Compositions comprising tetrafluoeopropene & carbon dioxide

• US 20060043331A1
• Filed: 04/29/2005
• Published: 03/02/2006
• Est. Priority Date: 04/29/2004
• Status: Active Grant

• Current Assignee: Honeywell International Inc.
• Original Assignee: Honeywell International Inc.
• Inventors: Singh, Rajiv R., Shankland, Ian
• Granted Patent: US 7,629,306 B2
• Time in Patent Office: Days
• US Class Current: 252/67
• CPC Class Codes: C08J 2203/06 CO2, N2 or noble gases
• CPC Class Codes: C08J 2203/162 Halogenated unsaturated hydrocarbons, e.g. H2C=CF2
• CPC Class Codes: C08J 2203/164 Perhalogenated unsaturated hydrocarbons, e.g. F2C=CF2
• CPC Class Codes: C08J 2203/182 of physical blowing agents, e.g. acetone and butane
• CPC Class Codes: C08J 9/127 Mixtures of organic and inorganic blowing agents
• CPC Class Codes: C09K 2205/106 Carbon dioxide
• CPC Class Codes: C09K 2205/126 Unsaturated fluorinated hydrocarbons
• CPC Class Codes: C09K 5/045 containing only fluorine as halogen

Abstract

Disclosed are compositions useful in a wide variety of applications, including heat transfer fluids which possess a highly desirable and unexpectedly superior combination of properties, and heat transfer systems and methods based on these fluids. The preferred heat transfer fluid comprises from about 1 to about 40 percent, on a weight basis, of carbon dioxide (CO₂) and from about 99 to about 60 percent, on a weight basis, of a compound having the Formula I XCF_zR_3-z (I), where X is a C₂ or a C₃ unsaturated, substituted or unsubstituted, alkyl radical, each R is independently Cl, F, Br, I or H, and z is 1 to 3. A preferred compound of Formula I is tetrafluoropropene, particularly 1,1,1,3-tetrafluoropropene and/or 1,1,1,3-tetrafluoropropene.

Claims

1. A composition comprising from about 1 to about 40 percent by weight of carbon dioxide (CO₂) and from about 60 to about 99 percent by weight of one or more compounds of Formula I, XCFzR3-z (I), where X is a C₂ or a C₃ unsaturated, substituted or unsubstituted, alkyl radical, each R is independently Cl, F, Br, I or H, and z is 1 to 3.

2. The composition of claim 1 wherein said one or more compounds of Formula I comprises 1,1,1,3-tetrafluoropropene (HFO-1234) and wherein said composition has a vapor pressure of at least about 30 psia at 35°

F.

3. The composition of claim 1 wherein said one or more compounds of Formula I comprises 1,1,1,3-tetrafluoropropene (HFO-1234ze).

4. The composition of claim 3 wherein said one or more compounds of Formula I comprises trans-1,1,1,3-tetrafluoropropene (transHFO-1234ze) and wherein said composition has a vapor pressure of at least about 30 psia at 35°

F.

5. The composition of claim 2 wherein said CO₂ is present in an amount of at least about 5 percent by weight and said trans-1,1,1,3-tetrafluoropropene is present in an amount not greater than about 95 percent by weight.

6. The composition of claim 1 wherein said one or more compounds of Formula I comprises 1,1,1,2-tetrafluoropropene (HFO-1234yf) and wherein said composition has a vapor pressure of at least about 30 psia at 35°

F.

7. The fluid of claim 6 wherein said CO₂ is present in an amount of at least about 3 percent by weight and said trans-1,1,1,2-tetrafluoropropene is present in an amount not greater than about 97 percent by weight.

8. The composition of claim 1 wherein said composition is non-flammable.

9. The composition of claim 1 and further comprising at least one adjuvant selected from the group consisting of supplemental lubricants, compatibilizers, surfactants, supplemental flame suppressants, solubilizing agents, dispersing agents, cell stabilizers, cosmetics, polishing agents, medicaments, cleaners, fire retarding agents, colorants, chemical sterilants, stabilizers, polyols, polyol premix components and combinations of two or more of these.

10. A heat transfer composition comprising the composition of claim 1 and further comprising at least one lubricant.

11. The heat transfer composition of claim 10 wherein said lubricant is 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) (PAOs), and combinations of these.

12. The heat transfer composition of claim 10 further comprising at least one compatibilizer.

13. The heat transfer composition of claim 12 comprising from about 0.5 to about 5 percent by weight of said at least one compatibilizer.

14. The heat transfer composition of claim 12 wherein said lubricant is present in an amount of from about 5 to about 50 percent by weight of the heat transfer composition.

15. The heat transfer composition of claim 10 further comprising one or more supplemental flame suppressants.

16. The heat transfer composition of claim 15 wherein said one or more flame suppressant(s) together are present in an amount of from about 0.5% to about 30% by weight of the heat transfer composition.

17. A refrigerant comprising the heat transfer composition of claim 10.

18. A refrigeration system comprising a heat transfer composition of claim 17.

19. A refrigeration system of claim 18 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, heat pump systems, and combinations of two or more of these.

20. A blowing agent comprising a composition of claim 1.

21. A blowing agent of claim 20 wherein said compound of formula I and said CO₂ together comprise at least about 5% by weight of the blowing agent.

28. A method of replacing an existing refrigerant contained in a refrigerant system comprising removing at least a portion of said existing refrigerant from said system and replacing at least a portion of said existing refrigerant by introducing into said system a refrigerant composition comprising a composition of claim 1.

29. The method of claim 28 wherein said existing refrigerant is selected from the group consisting of HFC-134a, R-12, R-404A, R-500, HFC-152a, HFC-125, HFC-143a, HFC-32, HCFC-22, R-407C and R-410A and combinations of these.

31. The method of claim 29 wherein said existing refrigerant is selected from the group consisting of HFC-134a, HFC-143a, HFC-125, HFC-32 and combinations of these.

32. The method of claim 28 wherein said existing refrigerant system comprises at least a first compressor having a first displacement and further comprising the step of removing said first compressor from the system and inserting in said system at least a second compressor having a larger displacement than said first compressor.

33. The method of claim 28 wherein said existing refrigerant system is selected from the 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, heat pump systems, and combinations of two or more of these.

34. The method of claim 28 wherein the capacity of the system after said replacement step is at least about at least about 90% of the system capacity prior to said removal step.

35. The method of claim 28 wherein the mass flow of the system after said replacement step is at least about at least about 90% of the mass flow of the system prior to said removal step.

36. The method of claim 28 wherein said refrigerant in accordance with claim 10 has a Global Warming Potential (GWP) of not greater than about 1000.

37. A sprayable composition comprising a material to be sprayed and a propellant comprising the composition of claim 1.

38. The sprayable composition of claim 37 in the form of an aerosol.

39. The sprayable composition of claim 38 wherein said material to be sprayed is selected from the group consisting of cosmetics, cleaning solvent, lubricants and medicinal materials.

40. The sprayable composition of claim 39 comprising a medicinal material and wherein said medicinal material is a drug or a biologically active material.

41. A method of sterilizing an article comprising contacting said article with a composition comprising the composition of claim 1.

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

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

44. The composition of claim 1 in the form of a heat transfer fluid having a refrigeration capacity substantially matching that of R-22.

45. The composition of claim 1 in the form of a heat transfer fluid having a refrigeration capacity substantially matching that of R-407C.

46. The composition of claim 1 in the form of a heat transfer fluid having a refrigeration capacity substantially matching that of R-410A.

47. The composition of claim 1 in the form of a heat transfer fluid having a refrigeration capacity substantially matching that of R-404A.

48. The composition of claim 1 in the form of a heat transfer fluid having a refrigeration capacity substantially natching that of R-507A.

49. A process for changing the heat content of a body comprising providing the composition of claim 1 and transferring heat between said composition and said body.

51. A sprayable composition comprising a material to be sprayed and a propellant comprising an azeotrope-like composition of claim 1.

52. A sprayable composition according to claim 51 wherein the sprayable composition is an aerosol.

53. A sprayable composition according to claim 51 wherein the sprayable material is a drug or a biologically active material.

54. A sprayable composition according to claim 51 wherein the sprayable material is a medicinal material such as anti-asthma and anti-halitosis medications.

22. A blowing agent consisiting essentially of one or more compounds of formula I and CO₂

23. A foamable composition comprising the blowing agent of claim 22.

24. The foamable composition of claim 23 wherein said one or more components capable of forming foam comprise one or more components capable of forming foam are selected from the group consisting of thermoplastic foams, polystyrene foams, polyethylene foams, low density polyethylene foams, extruded thermoplastic foams, polyurethane foams, polyisocyanurate foams and phenolic foams.

25. The foamable composition of claim 23 further comprising at least one additive selected from the group consisting of dispersing agents, cell stabilizers, surfactants, flame retardants and combinations of two or more of these.

26. A foam formed from the foamable composition of claim 25.

27. A closed cell foam comprising the foam of claim 26.

30. The method of claim 30 wherein said existing refrigerant is selected from the group consisting of R-407C, R-404A, R-410A, HCFC-22 and combinations of these.

50. An improved heat transfer system comprising at least one heat transfer fluid and one or more vessels for evaporating and condensing the heat transfer fluid, the improvement characterized by said at least one heat transfer fluid being a non-flammable fluid consisting essentially of one or more compounds of Formula I XCFzR3-z (I), where X is a C₂ or a C₃ unsaturated, substituted or unsubstituted, alkyl radical, each R is independently Cl, F, Br, I or H, and z is 1 to 3 and carbon dioxide (CO₂).