HFO-1234ZE, HFO-1225ZC, AND HFO-1234YF CONTAINING COMPOSITIONS AND PROCESSES FOR PRODUCING AND USING THE COMPOSITIONS

Abstract

An object of the present invention is to provide a composition containing HFO-1234zeE that can maintain the good properties of HFO-1234zeE. [Solution] The present invention relates to a fluoropropene refrigerant 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 is 0.5 wt % based on the total weight of the fluoropropene composition, and the total amount of E-1,3,3,3-tetrafluoropropene is 99.5 wt % based on the total weight of the fluoropropene composition.

Description

[Technical Field]

[0001] (Related Applications) This application claims the benefit of PCT Application No. PCT / US20 / 029690, filed April 24, 2020. The disclosure of Application No. PCT / US20 / 029690 is incorporated herein by reference.

[0002] FIELD OF THE INVENTION The present invention relates to tetrafluoropropene compositions and methods for making and using the compositions. In particular, the present invention relates to compositions containing E-1,3,3,3-tetrafluoropropene (HFO-1234ze), 1,1,3,3,3-pentafluoropropene (HFO-1225zc), and 2,3,3,3-tetrafluoropropene (HFO-1234yf), methods for using the same, and a method for making products containing 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 technology]

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

[0004] In addition to the problem of ozone depletion, another environmental problem for many of these applications is global warming.Therefore, there is a need for compositions that meet low ozone depletion standards and have low global warming potential.It is believed that certain hydrofluoroolefin compositions can meet both of these goals.Therefore, there is also a need for an economical manufacturing process that can provide these compositions.

[0005] HFC-1234ze (CF3CH=CHF) and HFC-1234yf (CF3CF=CH2), both of which have zero ozone depletion potential and low global warming potential, have been recognized as potential refrigerants. In particular, the E isomer of HFO-1234ze (HFO-1234zeE) has proven useful in refrigeration applications. U.S. Patent No. 7,862,742 discloses compositions containing HFO-1234ze and HFO-1234yf. U.S. Patent No. 9,302,962 discloses a method for producing HFO-1234ze. The disclosures of U.S. Patent Nos. 7,862,742 and 9,9,302,962 are incorporated herein by reference in their entireties.

[0006] Catalytic dehydrofluorination of HFC-245fa generally produces a mixture of the E and Z isomers of HFC-1234ze. Depending on the specific catalyst selected, the amount of the Z isomer can vary between 15% and 23%. Alternatively, liquid-phase dehydrofluorination using an aqueous solution of caustic or other strong base produces a mixture of both isomers. The ratio of the two isomers varies slightly with temperature, but about 13% to about 15% of the Z isomer is typically formed. Since the E isomer is most useful in refrigeration applications, after separation of the E isomer from the Z isomer, the Z isomer is typically either isomerized to the E isomer in a separate step or converted back to 245fa by adding hydrogen fluoride. Both of these alternative methods require additional steps that increase costs.

[0007] There is a need in the art for compositions comprising HFO-1234zeE that can maintain the good properties of HFO-1234zeE. There is a further need for processes that can produce compositions of HFO-1234ze and HFO-1234yf that minimize or eliminate the need for purification or separation steps to remove excess HFO-1234yf. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] PCT Application No. PCT / US20 / 029690 Summary of the Invention

[0009] A fluoropropene composition containing E-1,3,3,3-tetrafluoropropene, 1,1,3,3,3-pentafluoropropane, and 2,3,3,3-tetrafluoropropene is described. 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.

[0010] Additionally, the present disclosure includes a method for producing a mixture of 1,3,3,3-tetrafluoropropene and 2,3,3,3-tetrafluoropropene by contacting a mixture of 1,1,1,3,3-pentafluoropropane and Z-1,3,3,3-tetrafluoropropene in the vapor phase, preferably in the presence of an oxygen-containing gas, with a catalyst comprising at least one catalyst selected from the group consisting of fluorinated CrO and Cr / Ni on fluorided alumina to form a mixture comprising Z-1,3,3,3-tetrafluoropropene, E-1,3,3,3-tetrafluoropropene, 1,1,3,3,3-pentafluoropropene, 2,3,3,3-tetrafluoropropene, hydrogen fluoride, and optionally unreacted 1,1,1,3,3-pentafluoropropane. In one embodiment, the process of the present invention produces useful compositions without the need for purification or separation steps, including steps to remove excess 2,3,3,3-tetrafluoropropene (HFO-1234yf) or 1,1,3,3,3-pentafluoropropene.

[0011] Additionally, the present disclosure includes a fluoropropene composition formed by a process of contacting a mixture of 1,1,1,3,3-pentafluoropropane and Z-1,3,3,3-tetrafluoropropene, optionally in the presence of an oxygen-containing gas, in the vapor phase with a catalyst comprising at least one catalyst selected from the group consisting of fluorinated Cr2O3 and Cr / Ni on fluorided alumina.

[0012] In one embodiment, the process of the present invention produces a composition comprising HFO-1234ze(E), HFO-1225zc, and HFO-1234yf, wherein 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 a further embodiment, the composition comprises a ternary near-azeotropic composition comprising HFO-1234ze(E), HFO-1234yf, and HFO-1225zc.

[0013] One embodiment relates to any of the preceding combinations, wherein 2,3,3,3-tetrafluoropropene is present in the fluoropropene composition in an amount of 0.0001 to 0.9 weight percent, based on the total weight of the fluoropropene composition.

[0014] One embodiment relates to any of the preceding combinations, wherein 2,3,3,3-tetrafluoropropene is present in the fluoropropene composition in an amount of 0.001 to 0.8 weight percent, based on the total weight of the fluoropropene composition.

[0015] One embodiment relates to any of the preceding combinations, wherein 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.

[0016] One embodiment relates to any of the preceding combinations, wherein 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.

[0017] One embodiment relates to any of the preceding combinations, wherein 2,3,3,3-tetrafluoropropene is present in an amount from 0.01 to 1.0 mole percent.

[0018] One embodiment relates to any of the preceding combinations, wherein 2,3,3,3-tetrafluoropropene is present in an amount from 0.1 to 0.9 mole percent.

[0019] One embodiment relates to any of the preceding combinations, wherein 2,3,3,3-tetrafluoropropene is present in an amount from 0.2 to 0.4 mole percent.

[0020] One embodiment relates to any of the preceding combinations, wherein 2,3,3,3-tetrafluoropropene is present in an amount from 0.3 to 0.4 mole percent.

[0021] Another embodiment relates to any of the foregoing combinations, wherein 1,1,3,3,3-pentafluoropropene is present in the fluoropropene composition in an amount of 0.0001 to 0.9 wt %, preferably 0.001 to 0.8 wt %, more preferably 0.01 to 0.6 wt %, and most preferably 0.1 to 0.4 wt %, based on the total weight of the fluoropropene composition.

[0022] Another embodiment relates to any of the foregoing combinations, wherein E-1,3,3,3-tetrafluoropropene is present in the fluoropropene composition in an amount of 50.0 wt. % or greater, preferably 75.0 wt. % or greater, more preferably 99.0 wt. % or greater, even more preferably 99.5 wt. % or greater, and most preferably 99.8 wt. % or greater, based on the total weight of the fluoropropene composition.

[0023] Another embodiment relates to any combination of 2,3,3,3-tetrafluoropropene and 1,1,3,3,3-pentafluoropropene in the fluoropropene composition, wherein the total amount of 2,3,3,3-tetrafluoropropene and 1,1,3,3,3-pentafluoropropene in the fluoropropene composition is from 0.001 to 0.9 wt. %, preferably from 0.1 to 0.8 wt. %, and most preferably from 0.3 to 0.5 wt. %, based on the total weight of the fluoropropene composition.

[0024] One embodiment relates to any of the foregoing combinations, wherein the fluoropropene composition further comprises R-134, preferably in an amount of 1.0 to 40.0 wt %, more preferably in an amount of 30.0 to 40.0 wt %, and most preferably in an amount of 35.0 to 40.0 wt %, based on the total weight of the fluoropropene composition.

[0025] One embodiment relates to any of the foregoing combinations, wherein the fluoropropene composition further comprises R-1336mzzE and / or R-227ea, preferably in an amount of 15.0 to 20.0 wt. % R-1336mzzE and 2.0 to 5.0 wt. % R-227ea, based on the total weight of the fluoropropene composition.

[0026] One embodiment relates to any combination of the preceding, wherein the fluoropropene composition optionally additionally comprises one or more of R-143a, R-152a, TFP (trifluoropropyne), 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.

[0027] One embodiment relates to any of the foregoing combinations, wherein the sum of the amounts of R-143a, R-152a, TFP, R-1233xf, R-1233zd(E), and R-1233zd(Z) is from 0.001 mole percent to 2 mole percent based on the total fluoropropene composition.

[0028] One embodiment relates to any of the preceding combinations, wherein the fluoropropene composition comprises R-1233zd(E) in an amount from 0.7 mole percent to 1.15 mole percent, based on the total fluoropropene composition.

[0029] One embodiment relates to any of the preceding combinations, wherein the fluoropropene composition comprises R-1233zd(Z) in an amount from 0.05 mole percent to 0.25 mole percent, based on the total fluoropropene composition.

[0030] One embodiment relates to any of the preceding combinations, wherein the fluoropropene composition comprises R-143a in an amount from 0.05 mole percent to 0.25 mole percent, based on the total fluoropropene composition.

[0031] 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, trifluoropropyne, 356mff, 1326mxz, HFC-245fa, and HFC-245cb.

[0032] One embodiment relates to any combination of the foregoing, wherein the sum of the amounts of 1224yd, 1224zc, 1326mxz, 113, 32, 23, trifluoropropyne, 356mff, 1326mxz, HFC-245fa, and HFC-245cb is from 0.001 mole percent to 2 mole percent based on the total fluoropropene composition.

[0033] One embodiment relates to any combination of the foregoing, wherein the composition is near-azeotropic.

[0034] A further embodiment of the present invention is a method for producing a mixture of 1,3,3,3-tetrafluoropropene and 2,3,3,3-tetrafluoropropene, comprising the steps of: (a) contacting a mixture of 1,1,1,3,3-pentafluoropropane and Z-1,3,3,3-tetrafluoropropene in the vapor phase with a catalyst comprising at least one catalyst selected from the group consisting of fluorinated CrO and Cr / Ni on fluorided alumina 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-pentafluoropropene, 2,3,3,3-tetrafluoropropene, hydrogen fluoride, and optionally unreacted 1,1,1,3,3-pentafluoropropane; The mixture comprises 0.00001% to 1.0% by weight of 2,3,3,3-tetrafluoropropene and greater than 0 and less than 1.0% by weight of 1,1,3,3,3-pentafluoropropene.

[0035] Another embodiment of the present invention is a method for producing a mixture of fluoropropenes of formula CF3CH=CHF and fluoropropenes of formula CF3CF=CH2, comprising the steps of: (a) contacting a mixture of vapor phase 1,1,1,3,3-pentafluoropropane and Z-1,3,3,3-tetrafluoropropene with a catalyst comprising at least one catalyst selected from the group consisting of fluorinated CrO or Cr / Ni on fluorinated alumina 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, 2,3,3,3-tetrafluoropropene, hydrogen fluoride, and optionally unreacted 1,1,1,3,3-pentafluoropropane; The mixture comprises 0.00001% to 1.00% of 2,3,3,3-tetrafluoropropene.

[0036] One embodiment of the present invention relates to any of the preceding combinations, wherein the mixture of 1,1,1,3,3-pentafluoropropane and Z-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.

[0037] One embodiment of the present invention relates to any of the foregoing combinations, wherein at least 94%, preferably at least 98%, of the 1,1,1,3,3-pentafluoropropane is converted to E-1,3,3,3-tetrafluoropropene.

[0038] One embodiment of the present invention relates to any combination of the above, wherein the method comprises: (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 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).

[0039] One embodiment of the present invention relates to any of the foregoing combinations, wherein the hydrogen fluoride produced in step (a) is separated and recovered.

[0040] One embodiment of the present invention relates to any of the foregoing combinations, wherein the oxygen-containing gas is oxygen or air.

[0041] One embodiment of the present invention relates to any of the foregoing combinations, wherein the mixture of 1,1,1,3,3-pentafluoropropane and 1,3,3,3-tetrafluoropropene contains 0.1 to 0.8 wt. % 2,3,3,3-tetrafluoropropene, preferably 0.2 to 0.6 wt. % 2,3,3,3-tetrafluoropropene, and more preferably 0.3 to 0.4 wt. % 2,3,3,3-tetrafluoropropene.

[0042] A further embodiment of the present invention relates to any of the foregoing combinations, wherein the mixture of 1,1,1,3,3-pentafluoropropane and Z-1,3,3,3-tetrafluoropropene comprises at least 7% by weight of Z-1,3,3,3-tetrafluoropropene.

[0043] One embodiment of the present invention relates to any of the preceding combinations, wherein said mixture of 1,1,1,3,3-pentafluoropropane and Z-1,3,3,3-tetrafluoropropene comprises at least 10% by weight of Z-1,3,3,3-tetrafluoropropene.

[0044] One embodiment of the present invention relates to any of the aforementioned combinations, wherein at least 94% by weight of the 1,1,1,3,3-pentafluoropropane is converted to the E isomer of 1,3,3,3-tetrafluoropropene.

[0045] One embodiment of the present invention relates to any of the aforementioned combinations, wherein at least 98% by weight of the 1,1,1,3,3-pentafluoropropane is converted to the E isomer of 1,3,3,3-tetrafluoropropene.

[0046] One embodiment of the present invention relates to any of the foregoing combinations, further comprising 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).

[0047] One embodiment of the present invention relates to any of the foregoing combinations, wherein the hydrogen fluoride produced in step (a) is separated and recovered.

[0048] One embodiment of the present invention relates to any of the foregoing combinations, wherein the oxygen-containing gas is oxygen or air.

[0049] One embodiment of the present invention relates to any of the foregoing combinations, wherein the mixture comprises 0.1 to 0.5 mole percent of 2,3,3,3-tetrafluoropropene.

[0050] One embodiment of the present invention relates to any of the foregoing combinations, wherein the mixture comprises 0.2 to 0.4 mole percent of 2,3,3,3-tetrafluoropropene.

[0051] One embodiment of the present invention relates to any of the foregoing combinations, wherein the mixture comprises 0.3 to 0.4 mole percent of 2,3,3,3-tetrafluoropropene.

[0052] Another embodiment of the present invention relates to any combination of the aforementioned processes and the fluoropropene compositions produced by these processes.

[0053] Further embodiments of the present invention relate to any combination of the preceding embodiments, including 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 the following: (a) Contains one or more of R-143a, R-152a, TFP, R-1233xf, R-1233zd(E), R-1233zd(Z), 1224yd, 1224zc, 1326mxz, 113, 32, 23, 356mff, 1326mxz, HFC-245fa, HFC-245cb, 1234zc, 1234yc, 1234ye, 134a, 1225ye(Z and E), 114, 124, and 236fa; (b) Contains one or more of R-143a, R-152a, TFP, R-1233xf, R-1233zd(E), R-1233zd(Z), 1224yd, 1224zc, 1326mxz, 113, 32, 23, 356mff, 1326mxz, HFC-245fa, and HFC-245cb; (c) one or more 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, and CF3I; (d) A refrigerant composition comprising at least one element selected from the group consisting of combinations thereof.

[0054] One embodiment of the present invention relates to a fluoropropene composition further comprising a lubricant selected from the group consisting of mineral oils such as paraffins, naphthenes and aromatics, alkylaryls such as linear and branched alkyl alkylbenzenes, synthetic paraffins, synthetic naphthenes, poly(alphaolefins), polyol esters, polyalkylene glycols, and polyvinyl ethers.

[0055] One embodiment of the present disclosure comprises: Providing goods; contacting the article with a heat transfer medium; The present invention relates to a process for treating a surface, wherein the heat transfer medium comprises the fluoropropene composition of any of the preceding embodiments.

[0056] One embodiment of the present disclosure comprises: Providing a surface; contacting the surface with a treatment composition; the surface includes a treatable material deposited thereon; The present invention relates to a process for treating a surface, wherein the treating composition comprises the fluoropropene composition of any of the preceding embodiments.

[0057] One embodiment of the present invention relates to such a process for treating a surface in which the treatment composition substantially dissolves the treatable material.

[0058] One embodiment of the present invention comprises: Providing a solute; contacting the solute with a solvent; The present invention relates to a process for forming a composition wherein the solvent comprises the fluoropropene composition of any of the preceding embodiments.

[0059] One embodiment of the present invention comprises: an evaporator, a condenser, a compressor, an expansion device, and a heat transfer medium; The present invention relates to a refrigeration system in which the heat transfer medium comprises the fluoropropene composition of any of the preceding embodiments.

[0060] One embodiment of the present invention relates to a refrigeration device comprising the fluoropropene composition of any combination of the preceding embodiments.

[0061] One embodiment of the present invention relates to the use of a fluoropropene, and one embodiment of the present invention relates to a fluoropropene composition of any combination of the preceding embodiments for use in a refrigeration system, preferably a medium temperature refrigeration system.

[0062] The composition of any combination of the preceding embodiments is preferably in a medium temperature refrigerator.

[0063] One embodiment of the present invention relates to a method of producing refrigeration, the method comprising evaporating a composition of any combination of the preceding embodiments in the vicinity of an object to be cooled, and then condensing the composition.

[0064] One embodiment of the present invention 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 a composition of any combination of the preceding embodiments to a refrigeration, air conditioning, or heat pump apparatus that uses, is being used, or is designed to use the high GWP refrigerant.

[0065] One embodiment of the present invention relates to a refrigeration system, an air conditioning system, or a heat pump system containing the composition of any combination of the preceding embodiments. The refrigeration system is preferably a stationary or mobile refrigeration system, and the air conditioning system is preferably a mobile air conditioning system, more preferably an automotive air conditioning system.

[0066] One embodiment of the present invention comprises: Providing goods; contacting the article with a heat transfer medium; The present invention relates to a process for transferring heat, wherein the heat transfer medium comprises the fluoropropene composition of any combination of the preceding embodiments, including the near-azeotropic composition produced by the method of the present invention.

[0067] One embodiment of the present disclosure comprises: Providing a surface; contacting the surface with a treatment composition; The present invention relates to a process for treating a surface, wherein the surface comprises a treatable material deposited thereon, and the treating composition comprises the fluoropropene composition of any combination of the preceding embodiments.

[0068] One embodiment of the present invention relates to any combination of the foregoing, wherein the treatment composition substantially dissolves the treatable material.

[0069] One embodiment of the present invention comprises: providing a solute; and contacting the solute with a solvent; The present invention relates to a process for forming a composition wherein the solvent comprises the fluoropropene composition of any of the previous embodiments.

[0070] Another embodiment of the present invention is an evaporator and a condenser; a compressor and an expansion device; a heat transfer medium; The present invention relates to a refrigeration system in which the heat transfer medium comprises the fluoropropene composition of any combination of the preceding embodiments and includes the near-azeotropic composition produced by the method of the present invention.

[0071] The foregoing general description and the following detailed description are exemplary and explanatory only and are not limiting of the invention as defined in the appended claims. The various embodiments of the invention can be used alone or in combination with each other. Other features and advantages of the present invention will be apparent from the following more detailed description of the preferred embodiment, taken in conjunction with the accompanying drawings which illustrate, by way of example, the principles of the invention. DETAILED DESCRIPTION OF THE INVENTION

[0072] A fluoropropene composition containing E-1,3,3,3-tetrafluoropropene, 1,1,3,3,3-pentafluoropropane, and 2,3,3,3-tetrafluoropropene is described. 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.

[0073] The present disclosure further includes a method for producing a mixture of fluoropropenes of the formula CFCH=CHF, fluoropropenes of the formula CF=CHCF, and fluoropropenes of the formula CFCF=CH, comprising contacting a mixture of 1,1,1,3,3-pentafluoropropane and Z-1,3,3,3-tetrafluoropropene in the vapor phase, optionally in the presence of an oxygen-containing gas, with a catalyst comprising at least one catalyst selected from the group consisting of fluorinated CrO or Cr / Ni on fluorided alumina, to form a mixture comprising Z-1,3,3,3-tetrafluoropropene, E-1,3,3,3-tetrafluoropropene, 1,1,3,3,3-pentafluoropropene, 2,3,3,3-tetrafluoropropene, and optionally unreacted 1,1,1,3,3-pentafluoropropane. Without being bound by any theory or explanation, higher contact temperatures and / or increased length of catalyst contact time may increase the amount of 1,1,3,3,3-pentafluoropropene.

[0074] Certain dehydrofluorination reactions are well known in the art. The dehydrofluorination of HFC-245fa has been particularly studied. Both gas-phase and liquid-phase processes are known. 1,3,3,3-tetrafluoropropene (HFO-1234ze) exists as both the Z and E isomers about its double bond. Both gas-phase and liquid-phase processes are known to produce mixtures of both the Z and E isomers, with the E isomer predominating. The selectivity in producing the Z isomer can vary from about 10% to about 23%, depending on the temperature and catalyst selection. The boiling point of the E isomer at 1 atm is about −19° C., while the boiling point of the Z isomer is about +9° C. For many applications, the E isomer is preferred. To minimize yield losses in the form of the usually undesired Z isomer, it is necessary to add an isomerization step to isomerize the Z isomer to the E isomer, or an additional fluorination step to convert HFO-1234ze(Z) back to HFC-245fa.

[0075] Dehydrofluorination reactions according to embodiments of the present disclosure can result in compositions of HFO-1234ze(E), HFO-1225zc, and HFO-1234yf that minimize or eliminate the need for purification or separation steps to remove excess HFO-1234yf or HFO-1225zc. In some cases, the compositions may be azeotropic or near-azeotropic, and may include azeotropic or near-azeotropic compositions. An azeotropic composition refers to 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 evaporated or distilled liquid (i.e., the mixed distillate / reflux without a change in composition). Constant-boiling compositions are characterized as azeotropes because they exhibit either a maximum or minimum boiling point compared to non-azeotropic mixtures of the same compounds. During operation, azeotropic compositions do not fractionate within refrigeration or air conditioning systems. Furthermore, azeotropic compositions do not fractionate upon leakage from a refrigeration or air conditioning system. In situations where one component of the mixture is flammable, fractionation during leakage can result in a flammable composition either inside or outside the system.

[0076] A near-azeotropic composition refers to a substantially constant-boiling liquid mixture of two or more compositions that essentially behaves as a 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 was evaporated or distilled (i.e., a mixed distillate / reflux without substantial compositional change). Another way to characterize a near-azeotropic composition is that the bubble point vapor pressure and dew point pressure of the composition at a particular temperature are substantially the same. As used herein, a composition of the present invention is near-azeotropic if, after removal of fifty percent (50%) by weight of the composition, such as by evaporation or boiling, the difference in vapor pressure between the original composition and the composition remaining after removal of 50 percent (50%) by weight of the original composition is less than about ten percent (10%).

[0077] According to one embodiment of the present invention, the compositions of the present invention have a flammability rating of A2L as determined by ASHRAE Standard 34 and ASTM E681-09.

[0078] Numerous aspects and embodiments have been described above, and these are merely illustrative and not limiting. After reading this specification, skilled artisans will appreciate that other aspects and embodiments are possible without departing from the scope of the invention.

[0079] Other features and advantages of any one or more of the embodiments will be apparent from the following detailed description and from the claims.

[0080] Specific dehydrofluorination processes are well 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 the reaction vessel or reactor should preferably be constructed of a material that is resistant to the corrosive effects of hydrogen fluoride, such as nickel and its alloys, including Hastelloy, Monel, and Inconel, or a fluoropolymer-lined vessel. These may be single tubes or multiple tubes filled with a dehydrofluorination catalyst.

[0081] Catalysts useful in the process include chromium-based catalysts, such as fluorinated chromium oxide, which may be unsupported or supported on a carrier such as activated carbon, graphite, graphite fluoride, or alumina fluoride. The chromium catalyst may be used alone or in the presence of a cocatalyst selected from nickel, cobalt, manganese, or zinc salts. In one embodiment, the chromium catalyst is a high surface area chromium oxide or chromium / nickel on fluorinated alumina (Cr / Ni / AlF), the preparation of which is reported in EP 0 486 333 A1, the disclosure of which is incorporated herein by reference. In another embodiment, the catalyst is a fluorinated Guignet's 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). The chromium catalyst is preferably activated prior to use, typically by heating the catalyst to 350-400°C under flowing nitrogen for a period of time, followed by further heating under flowing HF and nitrogen or air for a period of time.

[0082] In one embodiment, the fluoride-activated Guinea green catalyst used in the present invention is produced by reacting (combining) boric acid with an alkali metal dichromate at 500°C to 800°C, followed by hydrolysis of the reaction product. Therefore, the Guinea green contains boron, an alkali metal, and water of hydration. Typical alkali metal dichromates are sodium dichromate and / or potassium dichromate. The reaction is typically followed by cooling the reaction product in air, crushing the solid to produce a powder, followed by hydrolysis, filtering, drying, milling, and screening. Although Guinea green is a bluish-green color, it is primarily known as a green pigment, and thus green pigments are commonly referred to as Guinea green. When used as a catalyst, it is also referred to as Guinea green, as disclosed in U.S. Pat. No. 3,413,363. U.S. Patent No. 6,034,289 discloses a Cr2O3 catalyst, preferably in the alpha form, and also discloses Guinea Green as a commercially available green pigment having the composition: 79-83% Cr2O3, 16-18% HO, and 51.5-2.7% BO (sentence spanning columns 2-3), convertible to the alpha form (column 3, I.3). U.S. Patent No. 7,985,884 describes the presence of alkali metals in Guinea Green (54.5% Cr, 1.43% B, 3400 ppm Na, and 120 ppm K) in the Guinea Green composition disclosed in Example 1. The disclosures of the aforementioned patents and patent applications are incorporated herein by reference.

[0083] The physical form of the catalyst is not critical and may include, for example, pellets, extrudates, powders, or granules. Fluoride activation of the catalyst is preferably carried out in the final form of the catalyst.

[0084] In one embodiment, the present invention relates to feeding a mixture of HFC-245fa and at least about 10 wt. % of the Z isomer of HFO-1234ze to a dehydrofluorination reactor in the presence of an oxygen-containing gas to suppress the formation of further Z isomers so that the HFC-245fa converted by dehydrofluorination produces substantially only E-HFO-1234ze, HFO-1234zc, and HFO-1234yf. Feed levels below about 10% suppress the formation of further Z-1234ze to some extent. Feed levels above about 10 wt. % of Z-1234ze simply result in the presence of additional material that must be separated and recycled. The amount of Z-1234ze required to suppress further formation of Z isomer products depends to some extent on the conversion rate. At 70% conversion of 245fa, about 10-11% of the Z isomer is required in the feed. At 80% conversion, approximately 13% Z isomer is required in the feed.

[0085] In one embodiment, the reaction vessel may be maintained at a temperature of 200°C to 425°C. In another embodiment, the reaction vessel may be maintained at a temperature of 250°C to 350°C. In yet another embodiment, the reaction vessel may be maintained at a temperature of 275°C to 325°C, or 350°C to 410°C.

[0086] The reaction pressure can be subatmospheric, atmospheric, or superatmospheric. In one embodiment, the reaction is carried out at a pressure of 14 psig to about 100 psig. In another embodiment, the reaction is carried out at a pressure of 14 psig to about 60 psig. In another embodiment, the reaction is carried out at a pressure of 40 psig to about 85 psig. In another embodiment, the reaction is carried out at a pressure of 50 psig to 75 psig. Generally, increasing the pressure in the reactor above atmospheric pressure serves to increase the contact time of the reactants in the process. Longer contact times naturally increase the conversion rate in the process without the need for higher temperatures.

[0087] Depending on the reactor temperature and contact time, the reactor output mixture will contain different amounts of unreacted HFC-245fa. In certain embodiments, E-1,3,3,3-tetrafluoropropene, 1,1,3,3,3-pentafluoropropene, and HFO-1234yf can be separated from Z-1,3,3,3-tetrafluoropropene, hydrogen fluoride, and any unreacted HFC-245fa, which are recycled back to the reactor along with additional HFC-245fa. The hydrogen fluoride may be removed by scrubbing by passing the reactor effluent through an aqueous caustic solution, or the hydrogen fluoride may be removed by distillation. In particularly preferred embodiments, the compositions formed from the processes of the present disclosure comprise both 1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), HFO-1225zc, and 2,3,3,3-tetrafluoropropene (HFO-1234yf), which are not separated.

[0088] In one embodiment, the reactor feed is preheated in the vaporizer to a temperature of about 30° C. to about 100° C. In another embodiment, the reactor feed is preheated in the vaporizer to a temperature of about 30° C. to about 80° C.

[0089] 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.

[0090] In one embodiment, the product mixture contains 0.01% to 1.00% HFO-1234yf, alternatively 0.05% to 0.95% HFO-1234yf, alternatively 0.10% to 0.90% HFO-1234yf, alternatively 0.20% to 0.80% HFO-1234yf, alternatively 0.01% to 0.20% HFO-1234yf, alternatively 0.10% to 0.30% HFO-1234yf, alternatively 0.20% to 0.40% HFO-1234yf Alternatively, the product mixture may comprise (on a molar basis) HFO-1234yf, alternatively from 0.30% to 0.50% HFO-1234yf, alternatively from 0.30% to 0.40% HFO-1234yf, alternatively from 0.40% to 0.60% HFC-1234yf, alternatively from 0.50% to 0.70% HFO-1234yf, alternatively from 0.60% to 0.80% HFO-1234yf, alternatively from 0.70% to 0.70% HFO-1234yf, alternatively from 0.80% to 1.00% HFO-1234yf. In another embodiment, the aforementioned product mixture further comprises (on a molar basis) HFO-1225zc, wherein HFO-1225zc is present in an amount equal to 10% of the HFO-1234yf.

[0091] In some embodiments, the fluoropropene composition further 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 from 0.00001 mole percent to 2 mole percent based on the total fluoropropene composition. In one embodiment, the fluoropropene composition comprises R-1233zd(E) in an amount from 0.7 mole percent to 1.15 mole percent based on the total heat transfer medium. In one embodiment, the fluoropropene composition comprises R-1233zd(Z) in an amount from 0.05 mole percent to 0.25 mole percent based on the total heat transfer medium. In one embodiment, the fluoropropene composition comprises HFO-1234zeZ in an amount of 0.05 mole percent to 0.25 mole percent, based on the total fluoropropene composition. In one embodiment, the fluoropropene composition comprises R-143a in an amount of 0.05 mole percent to 0.25 mole percent, based on the total fluoropropene composition.

[0092] In other embodiments, the fluoropropene composition optionally includes one or more of 1224yd, 1224zc, 1326mxz, 113, 32, 23, trifluoropropyne, 356mff, 1326mxz, HFC-245fa, and HFC-245cb. The amount of the foregoing compositions can range from about 0.001 to about 1 mol %, from about 0.001 to about 0.9 mol %, and in some cases from about 0.001 to about 0.7 mol %.

[0093] In one particular embodiment, the sum of the amounts of 1224yd, 1224zc, 1326mxz, 113, 32, 23, trifluoropropyne, 356mff, 1326mxz, HFC-245fa, and HFC-245cb is from 0.001 to 2 mole percent based on the total fluoropropene composition. The amounts of the foregoing compositions can range from about 0.001 to about 0.1 mole percent, from about 0.001 to about 0.09 mole percent, and in some cases from about 0.001 to about 0.07 mole percent.

[0094] In another specific embodiment, the compositions of the present invention may comprise greater than about 99 wt.% HFO-1234ze(E) and, for example, 99.5 to 99.99 wt.%, 99.6 to 99.9 wt.%, or in some cases about 99.7 to 99.99 wt.% HFO-1234ze(E), the remainder comprising HFO-1225zc and HFO-1234yf. The compositions of the present invention may also contain at least one additional component 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, trifluoropropyne, 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 combined total amount of HFO-1225zc, HFO-1234yf, and additional compound(s) may range from greater than 0 to less than about 1 wt %, for example, from greater than 0 to 0.3, from greater than 0 to 0.1, and in some cases, from greater than 0 to 0.01 mole %. Specific examples of the above compositions are shown in Table A below.

[0095] [Table 1] * Examples include HFO-1234zc, HFO-1234yc, and HFO-1234ye.

[0096] The compositions of the present invention can be prepared by any convenient method for combining the desired amounts of the individual components. A preferred method is to measure the desired amounts of the components and then combine the components in a suitable container. Agitation may be used if desired.

[0097] An alternative means for producing the compositions of the present invention may be a process for producing a refrigerant blend composition, the refrigerant blend composition comprising a composition disclosed herein, the process comprising: (i) recycling a volume of one or more components of the refrigerant composition from at least one refrigerant container; (ii) removing impurities sufficiently to permit recycling of the one or more recycled components; and (iii) optionally combining all or a portion of the volume of the recycled components with at least one additional refrigerant composition or component.

[0098] The refrigerant container may be any container that contains a refrigerant blend composition used in a refrigeration, air conditioning, or heat pump system. The refrigerant container may be a refrigeration, air conditioning, or heat pump system that uses the refrigerant blend. The refrigerant container may also be a storage container for recovering reclaimed refrigerant blend components, including, but not limited to, a pressurized gas cylinder.

[0099] By residual refrigerant is meant any amount of refrigerant blend or refrigerant blend component that may be drained from the refrigerant container by any method known for transferring refrigerant blends or refrigerant blend components.

[0100] The impurity may be any component in the refrigerant blend or refrigerant blend component due to its use in a refrigeration, air conditioning, or heat pump system. Such impurities include particles, including but not limited to, refrigeration lubricants, metal salts, or elastomer particles, as previously described herein, that may be present in the refrigeration, air conditioning, or heat pump system, and any other contaminants that may adversely affect the performance of the refrigerant blend composition.

[0101] Such impurities may be sufficiently removed to permit reuse of the refrigerant blend or refrigerant blend components without adversely affecting the performance or equipment in which the refrigerant blend or refrigerant blend components are used.

[0102] To produce a composition that meets the specifications required for a given product, it may be necessary to provide additional refrigerant blend or refrigerant blend components to the remaining refrigerant blend or refrigerant blend components. For example, if a refrigerant blend has three components within a particular weight percent range, it may be necessary to add one or more components in a given amount to restore the composition to within the specification limits.

[0103] The compositions of the present invention have zero or low ozone depletion potential and low global warming potential (GWP). Additionally, the compositions of the present invention will have a global warming potential lower than many hydrofluorocarbon refrigerants currently in use. One aspect of the present invention is to provide refrigerants with 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 invention is to reduce the net GWP of a refrigerant mixture by adding a fluoroolefin to the mixture.

[0104] The compositions of the present invention may be used in combination with R134a (or HFC-134a, 1,1,1,2-tetrafluoroethane), R22 (or HCFC-22, chlorodifluoromethane), R123 (or HFC-123, 2,2-dichloro-1,1,1-trifluoroethane), R11 (CFC-11, fluorotrichloromethane), 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 (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)

[0013] The compositions of the present invention may be useful as low global warming potential (GWP) replacements for currently used refrigerants, including, but not limited to, 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).

[0105] Fluoropropene compositions can be useful in a variety of applications. In one embodiment, the fluoropropene composition may be used as a refrigerant. In some embodiments, the fluoropropene composition may be used as a replacement for older generation refrigerants (e.g., R404A, R502) to provide a more environmentally friendly composition. In some embodiments, the fluoropropene composition may be a hydrofluoroolefin composition. In one embodiment, the fluoropropene composition comprises 99 mole percent to 99.99 mole percent 1,3,3,3-tetrafluoropropene (HFO-1234ze)(E), and 0.0001 mole percent to 1.0 mole percent 1,1,3,3,3-pentafluoropropene (HFO-1225zc) and 2,3,3,3-tetrafluoropropene (HFO-1234yf). In another embodiment, the fluoropropene composition is a near-azeotropic composition that is substantially free of HFO-1234ze(Z). By substantially free, it is meant that the fluoropropene composition contains less than about 1000 ppm, less than about 500 ppm, and typically less than about 100 ppm HFO-1234ze(Z).

[0106] In many cases, replacement refrigerants are most useful if they can be used in original refrigeration equipment designed for a different refrigerant. The compositions of the present invention may be useful as a replacement for the refrigerant in the original equipment. In addition, the compositions of the present invention may be useful as a replacement for the refrigerant in equipment designed to use the above-mentioned refrigerant.

[0107] In one embodiment, the fluoropropene compositions of the present invention described above can be blended with other fluorochemicals. An 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.

[0108] In one embodiment, the fluoropropene compositions of the present invention described above are combined 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 the 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% by weight of the refrigerant composition. In one particular embodiment, the fluoropropene compositions of the present invention can be used as a source of HFO-1234ze for preparing R444, R446A / B, R447B, R448A, R450A, R456, R459A / B, R460A / B / C, R464A, 515A, and 515B.

[0109] In some embodiments, the fluoropropene compositions described above may be used in refrigeration systems. 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 fluoropropene composition. That is, the compositions of the present invention may further comprise a lubricant. The heat transfer medium may further comprise at least one lubricant, including lubricants suitable for use in refrigerants or air conditioning systems. Among these lubricants are those conventionally used in compression refrigeration systems 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 8.1-8.21, which is incorporated herein by reference. The lubricants of the present invention may include what is commonly known in the field of compression refrigeration lubrication as "mineral oil." Mineral oils include paraffins (i.e., saturated hydrocarbons with straight and branched carbon chains), naphthenes (i.e., cyclic or ring-structured saturated hydrocarbons, which may be paraffins), and aromatics (i.e., unsaturated cyclic hydrocarbons containing one or more rings characterized by alternating double bonds). The lubricants of the present invention also include what are commonly known in the field of compression refrigeration lubrication as "synthetic oils." Synthetic oils include alkylaryls (i.e., linear and branched alkylalkylbenzenes), synthetic paraffins and naphthenes, silicones, and poly-alpha-olefins.Representative conventional lubricants of this invention are commercially available BVM 100 N (a paraffinic mineral oil sold by BVA Oils), naphthenic mineral oils sold by Crompton Co. under the trade names Suniso® 3GS and Suniso® 5GS, naphthenic mineral oils sold by Pennzoil under the trade name Sontex® 372LT, naphthenic mineral oils sold by Calumet Lubricants under the trade name Calumet® RO-30, linear alkyl benzenes sold by Shrieve Chemicals under the trade names Zerol® 75, Zerol® 150, and Zerol® 500, and branched alkyl benzenes sold by Nippon Oil under the trade name HAB22.

[0110] In one embodiment, the lubricant component can include those designed for use with refrigerants and compatible with the fluoropropene compositions of the present invention 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," edited by R.L.Shubkin and Marcel Dekker, 1993. Such lubricants include, but are not limited to, polyol esters (POEs) such as Castrol® 100 (Castrol, United Kingdom), polyalkylene glycols (PAGs) such as RL-488A manufactured by Dow (Dow Chemicals, Midland, Michigan), and polyvinyl ethers (PVEs).

[0111] The lubricant of the present invention is selected by considering the requirements of a given compressor and the environment to which the lubricant will be exposed. The amount of lubricant can range from about 1 to about 50 weight percent, from about 1 to about 20 weight percent, and in some cases from about 1 to about 3 weight percent of the refrigerant composition. In one specific embodiment, the refrigerant composition is combined with a PAG lubricant for use in an A / C system for a vehicle having an internal combustion engine. In another specific embodiment, the refrigerant composition is combined with a POE lubricant for use in an A / C system for a vehicle having an electric or hybrid-electric drivetrain.

[0112] In one embodiment, a refrigerant composition desirably comprises the near-azeotropic composition of the present invention, at least one lubricant, and at least one additive capable of improving the life of the refrigerant and air conditioning system and compressor durability. In one aspect of the present invention, the refrigerant composition described above comprises at least one member selected from the group consisting of an acid scavenger, a performance improver, and a flame suppressant.

[0113] In another embodiment, the fluoropropene composition may be used in a process for transferring heat. The process may include providing an article and contacting the article with a heat transfer medium comprising the fluoropropene composition. In some embodiments, the article may 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 body suit).

[0114] In another embodiment, the fluoropropene composition may be used in a process for treating a surface. The process may include providing a surface having a treatable material deposited thereon and contacting the surface with a treatment composition comprising the fluoropropene composition. In some embodiments, the treatment composition may substantially dissolve the treatable material.

[0115] In another embodiment, the fluoropropene composition may be used in a process for forming a composition. The process includes providing a solute and contacting the solute with a solvent comprising the fluoropropene composition. In some embodiments, the fluoropropene composition can substantially dissolve the solute.

[0116] The present invention further relates to a refrigeration system comprising the fluoropropene composition of the present invention.

[0117] The present invention further relates to the fluoropropene compositions of the present invention for use in refrigeration systems.

[0118] The chillers referred to herein are preferably low temperature or medium temperature chillers, more preferably medium temperature chillers. Low temperature generally refers to evaporator temperatures of about -17.8°C (0°F) or below, while medium temperature generally refers to evaporator temperatures of about 0°C to 10°C or below.

[0119] The present invention further relates to the use of the fluoropropene compositions of the present invention in refrigeration systems, preferably medium temperature refrigeration systems.

[0120] A chiller is a type of air conditioning / refrigeration device. Chillers are described, for example, in PCT Application No. PCT / US2011 / 032072 (corresponding to U.S. Patent Application No. 2013 / 025299, the disclosure of which is incorporated herein by reference). The present disclosure relates, for example, to vapor compression chillers. Such vapor compression chillers may be either flooded evaporator chillers or direct expansion chillers. Both flooded evaporator chillers and direct expansion chillers may be air-cooled or water-cooled. In water-cooled embodiments, such chillers are typically associated with a cooling tower for heat removal from the system. In air-cooled embodiments, the chiller is equipped with a refrigerant-to-air finned-tube condenser coil and a fan to remove heat from the system. Air-cooled chiller systems are generally less expensive than equivalent-capacity water-cooled chiller systems, including cooling towers and water pumps. However, water-cooled systems may be more efficient under many operating conditions due to their lower condensing temperatures.

[0121] Chillers, including both flooded evaporator and direct expansion chillers, can be coupled with air handling and distribution systems to provide comfort conditioning (air cooling and dehumidification) to large commercial buildings, including hotels, office buildings, hospitals, universities, etc. In another embodiment, chillers, most likely air-cooled direct expansion chillers, have found further utility in naval submarines and surface ships.

[0122] To illustrate how the chiller operates, reference is made to the figures in PCT Application No. PCT / US2011 / 032072. A water-cooled, flooded evaporator chiller is shown in FIG. 1. In this chiller, a warm liquid first heat transfer medium containing water, and in some embodiments, an additive such as glycol (e.g., ethylene glycol or propylene glycol), enters the chiller from a refrigeration system, such as a built-up refrigeration system, shown entering at arrow 3 through coils 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 a liquid refrigerant, as shown in the cooler section of the evaporator. The liquid refrigerant evaporates at a lower temperature than the temperature of the warm first heat transfer medium flowing through coil 9. The cooled first heat transfer medium is recirculated back to the built-up refrigeration system, as shown by arrow 4, through a turn in coil 9. The liquid refrigerant evaporates and is drawn into a compressor 7, where the pressure and temperature of the refrigerant vapor increase, as shown in the cooler section of evaporator 6 in FIG. 1. The compressor compresses this vapor so that it can condense in the condenser 5 at a higher pressure and temperature than the vapor exiting the evaporator. The second heat transfer medium, a liquid in the case of a water-cooled chiller, enters the condenser from the cooling tower (arrow 1 in FIG. 1) via coils or tube bundle 10 in the condenser 5. The second heat transfer medium is warmed in the process and returned to the cooling tower or the environment via coil 10 and a return loop (arrow 2). This second heat transfer medium cools the vapor in the condenser, causing the vapor to condense into liquid refrigerant, resulting in liquid refrigerant in the cooler section of the condenser, as shown in FIG. 1. The liquid refrigerant condensed in the condenser flows back to the evaporator through an expansion device 8, which may be an orifice, capillary tube, or expansion valve. The expansion device 8 reduces the pressure of the liquid refrigerant, partially converting it to vapor. When the pressure drops between the condenser and evaporator, the liquid refrigerant is said to spurt out. The jet cools the refrigerant, both liquid refrigerant and refrigerant vapor, to a saturation temperature at the evaporator pressure, so that both liquid refrigerant and refrigerant vapor are present in the evaporator.

[0123] It should be noted that with single-component refrigerant compositions, 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, evaporation occurs at a constant temperature. However, when a refrigerant blend (or mixture) is used, as in the present invention, the liquid refrigerant and the refrigerant vapor in the evaporator (or condenser) may have different compositions. This can lead to system inefficiencies and equipment difficulties, making single-component refrigerants more desirable. Because an azeotropic or azeotrope-like composition essentially functions as a single-component refrigerant in the chiller, the liquid and vapor compositions are essentially the same, reducing any inefficiencies that might arise from using a non-azeotropic or non-azeotrope-like composition.

[0124] Chillers with cooling capacities greater than 700 kW typically employ flooded evaporators, in which 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 a larger refrigerant volume, but allow for closer temperatures and higher efficiency. Chillers with capacities less than 700 kW typically employ an evaporator with the refrigerant flowing in the tubes and the heat transfer medium in the condenser surrounding the evaporator and tubes, i.e., the heat transfer medium is on the shell side. Such chillers are called direct expansion (DX) chillers. One embodiment of a water-cooled direct expansion chiller is shown in FIG. 2. In a chiller such as that shown in FIG. 2, a first liquid heat transfer medium, which is a warm liquid such as hot water, enters an evaporator 6′ at inlet 14. Most of the liquid refrigerant (along with a small amount of refrigerant vapor) enters the evaporator coil or tube bundle 9′ at arrow 3′ and evaporates. As a result, 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 object 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 object being cooled. Refrigerant vapor exits the evaporator at arrow 4' and is sent to compressor 7', where it is compressed and exits as a high-temperature, high-pressure refrigerant vapor. This refrigerant vapor enters condenser 5' at 1' through condenser coil or tube bundle 10'. The refrigerant vapor is cooled to a liquid in the condenser by a second liquid heat transfer medium, such as water. 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, and the refrigerant vapor becomes a liquid refrigerant, which warms the second heat transfer medium in the condenser. The second liquid heat transfer medium exits the condenser through heat transfer medium outlet 18. The condensed refrigerant exits the condenser through cooler coil 10', shown in FIG. 2, and flows through expansion device 12, which may include an orifice, capillary tube, or expansion valve. Expansion device 12 reduces the pressure of the liquid refrigerant. A small amount of vapor is produced as a result of the expansion and enters the evaporator along with the liquid refrigerant through coil 9' to repeat the cycle.

[0125] Vapor compression chillers can be distinguished by the type of compressor they use. The present invention includes chillers that utilize centrifugal compressors and positive displacement compressors. In one embodiment, the compositions disclosed herein are useful in chillers that utilize centrifugal compressors, referred to as centrifugal chillers.

[0126] Centrifugal compressors use rotating elements to accelerate the refrigerant radially and typically include an impeller and diffuser housed in a casing. Centrifugal compressors usually take fluid in at the impeller eye, or central inlet of a circularly moving impeller, and accelerate the fluid radially outward. Some static pressure rise occurs within the impeller, but the majority of the pressure rise occurs in the diffuser section of the casing, where velocity is converted to static pressure. Each impeller-diffuser pair is a compressor stage. Centrifugal compressors are constructed with one to twelve or more stages, depending on the desired final pressure and the volume of refrigerant being handled.

[0127] The pressure ratio or compression ratio of a compressor is the ratio of the absolute discharge pressure to the absolute suction pressure. The pressure delivered by a centrifugal compressor is virtually constant over a relatively wide range of volumes. The pressure that a centrifugal compressor can develop depends on the tip speed of the impeller. Tip speed is the speed of the impeller measured at its outermost tip and is related to the impeller diameter and its revolutions per minute. The capacity of a centrifugal compressor is determined by the size of the flow path through the impeller. This makes the size of the compressor more dependent on the required pressure than on capacity.

[0128] In another embodiment, the compositions disclosed herein are useful in positive displacement chillers, which utilize either a positive displacement compressor, a reciprocating compressor, a screw compressor, or a scroll compressor. Chillers that utilize a screw compressor are referred to as screw chillers.

[0129] A positive displacement compressor draws vapor into a chamber, which reduces its volume, compressing the vapor. Once compressed, the vapor is forced out of the chamber by further reducing the chamber's volume to zero or near zero.

[0130] Reciprocating compressors use pistons driven by a crankshaft. Reciprocating compressors can be either stationary or portable, single-stage or multi-stage, and can be driven by electric motors or internal combustion engines. Small reciprocating compressors, ranging from 5 to 30 horsepower, are found in automotive applications and are typically for intermittent use. Larger reciprocating compressors, up to 100 horsepower, are found in a wide range of industrial applications. Discharge pressures can range from low to very high (over 5000 psi, or 35 MPa).

[0131] Screw compressors use two intermeshing, rotating, positive displacement helical screws to force gas into a smaller space. Screw compressors are typically for continuous operation in commercial and industrial applications and can be either stationary or portable. Applications can include those with 5 horsepower (3.7 kW) to over 500 horsepower (375 kW) and low to very high pressures (greater than 1200 psi, or 8.3 MPa).

[0132] Scroll compressors are similar to screw compressors in that they contain two interleaved spiral scrolls to compress the gas. The outlet is more pulsating than the outlet of a rotary screw compressor.

[0133] In chillers using scroll or reciprocating compressors, less than 150 kW capacity, brazed plate heat exchangers are used in the evaporator instead of the shell-and-tube heat exchangers used in larger chillers. Brazed plate heat exchangers reduce system volume and refrigerant charge.

[0134] The present invention further relates to a process for producing refrigeration, comprising evaporating a composition of the present invention in the vicinity of a body to be cooled and then condensing the composition.

[0135] The present invention further relates to refrigeration, air conditioning, or heat pump equipment containing the compositions of the present invention.

[0136] The present invention further relates to a mobile air conditioning unit comprising the composition of the present invention.

[0137] As used herein, mobile refrigeration or air conditioning refers to any refrigeration or air conditioning unit incorporated into a road, rail, sea, or air transportation unit. Additionally, units meant to provide refrigeration or air conditioning to any mobile carrier-independent system, known as "intermodal" systems, are included in the present invention. Such intermodal systems include "containers" (intermodal sea / land transport) and "swap bodies" (intermodal road and rail transport). The present invention is particularly useful for road transport refrigeration or air conditioning units, such as automotive air conditioning units or refrigerated road transport equipment.

[0138] In another embodiment, the present invention relates to a blowing agent composition comprising the fluoroolefin-containing composition (e.g., a near-azeotrope-containing composition) described herein for use in preparing a blowing agent. In other embodiments, the present invention provides foamable compositions, preferably polyurethane and polyisocyanate foam compositions, and methods for preparing foams. In such foam embodiments, one or more of the present fluoroolefin-containing compositions are included as a blowing agent in a foamable composition, which preferably contains one or more additional components capable of reacting and foaming under appropriate conditions to form a foam or cellular structure. Any of the methods known in the art, such as those described in "Polyurethanes Chemistry and Technology," Vol. I, II, Saunders and Frisch, 1962, John Wiley and Sons, New York, NY, incorporated herein by reference, can be used or applied in accordance with foam embodiments of the present invention.

[0139] The present invention further relates to a method of forming a foam, comprising: (a) adding a fluoroolefin-containing composition to the foamable composition of the present invention; and (b) reacting the foamable composition under conditions effective to form a foam.

[0140] Another embodiment of the present invention relates to the use of the fluoroolefin-containing compositions described herein (e.g., compositions of HFO-1234ze(E), HFO-1225zc, and HFO-1234yf can be near-azeotropic compositions) for use as a propellant in a sprayable composition. Furthermore, the present invention relates to a sprayable composition comprising the fluoroolefin-containing compositions described herein. Active ingredients to be sprayed along with inert ingredients, solvents, and other materials may be present in the sprayable composition. Preferably, the sprayable composition is an aerosol. Active substances suitable for spraying include, but are not limited to, cosmetic ingredients such as deodorants, fragrances, hairsprays, detergents, and abrasives, as well as pharmaceuticals such as anti-asthma medications and breath fresheners.

[0141] The present invention further relates to a process for making an aerosol product, comprising adding a fluoroolefin-containing composition described herein to an active ingredient in an aerosol container, wherein the composition functions as a propellant.

[0142] As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that includes a list of elements is not necessarily limited to those elements, but may include other elements not expressly listed or inherent in such process, method, article, or apparatus. Furthermore, unless expressly stated to the contrary, "or" refers to an inclusive "or," not 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 absent), A is false (or absent) and B is true (or present), and both A and B are true (or present).

[0143] The transitional phrase "consisting of" excludes any unspecified element, step, or ingredient. In the context of a claim, such a phrase limits the claim to include materials other than those recited, except for impurities normally associated with the material. When the phrase "consists of" appears within a clause in the body of a claim rather than immediately following the introductory section, the phrase limits only the elements recited in that clause and does not exclude other elements from the claim as a whole. The transitional phrase "consisting essentially of" is used to define compositions, methods, and compositions that include materials, steps, mechanisms, components, or elements in addition to those literally disclosed, provided that these additionally included materials, steps, mechanisms, components, or elements do not materially affect the basic and novel feature(s) of the claimed invention, particularly the mechanism of action for achieving any desired results of the inventive process. The term "consisting essentially of" has a meaning intermediate between "comprising" and "consisting of."

[0144] In the foregoing combination of embodiments of the invention, the composition may comprise, consist essentially of, or consist of HFO-1234ze(E), HFO-1225zc, and HFO-1234yf.

[0145] Additionally, the use of "a" or "an" is used to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be interpreted to include one or at least one, and the singular also includes the plural unless it is clear that a different meaning is intended.

[0146] 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 invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, 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 specific passage is cited. In case of conflict, the present specification, including definitions, will control. Furthermore, the materials, methods, and examples are illustrative only and not intended to be limiting. [Example]

[0147] The concepts described herein are further illustrated in the following examples, which do not limit the scope of the invention as described in the claims.

[0148] Example 1 Table 1 shows the cooling performance of various refrigerant compositions, including 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: Condenser temperature = 47.0C Evaporator temperature = 7.0C Supercooling=12.0K Overheating=3.0K Compressor efficiency = 0.7 Average heat exchange temperature set point Overheating is included in the refrigeration effect Cooling load=3.517kW Compressor displacement = 0.00283168438736 (m^3 / min)

[0149] [Table 2-1]

[0150] [Table 2-2]

[0151] Some compositions, particularly those containing HFO-1234ze(E), HFO-1225zc, and HFO-1234yf, have higher capacities than pure HFO-1234ze(E) or others, such as R-515B and R-450A. The energy efficiency (COP) of these compositions is often similar to that of HFO-1234ze(E), indicating that they may be alternative refrigerants for HFO-1234ze(E) or others, such as R-515B and R-450A, in refrigeration and air-conditioning applications, particularly stationary air-conditioning applications.

[0152] Example 2 Table 2 contains data on the effect of vapor leakage for various refrigerant compositions including HFO-1234ze(E), HFO-1225zc, and HFO-1234yf, in comparison with HFO-1234ze(E).

[0153] The following conditions were applied: an initial composition is charged to a container at a temperature of about 25°C and the initial vapor pressure of this composition is measured. While the temperature is held constant, the composition is allowed to leak from the container until 50 weight percent of the initial composition has been removed, at which point the vapor pressure of the composition remaining in the container is measured. ΔP% gives the relative pressure difference in %.

[0154] [Table 3-1]

[0155] [Table 3-2]

[0156] The difference in vapor pressure between the original composition and the composition remaining after 50 weight percent removal is less than about 10 percent for some compositions of the present invention, indicating that some of the compositions of the present invention are azeotropic or near-azeotropic.

[0157] Example 3 Table 3 shows the cooling performance of the refrigerant compositions of the present invention under typical medium temperature chiller conditions. The data is based on the following conditions: Condenser temperature = 37.78℃ Evaporator temperature = 4.44℃ Superheat=6.0K Compressor efficiency = 0.85 Average heat exchange temperature set point 100% of the superheat is included in the refrigerant effect Molar quality of vapor entering the evaporator: q_4 Cooling load=1.00004194kW Compressor displacement = 0.1 (m^3 / min) Also included are GWP values ​​for the compositions of the present invention compared to HFO-1234ze(E).

[0158] [Table 4]

[0159] As can be seen, compositions containing HFO-1234ze(E), HFO-1225zc, and HFO-1234yf have higher capacity than pure HFO-1234ze(E), while still maintaining the very low GWP of HFO-1234ze(E). The energy efficiency (COP) is also comparable to that of HFO-1234ze(E), indicating the compositions of the present invention may be good alternatives for HFO-1234ze(E) in medium-temperature chiller applications.

[0160] Example 4 According to ASHRAE standards, the heat of combustion is a measure of the effect a compound has on the flammable properties of a material. The results for various refrigerant compositions including HFO-1234ze(E), HFO-1225zc, and HFO-1234yf compared to HFO-1234ze(E) are shown in Table 4.

[0161] [Table 5]

[0162] The results show that all of the compositions of the invention with 1225zc are less flammable than the corresponding controls. Therefore, compositions containing HFO-1234ze(E), HFO-1225zc, and HFO-1234yf are preferred in use.

[0163] Example 5 Table 5 discloses the reaction products of the dehydrofluorination of 245fa in the presence of Z-HFC-1234ze (mol %) over various catalysts.

[0164] [Table 6] * Includes 236fa, 1225zc, 1225ye (E and / or Z), and 1234zc.

[0165] An Inconel tube (½ inch OD) was loaded with 10 cc (8 gm) of catalyst (see Table 5). After loading the tubular reactor, the temperature of the catalyst bed was increased 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 pumped in at 20 cc / min for 60 minutes. The temperature was increased 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. The HF was then turned off and the reactor was purged with nitrogen at 30 cc / min. The reactor temperature was then stabilized at 300°C, the nitrogen flow was stopped, and either CF3CH2CHF2 or CF3CH2CHF2 with 10.5–11% Z-1234ze was introduced at 1.44 mL / h. The contact time in the reactor was 45 seconds. CF3CH2CHF2 was 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 are expressed as mole percent. The results are summarized in Table 5. Grab samples were also taken for offline GCMS analysis. Surprisingly, it was found that Other in Table 5 contained 236fa, 1225zc, 1225ye (E and Z), and 1234zc.

[0166] While any suitable GCMS equipment, method, and parameters can be used to detect compounds that may be present in the compositions of the invention, one suitable method is to use a single RTX-1 column.

[0167] Example 6 An Inconel tube (½ inch {13 mm} OD) was packed with 5 cc (3.9 grams) of Cr2O3 catalyst (Louisville Cr) 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 flow (4% by volume O2) and either CF3CH2CHF2 (245fa alone) or CF3CH2CHF2 with 13.3 mol% (equivalent to 11.5% by weight) Z-1234ze were delivered at 0.67 mL / h. The contact time in the reactor was 38 seconds. 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 flow was stopped and the reaction was continued for another 72 hours in the absence of oxygen-containing gas. The catalyst began to deactivate at approximately 120 hours total reaction time when run with 245fa alone and at approximately 136 hours total reaction time when run with 245fa containing Z-1234ze. The results, expressed as mole percents of Z-1234ze, 245fa, and E-1234ze, are summarized in the table below.

[0168] [Table 7]

[0169] It should be noted that not all of the operations or embodiments described above in the general description are required, that some of the operations may not be required, and that one or more additional operations may be performed in addition to the operations described above. Furthermore, the order in which the operations are listed is not necessarily the order in which they are performed.

[0170] Benefits, other advantages, and solutions to problems have been described above with reference to specific embodiments. However, these benefits, advantages, solutions to problems, and any features that may produce or make more apparent any benefit, advantage, or solution are not to be construed as essential, necessary, or essential features in any or all of the claims.

[0171] It should be understood that certain features that are, for clarity, described herein in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features that are, for brevity, described in the context of a single embodiment may also be provided separately or in any subcombination. Further, references to values ​​stated in ranges include each and every value within that range.

[0172] While the present invention has been described with reference to preferred embodiments, those skilled in the art will recognize that various changes can be made and equivalents can be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications can be made to adapt a particular situation or material to the teachings of the invention without departing from essential scope thereof. Therefore, it is not intended that the invention be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but rather, the invention is intended to include all embodiments falling within the scope of the appended claims.

Claims

1. E-A fluoropropene refrigerant composition consisting of 1,3,3,3-tetrafluoropropene, 1,1,3,3,3-pentafluoropropene, and 2,3,3,3-tetrafluoropropene, A refrigerant composition, wherein the total amount of 1,1,3,3,3-pentafluoropropene and 2,3,3,3-tetrafluoropropene is 0.5 wt % based on the total weight of the fluoropropene composition, and the total amount of E-1,3,3,3-tetrafluoropropene is 99.5 wt % based on the total weight of the fluoropropene composition.

2. 2. The refrigerant composition of claim 1, 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.

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

4. 4. The refrigerant composition according to claim 1, wherein the composition is a near-azeotropic composition.

Images