Measurements of isothermal vapor-liquid equilibrium for 2,3,3,3-tetrafluoroprop-1-ene + 1,1,1,2-tetrafluoroethane + propane system at temperatures from 283.15 to 323.15 K

doi:10.1016/j.jct.2018.10.028

The Journal of Chemical Thermodynamics

Volume 131, April 2019, Pages 111-116

https://doi.org/10.1016/j.jct.2018.10.028 Get rights and content

Highlights

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Isothermal VLE data for R1234yf + R134a + R290 were measured at 283.15–323.15 K.
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VLE data were correlated by using Wilson-RK, NRTL-RK and PR-WS-MUNIFAC model.
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Two new functional groups of C2H2F and CH2F were defined.
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Group parameters of C2H2F and CH2F were obtained by regressing the VLE data.

Abstract

Isothermal vapor liquid equilibrium (VLE) data of the alternative 2,3,3,3-tetrafluoroprop-1-ene + 1,1,1,2-tetrafluoroethane + propane ternary mixture over the temperature range of 283.15–323.15 K at 10 K intervals were measured using a circulation type apparatus. The experimental VLE data were correlated by Wilson-RK model, NRTL-RK model and PR-WS-MUNIFAC model. All of the models can well present the experimental data. The average absolute relative deviation (AARD) of pressure are within 0.60% and the maximum average absolute deviation (AAD) of vapor mass fraction is 0.0154 for the PR-WS-MUNIFAC model. Based on the UNIFAC (Dortmund) method, the two new functional groups of C2H2F and CH2F were divided and the relevant group parameters were obtained by fitting the experimental data.

Introduction

The mixe-refrigerant cycle is generally different from the cycle of the single-component. Using the unique physical properties of the mixtures, the refrigerant cycle can approach the Lorenz-Cycle or perform an auto-cascade refrigerant cycle with a single compressor. Here, the vapor liquid equilibrium (VLE) characteristics of mixtures play an essential role. At present, limited to international conventions, alternatives refrigerants have become a hot and difficult problem in the refrigeration and air-conditioning industry. In recent years, 2,3,3,3-tetrafluoroprop-1-ene(R1234yf) has been widely accepted as a promising and environment-friendly alternative refrigerant because of its GWP < 1, ODP = 0, a very short atmospheric life time of 0.03 year [1], and vapor pressure and other thermodynamics properties similar to those of 1,1,1,2-tetrafluoroethane(R134a). However, the smaller latent heat of R1234yf leads to larger pressure drops and mass flow rates in heat exchangers and connection pipes, which results in a lower coefficient of performance (COP). To overcome this shortcoming, some R1234yf + HFCs or HCs binary and ternary mixtures were proposed and their thermophysical properties were experimentally measured, such as R134a + R1234yf [2], [3], 1,1-difluoroethane(152a) + R1234yf [4], isobutene (R600a) + R1234yf [5], fluoroethane (R161) + R1234yf [6], R134a + R600a + R1234yf [7], R134a + DME + R1234yf [8], difluoromethane (R32) + R1234yf [9], ammonia (R717) + R1234yf [10] and propane (R290) + R1234yf [11]. R290 has the advantages of no fluorine, low carbon, and high latent heat of vaporization. It will be a good alternative to mix R290 and R1234yf according to a certain mass ratio. However, R290 is a flammable refrigerant, and R1234yf also has micro flammability. It is possible to greatly reduce the flammability by adding nonflammable refrigerant R134a into the R1234yf + R290 binary system. Thus, the ternary mixture of R1234yf + R290 + R134a system will be a promising alternative refrigerant with environment-friendly thermodynamic.

VLE data is the fundamental thermodynamics property which facilitates the design of separation processes and provides the basic necessary to develop commercial technique. In the last article [12], we had used the PR-WS-MUNIFAC model to predict the VLE behavior over the temperatures from 253.15 K to 313.15 K and carried out qualitative analysis of the prediction results. However, the relevant model parameters are incomplete and the prediction results need the verification of experimental data. Thus, in this study, we further research the VLE characteristics of R1234yf + R290 + R134a system experimentally and the isothermal data were measured from 283.15 K to 323.15 K using a circulation type apparatus. All of the experimental data were correlated by Peng Robinson (PR) equation of state (EoS) with the Wong-Sandler (WS) mixing rule and the modified group contribution activity model of UNIFAC (PR-WS-MUNIFAC model) [13], as well as the Wilson-RK model and the NRTL-RK model.

Section snippets

Materials

The purity and suppliers of the chemicals used in these measurements are summarized in Table 1. The chemicals were used without further purification, as their GC analysis did not indicate the presence of any significant impurities. The critical properties and acentric factors of R1234yf, R290 and R134a are shown in Table 2.

Apparatus

The VLE properties were measured using a recirculation method. The apparatus consists of an equilibrium cell, a sampling circulation and analysis system, a thermostat liquid

Modelling details

The excess Gibbs free energy-equation of state ( $G^{E} - E o S$ ) model is a new idea to calculate the phase equilibria with respect to the traditional methods of activity coefficient method and EoS. The prediction model was built by using the PR EoS combined with the WS mixing rule. The modified group contribution activity model (UNIFAC-PSRK) was used in the PR-WS (PR-WS-MUNIFAC model). The PR EoS can be written as follows: $p = \frac{RT}{v - b} - \frac{a}{v^{2} + 2 b v - b^{2}}$ $a = \frac{0.457235 R^{2} T_{C}^{2}}{p_{c}} {[1 + k (1 - T_{r}^{0.5})]}^{2}; b = \frac{0.077796 R T_{c}}{p_{c}}$ $k = 0.37464 + 1.54226 ω -$

Results and discussion

All refrigerants used in this paper were not purified after the experiment. VLE data of R1234yf + R134a + R290 system were measured cover the temperature range of 283.15–323.15 K at 10 K intervals. The GC112A gas chromatograph with FID detector was used to analyze the components of the mixture. The temperature of the column box was set at 90 °C, the temperature of the injector and detector were 120 °C, and the injection volume is 15 μl. The experimental VLE data are listed in Table 3.

The

Conclusions

The experimental VLE data of R1234yf + R134a + R290 were measured over the temperature range of 283.15–323.15 K at 10 K intervals. The NRTL-RK model, Wilson-RK model and the PR-WS-MUNIFAC model were used to correlate the experimental data. The AARD of pressure are 0.33%, 0.40% and 0.59%, and the AAD of vapor phase mass fraction are 0.0054 & 0.0057, 0.0128 & 0.0121 and 0.0154 & 0.0138 for Wilson-RK model, NRTL-RK model and PR-WS-MUNIFAC model, respectively. It can be concluded that the

Acknowledgments

This work was supported by the National Natural Science Foundation of China (No. 5117612), the National Natural Science Foundation of China (51606126) and the Natural Science Foundation of Shanghai (15ZR1428800).

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Cited by (2)

Experimental investigation on vapor liquid equilibrium and azeotropic behavior for the 1,1,1,2-tetrafluoroethane (R134a) + propane (R290) system at temperatures from 253.15 to 303.15 K
2020, International Journal of Refrigeration
This study reports a set of new vapor liquid equilibrium (VLE) data for the binary mixture of 1,1,1,2-tetrafluoroethane (R134a) + propane (R290) at temperatures from 253.15 to 303.15 K, and the saturated vapor pressures of R290 and R134a at temperatures ranging from 253.15 to 323.15 K using a recirculation apparatus with view windows. The VLE data were correlated with the well-known NRTL-RK, Wilson-RK, and UNIQ-RK models. The results indicated that all the models showed good agreement with the experimental data. The average absolute relative deviations of pressure (AARDp) were between 0.01% and 0.02%, while the average absolute deviations of vapor phase mole fraction (AADy) were between 0.0035 and 0.0041. Positive azeotropic behavior could be observed for the R134a + R290 system, and the azeotropic point data at six temperatures from 253.15 to 303.15 K were presented.
Hydrogenolysis of Glycerol to Propylene Glycol: Energy, Tech-Economic, and Environmental Studies
2022, Frontiers in Chemistry

View full text

Measurements of isothermal vapor-liquid equilibrium for 2,3,3,3-tetrafluoroprop-1-ene + 1,1,1,2-tetrafluoroethane + propane system at temperatures from 283.15 to 323.15 K

Highlights

Abstract

Introduction

Section snippets

Materials

Apparatus

Modelling details

Results and discussion

Conclusions

Acknowledgments

Int. J. Refrig.

Fluid Phase Equilib.

Fluid Phase Equilib.

Fluid Phase Equilib.

Fluid Phase Equilib.

Fluid Phase Equilib.

Int. J. Refrig.

J. Chem. Thermodyn.

J. Chem. Thermodyn.

Chem. Eng. Sci.

J. Chem. Thermodyn.

Measurements of isothermal vapor-liquid equilibrium for 2,3,3,3-tetrafluoroprop-1-ene + 1,1,1,2-tetrafluoroethane + propane system at temperatures from 283.15 to 323.15 K