HFO-1234ZE and HFO-1234YF compositions and processes for manufacturing and using the compositions

Abstract

A fluoropropene composition comprising Z-1,3,3,3-tetrafluoropropene, E-1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, and optionally 1,1,1,3,3-pentafluoropropane, wherein the 2,3,3,3-tetrafluoropropene is present in an amount of 0.001 to 1.0%. Methods for making the fluoropropenes, methods for using the fluoropropenes, and the formed compositions are also disclosed.

Description

Technical Field

[0001] (Cross - Reference to Related Applications) This application claims the benefit of Application No. 62 / 750991, filed on Oct. 26, 2018. The disclosure of Application No. 62 / 750991 is incorporated herein by reference.

[0002] (Field of the Invention) The present invention relates to tetrafluoropropene compositions and methods for manufacturing and using such compositions, and more particularly to methods for manufacturing and using products containing 1,3,3,3 - tetrafluoropropene (HFO - 123ze) and 2,3,3,3 - tetrafluoropropene (HFO - 1234yf) prepared from 1,1,1,3,3 - pentafluoropropane (HFC - 245fa).

Background Art

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

[0004] In addition to the problem of ozone depletion, another environmental problem in many of these applications is global warming. Therefore, there is a need for compositions that meet low ozone depletion standards and have a low global warming potential. Certain hydrofluoroolefins are thought to meet both of these goals. Thus, there is also a need for an economical manufacturing process to provide these compositions.

[0005] HFC-1234ze (CF3CH=CHF) and HFC-1234yf (CF3CF=CH2), both possessing zero ozone depletion potential and low global warming potential, are recognized as potential refrigerants. 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. Patents No. 7,862,742 and No. 9,302,962 are incorporated herein by reference in their entirety.

[0006] Catalytic dehydrofluoridation 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 Z isomer can vary between 15 and 23%. Alternatively, a mixture of both isomers can be produced by liquid-phase dehydrofluoridation using aqueous solutions of caustic or other strong bases. The ratio of the two isomers varies slightly with temperature, but typically about 13-15% Z isomer is formed. Since the E isomer is most useful for cooling applications, after separating the E isomer from the Z isomer, the Z isomer is typically either isomerized to the E isomer in a separate process or converted to 245fa by adding hydrogen fluoride. Both of these alternative methods require additional steps that increase costs. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Application No. 62 / 750991 [Patent Document 2] U.S. Patent No. 7,862,742 [Patent Document 3] U.S. Patent No. 9,302,962 [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] In this technology, there is a need for a process that can produce near-azeotropic compositions of HFO-1234ze and HFO-1234yf, minimizing or eliminating the need for purification or separation steps to remove excess HFO-1234yf. In particular, there is a need in this technology for an economical process for producing near-azeotropic compositions containing HFO-1234ze and HFO-1234yf greater than 0 and less than 1% by weight. [Means for solving the problem]

[0009] A fluoropropene composition comprising Z-1,3,3,3-tetrafluoropropene, E-1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, and optionally 1,1,1,3,3-pentafluoropropane is described. 2,3,3,3-tetrafluoropropene is present in an amount of 0.001 to 1.0 mol%.

[0010] In addition, the disclosure includes a method for producing a mixture of fluoropropene of formula CF3CH=CHF and fluoropropene of formula CF3CF=CH2, 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 fluorinated Cr2O3 or Cr / Ni supported on fluorinated alumina, in the presence of an oxygen-containing gas, to form a mixture comprising Z-1,3,3,3-tetrafluoropropane, E-1,3,3,3,-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, and optionally unreacted 1,1,1,3,3-pentafluoropropane. In one embodiment, the method of the present invention produces a useful composition without requiring a purification or separation step, which includes a step of removing an excess amount of 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0011] Furthermore, the present disclosure includes a fluoropropene composition formed by a method of contacting a mixture of gas-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 Cr2O3 or Cr / Ni supported on fluorinated alumina, in the presence of an optionally oxygen-containing gas.

[0012] In one embodiment, the process of the present invention produces a near-azeotropic composition containing HFO-1234ze(E) and HFO-1234yf, and the azeotropic composition is useful as a refrigerant.

[0013] One embodiment relates to any of the aforementioned combinations in which 2,3,3,3-tetrafluoropropene is present in an amount of 0.01 to 1.0 mol%.

[0014] One embodiment relates to any of the aforementioned combinations in which 2,3,3,3-tetrafluoropropene is present in an amount of 0.1 to 0.9 mol%.

[0015] One embodiment relates to any of the aforementioned combinations in which 2,3,3,3-tetrafluoropropene is present in an amount of 0.2 to 0.4 mol%.

[0016] One embodiment relates to any of the aforementioned combinations in which 2,3,3,3-tetrafluoropropene is present in an amount of 0.3 to 0.4 mol%.

[0017] One embodiment relates to any combination of the above, wherein the fluoropropene composition further optionally comprises one or more of R-143a, R-152a, TFP (trifluoropropine), R-1233xf, R-1233zd(E), or R-1233zd(Z).

[0018] One embodiment relates to any combination of the above, wherein the total amount of R-143a, R-152a, TFP, R-1233xf, R-1233zd(E), and R-1233zd(Z) is 0.001 mol% to 2 mol% based on the total fluoropropene composition.

[0019] One embodiment relates to any of the foregoing combinations, wherein the fluoropropene composition comprises R-1233zd(E) in an amount of 0.7 mol% to 1.15 mol% based on the total fluoropropene composition.

[0020] One embodiment relates to any of the foregoing combinations, wherein the fluoropropene composition comprises R-1233zd(Z) in an amount of 0.05 mol% to 0.25 mol% based on the total fluoropropene composition.

[0021] One embodiment relates to any of the foregoing combinations, wherein the fluoropropene composition comprises R-143a in an amount of 0.05 mol% to 0.25 mol% based on the total fluoropropene composition.

[0022] One embodiment relates to any of the foregoing combinations, wherein the fluoropropene composition optionally comprises one or more of 1224yd, 1224zc, 1326mxz, 113, 32, 23, trifluoropropene, 356mff, 1326mxz, HFC-245fa, and HFC-245cb.

[0023] One embodiment relates to any of the foregoing combinations, wherein the total amount of 1224yd, 1224zc, 1326mxz, 113, 32, 23, trifluoropropene, 356mff, 1326mxz, HFC-245fa, and HFC-245cb is 0.001 mol% to 2 mol% based on the total fluoropropene composition.

[0024] One embodiment relates to any of the foregoing combinations, wherein the composition is near-azeotropic.

[0025] Another embodiment of the present invention is The process includes contacting a mixture of gas-phase 1,1,1,3,3-pentafluoropropane and Z-1,3,3,3-tetrafluoropropene with a catalyst containing at least one catalyst selected from the group consisting of fluorinated Cr2O3 or Cr / Ni supported on fluorinated alumina, in the presence of an oxygen-containing gas, to form a mixture containing 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 present invention relates to a method for producing a mixture of a fluoropropene of formula CF3CH=CHF and a fluoropropene of formula CF3CF=CH2, containing 0.01% to 1.00% of 2,3,3,3-tetrafluoropropene.

[0026] One embodiment of the present invention relates to any of the aforementioned combinations of 1,1,1,3,3-pentafluoropropane and Z-1,3,3,3-tetrafluoropropene, wherein the mixture contains at least 7% by weight of Z-1,3,3,3-tetrafluoropropene.

[0027] One embodiment of the present invention relates to any combination of the above, wherein the mixture of 1,1,1,3,3-pentafluoropropane and Z-1,3,3,3-tetrafluoropropene contains at least 10% by weight of Z-1,3,3,3-tetrafluoropropene.

[0028] One embodiment of the present invention relates to any of the aforementioned combinations in which at least 94% by weight of 1,1,1,3,3-pentafluoropropane is converted to the E isomer of 1,3,3,3-tetrafluoropropene.

[0029] One embodiment of the present invention relates to any of the aforementioned combinations in which at least 98% by weight of 1,1,1,3,3-pentafluoropropane is converted to the E isomer of 1,3,3,3-tetrafluoropropene.

[0030] One embodiment of the present invention relates to any combination of the above, further comprising the steps of: 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 returning the mixture of Z-1,3,3,3-tetrafluoropropene or Z-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane to step (a) for reuse.

[0031] One embodiment of the present invention relates to any of the aforementioned combinations in which the hydrogen fluoride generated in step (a) is separated and recovered.

[0032] One embodiment of the present invention relates to any combination of the above, wherein the oxygen-containing gas is oxygen or air.

[0033] One embodiment of the present invention relates to any of the aforementioned combinations in which the mixture contains 0.1 to 0.5 mol% of 2,3,3,3-tetrafluoropropene.

[0034] One embodiment of the present invention relates to any of the aforementioned combinations in which the mixture contains 0.2 to 0.4 mol% of 2,3,3,3-tetrafluoropropene.

[0035] One embodiment of the present invention relates to any of the aforementioned combinations in which the mixture contains 0.3 to 0.4 mol% of 2,3,3,3-tetrafluoropropene.

[0036] Another embodiment of the present invention relates to any combination of the methods described above and the fluoropropene compositions produced by these methods.

[0037] One embodiment of the present invention is The process of providing goods, The process includes bringing an article into contact with a heat transfer medium, The present invention relates to a heat transfer process in which the heat transfer medium comprises a fluoropropene composition in any combination of the embodiments described above, and a near-azeotropic composition produced by the method of the present invention.

[0038] One embodiment of this disclosure is, The process of providing a surface, The process includes bringing the surface into contact with the treatment composition, The present invention relates to a process for treating a surface, wherein the surface comprises a treatable material deposited thereon, and the treatment composition comprises a fluoropropene composition in any combination of the embodiments described above.

[0039] One embodiment of the present invention relates to any of the aforementioned combinations in which the processing composition substantially dissolves the material to be processed.

[0040] One embodiment of the present invention is The process includes the steps of providing a solute and bringing the solute into contact with a solvent. The present invention relates to a process for forming a composition in which the solvent comprises a fluoropropene composition of any of the embodiments described above.

[0041] Another embodiment of the present invention is, Evaporator and condenser, A compressor and an expansion device, Includes a heat transfer medium, The present invention relates to a cooling system in which the heat transfer medium comprises a fluoropropene composition in any combination of the embodiments described above, and a near-azeotropic composition produced by the method of the present invention.

[0042] The above general description and the following "Modes for Carrying Out the Invention" are merely illustrative and descriptive, and do not limit the invention as defined in the appended claims. Embodiments of the invention can be used individually or in combination with each other. Other features and advantages of the invention will become apparent from the following more detailed description of preferred embodiments illustrating the principles of the invention by example. [Modes for carrying out the invention]

[0043] A method for producing a mixture of fluoropropene of formula CF3CH=CHF and fluoropropene of formula CF3CF=CH2 is described, which optionally comprises contacting a mixture of gas-phase 1,1,1,3,3-pentafluoropropane and Z-,1,3,3,3-tetrafluoropropene on fluorinated alumina with a catalyst comprising at least one catalyst selected from the group consisting of fluorinated Cr2O3 or Cr / Ni, 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, and optionally unreacted 1,1,1,3,3-pentafluoropropane.

[0044] Dehydrofluoridation reactions are well known in the art. Particular research has been conducted on the dehydrofluoridation treatment of HFC-245fa. Both gas-phase and liquid-phase methods are well known. 1,3,3,3-tetrafluoropropene (HFO-1234ze) exists as both Z and E isomers with respect to the double bond. In both gas-phase and liquid-phase methods, a mixture of Z and E isomers is known to be produced, with the E isomer being overwhelmingly more abundant. The selectivity in the production of the Z isomer can vary from about 10% to about 23%, depending on the temperature and the choice of catalyst. At 1 atm, the boiling point of the E isomer is approximately -19°C, while the boiling point of the Z isomer is approximately +9°C. In many applications, the E isomer is preferred. To minimize yield loss in the form of the Z isomer, which is usually undesirable, 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 HFC-1234ze(Z) back to HFC-245fa.

[0045] The defluorination-fluorination reaction according to embodiments of this disclosure yields an azeotrope, and in most cases yields a near-azeotropic composition of HFO-1234ze(E) and HFO-1234yf, minimizing or eliminating the need for purification or separation steps to remove excess HFO-1234yf. An azeotropic composition means a constant-boiling mixture of two or more substances that behave as a single substance. One way to characterize an azeotropic composition is that the vapor produced by the partial evaporation or distillation of a liquid has the same composition as the evaporated or distilled liquid (i.e., a mixed distillate / reflux with no change in composition). A constant-boiling composition is characterized as azeotropic because it exhibits either the highest or lowest boiling point compared to a non-azeotropic mixture of the same compound. During operation, the azeotropic composition is not fractionally distilled within the cooling or air conditioning system. Furthermore, the azeotropic composition is not fractionally distilled upon leakage from the cooling or air conditioning system. In situations where one component of the mixture is flammable, fractional distillation during leakage can lead to flammable compositions either within or outside the system.

[0046] A near-azeotropic composition refers to a substantially constant-boiling point liquid mixture of two or more compounds that essentially behave as a single substance. One way to determine the characteristics of a near-azeotropic composition is that the vapor produced by partial evaporation or distillation of the liquid has substantially the same composition as the evaporated or distilled liquid (i.e., a mixed distillate / reflux with substantially no change in composition). Another way to characterize a near-azeotropic composition is that the foaming point vapor pressure and dew point pressure of the composition at a particular temperature are substantially the same. In particular, a composition of the present invention is a near-azeotropic composition if, after removing 50% by weight of the composition by evaporation or boiling, the difference in vapor pressure between the original composition and the composition remaining after removing 50% by weight of the original composition is less than about 10%.

[0047] According to one embodiment of the present invention, the near-azeotropic composition of the present invention has a flammability rating of A2L as determined by ASHRAE Standard 34 and ASTM E681-09.

[0048] Numerous aspects and embodiments are described above, but these are merely illustrative and not limiting. After reading this specification, those skilled in the art will understand that other aspects and embodiments are possible without departing from the scope of the present invention.

[0049] Any one or more other features and advantages of the embodiments will become apparent from the following “Modes for Carrying Out the Invention” and claims.

[0050] Specific dehydrofluoridation treatments are well known in the art and are preferably carried out in the vapor phase. The dehydrofluoridation reaction can be carried out in any suitable reactor or vessel, which should preferably consist of a vessel lined with a material resistant to the corrosive effects of hydrogen fluoride, such as nickel and its alloys such as Hastelloy, Monel, and Inconel, or with a fluoropolymer. These may be a single tube or a number of tubes filled with the dehydrofluoridation catalyst.

[0051] Useful catalysts 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, fluorinated graphite, or fluorinated alumina. The chromium catalyst may be used alone or in the presence of a co-catalyst selected from nickel, cobalt, manganese, or zinc salts. In one embodiment, the chromium catalyst is chromium / nickel (Cr / Ni / AlF3) on high-surface-area chromium oxide or fluorinated alumina, the production of which is reported in European Patent No. 486,333. In another embodiment, the catalyst is Guignet's green catalyst. Additional suitable catalysts include, but are not limited to, JM 62-2 (chromium catalyst available from Johnson Matthey), LV (chromium catalyst available from Chemours), JM-62-3 (chromium catalyst available from Johnson Matthey), and Newport Chrome (chromium catalyst available from Chemours). Chromium catalysts are typically preferably activated before use by a procedure that involves heating the catalyst to 350-400°C under a flow of nitrogen for a certain period of time, followed by further heating the catalyst under a flow of HF and nitrogen or air for a certain period of time.

[0052] In one embodiment, the fluoride-activated Guinet 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, Guinet green contains boron, alkali metal, and water of hydration. Typical alkali metal dichromates are sodium and / or potassium dichromate. Following the reaction, typically, the reaction product is cooled in air, the solid is pulverized to produce a powder, and then hydrolysis, filtration, drying, milling, and screening steps are performed. Guinet green is bluish-green in color, but is primarily known as a green pigment, and therefore green pigments are generally called Guinet green. When used as a catalyst, it is also called Guinet green, as disclosed in U.S. Patent No. 3,413,363. U.S. Patent No. 6,034,289 discloses that the Cr2O3 catalyst is preferably of the alpha type, and Guinet Green is disclosed as a commercially available green pigment having composition: Cr2O3 79-83%, H2O 16-18%, B2O 51.5-2.7% (crosslinking rows 2 and 3), which can be converted to the alpha form (rows 3, I.3). U.S. Patent No. 7,985,884 states that the composition of Guinet Green disclosed in Example 1 contains alkali metals in Guinet Green (54.5% Cr, 1.43% B, 3,400 ppm Na, and 120 ppm K).

[0053] The physical form of the catalyst is not important and can include, for example, pellets, extruded products, powders, or granules. Fluoride activation of the catalyst is preferably carried out in the final form of the catalyst.

[0054] In one embodiment, the present invention relates to the suppression of further Z isomer formation by supplying a mixture of HFC-245fa and at least about 10 wt% of the Z isomer of HFO-1234ze to a dehydrofluoride reactor in the presence of an oxygen-containing gas, so that the HFC-245fa converted by the dehydrofluoride treatment substantially produces only E-HFO-1234ze and HFO-1234yf. When the supply is less than about 10%, the formation of further Z-1234ze is suppressed to some extent. When the supply of Z-1234ze exceeds about 10 wt%, it only results in the presence of additional material that must be separated and reused. The amount of Z-1234ze required to suppress further formation of Z isomer products depends to some extent on the conversion rate. At a 70% conversion rate of 245fa, about 10-11% of Z isomers are required in the supply. At an 80% conversion rate, about 13% of Z isomers are required in the supply.

[0055] In one embodiment, the reaction vessel can be maintained at a temperature of 200°C to 375°C. In another embodiment, the reaction can be carried out at a temperature of approximately 250°C to 350°C. In yet another embodiment, the reaction vessel can be maintained at a temperature of 275°C to 325°C.

[0056] The reaction pressure can be lower than atmospheric pressure, atmospheric pressure, or higher than atmospheric pressure. 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 yet another embodiment, the reaction is carried out at a pressure of 40 psig to about 85 psig. In yet another embodiment, the reaction is carried out at a pressure of 50 psig to about 75 psig. Generally, a reactor pressure higher than atmospheric pressure acts to increase the contact time of the reactants in this process. A longer contact time inevitably increases the degree of conversion in the process, so there is no need to raise the temperature.

[0057] Depending on the reactor temperature and contact time, the reactor product mixture will contain different amounts of unreacted HFC-245fa. Next, E-1,3,3,3-tetrafluoropropene and HFO-1234yf can be separated from Z-1,3,3,3-tetrafluoropropene, hydrogen fluoride, and all unreacted HFC-245fa and returned to the reactor for reuse along with the additional HFC-245fa. Hydrogen fluoride may be removed by scrubbing by passing the reactor effluent through a caustic aqueous solution, or hydrogen fluoride may be removed by distillation. In a particularly preferred embodiment, the composition formed from the process of the present disclosure contains both 1,3,3,3-tetrafluoropropene (HFO-1234ze(E)) and 2,3,3,3-tetrafluoropropene (HFO-1234yf), which are not separated.

[0058] In one embodiment, the reactor feed is preheated in the vaporizer to a temperature of approximately 30°C to approximately 100°C. In another embodiment, the reactor feed is preheated in the vaporizer to a temperature of approximately 30°C to approximately 80°C.

[0059] In some embodiments, an inert diluent gas is used as a carrier gas for hydrochlorofluoropropane. In one embodiment, the carrier gas is selected from nitrogen, argon, helium, or carbon dioxide.

[0060] In one embodiment, the resulting mixture contains 0.01% to 1.00% HFO-1234yf, or 0.05% to 0.95% HFO-1234yf, or 0.10% to 0.90% HFO-1234yf, or 0.20% to 0.80% HFO-1234yf, or 0.01% to 0.20% HFO-1234yf, or 0.10% to 0.30% HFO-1234yf, or 0.20% to 0.40% HFO-1234yf , or containing 0.30% to 0.50% HFO-1234yf, or 0.30% to 0.40% HFO-1234yf, or 0.40% to 0.60% HFC-1234yf, or 0.50% to 0.70% HFO-1234yf, or 0.60% to 0.80% HFO-1234yf, or 0.70% to 0.70% HFO-1234yf, or 0.80% to 1.00% HFO-1234yf (molar basis).

[0061] In some embodiments, the fluoropropene composition optionally further comprises one or more of R-143a, R-152a, TFP, R-1233xf, R-1233zd(E), or R-1233zd(Z). In some embodiments, the total amount of R-143a, R-152a, TFP, R-1233xf, R-1233zd(E), and R-1233zd(Z) based on the total fluoropropene composition is 0.01 mol% to 2 mol%. In one embodiment, the fluoropropene composition contains 0.7 mol% to 1.15 mol% of R-1233zd(E) based on the total heat transfer medium. In one embodiment, the fluoropropene composition contains 0.05 mol% to 0.25 mol% of R-1233zd(Z) based on the total heat transfer medium. In one embodiment, the fluoropropene composition contains 0.05 mol% to 0.25 mol% of R-143a based on the total fluoropropene composition.

[0062] In other embodiments, the fluoropropene composition optionally comprises one or more of 1224yd, 1224zc, 1326mxz, 113, 32, 23, trifluoropropine, 356mff, 1326mxz, HFC-245fa, and HFC-245cb.

[0063] In one particular embodiment, the total amounts of 1224yd, 1224zc, 1326mxz, 113, 32, 23, trifluoropropine, 356mff, 1326mxz, HFC-245fa, and HFC-245cb are 0.001 mol% to 2 mol% based on the total fluoropropene composition.

[0064] Fluoropropene compositions can be useful in a variety of applications. In one embodiment, a fluoropropene composition may be used as a refrigerant. In some embodiments, a fluoropropene composition may be used as a substitute for older generation refrigerants (e.g., R404A, R502) to provide a more environmentally friendly composition. In some embodiments, a fluoropropene composition may be a hydrofluoroolefin composition. In one embodiment, a fluoropropene composition contains 99 mol% to 99.99 mol% of 1,3,3,3-tetrafluoropropene (HFO-1234ze)(E) and 0.01 mol% to 1.0 mol% of 2,3,3,3-tetrafluoropropene (HFO-1234yf). In another embodiment, a fluoropropene composition is a near-azeotropic composition that is substantially free of HFO-1234ze(Z). Substantially free means that the fluoropropene composition contains less than about 1000 ppm, less than about 500 ppm, typically less than about 100 ppm of HFO-1234ze(Z).

[0065] In one embodiment, the fluoropropene composition of the present invention can be blended with other fluorochemicals. This embodiment of the present invention includes the near-azeotropic composition of the present invention (e.g., HFO-1234ze(E) and HFO-1234yf) and 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, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethyl ether, CF3SCF 3、 This relates to a refrigerant composition comprising at least one compound selected from the group consisting of CO2, CF3I, and combinations thereof.

[0066] In some embodiments, fluoropropene compositions may be used in cooling systems. One embodiment of a cooling system includes an evaporator, a condenser, a compressor, an expansion device, and a heat transfer medium. The heat transfer medium includes a fluoropropene composition. The heat transfer medium may further include at least one lubricant, which is suitable for use in refrigerants or air conditioning systems. Among these lubricants are those conventionally used in compressed refrigeration systems utilizing chlorofluorocarbon refrigerants. Such lubricants and their properties are discussed in Chapter 8, titled "Lubricants in Refrigeration Systems," pp. 8.1-8.21, of the 1990 ASHRAE Handbook, Refrigeration Systems and Applications, incorporated herein by reference. The lubricants of the present invention may include those commonly known as "mineral oil" in the field of compressed refrigerant lubrication. Mineral oils include paraffins (i.e., saturated hydrocarbons with linear and branched carbon chains), naphthenes (i.e., cyclic or cyclic 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 further include those commonly known as "synthetic oils" in the field of compressed refrigerant lubrication. Synthetic oils include alkylaryls (i.e., linear and branched alkylalkylbenzenes), synthetic paraffins and naphthenes, silicones, and poly-alpha-olefins.Typical conventional lubricants of the present invention include commercially available BVM 100 N (paraffinic mineral oil sold by BVA Oils), naphthenic mineral oil sold by Crompton Co. under the trademarks Suniso® 3GS and Suniso® 5GS, naphthenic mineral oil sold by Pennzoil under the trademark Sontex® 372LT, naphthenic mineral oil sold by Calumet Lubricants under the trademark Calumet® RO-30, linear alkylbenzenes sold by Shrieve Chemicals under the trademarks Zerol® 75, Zerol® 150, and Zerol® 500, and branched alkylbenzenes sold by Nippon Oil under the trademark HAB22.

[0067] In one embodiment, the lubricant component may be designed for use with a refrigerant and may be miscible with the fluoropropene composition of the present invention (e.g., a near-azeotropic composition) under the operating conditions of the compressed refrigerant and the air conditioning system. Such lubricants and their properties are discussed in "Synthetic Lubricants and High-Performance Fluids," edited by RLShubkin and Marcel Dekker, 1993. Examples of 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 from Dow Chemical (Midland, Michigan), and polyvinyl ethers (PVEs).

[0068] The lubricant of the present invention is selected by taking into consideration the requirements of a given compressor and the environment to which the lubricant will be exposed. The amount of lubricant may range from about 1 to about 50, about 1 to about 20, and in some cases about 1 to about 3% by weight of the refrigerant composition. In one specific embodiment, the aforementioned refrigerant composition is combined with a PAG lubricant for use in an A / C system for an automobile having an internal combustion engine. In another specific embodiment, the aforementioned refrigerant composition is combined with a POE lubricant for use in an A / C system for an automobile having an electric or hybrid electric drivetrain.

[0069] In one embodiment, the refrigerant composition comprises the near-azeotropic composition of the present invention, at least one lubricant, and at least one additive that can improve the life of the refrigerant and preferably the life of the air conditioning system and the durability of the compressor. In one aspect of the present invention, the aforementioned refrigerant composition comprises at least one component selected from the group consisting of acid scavengers, performance enhancers, and flame suppressants.

[0070] In another embodiment, the fluoropropene composition may be used in a heat transfer process. The process may include the steps of providing an article and bringing the article into contact with a heat transfer medium containing the fluoropropene composition. In some embodiments, the article may include electrical equipment (e.g., circuit boards, computers, displays, semiconductor chips, or transformers), heat transfer surfaces (e.g., heat sinks), or clothing articles (e.g., bodysuits).

[0071] In another embodiment, the fluoropropene composition may be used in a process for treating a surface. The process may include the steps of providing a surface having a treatable material deposited thereon, and contacting the surface with a treatment composition containing the fluoropropene composition. In some embodiments, the treatment composition can substantially dissolve the treatable material.

[0072] In another embodiment, the fluoropropene composition may be used in a process for forming a composition. This process includes the steps of providing a solute and contacting the solute with a solvent containing the fluoropropene composition. In some embodiments, the fluoropropene composition can substantially dissolve the solute.

[0073] In another embodiment, the present invention relates to a foaming agent composition comprising a fluoroolefin-containing composition (e.g., a near-azeotropic composition) described herein for use in the preparation of foams. In yet another embodiment, the present invention provides foaming compositions, preferably polyurethane and polyisocyanate foam compositions, and methods for preparing foams. In such embodiments of foams, one or more of the fluoroolefin-containing compositions are included in the foaming composition as foaming agents, and the compositions preferably include one or more additional components that can react and foam under suitable conditions to form a foam or buoyant structure. Any of the methods well known in the art, such as those described herein by reference in "Polyurethanes Chemistry and Technology," Volumes I and II, Saunders and Frisch, 1962, John Wiley and Sons, New York, NY, may be used or applied in accordance with embodiments of the present invention.

[0074] The present invention further relates to a method for forming a foam, comprising the steps of (a) adding a fluoroolefin-containing composition to a foaming composition, and (b) reacting the foaming composition under conditions effective for forming a foam.

[0075] Another embodiment of the present invention relates to the use of the fluoroolefin-containing compositions described herein (e.g., near-azeotropic compositions of HFO-1234ze(E) and HFO-1234yf) as propellants in sprayable compositions. Furthermore, the present invention relates to sprayable compositions comprising the fluoroolefin-containing compositions described herein. Active components to be sprayed together with inert components, solvents, and other materials may be present in the sprayable composition. Preferably, the sprayable composition is an aerosol. Suitable active substances 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 drugs and breath fresheners.

[0076] The present invention further relates to a process for manufacturing an aerosol product, comprising the step of adding a fluoroolefin-containing composition described herein to an active ingredient in an aerosol container, wherein the composition functions as a propellant.

[0077] When used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” or any other variations thereof are intended to encompass non-exclusive inclusion. For example, a process, method, article, or apparatus that includes a list of elements may include other elements not expressly described for or specific to such process, method, article, or apparatus, but not necessarily limited to those elements. Furthermore, unless expressly stated otherwise, “or” means an inclusive “or” and not an exclusive “or.” For example, condition A or B is satisfied by any one of the following: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); and both A and B are true (or exist).

[0078] The transitional phrase “consisting of” excludes any unspecified elements, processes, or components. In the context of claims, with the exception of impurities normally associated with materials, such a phrase limits the claims to include materials other than those enumerated. When the phrase “consisting of” appears within a clause of the claims rather than immediately following the preface, it limits the elements described within that clause only, and does not exclude other elements from the claims as a whole. The transitional phrase “essentially consisting of” is used to define compositions and methods that include materials, processes, mechanisms, components, or elements in addition to those literally disclosed, provided that these additionally included materials, processes, mechanisms, components, or elements do not substantially affect the basic and novel features of the claimed invention, in particular the mechanism of operation for achieving any desired outcome of any of the processes of the invention. The term “essentially consisting of” has an intermediate meaning between “contains” and “consisting of.”

[0079] In the aforementioned combination of embodiments of the present invention, the near-azeotropic composition comprises and is based on or derived from HFO-1234ze(E) and HFO-1234yf.

[0080] Furthermore, the use of "a" or "an" is used to describe the elements and components described herein. This is done solely for convenience and to give a general sense of the scope of the invention. This description should be interpreted as including one or at least one, and the singular form also includes the plural form unless it is evident that it has a different meaning.

[0081] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art to which the present invention pertains. Similar or equivalent methods and materials to those described herein may be used in carrying out or testing embodiments of the present invention, but preferred methods and materials are described below. All publications, patent applications, patents, and other references referred herein are incorporated herein by reference in their entirety unless a specific section is cited. In the event of any inconsistency, including definitions, this specification shall prevail. Furthermore, materials, methods, and examples are merely illustrative and not intended to limit the scope of the invention. [Examples]

[0082] The concepts described herein will be further illustrated by the following examples, but this will not limit the scope of the invention as defined in the claims.

[0083] (Example 1) Example 1 shows the dehydrofluorination treatment of 245fa by passing it over Cr2O3 in the presence of Z-HFC-1234ze.

[0084] 10 cc (8 grams) of Cr2O3 catalyst (Johnson Mathey), prepared as follows, was packed into an Inconel tube (outer diameter 1.3 cm (1 / 2 inch)). Extruded chromium oxide was crushed and sieved through a 12 / 20 mesh sieve. After packing the reactor tube, the temperature of the catalyst layer 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 introduced at 20 cc / min for 60 minutes. The temperature was raised to 325°C for 300 minutes. Next, the nitrogen flow was reduced to 30 cc / min and the HF flow was increased to 30 cc / min for 30 minutes. Next, the nitrogen flow was reduced to 12 cc / min and the HF flow was increased to 48 cc / min for 60 minutes. Next, the nitrogen flow was stopped and the HF flow was increased to 48 cc / min for 30 minutes. Next, the reactor temperature was lowered to 250°C for 30 minutes. Then, the HF was stopped and the reactor was purged with nitrogen at a rate of 30 cc / min. Next, the reactor temperature was stabilized at 300°C, the nitrogen flow was stopped, and either CF3CH2CHF2 or CF3CH2CHF2 with a varying amount of Z-1234ze was introduced at a rate of 1.44 mL / hour. The contact time in the reactor was 45 seconds. The CF3CH2CHF2 was evaporated at 50°C. A portion of the reactor effluent was passed through a series of valves and analyzed by GC-MS. The amounts of Z-1234ze, 245fa, and E-1234ze are expressed as mol%. The results are summarized in Table 1.

[0085] [Table 1]

[0086] (Example 2) Example 2 shows the dehydrofluorination treatment of 245fa by passing it over Cr2O3 in the presence of Z-HFC-1234ze.

[0087] 10 cc (8 grams) of Cr2O3 catalyst (Guinet green) prepared as follows was packed into an Inconel tube (outer diameter 1.3 cm (1 / 2 inch)). Extruded chromium oxide was crushed and sieved through a 12 / 20 mesh sieve. After packing the reactor tube, the temperature of the catalyst layer 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 supplied at 20 cc / min for 60 minutes. The temperature was raised to 325°C for 300 minutes. Next, the nitrogen flow was reduced to 30 cc / min and the HF flow was increased to 30 cc / min for 30 minutes. Next, the nitrogen flow was reduced to 12 cc / min and the HF flow was increased to 48 cc / min for 60 minutes. Next, the nitrogen flow was stopped and the HF flow was increased to 48 cc / min for 30 minutes. The reactor temperature was then lowered to 250°C for 30 minutes. The HF was then stopped, and the reactor was purged with nitrogen at a rate of 30 cc / min. Next, the reactor temperature was stabilized at 300°C, the nitrogen flow was stopped, and either CF3CH2CHF2 or CF3CH2CHF2 with a varying amount of Z-1234ze was introduced at a rate of 1.44 mL / hour. The contact time in the reactor was 45 seconds. The CF3CH2CHF2 was evaporated at 50°C. A portion of the reactor effluent was passed through a series of valves and analyzed by GC-MS. The amounts of Z-1234ze, 245fa, and E-1234ze are expressed as mol%. The results are summarized in Table 2.

[0088] [Table 2]

[0089] (Example 3) Example 3 shows the dehydrofluorination treatment of 245fa by passing it over Cr2O3 in the presence of Z-HFC-1234ze.

[0090] 10 cc (8 grams) of Cr2O3 catalyst (Johnson Mathey), prepared as follows, was packed into an Inconel tube (outer diameter 1.3 cm (1 / 2 inch)). Extruded chromium oxide was crushed and sieved through a 12 / 20 mesh sieve. After packing the reactor tube, the temperature of the catalyst layer 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 introduced at 20 cc / min for 60 minutes. The temperature was raised to 325°C for 300 minutes. Next, the nitrogen flow was reduced to 30 cc / min and the HF flow was increased to 30 cc / min for 30 minutes. Next, the nitrogen flow was reduced to 12 cc / min and the HF flow was increased to 48 cc / min for 60 minutes. Next, the nitrogen flow was stopped and the HF flow was increased to 48 cc / min for 30 minutes. Next, the reactor temperature was lowered to 250°C for 30 minutes. Then, the HF was stopped and the reactor was purged with nitrogen at a rate of 30 cc / min. Next, the reactor temperature was stabilized at 300°C, the nitrogen flow was stopped, and either CF3CH2CHF2 or CF3CH2CHF2 with varying amounts of Z-1234ze was introduced at a rate of 1.44 mL / hour. The contact time in the reactor was 45 seconds. CF3CH2CHF2 was evaporated at 50°C. A portion of the reactor effluent was passed through a series of valves and analyzed by GC-MS. The amounts of Z-1234ze, 245fa, and E-1234ze are expressed as mol%. The results are summarized in Table 3.

[0091] [Table 3]

[0092] (Example 4) Example 4 shows the dehydrofluorination treatment of 245fa by passing it over Cr2O3 in the presence of Z-HFC-1234ze.

[0093] 10 cc (8 grams) of Cr2O3 catalyst (Newport Cr) prepared as follows was packed into an Inconel tube (outer diameter 1.3 cm (1 / 2 inch)). Extruded chromium oxide was crushed and sieved through a 12 / 20 mesh sieve. After packing into the reactor tube, the temperature of the catalyst layer 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 introduced at 20 cc / min for 60 minutes. The temperature was raised to 325°C for 300 minutes. Next, the nitrogen flow was reduced to 30 cc / min and the HF flow was increased to 30 cc / min for 30 minutes. Next, the nitrogen flow was reduced to 12 cc / min and the HF flow was increased to 48 cc / min for 60 minutes. Next, the nitrogen flow was stopped and the HF flow was increased to 48 cc / min for 30 minutes. Next, the reactor temperature was lowered to 250°C for 30 minutes. Then, the HF was stopped and the reactor was purged with nitrogen at a rate of 30 cc / min. Next, the reactor temperature was stabilized at 300°C, the nitrogen flow was stopped, and either CF3CH2CHF2 or CF3CH2CHF2 with a varying amount of Z-1234ze was introduced at a rate of 1.44 mL / hour. The contact time in the reactor was 45 seconds. The CF3CH2CHF2 was evaporated at 50°C. A portion of the reactor effluent was passed through a series of valves and analyzed by GC-MS. The amounts of Z-1234ze, 245fa, and E-1234ze are expressed as mol%. The results are summarized in Table 4.

[0094] [Table 4]

[0095] (Example 5) Example 5 shows the dehydrofluorination treatment of 245fa by passing it through fluorinated alumina in the presence of Z-HFC-1234ze.

[0096] Pack 10 cc (6.1 grams) of Al2O3 catalyst (purchased from Sigma-Aldrich) into an Inconel tube (outer diameter 1.3 cm (1 / 2 inch)). Crush the extruded Al2O3 and sift it through a 12 / 20 mesh sieve. After filling the reactor tube, raise the temperature of the catalyst layer to 300°C and purge with nitrogen (30 cc / min) for 200 minutes. Then reduce the nitrogen flow to 60 cc / min and introduce HF at 20 cc / min for 60 minutes. Raise the temperature to 325°C for 300 minutes. Then reduce the nitrogen flow to 30 cc / min and increase the HF flow to 30 cc / min for 30 minutes. Next, reduce the nitrogen flow to 12 cc / min and increase the HF flow to 48 cc / min for 60 minutes. Next, stop the nitrogen flow and increase the HF flow to 48 cc / min for 30 minutes. Next, the reactor temperature is lowered to 250°C for 30 minutes. Then, the HF is stopped and the reactor is purged with nitrogen at a rate of 30 cc / min. Next, the reactor temperature is stabilized at 300°C, the nitrogen flow is stopped, and either CF3CH2CHF2 or CF3CH2CHF2 with a varying amount of Z-1234ze is introduced at a rate of 1.44 mL / hour. The contact time in the reactor is 45 seconds.

[0097] CF3CH2CHF2 was evaporated at 50°C. A portion of the reactor effluent was passed through a series of valves and analyzed by GC-MS. The amounts of Z-1234ze, 245fa, and E-1234ze are expressed as mole percent. The results are summarized in Table 5.

[0098] [Table 5]

[0099] (Example 6) Table 6 discloses the reaction products of the dehydrogenation and fluorination of 245fa with various catalysts in the presence of Z-HFC-1234ze (mol%).

[0100] [Table 6]

[0101] 10 cc (8 gm) of catalyst was packed into an Inconel tube (1 / 2 inch OD) (see Table 6). After packing the reactor tube, the temperature of the catalyst layer was raised to 300°C and purged with nitrogen (30 cc / min) for 200 minutes. Then the nitrogen flow was reduced to 60 cc / min and HF was supplied at 20 cc / min for 60 minutes. The temperature was raised to 325°C for 300 minutes. Next, the nitrogen flow was reduced to 30 cc / min and the HF flow was increased to 30 cc / min for 30 minutes. Next, the nitrogen flow was reduced to 12 cc / min and the HF flow was increased to 48 cc / min for 60 minutes. Next, the nitrogen flow was stopped and the HF flow was increased to 48 cc / min for 30 minutes. Then the reactor temperature was lowered to 250°C for 30 minutes. After that, the HF was stopped and the reactor was purged with nitrogen at 30 cc / min. Next, the reactor temperature was stabilized at 300°C, the nitrogen flow was stopped, and either CF3CH2CHF2 or CF3CH2CHF2 in a concentration of 10.5-11% of Z-1234ze was introduced at a rate of 1.44 mL / hour. The contact time in the reactor was 45 seconds. The CF3CH2CHF2 was evaporated at 50°C. A portion of the reactor effluent was passed through a series of valves and analyzed by GC-MS. 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 6.

[0102] (Example 7) Table 7 shows the near-azeotropic properties of various compositions that can be produced by the method of the present invention by measuring the delta P of the vapor pressure with respect to the percentage change. The ΔP vapor pressure is the change in vapor pressure at -25°C after 50% vapor leakage, in which 50% of the vapor has been removed.

[0103] [Table 7]

[0104] (Example 8) Table 8 shows the cooling performance of various near-azeotropic compositions that can be produced by the method of the present invention, by comparing their cooling capacity and energy efficiency (COP) with HFO-1234ze(E). The data is based on the following conditions. T_condenser=47.0 degC T_evaporator=7.0 degC Supercooling=12.0 K Superheat = 3.0 K Compressor efficiency = 0.7 Average heat exchange temperature set point Overheating is included in the refrigerant effect.

[0105] Cooling load = 1.0 ton Compressor displacement = 0.1 (m^3 / min)

[0106] [Table 8]

[0107] Example 8 demonstrates that the near-azeotropic composition of the present invention is effective for use as a refrigerant and has refrigerant properties at least equivalent to those of HFO-1234ze(E).

[0108] Note that not all of the tasks or examples described above are necessary in the general description, and some parts of certain tasks may not be required. Furthermore, one or more additional tasks may be performed in addition to those described above. Also, the order in which the tasks are described is not necessarily the order in which they are performed.

[0109] Benefits, other advantages, and solutions to problems are described above in relation to specific embodiments. However, these benefits, advantages, solutions to problems, and any features that may give rise to or make more apparent any benefits, advantages, or solutions are not to be construed as essential, necessary, or indispensable features in any part or all of the claims.

[0110] For clarity, it should be understood that certain features described herein in the context of separate embodiments may be provided in combination within a single embodiment. Conversely, for brevity, various features described in the context of a single embodiment may also be provided separately or in any subcombination. Furthermore, references to values ​​given in ranges include each and all values ​​within that range.

[0111] While the present invention has been described with reference to preferred embodiments, those skilled in the art will understand that various modifications can be made without departing from the scope of the invention, and that equivalents can be used in place of certain elements. In addition, many modifications can be made without departing from the essential scope of the invention to adapt the teachings of the invention to specific situations or materials. Therefore, the present invention is not limited to the specific embodiments disclosed as the best mode intended to carry out the invention, and the present invention is intended to include all embodiments that fall within the scope of the appended claims.

Claims

1. A fluoropropene refrigerant composition comprising Z-1,3,3,3-tetrafluoropropene, E-1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, and optionally 1,1,1,3,3-pentafluoropropane, wherein E-1,3,3,3-tetrafluoropropene is present in an amount of 99 to 99.99 mol% based on the total amount of the composition, 2,3,3,3-tetrafluoropropene is present in an amount of 0.001 to 1.0 mol% based on the total composition, and Z-1,3,3,3-tetrafluoropropene is present in an amount of less than 1000 ppm.

2. The fluoropropene refrigerant composition according to claim 1, wherein the 2,3,3,3-tetrafluoropropene is present in an amount of 0.1 to 0.9 mol%.

3. The fluoropropene refrigerant composition according to claim 1, wherein the 2,3,3,3-tetrafluoropropene is present in an amount of 0.2 to 0.4 mol%.

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

5. The fluoropropene refrigerant composition according to claim 1, wherein the composition is near azeotropic.

6. It is a process of heat transfer, The process of providing goods, A step of bringing the aforementioned article into contact with a heat transfer medium, A process comprising, wherein the heat transfer medium comprises the fluoropropene refrigerant composition according to any one of claims 1 to 5.

7. A cooling system, Evaporator and condenser, Compressor and, An expansion device, a heat transfer medium, Includes, A cooling system wherein the heat transfer medium comprises the fluoropropene refrigerant composition described in any one of claims 1 to 5.

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