Compositions containing hfo-1234ze, hfo-1225zc, and hfo-1234yf and methods for making and using the same

Abstract

The present invention is entitled "Compositions Containing HFO-1234ze, HFO-1225zc, and HFO-1234yf and Methods for Making and Using the Same." A fluoropropene composition comprising E-1,3,3,3-tetrafluoropropene, 1,1,3,3,3-pentafluoropropene, and 2,3,3,3-tetrafluoropropene, wherein the total amount of 1,1,3,3,3-pentafluoropropene and 2,3,3,3-tetrafluoropropene is 1.0 wt% or less based on the total weight of the fluoropropene composition is disclosed. Methods of making the fluoropropene, compositions, and methods for using the fluoropropene composition are also disclosed.

Description

[0001] This application claims the benefit of PCT Application No. PCT / US20 / 029690, filed April 24, 2020. The disclosure of this application PCT / US20 / 029690 is hereby incorporated by reference. TECHNICAL FIELD

[0002] The present invention relates to tetrafluoropropene compositions and methods for making and using the same. The present invention is particularly directed to compositions comprising E-1,3,3,3-tetrafluoropropene (HFO-1234ze), 1,1,3,3,3-pentafluoropropene (HFO-1225zc), and 2,3,3,3-tetrafluoropropene (HFO-1234yf) and uses thereof, and methods for making products comprising 1,3,3,3-tetrafluoropropene (HFO-1234ze), 1,1,3,3,3-pentafluoropropene (HFO-1225zc), and 2,3,3,3-tetrafluoropropene (HFO-1234yf) from 1,1,1,3,3-pentafluoropropane (HFC-245fa). BACKGROUND

[0003] The fluorocarbon industry has been working for the past several decades to find replacements for the ozone-depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) that are being phased out by the Montreal Protocol. The solution for many applications has been the commercialization of hydrofluorocarbon (HFC) compounds for use as refrigerants, solvents, fire extinguishing agents, foam blowing agents, and propellants. These new compounds, which are currently the most widely used (such as HFC refrigerants, HFC-134a and HFC-125), have zero ozone depletion potential and are therefore not affected by the current phase-out provisions of the Montreal Protocol.

[0004] In addition to the problem of ozone depletion, global warming is another environmental problem in many of these applications. Therefore, there is a need for compositions that meet low ozone depletion standards and also have low global warming potential. Certain hydrofluoroolefin compositions are believed to meet both of these goals. Therefore, there is also a need for economical methods of making these compositions.

[0005] HFO-1234ze (CF3CH=CHF) and HFO-1234yf (CF3CF=CH2) both have zero ozone depletion and low global warming potential and have been identified as potential refrigerants. Specifically, the E-isomer of HFO-1234ze (HFO-1234zeE) has been shown to be useful in refrigeration applications. U.S. Patent 7,862,742 discloses compositions comprising HFO-1234ze and HFO-1234yf. U.S. Patent 9,302,962 discloses a process for making HFO-1234ze. The disclosures of U.S. Patent 7,862,742 and U.S. Patent 9,9,302,962 are hereby incorporated by reference in their entirety.

[0006] Catalytic dehydrofluorination of HFC-245fa typically produces a mixture of the E- and Z-isomers of HFC-1234ze. Depending on the specific catalyst selected, the amount of Z-isomer can vary between 15% and 23%. Dehydrofluorination in the liquid phase using aqueous solutions of caustic or other strong bases also produces a mixture of the two isomers. While the ratio of the two isomers can vary somewhat with temperature, typically about 13% to about 15% of the Z-isomer is formed. Since the E-isomer is most useful for refrigeration applications, after separation of the E-isomer from the Z-isomer, the Z-isomer is typically isomerized to the E-isomer in a separate step, or the Z-isomer is converted back to 245fa by addition of hydrogen fluoride. Both of these alternatives require additional steps, which increase cost.

[0007] There is a need in the art for compositions comprising HFO-1234zeE that can maintain the advantageous properties of HFO-1234zeE. There is also a need for a process that can make compositions of HFO-1234ze and HFO-1234yf that minimizes or eliminates the need for purification or separation steps to remove excess HFO-1234yf. SUMMARY

[0008] A fluoropropene composition is described comprising E-1,3,3,3-tetrafluoropropene, 1,1,3,3,3-pentafluoropropene, and 2,3,3,3-tetrafluoropropene. The total amount of 1,1,3,3,3-pentafluoropropene and 2,3,3,3-tetrafluoropropene in the composition is 1.0 wt% or less, based on the total weight of the fluoropropene composition.

[0009] Further, the present disclosure includes a process for making a mixture of 1,3,3,3- tetrafluoropropene and 2,3,3,3-tetrafluoropropene, the process comprising contacting a mixture of 1,1,1,3,3-pentafluoropropane and Z-1,3,3,3-tetrafluoropropene in the gas phase, preferably in the presence of an oxygen-containing gas, with a catalyst comprising at least one catalyst selected from the group consisting of fluorided Cr203and fluorided alumina supported Cr / Ni to form a mixture comprising Z-1,3,3,3-tetrafluoropropene, E-1,3,3,3-tetrafluoropropene, 1,1,3,3,3-pentafluoropropane, 2,3,3,3-tetrafluoropropene, hydrogen fluoride, and optionally unreacted 1,1,1,3,3-pentafluoropropane. One embodiment of the process of the present invention makes a useful composition without the need for purification or separation steps, including steps for removing excess 2,3,3,3-tetrafluoropropene (HFO-1234yf) or 1,1,3,3,3-pentafluoropropane.

[0010] Further, the present disclosure also includes a fluoropropene composition formed from the process of contacting a mixture of 1,1,1,3,3-pentafluoropropane and Z-1,3,3,3-tetrafluoropropene in the gas phase, optionally in the presence of an oxygen-containing gas, with a catalyst comprising at least one catalyst selected from the group consisting of fluorided Cr203and fluorided alumina supported Cr / Ni.

[0011] In one embodiment, the process of the present invention makes a composition comprising HFO-1234ze(E), HFO-1225zc, and HFO-1234yf, and the composition is useful as a refrigerant. In another embodiment, the composition comprises HFO-1225zc and a near-azeotropic composition comprising HFO-1234ze(E) and HFO-1234yf. In another embodiment, the composition comprises a three- component near-azeotropic composition comprising HFO-1234ze(E), HFO-1234yf, and HFO-1225zc.

[0012] One embodiment relates to any combination of the foregoing, wherein the 2,3,3,3- tetrafluoropropene is present in the fluoropropene composition in an amount of 0.0001 wt% to 0.9 wt%, based on the total weight of the fluoropropene composition.

[0013] One embodiment relates to any combination of the foregoing, wherein the 2,3,3,3- tetrafluoropropene is present in the fluoropropene composition in an amount of 0.001 wt% to 0.8 wt%, based on the total weight of the fluoropropene composition.

[0014] One embodiment relates to any combination of the foregoing, wherein the 2,3,3,3-tetrafluoropropene is present in the fluoropropene composition in an amount of 0.1 to 0.6 weight percent based on the total weight of the fluoropropene composition.

[0015] One embodiment relates to any combination of the foregoing, wherein the 2,3,3,3-tetrafluoropropene is present in the fluoropropene composition in an amount of 0.3 to 0.4 weight percent based on the total weight of the fluoropropene composition.

[0016] One embodiment relates to any combination of the foregoing, wherein the 2,3,3,3-tetrafluoropropene is present in an amount of 0.01 to 1.0 mol percent.

[0017] One embodiment relates to any combination of the foregoing, wherein the 2,3,3,3-tetrafluoropropene is present in an amount of 0.1 to 0.9 mol percent.

[0018] One embodiment relates to any combination of the foregoing, wherein the 2,3,3,3-tetrafluoropropene is present in an amount of 0.2 to 0.4 mol percent.

[0019] One embodiment relates to any combination of the foregoing, wherein the 2,3,3,3-tetrafluoropropene is present in an amount of 0.3 to 0.4 mol percent.

[0020] Another embodiment relates to any combination of the foregoing, wherein the 1,1,3,3,3-pentafluoropropene is present in the fluoropropene composition in an amount of 0.0001 to 0.9 weight percent, preferably in an amount of 0.001 to 0.8 weight percent, more preferably in an amount of 0.01 to 0.6 weight percent, and most preferably in an amount of 0.1 to 0.4 weight percent based on the total weight of the fluoropropene composition.

[0021] Another embodiment relates to any combination of the foregoing, wherein the E-1,3,3,3-tetrafluoropropene is present in the fluoropropene composition in an amount of 50.0 weight percent or more, preferably in an amount of 75.0 weight percent or more, more preferably in an amount of 99.0 weight percent or more, even more preferably in an amount of 99.5 weight percent or more, and most preferably in an amount of 99.8 weight percent or more based on the total weight of the fluoropropene composition.

[0022] Another embodiment relates to any combination of the foregoing, wherein the total amount of 2,3,3,3-tetrafluoropropene and 1,1,3,3,3-pentafluoropropene in the fluoropropene composition is 0.001 to 0.9 weight percent, preferably 0.1 to 0.8 weight percent, and most preferably 0.3 to 0.5 weight percent based on the total weight of the fluoropropene composition.

[0023] One embodiment relates to any combination of the foregoing, wherein the fluoropropene composition further comprises R-134 in an amount of 1.0 wt% to 40.0 wt%, more preferably in an amount of 30.0 wt% to 40.0 wt%, and most preferably in an amount of 35.0 wt% to 40.0 wt%, based on the total weight of the fluoropropene composition.

[0024] One embodiment relates to any combination of the foregoing, wherein the fluoropropene composition further comprises R-1336mzzE and / or R-227ea in an amount of 15.0 wt% to 20.0 wt% of R-1336mzzE and 2.0 wt% to 5.0 wt% of R-227ea, based on the total weight of the fluoropropene composition.

[0025] One embodiment relates to any combination of the foregoing, wherein the fluoropropene composition further optionally comprises one or more of the following: R-143a, R-152a, TFP (trifluoropropynyl), R-1233xf, R-1233zd(E), R-1233zd(Z), R236fa, and at least one HFO-1234 isomer, including at least one of HFO-1234zc, HFO-1234yc, and HFO-1234ye.

[0026] One embodiment relates to any combination of the foregoing, wherein the sum of the amounts of R-143a, R-152a, TFP, R-1233xf, R-1233zd(E), and R-1233zd(Z) is between 0.001 mole% and 2 mole%, based on the total fluoropropene composition.

[0027] One embodiment relates to any combination of the foregoing, wherein the fluoropropene composition comprises R-1233zd(E) in an amount of 0.7 mole% to 1.15 mole%, based on the total fluoropropene composition.

[0028] One embodiment relates to any combination of the foregoing, wherein the fluoropropene composition comprises R-1233zd(Z) in an amount of 0.05 mole% to 0.25 mole%, based on the total fluoropropene composition.

[0029] One embodiment relates to any combination of the foregoing, wherein the fluoropropene composition comprises R-143a in an amount of 0.05 mole% to 0.25 mole%, based on the total fluoropropene composition.

[0030] One embodiment relates to any combination of the foregoing, wherein the fluoropropene composition optionally comprises one or more of 1224yd, 1224zc, 1326mxz, 113, 32, 23, trifluoropropynyl, 356mff, 1326mxz, HFC-245fa, and HFC-245cb.

[0031] One embodiment relates to any combination of the foregoing, wherein the sum of the amounts of 1224yd, 1224zc, 1326mxz, 113, 32, 23, trifluoropropynyl, 356mff, 1326mxz, HFC-245fa, and HFC-245cb is between 0.001 mole % and 2 mole %, based on the total fluoropropene composition.

[0032] One embodiment relates to any combination of the foregoing, wherein the composition is near-azeotropic. Another embodiment of the present application relates to a process for making a mixture of 1,3,3,3-tetrafluoropropene and 2,3,3,3-tetrafluoropropene, the process comprising:

[0033] (a) contacting a mixture of 1,1,1,3,3-pentafluoropropane and Z-1,3,3,3- tetrafluoropropene in the gas phase with a catalyst to form a mixture comprising Z-1,3,3,3-tetrafluoropropene, E-1,3,3,3-tetrafluoropropene, 1,1,3,3,3- pentafluoropropane,

[0034] 2,3,3,3-tetrafluoropropene, hydrogen fluoride, and optionally unreacted 1,1,1,3,3- pentafluoropropane, the catalyst comprising at least one catalyst selected from the group consisting of fluorinated Cr203and fluorinated alumina

[0035] Cr / Ni on alumina,

[0036] wherein the mixture comprises 0.00001 wt % to 1.0 wt % of 2,3,3,3-tetrafluoropropene and greater than 0 wt % and less than 1.0 wt % of 1,1,3,3,3-pentafluoropropane.

[0037] Another embodiment of the present application relates to a process for making a mixture of a fluoropropene of the formula CF3CH=CHF and a fluoropropene of the formula CF3CF=CH2, the process comprising:

[0038] (a) contacting a mixture of 1,1,1,3,3-pentafluoropropane and Z-1,3,3,3- tetrafluoropropene in the gas phase in the presence of an oxygen-containing gas with a catalyst to form a mixture comprising Z-1,3,3,3-tetrafluoropropene, E-1,3,3,3- tetrafluoropropene, 2,3,3,3-tetrafluoropropene, hydrogen fluoride, and optionally unreacted 1,1,1,3,3-pentafluoropropane, the catalyst comprising at least one catalyst selected from the group consisting of

[0039] fluorided Cr203or fluorided alumina supported Cr / Ni catalysts,

[0040] wherein the mixture comprises 0.00001% to 1.00% of 2,3,3,3-tetrafluoropropene.

[0041] One embodiment of the present application relates to any combination of the foregoing, wherein the mixture of 1,1,1,3,3-pentafluoropropane and 1,3,3,3-tetrafluoropropene comprises at least 7% by weight of Z-1,3,3,3-tetrafluoropropene, preferably at least 10% by weight of Z-1,3,3,3-tetrafluoropropene.

[0042] One embodiment of the present application relates to any combination of the foregoing, wherein at least 94% by weight, preferably at least 98% of the 1,1,1,3,3-pentafluoropropane is converted to E-1,3,3,3-tetrafluoropropene.

[0043] One embodiment of the present application relates to any combination of the foregoing, wherein the process further comprises

[0044] (b) recovering Z-1,3,3,3-tetrafluoropropene, or a mixture of Z-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane, and recycling the Z-1,3,3,3-tetrafluoropropene, or the mixture of Z-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane, back to step (a).

[0045] One embodiment of the present application relates to any combination of the foregoing, wherein the hydrogen fluoride produced in step (a) is separated and recovered.

[0046] One embodiment of the present application relates to any combination of the foregoing, wherein the oxygen-containing gas is oxygen or air.

[0047] One embodiment of the present application relates to any combination of the foregoing, wherein the mixture of 1,1,1,3,3-pentafluoropropane and 1,3,3,3-tetrafluoropropene comprises 0.1% to 0.8% by weight of 2,3,3,3-tetrafluoropropene, preferably 0.2% to 0.6% by weight of 2,3,3,3-tetrafluoropropene, more preferably 0.3% to 0.4% by weight of 2,3,3,3-tetrafluoropropene.

[0048] Another embodiment of the present application relates to any combination of the foregoing, wherein the mixture of 1,1,1,3,3-pentafluoropropane and Z-1,3,3,3-tetrafluoropropene comprises at least 7 weight percent Z-1,3,3,3-tetrafluoropropene.

[0049] One embodiment of the present application relates to any combination of the foregoing, wherein the mixture of 1,1,1,3,3-pentafluoropropane and Z-1,3,3,3-tetrafluoropropene comprises at least 10 weight percent Z-1,3,3,3-tetrafluoropropene.

[0050] One embodiment of the present application relates to any combination of the foregoing, wherein at least 94 weight percent of the 1,1,1,3,3-pentafluoropropane is converted to the E-isomer of 1,3,3,3-tetrafluoropropene.

[0051] One embodiment of the present application relates to any combination of the foregoing, wherein at least 98 weight percent of the 1,1,1,3,3-pentafluoropropane is converted to the E-isomer of 1,3,3,3-tetrafluoropropene.

[0052] One embodiment of the present application relates to any combination of the foregoing, and further comprises recovering Z-1,3,3,3-tetrafluoropropene, or a mixture of Z-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane, and recycling the Z-1,3,3,3-tetrafluoropropene, or the mixture of Z-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane, back to step (a).

[0053] One embodiment of the present application relates to any combination of the foregoing, wherein the hydrogen fluoride produced in step (a) is separated and recovered.

[0054] One embodiment of the present application relates to any combination of the foregoing, wherein the oxygen-containing gas is oxygen or air.

[0055] One embodiment of the present application relates to any combination of the foregoing, wherein the mixture comprises 0.1 to 0.5 mol percent 2,3,3,3-tetrafluoropropene.

[0056] One embodiment of the present application relates to any combination of the foregoing, wherein the mixture comprises 0.2 to 0.4 mol percent 2,3,3,3-tetrafluoropropene.

[0057] One embodiment of the present application relates to any combination of the foregoing, wherein the mixture comprises 0.3 to 0.4 mol percent 2,3,3,3-tetrafluoropropene.

[0058] Another embodiment of the present application relates to any combination of the foregoing methods, and to fluoro-propene compositions made by these methods.

[0059] Another embodiment of the present application relates to any combination of the foregoing embodiments, and includes a refrigerant composition comprising Z-1,3,3,3-tetrafluoropropene, E-1,3,3,3-tetrafluoropropene, 1,1,3,3,3-pentafluoropropene, and 2,3,3,3-tetrafluoropropene, and at least one member selected from the group consisting of:

[0060] (a) the group comprises one or more of R-143a, R-152a, TFP, R-1233xf,

[0061] R-1233zd(E), R-1233zd(Z), 1224yd, 1224zc, 1326mxz, 113, 32,

[0062] 23, 356mff, 1326mxz, HFC-245fa, HFC-245cb 1234zc, 1234yc,

[0063] 1234ye, 134a, 1225ye(Z and E), 114, 124, and 236fa,

[0064] (b) the group comprises one or more of R-143a, R-152a, TFP, R-1233xf, R-1233zd(E), R-1233zd(Z), 1224yd, 1224zc, 1326mxz,

[0065] 113, 32, 23, 356mff, 1326mxz, HFC-245fa, and HFC-245cb,

[0066] (c) the group comprises one or more of HFC-1234ye, HFC-1243zf,

[0067] HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a,

[0068] HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa,

[0069] HFC-365mfc, R1336mzz(E), propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethyl ether, CF3SCF3, CO2, and CF3I;

[0070] (d) combinations thereof.

[0071] One embodiment of the present application relates to a fluoropropene composition further comprising a lubricant selected from mineral oils such as paraffins, naphthenes, and aromatics, alkyl aryl compounds such as linear and branched alkyl alkyl benzenes, synthetic paraffins, synthetic naphthenes, poly(alpha olefins), polyol esters, polyalkylene glycols, and polyvinyl ethers.

[0072] One embodiment of the present application relates to a method for treating a surface, the method comprising:

[0073] providing an article; and

[0074] contacting the article with a heat transfer medium;

[0075] wherein the heat transfer medium comprises a fluoropropene composition according to any combination of the preceding embodiments.

[0076] One embodiment of the present application relates to a method for treating a surface, the method comprising:

[0077] providing a surface; and

[0078] contacting the surface with a treatment composition;

[0079] wherein the surface comprises a treatable material deposited thereon; and

[0080] wherein the treatment composition comprises a fluoropropene composition of any combination of the preceding embodiments.

[0081] One embodiment of the present application relates to the method for treating a surface, wherein the treatment composition substantially dissolves the treatable material.

[0082] One embodiment of the present application relates to a method of forming a composition, the method comprising:

[0083] providing a solute;

[0084] contacting the solute with a solvent;

[0085] wherein the solvent comprises a fluoropropene composition according to any combination of the preceding embodiments.

[0086] One embodiment of the present application relates to a refrigeration system, the refrigeration system comprising:

[0087] an evaporator; a condenser; a compressor; an expansion device; and a heat transfer medium;

[0088] wherein the heat transfer medium comprises a fluoropropene composition according to any combination of the preceding embodiments.

[0089] One embodiment of the present application relates to a chiller apparatus comprising the fluoro-propene composition according to any combination of the preceding embodiments.

[0090] One embodiment of the present application relates to the fluoro-propene composition according to any combination of the preceding embodiments for use in a chiller apparatus, preferably in a medium temperature chiller apparatus.

[0091] One embodiment of the present application relates to the use of the fluoro-propene composition according to any combination of the preceding embodiments in a chiller apparatus, preferably in a medium temperature chiller apparatus.

[0092] One embodiment of the present application relates to a method of producing cooling, the method comprising evaporating the composition according to any combination of the preceding embodiments in the vicinity of a body to be cooled and then condensing the composition.

[0093] One embodiment of the present application relates to a method for replacing a high GWP refrigerant in a refrigeration, air-conditioning or heat pump apparatus, wherein the high GWP refrigerant is selected from the group consisting of R134a, R22, R123, R11, R245fa, R114, R236fa, R124, R12, R410A, R407C, R417A, R422A, R507A, R502 and R404A, the method comprising providing to a refrigeration, air-conditioning or heat pump apparatus using, having used or designed to use the high GWP refrigerant, the composition according to any combination of the preceding embodiments.

[0094] One embodiment of the present application relates to a refrigeration apparatus, air-conditioning apparatus or heat pump apparatus containing the composition according to any combination of the preceding embodiments, wherein the refrigeration apparatus is preferably a stationary or mobile refrigeration apparatus and the air-conditioning apparatus is preferably a mobile air-conditioning apparatus, more preferably an automotive air-conditioning apparatus.

[0095] One embodiment of the present application relates to a method for transferring heat, the method comprising:

[0096] Providing an article;

[0097] Bringing the article into contact with a heat transfer medium;

[0098] wherein the heat transfer medium comprises the fluoro-propene composition according to any combination of the preceding embodiments, and includes the near-azeotropic composition produced by the method of the present application.

[0099] One embodiment of the present application relates to a method for treating a surface, the method comprising:

[0100] Providing a surface;

[0101] contacting the surface with a treatment composition;

[0102] wherein the surface comprises a treatable material deposited thereon; and wherein the treatment composition comprises a fluoropropene composition of any combination of the foregoing embodiments.

[0103] One embodiment of the present application relates to any combination of the foregoing, wherein the treatment composition substantially dissolves the treatable material.

[0104] One embodiment of the present application relates to a method for forming a composition, the method comprising:

[0105] providing a solute; contacting the solute with a solvent;

[0106] wherein the solvent comprises a fluoropropene composition according to any of the foregoing embodiments.

[0107] Another embodiment of the present application relates to a refrigeration system, the refrigeration system comprising:

[0108] an evaporator; a condenser;

[0109] a compressor; an expansion device;

[0110] and a heat transfer medium;

[0111] wherein the heat transfer medium comprises a fluoropropene composition according to any combination of the foregoing embodiments, and includes a near-azeotropic composition made by the method of the present application.

[0112] The foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the application. The various embodiments of the present application can be used alone or in combination with each other. Other features and advantages of the present application will become apparent from the following detailed description of a preferred embodiment, taken in conjunction with the accompanying drawings, which illustrate, by way of example, the principles of the application. DETAILED DESCRIPTION

[0113] The present application describes a fluoropropene composition comprising E-1,3,3,3-tetrafluoropropene, 1,1,3,3,3-pentafluoropropene, and 2,3,3,3-tetrafluoropropene. The total amount of 1,1,3,3,3-pentafluoropropene and 2,3,3,3-tetrafluoropropene in the composition is 1.0 wt% or less, based on the total weight of the fluoropropene composition.

[0114] Further, the present disclosure includes a process for preparing a mixture of fluoropropenes of the formula CF3CH=CHF, the formula CF2=CHCF3, and the formula CF3CF=CH2, the process comprising contacting a mixture of 1,1,1,3,3-pentafluoropropane and Z-1,3,3,3-tetrafluoropropene in the gas phase with a catalyst comprising at least one catalyst selected from the group consisting of fluorided Cr203or fluorided alumina supported Cr / Ni, optionally in the presence of an oxygen-containing gas, to form a mixture comprising Z-1,3,3,3-tetrafluoropropene, E-1,3,3,3-tetrafluoropropene, 1,1,3,3,3-pentafluoropropane, 2,3,3,3-tetrafluoropropene, and optionally unreacted 1,1,1,3,3-pentafluoropropane. Without wishing to be bound by any theory or explanation, higher contact temperatures and / or increased catalyst contact time lengths can result in the formation of increased amounts of 1,1,3,3,3-pentafluoropropane.

[0115] Certain dehydrofluorination reactions are well known in the art. Dehydrofluorination of HFC-245fa has been studied in particular. Both gas phase and liquid phase processes are known. 1,3,3,3-tetrafluoropropene (HFO-1234ze) exists as both the Z-isomer and the E-isomer around the double bond. Both gas phase and liquid phase processes are known to produce a mixture of the Z-isomer and the E-isomer, with the E-isomer predominating. The selectivity to the Z-isomer can vary from about 10% to about 23% depending on the choice of temperature and catalyst. The E-isomer has a boiling point of about -19°C at 1 atm, while the Z-isomer has a boiling point of about 9°C. For many uses, the E-isomer is preferred. To minimize the yield loss of the Z-isomer form, which is generally not desired, it is necessary to add an isomerization step to isomerize the Z-isomer to the E-isomer, or to add a fluorination step to convert HFO-1234ze(Z) back to HFC-245fa.

[0116] The dehydrofluorination reaction according to embodiments of the present disclosure can result in a composition of HFO-1234ze(E), HFO-1225zc, and HFO-1234yf that minimizes or eliminates the need for purification or separation steps to remove excess HFO-1234yf or HFO-1225zc. In some cases, the composition can be azeotropic or near-azeotropic, or include an azeotropic composition or a near-azeotropic composition. By azeotropic composition is meant a constant-boiling mixture of two or more substances that behaves as a single substance. One way to characterize an azeotropic composition is that the vapor produced by partial evaporation or distillation of a liquid has the same composition as the liquid that is evaporated or distilled (i.e., the mixture distills / boils without a change in composition). Azeotropes are characterized by co-boiling because they exhibit a maximum or minimum boiling point compared to non-azeotropic mixtures of the same compounds. During operation, an azeotrope will not fractionate within a refrigeration system or air conditioning system. Additionally, an azeotrope will not fractionate upon leakage from a refrigeration system or air conditioning system. In cases where one component of the mixture is flammable, fractionation during a leak can result in the appearance of a flammable composition within or outside the system.

[0117] By near-azeotropic composition is meant a substantially constant-boiling liquid blend of two or more compounds that behaves as a substantially single substance. One way to characterize a near-azeotropic composition is that the vapor produced by partial evaporation or distillation of a liquid has substantially the same composition as the liquid that is evaporated or distilled, i.e., the blend distills / boils without a substantially change in composition. Another way to characterize a near-azeotropic composition is that the bubble point vapor pressure and the dew point vapor pressure of the composition are substantially the same at a particular temperature. In this context, a composition of the present invention is near-azeotropic if the difference in vapor pressure between the original composition and the composition remaining after 50% by weight (50 wt.%) of the original composition has been removed, such as by evaporation or boiling, is less than about 10%.

[0118] According to one embodiment of the present invention, the composition of the present invention has a flammability rating of A2L as determined by ASHRAE Standard 34 and ASTM E681-09.

[0119] Aspects and embodiments have been described above and are merely what examples can be made of and should not be taken as limiting. Upon reading this description, persons skilled in the art will appreciate changes, modifications or alterations to the described embodiments. The foregoing description details certain embodiments of the application. It will be appreciated, however, that details are for illustrative purposes only and are not intended to limit the scope of the application. Changes can be made to the details

[0120] Other features and benefits of any one or more embodiments will be apparent from the following detailed description, and from the claims.

[0121] Certain dehydrofluorinations are known in the art and are preferably carried out in the vapor phase. The dehydrofluorination reaction can be carried out in any suitable reaction vessel or reactor, but it should preferably be constructed of materials resistant to corrosion by hydrogen fluoride, such as nickel and its alloys, including Hastelloy, Monel, and Inconel, or vessels lined with fluoropolymers. These can be single tubes, or multiple tubes packed with dehydrofluorination catalyst.

[0122] Catalysts that can be used in the process include chromium-based catalysts such as fluorided chromium oxide, which can be unsupported, or supported on a support such as activated carbon, graphite, fluorided graphite, or aluminum fluoride. The chromium catalyst can be used alone, or in the presence of a promoter selected from a nickel, cobalt, manganese, or zinc salt. In one embodiment, the chromium catalyst is high surface area chromium oxide, or fluorided chromium / nickel on aluminum fluoride (Cr / Ni / AlF3), the preparation of which is reported in European Patent Application EP 0486333 Al; the disclosures of these patents are hereby incorporated by reference. In another embodiment, the catalyst is a fluorided Girard Green catalyst. Additional suitable catalysts include, but are not limited to, JM 62-2 (a chromium catalyst available from Johnson Matthey), LV (a chromium catalyst available from Chemours), JM-62-3 (a chromium catalyst available from Johnson Matthey), and Newport Chrome (a chromium catalyst available from Chemours). Preferably, the chromium catalyst is activated prior to use, typically by heating the catalyst to 350°C to 400°C under a stream of nitrogen for a period of time, followed by re-heating the catalyst under a stream of HF and nitrogen or air for a period of time.

[0123] In one embodiment, the Girard green used in the present application is prepared by reacting boric acid with an alkali dichromate at 500°C to 800°C, followed by hydrolysis of the reaction product, whereby the Girard green comprises boron, an alkali metal, and water of hydration. Common alkali dichromates are sodium dichromate and / or potassium dichromate. The reaction is typically followed by the steps of cooling the reaction product in air, crushing the solid to produce a powder, and then hydrolyzing, filtering, drying, grinding, and screening. Girard green is blue-green in color, but is most commonly known as a green pigment, whereby the pigment is commonly referred to as Girard green. When used as a catalyst, it is also referred to as Girard green, as disclosed in U.S. Patent 3,413,363. In U.S. Patent 6,034,289, Cr203catalysts are disclosed as preferably being in the alpha form, and Girard green is also disclosed as a commercially available green pigment having the following composition: Cr20379-83%, H20 16-18%, B205 1.5 to 2.7% (sentence bridging, cols. 2 and 3), which can be converted to the alpha form (col. 3, I. 3). U.S. Patent 7,985,884 confirms the presence of an alkali metal in the Girard green composition disclosed in embodiment 1 : 54.5% Cr, 1.43% B, 3,400 ppm Na, and 120 ppm K. The disclosures of the foregoing patents and patent applications are incorporated herein by reference.

[0124] The physical shape of the catalyst is not critical and can include, for example, pellets, extrudates, powders, or granules. Preferably, the fluorination of the catalyst is carried out on the final shape of the catalyst.

[0125] In one embodiment, the present application is directed to feeding a mixture of HFC-245fa and at least about 10 wt% of the Z-isomer of HFO-1234ze into a dehydrofluorination reactor in the presence of an oxygen-containing gas to inhibit the formation of additional Z-isomers, such that the HFC-245fa converted by dehydrofluorination produces substantially only E-HFO-1234ze, HFO-1225zc, and HFO-1234yf. Feedings of less than about 10% will result in some inhibition of the formation of additional Z-1234ze. Feedings of greater than about 10 wt% of Z-1234ze result in only the presence of additional material that must be separated and recycled. The amount of Z-1234ze required to inhibit further formation of Z-isomer products depends somewhat on the conversion. At 70% conversion of 245fa, about 10-11% of the Z-isomer in the feed is required. At 80% conversion, about 13% of the Z-isomer in the feed is required.

[0126] In one embodiment, the reaction vessel can be maintained at a temperature between 200°C and 425°C. In another embodiment, the reaction vessel can be maintained at a temperature between 250°C and 350°C. In yet another embodiment, the reaction vessel can be maintained at a temperature between 275°C and 325°C or between 350°C to 410°C.

[0127] The reaction pressure can be below atmospheric, at atmospheric, or above atmospheric. In one embodiment, the reaction is conducted at a pressure of 14 psig to about 100 psig. In another embodiment, the reaction is conducted at a pressure of 14 psig to about 60 psig. In yet another embodiment, the reaction is conducted at a pressure of 40 psig to about 85 psig. In yet another embodiment, the reaction is conducted at a pressure of 50 psig to 75 psig. Generally, increasing the pressure in the reactor above atmospheric will serve to increase the contact time of the reactants in the process. Longer contact times will necessarily increase the degree of conversion in the process without necessarily increasing the temperature.

[0128] Depending on the temperature of the reactor and the contact time, the product mixture from the reactor will contain varying amounts of unreacted HFC-245fa. In certain embodiments, the E-1,3,3,3-tetrafluoropropene, 1,1,3,3,3-pentafluoropropene, and HFO-1234yf can be separated from the Z-1,3,3,3-tetrafluoropropene, hydrogen fluoride, and any unreacted HFC-245fa, which is then recycled back to the reactor with additional HFC-245fa. The hydrogen fluoride can be removed by scrubbing by passing the reactor effluent through a caustic aqueous solution, or the hydrogen fluoride can be removed by distillation. In a particularly suitable embodiment, the composition formed by the process of the present disclosure contains unseparated 1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), HFO-1225zc, and 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0129] In one embodiment, the reactor feed is preheated in a vaporizer to a temperature of about 30°C to about 100°C. In another embodiment, the reactor feed is preheated in a vaporizer to a temperature of about 30°C to about 80°C.

[0130] In some embodiments, an inert diluent gas is used as a carrier gas for the hydrochlorofluoropropane. In one embodiment, the carrier gas is selected from nitrogen, argon, helium, or carbon dioxide.

[0131] In one embodiment, the product mixture comprises (on a mol basis) between 0.01% and 1.00% HFO-1234yf, alternatively between 0.05% and 0.95% HFO-1234yf, alternatively between 0.10% and 0.90% HFO-1234yf, alternatively between 0.20% and 0.80% HFO-1234yf, alternatively between 0.01% and 0.20% HFO-1234yf, alternatively between 0.10% and 0.30% HFO-1234yf, alternatively between 0.20% and 0.40% HFO-1234yf, alternatively between 0.30% and 0.50% HFO-1234yf, alternatively between 0.30% and 0.40% HFO-1234yf, alternatively between 0.40% and 0.60% HFC-1234yf, alternatively between 0.50% and 0.70% HFO-1234yf, alternatively between 0.60% and 0.80% HFO-1234yf, alternatively between 0.70% and 0.70% HFO-1234yf, alternatively between 0.80% and 1.00% HFO-1234yf. In another embodiment, the foregoing product mixture further comprises (on a mol basis) HFO-1225zc, wherein the HFO-1225zc is present in an amount equal to 10% HFO-1234yf.

[0132] In some embodiments, the fluoro-propene composition further optionally comprises one or more of R-143a, R-152a, TFP, R-1233xf, R-1233zd(E), or R-1233zd(Z). In some embodiments, the sum of the amounts of R-143a, R-152a, TFP, R-1233xf, R-1233zd(E), and R-1233zd(Z) is between 0.00001 mole % and 2 mole %, based on the total fluoro-propene composition. In one embodiment, the fluoro-propene composition comprises R-1233zd(E) in an amount of 0.7 mole % to 1.15 mole %, based on the total heat transfer medium. In one embodiment, the fluoro-propene composition comprises R-1233zd(Z) in an amount of 0.05 mole % to 0.25 mole %, based on the total heat transfer medium. In one embodiment, the fluoro-propene composition comprises HFO-1234zeZ in an amount of 0.05 mole % to 0.25 mole %, based on the total fluoro-propene composition. In one embodiment, the fluoro-propene composition comprises R-143a in an amount of 0.05 mole % to 0.25 mole %, based on the total fluoro-propene composition.

[0133] In other embodiments, the fluoropropene composition optionally comprises one or more of 1224yd, 1224zc, 1326mxz, 113, 32, 23, trifluoropropargyl, 356mff, 1326mxz, HFC-245fa, and HFC-245cb. The amount of the foregoing compounds can range from about 0.001 to about 1 mol%, about 0.001 to about 0.9, and in some cases about 0.001 to about 0.7 mol%.

[0134] In one specific embodiment, the sum of the amounts of 1224yd, 1224zc, 1326mxz, 113, 32, 23, trifluoropropargyl, 356mff, 1326mxz, HFC-245fa, and HFC-245cb, based on the total fluoropropene composition, is between 0.001 mole percent and 2 mole percent. The amount of the foregoing compounds can range from about 0.001 to about 0.1 mol%, about 0.001 to about 0.09, and in some cases about 0.001 to about 0.07 mol%.

[0135] In another specific embodiment, the compositions of the present application can comprise greater than about 99 weight percent HFO-1234ze(E), and for example 99.5 to 99.99, 99.6 to 99.9, and in some cases about 99.7 to 99.99 weight percent HFO-1234ze(E), with the balance comprising HFO-1225zc and HFO-1234yf. The compositions of the present application can also comprise at least one additional compound selected from the group consisting of HFC-134a, 245cb, 236fa, 1225ye isomers (e.g., E-1225ye and Z-1225ye), HFO-1234ze isomers (e.g., HFO-1234ze(Z)), HFC-245fa, HFC-124, HCFC-114, trifluoropropargyl, HFC-152a, and HFO-1234 isomers including at least one member selected from the group consisting of HFO-1234zc, HFO-1234yc, and HFO-1234ye. The total combined amount of HFO-1225zc, HFO-1234yf, and additional compounds can range from greater than 0 to less than about 1 weight percent, and for example greater than 0 to 0.3, greater than 0 to 0.1, and in some cases greater than 0 to 0.01 mol%. Specific examples of the foregoing compositions are shown in Table A below.

[0136] Table A

[0137] Component 134a 3.2 ppm 1225zc 1.5 ppm 1234yf 47 ppm 245cb co-elutes with 1234yf 236fa 1.1 ppm E-1234ze 99.98 wt% E-1225ye 0.6 ppm 1234 isomers 6.1 ppm 245fa 20.5 ppm 124 4.6 ppm Z-1234ze 87 ppm 114 14 ppm trifluoropropyne 1 ppm 152a 0.5 ppm Z-1225ye 4 ppm

[0138] *includes HFO-1234zc, HFO-1234yc, and HFO-1234ye

[0139] The compositions of the present application can be prepared by any convenient method of mixing the desired amounts of the individual components. The preferred method is to weigh the desired amounts of the components and then combine the components in an appropriate container. If desired, agitation can be used.

[0140] An alternative method for making the compositions of the present application can be a method for making a refrigerant blend composition, wherein the refrigerant blend composition comprises a composition as disclosed herein, the method comprising (i) withdrawing a volume of one or more components of a refrigerant composition from at least one refrigerant container, (ii) removing impurities sufficient to enable reuse of the one or more of the withdrawn components, (iii) and optionally combining all or a portion of the withdrawn volume of components with at least one additional refrigerant composition or component.

[0141] The refrigerant container can be any container in which a refrigerant blend composition has been stored for use in a refrigeration apparatus, air conditioning apparatus, or heat pump apparatus. The refrigerant container can be a refrigeration apparatus, air conditioning apparatus, or heat pump apparatus in which the refrigerant blend has been used. Additionally, the refrigerant container can be a storage container for collecting withdrawn refrigerant blend components, including but not limited to a pressurized cylinder.

[0142] Residual refrigerant refers to any amount of refrigerant blend or refrigerant blend component that can be removed from a refrigerant container by any method known for transferring refrigerant blends or refrigerant blend components.

[0143] Impurities can be any component of the refrigerant blend or refrigerant blend component as a result of its use in a refrigeration apparatus, air conditioning apparatus, or heat pump apparatus. Such impurities include, but are not limited to, refrigeration lubricants (those described earlier herein), particulates (including but not limited to metal, metal salt, or elastomer particulates that can have come out of the refrigeration apparatus, air conditioning apparatus, or heat pump apparatus), and any other contaminants that can adversely affect the performance of the refrigerant blend composition.

[0144] Such impurities can be removed sufficiently to allow reuse of the refrigerant blend or refrigerant blend component without adversely affecting performance or the equipment in which the refrigerant blend or refrigerant blend component will be used.

[0145] It can be necessary to provide additional refrigerant blend or refrigerant blend component to the residual refrigerant blend or refrigerant blend component in order to make a composition that meets the required specifications for a given product. For example, if a refrigerant blend has 3 components within a specific weight percent range, it can be necessary to add one or more of the components in a given amount in order to restore the composition to within the specification limits.

[0146] The compositions of the present application have zero or low ozone depletion potential and low global warming potential (GWP). In addition, the compositions of the present application will have a global warming potential that is less than many of the hydrofluorocarbon refrigerants currently in use. One aspect of the present application is to provide a refrigerant having a global warming potential of less than 1000, less than 500, less than 150, less than 100, or less than 50. Another aspect of the present application is to reduce the net GWP of a refrigerant mixture by adding a fluoroolefin to the mixture.

[0147] The compositions of the present application can be used as low global warming potential (GWP) replacements for currently used refrigerants including, but not limited to, R134a (or HFC-134a, 1,1,1,2-tetrafluoroethane), R22 (or HCFC-22, difluorochloromethane), R123 (or HFC-123, 2,2-dichloro-1,1,1-trifluoroethane), R11 (CFC-11, trichlorofluoromethane), R12 (CFC-12, dichlorodifluoromethane), R245fa (or HFC-245fa, 1,1,1,3,3-pentafluoropropane), R114 (or CFC-114, 1,2-dichloro-1,1,2,2-tetrafluoroethane), R236fa (or HFC-236fa, 1,1,1,3,3,3-hexafluoropropane), R124 (or HCFC-124, 2-chloro-1,1,1,2-tetrafluoroethane), R407C (ASHRAE designation for a blend of 52 weight percent R134a, 25 weight percent R125 (pentafluoroethane), and 23 weight percent R32 (difluoromethane)), R410A (ASHRAE designation for a blend of 50 weight percent R125 and 50 weight percent R32), R417A (ASHRAE designation for a blend of 46.6 weight percent R125, 50.0 weight percent R134a, and 3.4 weight percent n-butane), R422A (ASHRAE designation for a blend of 85.1 weight percent R125, 11.5 weight percent R134a, and 3.4 weight percent isobutane), R404A (ASHRAE designation for a blend of 44 weight percent R125, 52 weight percent R143a (1,1,1-trifluoroethane), and 4.0 weight percent R134a), and R507A (ASHRAE designation for a blend of 50 weight percent R125 and 50 weight percent R143a). In addition, the compositions of the present application can be used as replacements for R12 (CFC-12, dichlorodifluoromethane) or R502 (ASHRAE designation for a blend of 51.2 weight percent CFC-115 (chloropentafluoroethane) and 48.8 weight percent HCFC-22).

[0148] The fluoro-propene compositions can be used in a variety of applications. In one embodiment, the fluoro-propene compositions can be used as refrigerants. In some embodiments, the fluoro-propene compositions can be used as replacements for older generation refrigerants (e.g., R404A, R502) to provide more environmentally friendly compositions. In some embodiments, the fluoro-propene compositions can be hydrofluoro-olefin compositions. In one embodiment, the fluoro-propene composition comprises 99 mole % to 99.99 mole % 1,3,3,3-tetrafluoropropene (HFO-1234ze)(E) and 0.0001 mole % to 1.0 mole % 1,1,3,3,3-pentafluoropropene (HFO-1225zc) and 2,3,3,3-tetrafluoropropene (HFO-1234yf). In another embodiment, the fluoro-propene composition is a near-azeotrope composition substantially free of HFO-1234ze(Z). By substantially free is meant that the fluoro-propene composition comprises less than about 1000 ppm, less than about 500 ppm, and typically less than about 100 ppm of HFO-1234ze(Z).

[0149] Generally, replacement refrigerants are most useful if they can be used in original refrigeration equipment designed for different refrigerants. The compositions of the present invention can be used as replacements for the above-mentioned refrigerants in original equipment. Additionally, the compositions of the present invention can be used as replacements for the above-mentioned refrigerants in equipment designed to use the above-mentioned refrigerants.

[0150] In one embodiment, the foregoing fluoro-propene compositions of the present invention can be blended with other fluorine-containing compounds. This embodiment of the present invention relates to a refrigerant composition comprising a composition of the present invention (e.g., HFO-1234ze(E), HFO-1225zc, and HFO-1234yf) and at least one compound selected from the group consisting of HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, R1336mzz(E), propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethyl ether, CF3SCF3, CO2, CF3I, and combinations thereof.

[0151] In one embodiment, the foregoing fluoro-propene compositions of the present application are mixed with at least one additional refrigerant comprising a member selected from the group consisting of R32, R125, R134, R134a, 227ea, and R1336mzz(E). The amount of at least one additional refrigerant can range from about 5 to about 95, from about 50 to about 90, and in some cases from about 60 to about 80 weight percent of the refrigerant composition. In one particular embodiment, the fluoro-propene compositions of the present application can be used as a source of HFO-1234ze to make R444, R446A / B, R447B, R448A, R450A, R456, R459A / B, R460A / B / C, R464A, 515A, and 515B.

[0152] In some embodiments, the foregoing fluoro-propene compositions can be used in a refrigeration system. One embodiment of a refrigeration system includes an evaporator, a condenser, a compressor, an expansion device, and a heat transfer medium. The heat transfer medium comprises the fluoro-propene composition. That is, the compositions of the present application can further comprise a lubricant. The heat transfer medium or composition of the present application can further comprise at least one lubricant, including those suitable for use in refrigeration or air conditioning equipment. Among these lubricants are included those conventionally used in compression refrigeration equipment utilizing chlorofluorocarbon refrigerants. Such lubricants and their properties are discussed in the 1990 ASHRAE Handbook, Refrigeration Systems and Applications, Chapter 8, entitled "Lubricants in Refrigeration Systems," pages 8.1 to 8.21, incorporated herein by reference. The lubricants of the present application can include those conventionally known in the art of compression refrigeration lubrication as "mineral oils." Mineral oils include paraffinic (i.e., straight chain and branched chain carbon chain saturated hydrocarbons), naphthenic (i.e., cyclic or ring structure saturated hydrocarbons, which can be paraffinic), and aromatic (i.e., unsaturated cyclic hydrocarbons containing one or more rings characterized by alternating double bonds). The lubricants of the present application also include those conventionally known in the art of compression refrigeration lubrication as "synthetic oils." Synthetic oils include alkyl aryl compounds (i.e., straight chain and branched alkyl alkyl benzenes), synthetic paraffinic and naphthenic hydrocarbons, silicones, and poly-alpha-olefins. Representative conventional lubricants of the present application are BVM 100N (a paraffinic mineral oil sold by BVA Oils), a naphthenic mineral oil commercially available from Crompton Co. under the trademark 3GS and 5GS a naphthenic mineral oil commercially available from Crompton Co. under the trademark 372LT a naphthenic mineral oil commercially available from Pennzoil, a naphthenic mineral oil commercially available from Crompton Co. under the trademark RO-30 is a naphthenic mineral oil commercially available from Calumet Lubricants, can be trademarked 75、 150and 500linear alkylbenzenes commercially available from Shrieve Chemicals and branched alkylbenzenes sold by Nippon Oil as HAB 22.

[0153] In one embodiment, the lubricant component can include those designed for use with refrigerants and capable of miscibility with the fluoropropene compositions of the present application under the operating conditions of compression refrigeration and air conditioning equipment. Such lubricants and their properties are discussed in "Synthetic Lubricants and High-Performance Fluids," R. L. Shubkin, Editor, Marcel Dekker, 1993. Such lubricants include, but are not limited to, polyol esters (POE) such as 100 (Castrol, United Kingdom), polyalkylene glycols (PAG) such as RL-488A from Dow (Dow Chemical, Midland, Michigan), and polyvinyl ethers (PVE).

[0154] The lubricant of the present application is selected by considering the given compressor requirements and the environment in which the lubricant will be exposed. The amount of lubricant can range from about 1 to about 50, about 1 to about 20, and in some cases about 1 to about 3 weight percent of the refrigerant composition. In one particular embodiment, the foregoing compositions are combined with a PAG lubricant for use in a motor vehicle A / C system having an internal combustion engine. In another particular embodiment, the foregoing compositions are combined with a POE lubricant for use in a motor vehicle A / C system having an electric or hybrid electric drive train.

[0155] In one embodiment, it is desirable that the refrigerant composition comprises the near-azeotrope composition of the present application, at least one lubricant, and at least one additive that can improve the life of the refrigerant and air conditioning system and the durability of the compressor. In one aspect of the present application, the foregoing compositions comprise at least one member selected from the group consisting of: acid scavengers, performance enhancers, and flame suppressants.

[0156] In another embodiment, the fluoro-propene composition can be used in a method of transferring heat. The method can include providing an article, and contacting the article with a heat transfer medium comprising the fluoro-propene composition. In some embodiments, the article can include an electrical device (e.g., a circuit board, a computer, a display, a semiconductor chip, or a transformer), a heat transfer surface (e.g., a heat sink), or an article of clothing (e.g., a wetsuit).

[0157] In another embodiment, the fluoro-propene composition can be used in a method of treating a surface. The method can include providing a surface having a treatable material deposited thereon, and contacting the surface with a treatment composition comprising the fluoro-propene composition. In some embodiments, the treatment composition can substantially dissolve the treatable material.

[0158] In another embodiment, the fluoro-propene composition can be used in a method of forming a composition. The method includes providing a solute, and contacting the solute with a solvent comprising the fluoro-propene composition. In some embodiments, the fluoro-propene composition can substantially dissolve the solute.

[0159] The present application also relates to a chiller apparatus comprising the fluoro-propene composition of the present application.

[0160] The present application also relates to the fluoro-propene composition of the present application for use in a chiller apparatus.

[0161] The chiller apparatus as referred to herein is preferably a low temperature chiller apparatus or a medium temperature chiller apparatus, more preferably a medium temperature chiller apparatus. Low temperature generally refers to an evaporator temperature of about -17.8°C (0°F) or below, and medium temperature generally refers to an evaporator temperature of about 0°C to 10°C or below.

[0162] The present application also relates to the use of the fluoro-propene composition of the present application in a chiller apparatus, preferably in a medium temperature chiller apparatus.

[0163] A chiller is a type of air conditioning / refrigeration equipment. Chillers are described in, for example, PCT Application PCT / US2011 / 032072, which corresponds to US2013 / 025299; the disclosures of these patents are hereby incorporated by reference. The present disclosure relates to, for example, vapor compression chillers. Such vapor compression chillers can be flooded evaporator chillers or direct expansion chillers. Both flooded evaporator chillers and direct expansion chillers can be air-cooled or water-cooled. In embodiments where the chiller is water-cooled, such chillers are generally associated with a cooling tower to reject heat from the system. In embodiments where the chiller is air-cooled, the chiller is equipped with a refrigerant-to-air finned tube condenser coil and a fan to reject heat from the system. Air-cooled chiller systems are generally less costly than water-cooled chiller systems of equivalent capacity that include a cooling tower and a water pump. However, due to lower condensing temperatures, water-cooled systems can be more efficient under many operating conditions.

[0164] Chillers, including flooded evaporator chillers and direct expansion chillers, can be coupled with air handling and distribution systems to provide comfortable air conditioning (cooling and dehumidification of air) to large commercial buildings, including hotels, office buildings, hospitals, universities, etc. In another embodiment, chillers, most likely air-cooled direct expansion chillers, have found additional utility in naval submarines and surface ships.

[0165] To show how a chiller operates, refer to the figures of PCT application PCT / US201 1 / 032072. A water-cooled flooded evaporator chiller is shown in Figure 1. In this chiller, a first heat transfer medium, which is a warm liquid containing water and in some embodiments containing an additive such as a glycol (e.g. ethylene or propylene glycol), enters the chiller from a cooling system such as a building cooling system, shown as entering by arrows 3 through a coil or tube bundle 9 in an evaporator 6 having an inlet and an outlet. The warm first heat transfer medium is delivered to the evaporator where it is cooled by liquid refrigerant shown in the lower portion of the evaporator. The liquid refrigerant evaporates at a temperature lower than the temperature of the warm first heat transfer medium flowing through the coil 9. The cooled first heat transfer medium is recirculated back to the building cooling system as shown by arrows 4 via the return portion of the coil 9. The liquid refrigerant shown in the lower portion of the evaporator 6 in Figure 1 evaporates and is drawn into a compressor 7 which increases the pressure and temperature of the refrigerant vapor. The compressor compresses the vapor so that it can condense in a condenser 5 at a higher pressure and temperature than when the refrigerant vapor comes out of the evaporator. A second heat transfer medium, which is a liquid in the case of a water-cooled chiller, enters the condenser from a cooling tower at arrow 1 in Figure 1 via a coil or tube bundle 10 in the condenser 5. The second heat transfer medium is warm in the process and returns to the cooling tower or to the environment via the coil 10 return loop and arrow 2. This second heat transfer medium cools the vapor in the condenser and causes the vapor to condense into liquid refrigerant so that there is liquid refrigerant in the lower portion of the condenser as shown in Figure 1. The condensed liquid refrigerant in the condenser flows back to the evaporator through an expansion device 8 which can be an orifice, a capillary tube or an expansion valve. The expansion device 8 reduces the pressure of the liquid refrigerant and partially converts it into a vapor, in other words, the liquid refrigerant flashes when the pressure drops between the condenser and the evaporator. The flashing cools the refrigerant, both liquid refrigerant and refrigerant vapor, to the saturation temperature at the evaporator pressure so that both liquid refrigerant and refrigerant vapor are present in the evaporator.

[0166] It should be noted that in the case of a single component refrigerant composition, the composition of the vapor refrigerant in the evaporator is the same as the composition of the liquid refrigerant in the evaporator. In this case, the evaporation will occur at a constant temperature. However, if a refrigerant blend (or mixture) is used as in the present invention, the liquid refrigerant and the refrigerant vapor in the evaporator (or condenser) can have different compositions. This can result in system inefficiencies and equipment service difficulties, so single component refrigerants are more desirable. Azeotropic or azeotrope-like compositions will function in a chiller substantially as a single component refrigerant so that the liquid composition and the vapor composition are substantially the same, reducing any inefficiencies that can be caused by using a non-azeotropic or non-azeotrope-like composition.

[0167] Coolers with cooling capacities above 700 kW generally employ flooded evaporators, where the refrigerant in the evaporator and condenser surrounds a coil or tube bundle or other conduit of heat transfer medium (i.e., the refrigerant is on the shell side). Flooded evaporators require more refrigerant charge, but allow closer approach temperatures and higher efficiency. Coolers with refrigeration capacities below 700 kW generally employ evaporators with refrigerant flowing inside tubes and heat transfer medium in the evaporator and condenser surrounding the tubes, i.e., the heat transfer medium is on the shell side. Such coolers are referred to as direct expansion (DX) coolers. One embodiment of a water-cooled direct expansion cooler is shown in FIG. 2. In the cooler as shown in FIG. 2, a first liquid heat transfer medium, which is a warm liquid such as warm water, enters the evaporator 6' at inlet 14. Most of the liquid refrigerant, with a small amount of refrigerant vapor, enters the coil or tube bundle 9' in the evaporator at arrow 3' and evaporates. Thus, the first liquid heat transfer medium is cooled in the evaporator, and the cooled first liquid heat transfer medium exits the evaporator at outlet 16 and is sent to the body to be cooled, such as a building. In this embodiment of FIG. 2, it is this cooled first liquid heat transfer medium that cools the building or other body to be cooled. The refrigerant vapor exits the evaporator at arrow 4' and is sent to the compressor 7', where it is compressed and exits as high temperature, high pressure refrigerant vapor. The refrigerant vapor enters the condenser 5' through the condenser coil 10' or tube bundle at 1 '. The refrigerant vapor is cooled by the second liquid heat transfer medium in the condenser, such as water, and becomes a liquid. The second liquid heat transfer medium enters the condenser through condenser heat transfer medium inlet 20. The second liquid heat transfer medium extracts heat from the condensing refrigerant vapor, which becomes liquid refrigerant, and this warms the second liquid heat transfer medium in the condenser. The second liquid heat transfer medium exits through condenser heat transfer medium outlet 18. The condensed refrigerant liquid exits the condenser through the lower coil 10' as shown in FIG. 2 and flows through an expansion device 12, which can be an orifice, a capillary tube, or an expansion valve. The expansion device 12 reduces the pressure of the liquid refrigerant. The small amount of vapor produced by the expansion enters the evaporator through the coil 9' with the liquid refrigerant and the cycle is repeated.

[0168] Vapor compression coolers can be distinguished by the type of compressor they employ. The present invention includes coolers utilizing both centrifugal and positive displacement compressors. In one embodiment, the compositions as disclosed herein can be used in coolers utilizing centrifugal compressors, which are referred to herein as centrifugal coolers.

[0169] Centrifugal compressors use rotating elements to accelerate refrigerant radially, and generally include impellers and diffusers housed in a casing. Centrifugal compressors generally draw in fluid at the eye of the impeller or central inlet of a volute impeller, and accelerate it radially outward. Some static pressure rise occurs in the impeller, but most of the pressure rise occurs in the diffuser portion of the casing, where velocity is converted to static pressure. Each impeller-diffuser set is a stage of the compressor. Centrifugal compressors can be composed of 1 to 12 stages or more, depending on the desired final pressure and the volume of refrigerant to be handled.

[0170] The pressure ratio or compression ratio of a compressor is the ratio of the absolute discharge pressure to the absolute inlet pressure. The pressure delivered by a centrifugal compressor is virtually constant over a relatively wide range of capacities. The pressure that a centrifugal compressor can produce depends on the tip speed of the impeller. Tip speed is the speed of the impeller measured at the outermost tip of the impeller, and is related to the diameter of the impeller and its revolutions per minute. The capacity of a centrifugal compressor is determined by the passage size through the impeller. This makes the size of the compressor more dependent on the pressure required than on the capacity.

[0171] In another embodiment, the compositions as disclosed herein can be used in a positive displacement chiller that utilizes a positive displacement compressor, a reciprocating compressor, a screw compressor, or a scroll compressor. Chillers that utilize screw compressors will be referred to hereinafter as screw chillers.

[0172] Positive displacement compressors draw in vapor into a chamber, and the volume of the chamber is reduced to compress the vapor. After being compressed, the vapor is forced out of the chamber by further reducing the volume of the chamber to zero or nearly zero.

[0173] Reciprocating compressors use pistons driven by a crankshaft. They can be fixed or portable, single stage or multistage, and can be driven by electric motors or internal combustion engines. Small reciprocating compressors of 5 to 30 hp can be found in mobile applications, and are typically used for intermittent duty. Larger reciprocating compressors of up to 100 hp exist in large industrial applications. Discharge pressures can range from low to ultra-high pressure (>5000 psi or 35 MPa).

[0174] Screw compressors use two meshing, rotating positive displacement helical screws to force gas into a smaller space. Screw compressors are typically used for continuous operation in commercial and industrial applications, and can be fixed or portable. Their applications can be from 5 hp (3.7 kW) to over 500 hp (375 kW), and can be from low to ultra-high pressure (>1200 psi or 8.3 MPa).

[0175] Scroll compressors are similar to screw compressors and include two intermeshing helical shaped rotors to compress gas. The output is pulsed more than a rotary screw compressor.

[0176] For chillers using scroll or reciprocating compressors, the evaporator typically uses a brazed plate heat exchanger of 150 kW or less capacity rather than a tube and shell heat exchanger used in larger chillers. The brazed plate heat exchanger reduces system volume and refrigerant charge.

[0177] The present invention also relates to a process for producing cooling, said process comprising evaporating the composition of the present invention in the vicinity of a body to be cooled, and then condensing said composition.

[0178] The present invention also relates to a refrigeration, air-conditioning or heat pump apparatus containing the composition of the present invention.

[0179] The present invention also relates to a mobile air-conditioning apparatus containing the composition of the present invention.

[0180] As used herein, a mobile refrigeration apparatus or a mobile air-conditioning apparatus refers to any refrigeration or air-conditioning apparatus incorporated into a road, rail, sea or air transport unit. Furthermore, apparatuses intended to provide refrigeration or air-conditioning for systems independent of any mobile carrier, known as "intermodal" systems, are included in the present invention. Such intermodal systems include "containers" (sea / land intermodal transport) as well as "swap bodies" (road and rail intermodal transport). The present invention is particularly useful for road transport refrigeration or air-conditioning apparatuses, such as automotive air-conditioning apparatuses or refrigerated road transport apparatuses.

[0181] In another embodiment, the present invention relates to blowing agent compositions comprising a fluoroalkene-containing composition (e.g., a composition comprising a near-azeotrope) as described herein for making a foam. In other embodiments, the present invention provides foamable compositions, and preferably polyurethane and polyisocyanate foam compositions, and methods of making a foam. In such foam embodiments, one or more fluoroalkene-containing compositions of the present invention are included as a blowing agent in a foamable composition, which preferably comprises one or more additional components capable of reacting and foaming under suitable conditions to form a foam or porous structure. Any method well known in the art can be used or adapted for use in accordance with the foam embodiments of the present invention, such as those described in "Polyurethanes Chemistry and Technology" Volumes I and II, Saunders and Frisch, 1962, John Wiley and Sons, New York, N.Y., which is incorporated herein by reference.

[0182] The present application also relates to a method of forming a foam, the method comprising: (a) adding the fluoroalkene-containing composition of the present application to a foamable composition; and (b) reacting the foamable composition under conditions effective to form a foam.

[0183] Another embodiment of the present application relates to the use of a fluoroalkene- containing composition as described herein (e.g., a composition of HFO-1234ze(E), HFO- 1225zc, and HFO-1234yf, which can be near-azeotropic) as a propellant in a sprayable composition. In addition, the present application relates to a sprayable composition comprising a fluoroalkene-containing composition as described herein. Active ingredients to be sprayed can also be present in the sprayable composition, along with inert ingredients, solvents, and other materials. Preferably, the sprayable composition is an aerosol. Suitable active materials to be sprayed include, but are not limited to, cosmetic materials such as deodorants, perfumes, hair gels, cleaning agents, and polishes, and pharmaceutical materials such as anti-asthmatic and anti-oral halitosis pharmaceuticals.

[0184] The present application also relates to a method for preparing an aerosol product, the method comprising the step of adding a fluoroalkene-containing composition as described herein to an active ingredient in an aerosol container, wherein the composition is used as a propellant.

[0185] As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but can include other elements not expressly listed or inherent to such process, method, article, or apparatus. Further, unless expressly stated to the contrary, "or" refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).

[0186] The transitional phrase "consisting of" excludes any element, step, or ingredient not specified. If there is any conflict between a definition in a claim and a definition in the specification or any document incorporated by reference, the definition in the claim prevails. When the phrase "consisting of" follows the transitional phrase "comprising," as in "comprising... and consisting of," it defines the scope of a limitation according to the specification. The transitional phrase "consisting essentially of" is used to define a combination as having the specified materials, steps, features, components, or elements, plus an additional material, step, feature, component, or element that does not materially affect the basic and novel characteristics of the combination. The term "consisting essentially of" occupies a middle position between "comprising" and "consisting of."

[0187] In the foregoing combinations of embodiments of the application, the composition can comprise, consist essentially of, or consist of HFO-1234ze(E), HFO-1225zc, and HFO-1234yf.

[0188] Also, the use of "a" or "an" are employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the application. This description should be read to include one or at least one and the singular also includes the plural, unless it is obvious that it is meant otherwise.

[0189] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the application, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety unless a particular passage is cited. In case of conflict between the present specification and a document incorporated by reference, the present specification controls. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

[0190] Example

[0191] The concepts described herein will be further described in the following examples, which do not limit the scope of the application.

[0192] Example 1

[0193] Table 1 shows the cooling performance of various refrigerant compositions comprising HFO-1234ze(E), HFO-1225zc, and HFO-1234yf by comparing the cooling capacity (CAP_c) and energy efficiency (COP_c) with HFO-1234ze(E). The data is based on the following conditions.

[0194] Condenser temperature = 47.0 °C

[0195] Evaporator temperature = 7.0 °C

[0196] Subcooling = 12.0 K

[0197] Superheat = 3.0 K

[0198] Compressor efficiency = 0.7

[0199] Average heat exchanger temperature set point

[0200] Superheat included in refrigeration effect

[0201] Cooling load = 3.517 kW

[0202] Compressor displacement = 0.00283168438736 (m3 / min) Table 1

[0203]

[0204]

[0205]

[0206] Several compositions, and specifically those comprising HFO-1234ze(E), HFO-1225zc, and HFO-1234yf, have higher capacity than pure HFO-1234ze(E) or other substances such as R-515B and R-450A. In many cases, the energy efficiency (COP) of the present compositions are also similar to HFO-1234ze(E) compositions, indicating that these refrigerants can be replacement refrigerants for HFO-1234ze(E) or other refrigerants such as R-515B and R-450A in refrigeration and air conditioning equipment applications, and specifically in stationary air conditioning applications.

[0207] Example 2

[0208] Table 2 contains data regarding the vapor leakage impact of various refrigerant compositions comprising HFO-1234ze(E), HFO-1225zc, and HFO-1234yf by comparison with HFO-1234ze(E).

[0209] The following conditions are applied: the container is filled with the initial composition at a temperature of 25°C and the initial vapor pressure of the composition is measured. The composition is allowed to weep from the container while the temperature is kept constant until 50 wt% of the initial composition is removed, at which time the vapor pressure of the composition remaining in the container is measured. ΔP% gives the relative pressure difference in %.

[0210] Table 2

[0211]

[0212]

[0213]

[0214] For several compositions of the present application, the difference in vapor pressure between the initial composition and the composition remaining after 50 wt% is removed is less than about 10%. This indicates that several of the compositions of the present application will be azeotropic or near-azeotropic.

[0215] Example 3

[0216] Table 3 shows the cooling performance of the refrigerant compositions of the present application under typical mid-temperature chiller plant conditions. The data is based on the following conditions.

[0217] Condenser temperature = 37.78°C

[0218] Evaporator temperature = 4.44°C

[0219] Superheat = 6.0 K

[0220] Compressor efficiency = 0.85

[0221] Average heat exchanger temperature set point

[0222] 100% superheat included in refrigeration effect

[0223] Vapor molar mass into evaporator: q_4

[0224] Cooling load = 1.00004194 kW

[0225] Compressor displacement = 0.1 (m3 / min)

[0226] Also included is the GWP value of the compositions of the present application compared to HFO-1234ze(E).

[0227] Table 3

[0228]

[0229] Clearly, the compositions comprising HFO-1234ze(E), HFO-1225zc and HFO-1234yf have higher capacity than pure HFO-1234ze(E), but still maintain very low GWP of HFO-1234ze(E). Energy efficiency (COP) is also comparable to HFO-1234ze(E), indicating that the inventive compositions can be a good replacement refrigerant for HFO-1234ze(E) in medium temperature chiller equipment applications.

[0230] Example 4

[0231] According to ASHRAE standards, the heat of combustion is a measure of the flammability impact of a compound on a material.

[0232] The results of various refrigerant compositions comprising HFO-1234ze(E), HFO-1225zc and HFO-1234yf compared to HFO-1234ze(E) are given in Table 4.

[0233] Table 4

[0234]

[0235] The results show that the inventive compositions with 1225zc are all less flammable than the corresponding controls. Therefore, it is preferred to use compositions comprising HFO-1234ze(E), HFO-1225zc and HFO-1234yf.

[0236] Example 5

[0237] Table 5 discloses the reaction products (in mol%) of the dehydrofluorination of 245fa over various catalysts in the presence of Z-HFC-1234ze.

[0238] Table 5

[0239]

[0240] * comprising 236fa, 1225zc, 1225ye (E and / or Z) and 1234zc

[0241] A chromium-nickel-iron alloy tube (1 / 2 inch OD) was packed with 10 cc (8 gm) of catalyst (see Table 5). After loading the reactor tube, the temperature of the catalyst bed was raised to 300 °C and purged with nitrogen (30 cc / min) for 200 minutes. The nitrogen flow was then reduced to 60 cc / min and HF was fed at 20 cc / min for 60 minutes. The temperature was raised to 325 °C for 300 minutes. The nitrogen flow was then reduced to 30 cc / min and the HF flow was increased to 30 cc / min for 30 minutes. The nitrogen flow was then reduced to 12 cc / min and the HF flow was increased to 48 cc / min for 60 minutes. The nitrogen flow was then discontinued and the HF flow was increased to 48 cc / min for 30 minutes. The reactor temperature was then reduced to 250 °C for 30 minutes. After this time, the HF was turned off and the reactor was purged with 30 cc / min of nitrogen. The reactor temperature was then stabilized at 300 °C, the nitrogen flow was turned off, and CF3CH2CHF2or CF3CH2CHF2with 10.5-11% Z-1234ze was fed at 1.44 ml / h. The contact time in the reactor was 45 seconds. The CF3CH2CHF2was vaporized at 50 °C. A portion of the reactor effluent was passed through a series of valves and analyzed by GCMS. The amounts of Z-1234ze, 134a, 152b, TFP, 1234yf, 1233xf, E-1233zd, Z-1233zd, and E+Z-1234ze were expressed in mole %. The results are summarized in Table 5. Grab samples were also taken for off-line GCMS analysis. Surprisingly, Table 5 "other" was detected to contain 236fa, 1225zc, 1225ye (E and Z), and 1234zc.

[0242] While any GCMS equipment, methods, and parameters suitable for detecting compounds that can be present in the compositions of the present application can be employed, one suitable method uses a single RTX-1 column.

[0243] Example 6

[0244] A chromium-nickel-iron alloy tube (1 / 2 inch {13 mm} OD) was packed with 5 cc (3.9 gm) of Cr2O3 catalyst (Louisville Cr) which was activated as described in Example 5. After activation, the nitrogen flow was turned off and the reactor temperature was set to 400 °C. An air stream (4 vol% O2) was fed at 0.67 ml / h and either CF3CH2CHF2 (alone 245fa), or CF3CH2CHF2 with 13.3 mol% (corresponding to 11.5 wt%) of Z-1234ze. The contact time in the reactor was 38 seconds. The CF3CH2CHF2 was vaporized at 50 °C. A portion of the reactor effluent was passed through a series of valves and analyzed by GCMS. After 72 hours, the oxygen stream was stopped and the reaction was continued for another 72 hours in the absence of oxygen-containing gas. For the reaction run using 245fa alone, the catalyst started to deactivate at about 120 hours total time, for the reaction run of 245fa containing Z-1234ze, the catalyst started to deactivate at about 136 hours total time. The results are summarized in the table below, where the amounts of Z-1234ze, 245fa and E-1234ze are expressed in mol%:

[0245] Table 6

[0246] Z-ze % added 0 0 13.3 13.3 Oxygen Yes No Yes No Incoming composition 100 / 0 100 / 0 86.7 / 13.3 86.7 / 13.3 245fa conversion (%) 96.1 89.7 95.8 89.5 Z-ze in product (%) 22.9 21.1 22.7 20.8 245fa % recovered 3.9 10.4 3.8 9.3 E-ze % 73.2 68.6 73.5 69.9 E-ze yield % 73.2 60.2 85.0 80.9 E-ze selectivity % 76.2 76.4 88.7 90.2

[0247] It should be noted that not all of the activities described above in the general description or the examples are required, that a portion of a specific activity can not be required, and that one or more further activities can be performed in addition to those described. Still further, the order in which activities are listed are not necessarily the order in which they are performed.

[0248] Benefits, other advantages, and solutions to problems have been described above with regard to specific embodiments. However, the benefits, advantages, solutions to problems, and any feature(s) that can cause any benefit, advantage, or solution to occur or become more pronounced are not to be construed as a critical, required, or essential feature of any or all the claims.

[0249] It should be understood that certain features that are, individually, described in separate embodiments content herein can be provided in combination in a single embodiment. Conversely, various features that are, individually, described in the context of a single embodiment can also be provided separately or in any sub-combination. Moreover, references to values stated in ranges include each and every value within the range.

[0250] While the application has been described with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes can be made and equivalents can be substituted for elements thereof without departing from the scope of the application. In addition, many modifications can be made to adapt a particular situation or material to the teachings of the application without departing from the central scope thereof. Therefore, it is intended that the application not be limited to the particular embodiments disclosed as the best currently contemplated mode of carrying out this application but that the application will include all embodiments falling within the scope of the claims.

Claims

1. A fluoropropene refrigerant composition comprising E-1,3,3,3-tetrafluoropropene, 1,1,3,3,3-pentafluoropropene, and 2,3,3,3-tetrafluoropropene, wherein the amount of 1,1,3,3,3-pentafluoropropene is 0.0001 to 0.9% by weight, the amount of 2,3,3,3-tetrafluoropropene is 0.0001 to 0.9% by weight, the total amount of 1,1,3,3,3-pentafluoropropene and 2,3,3,3-tetrafluoropropene is 1.0% by weight or less, and the amount of E-1,3,3,3-tetrafluoropropene is 99.0% by weight or more, based on the total weight of the fluoropropene refrigerant composition.

2. The composition according to claim 1, wherein the 2,3,3,3-tetrafluoropropene is present in the fluoropropene refrigerant composition in an amount of 0.001 to 0.8% by weight, based on the total weight of the fluoropropene refrigerant composition.

3. The composition according to claim 1, wherein the 2,3,3,3-tetrafluoropropene is present in the fluoropropene refrigerant composition in an amount of 0.1 to 0.6% by weight, based on the total weight of the fluoropropene refrigerant composition.

4. The composition according to claim 1, wherein the 2,3,3,3-tetrafluoropropene is present in the fluoropropene refrigerant composition in an amount of 0.3 to 0.4% by weight, based on the total weight of the fluoropropene refrigerant composition.

5. The composition according to any one of claims 1 to 4, wherein the 1,1,3,3,3-pentafluoropropene is present in the fluoropropene refrigerant composition in an amount of 0.001 to 0.8% by weight, based on the total weight of the fluoropropene refrigerant composition.

6. The composition according to claim 5, wherein the 1,1,3,3,3-pentafluoropropene is present in the fluoropropene refrigerant composition in an amount of 0.01 to 0.6% by weight, based on the total weight of the fluoropropene refrigerant composition.

7. The composition according to claim 5, wherein the 1,1,3,3,3-pentafluoropropene is present in the fluoropropene refrigerant composition in an amount of 0.1 to 0.4% by weight, based on the total weight of the fluoropropene refrigerant composition.

8. The composition according to any one of claims 1 to 4, wherein the E-1,3,3,3-tetrafluoropropene is present in the fluoropropene refrigerant composition in an amount of 99.5% by weight or more, based on the total weight of the fluoropropene refrigerant composition.

9. The composition according to claim 8, wherein the E-1,3,3,3-tetrafluoropropene is present in the fluoropropene refrigerant composition in an amount of 99.8% by weight or more, based on the total weight of the fluoropropene refrigerant composition.

10. The composition according to any one of claims 1 to 4, further comprising R-1336mzzE and / or R-227ea. ​ 11. The composition of any one of claims 1 to 4, wherein the composition is a near-azeotropic composition.

12. The fluoro-propene refrigerant composition of any one of claims 1 to 4, further comprising a lubricant selected from the group consisting of mineral oils such as paraffinic, naphthenic, and aromatic hydrocarbons, alkyl aryl compounds such as linear and branched alkyl alkyl benzenes, synthetic paraffins, synthetic naphthenes, poly(alpha olefins), polyol esters, polyalkylene glycols, and polyvinyl ethers.

13. The fluoro-propene refrigerant composition of any one of claims 1 to 4, for use in a chiller apparatus.

14. The fluoro-propene refrigerant composition of claim 13, for use in a medium temperature chiller apparatus.

15. A method of making the fluoro-propene refrigerant composition of any one of claims 1 to 14, the method comprising: (a) contacting a mixture of 1,1,1,3,3-pentafluoropropane and Z-1,3,3,3- tetrafluoropropene in the gas phase with a catalyst to form a mixture comprising Z-1,3,3,3-tetrafluoropropene, E-1,3,3,3-tetrafluoropropene, 1,1,3,3,3- pentafluoropropane, 2,3,3,3-tetrafluoropropene, hydrogen fluoride, and optionally unreacted 1,1,1,3,3-pentafluoropropane, the catalyst comprising at least one catalyst selected from the group consisting of fluorided Cr203and fluorided alumina supported Cr / Ni, wherein the composition comprises 0.00001 wt% to 1.0 wt% of 2,3,3,3-tetrafluoropropene and greater than 0 wt% and less than 1.0 wt% of 1,1,3,3,3-pentafluoropropane.

16. The method of claim 15, wherein the fluoro-propene refrigerant composition comprises at least 7 wt% of Z-1,3,3,3-tetrafluoropropene.

17. The method of claim 15, wherein the fluoro-propene refrigerant composition comprises at least 10 wt% of Z-1,3,3,3-tetrafluoropropene.

18. The method of claim 15 or 16, wherein at least 94% of the 1,1,1,3,3- pentafluoropropane is converted to E-1,3,3,3-tetrafluoropropene.

19. The method of claim 18, wherein at least 98% of the 1,1,1,3,3- pentafluoropropane is converted to E-1,3,3,3-tetrafluoropropene.

20. The method of any one of claims 15 to 17, further comprising: (b) recovering Z-1,3,3,3-tetrafluoropropene, or a mixture of Z-1,3,3,3- tetrafluoropropene and 1,1,1,3,3-pentafluoropropane, and recycling the Z-1,3,3,3- tetrafluoropropene, or the mixture of Z-1,3,3,3-tetrafluoropropene and 1,1,1,3,3- pentafluoropropane, back to step (a).

21. The method of any one of claims 15 to 17, wherein the hydrogen fluoride produced in step (a) is separated and recovered.

22. The method of any one of claims 15-17, wherein the oxygen-containing gas is oxygen or air.

23. The method of any one of claims 15-17, wherein the composition comprises 0.1 to 0.8 weight percent 2,3,3,3-tetrafluoropropene.

24. The method of claim 23, wherein the composition comprises 0.2 to 0.6 weight percent 2,3,3,3-tetrafluoropropene.

25. The method of claim 23, wherein the composition comprises 0.3 to 0.4 weight percent 2,3,3,3-tetrafluoropropene.

26. A refrigeration system comprising: an evaporator; a condenser; a compressor; an expansion device; and a heat transfer medium; wherein the heat transfer medium comprises the fluoropropene refrigerant composition of any one of claims 1-14.

27. A chiller apparatus comprising the fluoropropene refrigerant composition of any one of claims 1-14.

28. Use of the fluoropropene refrigerant composition of any one of claims 1-14 in a chiller apparatus.

29. Use of the fluoropropene refrigerant composition of any one of claims 1-14 in a medium temperature chiller apparatus.

30. A method of producing cooling, the method comprising: evaporating the composition of any one of claims 1-14 in the vicinity of a body to be cooled, and then condensing the composition.

31. A refrigeration or air conditioning apparatus containing the composition of any one of claims 1-14.

32. The refrigeration or air conditioning apparatus of claim 31, wherein the refrigeration apparatus is a stationary or mobile refrigeration apparatus.

33. The refrigeration or air conditioning apparatus of claim 31, wherein the air conditioning apparatus is a mobile air conditioning apparatus.

34. The refrigeration or air conditioning apparatus of claim 31, wherein the air conditioning apparatus is an automotive air conditioning apparatus.

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