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Procedia Engineering00 (2017) 000–000

ScienceDirect www.elsevier.com/locate/procedia

Procedia Engineering 205 (2017) 1620–1626

10th International Symposium on Heating, Ventilation and Air Conditioning, ISHVAC2017, 19-
22 October 2017, Jinan, China

Theoretical Investigation on the Properties of R744/R290 Mixtures

Li Zhanga,∗, Chunguang Yanga, Huanying Liua, Ping Dua, Hongyan Gaoa
aa
School of Mechanical and Power Engineering, Dalian Ocean University, Dalian, , 116023,China

Abstract

At present, an interesting research is to find promising environmentally-friendly refrigerants in auto-cascade refrigeration cycle.
This paper proposed a refrigerant mixture of R744 and R290 due to its zero ozone depletion potential and negligible global
warming potential. The properties of R744, R290 and the mixtures refrigerant were analyzed. And performances comparisons
between R744, R290, R22 and R134a were investigated based on the simulation data. Then, the vapor-liquid phase equilibrium
properties of mixture were calculated. And the conversion relations of total mole fraction, vapor phase mole fraction, liquid phase
mole fraction, quality, equilibrium temperature and pressure were systematically analyzed. The results show that R744 and R290
are potential refrigerant. But each pure refrigerant has obvious disadvantage, it is a good choice that R744 and R290 are mixed
together into non-azeotropic mixture, which is suitable for auto-cascade refrigeration cycle due to a large temperature glide
during the phase changing.
© 2017 The Authors. Published by Elsevier Ltd.
© 2017 The Authors.
Peer-review Published by
under responsibility ofElsevier Ltd. committee of the 10th International Symposium on Heating, Ventilation and Air
the scientific
Peer-review under responsibility of the scientific committee of the 10th International Symposium on Heating, Ventilation and
Conditioning.
Air Conditioning.
Keywords: Auto-cascade refrigeration; Natural refrigerant; R744; R290

1. Introduction

Two professors in California University, Molina and Roland, pointed out that chlorofluorocarbon chlorine depleted
stratosphere ozone in 1974[1]. Then Montreal Protocol on substances that depletion ozone layer and Kyoto Protocol
on substance that contribution to global warming were successively promulgated, which were very important for
global environmental protection. Accordingly non-azeotropic refrigerant mixtures used in auto-cascade refrigeration
(ACR) cycle also transformed from Chlorofluorocarbon to environmentally friendly refrigerants [2, 3]. Natural
substances have become the favored refrigerants since the international communities paid more attention to the

* Corresponding author. Tel.: 15842673895

E-mail address: [email protected]

1877-7058 © 2017 The Authors. Published by Elsevier Ltd.

Peer-review under responsibility of the scientific committee of the 10th International Symposium on Heating, Ventilation and Air Conditioning.

1877-7058 © 2017 The Authors. Published by Elsevier Ltd.

Peer-review under responsibility of the scientific committee of the 10th International Symposium on Heating, Ventilation and
Air Conditioning.
10.1016/j.proeng.2017.10.304
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Li Zhang et al. / Procedia Engineering00 (2017) 000–000

environmental protection. Both R744 and R290 are environmental-friendly refrigerants due to the zero ozone
depletion, negligible global warming potentials and their excellent thermal properties[4- 10]. Lorentzen put forward
that R744 and R290 were the most potential refrigerants [11]. The properties of R744, R290 and their mixtures are
very important for the performance of the ACR cycle.

Nomenclature

m t total mass flow rate

m v mass flow rate of saturated vapor
m l mass flow rate of saturated liquid
xi mole fraction in liquid phase of R744 or R290
yi mole fraction in vapor phase of R744 or R290
zi total mole fraction of R744 or R290 in the mixture
q vapor quality

2. Thermal properties of R22 and R290

2.1. Fundamental parameters of R744 and R290

The fundamental properties of R744 and R290 are shown in Table1.

Table 1 The fundamental properties of R744 and R290

Molecular Freezing Boiling point Explosion

Refrigeration Code Combustibility ODP GWP
formula point(K) (K) limit %（v/v）

Combustion
Carbon dioxide CO2 R744 216.60 194.65 0 0 1
suppression
Propane C3H8 R290 85.53 231.06 Flammability 2.1-9.5 0 20

2.2. Other properties of R744 and R290

Fig.1-7 illustrates the comparisons between R744, R290, R22 and R134a, in which R22 and R134a have been
widely applied in the refrigeration system now.
Densities of four refrigerants are shown in Fig.1. It can be seen from Fig.1 that the density of R290 is lower than
that of other three refrigerants, and followed by R744. The densities of R744, R22 and R134a are 1.93, 2.43 and
2.45 times of R290, respectively.
Fig.2 shows the liquid viscosity of four refrigerants. It can be seen that the liquid viscosity of R744 and R290 is
obviously smaller than that of R22 and R134a. The liquid viscosity of R744, R22 and R134a are 1.01, 1.78 and 2.42
times of R290 than that of R290, respectively. Low density and liquid viscosity is very positive for reducing fluid
resistance and pressure drop.
Comparison of specific heat between R744, R290, R22 and R134a is presented in Fig.3. From Fig.3, it can be
seen that the specific heat of R290 and R744 is the much higher than that of R22 and R134a. The specific heat of
R290 is 1.35, 2.39 and 1.94 times than R744, R22 and R134a respectively.
Fig.4 shows the heat conductivity coefficient comparison between four refrigerants. It can be seen that the heat
conductivity coefficient of R744 is the highest, followed by propane. And the heat conductivity coefficient of R22
and R134a is a bit lower than that of R744 and R290. High heat conductivity coefficient contributes to increase heat
transfer efficiency, reduce heat transfer area, and save materials and operation cost.
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Fig.5 shows the comparison of the vapor heat between R744, R290, R22 and R134a. It can be seen that the vapor
heat of R290 is much higher than that of other refrigerants, and followed by R744. The vapor heat of specific heat of
R290 is 1.31, 1.82 and 1.87 times than R744, R22 and R134a respectively.

Fig.2 Viscosity comparison between R744, R290, R22 and R134a

Fig.1 Density comparison between R744, R290, R22 and R134a

Fig.3 Comparison of specific heat between R744, R290, R22 and Fig.4 Comparison of heat conductivity coefficient between R744,
R134a R290, R22 and R134a

Fig.5 Comparison of heat of vapor between R744, R290, R22 and Fig.6 Comparison of refrigeration capacity per unit volume between
R134a R744, R290, R22 and R134a

2
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Comparison of refrigeration capacity per unit volume between R744, R290, R22 and R134a is shown in Fig.6.
From Fig.6 it can be seen that R744 capacity per unit volume is much higher than that of other refrigerants, followed
by R290. The refrigeration capacity per unit volume of R744 is 7.62, 7.50 and 13.55 times than R290, R22 and
R134a respectively. High vapor heat contributes to reduce the circulation and charging of refrigeration. And high
refrigeration capacity per unit volume can reduce compressor cylinder capacity and size. So the compressor power
input is decreased.
Comparison of specific volume between R744, R290, R22 and R134a is shown in Fig.7. It can be seen that
R744 specific volume is much lower than that of other refrigerants. When the specific volume of the refrigerants is
low, it occupies small space, which contributes to reduce the size of tubes and equipments.

Fig.7 Comparison of specific volume between R744, R290, R22 and Fig.8 Comparison of saturated pressure between R744, R290, R22
R134a and R134a

Fig.8-9 presents the comparison of saturated pressure and temperature at -40℃ between R744, R290, R22 and
R134a. It can be seen from Fig.8 that R744 saturated pressure is much higher than other refrigerants. The saturated
pressure of R744 is 9.1, 9.6 and 19.7 times of R290, R22 and R134a respectively.
From Fig.9 we can see R744 saturated temperature is much lower than other refrigerants. The saturated
temperature of R744 at 0.601MPa is below zero. So R744 is a high pressure and low temperature refrigerants.
Through above data analysis, some conclusions about R744 and R290 are drawn as follow.
(1) R744
1) Density and viscosity are low. 2) Specific volume is very small. 3) Specific heat and heat conductivity
coefficient are big. 4) Heat of vapor is big. 5) Refrigeration capacity per unit volume is big. 6) At the same time, it
also has some disadvantages. For example, R744 is high pressure and low temperature refrigerant which requires
strict quality for seal performance and equipment confined pressure. Moreover, R744 can not be condensed by the
environment media.
(2) R290
1) Density and viscosity are low. 2) Specific heat is very high. 3) Heat conductivity coefficient is big. 4) Heat of
vapor and refrigeration capacity per unit volume is big. 5) In addition, R290 also has fatal weakness, such as poor
safety of combustibility and explosibility, and big specific volume.
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Fig.9 Comparison of saturated temperature between R744, R290, R22 and R134a

Fig.10 Vapor-liquid phase equilibrium graph of R744/R290 mixtures

3. Thermal properties of R744/R290 mixtures

It is a good choice that R744 and R290 are mixed together into non-azeotropic mixture. Although R744 pressure
is very high, the mixture pressure can be restricted to normal bearing pressure by mixing R290 into R744. At the
same time, the combustibility and explosibility of R290 can be brought under effective control by mixing R744 into
R290, which can ensure the system safety and overcome the disadvantage of big specific volume of R290. However,
the glide temperature of the R744/R290 mixture during the phase changing is very large, it isn’t suited to be used in
single or double stage compression refrigeration system as plain refrigerant mixture. The R744/R290 mixture can
realize cascade refrigeration in only one cycle, that is, auto-cascade refrigeration cycle, by using the characteristic of
the big boiling point temperature difference of R744 and R290, which can maximize two refrigerants’ strengths
whilst minimizing their weaknesses.
Fig.10 shows the vapor-liquid phase equilibrium graph of R744/R290 mixtures at 0.6MP and 1.6MPa,
respectively. It can be seen that R744/R290 mixture is a non-azeotropic refrigerant, that is, the temperature of the
mixture changes during the phase transition under the constant pressure. The temperature difference between dew
and bubble point is glide temperature, which is related to equilibrium pressure and the mole fraction of R744 or
R290. For example, when the pressure is 1.6MPa, the largest glide temperature is 31.6K, and the corresponding
mole fraction of R744 is 0.4.
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Li Zhang et al. / Procedia Engineering 205 (2017) 1620–1626 1625

Fig.12 Quality vs. R744 mole fraction

Fig.11 Mole fraction of the vapor-liquid mixtures

Fig.11 displays the relationship between z1 , z2 , y1 , y2 , x1 and x2 in the liquid vapor coexistent system. z1 is

the total R744 mole fraction in the mixture, and y1 and x1 are R744 mole fraction in vapor and liquid, respectively.

And z 2 is the total R290 mole fraction in the mixture, y2 and x2 are R290 mole fraction in vapor and liquid,
respectively. It can be seen that R744 vapor mole fraction is largest, then the total R744 mole fraction, and R744
liquid mole fraction is smallest, that is y1 > z1 > x1 . On the contrary, R290 liquid mole fraction is largest, then the
total R290 mole fraction, and R290 vapor mole fraction is smallest, that is, x 2 > z 2 > y 2 . Fig.12 shows that vapor
quality changes as a function of R744 mole fraction at 300.15K and 1.6MPa, 1.8MPa and 2.0MPa, respectively. The
vapor quality has a great effect on the vapor-liquid phase equilibrium rule of the mixtures, which is defined as

m v z1 − x1
q = = (1)
m t y1 − x1

Where, m  t is total mass flow rate, m v and m l are the mass flow rate of saturated vapor and liquid, respectively.
And it is also defined as

z2 − x 2
q = (2)
y2 − x 2

It can be observed that the vapor quality goes up with an increase in total R744 mole fraction in the mixture
under the constant temperature and pressure. According to phase equilibrium principle or Fig.10, as the temperature
and pressure are constant, R744 or R290 mole fraction in vapor and liquid are always the same whether or not the
total mole fraction of R744 or R290 changes, that is, y1 , x1 , y2 and x2 are all constant. And therefore, there is

linear relationship between the vapor quality and total R744 mole fraction. Additionally, at the same total R744
mole fraction, Fig.12 presents that the increasing of equilibrium pressure can reduce the vapor quality due to the
increasing of R744 mole fraction in vapor and liquid.
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The effect of the total mole fraction of R744 on the percentage of R744 and R290 is shown in Fig.13. It can be
seen that increasing the total mole fraction of R744 reduces the saturated liquid mole percentage of R744 and R290,
and increases the saturated vapor mole percentage of R744 and R290. The result is due to the increasing of the vapor
quality.

Fig.13 Percentage of R744 and propane vs. z1

4. Conclusions

A theoretical simulation was developed in this paper to analyze the performances of R744, R290 and their
mixtures, which is usually used in the auto-cascade refrigeration cycle. The results show that R744 and R290 are
good potential refrigerants. But the pressure bearing capacity and tightness requirements for equipments are very
high as a low temperature and high pressure refrigerant for R744. And it cannot be condensed at room temperatures.
At the same time, the application of R290 refrigerant is also restricted because of its inflammable and explosive
characteristics. It is a good choice that the mixtures of R744 and R290 are used in auto-cascade refrigeration cycle.
So the vapor-liquid phase equilibrium properties of mixture are calculated, and the conversion relations of total mole
fraction, vapor phase mole fraction, liquid phase mole fraction, quality, equilibrium temperature and pressure are
systematically analyzed.

References

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