COMPOSITIONS COMPRISING 1,1-DIFLUOROETHENE, TRIFLUOROMETHANE AND A THIRD COMPONENT

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 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), ethane (R-170) and carbon dioxide (R-744, CO.sub.2).

2. A composition according to claim 1 comprising: v) 1,1-difluoroethene (vinylidene fluoride, R-1132a); vi) trifluoromethane (R-23); and vii) one or more compound selected from hexafluoroethane (R-116) and/or ethane (R-170); and viii) carbon dioxide (R-744, CO.sub.2).

3. A composition according to claim 1 or 2 comprising: v) 1,1-difluoroethene (vinylidene fluoride, R-1132a); vi) trifluoromethane (R-23); and vii) one or more compound selected from hexafluoroethane (R-116) and/or ethane (R-170); and viii) less than about 50% by weight carbon dioxide (R-744, CO.sub.2).

4. A composition according to any the preceding claims comprising from about 1 to about 98% by weight R-1132a.

5. A composition according to any the preceding claims comprising from about 35 to about 95% by weight R-1132a.

6. A composition according to any the preceding claims comprising from about 1 to about 98% by weight R-23.

7. A composition according to any the preceding claims comprising up to about 80% by weight R-116.

8. A composition according to claim 7 comprising from about 1 to about 60% by weight R-116.

9. A composition according to any of the preceding claims comprising 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.

10. A composition according to claim 9 comprising 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.

11. A composition according to claim 10 comprising 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.

12. A composition according to any of the preceding claims comprising up to 40% by weight R-170.

13. A composition according to claim 12 comprising from about 1 to about 30% by weight R-170.

14. A composition according to any of the preceding claims comprising less than about 10% by weight carbon dioxide, which does not contain carbon dioxide.

15. A composition according to any of claims 1 to 13 comprising from about 1 to about 45% by weight carbon dioxide.

16. A composition according to claim 15 comprising from about 1 to about 30% by weight carbon dioxide.

17. A composition according to claim 16 comprising from about 1 to about 15% by weight carbon dioxide.

18. A composition according to any of claims 1 and 4 to 6 comprising about 1 to about 98% by weight R-1132a, about 1 to about 98% by weight R-23 and about 1 to about 50% by weight carbon dioxide.

19. A composition according to claim 18 comprising about 35 to 98% by weight R-1132a, about 1 to about 60% by weight R-23 and about 1 to about 20% by weight carbon dioxide.

20. A composition according to claim 19 comprising about 40 to about 60% by weight R-23.

21. A composition according to any of claim 16 or 18 to 20 comprising about 4 to about 16% by weight carbon dioxide.

22. A composition according to any of the preceding claims consisting essentially of stated components.

23. A composition according to any of the preceding claims which is azeotropic.

24. A composition according to any of the preceding claims, wherein the composition is less flammable than R-1132a alone.

25. A composition according to claim 24 wherein the composition has: a. a higher flammable limit; b. a higher ignition energy; and/or c. a lower flame velocity compared to R-1132a alone.

26. A composition according to any of the preceding claims which is non-flammable.

27. A composition according to claim 26 wherein the composition is non-flammable at ambient temperature, preferably wherein the composition is non-flammable at 60° C.

28. A composition according to any of the preceding claims which has a temperature glide in an evaporator or condenser of less than about 10 K, preferably less than about 5 K.

29. A composition according to any of the preceding claims which has a critical temperature of greater than about 0° C., preferably greater than about 10° C.

30. A composition according to any of the preceding claims whose volumetric refrigeration capacity is at least 90% of that of R-508 at comparable cycle conditions.

31. A composition according to any of the preceding claims whose compressor discharge temperature is within 15 K of that of R-508 at comparable cycle conditions.

32. A composition comprising a lubricant and a composition according to any of the preceding claims.

33. A composition according to claim 29, wherein the lubricant is selected from 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, preferably wherein the lubricant is selected from PAGs or POEs.

34. A composition comprising a stabiliser and a composition according to any of the preceding claims.

35. A composition according to claim 34, wherein the stabiliser is selected from diene-based compounds, phosphates, phenol compounds and epoxides, and mixtures thereof.

36. A composition comprising a flame retardant and a composition according to any of the preceding claims.

37. A composition according to claim 36, wherein the flame retardant is selected from the group consisting of tri-(2-chloroethyl)-phosphate, (chloropropyl) phosphate, tri-(2,3-dibromopropyl)-phosphate, tri-(1,3-dichloropropyl)-phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminium trihydrate, polyvinyl chloride, a fluorinated iodocarbon, a fluorinated bromocarbon, trifluoro iodomethane, perfluoroalkyl amines, bromo-fluoroalkyl amines and mixtures thereof.

38. A heat transfer device containing a composition as defined in any one of claims 1 to 37.

39. A heat transfer device according to claim 38 wherein the heat transfer device is a refrigeration device.

40. A heat transfer device according to claim 38 or 39 wherein the heat transfer device comprises an ultra-low temperature refrigeration system.

41. A heat transfer device according to any of claims 38 to 40 wherein the heat transfer device comprises a cascade system.

42. A sprayable composition comprising material to be sprayed and a propellant comprising a composition as defined in any of claims 1 to 37.

43. A method for cooling an article which comprises condensing a composition defined in any of claims 1 to 37 and thereafter evaporating the composition in the vicinity of the article to be cooled.

44. A method for heating an article which comprises condensing a composition as defined in any one of claims 1 to 37 in the vicinity of the article to be heated and thereafter evaporating the composition.

45. A method for extracting a substance from biomass comprising contacting biomass with a solvent comprising a composition as defined in any of claims 1 to 37, and separating the substance from the solvent.

46. A method of cleaning an article comprising contacting the article with a solvent comprising a composition as defined in any of claims 1 to 37.

47. A method of extracting a material from an aqueous solution or from a particulate solid matrix comprising contacting the aqueous solution or the particulate solid matrix with a solvent comprising a composition as defined in any of claims 1 to 37, and separating the material from the solvent.

48. A mechanical power generation device containing a composition as defined in any of claims 1 to 37.

49. A mechanical power generating device according to claim 48 which is adapted to use a Rankine Cycle or modification thereof to generate work from heat.

50. A method of retrofitting a heat transfer device comprising the step of removing an existing heat transfer composition, and introducing a composition as defined in any one of claims 1 to 37.

51. A method of claim 50 wherein the heat transfer device is a refrigeration device, preferably an ultra-low temperature refrigeration system.

52. A method of claim 51 wherein the refrigeration system cools a compartment to less than about −70° C., preferably less than about −80° C.

53. 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 as defined in any one of claims 1 to 37.

54. A method for generating greenhouse gas emission credit comprising (i) replacing an existing compound or composition with a composition as defined in any one of claims 1 to 37, wherein the composition as defined in any one of claims 1 to 37 has a lower GWP than the existing compound or composition; and (ii) obtaining greenhouse gas emission credit for said replacing step.

55. A method of claim 54 wherein the use of the composition of the invention results in a lower Total Equivalent Warming Impact, and/or a lower Life-Cycle Carbon Production than is attained by use of the existing compound or composition.

56. A method of claim 53 or 54 carried out on a product from the fields of air-conditioning, refrigeration, heat transfer, aerosols or sprayable propellants, gaseous dielectrics, flame suppression, solvents, cleaners, topical anesthetics, and expansion applications.

57. A method according to claim 53 or 54 wherein the product is selected from a heat transfer device, a sprayable composition, a solvent or a mechanical power generation device, preferably a heat transfer device.

58. A method according to claim 57 wherein the product is a heat transfer device, preferably an ultra-low temperature refrigeration system.

59. A method according to any of claims 50 to 58 wherein the existing compound or composition is a heat transfer composition, preferably wherein the heat transfer composition is a refrigerant selected from R-508A, R-508B, R-23 and R-13B1.

60. Any novel heat transfer composition substantially as hereinbefore described, optionally with reference to the examples.

Description

[0128] The invention is illustrated by the following non-limiting examples, with reference to the following drawings:

[0129] 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;

[0130] 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

[0131] Compositions of R-1132a, R-23 and R-116

[0132] 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.

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%

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-1132a content w/w R-23 content 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%

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%

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%

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-1132a content w/w R-23 content 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%

TABLE-US-00006 TABLE 6 Bubble Point Pressure at −40° C. in kPa R-1132a wt % R-23 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-1132a wt % R-23 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% 

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

[0133] Compositions of R-1132a, R-23 and R-170

[0134] 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.

[0135] The cycle conditions used in the modelling are as Table 1.

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 K 0 0 0 0.4397 glide Condenser temperature K 0 0 0 0.2223 glide Volumetric capacity kJ/m.sup.3 964 772 726 935 Cooling COP 2.32 2.29 2.26 2.41

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-23 w/w R-170 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%

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-23 w/w R-170 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%

TABLE-US-00011 TABLE 12 Compressor Pressure Ratio R-23 w/w R-170 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-23 w/w R-170 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% 

TABLE-US-00012 TABLE 13 Compressor Discharge Temperature in ° C. R-23 w/w R-170 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-23 w/w R-170 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% 

[0136] 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.

[0137] Compositions of R-1132a, R23 and Carbon Dioxide

[0138] 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.

[0139] The cycle conditions used in the modelling are as Table 1.

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

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

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

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 reference 91.4% 93.3% 94.6% 95.5% 95.7% 95.2% 94.0% 92.2% 89.8% COP relative to reference 94.0% 93.8% 93.6% 93.3% 92.9% 92.5% 92.1% 91.7% 91.3% Discharge temperature difference 3.2 6.2 9.6 13.5 18.0 23.2 29.2 36.0 43.9 (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

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 reference 93.9% 95.6% 96.9% 97.6% 97.6% 96.9% 95.6% 93.6% COP relative to reference 94.0% 93.7% 93.5% 93.1% 92.8% 92.3% 91.9% 91.4% Discharge temperature difference 5.5 8.7 12.3 16.5 21.2 26.8 33.1 40.4 (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

[0140] 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.

[0141] 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.

[0142] The invention is defined by the following claims.