1、4694 (RP-I 2 I 5) Measurements and Model Development for R=400 Series Refrigerants Vladimir Geller, D. Sc. Member ASHRAE ABSTRACT A literature survey to identifi the available thermody- namic property data for several R-400 series refrigerants and the binary pairs comprising these blends is conducte
2、d. The most accurate data are evaluated. Vapor-liquid equilibrium properties (bubble-point pressure and liquid density) and single-phase liquid PVT properties are measured for the binary mixtures R-22/124, R-22/125, R-22/142b, R-22/152a, R-l24/142b, and R-l24/152a, and also for R-401A (R-221 152424
3、53/13/34), R-402A (R-125/290/22 60/2/38), and R-409A (R-22/124/1426 60/25/15). Based on the measured thermodynamic propers data together with applicable liter- ature data, the binary interaction parameters in the Lemmon- Jacobsen (1999) mixture model arejttedfor all mixtures stud- ied. The aperiment
4、al data are compared with the values calculatedfrom REFPROP 6. O with the original and with the corrected binary interaction parameters. INTRODUCTION A number of HCFC-based zeotropic blends in the R-400 series are widely used today in CFC retrofit applications. Of these refrigerants, a number of dat
5、a sources for R-401A (R-221 402A (R- 125/290122,60/2138), R-402B (R- 1251290/22,3&/21 60), and R-409A (R-22/124/142b, 6012515) show significant deviation in thermodynamic property values when compared with the output of some widely used thermodynamic models. The ASHRAE Handbook does not contain data
6、 on these refrigerants. Properties of these refrigerants are, however, available from the manufacturers technical bulletins and the NIST refrigerant database REFPROP. Engineers retrofitting 152d124, 53/13/34), R-401B (R-22/152d124, 61/11/28), R- CFC equipment to HCFCs and field servicemen will typic
7、ally use the most convenient source of data available. This often results in an inconsistent charging of the machinery when the reference sources differ widely in their published data. The objective of this work is to measure the vapor-liquid equilibrium properties (bubble-point pressure and liquid
8、density) and single-phase liquid density of several R-400 series refiigerants as well as the binary mixtures R-221124, R-124/ 152a, R-125122, R-22/152a, R-22/142b, and R-l24/142b over a temperature range from 233 to 323 K (40 to 122“F), evaluate the measured data along with data on these systems fro
9、m the literature, fit the data to the mixture model used in REFPROP 6.0 in order to obtain the interaction parameters, and provide critically evaluated accurate thermodynamic property data for R-401A, R-401B, R-402A, R-402B, and R-409A. Literature Survey of Available Thermodynamic Property Data Ther
10、modynamic property data available in the literature for six binary and two ternary mixtures from the R-400 series refrigerants are listed in Table 1. Singh et al. (1999) measured VLE data of R-22/152a and R-221124 at five different compositions The pressure was measured with a diaphragm pressure tra
11、nsmitter. The uncer- tainty in pressure was estimated to be less than -t2 kPa (50.3 psia), and the uncertainty in temperature was estimated to be less than S0.05 K (&O. 1 OF). The measuring cell was charged with a premixed blend to give 60% to 65% liquid fill of the cell volume at the lowest tempera
12、ture. Liquid and vapor samples were taken at each temperature. The samples were analyzed by gas chromatography. V. Geiler is principal investigator at Thermophysics Research Center, San Francisco, Calif. 02004 ASHRAE. 3 Table 1. Summary of Experimental Data for Binary and Ternary Mixtures Author Pro
13、perties Temperature Pressure No. Points K OF MPa psia R-22/142b Dressner and Bier (1993) PVT 373-423 212-302 0.2-55 29-8000 107 Sand et al. (1994) Strm and Gren (1 993) 4 VLE 273 32 PVT 264-323 16-122 0.5- 1.5 73-2 18 48 - - Maezawa et al. (1992) VLE 280-400 44-260 0.3-4.4 44-638 46 Sousa et al. (19
14、92) Kumagai et al. (1991) Lame et. al (1990) Arnemann and Kruse (I 989) Valtz et al. (1986) PVT 300-370 80-206 0.7-19 98-2750 73 VLE, PVT 297-443 75-338 0.5-10 73-1450 422 VLE 253-333 -4-140 0.2-2 29-290 26 - 48 VLE 233-353 -40- 176 - VLE 298-372 77-21 O 0.3-4.3 44-624 19 Singh et al. (1999) Dressne
15、r and Bier (1 993) Sand et al. (1 994) R-221152a VLE 255-323 -1-122 0.1-1.6 15-232 16 PVT 333-423 140-302 0.3-57 44-8270 142 VLE 273 32 3 - - Strm and Gren (1 993) PVT 262-3 13 12-104 0.5-1.5 73-218 64 Wang et al. (1 992) Maezawa et al. ( 199 1 a) 31 VLE 372-385 210-233 - - VLE 280-380 44-224 0.3-4.
16、8 44-696 66 Lame et. al. (1990) VLE 253-333 4- 140 0.2-1.9 29-276 28 - 37 Arnemann and Kruse (1 989) VLE 233-353 40- 1 76 - Singh et al. (1 999) VLE 255-323 -1-122 O. 1-1.6 12-232 20 Sand et al. (1994) VLE 273 - - R-221124 3 R-l24/152a It Sand et al. (1994) VLE 273 32 - - R-1241142b Lee et al. (1996
17、) VLE 298,3 12 77,102 0.3-0.6 44-87 23 3 Sand et al. (1994) VLE 273 32 - Bobbo et al. (2002) VLE 258-303 5-86 0.3-1.8 44-26 1 57 R-1251290 Kayukawa and Watanabe (2001) PVT 305-380 89-224 0.2-4.9 29-7 1 1 187 Holcomb et al. (1998) VLE, PVT 280-364 44- 196 O 6-4.2 87-609 89 R-152a1142b Maezawa et al.
18、(I 99 1 c) VLE 280-400 44-260 O 3-4.2 44-6 15 48 R-221152a1142b Maezawa et ai. (1991b) VLE 280-390 44-242 0.3-4.3 44-630 71 R-2211241142b Bouchot and Richon (1998) VLE, PVT 253-333 -4-140 0.1-15.5 15-2210 13,000 4 ASHRAE Transactions: Research The measurements of VLE for the R- 124/R- 142b mixture w
19、ere reported by Lee et al. (1996). A recirculation-type appa- ratus with a magnetic pump was used. Vapor and liquid samples were analyzed chromatographically. The absolute calibration method was used for determining the vapor and liquid compositions. The uncertainty of composition was esti- mated to
20、 be within *0.002 mole fraction. The temperature was measured with a platinum resistance thermometer, and pres- sure was measured with a pressure transducer. The uncertain- ties in temperature and pressure were estimated to be less than k0.05 K (*O. 1 OF) and Sl kPa (SO. 15 psia). The purities of th
21、e samples were 99.95% for R-124 and 99.90% for R-142b. Dressner and Bier (1 993) measured PVT in the super- heated vapor phase for the mixtures R-22/142b and R-22/ 152a. A Burnett-type apparatus with an estimated uncertainty of *0.2% was used in these measurements. All measurements were carried out
22、at a composition of approximately 0.5/0.5 mole fraction. For the mixtures R-22/142b, R-22/152a, R-22/t24, R- 124/142b, and R-124/152a7 Sand et al. (1994) have published experimental bubble-point pressures in a range of composition from 0.2 to 0.8 mole fraction. The results were obtained by direct pr
23、essure measurements. Strm and Gren (1 993) measured single-phase liquid PVT data for the mixtures R-22/142b and R-22/152a at three and six compositions, respectively. Densities were determined by a vibrating tube method. Temperature control was provided by a precision thermostatic bath, and the temp
24、erature was measured with a platinum resistance thermometer with a sensitivity of kO.01 K (*0.02“F). The pressure was measured by a pressure transducer with a precision of %0.05%. The refrigerant R-22 had purity of 99.8 mass %, and R-142b and R-152a had purities better than 98 mass %. Sousa et al. (
25、1992) measured liquid density of the R-22/ 142b mixture. The measurements were carried out at a compo- sition of 0.44/0.56 mole fraction. A vibrating tube densimeter equipped with a high temperature-high pressure cell was used. The temperature of the densimeter cell was measured to within 0.07 K (*0
26、.14“F) with a thermocouple, and the pressure was measured with a Bourdon-type gauge accurate to 0.005 MPa (50.7 psia). The purities of the samples used were 99.85%. The uncertainties of the measured density data were estimated to be *0.08%. Wang et al. (1992) performed the measurements of the vapor-
27、liquid coexistence curve near the critical point for the mixture R-22/152a at three compositions. The method used was based on observing the behavior of the meniscus in an optical cell at the vapor-liquid interface and the critical opal- escence intensity. The temperature was measured with a plat- i
28、num resistance thermometer with the estimated uncertainty ofkO.O1 K (*0.02“F). The estimated uncertainty of the density and composition of the tested samples was not greater than 0.5% and 0.015%, respectively. A large volume of bubble-point pressure and saturated liquid density measurements was publ
29、ished by Maezawa et al. (1991a, 1991b, 1991c, 1992). The measurements were performed for the binary mixtures R-22/142b at four compo- sitions, R-22/152a at five compositions, R-152d142b at four compositions, and also for the ternary mixture R-22/152d 142b at six different compositions. A magnetic de
30、nsimeter coupled with a variable volume cell incorporating a metallic bellows was used for these measurements. The temperature of the sample was measured by a standard platinum resistance thermometer placed in the vicinity of the sample cell. The pressure was measured by a precision digital pressure
31、 gauge. The experimental uncertainties in temperature, pressure, density, and composition were estimated to be not greater than *0.015 K (*0.03“F), k0.002 MPa (k0.3 psia), 50.3%, and *O. 14%, respectively. The purities of the samples used were 99.97% for R-22, 99.8% for R-l42b, and 99.9% for R-152a.
32、 Detailed measurements of the PVT properties for the binary R-22/142b system were performed by Kumagai et al. (1 99 1). The PVT measurements were made at four composi- tions by a constant volume method coupled with isothermal expansion procedures. The temperature was measured by a platinum resistanc
33、e thermometer to within rtO.0 1 K (rt0.02“F). The sample pressure was transmitted to an external pressure measuring system through a diaphragm-type differential pres- sure detector by balancing the sample pressure with the pres- sure of nitrogen gas applied as the pressure-transmitting medium. The s
34、ensitivity of the pressure measurements was about 1 kPa (*O. 15 psia). The nitrogen pressure was measured with two different pressure gauges: an air piston gauge for low pressures and an oil-operated deadweight pressure gauge for high pressures. The uncertainty of the pressure measurements was less
35、than %i .4 kpa (*0.2 psia) and k3.0 kPa (50.4 psia), respectively. The uncertainty of the density measurements after the expansion procedure accumulates by repeating the expansion. The expansion procedures did not exceed three times, and the uncertainty of the density measurements was estimated to b
36、e less than 50.1%. Approximately half of the experimental points were obtained for the vapor-liquid coex- istence state in the two-phase region. These results were analyzed graphically, and the dew and bubble points were determined by finding the breaking point of each isochore on the P-T diagram. L
37、arue et al. (1 990) measured bubble-point pressure and saturated liquid density for the mixtures R-22/142b and R-22/ 152a at four compositions for each mixture. A variable- volume measuring cell was used for these experiments. The uncertainties in temperature and pressure were estimated to be not gr
38、eater than %0.01 K (k0.02“F) and *0.5%, respectively. The purities of the samples used were not indicated. bemann and Kruse (1989) have published the satu- rated-liquid density data for the mixtures R-22/142b and R-22/ 152a at eight compositions for R-22I142b and at seven compo- sitions for R-22/152
39、a. It should be noted that these data are given only in a graphic format. We have calculated saturated- liquid density for the mixture R-22/142b with the polynomial ASHRAE Transactions: Research 5 equation given in this paper and fitted the results to the mixture model. Valtz et al. (1986) measured
40、bubble-point pressure and saturated liquid molar volume for the mixture R-22/142b at different compositions. A variable-volume cell allowing the simultaneous determination of bubble-point pressure and saturated liquid density through pressure versus density measurements was used. The temperature was
41、 measured by thermocouples calibrated against a platinum resistance ther- mometer with an estimated uncertainty of 0.1 K (h0.2F). Three pressure transducers were used to cover the entire range of pressures. The uncertainties of the pressure and density measurements were estimated to be from 3 to 8 k
42、Pa (0.4 to 1.2 psia) and 0.2%, respectively. The purities of the samples used in this work were 98% for R-22 and 99.8% for R-142b. Bobbo et al. (2002), Kayukawaand Watanabe (2001), and Holcomb et al. (1998) have reported the thermodynamic prop- erty measurements for the mixture R-125/290. The measur
43、e- ments include detailed VLE data, near-saturation PVT data, and PVT data in the single-phase region and cover a wide range of temperature, pressure, and mixture composition. Only two literature sources were found for the thennody- namic properties of the ternary mixtures containing the refhg- eran
44、ts R-22, R-124, R-l42b, and R-152a. Maezawa et al. (1 99 i b) have measured bubble-point pressure and saturated liquid density of the ternary R-22/R- 152dR- 142b system at six different compositions. The experimental uncertainties in temperature, pressure, density, and composition were esti- mated t
45、o be not greater than h0.015 IS (*0.03“F), *0.02 MPa (*3 psia), *0.3%, andh0. 14%, respectively. The purities ofthe samples used were 99.97% for R-22, 99.8% for R-l42b, and 99.9% for R-152a. Bouchot and Richon (1 998) have measured VLE and PVT data for R-409A using a vibrating tube densimeter that w
46、as designed for isothermal runs for both measurement and calibration procedures. Temperatures were measured by two platinum resistance thermometers. The uncertainty in temper- ature measurements was estimated to be *0.25 K (*OSOF). The pressure measurements were provided with a strain gauge transduc
47、er. The uncertainty in the pressure measurements was estimated to be less than *3 kPa (rt0.4 psia). The estimated uncertainties in density were less than k0.3 kg/m3 (h0.02 lb/ fi3). More than 13,000 experimental points were measured (nine isotherms for vapor and nine isotherms for liquid). Each isot
48、herm was described, and the dew and bubble points were obtained from the treatment of each segment of isothenn in the vapor and liquid phases, respectively. THERMODYNAMIC PROPERTY MEASUREMENTS Detailed descriptions of our vapor-liquid equilibrium and PVT measuring devices are given in our earlier pa
49、per (Bivens et al. 1996). Vapor-liquid equilibrium properties were measured using a high-pressure cell constructed of a stainless steel cylinder with a sapphire visual tube. The volume of the cell was calibrated with distilled water before the measure- ments. The cell was immersed in a precision temperature bath having optical windows. The visual tube allowed us to deter- mine the level of phase equilibrium within the system and, therefore, the volume of the system occupied by the liquid phase. The design of this measuring device eliminated condensation of the refrigerant blend in
