Heat transfer compositions

• US 8,628,681 B2
• Filed: 01/12/2011
• Issued: 01/14/2014
• Est. Priority Date: 10/12/2007
• 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:
  US13/005,391
• Publication Number:
  US 20110162410A1
• Time in Patent Office: 1,098 Days
• Field of Search: 252/67, 252/68, 252/69, 252/364, 521/131, 621/14, 134/36, 605/31
• US Class Current: 252/67
• CPC Class Codes: C08J 2203/06 CO2, N2 or noble gases
• CPC Class Codes: C08J 2203/14 Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
• CPC Class Codes: C08J 2203/142 Halogenated saturated hydrocarbons, e.g. H3C-CF3
• CPC Class Codes: C08J 2207/04 Aerosol, e.g. polyurethane foam spray
• CPC Class Codes: C08J 9/127 Mixtures of organic and inorganic blowing agents
• CPC Class Codes: C08J 9/146 only fluorine as halogen atoms
• CPC Class Codes: C08J 9/149 Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143
• CPC Class Codes: C09K 2205/106 Carbon dioxide
• CPC Class Codes: C09K 2205/126 Unsaturated fluorinated hydrocarbons
• 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: C11D 7/02 Inorganic compounds
• CPC Class Codes: C11D 7/5018 Halogenated solvents

Abstract

A heat transfer composition comprising trans-1,3,3,3-tetrafluoropropene (R-1234ze(E)), carbon dioxide (R-744) and a third component selected from difluoromethane (R-32), 1,1-difluoroethane (R-152a), fluoroethane (R-161), 1,1,1,2-tetrafluoroethane (R-134a), propylene, propane and mixtures thereof.

Claims

1. A heat transfer composition comprising at least 45% trans-1,3,3,3-tetrafluoropropene (R-1234ze(E)), an amount of up to 10% carbon dioxide (R-744) and from 2 to 50% 1,1,12-tetrafluoroethane (R-134a).

2. A composition according to claim 1 comprising from about 45 to about 96% R-1234ze(E), from about 2 to about 6% by weight R-744 and from about 2 to about 50% by weight R-134a.

3. A composition according to claim 2 comprising from about 79 to about 96% R-1234ze(E), from about 2 to about 6% by weight R-744 and from about 2 to about 15% by weight R-134a.

4. A composition according to claim 3 comprising from about 79 to about 90% R-1234ze(E), from about 4 to about 6% by weight R-744 and from about 6 to about 15% by weight R-134a.

5. A composition according to claim 1, further comprising pentafluoroethane (R-125).

6. A composition according to claim 1, wherein the composition has a GWP of less than 1000, preferably less than 150.

7. A composition according to claim 1, wherein the temperature glide is less than about 10K, preferably less than about 8K.

8. A composition according to claim 1, wherein the composition has a volumetric refrigeration capacity within about 15%, preferably within about 10% of the existing refrigerant that it is intended to replace.

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

10. A composition according to claim 9 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-152a alone or R-1234yf alone.

11. A composition according to claim 1 which has a fluorine ratio (F/(F+H)) of from about 0.42 to about 0.7, preferably from about 0.44 to about 0.67.

12. A composition according to claim 1 which is non-flammable.

13. 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.

14. A composition according to claim 1, wherein the composition has a compressor discharge temperature within about 15K, preferably within about 10K, of the existing refrigerant that it is intended to replace.

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

16. A composition according to claim 15, 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.

17. A composition according to claim 15 further comprising a stabiliser.

18. A composition according to claim 17, wherein the stabiliser is selected from diene-based compounds, phosphates, phenol compounds and epoxides, and mixtures thereof.

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

20. A composition according to claim 19, 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.

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

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

23. Use of a composition defined in claim 1 in a heat transfer device.

24. A heat transfer device according to claim 22 which is a refrigeration device.

25. A heat transfer device according to claim 24 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.

26. A heat transfer device according to claim 24 which contains a compressor.

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

28. 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.

29. A foam obtained by foaming the foamable composition as defined in claim 28.

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

31. 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.

32. 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.

33. 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.

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

35. 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.

36. 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.

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

38. A mechanical power generating device according to claim 37 which is adapted to use a Rankine Cycle or modification thereof to generate work from heat.

39. 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.

40. A method of claim 39 wherein the heat transfer device is a refrigeration device.

41. A method according to claim 40 wherein the heat transfer device is an air conditioning system.

42. 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.

43. A method for preparing a heat transfer device as defined in claim 22, said heat transfer device containing R-134a, the method comprising introducing R-1243ze(E), R-744, any additional third component, and optionally R-125, a lubricant, a stabiliser and/or a flame retardant, into the heat transfer device.

44. A method according to claim 43 comprising the step of removing at least some of the existing R-134a from the heat transfer device before introducing the R-1243ze(E), R-744, any additional third component, and optionally the R-125, the lubricant, the stabiliser and/or the flame retardant.

45. 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 as defined in claim 1 has a lower GWP than the existing compound or composition;

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

46. A method of claim 45 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.

47. A method of claim 45 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.

48. A method according to claim 42 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.

49. A method according to claim 48 wherein the product is a heat transfer device.

50. A method according to claim 40 wherein the existing compound or composition is a heat transfer composition.

51. A method according to claim 43 wherein the heat transfer composition is a refrigerant selected from R-134a, R-1234yf and R-152a.

52. A composition according to claim 1 consisting essentially of R-1234ze(E), R-744 and R-134a.

53. A method according to claim 42 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.

54. A method according to claim 53 wherein the product is a heat transfer device.

55. A method according to claim 42 wherein the existing compound or composition is a heat transfer composition.

56. A method according to claim 53 wherein the heat transfer composition is a refrigerant selected from R-134a, R1234yf and R-152a.

57. A composition according to claim 1 wherein the R-744 is present in an amount of from 1 to 10% by weight.

58. A composition according to claim 57 wherein the R-744 is present in an amount of from about 2 to about 7% by weight.