.
Results show that adding R744 to HCs and dimethyl ether reduces the cycle perfor-
mance, even if acceptable values are always achieved for the COP. Main attractive of the
R744 natural refrigerant blends is connected with their GWP, ODP and ammability
properties lower than those of pure uids.
2011 Elsevier Ltd and IIR. All rights reserved.
Performance des cycles en cascade utilisant des me langes de
CO
2
et dautres frigorige` nes naturels
Mots cles : Dioxyde de carbone ; Hydrocarbure ; Syste` me a` cascade ; Basse tempe rature ; Mode lisation ; Syste` me frigorique
1. Introduction
In industrial applications, the cascade refrigeration cycle is
useful when lowtemperatures (i.e. below233.15 K) are required
(Stoecker, 1998). The conventional cascade system often relies
on R13 (chlorotriuoromethane) and R23 (triuoromethane) as
refrigerants. Due to the heavy environmental impact of these
two uids, however, several natural refrigerants, i.e. carbon
dioxide, ammonia, nitrous oxide and hydrocarbons, and their
blends have recently been considered for use in cascade
* Corresponding author. Tel.: 39 0712204277; fax: 39 0712204770.
E-mail address: g.dinicola@univpm.it (G. Di Nicola).
www. i i i r . or g
avai l abl e at www. sci encedi r ect . com
j our nal homepage: www. el sevi er . com/ l ocat e/ i j r ef r i g
i nt e r na t i o na l j our na l of r e f r i ge r a t i o n 3 4 ( 2 0 1 1 ) 1 4 3 6 e1 4 4 5
0140-7007/$ e see front matter 2011 Elsevier Ltd and IIR. All rights reserved.
doi:10.1016/j.ijrefrig.2011.05.004
refrigeration systems (Zha et al., 2002; Liu et al., 2002; Taylor,
2002; Pearson and Cable, 2003; Kruse and Ru ssmann, 2006; Lee
et al., 2006; Niu and Zhang, 2007; Getu and Bansal, 2008; Gong
et al., 2009; Bhattacharyyaa et al., 2009; Dopazo et al., 2009). In
particular, several studies evaluated ammonia as the high-
stage uid and carbon dioxide as the low-temperature stage
refrigerant (Zha et al., 2002; Liu et al., 2002; Taylor, 2002;
Pearson and Cable, 2003; Lee et al., 2006; Getu and Bansal,
2008; Bhattacharyyaa et al., 2009; Dopazo et al., 2009). In this
way, ammonia (R717) could be conned to a proper machine
room, while the safer carbon dioxide (R744) could be sent to
evaporators around the factory. The main drawback of using
carbon dioxide lies in its high pressures at normal boiling
temperature and its high melting temperature, which result in
a lower temperature limit for its use as a refrigerant. Lower
temperatures needed in some applications can be achieved by
using blends. That is why we recently (Di Nicola et al.,
2003a,b, 2005) turned our attention to R744 HFCs mixtures
as potentially suitable working uids in low-temperature
refrigeration applications. However, many of the chemicals
that show a nite value of the ODP cannot be considered as
a result of the Montreal protocol and its amendments. A
further limitation results from the Kyoto protocol and, in
Europe, from European directives imposing limitations on the
emission of greenhouse gases responsible for global warming
(GWP).
For this reason, in this paper we focused our attention on
other blends of carbon dioxide that contain hydrocarbons and
dimethyl ether, because they have a lower environmental
impact than HFCs. Blends considered are the following ones:
R744 R170 (ethane), R744 R1150 (ethylene), R744 R290
(propane), R744R1270(propylene), andR744RE170(dimethyl
ether).
System performance with these mixtures was analyzed
using a purpose-built program based on the
CarnahaneStarlingeDe Santis (CSD) Equation of State (EoS)
(De Santis et al., 1976) with the pure compound coefcients
updated in the light of the latest data in the literature.
Binary interaction parameters were derived from the VLE
data available in the literature (Poettman and Katz, 1945;
Haselden et al., 1951; Reamer et al., 1951; Akers et al., 1954;
Fredenslund and Mollerup, 1974; Gugnoni et al., 1974;
Table 1 e Properties of the investigated uids.
Fluid Melting
point (K)
Normal
boiling point (K)
Critical
temperature (K)
Critical
pressure (MPa)
Heat of fusion @
Melting point (kJ/mol)
Flammability
LFL (%)
R170 90.35 184.55 305.32 4.872 2859 3.20
R290 85.47 231.11 369.83 4.248 3524 2.30
R1150 103.99 104.00 282.34 5.041 3351 2.70
R1270 87.95 225.45 364.85 4.600 2936 2.00
RE170 131.65 248.31 400.10 5.370 4937 3.40
Nomenclature
a, b dimensional coefcients for the CSD EoS
c specic heat capacity [kJ kmol
1
K
1
]
COP coefcient of performance, dimensionless
CSD EoS CarnahaneStarlingeDeSantis Equation of State
GWP Global Warming Potential
h enthalpy [kJ kmol
1
]
HC HydroCarbon
HFC HydroFluoroCarbon
HX Heat eXchanger
K
i,j
binary interaction parameter in the CSD EoS,
dimensionless
_ m mass ow rate [kg s
1
]
ODP Ozone Depletion Potential
P pressure [kPa] or [MPa]
T temperature [K] or [

C]
R universal gas constant [kJ kmol
1
K
1
]
x composition, mole fraction of the liquid phase
y composition, mole fraction of the gas phase
X composition, weight fraction
XM ratio of mass ow rate of the low- and high-
temperature circuits in cascade systems,
dimensionless
Dh
m
enthalpy of freezing [kJ kmol
1
]
3 heat exchanger effectiveness, dimensionless
g activity coefcient, dimensionless
u acentric factor, dimensionless
subscripts or superscripts
bp at bubble point
cond condenser
evap evaporator
i,j components
in inlet
int intermediate
is isentropic
H high temperature
L low temperature
liq liquid
m at melting point
max maximum
out outlet
p at constant pressure
subcool sub-cooling
sup superheating
vap vapor
0 at zero pressure
0
low-temperature stage
i nt e r na t i ona l j o ur na l o f r e f r i g e r a t i o n 3 4 ( 2 0 1 1 ) 1 4 3 6 e1 4 4 5 1437
Hamam and Lu, 1974, 1976; Davalos et al., 1976; Ohgaki and
Katayama, 1977; Tsang and Streett, 1981; Acosta et al., 1984;
Jo nasson et al., 1995; Yucelen and Kidnay, 1999).
The investigation was conducted at xed temperatures, i.e.
(a) T
evap,L
203 K at the low-stage evaporator, and (b)
T
cond,H
313 K at the high-stage condenser. The temperature
of the low stage (203 K) is below the normal melting point of
R744 (216.59 K). The inuence of intermediate temperatures
and mixture compositions on the COP was investigated. The
mainadvantages of the blends considered were expected to be
the opportunity to use them at temperatures below the
normal melting temperatures of R744 and a drastic reduction
in the ammability risk in comparison with the use of pure
HCs and/or RE170.
All the calculations were done for the simple cycle (deno-
ted here with no HX) and for a cycle containing a suction/
liquid heat exchanger in the low stage with a heat exchanger
effectiveness (Kays and London, 1964) of 0.8 (denoted here
with HX). The model is very simple and it is used, along
with the refrigerant properties calculated with the CSD EoS,
simply to give us a trend of the situation.
2. Model for predicting blends behavior
below the R744 triple point
As pointed out above, in this paper we considered blends
containing R744 that allow to work in the low stage of
a cascade cycle at temperatures below the normal melting
temperatures of R744.
A blend containing R744 and intended for operation at
temperatures below 216.59 K must possess the two requisites:
its melting temperature has to be much lower than the R744
triple point and its temperature glide should be not too great.
These requisites are necessary in order to operate at temper-
atures as far as possible below 216.59 K, and to keep temper-
ature glides as low as possible during evaporation and
condensation and avoid fractionation. A good compromise for
the blend behavior would be a quasi-azeotropic mixture, an
azeotrope would be ideal.
Wechoseveuids (shownwiththeir properties inTable1),
as potential second components, among hydrocarbons (HCs),
also because of their ready availability for the experimental
work needed to establish the mixtures basic properties.
y (R744)
0.0 0.2 0.4 0.6 0.8 1.0
T
,

K
140
160
180
200
220
Fig. 1 e SLE for the R744 D R134a system. Black symbols
denote the experimental points while the lines denote the
Schro der equation (2).
x,y
0.0 0.2 0.4 0.6 0.8 1.0
P
,

k
P
a
0
200
400
600
800
1000
1200
1400
1600
1800
Fig. 2 e VLE behavior for R744 D RE170 at T [ 200 K (solid
lines), T [ 225 K (dashed lines), and T [ 250 K (dotted
lines).
x,y
0.0 0.2 0.4 0.6 0.8 1.0
P
,

k
P
a
0
500
1000
1500
2000
2500
Fig. 3 e VLE behavior for R744 D R170 at T [ 200 K (solid
lines), T [ 225 K (dashed lines), and T [ 250 K (dotted
lines).
x,y
0.0 0.2 0.4 0.6 0.8 1.0
P
,

k
P
a
0
500
1000
1500
2000
2500
3000
Fig. 4 e VLE behavior for R744 D R1150 at T [ 200 K (solid
lines), T [ 225 K (dashed lines), and T [ 250 K (dotted
lines).
i nt e r na t i o na l j our na l of r e f r i ge r a t i o n 3 4 ( 2 0 1 1 ) 1 4 3 6 e1 4 4 5 1438
To evaluate different options among the possible mixtures
without having to perform systematic tests in actual refriger-
ating systems demands a model for estimating the mixtures
properties and a computer software to simulate their behavior
in a vapor compression cascade cycle. The commercially
available computer packages are not completely reliable in
assessing the properties of R744 mixtures, when they have to
calculate conditions at temperatures below the carbon diox-
ides triple point. The only way to overcome this shortcoming
is to construct a predictive model starting from scratch with
data in the literature.
We chose to use a thermal equation of state (EoS), adding
a knowledge of the specic heat at zero pressure, to model
the thermodynamic properties of involved uids. Particularly
the CarnahaneStarlingeDe Santis (CSD) EoS (De Santis
et al., 1976) was used to obtain the pressureevolumee
temperatureecomposition (PVTx) parameters. The PVTx
parameters were supplemented with the ideal gas heat
capacity, thereby enabling us to describe all the
thermodynamic functions at each point in the cycle.
So, constructing a model for predicting the R744 blends
behavior at temperatures below 216.59 K implies three steps:
1. evaluating the solideliquid equilibrium (SLE) and the
eutectic compositionof the mixture in order to estimate the
lowest temperature limit to which the blend can be used as
uid;
2. evaluating the parameters of the EoS for the mixtures
components;
3. evaluating the behavior of the mixtures by determining
proper interaction parameters of the EoS.
x,y
0.0 0.2 0.4 0.6 0.8 1.0
P
,

k
P
a
0
200
400
600
800
1000
1200
1400
1600
1800
Fig. 5 e VLE behavior for R744 DR290 at T [200 K (solid
lines), T [225 K(dashed lines), and T [250 K(dotted lines).
x,y
0.0 0.2 0.4 0.6 0.8 1.0
P
,

k
P
a
0
200
400
600
800
1000
1200
1400
1600
1800
Fig. 6 e VLE behavior for R744 D R1270 at T [ 200 K (solid
lines), T [ 225 K (dashed lines), and T [ 250 K (dotted
lines).
Fig. 7 e Schematic layout of a cascade refrigeration cycle
(no HX).
Fig. 8 e Schematic layout of a cascade refrigeration cycle
with a suction-liquid heat exchanger (HX) on the low-
temperature-circuit (with HX).
i nt e r na t i ona l j o ur na l o f r e f r i g e r a t i o n 3 4 ( 2 0 1 1 ) 1 4 3 6 e1 4 4 5 1439
The abovementioned steps are described in detail in the
following paragraphs. The same model was used with good
results for other carbon dioxides blends in a previous paper
(Di Nicola et al., 2005).
2.1. Solideliquid equilibrium (SLE)
The SLE depends both on the crystals formed in solution and
on the properties of the liquid phase. Most organic systems
form eutectics: in this case, the course of the liquidus is well
described by the Schro der equation (Schro der, 1954), known
since the end of the 19th century. The exact course of the
liquidus for ideal mixtures (i.e. showing a small deviation
from Raoults law) depends mainly on the property of the
solute (R744 in our case) and, in the case of non-ideal
systems, on the property of the liquid phase.
Assuming that the studied systems form eutectics, the
solubility of the solid solute (R744) in any solvent can be
described by the Schro der equation; assuming that any differ-
ence between the heat capacity of the subcooled liquid solute
and solid solute can be disregarded, it takes the following form:
ln g
2
x
2

Dh
m
RT

1
T
T
m

(1)
where the subscript 2 denotes the solute and the subscript m
denotes property at melting point. We assumed as a rst
approximationthat our blendsbehavealmost ideally, i.e. that the
solutes activity coefcient, g
2
1; this means that we can write:
ln x
2

Dh
m
RT

1
T
T
m

(2)
This simplication leads to the consideration that the
solubility of the solid solute (R744) is independent of the
solvent over a wide range of compositions.
According to our past measurements on the SLE of
R744 HFCs (Di Nicola et al., 2006, 2007a,b, 2008, 2009, 2010),
the melting temperatures of R744 HC systems are presum-
ably independent of the second component and depend only
on the quantity of the R744, allowing operation down to
T 170 K for a presence of up to 50% in mass with no risk of
solidication, whatever the second component involved. An
example of the course of the liquidus is reported in Fig. 1,
where the experimental points for the SLE for the
R744 R134a system are reported together with the lines
denoting the Schro der equation.
2.2. Properties of the mixtures components
The CSDEoS (De Santis et al., 1976) can be used to evaluate the
properties of the R744 blends, providing the equation
parameters for the pure uids and the interaction
parameters for mixtures are known. The temperature
dependence of both EoS parameters and their respective
coefcients, and the equation for the temperature
dependence of the c
p
0
with the respective coefcients for
carbon dioxide, propane and propylene were taken from
REFPROP 5 (Huber et al., 1996) and for ethane, ethylene and
DME from REFPROP 7 (Lemmon et al., 2002). For the R744, the
parameters were retted involving the estimated property of
the supercooled liquid. The thermodynamic properties of
liquid R744 along the saturation line are well known down
to its freezing temperature, but not below 216.59 K when
carbon dioxide may remain liquid in the metastable (known
as supercooled) state. Needed supercooled liquid properties
were recalculated, according to the methods explained below.
First, the saturation pressure of supercooled R744 was
estimated by the LeeeKesler method (Lee and Kesler, 1975),
based on the corresponding state principle, which expresses
the generalization that equilibrium properties are universally
related to the critical properties. To apply this method, the
properties of a reference uid with an acentric factor similar
to that of R744 (u 0.2239) had to be explored. Here,
saturation data for R744 were estimated taking n-butane as
the reference uid (u 0.2).
Though no data are available, there are numerous tech-
niques for estimating pure liquid molar volumes along satu-
ration. We used the HankinsoneBrobsteThomson (HBT)
method (Hankinson and Thompson, 1979) and the Rackett
equation (Rackett, 1970; Spencer and Danner, 1972), both are
based on the knowledge of the critical parameters and
Table 2 e Operating conditions for the cycle calculations.
T
cond
(K)
T
evap
(K)
DT
SUP
(K)
DT
SUBCOOL
(K)
h
IS
(%)
High-temperature
circuit
313 213e283 10 5 0.7
Low-temperature
circuit
213e283 203 10 5 0.7
T
evap,H
T
condL
T
int
213e283 K.
C
O
P
Tint
210 220 230 240 250 260 270 280 290
0.6
0.7
0.8
0.9
1.0
1.1
Tint
210 220 230 240 250 260 270 280 290
0.6
0.7
0.8
0.9
1.0
1.1
8 . 0 = X H X H o n 8 . 0 = X H X H o n 8 . 0 = X H X H o n
with HX
8 . 0 = X H X H o n
Propylene
Propane
Ethylene
Ethane
DME
Propylene
Propane
Ethylene
Ethane
DME
with HX
Fig. 9 e COP for pure uids for no HX (left) and with HX (right).
i nt e r na t i o na l j our na l of r e f r i ge r a t i o n 3 4 ( 2 0 1 1 ) 1 4 3 6 e1 4 4 5 1440
acentric factor, and they produce negligible differences in
molar volumes. For the sake of clarity, data from the HBT
equation were used to determine the coefcients for the
CSD EoS.
The coefcients of the expressions describing the
temperature dependence of parameters a and b of the CSDEoS
were found by regression of the pressures and liquid molar
volumes along saturation. The two temperature dependences
of the CSD parameters are:
aT a
1
exp

a
2
T a
3
T
2

(3)
bT b
1
b
2
T b
3
T
2
(4)
The ideal gas heat capacity was calculated using the Wooley
equation (Wooley, 1954), valid from 210 to 1100 K. This
equation was slightly extended to a lower T (200 K).
The saturation pressure data of supercooled R744, together
with the values for the liquid molar volumes and with the
ideal heat capacity of supercooled R744 were reported else-
where (Di Nicola et al., 2005).
2.3. Properties of the mixtures
For the blends, the following mixing rules were applied:
a
XX
x
i
x
j
a
ij
(5)
where
a
ij

a
i
a
j

q

1 K
ij

(6)
and
b
X
x
i
b
i
(7)
The following averaged binary interaction parameters,
K
i,j
, were derived from VLE data in the literature (Poettman
and Katz, 1945; Haselden et al., 1951; Reamer et al., 1951;
Akers et al., 1954; Fredenslund and Mollerup, 1974; Gug-
noni et al., 1974; Hamam and Lu, 1974, 1976; Davalos et al.,
1976; Ohgaki and Katayama, 1977; Tsang and Streett, 1981;
Acosta et al., 1984; Jo nasson et al., 1995; Yucelen and Kid-
nay, 1999): K
1,2(R744R1270)
0.0591, K
1,2(R744R290)
0.1107,
K
1,2(R744R1150)
0.0561, K
1,2(R744R170)
0.1205,
K
1,2(R744RE170)
0.0391. The binary interaction parame-
ters were assumed to be independent of temperature and
their uncertainty was estimated to be within 0.0025.
The VLE at T 200 K, T 225 K, and T 250 K are shown in
Figs. 2e6, as an example of the binary systemss behavior.
Fromthe gure it is evident that R744 R170 and R744 R1150
showan azeotropic behavior, while R744 R290, R744 R1270
and R744 RE170 show a zeotropic behavior. Using these
parameters, the thermophysical properties of the ve binary
systems were calculated along the uid cycle.
3. Cycle analysis
The cascade systems combine two or more vapor compres-
sion units, each of one is an independent cycle, working on
separate refrigerants. Here we considered a system with two
circuits, where the high- and low-temperature systems have
to be balanced between them. This implies that the heat
absorbed in the high-temperature cascade (evaporator) must
be equal to the heat rejected in the low-temperature cascade
Table 3 e COP of the cascade cycle without the suction/liquid heat exchanger (no HX) and with the suction/liquid heat
exchanger (with HX) at T
int
[253.15 K, working with pure refrigerants or with the considered blends in the low-
temperature circuit. The performance difference between the system working with blends and pure uids (DCOP
bl-pf
) is
reported. X (R744) [ mass fraction, x (R744) [ mole fraction.
Pure uids COP
(no HX)
COP
(with HX)
Blends X (R744) x (R744) COP
(no HX)
DCOP
bl-pf
(no HX) (%)
COP
(with HX)
DCOP
bl-pf
(with HX) (%)
R170 (ethane) 0.93 0.97 R744 R170 0.50 0.41 0.90 3 0.93 4
R290 (propane) 0.97 1.01 R744 R290 0.50 0.50 0.86 11 0.87 14
R1150 (ethylene) 0.88 0.93 R744 R1150 0.50 0.39 0.88 0 0.91 2
R1270 (propylene) 0.97 1.00 R744 R1270 0.50 0.49 0.89 8 0.91 9
RE170 (DME) 0.97 0.99 R744 RE170 0.50 0.51 0.87 10 0.88 11
Tint
210 220 230 240 250 260 270 280 290
0.6
0.7
0.8
0.9
1.0
1.1
Tint
210 220 230 240 250 260 270 280 290
0.6
0.7
0.8
0.9
1.0
1.1
8 . 0 = X H X H o n 8 . 0 = X H X H o n
C
O
P
8 . 0 = X H X H o n 8 . 0 = X H X H o n with HX
Fig. 10 e COPfor R744DRE170indifferent proportions (mass fraction) for the twocycleconguration(noHX andwithHX):
pure RE170 esolid line; BdX(R744) [0.1; ,dX(R744) [0.2; 6dX(R744) [0.3; 7dX (R744) [0.4; and >dX(R744) [0.5.
i nt e r na t i ona l j o ur na l o f r e f r i g e r a t i o n 3 4 ( 2 0 1 1 ) 1 4 3 6 e1 4 4 5 1441
(condenser). In order to simulate the cascade cycle behavior,
we assumed the ideal condition that in the intermediate heat
exchanger (condensereevaporator) the intermediate temper-
ature between the two circuits (coupling temperature) is
T
int
T
cond,L
T
evap,H
, that means that there is no temperature
difference between the two uids, DT 0 (innite heat
exchanger surface). This simplication is in accordance with
the purposes of the present paper.
A schematic layout of a cascade refrigeration cycle is
illustrated in Fig. 7. The layout of the cycle also containing
a suction/liquid Heat Exchanger (HX) in the low stage, here
denoted with HX, is illustrated in Fig. 8.
The cycle parameters for the high stage were calculated
rst, followed by the low-stage parameters; then the COP of
the cascade cycle was assessed from the resulting quantities.
The high-stage requires the following input: evaporating
temperature (T
evap,H
), superheating temperature (T
sup,H
),
condensing temperature (T
cond,H
), sub-cooling temperature
(T
subcool,H
), and isentropic efciency (h
is,H
). R744 HCs blends
were considered for the low stage. The binary interaction
parameters can be applied as a default option, or they can be
modied by the user. The program enables the cycle analysis
of blends consisting of up to three components in various
proportions. For the low stage, we need to know the blend
composition, T
sup,L
, T
cond,L
, T
subcool,L
, and h
is,L
. For both stages,
h
is
includes all cycle irreversibilities (friction, electric motor
efciency, volumetric efciency, etc.).
In the case of zeotropic blends, given that the low-stage
condensation must be above the evaporating temperature of
the high-stage at least, we assumed the condition where
T
evap,H
T
bp, cond,L
.
As explained above the two systems have been designed
such that:
_ m0h
2
0 h
3
0 _ m

h
1
h
0
4

(8)
Introducing the parameter XM, dened as the ratio of the
mass owin the low-temperature-circuit ( _ m
0
) to the one in the
high-temperature-circuit ( _ m), we have:
XM _ m
0
= _ m (9)
Thus, the COP for the cascade system is calculated from:
COP
XMh
1
0 h
4
0
h
2
h
1
XMh
2
0 h
1
0
(10)
In order to study the performance of the low-temperature
circuit with the addition of a suction/liquid heat exchanger
(Fig. 8), the following equations were considered in the
computer program:
e Energy balance
h
30
h
40
h
10
h
60
(11)
e Heat exchanger effectiveness, 3
Tint
210 220 230 240 250 260 270 280 290
0.6
0.7
0.8
0.9
1.0
1.1
Tint
210 220 230 240 250 260 270 280 290
0.6
0.7
0.8
0.9
1.0
1.1
C
O
P

with HX 8 . 0 = X H X H o n with HX
Fig. 11 e COP for R744 DR170 indifferent proportions (mass fraction) for the two cycle conguration(no HX and withHX):
pure R170 e solid line; BdX (R744) [0.1; ,dX (R744) [0.2; 6dX (R744) [0.3; 7dX (R744) [0.4; and >dX (R744) [0.5.
C
O
P
Tint
210 220 230 240 250 260 270 280 290
0.6
0.7
0.8
0.9
1.0
1.1
Tint
210 220 230 240 250 260 270 280 290
0.6
0.7
0.8
0.9
1.0
1.1
8 . 0 = X H X H o n 8 . 0 = X H X H o n 8 . 0 = X H X H o n
with HX
8 . 0 = X H X H o n
with HX
Fig. 12 e COP for R744 D R1150 in different proportions (mass fraction) for the two cycle conguration (no HX and with
HX): pure R1150 e solid line; Bd X (R744) [ 0.1; ,d X (R744) [ 0.2; 6 d X (R744) [ 0.3; 7dX (R744) [ 0.4; and >d X
(R744) [ 0.5.
i nt e r na t i o na l j our na l of r e f r i ge r a t i o n 3 4 ( 2 0 1 1 ) 1 4 3 6 e1 4 4 5 1442
3
_
Q
_
Q
max

T
vap:out
T
vap:in

T
liq:in
T
vap:in

T
1
0 T
6
0
T
3
0 T
6
0
(12)
The thermodynamic analysis of the cycle was done using
the parameters given in Table 2. As previously mentioned, in
all the calculations the heat exchanger effectiveness (3) has
been set equal to 0.8.
3.1. Pure refrigerants as the low-temperature stage uid
The following pure uids in the low-temperature-circuit were
considered: R170, R290, R1150, R1270, and RE170. The COP of
the cascade cycle was calculated for each refrigerant and the
results are presented in Fig. 9. The inuence of the
intermediate temperature (T
int
) was investigated, considering
the relevance that this aspect had in literature (Agrawal,
1989; Jeong and Smith, 1994; Bhattacharyya et al., 2007; Getu
and Bansal, 2008). Particularly the applicability of Jeong and
Smiths rule (1994) was checked. In fact they demonstrated
that in reversible cycles the optimum coupling temperature
is represented by the square-root of the condensing
temperature, T
cond,H
, in the high-temperature circuit and
evaporating temperature, T
evap,L
, in the low-temperature
circuit, i.e.:
T
int

T
cond;H
T
evap:L
q
(13)
We plotted T
int
versus COP, as it is shown in Fig. 9. It is
possible to note that for all refrigerants, the COP clearly
depends on the intermediate temperature (T
int
). For all
systems with no HX, the maximum COP was observed for
temperatures between 240 and 260 K. These values are close
to T 258 K, which is the geometric mean (Eq. (13)) between
the two temperatures T
cond,H
and T
evap,L
. For the systems
with no HX, the maximum COP was achieved for RE170.
For the systems with the suction/liquid heat exchanger
(with HX), the maximum COP is only observed for R170
and R1150. For all the other uids, the COP increased
systematically with higher values of T
int
.
These results conrm that the same ratio between
condensing and evaporative temperature of each cycle of the
cascade system helps to increase the performance of the
system. Instead the analysis is complicated by the presence of
the suction/liquid heat exchanger. In the latter case in fact the
performances trend become strictly connected also to the
refrigerant used.
3.2. R744 blends as the low-temperature stage uid
The following blends were considered: R744 R170,
R744 R1150, R744 R290, R744 R1270, R744 RE170. The
Tint
210 220 230 240 250 260 270 280 290
0.6
0.7
0.8
0.9
1.0
1.1
Tint
210 220 230 240 250 260 270 280 290
0.6
0.7
0.8
0.9
1.0
1.1
8 . 0 = X H X H o n 8 . 0 = X H X H o n
C
O
P
8 . 0 = X H X H o n 8 . 0 = X H X H o n
with HX
Fig. 13 e COP for R744 D R290 in different proportions (mass fraction) for the two cycle conguration (no HX and with
HX): pure R290 e solid line; Bd X (R744) [ 0.1; ,d X (R744) [ 0.2; 6 d X (R744) [ 0.3; 7dX (R744) [ 0.4; and >d X
(R744) [ 0.5.
C
O
P
Tint
210 220 230 240 250 260 270 280 290
0.6
0.7
0.8
0.9
1.0
1.1
Tint
210 220 230 240 250 260 270 280 290
1.1
8 . 0 = X H X H o n 8 . 0 = X H X H o n 8 . 0 = X H X H o n
0.6
0.7
0.8
0.9
1.0
8 . 0 = X H X H o n
with HX
Fig. 14 e COP for R744 D R1270 in different proportions (mass fraction) for the two cycle conguration (no HX and with
HX): pure R1270 Be solid line; d X (R744) [ 0.1; ,d X (R744) [ 0.2; 6 d X (R744) [ 0.3; 7dX (R744) [ 0.4; and >d X
(R744) [ 0.5.
i nt e r na t i ona l j o ur na l o f r e f r i g e r a t i o n 3 4 ( 2 0 1 1 ) 1 4 3 6 e1 4 4 5 1443
COP for cascade systems equipped with those blends were
estimated in the same conditions as in Table 3, considering
T
int
T
cond,L
T
evap,H
as an independent variable. In
addition, each set of calculations was performed for ve
compositions: 0.1, 0.2, 0.3, 0.4 and0.5 inmass fractions of R744.
The COP is plotted versus T
int
in relation to the mixtures
composition in Figs. 10e14. As the Figures show, the higher
the content of R744, the lower the COP, except for the mixtures
of R1150 in no HX conguration, where the COP is inde-
pendent of the uids composition.
For the fact that carbon dioxide is the natural refrigerant
with the lower environmental impact and the lower am-
mability, those blends with a higher concentration of R744 are
considered particularly interesting for the purposes of this
research. Accordingly to ndings reported in Section 2.1, the
maximum content of CO
2
allowed in the mixtures is 50% in
mass in order to prevent solidication and so particular
evidence was given to the performance of such blends. The
respective COP values are shown in Table 3, where the
composition of the mixtures is expressed both in mass and
mole fractions. All reported data were obtained at
T
int
253.15 K. These ndings show that, in most of the
cascade systems investigated, the COP varied within a range
of 0.85e0.93 and it was lower for blends containing CO
2
than
for the pure uids here considered, particularly in presence
of the suction/liquid heat exchanger. In Table 3 the
performance difference between the system working with
blends and pure uids (DCOP
bl-pf
) is also reported: the
difference between the two corresponding congurations
(pure uid and blend) reaches a maximum using as
refrigerant propane (DCOP
bl-pf
14%), while the lower
value is for ethylene (DCOP
bl-pf
2%).
Comparing these results with those obtained previously by
us with the same model for R744 HFCs systems (Di Nicola
et al., 2005) reveals very similar COP values and trends, both
in composition and T
int
.
4. Conclusions
This paper presents a thermodynamic analysis on a cascade
refrigeration cycle using R744 HCs blends as the low-
temperature uid with a view to extending the applicability of
carbon dioxide in such systems below its triple point
(216.59 K).
The results show that COP of the cascade cycle with the
studied R744 blends reaches acceptable values, even if the
better performance is achieved using pure HCs refrigerants in
the low stage of cascade systems. Nevertheless the interest of
considering such blends remains and it is mainly related to
the lower environmental impact of R744 and particularly to its
ability to reduce HCs ammability.
Considering the intrinsic simplicity of the model used to
compare different blends, a more realistic model and experi-
mental work are needed to give recommendations on the
most suitable blend, and this work is currently underway.
Even if the inherent uncertainty of the model permits no nal
conclusions, there is no doubting that e for all the blends
considered here e the liquid/suction heat exchangers in the
low stage is capable of improving the systems performance,
and this aspect therefore also deserves further investigation.
The outcome of such further studies will also be interesting
with a view to conrming whether the R744 content in the
most suitable blends can make them tend towards non-
ammability.
r e f e r e n c e s
Acosta, J.C., Hevia, E., Leipziger, S., 1984. Dew and bubble point
measurements for carbon dioxide-propane mixtures. J. Chem.
Eng. Data 29, 304e308.
Agrawal, D.D., 1989. Prediction of optimum interstage
temperatures for cascade systems. J. Inst. Eng. (India) e Mech.
Eng. Div. 69 (51), 148e151. 19.
Akers, W.W., Kelley, R.E., Lipscomb, T.G., 1954. Carbon dioxide-
propane system. Ind. Eng. Chem. 46, 2535e2536.
Bhattacharyya, S., Bose, S., Sarkar, J., 2007. Exergy maximization of
cascade refrigeration cycles and its numerical verication for
a transcritical CO
2
-C
3
H
8
system. Int. J. Refrig. 30 (4), 624e632.
Bhattacharyyaa, S., Garaia, A., Sarkarb, J., 2009. Thermodynamic
analysis and optimization of a novel N
2
OeCO
2
cascade system
for refrigeration and heating. Int. J. Refrig. 32, 1077e1084.
Davalos, J., Anderson, W.R., Phelps, R.E., Kidnay, A.J., 1976. Liquid-
vapor equilibria at 250.00 K for systems containing methane,
ethane, and carbon dioxide. J. Chem. Eng. Data 21 (1), 81e84.
De Santis, R., Gironi, F., Marelli, L., 1976. Vapor-liquid equilibrium
from a hard-sphere equation of state. Ind. Eng. Chem.
Fundam. 15, 183e189.
Di Nicola G., Polonara F., Stryjek R., Tarnawski V., 2003a.
Thermodynamic analysis of CO
2
blends in cascade
refrigeration cycles. In: Proc. 72th Eurotherm Seminar,
Valencia, Spain.
Di Nicola G., Pacetti M., Polonara F., Stryjek R., 2003b. Blends of
carbon dioxide as working uids in cascade systems. In: Proc.
Int. Congr. on Refrig., Washington DC, USA.
Di Nicola, G., Giuliani, G., Polonara, F., Stryjek, R., 2005. Blends of
carbon dioxide and HFCs as working uids for the low-
temperature circuit in cascade refrigerating systems. Int. J.
Refrig. 28, 130e140.
Di Nicola, G., Giuliani, G., Polonara, F., Stryjek, R., 2006. Solid-
liquid equilibria for the CO
2
R125 and N
2
O R125 systems:
a new apparatus. J. Chem. Eng. Data 51, 2209e2214.
Di Nicola, G., Giuliani, G., Polonara, F., Stryjek, R., 2007a. Solid-
liquid equilibria for the CO
2
N
2
O, CO
2
R32 and N
2
O R32
systems. Fluid Phase Equilib. 256, 86e92.
Di Nicola, G., Giuliani, G., Polonara, F., Santori, G., Stryjek, R.,
2007b. Solid-liquid equilibria for the CO
2
R152a, and
N
2
O R152a systems. J. Chem. Eng. Data 52, 2451e2454.
Di Nicola, G., Santori, G., Stryjek, R., 2008. Solid-liquid equilibria
for the carbon dioxide 1,1-Tetrauoroethane and nitrous
oxide 1,1-Tetrauoroethane systems. J. Chem. Eng. Data 53,
1980e1983.
Di Nicola, G., Santori, G., Stryjek, R., 2009. Solid-liquid equilibria
for the CO
2
R143a, and N
2
O R143a systems. Int. J.
Thermophys. 30 (4), 1155e1164.
Di Nicola, G., Giuliani, G., Polonara, F., Santori, G., Stryjek, R., 2010.
Solid-liquid equilibria for the CO
2
R23, and N
2
O R23
systems. Int. J. Thermophys. doi:10.1007/s10765-008-0511-0.
Dopazo, J.A., Seara, J.F., Sieres, J., Uha, F.J., 2009. Theoretical
analysis of a CO
2
eNH
3
cascade refrigeration system for
cooling applications at low temperatures. Appl. Therm. Eng.
29, 1577e1583.
Fredenslund, A., Mollerup, J., 1974. Measurement and prediction
of equilibrium ratios for ethane carbon dioxide system.
i nt e r na t i o na l j our na l of r e f r i ge r a t i o n 3 4 ( 2 0 1 1 ) 1 4 3 6 e1 4 4 5 1444
J. Chem. Soc. Far. Trans. Phys. Chem. Condensed Phases 70,
1653e1660.
Getu, H.M., Bansal, P.K., 2008. Thermodynamic analysis of an
R744eR717 cascade refrigeration system. Int. J. Refrig. 31,
45e54.
Gong, M., Sun, Z., Wu, J., Zhang, Y., Meng, C., Zhou, Y., 2009.
Performance of R170 mixtures as refrigerants for refrigeration
at -80

C temperature range. Int. J. Refrig. 32, 892e900.
Gugnoni, R.J., Eldridge, J.W., Okay, V.C., Lee, T.J., 1974. Carbon
dioxide-ethane phase equilibrium and densities from
experimental measurements and B-W-R equation. AIChE J.
20 (2), 357e362.
Hankinson, R.W., Thompson, G.H., 1979. A new correlation for
saturated densities of liquid and their mixtures. AIChE J. 25,
653e663.
Hamam, S.E.M., Lu, B.C.Y., 1974. Vapor liquid equilibrium in the
ethane-carbon dioxide system. Can. J. Chem. Eng. 52, 283e288.
Hamam, S.E.M., Lu, B.C.Y., 1976. Isothermal vapor-liquid
equilibria in binary system propane-carbon dioxide. J. Chem.
Eng. Data 21, 200e204.
Haselden, G.G., Newitt, D.M., Shah, S.M., 1951. Two-Phase
equilibrium in binary and Ternary systems. V. Carbon dioxide-
ethylene, VI. Carbon dioxide-propylene. Roy. Soc., Series A
Math. and Phys. Sci. 209 (1096), 1e14.
Huber, M., Gallagher, J., McLinden, M., Morrison, G., 1996. NIST
Thermodynamic Properties of Refrigerants and Refrigerant
Mixtures Database (REFPROP) Version 5.0. National Institute of
Standards and Technology, Thermophysics Division.
Jeong, S., Smith Jr., J.L., 1994. Optimum temperature staging of
cryogenic refrigeration system. Cryog 34, 929e933.
Jo nasson, A., Persson, O., Fredenslund, A., 1995. High pressure
solubility of carbon dioxide and carbon Monoxide in dimethyl
ether. J. Chem. Eng. Data 40, 296e300.
Kays, W.M., London, A.L., 1964. Compact Heat Exchangers.
McGraw-Hill, New York.
Kruse, H., Ru ssmann, H., 2006. The natural uid nitrous
oxide e an option as substitute for low temperature synthetic
refrigerants. Int. J. Refrig. 29, 799e806.
Lee, B.I., Kesler, M.G., 1975. Generalized thermodynamic
correlation based on three-parameter corresponding states.
AIChE J. 21, 510e527.
Lee, T.S., Liu, C.H., Chen, T.W., 2006. Thermodynamic analysis of
optimal condensing temperature of cascade-condenser in
CO
2
/NH
3
cascade refrigeration systems. Int. J. Refrig 29,
1100e1108.
Lemmon, E.W., McLinden, M.O., Huber, M.L., 2002. NIST Reference
Fluid Thermodynamic and Transport Properties e REFPROP
Version 7.0. Physical and Chemical Properties Division,
National Institute of Standards and Technology.
Liu H., Gu Z., Li Y., 2002. Simulation of NH
3
/CO
2
two-stage
low temperature refrigeration system. In: Proc. of the
Ninth Refrig. and Air Cond. Conf., Purdue, West Lafayette,
pp. R18eR15.
Niu, B., Zhang, Y., 2007. Experimental studyof therefrigerationcycle
performance for the R744/R290 mixtures. Int. J. Refrig. 30, 37e42.
Ohgaki, K., Katayama, T., 1977. Isothermal vapor-liquid
equilibrium data for the ethane-carbon dioxide system at high
pressures. Fluid Phase Equilib. 1 (1), 27e32.
Pearson A., Cable P.J., 2003. A distribution warehouse with CO2 as
refrigerant. In: Proc. Of the 21st Int. Congr. of Refrig.,
Washington DC, pp. ICR0624.
Poettman, F.H., Katz, D.L., 1945. Phase behavior of binary carbon
dioxide-parafn systems. Ind. Eng. Chem. 37, 847e853.
Rackett, H.G., 1970. Equation of state for saturated liquids.
J. Chem. Eng. Data 15, 514e517.
Reamer, H.H., Sage, B.H., Lacey, W.N., 1951. Phase equilibria in
hydrocarbon systems: volumetric phase behavior of the
propane e Carbon dioxide system. Ind. Eng. Chem. 43,
2515e2520.
Schro der, I., 1954. Z. Phys. Chem., 11204, cfr.: Prigogine I., Defay R.
Chemical Thermodynamics. Longmans Green and Co.:
London. pp. 358.
Spencer, C.F., Danner, R.P., 1972. Improved equation for
prediction of saturated liquid density. J. Chem. Eng. Data 17,
234e241.
Stoecker, W.F., 1998. Industrial Refrigeration Handbook. McGraw-
Hill, New York.
Taylor, R., 2002. Carbon dioxide-based refrigerant systems.
ASHRAE J. September, 22e27.
Tsang, C.Y., Streett, W.B., 1981. Vapor-liquid equilibrium in the
system carbon ether. J. Chem. Eng. Data 26, 155e159.
Wooley, H.W., 1954. Thermodynamic functions for carbon dioxide
in the ideal gas state. J. Res. Nat. Bur. Stand. 52, 289e292.
Yucelen, B., Kidnay, A.J., 1999. Vapor-liquid equilibria in the
Nitrogen carbon dioxide propane system from 240 to 330 K
at pressures to 15 MPa. J. Chem. Eng. Data 44 (5), 926e931.
Zha S., Ma Y., Wang J., Li M., 2002. The thermodynamic analysis
and comparison on natural refrigerants cascade refrigeration
cycle. In: Proc. of the Fifth Gustav Lorentzen Conf. on Nat.
Work. Fluids, Guangzhou, China, pp. 157e163.
i nt e r na t i ona l j o ur na l o f r e f r i g e r a t i o n 3 4 ( 2 0 1 1 ) 1 4 3 6 e1 4 4 5 1445