Heat transfer compositions

• US 9,175,202 B2
• Filed: 02/15/2011
• Issued: 11/03/2015
• Est. Priority Date: 02/16/2010
• Status: Expired due to Fees

• Current Assignee: Mexichem, S.A.B. De C.V. (Orbia Advance Corporation, S.A.B. de C.V.)
• Original Assignee: Mexichem, S.A.B. De C.V. (Orbia Advance Corporation, S.A.B. de C.V.)
• Inventors: Low, Robert E
• Primary Examiner(s): MC GINTY, DOUGLAS J
• Application Number:
  US13/579,441
• Publication Number:
  US 20130193368A1
• Time in Patent Office: 1,722 Days
• Field of Search: 252/67, 252/68, 252/69, 252/364, 521/131, 621/14, 134/36, 605/31
• US Class Current: 1/1
• CPC Class Codes: C08J 9/146 only fluorine as halogen atoms
• CPC Class Codes: C09K 3/30 for aerosols aerosol containers B65D83/14
• CPC Class Codes: C09K 5/045 containing only fluorine as halogen
• CPC Class Codes: F25B 39/02 Evaporators
• CPC Class Codes: F25B 45/00 Arrangements for charging or discharging refrigerant
• CPC Class Codes: Y10T 29/49716 Converting

Abstract

The invention provides a heat transfer composition comprising trans-1,3,3,3-tetrafluoropropene (R-1234ze(E)), fluoroethane (R-161) and a third component selected from difluoromethane (R-32) and/or 1,1-difluoroethane (R-152a).

Claims

1. A heat transfer composition comprising from about 58 to about 93% by weight of R-1234ze(E), from about 5 to about 30% by weight of R-161, and from about 2 to about 12% by weight of R-32.

2. A composition according to claim 1 comprising from about 68 to about 91% by weight of R-1234ze(E), from about from about 5 to about 20% by weight of R-161, and from about 4 to about 12% by weight of R-32.

5. A composition according to claim 1 additionally comprising 1,1,1,2-tetrafluoroethane (R-134a).

6. A composition according to claim 5 comprising up to about 35% by weight of R-134a.

7. A composition according to claim 6 comprising from about 2 to about 20% by weight R-161, from about 2 to about 20% by weight of R-32, from about 25 to about 35% R-134a, and the balance R-1234ze(E).

8. A composition according to claim 1 consisting essentially of R-1234ze(E), R-161, R-32, and optionally R-134a.

9. A composition according to claim 1, wherein the composition has a GWP of less than 150.

10. A composition according to claim 1, wherein the temperature glide is less than about 10K.

11. A composition according to claim 1, wherein the composition has a volumetric refrigeration capacity within about 15%, of the existing refrigerant that it is intended to replace.

12. A composition according to claim 1, wherein the composition is less flammable than R-32 alone, R-161 alone, R-152a alone or R-1234yf alone.

13. A composition according to claim 12 wherein the composition has:

(a) a higher flammable limit;

(b) a higher ignition energy; and

/or

(c) a lower flame velocity compared to R-32 alone, R-161 alone, R-152a alone or R-1234yf alone.

14. A composition according to claim 1 which has a fluorine ratio (F/(F+H)) of from about 0.40 to about 0.67, preferably from about 0.45 to about 0.62.

15. A composition according to claim 1, wherein the composition has a cycle efficiency within about 5% of the existing refrigerant that it is intended to replace.

16. A composition according to claim 1, wherein the composition has a compressor discharge temperature within about 15K, of the existing refrigerant that it is intended to replace.

17. A composition comprising a lubricant and a composition according to claim 1.

18. A composition according to claim 17, 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.

19. A composition according to claim 17 further comprising a stabillizer.

20. A composition according to claim 19, wherein the stabillizer is selected from diene-based compounds, phosphates, phenol compounds and epoxides, and mixtures thereof.

21. A composition comprising a flame retardant and a composition according to claim 1.

22. A composition according to claim 21, 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, aluminum trihydrate, polyvinyl chloride, a fluorinated iodocarbon, a fluorinated bromocarbon, trifluoro iodomethane, perfluoroalkyl amines, bromo-fluoroalkyl amines and mixtures thereof.

23. A composition according to claim 1 which is a refrigerant composition.

24. A heat transfer device containing a composition as defined in claim 1.

25. A heat transfer device according to claim 24 which is a refrigeration device.

26. A heat transfer device according to claim 25 which is selected from group consisting of automotive air conditioning systems, residential air conditioning systems, commercial air conditioning systems, residential refrigerator systems, residential freezer systems, commercial refrigerator systems, commercial freezer systems, chiller air conditioning systems, chiller refrigeration systems, and commercial or residential heat pump systems.

27. A heat transfer device according to claim 25 which contains a compressor.

28. A blowing agent comprising a composition as defined in claim 1.

29. A foamable composition comprising one or more components capable of forming foam and a composition as defined in claim 1, wherein the one or more components capable of forming foam are selected from polyurethanes, thermoplastic polymers and resins, such as polystyrene, and epoxy resins, and mixtures thereof.

30. A foam obtainable from the foamable composition of claim 29.

31. A foam comprising a composition as defined in claim 1.

32. A sprayable composition comprising material to be sprayed and a propellant comprising a composition as defined in claim 1.

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

34. A method for heating an article which comprises condensing a composition as defined in claim 1 in the vicinity of the article to be heated and thereafter evaporating the composition.

35. A method for extracting a substance from biomass comprising contacting biomass with a solvent comprising a composition as defined in claim 1, and separating the substance from the solvent.

36. A method of cleaning an article comprising contacting the article with a solvent comprising a composition as defined in claim 1.

37. A method of extracting a material from an aqueous solution comprising contacting the aqueous solution with a solvent comprising a composition as defined in claim 1, and separating the substance from the solvent.

38. A method for extracting a material from a particulate solid matrix comprising contacting the particulate solid matrix with a solvent comprising a composition as defined in claim 1, and separating the material from the solvent.

39. A mechanical power generation device containing a composition as defined in claim 1.

40. A mechanical power generating device according to claim 39 which is adapted to use a Rankine Cycle or modification thereof to generate work from heat.

41. A method of retrofitting a heat transfer device comprising the step of removing an existing heat transfer fluid, and introducing a composition as defined in claim 1.

42. A method of claim 41 wherein the heat transfer device is a refrigeration device.

43. A method according to claim 41 wherein the heat transfer device is an air conditioning system.

44. 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 claim 1.

45. A method according to claim 44 wherein the product is selected from a heat transfer device, a blowing agent, a foamable composition, a sprayable composition, a solvent or a mechanical power generation device.

46. A method according to claim 45 wherein the product is a heat transfer device.

47. A method according to claim 44 wherein the existing compound or composition is a heat transfer composition.

48. A method according to claim 47 wherein the heat transfer composition is a refrigerant selected from R-134a, R-1234yf and R-152a.

49. A method for generating greenhouse gas emission credit comprising (i) replacing an existing compound or composition with a composition as defined in claim 1, wherein the composition has a lower GWP than the existing compound or composition;

and (ii) obtaining greenhouse gas emission credit for said replacing step.

50. A method for preparing a composition as defined in claim 1, which composition contains R-134a, the method comprising introducing R-1234ze(E), R-161, R-32 and/or R-152a, and optionally a lubricant, a stabilizer and/or an additional flame retardant, into a heat transfer device containing an existing heat transfer fluid which is R-134a.

51. A method according to claim 50 comprising the step of removing at least some of the existing R-134a from the heat transfer device before introducing the R-1234ze(E), R-161, R-32 and/or R-152a, and optionally the lubricant, the stabilizer and/or the additional flame retardant.

52. A method of claim 51 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 be attained by use of the existing compound or composition.

53. A method of claim 51 carried out on a product from the fields of air-conditioning, refrigeration, heat transfer, blowing agents, aerosols or sprayable propellants, gaseous dielectrics, cryosurgery, veterinary procedures, dental procedures, fire extinguishing, flame suppression, solvents, cleaners, air horns, pellet guns, topical anesthetics, and expansion applications.

56. A composition according to claim 6 comprising from about 2 to about 20% by weight R-161, from about 2 to about 20% by weight of the R-152a, from about 25 to about 43% R-134a, and the balance R-1234ze(E).

93. 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 claim 7.

94. A method according to claim 93 wherein the product is selected from a heat transfer device, a blowing agent, a foamable composition, a sprayable composition, a solvent or a mechanical power generation device.

95. A method according to claim 94 wherein the product is a heat transfer device.

3. A heat transfer composition comprising from about 50 to about 93% by weight of R-1234ze(E), from about 2 to about 20% by weight of R-161, and from about 5 to about 30% by weight of R-152a.

4. A composition according to claim 3 comprising from about 60 to about 83% by weight of R-1234ze(E), from about 12 to about 20% by weight of R-161, and from about 5 to about 20% by weight of R-152a.

54. A composition according to claim 3 additionally comprising 1,1,1,2-tetrafluoroethane (R-134a).

55. A composition according to claim 54 comprising up to about 43% by weight of R-134a.

57. A composition according to claim 3 consisting essentially of R-1234ze(E), R-161, R-32, and optionally R-134a.

58. A composition according to claim 3 wherein the composition has a GWP of less than 150.

59. A composition according to claim 3, wherein the temperature glide is less than about 10K.

60. A composition according to claim 3, wherein the composition has a volumetric refrigeration capacity within about 15%, of the existing refrigerant that it is intended to replace.

61. A composition according to claim 3, wherein the composition is less flammable than R-32 alone, R-161 alone, R-152a alone or R-1234yf alone.

62. A composition according to claim 61 wherein the composition has:

(a) a higher flammable limit;

(b) a higher ignition energy; and

/or

(c) a lower flame velocity compared to R-32 alone, R-161 alone, R-152a alone or R-1234yf alone.

63. A composition according to claim 3 which has a fluorine ratio (F/(F+H)) of from about 0.40 to about 0.67, preferably from about 0.45 to about 0.62.

64. A composition according to claim 3, wherein the composition has a cycle efficiency within about 5% of the existing refrigerant that it is intended to replace.

65. A composition according to claim 3, wherein the composition has a compressor discharge temperature within about 15K, of the existing refrigerant that it is intended to replace.

66. A composition comprising a lubricant and a composition according to claim 3.

67. A composition according to claim 66, 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.

68. A composition according to claim 66 further comprising a stabilizer.

69. A composition according to claim 68, wherein the stabilizer is selected from diene-based compounds, phosphates, phenol compounds and epoxides, and mixtures thereof.

70. A composition comprising a flame retardant and a composition according to claim 3.

71. A composition according to claim 70, 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.

72. A composition according to claim 3 which is a refrigerant composition.

73. A heat transfer device containing a composition as defined in claim 3.

74. A heat transfer device according to claim 73 which is a refrigeration device.

75. A heat transfer device according to claim 74 which is selected from group consisting of automotive air conditioning systems, residential air conditioning systems, commercial air conditioning systems, residential refrigerator systems, residential freezer systems, commercial refrigerator systems, commercial freezer systems, chiller air conditioning systems, chiller refrigeration systems, and commercial or residential heat pump systems.

76. A heat transfer device according to claim 74 which contains a compressor.

77. A blowing agent comprising a composition as defined in claim 3.

78. A foamable composition comprising one or more components capable of forming foam and a composition as defined in claim 3, wherein the one or more components capable of forming foam are selected from polyurethanes, thermoplastic polymers and resins, such as polystyrene, and epoxy resins, and mixtures thereof.

79. A foam obtainable from the foamable composition of claim 78.

80. A foam comprising a composition as defined in claim 3.

81. A sprayable composition comprising material to be sprayed and a propellant comprising a composition as defined in claim 3.

82. A method for cooling an article which comprises condensing a composition defined in claim 3 and thereafter evaporating the composition in the vicinity of the article to be cooled.

83. A method for heating an article which comprises condensing a composition as defined in claim 3 in the vicinity of the article to be heated and thereafter evaporating the composition.

84. A method for extracting a substance from biomass comprising contacting biomass with a solvent comprising a composition as defined in claim 3, and separating the substance from the solvent.

85. A method of cleaning an article comprising contacting the article with a solvent comprising a composition as defined in claim 3.

86. A method of extracting a material from an aqueous solution comprising contacting the aqueous solution with a solvent comprising a composition as defined in claim 3, and separating the substance from the solvent.

87. A method for extracting a material from a particulate solid matrix comprising contacting the particulate solid matrix with a solvent comprising a composition as defined in claim 3, and separating the material from the solvent.

88. A mechanical power generation device containing a composition as defined in claim 3.

89. A mechanical power generating device according to claim 88 which is adapted to use a Rankine Cycle or modification thereof to generate work from heat.

90. A method of retrofitting a heat transfer device comprising the step of removing an existing heat transfer fluid, and introducing a composition as defined in claim 3.

91. A method of claim 90 wherein the heat transfer device is a refrigeration device.

92. A method according to claim 91 wherein the heat transfer device is an air conditioning system.

96. A method according to claim 90 wherein the existing compound or composition is a heat transfer composition.

97. A method according to claim 96 wherein the heat transfer composition is a refrigerant selected from R-134a, R-1234yf and R-152a.

98. A method for generating greenhouse gas emission credit comprising (i) replacing an existing compound or composition with a composition as defined in claim 3, wherein the composition has a lower GWP than the existing compound or composition;

and (ii) obtaining greenhouse gas emission credit for said replacing step.

99. A method for preparing a composition as defined in claim 3, which composition contains R-134a, the method comprising introducing R-1234ze(E), R-161, R-32 and/or R-152a, and optionally a lubricant, a stabilizer and/or an additional flame retardant, into a heat transfer device containing an existing heat transfer fluid which is R-134a.

100. A method according to claim 99 comprising the step of removing at least some of the existing R-134a from the heat transfer device before introducing the R-1234ze(E), R-161, R-32 and/or R-152a, and optionally the lubricant, the stabilizer and/or the additional flame retardant.

101. A method of claim 100 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 be attained by use of the existing compound or composition.

102. A method of claim 99 carried out on a product from the fields of air-conditioning, refrigeration, heat transfer, blowing agents, aerosols or sprayable propellants, gaseous dielectrics, cryosurgery, veterinary procedures, dental procedures, fire extinguishing, flame suppression, solvents, cleaners, air horns, pellet guns, topical anesthetics, and expansion applications.