Compositions

Abstract

The present invention provides a composition, such as a refrigerant composition comprising 1,1-difluoroethene (vinylidene fluoride, R-1132a); trifluoromethane (R-23); and one or more compound selected from hexafluoroethane (R-116), ethane (R-170) and carbon dioxide (R-744, CO.sub.2).

Claims

1. A refrigeration system comprising a composition, the composition comprising: i) 1,1-difluoroethene (vinylidene fluoride, R-1132a); ii) trifluoromethane (R-23); and iii) one or more compound selected from hexafluoroethane (R-116) and ethane (R-170); and iv) about 4% to about 8% of dioxide (R-744, CO.sub.2).

2. The refrigeration system of claim 1, wherein the composition comprises from about 1 to about 98% by weight R-1132a.

3. The refrigeration system of claim 1, wherein the composition comprises from about 1 to about 98% by weight R-23.

4. The refrigeration system of claim 3, wherein the composition comprises about 20 to about 60% by weight R-23.

5. The refrigeration system of claim 1, wherein the composition comprises up to about 80% by weight R-116.

6. The refrigeration system of claim 1, wherein the composition comprises from about 1 to about 40% by weight R-116, from about 5 to about 98% by weight R-1132a and from about 5 to about 98% by weight R-23; or from about 1 to about 30% by weight R-116, from about 20 to about 90% by weight R-1132a and from about 5 to about 95% by weight R-23; or from about 1 to about 25% by weight R-116, from about 30 to about 80% by weight R-1132a and from about 5 to about 90% by weight R-23.

7. The refrigeration system of claim 1, wherein the composition comprises up to about 40% by weight R-170.

8. The refrigeration system of claim 1, wherein the refrigeration system cools a compartment to less than −70° C.

9. The refrigeration system of claim 1, wherein the composition is less flammable than R-1132a alone.

10. The refrigeration system of claim 1, further comprising a lubricant selected from the group consisting of mineral oil, silicone oil, polyalkyl benzenes (PABs), polyol esters (POEs), polyalkylene glycols (PAGs), polyalkylene glycol esters (PAG esters), polyvinyl ethers (PVEs), poly (alpha-olefins) and combinations thereof.

11. The refrigeration system of claim 1, further comprising a stabiliser selected from the group consisting of diene-based compounds, phosphates, phenol compounds, epoxides, and mixtures thereof.

12. The refrigeration system of claim 1, further comprising a flame retardant selected from the group consisting of tri-(2-chloroethyl)-phosphate, (chloropropyl) phosphate, tri-(2,3-dibromopropyl)-phosphate, tri-(1,3-dichloropropyl)-phosphate, diammonium phosphate, antimony oxide, aluminium trihydrate, polyvinyl chloride, a fluorinated iodocarbon, a fluorinated bromocarbon, trifluoro iodomethane, perfluoroalkyl amines, bromo-fluoroalkyl amines, and mixtures thereof.

13. A heat transfer device containing a composition, the composition comprising: i) 1,1-difluoroethene (vinylidene fluoride, R-1132a); ii) trifluoromethane (R-23); and iii) one or more compound selected from hexafluoroethane (R-116) and ethane (R-170); and iv) about 4% to about 8% of dioxide (R-744, CO.sub.2).

14. The heat transfer device of claim 13, wherein the heat transfer device is a refrigeration device selected from an ultra-low temperature refrigeration system and a cascade system.

15. A method for reducing the environmental impact arising from the operation of a product comprising an existing compound or composition, the method comprising replacing at least partially the existing compound or composition with a composition comprising: i) 1,1-difluoroethene (vinylidene fluoride, R-1132a); ii) trifluoromethane (R-23); and iii) one or more compound selected from hexafluoroethane (R-116) and ethane (R-170); and iv) about 4% to about 8% of dioxide (R-744, CO.sub.2).

16. The method of claim 15 wherein the product is selected from a heat transfer device, a sprayable composition, a solvent or a mechanical power generation device.

17. The method of claim 15 wherein the product is an ultra-low temperature refrigeration system, optionally wherein the existing compound or composition is selected from R-508A, R-508B, R-23 and R-1361.

Description

(1) The invention is illustrated by the following non-limiting examples, with reference to the following drawings:

(2) FIG. 1 shows a plot of R-23 concentration against capacity relative to R-508A for compositions of R-1132a, R-23 and carbon dioxide;

(3) FIG. 2 shows a plot of R-23 concentration against coefficient of performance relative to R-508A for compositions of R-1132a, R-23 and carbon dioxide.

EXAMPLES

(4) Compositions of R-1132a, R-23 and R-116

(5) The performance of ternary compositions of the invention are provided in the following Tables 2 to 6, which list the volumetric cooling capacity, COP, compressor pressure ratio, compressor discharge temperature and bubble point pressure for a range of ternary compositions. The table ordinates are R-23 and R-1132a content as weight percentages with the R-116 content being inferred by difference.

(6) TABLE-US-00001 TABLE 1 Cycle conditions for modelling ternary compositions Cycle conditions for modelling Condensing temperature ° C. −40 Evaporating temperature ° C. −85 Suction temperature ° C. same as evaporator outlet Isentropic efficiency 65% Subcooling K    5 Evaporator superheat K    5 Compressor clearance ratio  3%

(7) TABLE-US-00002 TABLE 2 Volumetric cooling capacity in kJ/m.sup.3 R-23 content R-1132a content w/w w/w 0% 5% 10% 15% 20% 25% 30% 35% 40% 45% 50%  0% 542 576 607 634 657 678 696 712 725 736 744  5% 566 604 638 668 695 718 738 756 771 783 792 10% 589 631 668 701 730 756 778 798 815 828 838 15% 611 656 696 732 763 791 816 838 856 871 882 20% 631 679 723 761 795 825 852 876 896 912 924 25% 651 702 748 789 825 858 887 912 934 952 964 30% 668 722 771 815 854 888 919 947 970 989 1002 35% 685 742 793 839 880 916 949 979 1004 1025 1038 40% 700 760 814 862 904 943 978 1009 1036 1058 1072 45% 714 776 833 883 927 967 1003 1037 1066 1089 1104 50% 726 791 850 902 948 989 1027 1062 1093 1118 1134 55% 737 804 865 919 966 1008 1047 1083 1116 1143 60% 747 816 879 934 982 1025 1064 1101 1135 65% 755 826 891 947 996 1039 1078 1115 70% 762 835 901 959 1007 1050 1088 75% 767 842 910 968 1017 1059 80% 771 847 917 976 1025 85% 773 851 923 983 90% 774 854 928 95% 773 855 100%  772 R-23 content R-1132a content w/w w/w 55% 60% 65% 70% 75% 80% 85% 90% 95% 100%  0% 749 752 753 753 751 748 744 739 733 726  5% 798 801 802 802 800 797 794 789 783 10% 844 848 849 849 847 845 841 836 15% 889 893 894 894 892 890 886 20% 931 935 936 936 935 932 25% 972 975 976 976 974 30% 1010 1013 1014 1013 35% 1046 1049 1049 40% 1080 1082 45% 1111 50% 55% 60% 65% 70% 75% 80% 85% 90% 95% 100% 

(8) TABLE-US-00003 TABLE 3 Cooling Coefficient of Performance (COP) R-23 content R-1132a content w/w w/w 0% 5% 10% 15% 20% 25% 30% 35% 40% 45% 50%  0% 2.32 2.29 2.26 2.24 2.23 2.22 2.21 2.21 2.21 2.21 2.21  5% 2.32 2.30 2.28 2.27 2.26 2.25 2.25 2.24 2.24 2.25 2.25 10% 2.33 2.31 2.30 2.29 2.28 2.28 2.28 2.28 2.28 2.28 2.28 15% 2.33 2.32 2.32 2.31 2.31 2.31 2.31 2.31 2.31 2.31 2.32 20% 2.34 2.33 2.33 2.33 2.33 2.33 2.33 2.34 2.34 2.34 2.34 25% 2.34 2.34 2.34 2.35 2.35 2.35 2.36 2.36 2.37 2.37 2.37 30% 2.34 2.35 2.36 2.36 2.37 2.37 2.38 2.38 2.39 2.39 2.39 35% 2.34 2.36 2.37 2.38 2.38 2.39 2.40 2.40 2.41 2.41 2.41 40% 2.34 2.36 2.38 2.39 2.40 2.41 2.41 2.42 2.43 2.43 2.43 45% 2.34 2.37 2.38 2.40 2.41 2.42 2.43 2.44 2.45 2.45 2.45 50% 2.34 2.37 2.39 2.41 2.42 2.43 2.44 2.45 2.46 2.47 2.46 55% 2.34 2.37 2.40 2.42 2.43 2.44 2.45 2.46 2.47 2.48 60% 2.34 2.37 2.40 2.42 2.44 2.45 2.46 2.47 2.48 65% 2.34 2.37 2.40 2.43 2.44 2.45 2.46 2.47 70% 2.33 2.37 2.41 2.43 2.45 2.46 2.47 75% 2.33 2.37 2.41 2.43 2.45 2.46 80% 2.32 2.37 2.41 2.43 2.45 85% 2.31 2.36 2.41 2.43 90% 2.31 2.36 2.40 95% 2.30 2.35 100%  2.29 R-23 content R-1132a content w/w w/w 55% 60% 65% 70% 75% 80% 85% 90% 95% 100%  0% 2.21 2.22 2.22 2.22 2.23 2.23 2.24 2.25 2.25 2.26  5% 2.25 2.25 2.26 2.26 2.26 2.27 2.27 2.28 2.28 10% 2.28 2.29 2.29 2.29 2.29 2.30 2.30 2.31 15% 2.32 2.32 2.32 2.32 2.32 2.33 2.33 20% 2.34 2.34 2.35 2.35 2.35 2.35 25% 2.37 2.37 2.37 2.37 2.37 30% 2.39 2.39 2.39 2.39 35% 2.41 2.41 2.41 40% 2.43 2.42 45% 2.44 50% 55% 60% 65% 70% 75% 80% 85% 90% 95% 100% 

(9) TABLE-US-00004 TABLE 4 Compressor Pressure Ratio R-23 content R-1132a content w/w w/w 0% 5% 10% 15% 20% 25% 30% 35% 40% 45% 50%  0% 7.85 7.63 7.43 7.28 7.15 7.05 6.98 6.92 6.88 6.86 6.86  5% 7.87 7.65 7.46 7.30 7.18 7.08 7.01 6.95 6.91 6.90 6.90 10% 7.89 7.66 7.47 7.31 7.19 7.10 7.02 6.97 6.93 6.92 6.92 15% 7.90 7.67 7.48 7.32 7.20 7.11 7.03 6.98 6.94 6.93 6.94 20% 7.90 7.67 7.48 7.33 7.21 7.11 7.04 6.99 6.95 6.94 6.95 25% 7.91 7.67 7.48 7.33 7.21 7.12 7.04 6.99 6.95 6.94 6.95 30% 7.91 7.68 7.48 7.33 7.21 7.12 7.05 6.99 6.95 6.94 6.96 35% 7.92 7.68 7.48 7.33 7.21 7.12 7.05 6.99 6.96 6.94 6.96 40% 7.92 7.68 7.48 7.33 7.21 7.12 7.05 6.99 6.96 6.95 6.97 45% 7.93 7.69 7.48 7.33 7.21 7.13 7.06 7.00 6.96 6.95 6.97 50% 7.95 7.69 7.49 7.33 7.22 7.13 7.07 7.01 6.97 6.95 6.98 55% 7.96 7.70 7.49 7.34 7.23 7.15 7.08 7.03 6.98 6.97 60% 7.98 7.71 7.50 7.35 7.24 7.17 7.10 7.05 7.01 65% 8.00 7.73 7.51 7.36 7.26 7.19 7.14 7.09 70% 8.03 7.75 7.53 7.38 7.28 7.22 7.17 75% 8.06 7.77 7.55 7.40 7.31 7.25 80% 8.10 7.80 7.57 7.42 7.33 85% 8.14 7.84 7.59 7.44 90% 8.19 7.87 7.61 95% 8.24 7.91 100%  8.30 R-23 content R-1132a content w/w w/w 55% 60% 65% 70% 75% 80% 85% 90% 95% 100%  0% 6.87 6.90 6.93 6.97 7.02 7.06 7.11 7.16 7.21 7.26  5% 6.92 6.95 6.99 7.04 7.09 7.14 7.20 7.27 7.33 10% 6.94 6.98 7.03 7.08 7.13 7.19 7.26 7.32 15% 6.96 7.00 7.05 7.10 7.16 7.22 7.29 20% 6.97 7.02 7.07 7.12 7.18 7.24 25% 6.98 7.03 7.09 7.14 7.20 30% 6.99 7.05 7.10 7.16 35% 7.00 7.06 7.12 40% 7.02 7.08 45% 7.03 50% 55% 60% 65% 70% 75% 80% 85% 90% 95% 100% 

(10) TABLE-US-00005 TABLE 5 Compressor Discharge Temperature in ° C. R-23 content R-1132a content w/w w/w 0% 5% 10% 15% 20% 25% 30% 35% 40% 45% 50%  0% −14.04 −12.41 −11.00 −9.75 −8.60 −7.51 −6.46 −5.41 −4.33 −3.19 −1.97  5% −10.66 −9.12 −7.79 −6.62 −5.53 −4.51 −3.52 −2.52 −1.48 −0.37 0.84 10% −7.32 −5.87 −4.64 −3.54 −2.54 −1.59 −0.66 0.27 1.26 2.34 3.53 15% −4.00 −2.66 −1.52 −0.52 0.41 1.28 2.13 2.99 3.92 4.95 6.12 20% −0.69 0.54 1.57 2.48 3.31 4.10 4.87 5.66 6.52 7.50 8.65 25% 2.62 3.73 4.65 5.46 6.20 6.90 7.58 8.29 9.07 10.00 11.12 30% 5.93 6.91 7.72 8.42 9.07 9.68 10.27 10.89 11.59 12.47 13.56 35% 9.25 10.10 10.79 11.39 11.94 12.46 12.96 13.48 14.10 14.91 15.98 40% 12.60 13.31 13.88 14.37 14.83 15.25 15.66 16.08 16.61 17.35 18.39 45% 15.97 16.55 16.99 17.38 17.74 18.07 18.38 18.71 19.14 19.80 20.80 50% 19.38 19.81 20.13 20.41 20.68 20.94 21.16 21.40 21.71 22.28 23.23 55% 22.84 23.13 23.31 23.49 23.69 23.87 24.02 24.17 24.39 24.82 60% 26.35 26.49 26.55 26.63 26.76 26.88 26.99 27.09 27.21 65% 29.93 29.91 29.84 29.84 29.91 30.00 30.08 30.15 70% 33.58 33.41 33.21 33.12 33.14 33.22 33.29 75% 37.31 36.97 36.64 36.47 36.45 36.51 80% 41.12 40.61 40.13 39.87 39.81 85% 45.01 44.32 43.68 43.31 90% 48.99 48.09 47.27 95% 53.05 51.93 100%  57.19 R-23 content R-1132a content w/w w/w 55% 60% 65% 70% 75% 80% 85% 90% 95% 100%  0% −0.67 0.68 2.06 3.44 4.78 6.09 7.34 8.54 9.69 10.78  5% 2.15 3.53 4.94 6.35 7.73 9.08 10.39 11.67 12.91 10% 4.84 6.23 7.65 9.07 10.47 11.84 13.17 14.48 15% 7.42 8.82 10.24 11.67 13.06 14.43 15.77 20% 9.94 11.33 12.76 14.18 15.56 16.91 25% 12.41 13.80 15.22 16.63 18.00 30% 14.85 16.24 17.66 19.05 35% 17.27 18.67 20.08 40% 19.68 21.09 45% 22.10 50% 55% 60% 65% 70% 75% 80% 85% 90% 95% 100% 

(11) TABLE-US-00006 TABLE 6 Bubble Point Pressure at −40° C. in kPa R-23 R-1132a wt % wt % 0 5% 10% 15% 20% 25% 30% 35% 40% 45% 50% 0 540.1 579.0 610.3 635.5 655.5 671.4 683.8 693.4 700.5 705.7 709.2  5% 563.4 604.1 637.2 664.0 685.6 703.0 716.9 728.0 736.7 743.5 748.7 10% 584.0 626.4 661.0 689.2 712.1 730.8 746.0 758.3 768.3 776.3 782.8 15% 602.2 646.1 682.0 711.4 735.5 755.2 771.4 784.7 795.7 804.8 812.4 20% 618.3 663.4 700.5 731.0 756.0 776.6 793.7 807.9 819.7 829.6 838.0 25% 632.4 678.7 716.8 748.2 774.1 795.5 813.2 828.1 840.5 851.1 860.1 30% 644.8 692.2 731.2 763.4 790.0 812.0 830.4 845.8 858.8 869.8 879.4 35% 655.7 704.0 743.8 776.7 803.9 826.6 845.4 861.3 874.7 886.2 896.1 40% 665.2 714.3 754.9 788.5 816.3 839.4 858.7 875.0 888.7 900.5 910.8 45% 673.4 723.4 764.7 798.8 827.1 850.7 870.4 887.0 901.1 913.2 923.7 50% 680.4 731.2 773.2 807.9 836.7 860.7 880.8 897.7 912.1 924.4 935.0 55% 686.5 738.1 780.7 816.0 845.3 869.6 890.0 907.2 921.8 934.4 60% 691.6 744.0 787.2 823.1 852.8 877.6 898.3 915.8 930.6 65% 695.9 749.0 792.9 829.3 859.5 884.7 905.7 923.5 70% 699.3 753.3 797.9 834.8 865.5 891.0 912.5 75% 702.1 756.8 802.1 839.6 870.8 896.8 80% 704.2 759.8 805.7 843.9 875.6 85% 705.7 762.1 808.8 847.5 90% 706.5 763.8 811.3 95% 706.7 764.9 100%  706.2 R-23 R-1132a wt % wt % 55% 60% 65% 70% 75% 80% 85% 90% 95% 100% 0 711.2 711.8 711.3 709.7 706.9 703.1 698.1 692.0 684.4 675.4  5% 752.4 755.0 756.6 757.2 757.0 755.9 754.0 751.2 747.5 10% 788.0 792.1 795.3 797.7 799.3 800.4 800.8 800.6 15% 818.7 823.9 828.4 832.1 835.2 837.8 839.9 20% 845.1 851.3 856.6 861.4 865.6 869.3 25% 867.9 874.8 880.8 886.3 891.3 30% 887.7 895.0 901.6 907.6 35% 904.8 912.5 919.5 40% 919.7 927.7 45% 932.9 50% 55% 60% 65% 70% 75% 80% 85% 90% 95% 100% 

(12) TABLE-US-00007 TABLE 7 Pure fluid vapour pressures at this condition R23 706.2 kPa R1132a 675.4 kPa R116 540.1 kPa Maximum 706.2 kPa

(13) Compositions of R-1132a, R-23 and R-170

(14) The performance of ternary compositions of the invention are provided in the following Tables 10 to 13, which list the volumetric cooling capacity, COP, compressor pressure ratio and compressor discharge temperature for a range of ternary compositions. The table ordinates are R-23 and R-170 content as weight percentages with the R-1132a content being inferred by difference.

(15) The cycle conditions used in the modelling are as Table 1.

(16) TABLE-US-00008 TABLE 9 Reference fluid performance - pure components R170 R23 R1132a R508A Evaporator pressure bar 1.23 0.85 0.93 1.11 Condenser pressure bar 7.79 7.06 6.75 8.53 Pressure ratio 6.33 8.30 7.26 7.71 Volumetric efficiency 90.9% 88.2% 87.5% 86.2% Discharge temperature ° C. 39.5 57.2 10.8 11.4 Volumetric flowrate m.sup.3/hr 37.3 46.7 49.6 38.5 Evaporator temperature glide K 0 0 0 0.4397 Condenser temperature glide K 0 0 0 0.2223 Volumetric capacity kJ/m.sup.3 964 772 726 935 Cooling COP 2.32 2.29 2.26 2.41

(17) TABLE-US-00009 TABLE 10 Volumetric cooling capacity in kJ/m.sup.3 R-170 R-23 w/w w/w 0% 5% 10% 15% 20% 25% 30% 35% 40% 45% 50%  0% 726 744 761 778 794 809 823 835 847 856 864  5% 789 812 834 856 877 899 919 939 958 975 991 10% 843 869 895 922 948 974 1000 1026 1051 1075 1098 15% 887 916 946 976 1007 1037 1068 1098 1128 1158 1186 20% 923 956 989 1022 1056 1090 1125 1160 1194 1228 1261 25% 953 988 1024 1060 1097 1135 1173 1212 1251 1291 1329 30% 977 1014 1052 1091 1131 1172 1214 1256 1300 1344 1389 35% 996 1035 1075 1116 1158 1202 1246 1292 1339 1387 1438 40% 1009 1050 1092 1135 1179 1224 1270 1317 1366 1417 1470 45% 1018 1060 1103 1148 1193 1239 1286 1334 1383 1434 1487 50% 1024 1066 1111 1156 1202 1249 1297 1345 1393 1443 1493 55% 1025 1069 1114 1160 1208 1255 1303 1351 1399 1446 60% 1024 1069 1115 1162 1211 1259 1308 1355 1402 65% 1021 1066 1113 1162 1212 1262 1311 1359 70% 1016 1062 1111 1161 1213 1264 1315 75% 1010 1056 1106 1159 1213 1267 80% 1002 1050 1102 1157 1214 85% 994 1042 1096 1155 90% 984 1034 1090 95% 975 1026 100%  964 R-170 R-23 w/w w/w 55% 60% 65% 70% 75% 80% 85% 90% 95% 100%  0% 869 871 871 867 860 850 837 820 798 772  5% 1006 1018 1029 1037 1043 1049 1054 1059 1065 10% 1119 1139 1156 1172 1187 1203 1221 1243 15% 1212 1236 1256 1274 1291 1307 1324 20% 1292 1319 1341 1358 1373 1386 25% 1365 1395 1419 1435 1447 30% 1432 1470 1496 1511 35% 1490 1541 1576 40% 1527 1589 45% 1542 50% 55% 60% 65% 70% 75% 80% 85% 90% 95% 100% 

(18) TABLE-US-00010 TABLE 11 Cooling Coefficient of Performance (COP) R-170 R-23 w/w w/w 0% 5% 10% 15% 20% 25% 30% 35% 40% 45% 50%  0% 2.26 2.27 2.28 2.29 2.30 2.31 2.32 2.33 2.33 2.34 2.34  5% 2.29 2.30 2.31 2.32 2.33 2.34 2.35 2.36 2.37 2.38 2.39 10% 2.30 2.32 2.33 2.34 2.36 2.37 2.38 2.39 2.40 2.41 2.42 15% 2.32 2.33 2.35 2.36 2.37 2.39 2.40 2.41 2.42 2.43 2.44 20% 2.33 2.35 2.36 2.37 2.39 2.40 2.42 2.43 2.44 2.45 2.46 25% 2.34 2.35 2.37 2.39 2.40 2.42 2.43 2.44 2.46 2.47 2.48 30% 2.35 2.36 2.38 2.40 2.41 2.43 2.44 2.46 2.48 2.49 2.50 35% 2.35 2.37 2.39 2.40 2.42 2.44 2.46 2.47 2.49 2.51 2.53 40% 2.36 2.37 2.39 2.41 2.43 2.45 2.47 2.49 2.50 2.52 2.54 45% 2.36 2.38 2.40 2.42 2.43 2.45 2.47 2.49 2.51 2.53 2.55 50% 2.36 2.38 2.40 2.42 2.44 2.46 2.48 2.50 2.52 2.54 2.55 55% 2.36 2.38 2.40 2.42 2.44 2.46 2.48 2.50 2.52 2.54 60% 2.36 2.38 2.40 2.42 2.44 2.47 2.49 2.51 2.52 65% 2.35 2.37 2.40 2.42 2.45 2.47 2.49 2.51 70% 2.35 2.37 2.40 2.42 2.45 2.48 2.50 75% 2.35 2.37 2.39 2.42 2.45 2.48 80% 2.34 2.36 2.39 2.42 2.46 85% 2.34 2.36 2.39 2.43 90% 2.33 2.36 2.39 95% 2.33 2.35 100%  2.32 R-170 R-23 w/w w/w 55% 60% 65% 70% 75% 80% 85% 90% 95% 100%  0% 2.35 2.35 2.35 2.35 2.35 2.34 2.33 2.32 2.31 2.29  5% 2.40 2.40 2.41 2.41 2.41 2.42 2.42 2.42 2.43 10% 2.43 2.44 2.44 2.45 2.46 2.47 2.48 2.50 15% 2.45 2.46 2.46 2.46 2.47 2.47 2.48 20% 2.47 2.47 2.47 2.47 2.46 2.46 25% 2.49 2.49 2.48 2.47 2.46 30% 2.52 2.52 2.51 2.49 35% 2.55 2.56 2.55 40% 2.57 2.59 45% 2.57 50% 55% 60% 65% 70% 75% 80% 85% 90% 95% 100% 

(19) TABLE-US-00011 TABLE 12 Compressor Pressure Ratio R-170 R-23 w/w w/w 0% 5% 10% 15% 20% 25% 30% 35% 40% 45% 50%  0% 7.26 7.28 7.30 7.31 7.33 7.34 7.36 7.38 7.40 7.43 7.46  5% 7.12 7.13 7.14 7.15 7.16 7.17 7.17 7.18 7.20 7.21 7.23 10% 6.99 7.00 7.00 7.01 7.01 7.01 7.01 7.01 7.01 7.01 7.02 15% 6.88 6.89 6.89 6.88 6.88 6.87 6.87 6.86 6.86 6.86 6.86 20% 6.79 6.79 6.78 6.78 6.77 6.75 6.74 6.73 6.72 6.72 6.72 25% 6.71 6.70 6.69 6.68 6.67 6.65 6.63 6.62 6.60 6.59 6.58 30% 6.64 6.63 6.61 6.60 6.58 6.55 6.53 6.51 6.48 6.46 6.44 35% 6.58 6.56 6.55 6.52 6.50 6.47 6.44 6.41 6.38 6.35 6.31 40% 6.52 6.51 6.49 6.46 6.43 6.40 6.37 6.33 6.30 6.26 6.22 45% 6.48 6.46 6.44 6.41 6.38 6.34 6.31 6.27 6.23 6.20 6.16 50% 6.45 6.43 6.40 6.37 6.33 6.29 6.26 6.22 6.19 6.15 6.12 55% 6.42 6.40 6.37 6.33 6.29 6.25 6.21 6.18 6.14 6.12 60% 6.40 6.38 6.34 6.30 6.26 6.21 6.17 6.13 6.11 65% 6.38 6.36 6.32 6.27 6.22 6.17 6.13 6.09 70% 6.37 6.34 6.30 6.25 6.19 6.13 6.08 75% 6.36 6.33 6.28 6.22 6.15 6.08 80% 6.35 6.32 6.26 6.19 6.10 85% 6.35 6.31 6.25 6.16 90% 6.34 6.30 6.23 95% 6.34 6.30 100%  6.33 R-170 R-23 w/w w/w 55% 60% 65% 70% 75% 80% 85% 90% 95% 100%  0% 7.49 7.54 7.59 7.65 7.73 7.81 7.91 8.02 8.15 8.30  5% 7.25 7.28 7.31 7.35 7.40 7.44 7.48 7.52 7.56 10% 7.03 7.05 7.07 7.09 7.11 7.12 7.11 7.07 15% 6.87 6.89 6.91 6.95 6.97 7.00 7.00 20% 6.73 6.75 6.79 6.84 6.90 6.94 25% 6.59 6.61 6.67 6.74 6.83 30% 6.43 6.44 6.50 6.61 35% 6.28 6.25 6.29 40% 6.17 6.11 45% 6.11 50% 55% 60% 65% 70% 75% 80% 85% 90% 95% 100% 

(20) TABLE-US-00012 TABLE 13 Compressor Discharge Temperature in ° C. R-170 R-23 w/w w/w 0% 5% 10% 15% 20% 25% 30% 35% 40% 45% 50%  0% 10.8 12.1 13.4 14.8 16.2 17.7 19.2 20.8 22.5 24.3 26.2  5% 13.0 14.3 15.7 17.1 18.5 20.0 21.5 23.2 24.9 26.7 28.7 10% 14.9 16.2 17.6 19.0 20.4 21.8 23.4 24.9 26.6 28.4 30.3 15% 16.6 17.9 19.2 20.6 22.0 23.4 24.9 26.4 28.1 29.8 31.7 20% 18.1 19.4 20.8 22.1 23.4 24.8 26.2 27.7 29.3 30.9 32.7 25% 19.6 20.9 22.2 23.5 24.8 26.1 27.5 28.8 30.3 31.8 33.5 30% 21.0 22.2 23.5 24.8 26.0 27.3 28.6 29.9 31.2 32.6 34.0 35% 22.3 23.6 24.9 26.1 27.3 28.5 29.8 31.0 32.2 33.4 34.6 40% 23.7 25.0 26.2 27.4 28.6 29.8 31.0 32.2 33.3 34.5 35.6 45% 25.0 26.3 27.6 28.8 30.0 31.2 32.4 33.5 34.7 35.9 37.0 50% 26.4 27.7 29.0 30.2 31.4 32.6 33.8 35.0 36.2 37.4 38.6 55% 27.8 29.1 30.4 31.7 32.9 34.1 35.3 36.5 37.8 39.1 60% 29.2 30.6 31.9 33.1 34.3 35.5 36.8 38.0 39.3 65% 30.6 32.0 33.3 34.5 35.7 36.9 38.2 39.5 70% 32.0 33.4 34.7 35.9 37.1 38.3 39.5 75% 33.3 34.7 36.0 37.2 38.4 39.5 80% 34.6 36.1 37.4 38.5 39.6 85% 35.9 37.4 38.6 39.7 90% 37.1 38.6 39.8 95% 38.3 39.8 100%  39.5 R-170 R-23 w/w w/w 55% 60% 65% 70% 75% 80% 85% 90% 95% 100%  0% 28.3 30.6 33.0 35.7 38.6 41.7 45.1 48.8 52.8 57.2  5% 30.8 33.1 35.6 38.4 41.3 44.5 48.0 51.6 55.5 10% 32.4 34.7 37.2 40.0 42.9 46.0 49.2 52.4 15% 33.8 36.1 38.6 41.5 44.5 47.7 51.1 20% 34.8 37.1 39.8 42.8 46.0 49.5 25% 35.4 37.7 40.5 43.7 47.3 30% 35.7 37.7 40.5 44.0 35% 35.9 37.3 39.7 40% 36.6 37.5 45% 38.1 50% 55% 60% 65% 70% 75% 80% 85% 90% 95% 100% 

(21) It can be seen that by using compositions of the invention it is possible to achieve improvements in capacity and COP compared to the pure fluid performances and also to achieve reduced compressor pressure ratio. Furthermore it is possible to achieve compressor discharge temperatures that are lower than those to be expected from use of R-508A or R-508B.

(22) Compositions of R-1132a, R23 and Carbon Dioxide

(23) The performance of ternary compositions of the invention are provided in the following Tables 15 to 18, which list performance characteristics for a range of ternary compositions. Plots of capacity and coefficient of performance of the compositions relative to R-508A against R-23 concentration are shown in FIGS. 1 and 2.

(24) The cycle conditions used in the modelling are as Table 1.

(25) TABLE-US-00013 TABLE 14 Calculated performance of reference (r508b) and pure components R508A R1132a R23 Capacity relative to reference 100.0% 83.4% 79.3% COP relative to reference 100.0% 94.2% 91.3% Discharge temperature difference 0.0 −3.8 46.1 (K) Pressure ratio — 7.71 6.74 8.35 Condenser glide K 0.2 0.0 0.0 Evaporator glide K 0.4 0.0 0.0 Condensing pressure bar 8.53 7.01 7.06 Evaporating pressure bar 1.11 1.04 0.85 COP — 2.41 2.27 2.20 Discharge temperature ° C. 11.4 7.6 57.5 Volumetric capacity kJ/m3 935 780 742

(26) TABLE-US-00014 TABLE 15 CO.sub.2 4% 4% 4% 4% 4% 4% 4% 4% 4% 4% R23 0% 10% 20% 30% 40% 50% 60% 70% 80% 90% R1132a Quantity Units 96% 86% 76% 66% 56% 46% 36% 26% 16% 6% Capacity relative to 86.2% 88.2% 89.8% 90.8% 91.3% 91.2% 90.4% 88.9% 86.8% 84.1% reference COP relative to reference 94.1% 94.0% 93.8% 93.5% 93.3% 92.9% 92.5% 92.2% 91.8% 91.4% Discharge temperature −1.5 1.3 4.4 7.9 11.9 16.4 21.7 27.8 34.7 42.5 difference (K) Pressure ratio — 6.8 6.8 6.9 7.0 7.1 7.3 7.4 7.6 7.9 8.1 Condenser glide K 0.4 0.4 0.4 0.3 0.2 0.2 0.2 0.3 0.4 0.4 Evaporator glide K 0.2 0.2 0.1 0.1 0.1 0.2 0.4 0.6 0.6 0.5 Condensing pressure bar 7.23 7.41 7.56 7.68 7.75 7.79 7.78 7.71 7.60 7.42 Evaporating pressure bar 1.07 1.08 1.09 1.10 1.09 1.07 1.04 1.01 0.96 0.91 COP — 2.27 2.26 2.26 2.25 2.25 2.24 2.23 2.22 2.21 2.20 Discharge temperature ° C. 9.9 12.7 15.8 19.3 23.3 27.8 33.1 39.2 46.1 53.9 Volumetric capacity kJ/m.sup.3 806 824 839 849 854 853 845 831 812 786

(27) TABLE-US-00015 TABLE 16 R744 8% 8% 8% 8% 8% 8% 8% 8% 8% 8% R23 0% 10% 20% 30% 40% 50% 60% 70% 80% 90% R1132a Quantity Units 92% 82% 72% 62% 52% 42% 32% 22% 12% 2% Capacity relative to 88.8% 90.8% 92.3% 93.2% 93.6% 93.3% 92.3% 90.6% 88.4% 85.5% reference COP relative to reference 94.1% 93.9% 93.7% 93.4% 93.1% 92.7% 92.3% 91.9% 91.5% 91.1% Discharge temperature 0.8 3.7 7.0 10.7 14.9 19.8 25.4 31.8 39.2 47.6 difference (K) Pressure ratio — 6.8 6.9 6.9 7.0 7.2 7.3 7.5 7.7 7.9 8.2 Condenser glide K 0.7 0.7 0.6 0.5 0.4 0.4 0.4 0.5 0.6 0.6 Evaporator glide K 0.3 0.2 0.2 0.2 0.2 0.3 0.5 0.7 0.7 0.5 Condensing pressure bar 7.45 7.62 7.76 7.87 7.94 7.97 7.94 7.87 7.74 7.55 Evaporating pressure bar 1.10 1.11 1.12 1.12 1.11 1.09 1.06 1.02 0.97 0.92 COP — 2.27 2.26 2.26 2.25 2.24 2.23 2.22 2.22 2.21 2.20 Discharge temperature ° C. 12.2 15.1 18.4 22.1 26.3 31.2 36.8 43.2 50.6 59.0 Volumetric capacity kJ/m.sup.3 831 849 863 872 875 872 863 847 826 799

(28) TABLE-US-00016 TABLE 17 R744 12% 12% 12% 12% 12% 12% 12% 12% 12% R23 0% 10% 20% 30% 40% 50% 60% 70% 80% R1132a Quantity Units 88% 78% 68% 58% 48% 38% 28% 18% 8% Capacity relative to 91.4% 93.3% 94.6% 95.5% 95.7% 95.2% 94.0% 92.2% 89.8% reference COP relative to reference 94.0% 93.8% 93.6% 93.3% 92.9% 92.5% 92.1% 91.7% 91.3% Discharge temperature 3.2 6.2 9.6 13.5 18.0 23.2 29.2 36.0 43.9 difference (K) Pressure ratio — 6.8 6.9 7.0 7.1 7.2 7.4 7.6 7.8 8.0 Condenser glide K 0.9 0.8 0.7 0.6 0.5 0.5 0.5 0.6 0.7 Evaporator glide K 0.4 0.3 0.2 0.2 0.3 0.4 0.6 0.7 0.7 Condensing pressure bar 7.65 7.82 7.95 8.05 8.12 8.13 8.10 8.01 7.87 Evaporating pressure bar 1.12 1.13 1.14 1.14 1.13 1.10 1.07 1.03 0.98 COP — 2.27 2.26 2.26 2.25 2.24 2.23 2.22 2.21 2.20 Discharge temperature ° C. 14.6 17.6 21.0 24.9 29.4 34.6 40.6 47.4 55.3 Volumetric capacity kJ/m.sup.3 855 872 885 893 894 890 879 862 839

(29) TABLE-US-00017 TABLE 18 R744 16% 16% 16% 16% 16% 16% 16% 16% R23 0% 10% 20% 30% 40% 50% 60% 70% R1132a Quantity Units 84% 74% 64% 54% 44% 34% 24% 14% Capacity relative to 93.9% 95.6% 96.9% 97.6% 97.6% 96.9% 95.6% 93.6% reference COP relative to reference 94.0% 93.7% 93.5% 93.1% 92.8% 92.3% 91.9% 91.4% Discharge temperature 5.5 8.7 12.3 16.5 21.2 26.8 33.1 40.4 difference (K) Pressure ratio — 6.9 6.9 7.0 7.1 7.3 7.4 7.6 7.8 Condenser glide K 1.0 0.9 0.8 0.6 0.6 0.5 0.6 0.7 Evaporator glide K 0.4 0.3 0.3 0.3 0.3 0.5 0.7 0.8 Condensing pressure bar 7.85 8.01 8.14 8.23 8.28 8.29 8.24 8.14 Evaporating pressure bar 1.15 1.16 1.16 1.16 1.14 1.12 1.08 1.04 COP — 2.26 2.26 2.25 2.24 2.24 2.22 2.21 2.20 Discharge temperature ° C. 16.9 20.1 23.7 27.9 32.6 38.2 44.5 51.8 Volumetric capacity kJ/m.sup.3 878 894 906 912 913 906 894 876

(30) This data shows that ternary compositions of R-1132a, R23 and carbon dioxide are suitable as drop-in replacements for R-508 compositions. In particular it is noted that compositions including about 20 to about 60% by weight R-23 provide for both an optimised capacity, which when combined with flammability reducing characteristics of R-23 may be particularly desirable.

(31) Preferences and options for a given aspect, feature or parameter of the invention should, unless the context indicates otherwise, be regarded as having been disclosed in combination with any and all preferences and options for all other aspects, features and parameters of the invention.

(32) The invention is defined by the following claims.