1234ze (E) Propane
1234ze (E) Propane
1234ze (E) Propane
available at www.sciencedirect.com
w w w . i i fi i r . o r g
Xueqiang Dong a,b, Maoqiong Gong a,*, Jun Shen a, Jianfeng Wu a,**
a
Key Laboratory of Cryogenics, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, P.O. Box 2711, Beijing 100190,
China
b
Graduate University of Chinese Academy of Sciences, Beijing 100039, China
Article history: The VLE data for the binary system of R1234ze(E) þ R290 were measured with a recircula-
Received 21 November 2010 tion method at four temperatures (258.150, 263.150, 273.150 and 283.150 K). The measured
Received in revised form uncertainties of the temperature, pressure, and compositions are 5 mK, 0.0005 MPa,
19 February 2011 and 0.005, respectively. All the experimental data were correlated by the PengeRobinson
Accepted 16 March 2011 (PR) EoS with the HuroneVidal (HV) mixing rule involving the non-random two-liquid
Available online 24 March 2011 (NRTL) activity coefficient (PReHVeNRTL) model. Azeotropic behavior can be found at the
measured temperature range.
Keywords: ª 2011 Elsevier Ltd and IIR. All rights reserved.
R290
Azeotropic mixtures
Equilibrium
Refrigerant
The use of the chlorofluorocarbon (CFC) and hydro- The apparatus used in this work is the same as used in our
chlorofluorocarbon (HCFC) refrigerants has been prohibited previous work (Dong et al., 2011). It is based on the vapor-
with the implementation of the Montreal protocol and its phase recirculation method and shown in Fig. 1. A 150 ml
modifications because of their high ozone depletion poten- stainless steel cell equipped with two glasses was immerged
tial (ODP) values. Searching for the high efficient and envi- in the isothermal liquid bath. The bath is full with alcohol
ronment friendly alternative refrigerants becomes one of the which was cooled by a refrigerating machine and heated by an
most important tasks for the refrigeration industry. The electric heater. To obtain a uniform temperature distribution,
former investigations show that it is very hard to find two stainless steel stirrers with speed controller were located
appropriate pure substance candidates. Therefore, mixed in the bottom of liquid bath. The Shimaden SR 253 digital
refrigerants especially the azeotropes are becoming more controllers were used to control the temperature of the bath
and more attractive for their behaviors are very nearly as by changing the power of the electric heater. The liquid bath
pure substance at their azeotropic compositions. The was placed in a vacuum vessel to prevent the heat transfer to
performance and the optimal concentration of the mixed the environment and frosting on the bath. The inner of the cell
refrigerants can be estimated by their thermodynamic can be seen through the glasses on the two sides of liquid bath
properties, such as the vaporeliquid equilibrium (VLE) data. and vacuum vessel. A self-made magnetic pump outside the
VLE data of some binary mixtures have been measured in vacuum vessel was used to accelerate the equilibrium
our previous work (Dong et al., 2010a, b, 2011). In this study, process. The vapor phase at the top of the equilibrium cell was
isothermal VLE data for (trans-1,3,3,3-tetrafluoropropene driven into the liquid phase by the pump. A copper tube with
(R1234ze(E)) þ propane (R290)) systems were measured by distributed nozzles was located at the end of the recirculation
a recirculation apparatus with view windows at four loop to make the return vapor phase mix evenly with the
temperatures (258.150, 263.150, 273.150 and 283.150 K), and liquid phase. The temperature in the equilibrium cell was
the azeotropic behavior was found at each measured measured by a 25 U standard platinum resistance thermom-
temperature. R1234ze(E) and R290 are good components with eter which was inserted in the cell. It was calibrated by the
zero ODP and very low global warming potential (GWP) Cryogenic Metrology Station of the Chinese Academy of
values. Their mixtures are friendly to the environment. Sciences based on the 1990 International Temperature Scale
(ITS 90) with an uncertainty less than 3 mK. The combined
standard uncertainty of the temperature measurement is
estimated to be less than 5 mK. A Mensor series 6000 digital
2. Experimental section pressure transducer was used to measure the pressure in the
cell. The transducer has two full scales of 1.25 MPa and
2.1. Materials 2.5 MPa with uncertainties of 0.00025 MPa and 0.0005 MPa,
respectively. In this work, the full scale of 1.25 MPa was used.
R1234ze(E) was supplied by Nanjing Yuji Tuohao Co with The combined standard uncertainty of the pressure
a declared mole fraction of 0.995. R290 was provided by Dalian measurement is estimated to be 0.0005 MPa. The composi-
Special Gas Industry Company with a declared mole fraction tions of the vapor and liquid phase were analyzed by a Shi-
of >0.999. Both of the materials were used without further madzu GC2014 gas chromatograph equipped with a thermal
purification. conductivity detector (TCD). The gas chromatograph was
1240 i n t e r n a t i o n a l j o u r n a l o f r e f r i g e r a t i o n 3 4 ( 2 0 1 1 ) 1 2 3 8 e1 2 4 3
Fig. 1 e Schematic diagram of the experimental system. 1, Temperature and pressure indicator; 2, digital controller; 3,
refrigerating machine; 4, evaporator; 5, stirrer; 6, electric heater; 7, equilibrium cell; 8, view windows; 9, vacuum pump; 10,
isothermal liquid bath; 11, vacuum vessel; 12, motor; 13, gas chromatograph; 14, feed system; 15, magnetic pump.
calibrated by the mixtures that were pre-prepared gravimet- At last, the content of the cell was evacuated and the satu-
rically. The uncertainty of the composition measurement is rated vapor pressure data of R290 were measured.
estimated to be less than 0.005 in mole fraction.
The system was firstly evacuated to remove the residual The VLE data for the binary system of R1234ze(E) þ R290 were
impurities at room temperature. Small amounts of pure measured at four temperatures (258.150, 263.150, 273.150 and
R1234ze(E) were then driven into the cell and degassed from 283.150 K). All the experimental data were correlated by the
the cell for at least three times to purge the total system. While PengeRobinson (Peng and Robinson, 1976) equation of state
the temperature of the liquid bath was decreasing, the pure (PR EoS) incorporating the HuroneVidal (HV) mixing rule
R1234ze(E) was driven into the equilibrium cell. After the (Huron and Vidal, 1979) utilizing the non-random two-liquid
desired temperatures were reached and maintained for at (NRTL) activity coefficient model (Renon and Prausnitz, 1968).
least 1 h with the continuous work of the magnetic pump, and The critical temperatures, critical pressures, and acentric
the temperature fluctuation in the cell was less than 3 mK factors for R1234ze(E) and R290 used in the correlation are
for at least 10 min, the saturated vapor pressure data of shown in Table 1. The saturated vapor pressures data of R290
R1234ze(E) were obtained. Suitable amount of R290 was then
charged into the cell and mixed sufficiently with R1234ze(E)
under the work of magnetic pump. After the desired temper-
atures were reached and maintained for at least 1 h, and the Table 1 e Critical parameters and acentric factors for
fluctuation of the temperature in the cell was less than 3 mK R1234ze(E) and R290.
for at least 10 min, the equilibrium state was considered to be Compound Tc (K) Pc (MPa) u
reached. The pressure in the cell was recorded from the digital a a
R1234ze(E) 382.51 3.632 0.3086b
pressure transducer. The vapor and liquid mole fractions were R290c 369.89 4.251 0.1521
measured by the gas chromatograph at least three times, and
then the average value was recorded. Repeating this process a Values from Higashi and Tanaka (2010).
b Values from Akasaka (2010).
by adding the more volatile component (R290 in this work)
c Values from Refprop (Lemmon et al., 2007).
step by step, VLE data of other concentration were measured.
i n t e r n a t i o n a l j o u r n a l o f r e f r i g e r a t i o n 3 4 ( 2 0 1 1 ) 1 2 3 8 e1 2 4 3 1241
T ¼ 263.150 K
RTc 0.3453 0.000 0.000 0.3444 0.0000 0.0009 0.0000
b ¼ 0:077796 (3)
pc 0.3576 0.120 0.131 0.3574 0.1303 0.0002 0.0007
0.3574 0.203 0.183 0.3572 0.1820 0.0002 0.0010
where 0.3458 0.388 0.257 0.3459 0.2613 0.0001 0.0043
2 0.3374 0.463 0.287 0.3380 0.2902 0.0006 0.0032
aðTÞ ¼ 1 þ 0:37464 þ 1:54226u 0:26992u2 1 T0:5
r (4) 0.3111 0.627 0.357 0.3119 0.3628 0.0008 0.0058
0.2983 0.685 0.394 0.2982 0.3973 0.0001 0.0033
T 0.2670 0.785 0.476 0.2673 0.4777 0.0003 0.0017
Tr ¼ (5) 0.2153 0.902 0.639 0.2140 0.6489 0.0013 0.0099
Tc
0.1464 1.000 1.000 0.1486 1.0000 0.0022 0.0000
pc and Tc are the critical pressure and temperature, respec-
T ¼ 273.150 K
tively, and u is the acentric factor.
0.4745 0.000 0.000 0.4732 0.0000 0.0013 0.0000
The HV mixing rules are given as 0.4915 0.120 0.131 0.4915 0.1312 0.0000 0.0002
X 0.4918 0.203 0.187 0.4918 0.1858 0.0000 0.0012
aii gE 0.0001 0.0036
a¼b xi N (6) 0.4762 0.390 0.270 0.4763 0.2736
bii C 0.4648 0.463 0.292 0.4653 0.3051 0.0005 0.0131
0.4267 0.626 0.388 0.4286 0.3864 0.0019 0.0016
X
b¼ xi bii (7) 0.4099 0.685 0.424 0.4098 0.4240 0.0001 0.0000
0.3697 0.784 0.505 0.3687 0.5089 0.0010 0.0039
where gEN is the excess Gibbs energy at infinite pressure and C 0.3000 0.904 0.678 0.2977 0.6866 0.0023 0.0086
is a constant. For the PR EoS, C is 0.623225. 0.2154 1.000 1.000 0.2177 1.0000 0.0023 0.0000
The NRTL activity coefficient model was used to calculate T ¼ 283.150 K
the excess Gibbs energy in the form 0.6367 0.000 0.000 0.6353 0.0000 0.0014 0.0000
P 0.6598 0.121 0.132 0.6592 0.1321 0.0006 0.0001
s G x 0.6601 0.205 0.191 0.6601 0.1904 0.0000 0.0006
gE X j ji ji j
¼ xi P (8) 0.6404 0.388 0.281 0.6402 0.2856 0.0002 0.0046
RT Gli xl 0.5735 0.629 0.412 0.5752 0.4124 0.0017 0.0004
l
0.4995 0.782 0.534 0.4996 0.5368 0.0001 0.0028
Aji 0.4097 0.909 0.705 0.4044 0.7237 0.0053 0.0187
sji ¼ (9) 0.3070 1.000 1.000 0.3095 1.0000 0.0025 0.0000
T
a Dp ¼ pexp pcal .
Gji ¼ exp aji sji (10) b Dy ¼ y1exp y1cal .
1242 i n t e r n a t i o n a l j o u r n a l o f r e f r i g e r a t i o n 3 4 ( 2 0 1 1 ) 1 2 3 8 e1 2 4 3
0.7 0.005
0.6 0.000
0.5
-0.005
y1exp-y1cal
p/MPa
0.4
-0.010
0.3
-0.015
0.2
-0.020
0.1 0.0 0.2 0.4 0.6 0.8 1.0
0.0 0.2 0.4 0.6 0.8 1.0 x1
x1, y1
Fig. 4 e Deviations of the mole fraction of the vapor phase
Fig. 2 e Vaporeliquid equilibrium diagram for the between the experimental data and the calculated data. -,
R1234ze(E) (1) D R290 (2) system at four temperatures. -, 258.150 K; C, 263.150 K; :, 273.150 K; ;, 283.150 K.
258.150 K; C, 263.150 K; :, 273.150 K; ;, 283.150 K. Solid
lines, calculated using the PReHVeNRTL model.
!
X
N jpexp pcal j Table 4 e Binary parameters and deviations for
F¼ (12) R1234ze(E) D R290 system.
i¼1
pexp
T (K) 258.150 263.150 273.150 283.150
where N is the number of the experimental data points and
Aij (K) 105.211 97.998 77.891 74.871
pexp and pcal are the pressures obtained from the experiment
Aji (K) 333.125 336.863 349.255 339.361
and calculation, respectively.
AARD pa 0.33 0.30 0.30 0.35
The experimental and calculated VLE data are reported in AAD yb 0.0028 0.0030 0.0032 0.0033
Table 3 and plotted in Fig. 2. The symbols pexp refers to the P
a AARD p ¼ ð100=NÞ ni¼1 ðjPexp Pcal j=Pexp Þ.
pressures of the systems; x1exp and y1exp represent the mole P
b AAD y ¼ N i¼1 ðjy iexp yical j=NÞ.
fractions of the liquid and vapor phases for R1234ze(E),
respectively; y1cal refers to the calculated mole fraction of the
vapor phase; Dp and Dy represent the deviations between the
experimental data and the calculated values. Fig. 2 shows are shown in Figs. 3 and 4, respectively. The average absolute
that the correlated results agree well with the experimental deviations (AAD) of vapor-phase mole fraction and the
data at each temperature. The relative deviations of the average absolute relative deviations (AARD) of pressure are
pressures and the deviations of vapor-phase mole fraction presented in Table 4. The values of the adjustable parameters
Aij and Aji in the NRTL model are also shown in Table 4.
Azeotropic behavior can be found at these four temperatures.
2.0 The azeotropic pressure and composition at each tempera-
ture can be determined by solving the following equation
1.5 (Bejan, 1997):
1.0 dp
( Pexp-Pcal) /Pexp×100
¼0 (13)
dx1
0.5
The results are shown in Table 5. The symbols x1,az and paz
0.0 represent the calculated azeotropic compositions of
-0.5 R1234ze(E) and pressures, respectively.
-1.0
-1.5