Compositions comprising 2,3,3,3-tetrafluoropropene, and methods for making and using compositions

Abstract

To provide compositions that may be useful as heat transfer compositions.SOLUTION: A composition comprises 1234yf, 134a, 1140, and at least one of 1234ze-E and 1234ze-Z.SELECTED DRAWING: None

Description

[Technical field]

[0001] (Reference to Related Application) This application claims the benefit of Application No. 62 / 971,347, filed February 7, 2020. The disclosure of Application No. 62 / 971,347 is incorporated herein by reference.

[0002] FIELD OF THEINVENTION The present disclosure relates to the field of compositions that may be useful as heat transfer compositions, aerosol propellants, foaming agents, blowing agents, solvents, cleaning agents, dispersion media, displacement drying agents, buffing agents, polymerization media, expansion agents for polyolefins and polyurethanes, gaseous dielectrics, fire extinguishing agents, and fire suppression agents in liquid or gas form. The present disclosure also relates to compositions and methods that are useful for producing heat transfer agents. In particular, the present disclosure relates to compositions that may be useful as heat transfer compositions, such as 2,3,3,3-tetrafluoropropene (HFO-1234yf, or 1234yf). [Background technology]

[0003] U.S. Patent Application Publication No. 2017 / 0166500 discloses a process and method for producing HFO-1234yf by dehydrohalogenating a reactant stream of 2-chloro-1,1,1,2-tetrafluoropropane that is substantially free of impurities, the disclosures of which are incorporated herein by reference. Summary of the Invention [Means for solving the problem]

[0004] One embodiment of the present invention provides a composition comprising 1234yf, 1225zc, 1234ze-E, 1234ze-Z, 1243zf, 1140, Z-1225ye, E-1225ye, and HFC134a.

[0005] The composition of the present invention can further comprise at least one additional compound. In one embodiment, the additional compound comprises at least one member selected from the group consisting of 1131a, 244bb, 1233xf, 244cc, 1224yd, HFP, 1122, 1122a, 12, E-1131, Z-1131, 245cb, 3,3,3-trifluoropropyne, 347 isomers including 124, 142b, 254eb, 347mpy and 347mef, and combinations thereof.

[0006] In one embodiment of the invention, the at least one additional compound or said additional compounds further comprise at least one member selected from the group consisting of HFC-245cb, CFC-12, HCC-1140, HFC-254eb, HCFC-1122, HCFC-124, HCFC-142b, HCFC-151a, HFC-152a, and 3,3,3-trifluoropropyne.

[0007] In another embodiment of the present invention, the at least one additional compound or the aforementioned additional compounds further comprise at least one additional compound selected from the group consisting of HCFC-243db, HCFC-244db, HFC-245cb, HFC-245fa, HCFO-1233xf, HCFO-1233zd, HCFC-253fb, HCFC-234ab, HCFC-243fa, ethylene, HFC-23, CFC-13, HFC-143a, HFC-152a, HFC-236fa, HCO-1130, HCO-1130a, HFO-1336, HCFC-133a, HCFC-254fb, HCFC-1131, HFC-1141, HCFO-1242zf, HCFO-1223xd, HCFC-233ab, HCFC-226ba, and HFC-227ca.

[0008] In one embodiment of the present invention, the composition contains greater than 0 and less than about 1 total weight percent of at least one additional compound.

[0009] In another embodiment of the present invention, the composition of the present invention comprises 1234yf, and the total amount of 1225zc, 1234ze, 1243zf, 1140, Z-1225ye, E-1225ye, and HFC134a is greater than 0% and less than 1% by weight. In one aspect of this embodiment, the composition of the present invention comprises 1234yf, and the total amount of 1225zc, 1234ze, 1243zf, 1140, Z-1225ye, E-1225ye, HFC134a, and at least one additional compound is greater than 0% and less than 1% by weight.

[0010] In another embodiment of the invention, the 347 isomer comprises at least one member selected from the group consisting of 347mpy and 347mef.

[0011] In another embodiment of the present invention, the composition of the present invention further comprises at least one member selected from the group consisting of 32, 125 and 161.

[0012] In another embodiment of the present invention, there is provided a composition comprising HCFC-244bb and at least one additional compound selected from the group consisting of 1120, 1334, 244cc, 1233xf, 1223xd, 1224, 225ba, 226ca, 233ab, 233da, 234bb, 234da, 235ca, 235da, 235ea, 243ab, 243db, 244db, 244eb, 253db, 253fb, 1224yd-E, 1233zd, 235cb and 1224yd-Z, 1326, 1223 isomers and combinations thereof. In one aspect of this embodiment, the composition may contain HCFC-244bb in the range of greater than 0 weight percent to 99.99 weight percent.

[0013] In one embodiment of the present invention, a composition containing 244bb can be used to prepare a 1234yf composition of the present invention. One aspect of this embodiment includes a method of preparing a 1234yf-containing composition of the present invention by reacting any combination of the aforementioned 244bb-containing compositions. In one particular embodiment of this embodiment, the reaction includes a dehydrochlorination reaction.

[0014] In one embodiment, the composition of the present invention comprises a refrigerant comprising any combination of the aforementioned composition and at least one lubricant.

[0015] One embodiment of the present invention includes a method of transferring heat comprising using any combination of the aforementioned refrigerant compositions as a working fluid in a heat transfer system. In one aspect, the method relates to a heat transfer system comprising at least one member selected from the group consisting of an air conditioner, a freezer, a refrigerator, a heat pump, a water chiller, a flooded evaporator chiller, a direct expansion chiller, a walk-in cooler, a heat pump, a mobile refrigerator, a mobile air conditioning unit, and combinations thereof.

[0016] Another embodiment of the present invention includes a container containing any of the aforementioned 1234yf-containing compositions.

[0017] The embodiments of the present invention may be used alone or in combination with each other. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] HFO-1234yf is useful as a refrigerant, heat transfer fluid, aerosol propellant, and foaming agent, among other applications.HFO-1234yf also has a low global warming potential (GWP), as reported in VC Papadimitriou, et al. in Physical Chemistry Chemical Physics, 2007, Vol. 9, pp. 1-13, which is incorporated herein by reference.HFO-1234yf is useful to replace saturated HFC refrigerants with higher GWP.

[0019] As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," or any other variation thereof, are intended to cover non-exclusive inclusions. For example, a composition, process, method, article, or device that includes recited elements is not necessarily limited to only those elements, but may include other elements not expressly recited or associated with such composition, process, method, article, device, etc. 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).

[0020] The transitional phrase "consisting of" excludes any element, step, or ingredient not specified. When in a claim, such a phrase excludes the inclusion of materials other than those recited, except for impurities normally accompanying the materials. When the phrase "consisting of" appears within a clause in the body of a claim rather than immediately following the preamble, the phrase is intended to limit only the elements set forth in that clause and does not exclude other elements from the claim as a whole.

[0021] The transitional phrase "consisting essentially of" is used to define compositions, methods, and methods that include materials, steps, features, ingredients, or elements in addition to those literally disclosed, provided that these additionally included materials, steps, features, ingredients, or elements have a substantial effect on the basic and novel characteristics of the claimed invention, particularly the mode of action for achieving any desired result of the inventive process. The term "consisting essentially of" has a meaning intermediate between "comprising" and "consisting of."

[0022] It should be readily understood that where applicants have defined an invention or a portion thereof with open-ended terms such as "comprising," the description should be construed to also include inventions using the terms "consisting essentially of" or "consisting of" (unless otherwise expressly stated).

[0023] 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.

[0024] One embodiment of the present invention provides a composition comprising 1234yf, a balance including up to 1 wt% 134a, optionally greater than 0 wt% and less than about 0.5 wt% 134a, up to 100 ppmw 1140, optionally greater than 0 ppmw and less than about 60 ppmw 1140, and up to 500 ppmw each of 1225zc, 1234ze, 1243zf, Z-1225ye, and E-1225ye, optionally greater than 0 ppmw and less than about 250 ppmw each of 1225zc, 1234ze, 1243zf, Z-1225ye, and E-1225ye. In one aspect of this embodiment, the composition comprises: i) 1234yf, 134a, 1140, and 1225zc; ii) at least one of 1234yf, 134a, 1140, and 1234ze-E and 1234ze-Z; iii) 1234yf, 134a, 1140, and 1243zf; and iv) at least one of 1234yf, 134a, 1140, and Z-1225ye and E-1225ye. and v) any combination of i)-iv) with at least one additional compound (described below), or vi) the combination of v), wherein the total amount of 134a, 1140, 1225zc, 1234ze-E and 1234ze-Z, 1243zf, Z-1225ye, E-1225ye and the additional compound is greater than 0% and less than 1% by weight.

[0025] The composition of the present invention described above can further comprise at least one additional compound. In one embodiment, the additional compound comprises at least one member selected from the group consisting of i) one or more of 1131a, 1233xf, 1224yd, 1225zc, HFP, 1122, 1122a, E-1131, Z-1131, and 3,3,3-trifluoropropyne, which are greater than 0 ppmw and up to 25 ppmw, up to 250 ppmw, and in some cases up to 500 ppmw, and ii) one or more of 244bb, 244cc, 12, 245cb, 124, 142b, 254eb, and 347 isomers (including 347mpy, 347mef, and combinations thereof) up to 1%. In one aspect of this embodiment, the amount of the additional compounds includes greater than 0 ppmw and less than about 250 ppmw of one or more of 1131a, 1233xf, 1224yd, HFP, 1122, 1122a, E-1131, Z-1131, and 3,3,3-trifluoropropyne. In another aspect of this embodiment, the amount of the additional compounds includes greater than 0% and less than about 0.5% of one or more of the 347 isomers, including 244bb, 244cc, 12, 245cb, 124, 142b, 254eb, 347mpy, and 347mef.

[0026] In one embodiment of the present invention, the aforementioned composition further comprises an additional compound comprising at least one member selected from the group consisting of HFC-245cb, CFC-12, HFC-254eb, HCFC-1122, HCFC-124, HCFC-142b, HCFC-151a, HFC-152a, 3,3,3-trifluoropropyne, 1122a-Z, and combinations thereof. In one aspect of this embodiment, the amount of the additional compound comprises fluoroolefin compounds greater than 0 ppmw and less than 500 ppmw. In another aspect of this embodiment, the amount of the additional compound comprising 1140 is greater than 0 ppmw and less than 100 ppmw. In a further aspect of this embodiment, the amount of the additional compound comprising saturates is greater than 0% and less than 1%, in some cases greater than 0% and less than 0.5%.

[0027] In another embodiment of the invention, the aforementioned additional compounds further comprise additional compounds comprising at least one additional compound selected from the group consisting of HCFC-243db, HCFC-244db, HFC-245cb, HFC-245fa, HCFO-1233xf, HCFO-1233zd, HCFC-253fb, HCFC-234ab, HCFC-243fa, ethylene, HFC-23, CFC-13, HFC-143a, HFC-152a, HFC-236fa, HCO-1130, HCO-1130a, HFO-1336, HCFC-133a, HCFC-254fb, HCFC-1131, HFC-1141, HCFO-1242zf, HCFO-1223xd, HCFC-233ab, HCFC-226ba, and HFC-227ca. In one aspect of this embodiment, the amount of additional compounds includes fluoroolefin compounds from greater than 0 ppmw to less than 500 ppmw. In another aspect of this embodiment, the amount of additional compounds including saturates is from greater than 0% to less than 1%, and in some cases from greater than 0% to less than 0.5%.

[0028] In one embodiment of the invention, the aforementioned composition contains a total weight percent of at least one additional compound that is greater than 0 and less than about 1. In another embodiment of the invention, the aforementioned composition comprises a total weight percent of at least one additional compound that is greater than 0 and less than 0.5, greater than 0 and less than 0.2, and in some cases greater than 0 and less than 0.1.

[0029] In the aforementioned embodiment of the 1234yf-containing composition, the additional compounds may provide various benefits. Examples of such benefits include reduced flammability when using additional compounds such as, for example, 347 isomers, 1224yd, 1233xf, 244bb, 244cc, 245cb, HFP134a, 1225ye, and 1225zc. When the additional compounds include chlorinated compounds, the additional compounds can provide improved lubricity and protect the compressor by binding to and passivating metal surfaces. Furthermore, certain chlorinated compounds such as 1224yd, 1233xf, 244bb, and 244cc can provide improved chemical stability and can increase the stability of 1234yf by reducing polymerization acting as a chain transfer agent. Furthermore, certain additional compounds can provide improved miscibility with lubricating oils and aid in leak detection. Certain additional compounds can also provide improved refrigeration performance, such as trifluoropropyne, which has a lower boiling point than 1234yf.

[0030] In another embodiment of the present invention, there is provided a composition comprising HCFC-244bb and at least one additional compound selected from the group consisting of 1120, 1334, 244cc, 1233xf, 1223xd, 1224, 225ba, 226ca, 233ab, 233da, 234bb, 234da, 235ca, 235da, 235ea, 243ab, 243db, 244db, 244eb, 253db, 253fb, 1224yd-E, 1233zd, 235cb and 1224yd-Z, 1326, 1223 isomers (including 1223xd) and combinations thereof. In one aspect of this embodiment, the composition may contain HCFC-244bb in the range of greater than 0 weight percent to 99.99 weight percent. In one aspect of this embodiment, the amount of the additional compounds ranges from greater than 0% to less than 1% by weight, and in some cases, greater than 0% to less than 0.5% by weight. In another aspect of this embodiment, the amount of the additional compounds including 1224yd is greater than 0% to less than 2% by weight, and in some cases, greater than 0% to less than 1% by weight. In a further aspect of this embodiment, the amount of the additional compounds including 1233xf is greater than 0% to less than 5% by weight, and in some cases, greater than 0% to less than 2.5% by weight.

[0031] In one embodiment, the HCFC-244bb-containing composition can be prepared by blending the components of the composition. In another embodiment, the HCFC-244bb-containing composition is produced by i) hydrofluorinating 1233xf in the liquid phase using an antimony catalyst, ii) purifying to remove unreacted HF and some organic by-products, and iii) optionally blending additional components of the composition into the 244bb-containing reaction product.

[0032] In one embodiment of the invention, a composition comprising 244bb can be used to produce the 1234yf composition of the present invention. Although the 244bb-containing composition can be used in any suitable process for producing 1234yf, one example of such a process is disclosed in U.S. Patent Publication No. 20150315108, the disclosures of which are incorporated herein by reference.

[0033] In the above-mentioned 244bb-containing composition, the additional compound may provide various benefits. For example, the additional compound may include at least one of 1120, 1334, 244cc, 1223xd, 1224, 225ba, 226ca, 233ab, 233da, 234bb, 234da, 235ca, 235da, 235ea, 243ab, 243db, 244db, 244eb, 253db, 253fb, 1224yd-E, 1233zd, 235cb, and 1224yd-Z, 1326, and 1223 isomers (including 1223xd) can function as a solvent, for example, to increase the dehydrochlorination of 244bb by caustic. In one embodiment, the composition including at least one additional compound provides a cost-effective intermediate for use in further processing or acts as a carrier for another compound (e.g., additional compounds including 1233xf can be used together with 244bb, where less than 2.5 wt. % of 1233xf does not adversely affect the gas-phase desalination of 244bb).

[0034] The compositions disclosed herein, including HFO-1234yf, are useful as low global warming potential (GWP) heat transfer compositions, aerosol propellants, foaming agents, blowing agents, solvents, cleaning agents, dispersion media, displacement drying agents, buffing agents, polymerization media, expansion agents for polyolefins and polyurethanes, gaseous dielectrics, fire extinguishing agents, and fire suppression agents in liquid or gas form. By low GWP compositions, it is meant that the overall GWP of the composition is less than 750, less than 150, less than 10, and in some cases less than about 1. The disclosed compositions can act as working fluids used to transport heat from a heat source to a heat sink. Such heat transfer compositions may also be useful as refrigerants in cycles where the fluid undergoes a phase change, i.e., changes from liquid to gas and vice versa. Exemplary heat transfer systems include, but are not limited to, air conditioners, freezers, refrigerators, heat pumps, water coolers, flooded evaporator chillers, direct expansion chillers, walk-in coolers, heat pumps, mobile refrigerators, mobile air conditioning units, and combinations thereof.

[0035] As used herein, mobile refrigeration, mobile air conditioning, or mobile heating equipment refers to any refrigeration, air conditioning, or heating equipment incorporated into a transportation unit for road, rail, sea, or air. Additionally, mobile refrigeration or air conditioning equipment units include equipment that is independent of any moving carrier and is known as an "intermodal" system. Such intermodal systems include "containers" (combined sea / land transportation) as well as "swap bodies" (combined road / rail transportation).

[0036] As used herein, a stationary heat transfer system is a system associated with or attached to any type of building. These stationary applications can be stationary air conditioning and heat pumps (including but not limited to chillers, high temperature heat pumps, residential, commercial, or industrial air conditioning systems, and also window, ductless, ducted, packaged terminal, chillers, and those that are external but connected to the building, such as rooftop systems). In stationary cooling applications, the disclosed compositions can be useful in installations including commercial, industrial, or residential coolers and freezers, ice makers, self-contained coolers and freezers, flooded evaporator chillers, direct expansion chillers, walk-in and reach-in coolers and freezers, and combination systems. In some embodiments, the disclosed compositions can be used in supermarket refrigeration systems.

[0037] In one embodiment of the present invention, the 1234yf-containing composition is used as a refrigerant and further comprises at least one lubricant. The lubricant component of the refrigerant composition can include those suitable for use with refrigeration or air conditioning equipment. Among these lubricants are those conventionally used in compression refrigeration equipment utilizing chlorofluorocarbon refrigerants. Such lubricants and their properties are discussed in the 1990 ASHRAE Handbook, Refrigeration Systems and Applications, Chapter 8, entitled "Lubricants in Refrigeration Systems", pages 8.1-8.21, which is incorporated herein by reference. The lubricants of the present invention may include those commonly known in the field of compression refrigeration lubrication as "mineral oils". Mineral oils include paraffins (i.e., saturated hydrocarbons of 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 further include those commonly known in the field of compression refrigeration lubrication as "synthetic oils". Synthetic oils include alkylaryls (i.e., linear and branched alkyl alkylbenzenes), synthetic paraffins and naphthenes, silicones, and poly-alpha-olefins. Representative conventional lubricants of the present invention are commercially available BVM 100 N (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 HAB 22.

[0038] In another embodiment, the lubricant component of the refrigerant composition of the present invention can include those designed for use with hydrofluorocarbon refrigerants and miscible with the refrigerants and inhibitors 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 RLShubkin and Marcel Dekker, 1993. Such lubricants include, but are not limited to, polyol esters (POEs) such as Castrol® 100 (Castrol, UK), polyalkylene glycols (PAGs) such as RL-488A manufactured by Dow (Dow Chemicals, Midland, Mich.), and polyvinyl ethers (PVEs). The lubricants of the present invention are 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% by weight, from about 1% to about 20% by weight, and in some cases from about 1% to about 3% by weight. In one specific embodiment, the refrigerant compositions are 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 compositions are combined with a POE lubricant for use in a heat pump system for a vehicle having an electric or hybrid electric drivetrain.

[0039] In one embodiment of the present invention, the 1234yf-containing composition further comprises an effective amount of at least one inhibitor. By "inhibitor" is meant to refer to at least one compound according to the present invention that reduces, if not eliminates, the conversion of hydrofluoroolefins to oligomers or polymers. Although the oligomerization or homopolymerization reaction may be accelerated by relatively high temperatures, such reactions may also occur under ambient conditions depending on the concentration and type of initiator (e.g., contaminant). The inhibitor can function as a radical inhibitor to stabilize the refrigerant and does not affect the refrigeration performance or the compatibility of the refrigerant composition with refrigeration oils and components. The stabilized refrigerant composition may be useful in cooling systems and as a replacement for existing refrigerants with higher global warming potential. Examples of suitable inhibitors include hydrocarbons including cyclic monoterpenes, terpenes, lipophilic organic compounds including tocopherols including α-tocopherol, phenols, benzene-1,4-diols, and the like, which have the chemical formula C. 6 H 4 (OH) 2 In another embodiment of the present invention, when the 1234yf-containing composition is used as a refrigerant, an inhibitor is present in the liquid 1234yf-containing composition and the lubricant, as described in WO2019213004, WO2020222864 and WO2020222865, the disclosures of which are incorporated herein by reference. The composition may contain any amount of inhibitor from 0.001% to 1% by weight of any of the stabilizers listed above, and in most cases may preferably include d-limonene.

[0040] In another embodiment of the present invention, the 1234yf-containing composition of the present invention is blended with at least one of hydrofluoroolefins, hydrofluorocarbons, hydrocarbons, and carbon dioxide to obtain a refrigerant composition. In one embodiment, the refrigerant composition comprises any of the aforementioned HFO-1234yf-containing compositions of the invention and at least one member selected from the group consisting of HFO-1234ze; HFC-32; HFC-125; HFC-32 and HFC-125; HFC-134a; HFC-152a; HFC-161, HFC-236fa; HFC-227ea; HFO-1225ye and HFC-32; HFO-1225ye and HFC-134a; HFO-1225ye, HFC-134a, and HFC-32; HFO-1225ye and HFO-1234yf; and HFO-1225ye, HFO-1225ye, HFO-1225ye and HFC-125. In another embodiment, the refrigerant composition comprises a composition disclosed in U.S. Patent No. 10,533,120, and any of the aforementioned HFO-123yf-containing compositions of the present invention are used as the 1234yf component of the composition disclosed in U.S. Patent No. 10,533,120, the disclosures of which are incorporated herein by reference. The amount of hydrofluoroolefin, hydrocarbon, hydrocarbon and carbon dioxide blended can range from about 1% to about 90% by weight, from about 5% to about 75% by weight, and in some cases can range from about 10% to about 50% by weight. In one particular embodiment, the compositions of the present invention comprise at least one member selected from the group consisting of 1225zc, 1234ze, 1243zf, 1140, Z-1225ye, E-1225ye, and HFC134a, wherein the total amount of the member is greater than 0 wt% and less than 1 wt%, 32 in an amount ranging from about 1 wt% to about 60 wt%, from about 5 wt% to 70 wt%, and from about 20 wt% to 40 wt%, with the balance being 1234yf.In another specific embodiment, the compositions of the present invention comprise at least one member selected from the group consisting of 1225zc, 1234ze, 1243zf, 1140, Z-1225ye, E-1225ye, and HFC134a, wherein the total amount of the member is greater than 0 wt% and less than 1 wt%, 32 in an amount ranging from about 1 wt% to about 70 wt%, from about 5 wt% to 70 wt%, and from about 20 wt% to 40 wt%, 125 in an amount ranging from 1 wt% to about 70 wt%, from about 5 wt% to 70 wt%, and from about 20 wt% to 50 wt%, and the balance 1234yf. In another particular embodiment, the compositions of the present invention comprise at least one member selected from the group consisting of 1225zc, 1234ze, 1243zf, 1140, Z-1225ye, E-1225ye, and HFC134a, wherein the total amount of the member is greater than 0 wt% and less than 1 wt%, 161 in an amount ranging from about 1 wt% to about 40 wt%, from about 1 wt% to 25 wt%, and from about 1 wt% to 10 wt%, with the balance being 1234yf.

[0041] In another embodiment, any of the 1234yf compositions of the present invention described above are blended with 1234ze. In one aspect, the composition comprises 1% to 99.5% by weight of 1234yf or 1234ze, and greater than 0% and less than 1% by weight of at least one member selected from the group consisting of 1225zc, 1243zf, 1140, Z-1225ye, E-1225ye, and HFC134a. In a particular aspect, the composition comprises at least 98% to 99.9% by weight of 1234ze, typically at least about 99.5% by weight of 1234ze, with the remainder comprising 1234yf, 1225zc, 1234ze, 1243zf, 1140, Z-1225ye, E-1225ye, and HFC134a. The compounds that make up the compositions of the present disclosure are defined in Table 1.

[0042] [Table 1-1]

[0043] [Table 1-2]

[0044] Dehydrochlorination of HCFC-244bb-containing compositions In some embodiments, dehydrochlorination of HCFC-244bb is used to prepare HFO-1234yf. In one aspect of the invention, a 244bb-containing composition of the invention is dehydrochlorinated to produce a HFO1234yf-containing composition.

[0045] In one embodiment, the dehydrochlorination of HCFC-244bb containing compositions of the present invention to HFO1234yf is carried out in the vapor phase.

[0046] In one embodiment, the vapor phase dehydrochlorination is carried out in the presence of a catalyst. In one embodiment, the catalyst is selected from carbon and / or metal based catalysts. In one embodiment, the catalyst can be selected from activated carbon, nickel based catalysts, palladium based catalysts, or any combination of these catalysts. In one embodiment, the catalyst can be selected from the group consisting of Ni mesh, palladium on carbon, palladium on aluminum oxide, or combinations thereof.

[0047] In one embodiment, the HFO-1234yf-containing composition of the invention is prepared by thermal dehydrochlorination of the HCFC-244bb-containing composition of the invention. In one embodiment, the reaction occurs in the absence of a catalyst. In one embodiment, the HCFC-244bb is introduced into one or more reaction vessels maintained at a temperature high enough to effect thermal dehydrochlorination of the HCFC-244bb. In one embodiment, multiple reactors can be used, as described in WO2020018764(A1), the disclosures of which are incorporated herein by reference. In one embodiment, the temperature is high enough to effect at least 5%, sometimes at least 10%, typically at least 15%, and sometimes at least 25% conversion of the thermal dehydrochlorination of the HCFC-244bb (e.g., 5 to 10% conversion in each reactor when multiple reactors are used). In another embodiment, the temperature is high enough to effect at least 40% conversion of the thermal dehydrochlorination of the HCFC-244bb. In yet another embodiment, the temperature is high enough to provide a conversion rate of at least 80% for the thermal dehydrochlorination of HCFC-244bb. In yet another embodiment, the temperature is high enough to provide a conversion rate of at least 15%, and in some cases at least 30%, 50%, and 80% for the thermal dehydrochlorination of HCFC-244bb for at least 12 hours of continuous operation. In one embodiment, unconverted 244bb can be separated from the 1234yf product and recycled to the reactor.

[0048] In one embodiment, the HCFC-244bb-containing composition of the present invention is introduced into a reaction vessel that is maintained at a temperature in the range of about 350 to about 550° C., and in some cases in the range of about 420 to about 520° C. In another embodiment, the temperature of the reaction vessel is maintained in the range of about 500° C. to about 650° C. In yet another embodiment, the temperature of the reaction vessel is maintained at a temperature high enough to pyrolyze HCFC-244bb to HFO-1234yf with a selectivity of 80% or greater. In yet another embodiment, the temperature of the reaction vessel is maintained at a temperature high enough to pyrolyze HCFC-244bb to HFO-1234yf with a selectivity of 85%, and in some cases with a selectivity of about 95 to about 99%.

[0049] In one embodiment, the reaction zone is a reaction vessel constructed of corrosion-resistant materials, which in one embodiment include alloys, such as nickel-based alloys such as Hastelloy®, nickel-chromium alloys available from Special Metals Corp. under the trademark Inconel® (hereinafter "Inconel®"), or nickel-copper alloys available from Special Metals Corp. (New Hartford, NY) under the trademark Monel®, or the vessel has a fluoropolymer lining.

[0050] In one embodiment, the HCFC-244bb containing composition of the present invention is preheated and vaporized in a vaporizer to a temperature of about 30° C. to about 100° C. In another embodiment, the HCFC-244bb is preheated in a vaporizer to a temperature of about 60° C. to about 90° C. The pressure can be about 50 to about 150 psig, and in some cases can range from about 60 to about 110 psig. The 244bb vapor can be heated to the reactor temperature in one or more heat exchangers and / or with electric heaters. In one aspect of this embodiment, the hot effluent gas from the reactor can be used to heat the 244bb feed gas.

[0051] In some embodiments, a diluent gas is used as a carrier gas for HCFC-244bb. In one embodiment, the carrier gas is selected from nitrogen, argon, helium, or carbon dioxide. In one aspect of this embodiment, HCl provided as a reaction product is used as the diluent gas.

[0052] Another embodiment of the invention relates to storing the aforementioned 1234yf-containing compositions in the gas and / or liquid phase in a sealed container in which the oxygen and / or water concentration in the gas and / or liquid phase ranges from about 3 ppm to less than about 3,000 ppm by volume, from about 5 ppm to less than about 150 ppm by volume, and in some cases from about 5 ppm to less than about 75 ppm by volume at a temperature of about 25° C. In one aspect of this embodiment, a refrigerant comprises a 1234yf-containing composition of the invention, and in a further aspect, the refrigerant composition further comprises greater than about 0% and less than 1% by weight of any combination of the aforementioned additional compounds.

[0053] The containers for storing the aforementioned compositions can be constructed of any suitable material and design that can seal the composition while maintaining the gas and liquid phases. Examples of suitable containers include pressure-resistant containers such as tanks, filled cylinders, and secondary filled cylinders. The containers can be constructed from any suitable material, such as carbon steel, manganese steel, chromium-molybdenum steel, especially low alloy steel, stainless steel, and in some cases aluminum alloys. The 1234yf-containing compositions stored in these containers can be transferred to heat transfer systems and used as working fluids.

[0054] Without wishing to be bound by any theory or explanation, it is believed that one skilled in the art can use the description herein to best utilize the present invention. Therefore, the following specific embodiments are to be construed as merely illustrative, and are not constraining in any way to the remainder of the disclosure or the appended claims. The following examples are illustrative of certain embodiments and aspects of the present invention, and are not intended to limit the scope of the appended claims. EXAMPLES

[0055] General procedure for product analysis The following general procedure illustrates the method used to analyze the products of the fluorination reaction. Other methods can be used to analyze the fluorochemical composition, so long as the method can adequately separate the components of the composition, detect the separated components, and resolve potentially overlapping signals for the detected components. A portion of the total reactor effluent was sampled for organic product analysis using a gas chromatograph equipped with a flame ionization detector (FID) and / or a mass spectrometer detector (GC / MS). The gas chromatography utilized two GC columns, an RTX-1 and a Gaspro column.

[0056] Example 1 The 244bb composition was analyzed using the product analysis described above, and the analytical results are shown in Table 1 below.

[0057] [Table 2]

[0058] The HCFC-244bb-containing composition of this example is produced by i) hydrofluorinating 1233xf in the liquid phase using an antimony catalyst, and ii) purifying to remove unreacted HF and organic by-products. The purified product 244bb was stored in a container and a sample was removed from the container for analysis.

[0059] Example 2 The composition of Example 1 was converted to HFO-1234yf by vaporizing the liquid 244bb obtained from the storage vessel, further heating the vaporized 244bb to reaction temperature, and then feeding it to a reactor system for dehydrochlorination to produce a HFO-1234yf-containing composition. The liquid 244bb was recycled and combined with the 244bb obtained from the storage vessel prior to the vaporizer. This composition was analyzed according to the product analysis described above. The process was carried out continuously, and the feed and product compositions of Tables 1 and 2, respectively, were analyzed simultaneously. The results of the analysis of the HFO-1234yf-containing composition are shown in Table 2 below.

[0060] [Table 3]

[0061] Example 3 The refrigeration performance of the HFO-1234yf-containing composition produced in Example 2 was evaluated using ThermPy cycle conditions (ThermPy is a refrigerant performance program based on Refprop10), and the evaluation results are shown in Table 3 below.

[0062] ThermPy Cycle Conditions - Mid-Temperature Refrigeration Condenser temperature = 40℃ Evaporator temperature = -7℃ Subcooling amount = 0K Return gas temperature = 18°C Isentropic efficiency = 70%

[0063] [Table 4]

[0064] [Table 5]

[0065] Table 3 shows that the compositions of the present invention are suitable for use as refrigerants. Table 3 further shows that the compositions of the present invention have refrigeration performance comparable to HFO-1234yf. Thus, the compositions of the present invention are suitable for replacing relatively pure HFO-1234yf.

[0066] Example 4 The refrigeration performance of the HFO-1234yf-containing composition produced in Example 2 blended with 32 was evaluated using ThermPy cycle conditions (ThermPy is a refrigerant performance program based on Refprop 10). The evaluation results are shown in Tables 4, 5, and 6.

[0067] ThermPy Cycle Conditions - Air Conditioning Condenser temperature = 46.1℃ Evaporator temperature = 10℃ Subcooling amount = 8.3K Superheat amount=11.1K Isentropic efficiency = 70%

[0068] [Table 6]

[0069] [Table 7]

[0070] ThermPy Cycle Conditions - Mid-Temperature Refrigeration Condenser temperature = 40℃ Evaporator temperature = -7℃ Subcooling amount = 0K Return gas temperature = 18°C Isentropic efficiency = 70%

[0071] [Table 8]

[0072] [Table 9]

[0073] ThermPy Cycle Conditions - Mid-Temperature Refrigeration Condenser temperature = 40℃ Evaporator temperature = -7℃ Subcooling amount = 0K Return gas temperature = 18°C Isentropic efficiency = 70%

[0074] [Table 10]

[0075] [Table 11]

[0076] Tables 4, 5 and 6 show that the compositions of the present invention are suitable for blending with 32 to obtain useful refrigerants.

[0077] Although the present invention has been described with reference to preferred embodiments, those skilled in the art will recognize that various changes can be made without departing from the scope of the invention and that equivalents can be substituted for its elements. In addition, many modifications can be made to adapt a particular situation or material to the teachings of the invention without departing from the 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 the invention is intended to include all embodiments falling within the scope of the appended claims.

Claims

1. A composition comprising 1234yf, 134a, 1140, and at least one of 1234ze-E and 1234ze-Z.

2. Maximum 1%, preferably less than 0.5% by weight of 134a; 1140 with a maximum of 100 ppmw, preferably less than 60 ppmw; 1234ze up to 500 ppmw, preferably less than 250 ppmw; The composition of claim 1 comprising:

3. 2. The composition of claim 1 further comprising 1243zf, preferably up to 500 ppmw of 1243zf, more preferably less than 250 ppmw of 1243zf.

4. 4. The composition of claim 1, 2 or 3, further comprising at least one additional compound.

5. The additional compound is: (i) greater than 0 ppmw and up to 500 ppmw, preferably up to 250 ppmw, more preferably up to 25 ppmw, of one or more of 1131a, 1233xf, 1224yd, 1225zc, HFP, 1122, 1122a, E-1131, Z-1131, and 3,3,3-trifluoropropyne; (ii) up to 1% of one or more of the 347 isomers, including 244bb, 244cc, 12, 245cb, 124, 142b, 254eb, 347mpy, and 347mef; 5. The composition of claim 4, comprising at least one member selected from the group consisting of:

6. The additional compound is: greater than 0 ppmw, up to 250 ppmw, of one or more of 1131a, 1233xf, 1224yd, HFP, 1122, 1122a, E-1131, Z-1131, and 3,3,3-trifluoropropyne; or greater than 0% by weight and up to 0.5% by weight of one or more of the 347 isomers, including 244bb, 244cc, 12, 245cb, 124, 142b, 254eb, 347mpy and 347mef; 6. The composition according to claim 4 or 5.

7. 5. The composition of claim 4, wherein the additional compound comprises at least one member selected from the group consisting of HFC-245cb, CFC-12, HFC-254eb, HCFC-1122, HCFC-124, HCFC-142b, HCFC-151a, HFC-152a, 3,3,3-trifluoropropyne, 1122a-Z, and combinations thereof.

8. The additional compounds are HCFC-243db, HCFC-244db, HFC-245cb, HFC-245fa, HCFO-1233xf, HCFO-1233zd, HCFC-253fb, HCFC-234ab, HCFC-243fa, ethylene, HFC-23, CFC-13, HFC-143a, HFC-152a, HFC-236fa, HCO-1 5. The composition of claim 4 comprising at least one member selected from the group consisting of HCFC-130, HCO-1130a, HFO-1336, HCFC-133a, HCFC-254fb, HCFC-1131, HFC-1141, HCFO-1242zf, HCFO-1223xd, HCFC-233ab, HCFC-226ba, and HFC-227ca.

9. 9. The composition of any of claims 4 to 8, comprising a total weight percent of said at least one additional compound that is greater than 0 and less than 1, preferably greater than 0 and less than 0.5, more preferably greater than 0 and less than 0.2, and most preferably greater than 0 and less than 0.1%.

10. 10. The composition of any of claims 1 to 9, further comprising between 0.001% and up to 1% by weight of an inhibitor, preferably one or more terpenes, more preferably d-limonene.

11. A refrigerant composition comprising the composition of any one of claims 1 to 10 and at least one lubricant.

12. 12. A method of transferring heat comprising using the composition of claims 1 to 11 as a working fluid in a heat transfer system.

13. 13. The method of claim 12, wherein the heat transfer system comprises at least one member selected from the group consisting of an air conditioner, a freezer, a refrigerator, a heat pump, a water chiller, a flooded evaporator chiller, a direct expansion chiller, a walk-in cooler, a heat pump, a mobile refrigerator, a mobile air conditioning unit, and combinations thereof.

14. 11. A container comprising a gas phase and a liquid phase of the composition of any one of claims 1 to 10, wherein the amount of oxygen and water concentration in the gas phase and liquid phase ranges from 3 ppm by volume to less than 3,000 ppm by volume at a temperature of 25°C.

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