Azeotrope or azeotrope like compositions comprising 1234yf

Abstract

The present invention provides azeotropic or azeotrope-like compositions comprising 1234yf and at least one component selected from a group comprising of R-134, and R-134a. The compositions of the present invention are useful as refrigerants, heat transfer fluids, foam blowing agents, aerosol propellants, and fire suppression and fire extinguishing agents.

Claims

1. A composition comprising about 30% to 65% of R-1234yf, about 2% to 15% of R-134, about 2% to 15% of R-152a and about 15% to 45% of R-32, wherein all percentages are in mole %.

2. The composition as claimed in claim 1 further comprising a lubricant selected from the group consisting of polyol esters, polyalkylene glycols, polyvinyl ethers, mineral oil, alkylbenzenes, synthetic paraffins, synthetic naphthenes, and poly(alpha)olefins.

3. The composition as claimed in claim 1, wherein the composition has a GWP of less than 1500.

4. The composition as claimed in claim 1, wherein the composition is useful as a heat transfer fluid, a refrigerant, a foam blowing agent, an aerosol propellant, a fire suppression agent, and a fire extinguishing agent.

5. The composition as claimed in claim 1, wherein the composition comprises about 30% to 65% of R-1234yf, about 2% to 15% of R-134, about 2% to 15% of R-152a and about 20% to 45% of R-32, wherein all percentages are in mole %.

6. A composition comprising about 30% to 65% of R-1234yf, about 2% to 15% of R-134, about 5% to 45% of R-134a and about 2% to 15% of R-152a, wherein all percentages are in mole %.

7. The composition as claimed in claim 6, further comprising a lubricant selected from the group consisting of polyol esters, polyalkylene glycols, polyvinyl ethers, mineral oil, alkylbenzenes, synthetic paraffins, synthetic naphthenes, and poly(alpha)olefins.

8. The composition as claimed in claim 6, wherein the composition has a GWP of less than 1500.

9. The composition as claimed in claim 6, wherein the composition is useful as a heat transfer fluid, a refrigerant, a foam blowing agent, an aerosol propellant, a fire suppression agent, and a fire extinguishing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) As used herein, the term R-1234yf refers to 2,3,3,3-Tetrafluoropropene; R-134a refers to 1,1,1,2-Tetrafluoroethane; R-134 refers to 1,1,2,2-Tetrafluoroethane; R-1243zf refers to 3,3,3-Trifluoroprop-1-ene; R-32 refers to Difluoromethane; R-125 refers to 1,1,1,2,2-Pentafluoroethane; R-143a refers to 1,1,1-Trifluoroethane; R-152a refers to 1,1-Difluoroethane; R-161 refers to Monofluoroethane; R-227ea refers to 1,1,1,2,3,3,3-Heptafluoropropane; R-236ea refers to 1,1,1,2,3,3-Hexafluoropropane; R-236fa refers to 1,1,1,3,3,3-Hexafluoropropane; R-245fa refers to 1,1,1,3,3-Pentafluoropropane; R-600a refers to isobutane; R-600 refers to n-butane and R-365mfc refers to 1,1,1,3,3-Pentafluorobutane. As used herein, the term “azeotrope or azeotrope-like” is intended in its broad sense to include both compositions that are strictly azeotropic and compositions that behave like azeotropic mixtures. An azeotropic mixture is a system of two or more components in which the liquid composition and vapor composition are equal at the stated pressure and temperature. In practice, this means that the components of an azeotropic mixture are constant boiling and cannot be separated during a phase change. The azeotrope-like compositions of the invention may include additional components that do not form new azeotrope-like systems.

(2) The present invention provides an azeotropic or azeotrope-like composition comprising R-1234yf and at least one selected from R-134 or R-134a.

(3) The present invention provides an azeotropic or azeotrope-like composition comprising R-1234yf and R-134.

(4) In one embodiment, present invention relates to a composition comprising about 50 mole % to about 99 mole % of R-1234yf, and about 1 mole % to about 50 mole % R-134.

(5) In another embodiment, present invention relates to a binary azeotropic or azeotrope-like composition comprising about 80 mole % to about 98 mole % of R-1234yf, and about 2 mole % to about 20 mole % R-134.

(6) In another embodiment, the binary azeotropic composition further comprising a lubricant selected from the group consisting of polyol esters, polyalkylene glycols, polyvinyl ethers, mineral oil, alkylbenzenes, synthetic paraffins, synthetic naphthenes, and poly(alpha)olefins.

(7) In another embodiment, the binary azeotropic compositions of the present invention are useful in processes for producing cooling or heat, as heat transfer fluids, refrigerants, foam blowing agents, aerosol propellants, and fire suppression and fire extinguishing agents.

(8) In another embodiment, the present invention provides a refrigerant composition comprising an azeotropic composition comprising 80 mole % to about 98 mole % of R-1234yf, and about 2 mole % to about 20 mole % R-134.

(9) In another embodiment, present invention relates to a binary azeotropic or azeotrope-like composition comprising about 90 mole % of R-1234yf, and about 10 mole % R-134.

(10) In another embodiment, the binary azeotropic composition has GWP of less than 1500.

(11) In another embodiment, the binary azeotropic composition has GWP of less than 750.

(12) In another embodiment, the binary azeotropic composition has GWP of less than 500.

(13) In another embodiment, the present invention provides a refrigerant composition comprising R-1234yf, R-134 that can be near azeotropic composition or zeotropic composition.

(14) In another embodiment, the present invention provides a composition comprising R-1234yf, R-134 and one or more additional component selected from a group consisting of R-1234ye, R-1243zf, R-32, R-125, R-134a, R-143a, R-152a, R-161, R-227ea, R-236ea, R-236fa, R-245fa, R-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane.

(15) In another embodiment, the composition comprising R-1234yf, R-134 and R-32.

(16) In another embodiment, a refrigerant composition comprising 30% to 60% of R-1234yf, 4% to 15% of R-134 and 20% to 65% of R-32.

(17) In another embodiment, the composition comprising R-1234yf, R-134 and R-32.

(18) In another embodiment, a refrigerant composition comprising 40% to 45% of R-1234yf, 4% to 6% of R-134 and 50% to 55% of R-32 wherein the composition has GWP less than 750.

(19) In another embodiment, the composition comprising R-1234yf, R-134, R-32 and R-152a. In another embodiment, a refrigerant composition comprising 40% to 45% of R-1234yf, 4% to 6% of R-134, 20% to 65% of R-32 and 2% to 15% of R-152a.

(20) In another embodiment, the composition comprising R-1234yf, R-134, R-32 and R-125. In another embodiment, a refrigerant composition comprising 40% to 45% of R-1234yf, 4% to 6% of R-134, 20% to 65% of R-32 and 2% to 15% of R-125.

(21) In another embodiment, the composition comprising R-1234yf, R-134, R-32, R-152a, and R-143a. In another embodiment, a refrigerant composition comprising 40% to 45% of R-1234yf, 4% to 6% of R-134, 20% to 65% of R-32, 2% to 15% of 152a and 2% to 10% of R-143a.

(22) In another embodiment, the composition comprising R-1234yf, R-134, R-32, R-152a, and R-125. In another embodiment, a refrigerant composition comprising 40% to 45% of R-1234yf, 4% to 6% of R-134, 20% to 65% of R-32, 2% to 15% of 152a and 2% to 10% of R-125.

(23) In another embodiment, the composition comprising R-1234yf, R-134, R-32, R-600a, and R-125. In another embodiment, a refrigerant composition comprising 40% to 45% of R-1234yf, 4% to 6% of R-134, 20% to 65% of R-32, 2% to 15% of 600a and 2% to 10% of R-125.

(24) In another embodiment, the composition comprising R-1234yf, R-134, R-32, R-227ea, and R-125. In another embodiment, a refrigerant composition comprising 40% to 45% of R-1234yf, 4% to 6% of R-134, 20% to 65% of R-32, 2% to 15% of 227ea and 2% to 10% of R-125.

(25) In another embodiment, a refrigerant composition comprising R-1234yf, R-134 and R-152a. In another embodiment, a refrigerant composition comprising 30% to 80% of R-1234yf, 4% to 15% of R-134 and 5% to 55% of R-152a.

(26) In another embodiment, the composition comprising R-1234yf, R-134 and additional component has GWP of less than 1500.

(27) In another embodiment, the composition comprising R-1234yf, R-134 and additional component has GWP of less than 750.

(28) In another embodiment, the composition comprising R-1234yf, R-134 and additional component has GWP of less than 500.

(29) In another embodiment, the composition comprising R-1234yf, R-134 and additional component further comprises a lubricant selected from the group consisting of polyol esters, polyalkylene glycols, polyvinyl ethers, mineral oil, alkylbenzenes, synthetic paraffins, synthetic naphthenes, and poly(alpha)olefins.

(30) In another embodiment, the compositions comprising R-1234yf, R-134 and additional component of the present invention are useful in processes for producing cooling or heat, as heat transfer fluids, foam blowing agents, aerosol propellants, and fire suppression and fire extinguishing agents.

(31) In another embodiment, the present invention provides a refrigerant composition comprising R-1234yf, R-134a, and one or more additional component selected from R-1234ye, R-1243zf, R-32, R-125, R-143a, R-152a, R-161, R-227ea, R-236ea, R-236fa, R-245fa, R-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane.

(32) In another embodiment, the present invention provides a composition comprising 10 mole % to 55 mole % of R-134a and 35 mole % to 90 mole % of 1234yf.

(33) In another embodiment, the present invention provides a refrigerant composition comprising 10 mole % to 35 mole % of R-134a and 60 mole % to 90 mole % of 1234yf, and one or more additional component selected from R-1234ye, R-1243zf, R-32, R-125, R-143a, R-152a, R-161, R-227ea, R-236ea, R-236fa, R-245fa, R-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane.

(34) In another embodiment, the present invention provides an azeotropic or azeotrope like composition comprising R-1244yf, R-134 and additionally R-134a.

(35) In another embodiment, the present invention provides a composition comprising about 35 mole % to 80% mole % of 1234yf, about 1 mole % to about 49% of R-134a and about 1 mole % to about 49% of R-134.

(36) In another embodiment, the present invention provides ternary azeotropic or azeotrope like composition comprising about 65 mole % to 85 mole % of 1234yf, about 4 mole % to about 20% of R-134a and about 5 mole % to about 15% of R-134.

(37) In another embodiment, the composition comprising R-1234yf, R-134, R-134a and additional component further comprises a lubricant selected from the group consisting of polyol esters, polyalkylene glycols, polyvinyl ethers, mineral oil, alkylbenzenes, synthetic paraffins, synthetic naphthenes, and poly(alpha)olefins.

(38) In another embodiment, the compositions comprising R-1234yf, R-134 and R-134a of the present invention are useful in processes for producing cooling or heat, as heat transfer fluids, foam blowing agents, aerosol propellants, and fire suppression and fire extinguishing agents.

(39) In another embodiment, the present invention provides a refrigerant comprising an azeotropic composition comprising R-1234yf, R-134, and R-134a.

(40) In another embodiment, the compositions comprising R-1234yf, R-134, and R-134a has GWP of less than 1500.

(41) In another embodiment, the compositions comprising R-1234yf, R-134, and R-134a has GWP of less than 750.

(42) In another embodiment, the compositions comprising R-1234yf, R-134, and R-134a has GWP of less than 500.

(43) In another embodiment, the present invention provides a composition comprising R-1234yf, R-134a, R-134 and further comprises one or more additional component selected from R-1234ye, R-1243zf, R-32, R-125, R-143a, R-152a, R-161, R-227ea, R-236ea, R-236fa, R-245fa, R-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane.

(44) In another embodiment, the present invention provides a composition comprising R-1234yf, R-134a, R-134, and R-32.

(45) In another embodiment, a refrigerant composition comprising 40% to 45% of R-1234yf, 2% to 6% of R-134, 5% to 45% 134a and 10% to 45% of R-32.

(46) In another embodiment, a refrigerant composition comprising 40% to 45% of R-1234yf, 4% to 6% of R-134, 5% to 45% 134a and 2% to 10% of R-600a.

(47) In another embodiment, a refrigerant composition comprising 40% to 45% of R-1234yf, 4% to 6% of R-134, 5% to 45% 134a, 25 to 10% of R-600a and 2% to 10% of R-125.

(48) In another embodiment, the composition comprising R-1234yf, R-134, R-134a, R-32, R-152a, and R-143a. In another embodiment, a refrigerant composition comprising 40% to 45% of R-1234yf, 4% to 6% of R-134, 5% to 35% of 134a, 20% to 65% of R-32, 2% to 15% of 152a and 2% to 10% of R-143a.

(49) In another embodiment, the composition comprising R-1234yf, R134a, R-134, R-32, and R-152a. In another embodiment, a refrigerant composition comprising 30% to 65% of R-1234yf, 4% to 8% of R-134, 5% to 50% of 134a, 20% to 65% of R-32, 2% to 25% of 152a.

(50) In another embodiment, the composition comprising R-1234yf, R-134, R-32, R-134a, and R-125. In another embodiment, a refrigerant composition comprising 40% to 45% of R-1234yf, 4% to 6% of R-134, 5% to 35% of 134a, 20% to 65% of R-32, and 2% to 10% of R-125.

(51) In another embodiment, the composition comprising R-1234yf, R-134, R-32, R-134a, and R-227ea. In another embodiment, a refrigerant composition comprising 40% to 45% of R-1234yf, 4% to 6% of R-134, 5% to 35% of 134a, 20% to 65% of R-32, and 2% to 10% of R-227ea.

(52) In another embodiment, the composition comprising R-1234yf, R-134, R-32, R-134a, and R-600a. In another embodiment, a refrigerant composition comprising 40% to 45% of R-1234yf, 4% to 6% of R-134, 5% to 35% of 134a, 20% to 65% of R-32, and 2% to 10% of R-600a.

(53) In another embodiment, the compositions comprising R-1234yf, R-134 and R-134a further comprises a lubricant selected from the group consisting of polyol esters, polyalkylene glycols, polyvinyl ethers, mineral oil, alkylbenzenes, synthetic paraffins, synthetic naphthenes, and poly(alpha)olefins.

(54) In another embodiment, the composition comprising R-1234yf, R-134a, R-134 and additional component has GWP of less than 1500.

(55) In another embodiment, the composition comprising R-1234yf, R-134a, R-134 and additional component has GWP of less than 750.

(56) In another embodiment, the composition comprising R-1234yf, R-134a, R-134 and additional component has GWP of less than 500.

(57) In another embodiment the composition comprising R-1234yf, R-134a, R-134 and additional component are useful in processes for producing cooling or heat, as heat transfer fluids, foam blowing agents, aerosol propellants, and fire suppression and fire extinguishing agents.

(58) The compositions of the present invention can specifically be prepared by reaction of difluorochloromethane (R-22)/tetrafluoroethene (TFE) and chloromethane (R-40)/methane. The reaction of difluorochloromethane (R-22)/tetrafluoroethene (TFE) and chloromethane (R-40)/methane may be carried out in the presence of initiator selected from from the group consisting of carbon tetrachloride, hexachloroethane, trichloroacetylchloride, chloroform, phosgene, thionyl chloride, sulfonyl chloride, trichloromethylbenzene, organic hypochlorites and inorganic hypochlorites or mixture thereof.

(59) The reaction of difluorochloromethane (R-22)/tetrafluoroethene (TFE) and chloromethane (R-40)/methane is carried out at a temperature in the range of 500 to 850° C.

(60) The azeotropic or azeotrope-like compositions of the present invention are isolated from the outlet composition that obtained from the reaction of TFE and R40.

(61) The present compositions have utility in a wide range of applications. For example, one embodiment of the present invention relates to blowing agent, heat transfer compositions, aerosol and cleaning, and refrigerant compositions comprising the present azeotrope-like compositions.

(62) In another embodiment of this aspect of the present invention, the azeotrope or azeotrope like composition additionally comprises of about less than 0.5% of non-absorbable gases.

(63) In another embodiment of this aspect of the present invention, the refrigerant composition may contain optional components selected from the group consisting of lubricants, dyes (including Ultra Violet dyes), solubilizing agents, compatibilizers, stabilizers, tracers, perfluoropolyethers, anti-wear agents, extreme pressure agents, corrosion and oxidation inhibitors, metal surface energy reducers, metal surface deactivators, free radical scavengers, foam control agents, viscosity index improvers, pour point depressants, detergents, viscosity adjusters, and mixtures thereof. Indeed, many of these optional other components fit into one or more of these categories and may have qualities that lend themselves to achieve one or more performance characteristic.

(64) In another embodiment of this aspect, the present invention provides a refrigeration process using the refrigerant composition of the present invention comprising the steps of:

(65) a) Condensing the refrigerant composition;

(66) b) Evaporating the refrigerant composition.

(67) These compositions of the present invention tend to exhibit relatively low global warming potentials (“GWPs”).

(68) It is against this and other backgrounds, which shall be filed in a detailed manner in complete specifications, in due course, the present invention is brought out and explained in following non-limiting examples.

EXAMPLES

(69) The azeotrope or azeotrope-like composition of the invention can be used as refrigerant compositions and tested with standard ASHRAE modeling program maintaining indoor at 27° C. dry bulb temperature (DBT) and 19° C. wet bulb temperature (WBT) and outdoor at 35 DBT and 24 WBT.

(70) The refrigerant compositions of the present invention are enlisted in Table 1

(71) The comparison of the compositions of the present inventions with R-22 is listed in Table 2. The comparison of the present inventions with R-404 is listed in Table 3.

(72) TABLE-US-00001 TABLE 1 All quantities are calculated as Mass % Comp R1234yf R134 R134a R32 R125 R152a R600 R227ea R143A GWP 1 65.16 7.24 22.00 5.00 0.60 391 2 58.50 6.50 22.00 8.00 5.00 645 3 58.50 6.50 22.00 8.00 5.00 484.5 4 54.00 6.00 9.70 10.00 10.30 10.00 946 5 63.00 7.00 30.00 284 6 63.00 7.00 28.00 2.00 273 7 36.00 4.00 30.00 30.00 1200 8 54.00 6.00 30.00 10.00 589.5 9 64.80 7.20 23.00 5.00 397.5 10 48.00 3.00 36.00 13.00 691 11 57.85 6.40 35.75 316 12 64.80 7.20 22.00 4.00 2.00 359 13 48.50 7.20 8 26.30 10.00 378.5 14 42.50 4.72 18 27.78 7.00 698.5 15 38.00 4.22 18 31.78 8.00 498 16 42.50 4.72 25 22.00 5.78 722 17 38.00 4.22 15 37.78 5.00 658 18 48.50 5.39 46.11 661 19 34.00 3.78 18 44.22 577 20 34.00 3.78 16 18.00 28.22 412.5

(73) TABLE-US-00002 TABLE 2 Refrigerant Cooling Quantity Power compositions Capacity Charged Consumption COP ODP GWP R22 100% 100% 100% 100% 0.055 1760 Composition 1 105.1 100 100.2 104.8 0 391 Composition 2 103.2 100 101.1 102.0 0 645 Composition 3 102.1 100 100.8 101.2 0 484.5

(74) TABLE-US-00003 TABLE 3 Refrigerant Cooling Quantity Power compositions Capacity Charged Consumption COP ODP GWP R404A 100% 100% 100% 100% 0 3922 Composition 7 105.9 100 114.7 92.22 0 1200 Composition 8 99.1 100 101.2 97.92 0 589.5 Composition 9 97 100 95.2 101.9 0 397.5

(75) The comparative data for enthalpy of evaporation is given in Table-4 below.

(76) TABLE-US-00004 TABLE 4 Molar mass Enthalpy (Kg/Kmol) (kj/kg) at −25° C. at 25° C. at −25°C at 25° C. in vapour in liquid in vapour in liquid Refrigerant phase phase phase phase R404a 97.604 97.604 352.33 236.3 R22 86.46 86.46 394.9 230.29  Composition 1 89.51 89.51 377.49 236.92  Composition 2 91.27 91.27 374.36 236.46  Composition 3 87.57 87.57 361.59 237.16  Composition 4 101.24 101.24 354.32 234.81  Composition 5 83.49 83.49 366.86 237.85  Composition 6 84.06 84.06 389.87 237.76  Composition 7 84.63 84.63 383.67 237.58  Composition 8 83.87 83.87 387.84 237.75  Composition 9 89.08 89.08 378.51 236.89 Composition 10 79.96 79.96 395.45 238.49 Composition 11 79.54 79.54 398.64 238.57 Composition 12 88.54 88.54 378.73 237.32 Composition 13 81.22 81.22 403.06 238.26 Composition 14 84.2 84.2 392.39 237.49 Composition 15 76.95 76.95 404.99 240.31 Composition 16 89.22 89.22 385.28 236.54 Composition 17 77.55 77.55 407.39 238.72 Composition 18 107.52 107.52 378.51 248.37 Composition 19 73.44 73.44 420.21 239.51 Composition 20 79.04 79.04 419.59 238.99

(77) As depicted in the Tables above, the refrigerant compositions of the present invention exhibit good cooling capacity and will operate in substantially the same manner as the legacy R22 and 404A refrigerant under the same conditions. The performance factor is almost close to R22 and have ZERO ODP and very low GWP.

(78) The refrigerant composition of the present invention has higher specific heat capacity as given in Table-5 below. Cp (Specific Heat in constant pressure) is the amount of heat required to increase temperature by 1° C. when heat is given at constant pressure, Cv (Specific heat in constant volume) means the amount of heat required to increase temperature by 1° C., when heat is given at constant volume.

(79) TABLE-US-00005 TABLE-5 Cp/Cv Cp/Cv Cp/Cv at −25° C. at −25° C. at 25° C. in liquid in vapour in liquid Refrigerant phase phase phase R404a 1.5327 1.1859 1.6678 R22 1.690 1.249 1.819  Composition 1 1.5413 1.1842 1.673  Composition 2 1.5409 1.1825 1.671  Composition 3 1.5445 1.188 1.673  Composition 4 1.5186 1.1637 1.625  Composition 5 1.5626 1.202 1.713  Composition 6 1.5569 1.1981 1.700  Composition 7 1.5788 1.2157 1.744  Composition 8 1.568 1.2061 1.723  Composition 9 1.5444 1.1866 1.679 Composition 10 1.5865 1.223 1.759 Composition 11 1.5798 1.2165 1.744 Composition 12 1.5404 1.1839 1.671 Composition 13 1.5576 1.1999 1.684 Composition 14 1.5674 1.2027 1.704 Composition 15 1.5728 1.2097 1.716 Composition 16 1.5473 1.1853 1.661 Composition 17 1.5948 1.2259 1.754 Composition 18 1.5106 1.1706 1.580 Composition 19 1.6126 1.2397 1.779 Composition 20 1.5422 1.1926 1.638