Heat transfer compositions

Abstract

The invention provides a heat transfer composition comprising (i) a first component selected from trans-1,3,3,3-tetrafluoropropene (R-1234ze(E)), cis-1,3,3,3-tetrafluoropropene (R-1234ze(Z)) and mixtures thereof; (ii) carbon dioxide (R-744); and (iii) a third component selected from difluoromethane (R-32) 1,1,1,2-tetrafluoroethane (R-134a) and mixtures thereof.

1 . A heat transfer composition comprising:
 (i) a first component selected from trans-1,3,3,3-tetrafluoropropene (R-1234ze(E)), cis-1,3,3,3-tetrafluoropropene (R-1234ze(Z)) and mixtures thereof;   (ii) carbon dioxide (R-744); and   (iii) a third component selected from difluoromethane (R-32), 1,1,1,2-tetrafluoroethane (R-134a) and mixtures thereof.   
     
     
         2 . A composition according to  claim 1  wherein the first component comprises R-1234ze(E). 
     
     
         3 . A composition according to  claim 1  or  2  comprising at least about 15% by weight R-1234ze(E). 
     
     
         4 . A composition according to any of the preceding claims comprising up to about 35% by weight R-744, preferably about 30% by weight R-744. 
     
     
         5 . A composition according to  claim 4  comprising from about 4 to about 30% R-744 by weight, preferably from about 4 to about 28% by weight, or from about 8 to about 30% by weight, or from about 10 to about 30% by weight. 
     
     
         6 . A composition according to any of the preceding claims comprising up to about 60% by weight of the third component, preferably up to about 50% by weight. 
     
     
         7 . A composition according to any of the preceding claims comprising from about 10 to about 95% R-1234ze(E) by weight, from about 2 to about 30% by weight R-744, and from about 3 to about 60% by weight of the third component. 
     
     
         8 . A composition according to any of the preceding claims which has a critical temperature of greater than about 65° C., preferably greater than about 70° C. 
     
     
         9 . A composition according to any of the preceding claims wherein the third component comprises R-134a, preferably from about 2 to about 50% R-134a. 
     
     
         10 . A composition according to any of the preceding claims comprising from about 20 to about 94% by weight R-1234ze(E), from about 2 to about 30% by weight R-744 and from about 4 to about 50% by weight R-134a. 
     
     
         11 . A composition according to  claim 10  comprising from about 60 to about 92% R-1234ze(E), from about 4 to about 30% by weight R-744 and from about 4 to about 10% by weight R-134a, preferably comprising from about 62 to about 86% R-1234ze(E), from about 10 to about 28% by weight R-744 and from about 4 to about 10% by weight R-134a. 
     
     
         12 . A composition according to  claim 10  comprising from about 20 to about 86% R-1234ze(E), from about 4 to about 30% by weight R-744 and from about 10 to about 50% by weight R-134a, preferably comprising from about 22 to about 80% R-1234ze(E), from about 10 to about 28% by weight R-744 and from about 10 to about 50% by weight R-134a. 
     
     
         13 . A composition according to any of  claims 1  to  8  wherein the third component comprises R-32, preferably from about 2 to about 30% by weight R-32. 
     
     
         14 . A composition according to  claim 13  comprising from about 60 to about 91% by weight R-1234ze(E), from about 4 to about 30% by weight R-744 and from about 5 to about 30% by weight R-32, preferably comprising from about 58 to about 85% R-1234ze(E), from about 10 to about 28% by weight R-744 and from about 5 to about 30% by weight R-32. 
     
     
         15 . A composition according to  claim 13  comprising from about 50 to about 88% by weight R-1234ze(E), from about 4 to about 30% by weight R-744 and from about 2 to about 20% by weight R-32. 
     
     
         16 . A composition according to any of  claims 1  to  8  wherein the third component comprises R-134a and R-32. 
     
     
         17 . A composition according to  claim 16  comprising from about 5 to about 95% by weight R-1234ze(E), from about 4 to about 30% by weight R-744, from about 2 to about 30% by weight R-32 and from about 2 to about 50 by weight R-134a, preferably comprising from about 5 to about 92% by weight R-1234ze(E), from about 4 to about 30% by weight R-744, from about 2 to about 25% by weight R-32 and from about 2 to about 40% by weight R-134a. 
     
     
         18 . A composition according to  claim 17  comprising from about 30 to about 81% by weight R-1234ze(E), from about 10 to about 30% by weight R-744, from about 5 to about 30% by weight R-32 and from about 4 to about 10 by weight R-134a, preferably comprising from about 37 to about 81% by weight R-1234ze(E), from about 10 to about 28% by weight R-744, from about 5 to about 25% by weight R-32 and from about 4 to about 10 by weight R-134a. 
     
     
         19 . A composition according to  claim 17  comprising from about 5 to about 75% by weight R-1234ze(E), from about 10 to about 30% by weight R-744, from about 5 to about 25% by weight R-32 and from about 10 to about 50 by weight R-134a, preferably comprising from about 7 to about 75% by weight R-1234ze(E), from about 10 to about 28% by weight R-744, from about 5 to about 25% by weight R-32 and from about 10 to about 40 by weight R-134a. 
     
     
         20 . A composition according to any of the preceding claims consisting essentially of R-1234ze(E), R-744 and the third component. 
     
     
         21 . A composition according to any of  claims 1  to  19 , further comprising pentafluoroethane (R-125). 
     
     
         22 . A composition consisting essentially of from about 4 to about 34% by weight carbon dioxide (R-744) and from about 66 to about 96% by weight trans-1,3,3,3-tetrafluoropropene (R-1234ze(E)). 
     
     
         23 . A composition according to  claim 21  consisting essentially of from about 4 to about 30% by weight R-744 and from about 70 to about 96% by weight R-1234ze(E). 
     
     
         24 . A composition according to  claim 22  consisting essentially of from about 6 to about 30% by weight R-744 and from about 70 to about 94% by weight R-1234ze(E). 
     
     
         25 . A composition according to any of  claims 22  to  24  which has a critical temperature of greater than about 70° C. 
     
     
         26 . A composition according to any of the preceding claims, wherein the composition has a GWP of less than 1000, preferably less than 150. 
     
     
         27 . A composition according to any of the preceding claims, 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. 
     
     
         28 . A composition according to any of the preceding claims, wherein the composition is less flammable than R-32 alone or R-1234yf alone. 
     
     
         29 . A composition according to  claim 28  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 or R-1234yf alone. 
     
     
         30 . A composition according to any of the preceding claims 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. 
     
     
         31 . A composition according to any of the preceding claims which is non-flammable. 
     
     
         32 . A composition according to any of the preceding claims, wherein the composition has a cycle efficiency within about 5% of the existing refrigerant that it is intended to replace. 
     
     
         33 . A composition according to any of the preceding claims, 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. 
     
     
         34 . A composition comprising a lubricant and a composition according to any of the preceding claims. 
     
     
         35 . A composition according to  claim 34 , 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. 
     
     
         36 . A composition according to  claim 34  or  35  further comprising a stabiliser. 
     
     
         37 . A composition according to  claim 36 , wherein the stabiliser is selected from diene-based compounds, phosphates, phenol compounds and epoxides, and mixtures thereof. 
     
     
         38 . A composition comprising a flame retardant and a composition according to any of the preceding claims. 
     
     
         39 . A composition according to  claim 38 , 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. 
     
     
         40 . A composition according to any of the preceding claims which is a refrigerant composition. 
     
     
         41 . A heat transfer device containing a composition as defined in any one of  claims 1  to  40 . 
     
     
         42 . Use of a composition defined in any of  claims 1  to  40  in a heat transfer device. 
     
     
         43 . A heat transfer device according to  claim 41  or  42  which is a refrigeration device. 
     
     
         44 . A heat transfer device according to  claim 43  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, preferably wherein the heat transfer device is an automobile air-conditioning system. 
     
     
         45 . A heat transfer device according to  claim 43  or  44  which contains a compressor. 
     
     
         46 . A blowing agent comprising a composition as defined in any of  claims 1  to  40 . 
     
     
         47 . A foamable composition comprising one or more components capable of forming foam and a composition as defined in any of  claims 1  to  40 , 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. 
     
     
         48 . A foam obtainable from the foamable composition as defined in  claim 47 . 
     
     
         49 . A foam according to  claim 48  comprising a composition as defined in any one of  claims 1  to  41 . 
     
     
         50 . A sprayable composition comprising material to be sprayed and a propellant comprising a composition as defined in any of  claims 1  to  40 . 
     
     
         51 . A method for cooling an article which comprises condensing a composition defined in any of  claims 1  to  40  and thereafter evaporating the composition in the vicinity of the article to be cooled. 
     
     
         52 . A method for heating an article which comprises condensing a composition as defined in any one of  claims 1  to  40  in the vicinity of the article to be heated and thereafter evaporating the composition. 
     
     
         53 . 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  40 , and separating the substance from the solvent. 
     
     
         54 . A method of cleaning an article comprising contacting the article with a solvent comprising a composition as defined in any of  claims 1  to  40 . 
     
     
         55 . A method of extracting a material from an aqueous solution comprising contacting the aqueous solution with a solvent comprising a composition as defined in any of  claims 1  to  40 , and separating the substance from the solvent. 
     
     
         56 . 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 any of  claims 1  to  40 , and separating the material from the solvent. 
     
     
         57 . A mechanical power generation device containing a composition as defined in any of  claims 1  to  40 . 
     
     
         58 . A mechanical power generating device according to  claim 57  which is adapted to use a Rankine Cycle or modification thereof to generate work from heat. 
     
     
         59 . 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 any one of  claims 1  to  40 . 
     
     
         60 . A method of  claim 59  wherein the heat transfer device is a refrigeration device. 
     
     
         61 . A method according to  claim 60  wherein the heat transfer device is an air conditioning system. 
     
     
         62 . 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  40 . 
     
     
         63 . A method for preparing a composition as defined in any of  claims 1  to  40 , and/or a heat transfer device as defined in any of  claims 41  or  43  to  45 , which composition or heat transfer device contains R-134a, the method comprising introducing R-1234ze(E), R-744, the third component, and optionally R-125, a lubricant, a stabiliser and/or a flame retardant, into a heat transfer device containing an existing heat transfer fluid which is R-134a. 
     
     
         64 . A method according to  claim 63  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-744, the third component, and optionally the R-125, the lubricant, the stabiliser and/or the flame retardant. 
     
     
         65 . 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  40 , wherein the composition as defined in any one of  claims 1  to  40  has a lower GWP than the existing compound or composition; and (ii) obtaining greenhouse gas emission credit for said replacing step. 
     
     
         66 . A method of  claim 65  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. 
     
     
         67 . A method of  claim 65  or  66  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. 
     
     
         68 . A method according to  claim 62  or  67  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. 
     
     
         69 . A method according to  claim 68  wherein the product is a heat transfer device. 
     
     
         70 . A method according to any one of  claims 60  or  63  to  67  wherein the existing compound or composition is a heat transfer composition. 
     
     
         71 . A method according to  claim 70  wherein the heat transfer composition is a refrigerant selected from R-134a, R-1234yf, R-152a, R-404A, R-410A, R-507, R-407A, R-407B, R-407D, R-407E and R-407F. 
     
     
         72 . Any novel heat transfer composition substantially as hereinbefore described, optionally with reference to the examples.