High-purity fluoroolefin composition and impurity removal method

Abstract

The present invention relates to a method for manufacturing, blending, filling, displacing, and packaging a fluorinated olefin-containing composition that does not contain oxygen and oxidation components and / or does not contain an oligomer inhibitor and / or moisture.

Description

Technical Field

[0001] (Cross - Reference to Related Applications) This application claims priority under 35 U.S.C. 119(e) to U.S. Provisional Patent Application No. 63 / 344,859, filed May 23, 2022, entitled "HIGH PURITY FLUOROOLEFIN COMPOSITIONS - IMPURITY REMOVAL", the entire content of which is incorporated herein by reference.

[0002] (Field of the Invention) The present invention relates to high - purity HFO and / or HFC - containing components and blends (with or without oligomer or polymer inhibitors) substantially free of oxygen or oxidizing components, and methods for manufacturing, blending, filling, displacing, and packaging the above - mentioned components and blends.

Background Art

[0003] Tetrafluoropropenes such as HFO-1234yf and HFO-1234ze are molecules that are stable under refrigeration use conditions, similar to HCFOs such as HFC-125, HFC-134a, HFC-134, HFC-23, E-HCFO-1233zd, Z-HCFO-1233zd, and HFOs such as E-HFO-1336mzz and Z-HFO-1336mzz. Any of these may be blended with HFO-1234yf and / or HFO-Z / E-1234ze and used as heat transfer / refrigerant materials. However, fluoroolefins such as HFO-1234yf may oligomerize or homopolymerize in the presence of air during use, storage, and / or under harsh conditions. One solution is to use inhibitors such as terpenes, terpenoids, terpinene, linear unsaturated hydrocarbons, and phenolic compounds, which are disclosed in U.S. Patent Publications Nos. 20210108119 and 20210040368, respectively, each disclosure of which is hereby incorporated by reference in its entirety.Furthermore, ethane, propane, cyclopropane, propylene, butane, butene, isobutane, isobutene, 2-methylbutane, meta-, ortho- or para-xylene, alpha (α)-methylstyrene, 2-methyl-alpha-methylstyrene (α,2-dimethylstyrene), 3-methyl-alpha-methylstyrene (α,3-dimethylstyrene), and 4-methyl-alpha-methylstyrene (α,4-dimethylstyrene), or a mixture of two or more thereof, in an effective amount, generally less than 0.5 weight percent, for example, as disclosed in U.S. Provisional Patent Application No. 63 / 321,118, entitled "HYDROCARBON ADDITIVES FOR 1234YF AND HFC COMPOSITIONS, METHODS FOR THEIR PRODUCTION, STORAGE AND USAGE", filed on March 18, 2022, and U.S. Provisional Patent Application No. 63 / 321,120, entitled "HYDROCARBON ADDITIVES FOR 1234YF COMPOSITION AND METHODS FOR THEIR PRODUCTION, STORAGE AND USAGE", filed on March 18, 2022, also inhibit oligomerization or homopolymerization, and each disclosure is hereby incorporated by reference in its entirety. The inhibitors disclosed in U.S. Patent Publication Nos. 20210108119 and 20210040368 effectively react with oxygen and / or function as chain transfer agents to stop oligomer / polymer chain growth and limit the amount of oligomer / polymer by-products to a maximum of 0.03 weight percent or 300 ppm, or a maximum of 200 ppm, or preferably at most 100 ppm. However, the presence of the inhibitor can further reduce the purity of the refrigerant sent to the refrigerant system. Therefore, desirably, to provide a high-purity HFO and / or HFC-containing composition, oxygen contaminants and moisture, as well as HFO-1234yf and / or HFO-Z / E-1234ze, or other HFOs, HCFOs, HFCs, HCCs, HCFCs, and carbon dioxide (CO. 2Any oligomeric or polymeric inhibitor (sometimes collectively referred to herein as "inhibitor" or "inhibitors") component from , specifically, HFC-32, HFC-125, HFC-134a, HFC-134, HFC-23, HFC-227ea, HFC-152a, E-HCFO-1233zd, Z-HCFO-1233zd, E-HFO-1336mzz and Z-HFO-1336mzz, HFO-1132a, and HFO-Z / E-1132 components, or any other additional refrigerant component, is removed alone or in blend, before or during the filling, blending, regeneration, and packaging of these heat transfer / refrigerant materials.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Summary of the Invention

Means for Solving the Problems

[0005] Disclosed are methods for manufacturing, providing, blending, filling, replacing, and packaging a high-purity fluorolefin-containing composition substantially free of oxygen and containing at least 2,3,3,3-tetrafluoropropene, as well as a high-purity heat transfer / refrigerant composition and feed substantially free of oxygen and containing 2,3,3,3-tetrafluoropropene.

[0006] A method is disclosed herein for reducing the level of oxygen in a fluorolefin-containing composition comprising at least 2,3,3,3-tetrafluoropropene to a level of less than about 10 ppm, or to a level of less than about 5 ppm.

[0007] High purity, substantially oxygen-free 1,3,3,3-tetrafluoropropene ((E / Z)-HFO-1234ze), HFC-32, HFC-125, HFC-134a, HFC-134, HFC-23, E-HCFO-1233zd, Z-HCFO-1233zd, E-HFO-1336mzz and Z-HFO-1336mzz components, compositions and blends, and methods of making, blending and packaging these components, compositions and blends are disclosed herein.

[0008] Disclosed herein are techniques for determining, removing / eliminating, or reducing / minimizing contaminants (such as oxygen, oxidation compounds, and / or oligomer inhibitors, or polymer inhibitors, etc.) present in a fluorolefin-containing composition from a stored heat transfer / refrigerant composition, e.g., a tank, container, or canister filled with at least one HFO component alone or blended with other HFO, HCFO, HFC, HCC, or HCFC components (fresh, recycled, unrecovered, used, or spent).

[0009] Disclosed herein is the analysis of unstabilized neat or oligomer / polymer inhibitor-stabilized HFO, HCFO, HFC, HCC, or HCFC components, compositions, or blends, and optionally carbon dioxide (CO 2comprising ), and contacting the component or composition with a compound capable of effectively reducing the oxygen level of the unstabilized neat, or stabilized HFO, HFCO, HFC, HCC, or HCFC component, composition, or blend that inhibits oligomers / polymers to at most about 10 ppm, preferably at most about 5 ppm, and optionally analyzing the component, composition, and blend substantially free of oxygen, a technique for improving the stability of a high-purity fluoroolefin-containing composition is disclosed. Sources of the component, composition or blend include, but are not limited to, process streams, refrigerant circuits, refrigerant equipment, and storage containers such as tanks, containers or canisters.

[0010] Disclosed herein are high-purity, substantially inhibitor-free, optionally water-free fluoroolefin-containing components, compositions and blends comprising at least 2,3,3,3-tetrafluoropropene, and methods for producing such components, compositions and blends, and methods for using high-purity, substantially inhibitor-free, optionally water-free fluoroolefin-containing components, compositions and blends in refrigerant / heat transfer equipment.

[0011] Also disclosed is a method for producing a high-purity fluoroolefin-containing composition substantially free of water, oligomer / polymer inhibitors, and / or oxygen, and filling the refrigerant equipment with the high-purity fluoroolefin-containing composition substantially free of water, oligomer / polymer inhibitors, and / or oxygen.

[0012] Disclosed herein is also a method of contacting a fluoroolefin-containing composition comprising at least one HFO, HCFO, HFC, HCC and HCFC component with a reducing metal oxide compound capable of removing or eliminating at least one of oxygen and oxidation compounds.

[0013] In this specification, a method is disclosed for contacting a fluorinated olefin-containing composition comprising at least 2,3,3,3-tetrafluoropropene with a compound adapted to remove at least one of oxygen and oxidation compounds without cleaving the C-F bond attached to the double bond of 2,3,3,3-tetrafluoropropene.

[0014] In this specification, a method is disclosed for contacting a fluorinated olefin-containing composition comprising at least 2,3,3,3-tetrafluoropropene with a compound suitable for removing oligomer inhibitors or polymer inhibitors in a stabilized fluorinated olefin-containing composition comprising at least 2,3,3,3-tetrafluoropropene and for eliminating or reducing moisture.

[0015] In this specification, a method is disclosed for blending a substantially oxygen-free fluorinated olefin-containing composition comprising at least 2,3,3,3-tetrafluoropropene with at least one of 1,3,3,3-tetrafluoropropene (HFO-Z / E-1234ze), HFC-32, HFC-125, HFC-134a, HFC-134, HFC-23, HFC-227ea, HFO-Z / E-1132, HFO-1132a, E-HCFO-1233zd, Z-HCFO-1233zd, E-HFO-1336mzz and Z-HFO-1336mzz, which is also substantially oxygen-free.

[0016] In this specification, storage containers, tanks and canisters filled with substantially oxygen-free 2,3,3,3-tetrafluoropropene alone or in combination with at least one additional substantially oxygen-free component selected from 1,3,3,3-tetrafluoropropene (HFO-Z / E-1234ze), HFC-32, HFC-125, HFC-134a, HFC-134, HFC-23, HFC-227ea, HFO-Z / E-1132, HFO-1132a, E-HCFO-1233zd, Z-HCFO-1233zd, E-HFO-1336mzz and Z-HFO-1336mzz are disclosed.

[0017] As used herein, a storage container, tank, and canister filled with substantially oxygen-free 2,3,3,3-tetrafluoropropene alone or in combination with HFO-Z / E-1234ze, optionally containing at least one additional substantially oxygen-free component selected from HFC-32, HFC-125, HFC-134a, HFC-134, HFC-23, HFC-227ea, E-HCFO-1233zd, Z-HCFO-1233zd, E-HFO-1336mzz, and Z-HFO-1336mzz under pressure is disclosed.

[0018] As used herein, a method for preparing and filling a refrigerant facility using a high-purity, substantially water-free, oligomer / polymer inhibitor-free, and oxygen-free fluoroolefin-containing composition is disclosed.

[0019] As used herein, a method for preparing and filling a refrigerant facility using a high-purity, substantially water- and oligomer / polymer inhibitor-free fluoroolefin-containing composition is disclosed.

[0020] As used herein, a method for producing a high-purity fluoroolefin-containing composition is also disclosed by contacting a fluoroolefin composition stabilized with an inhibitor with an absorbent bed for removing the inhibitor and its oxidation products. The inhibitor-free fluoroolefin composition may be used to produce, blend, fill, displace, and package a composition containing a substantially oxygen-free fluoroolefin, such as HFO-1234yf, and filling a refrigerant system, or may be further treated with a reduced metal oxide to reduce or remove oxygen and / or oxidation compounds to form a suitable high-purity fluoroolefin. To ensure that high-purity HFO-1234yf enters the refrigerant facility and / or system, absorbents such as silica gel or mineral oil can be used to remove or wash away inhibitors, especially terpenes, and their oxidation products, and other materials such as molecular sieves, carbon, activated carbon, alumina, and diatomaceous earth may also be used.

[0021] This specification discloses a technique for improving the stability of a high-purity fluoroolefin-containing composition by a process of removing / eliminating or reducing contaminants such as oxygen and oxidation compounds or oligomer inhibitors or polymer inhibitors. The supply of the fluoroolefin-containing composition to be treated includes, but is not limited to, refrigerant equipment, refrigerant circuits, storage containers such as containers, tanks, or canisters filled with at least one high-purity HFO and HCFO alone or in a blend, and then contacting with a reducing metal oxide to reduce or remove the oxygen present in the high-purity fluoroolefin-containing composition.

[0022] This specification discloses a technique for removing / eliminating or reducing contaminants such as oxygen and oxidation compounds or oligomer inhibitors or polymer inhibitors in a fluoroolefin-containing composition collected in a storage container, such as a container, tank, or canister, filled with at least one HFO and HFCO compound alone or in a blend with HFO, HFCO, HFC, HCC, HCFC, and then recycling and / or regenerating.

[0023] This specification discloses a technique for improving the stability of a stabilized fluoroolefin-containing composition by a process of contacting the stabilized fluoroolefin-containing composition, such as HFO-1234yf alone or in combination with HFO-Z / E-1234ze (optionally containing at least one of HFC-125, HFC-134a, HFC-134, HCC-23, HFC-227ea, HFO-Z / E-1132, HFO-1132a, HCFO-Z / E-1233zd, and HFO-Z / E-1336mzz) with a reducing metal oxide for reducing or eliminating oxygen.

[0024] In this specification, a method is disclosed for reducing or eliminating oxygen by contacting a fluorinated olefin-containing composition, such as HFO-1234yf alone or in combination with HFO-Z / E-1234ze, with a reduced metal oxide, and optionally blending the substantially oxygen-free HFO-1234yf or HFO-1234yf / HFO-Z / E-1234ze blend with at least one of HFC-125, HFC-134a, HFC-134, HFC-23, HFC-227ea, HFO-Z / E-1132, HFO-1132a, E-HCFO-1233zd, Z-HCFO-1233zd, E-HFO-1336mzz, and Z-HFO-1336mzz.

[0025] In this specification, (1) a process of contacting a fluorinated olefin-containing composition, such as HFO-1234yf alone or in combination with HFO-Z / E-1234ze, with a reduced metal oxide to reduce or eliminate oxygen and form a substantially oxygen-free stream with HFO-1234yf alone or in combination with HFO-Z / E-1234ze; (2) a process of contacting at least one of HFC-125, HFC-134a, HFC-134, HFC-23, HFC-227ea, E-HCFO-1233zd, Z-HCFO-1233zd, E-HFO-1336mzz, and Z-HFO-1336mzz with a reduced metal oxide to reduce or eliminate oxygen and form a substantially oxygen-free stream of at least one of HFC-125, HFC-134a, HFC-134, HFC-23, HFC-227ea, HCFO-Z / E-1233zd, HFO-Z / E-1132, HFO-1132a, and HFO-Z / E-1336mzz; (3) a process of packaging substantially oxygen-free HFO-1234yf alone and / or with substantially oxygen-free HFO-Z / E-1234ze and / or the blend of (1); or a process of blending (1) and (2) is disclosed.

[0026] In this specification, a technique for improving the stability of a fluoroolefin-containing composition is disclosed by a process of contacting an unstabilized or stabilized feed of HFO-1234yf alone or in combination with at least one of HFC-125, HFC-134a, HFC-134, HFC-23, HCFO-Z / E-1233zd, and HFO-Z / E-1336mzz, which can be from a high-purity or recycled source (a "recycled" refrigerant derived from treating used / spent refrigerant to remove impurities and / or reconstituted to comply with ASHRAE). The feed source includes, but is not limited to, (1) a storage container filled with at least HFO-1234yf and HFO-Z / E-1234ze alone or in combination with at least one of HFC-125, HFC-134a, HFC-134, HFC-23, HFO-Z / E-1132, HFO-1132a, HFO-Z / E-1233zd, and HFO-Z / E-1336mzz, such as a container, tank, or canister, each of which may be from a high-purity or recycled source that is either stabilized with at least one inhibitor that effectively reacts with oxygen and / or acts as a chain transfer agent to stop the oligomer / polymer chain growth of HFO-1234yf or is unstabilized.

[0027] In this specification, a technique for improving the stability of a fluoroolefin-containing composition is disclosed, in which an unstabilized or stabilized feed of HFO-1234yf and HFO-Z / E-1234ze is contacted alone or in combination with at least one of HFC-32, HFC-125, HFC-134a, HFC-134, HFC-23, HFC-227ea, HFO-Z / E-1132, HFO-1132a, HCFO-Z / E-1233zd, and HFO-Z / E-1336mzz (which may be from a high-purity (fresh source) or a recycled source (a "recycled" refrigerant obtained by treating used refrigerant to remove impurities and / or reconstituting it to meet ASHRAE standards)). The feed source includes, but is not limited to, (1) a storage container filled with at least HFO-1234yf and HFO-Z / E-1234ze alone or in combination with at least one of HFC-125, HFC-134a, HFC-134, HFC-23, HCFO-Z / E-1233zd, and HFO-Z / E-1336mzz, such as a container, tank, or canister.

[0028] In this specification, a system and method are disclosed that use an oxygen removal column containing a zero-valent or low-valent transition metal or reduced transition metal oxide that can effectively reduce the oxygen level to about 10 ppm to less than about 0 ppm and all values in between. The transition metals include Cu, Ti, V, Mn, Fe, Co, Zn, Ni, and Pd, and the oxygen removal proceeds without cleavage of the C-F bond of at least the HFO-1234yf fluoroolefin component of the composition for the loading, filling, blending, and packaging of the product.

[0029] In one embodiment, 2,3,3,3-tetrafluoropropene (HFO-1234yf) alone or in combination with (Z / E)-1,1,1,3-tetrafluoropropene (HFO-Z / E-1234ze, R-1234ze or 1234ze) containing 0 to 100 wt% of HFO-1234yf and 0.01 to 99.9 wt% of HFO-Z / E-1234ze is passed through a bed of silica or molecular sieve, carbon, activated carbon, alumina, diatomaceous earth or other suitable material to remove or reduce moisture and any oligomer or polymer inhibitor including, but not limited to, d-limonene and α-terpinene, 2-methylbutane, meta-, ortho- or para-xylene, alpha (α)-methylstyrene, 2-methyl-α-methylstyrene (α,2-dimethylstyrene), 3-methyl-α-methylstyrene (α,3-dimethylstyrene) and 4-methyl-α-methylstyrene (α,4-dimethylstyrene).

[0030] In another embodiment, HFO-1234yf alone or in combination with HFO-Z / E-1234ze optionally containing at least one of HFC-125, HFC-134a, HFC-134, HFC-23, HFC-227ea, HFO-Z / E-1132, HFO-1132a, HCFO-Z / E-1233zd, and HFO-Z / E-1336mzz is passed through a silica bed to remove or reduce moisture and oligomer / polymer inhibitors and then through an oxygen removal column.

[0031] In one embodiment, 2,3,3,3-tetrafluoropropene (HFO-1234yf) alone or in combination with (Z / E)-1,1,1,3-tetrafluoropropene (HFO-Z / E-1234ze, R-1234ze or 1234ze) containing greater than 0 to 100 weight percent of HFO-1234yf and 0.01 to 99.9 weight percent of HFO-Z / E-1234ze is contacted with a reducing metal oxide at ambient temperature in a treatment zone to reduce the oxygen content to about 10 ppm or less, preferably about 5 ppm or less, including all values and ranges between 0 ppm and therebetween.

DETAILED DESCRIPTION OF THE INVENTION

[0032] As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," or any other variations thereof are intended to cover non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises the recited elements is not necessarily limited to only those elements, but may include other elements not expressly recited or inherent to such composition, process, method, article, or apparatus. Further, unless expressly stated to the contrary, "or" refers to an inclusive "or" and not an exclusive "or." For example, the condition A or B is satisfied by any one of the following: namely, 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).

[0033] The transitional phrase "consisting of" excludes any unrecited element, step, or ingredient. In the context of a claim, such a phrase serves to close the claim to the inclusion of materials other than those recited, except for impurities ordinarily associated with the recited materials. When the phrase "consists of" appears in a clause within the body of the claim rather than immediately following the preamble, the phrase limits the claim to only the elements recited within that clause and does not exclude other elements from the claim as a whole.

[0034] The transitional phrase "consisting essentially of" is used to define a composition or method that includes materials, steps, mechanisms, components, or elements, in addition to those literally disclosed, provided that these additionally included materials, steps, mechanisms, components, or elements do not materially affect the basic and novel characteristics of the claimed invention, particularly the mechanism of action for achieving any desired result of the process of the present invention. The term "consisting essentially of" has an intermediate meaning between "comprising" and "consisting of".

[0035] It should be readily understood that where the applicants have defined the invention or a part thereof in terms of non-limiting terms such as "comprising" (unless otherwise specified), the description should be construed as also including inventions using the terms "consisting essentially of" or "consisting of".

[0036] Also, the use of "a" or "an" is employed to describe the elements and components described herein. This is merely for convenience and is for the purpose of giving a general meaning to the scope of the present invention. This description should be construed as including one or at least one, and the singular form also includes the plural form unless it is clear that it has a different meaning. The AHRI 2019 Standard for Specifications for Refrigerants sets the maximum levels of air and non-condensable components, for example, at about 1.5 volume percent at 25 °C for single refrigerants such as R-12, R-13, R-22, R-23, R-32, R-114, R-115, R-116, R-124, R-125, R-134a, R-142b (2 volume %), R-143a, R-152a, R-218, R-227ea, R236fa, R1234yf, and R-1234ze(E), and about 0.315 volume percent, or approximately 3150 ppm, for oxygen (about 21% of air). Despite the AHRI standard, such high oxygen contents can lead to oligomerization / polymerization of HFO-1234yf and other fluoroolefins during storage and use, and the oxygen content can further increase during storage, filling, use, recycling, and reuse.

[0037] The present invention relates to products and methods for producing high-purity HFO-1234yf fluorolefin-containing compositions and blends having an oxygen content of at most 5 ppm, 6 ppm, 7 ppm, 8 ppm, 9 ppm or 10 ppm in order to avoid oligomerization / polymerization of at least the HFO-1234yf component. Oxygen is similarly removed from any additional HFO, HCFO, HFC, HCC, or HCFC components blended with HFO-1234yf and / or HFO-Z / E-1234ze, even if the refrigerant is such that AHRI does not set the non-condensable limit to 1.5 volume percent.

[0038] Oxygen contaminants are removed by contacting the stream of the HFO-1234yf and / or HFO-Z / E-1234ze component, or any additional HFO, HCFO, HFC, HCC, or HCFC components being blended, with a compound that removes oxygen contaminants without cleaving the C-F bond in fluorolefins such as 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0039] Suitable oxygen scavenging reagents for removing or reducing oxygen from fluorolefin-containing mixtures at room temperature, for example 20 °C to 30 °C, include, but are not limited to, zero-valent or low-valent transition metals, and reduced oxides of transition metals (the transition metals are selected from Cu, Ti, V, Mn, Fe, Co, Zn, Ni, and Pd). Zero-valent or low-valent transition metals and reduced oxides of transition metals can be obtained commercially or can be prepared by heating transition metal oxides in a vessel such as a tube or column at elevated temperature (for example, 100 °C to 300 °C) in the presence of a reducing agent such as hydrogen. Suitable metal oxides for such reduction include, for example, CuO, TiO 2 、V 2 O 5 、Mn 2 O 3 、Fe 2 O 3 、Co 3 O 4, ZnO, NiO, PdO, etc. Other deoxidizing reagents include ascorbate, NaHSO 3 , Na 2 SO 3 , Na 2 S 2 O 5 , Na 2 S 2 O 3 , Na 2 S 2 O 4 , polyhydroxybenzene compounds such as pyrogallol; Ti(III) salts, Cr(II) salts, Sn(II) salts, Fe(II) salts; solutions of nitrites and hypophosphites. The removal of oxygen from the fluoroolefin composition can be carried out by passing the fluoroolefin composition through a column or bed of the deoxidizing agent at 20°C to 30°C. In embodiments where oxygen removal is affected by a solution of ascorbate, the treated fluoroolefin-containing composition is preferably dried by passing it through a bed or tube containing a desiccant such as CaSO 4 , CaCl 2 , Na 2 SO 4 , MgSO 4 , silica gel, or molecular sieve.

[0040] Several metals / metal oxides are known as oxygen scavengers, but generally these compounds are very reactive towards fluoroolefins based on the technical literature. The metals / metal oxides present in known oxygen scavengers have been used to cleave the C-F bond to form a more stable metal fluoride bond. Cleavage of the C-F bond in fluoroolefins (C=C-F) is very common. See Ristic-Petrovic, D. et al., Organometallics 2003, 22, 4647-4657, Ahrens, T. et al. Chem. Rev. 2015, 115, 931-972 (each incorporated herein by reference). It was surprising that certain reduced metal oxides of Cu, Ti, V, Mn, Fe, Co, Zn, Ni, and Pd perform the intended function of removing oxygen without cleaving the C-F bond in 2,3,3,3-tetrafluoropropene or other fluoroolefins.

[0041] The metal-fluorine bond (e.g., Cu-F ~431 kJ / mol) is more stable than the metal-oxygen (e.g., Cu-O ~343 kJ / mol) bond, and there is an energy driving force for the reaction of the metal oxide (the product of oxygen capture) with the organic fluorine compound. Thus, it was not expected and not obvious that a material useful for scrubbing oxygen from inert gases (Ar, N 2 )), hydrocarbons, and normal olefins (ethylene, propylene) could remove oxygen contaminants from 2,3,3,3-tetrafluoropropene without significantly degrading the organic fluorine compound.

[0042] Representative additional HFO, HFCO, HFC, HCC, HCFC components include, but are not limited to, those listed in Table 1 below.

[0043]

Table 1-1

[0044]

Table 1-2

[0045] Some of the compounds in Table 1 exist as different configurational isomers or stereoisomers. If no specific isomer is designated, the present invention is intended to include all single configurational isomers, single stereoisomers, single geometric isomers, or any combination of these in any ratio. For example, the name HFO-Z / E-1234ze means it includes the E-HFO-HFO1234ze (HFO-1234ze(E)) isomer, the Z-HFO-1234ze (HFO-1234ze(Z)) isomer, and a mixture of the E and Z isomers of HFO-1234ze.

[0046] One embodiment of the invention disclosed herein involves contacting a fluorolefin-containing feed having an oxygen content of 100 ppm to about 5000 ppm, such as HFO-1234yf and / or HFO-1234ze, with a metal oxide at a temperature sufficient to reduce or remove oxygen without cleaving the C-F bond of HFO-1234yf and recover substantially oxygen-free HFO-1234yf and / or HFO-Z / E-1234ze, for example, at 20°C to 30°C.

[0047] The fluorolefin-containing feed to be treated in the present invention contains one or more hydrofluorocarbon compounds conforming to AHRI standards, and the total amount of air and other non-condensable impurities may promote the oligomerization / polymerization of fluorolefin components such as HFO-1234yf.

[0048] In another embodiment of the invention disclosed herein, substantially oxygen-free HFO-1234yf and / or HFO-Z / E-1234ze are packaged in a storage container under pressure.

[0049] In another embodiment of the invention disclosed herein, substantially oxygen-free HFO-1234yf and / or HFO-Z / E-1234ze is blended with at least one of HFO-1243zf, Z-HFO-1336mzz, E-HFO-1336mzz, HFO-Z / E-1327mz, HCFO-1122, HCFO-Z / E-1122a, HFO-1123, HCFO-Z / E-1233zd, HCFO-Z / E-1224yd, HFO-1132a, and HFO-Z / E-1132, CFO-Z / E-1112, E-HFO-1225ye, Z-HFO-1225ye, HFO-1234zc, HFO-Z / E-1234ye, HFO-1234yc, HFO-1225zc and HFC-152a in which oxygen is reduced or removed.

[0050] The present invention further includes the step of removing stabilizers from a fluoroolefin composition to produce a high-purity HFO-1234yf and / or HFO-Z / E-1234ze composition with any additional HFO, HFCO, HFC, HCC, or HCFC components. U.S. Patent Application Publication No. 2021 / 0108119 and U.S. Patent Application Publication No. 2021 / 0040368 disclose that oligomeric or polymeric inhibitors are added to HFO-1234yf and / or HFO-Z / E-1234ze compositions and blends, each disclosure being incorporated herein by reference in its entirety. These stabilizer compounds effectively react with oxygen and / or function as chain transfer agents to stop the growth of polymer chains of, for example, HFO-1234yf, but their presence further reduces the purity of the refrigerant going to the refrigerant system. To return the stabilized composition to the desired high purity, it is necessary to remove the stabilizer. By contacting the stabilized HFO-1234yf composition with silica or mineral oil, the stabilizer and any moisture that may be present are removed, producing a high-purity HFO-1234yf and / or HFO-1234ze-containing composition.

[0051] In certain embodiments disclosed herein, inhibitor stabilizers that may be added or removed include, but are not limited to, d-limonene and α-terpinene having the following structures:

[0052]

Chem.

[0053] In another embodiment disclosed herein, the inhibition stabilizers include, but are not limited to, α-tocopherol, butylated hydroxytoluene, 4-methoxyphenol, and benzene-1,4-diol.

[0054] In another embodiment disclosed herein, the inhibition stabilizer includes at least two inhibitors, such as, but not limited to, pairs including limonene, pinene, terpinene, ethane, propane, cyclopropane, propylene, butane, butene, isobutane, and isobutene.

[0055] In another embodiment disclosed herein, the inhibition stabilizers include, but are not limited to, limonene and propane, or pinene and propane.

[0056] The additional one or more HFO, HCFO, HFC, HCC, or HCFC components include, but are not limited to, HFO-1243zf, HFO-Z-1336mzz, HFO-E-1336mzz, HFO-Z / E-1327mz, HCFO-1122, HCFO-Z / E-1122a, HFO-1123, HCFO-Z / E-1233zd, HCFO-Z / E-1224yd, HFO-Z / E-1132, HFO-1132a, CFO-Z / E-1112, E-HFO-1225ye, Z-HFO-1225ye, HFO-1234zc, HFO-Z / E-1234ye, HFO-1234yc, HFO-1225zc, and HFC-152a (see Table 1).

[0057] In one embodiment disclosed herein, HFO-1234yf is alone or includes at least one of HFC-32, HFC-125, HFC-134a, and carbon dioxide, and includes one of d-limonene and α-terpinene.

[0058] In another embodiment disclosed herein, HFO-1234yf and HFO-Z / E-1234ze include one of d-limonene and α-terpinene, and optionally at least one of the following additional components: HFO-1243zf, HFO-Z-1336mzz, HFO-E-1336mzz, HFO-Z / E-1327mz, HFO-1122, HFO-Z / E-1122a, HFO-1123, HFO-Z / E-1233zd, HFO-1224yd, HFO-Z / E-1132, HFO-1132a, HCFO-1112, HFO-E-1225ye, HFO-Z-1225ye, HFO-1234zc, HFO-Z / E-1234ye, HFO-1234yc, HFO-1225zc, and HFC-152a.

[0059] Definitions As used herein, a refrigerant is a compound or mixture of compounds in which a fluid undergoes a phase change from a liquid to a gas and functions as a heat transfer fluid in a cycle that returns to its original state.

[0060] As used herein, a cooling circuit may be part of a movable or stationary heat transfer system that is fixed in a predetermined position during operation. A stationary heat transfer system may be located, attached, or associated within a building, or may be a stand-alone device located outdoors, such as a soft drink vending machine. These stationary applications may include, but are not limited to, stationary air conditioning units and heat pumps; chillers; high temperature heat pumps; residential, commercial, or industrial air conditioning systems (including residential heat pumps). In stationary refrigeration applications, the disclosed stabilized or purified compositions or blends may be useful in various items of equipment including: commercial, industrial, or residential refrigerators and freezers; ice makers; built-in coolers and freezers; flooded evaporator chillers; direct expansion chillers; walk-in and reach-in coolers and freezers; combined systems. In some embodiments, the disclosed compositions may be used in a supermarket cooling system. Further, stationary applications may utilize a secondary loop system, where a secondary fluid is cooled by a primary refrigerant and then the secondary fluid is pumped to a remote location to provide a cooling effect.

[0061] A heat transfer medium such as a refrigerant (also referred to herein as a heat transfer fluid, heat transfer composition, heat transfer fluid composition, or refrigerant composition) is a working fluid used to carry heat from a heat source to a heat sink.

[0062] As used herein, the term "lubricant" means any composition or material added to a compressor (and contacting any heat transfer composition in use within any heat transfer system) that provides lubrication to the compressor to assist in preventing component seizure.

[0063] As used herein, a compatibilizer is a compound that improves the solubility of the working fluid of the disclosed composition in a heat transfer system lubricant. In some embodiments, the compatibilizer improves oil return to the compressor. In some embodiments, the composition is used with a system lubricant to reduce the viscosity of the oil-rich phase.

[0064] As used herein, the phrase "substantially inhibitor-free" means an inhibitor content of about 10 ppm or less (including 0 ppm), preferably about 5 ppm or less (including 0 ppm), and all values and ranges therebetween.

[0065] As used herein, the phrase "moisture-free" means a moisture content of about 10 ppm or less (including 0 ppm), preferably about 5 ppm or less (including 0 ppm), and all values and ranges therebetween.

[0066] As used herein, the phrase "oxygen-free" means an oxygen content of about 10 ppm or less (including 0 ppm), preferably about 5 ppm or less (including 0 ppm), and all values and ranges therebetween.

[0067] "Inhibitor" means at least one compound according to the present invention that reduces, if not eliminates, the conversion of hydrofluoroolefins to oligomers or polymers. Oligomerization or homopolymerization reactions can be accelerated by relatively high temperatures, but such reactions can also occur under ambient conditions depending on the concentration and type of initiator (e.g., contaminants). Inhibitors can function as radical inhibitors or chain transfer agents without affecting the refrigeration performance of the composition or its compatibility with refrigerant oils and equipment (e.g., resins used in seals). The stabilized composition can be useful in cooling / heating systems and as an alternative to existing refrigerants with higher global warming potential.

[0068] As used herein, the term "fluoroolefin" describes an unsaturated compound containing carbon atoms, fluorine atoms, and optionally hydrogen atoms. As used herein, the term "chlorofluoroolefin" describes an unsaturated compound containing carbon atoms, chlorine atoms, fluorine atoms, and optionally hydrogen atoms. In one embodiment, the fluoroolefins used in the compositions of the present invention include compounds having 3 to 12 carbon atoms. In another embodiment, the fluoroolefins include compounds having 3 to 10 carbon atoms, and in yet another embodiment, the fluoroolefins include compounds having 3 to 7 carbon atoms.

[0069] As described herein, the phrase "effective amount" refers to the amount of an inhibitor of the present invention that, when added to a composition containing at least one fluoroolefin, prevents oligomerization or polymerization of the fluoroolefin so as not to degrade performance when used, for example, in a cooling device, as compared to a composition without an inhibitor. In the case of a cooling device, such an effective amount of inhibitor can be determined by testing under the conditions of the standard test ASHRAE 97-2007 (RA 2017).

[0070] In one embodiment of the present invention, HFO-1234yf from a storage container that does not contain an inhibitor is first analyzed using known techniques such as GC-MS to determine the composition and optionally the oxygen content. In one embodiment, the oxygen content is generally from about 100 ppm to about 5000 ppm or more. Suitable techniques for analyzing the oxygen content include infrared sensors, UV sensors, NIR sensors, ion mobility or plasma chromatography, gas chromatography, refractive index measurement, mass spectrometry, high temperature thick film sensors, thin film field effect sensors, peristatic sensors, taguchi sensors, and the quartz microbalance sensor disclosed in US Patent Application Publication No. 2008 / 0069177, but are not limited thereto, and the entire disclosure is incorporated herein by reference, particularly from line 42 of column 3 to line 15 of column 8. The HFO-1234yf is then contacted with a reducing metal oxide under ambient conditions to remove or reduce any oxygen present and tested again as described above. For example, substantially oxygen-free HFO-1234yf containing less than about 10 ppm, less than 5 ppm, less than 4 ppm, less than 3 ppm, or preferably less than 2 ppm is repackaged into a storage container as neat HFO-1234yf or blended with other components that have been similarly treated to reduce the oxygen content to less than about 10 ppm, less than 5 ppm, and all values in between.

[0071] In another embodiment of the present invention, an HFO-1234yf composition containing an oligomerization or polymerization inhibitor, including but not limited to limonene, pinene and terpinene, and their oxidation products, is analyzed using optionally known techniques to determine the composition, identify the inhibitor, and optionally determine the oxygen content. Suitable oxygen analyzers include, but are not limited to, infrared sensors, UV sensors, NIR sensors, ion mobility or plasma chromatographs, gas chromatography, refractive index measurement, mass spectrometry, high temperature thick film sensors, thin film field effect sensors, peristaltic sensors, taguchi sensors and quartz crystal microbalance sensors. Thereafter, the composition is contacted with a bed of silica gel to remove the inhibitor and any moisture that may be present. The composition may be retested to confirm that the inhibitor and any moisture have been removed and, if acceptable, may be used as a source of pure HFO-1234yf and then filled into a cooling device. Optionally, once the inhibitor and moisture have been removed, the composition may be further contacted with a reduced metal oxide to reduce or remove any oxygen that may be present and then optionally analyzed again to determine the oxygen content.

[0072] In some aspects, the HFO-1234yf and / or HFO-1234ze feed may include a feed stream or storage container, such as a container, tank, or canister, but is not limited thereto, and other HFO, HCFO, HFC, HCC, HCFC component feeds may similarly include any design of feed stream or storage container suitable for storing HFO, HCFO, HFC, HCC, and HCFC, but is not limited thereto.

[0073] In some aspects of the present invention, substantially oxygen-free HFO-1234yf is blended with HFC-32. Difluoromethane (HFC-32 or R-32) is commercially available or can be produced by methods known in the art, such as dechlorofluorination of methylene chloride. In either case, HFC-32 is treated to have an oxygen content of less than about 10 ppm, preferably less than about 5 ppm.

[0074] In one embodiment, the HFC-32 component of the composition of the present invention comprises HFC-32 having a purity of more than 99% by weight, more than 99.5% by weight, and in some cases more than 99.5 to 99.98% by weight. After contacting with a reduced metal oxide, the oxygen content of the HFC-32 is less than 10 ppm, less than 5 ppm, and all values therebetween.

[0075] In another specific embodiment, the HFC-32 component comprises HFC-32 in excess of 99.99% by weight. After contacting with a metal oxide, the oxygen content of the HFC-32 is 10 ppm or less, 5 ppm or less, and all values therebetween. In one embodiment, the HFC-32 component further comprises at least one additional compound selected from HFC-23 (trifluoromethane), HCFC-31 (chlorofluoromethane), HFC-41 (fluoromethane), HFC-143a (1,1,1-trifluoroethane), HCFC-22 (chlorodifluoromethane), CFC-12 (dichlorodifluoromethane), HCC-40 (chloromethane), and HFC-134a (1,1,1,2-tetrafluoroethane), each of which is treated to have an oxygen content of less than about 10 ppm, less than about 5 ppm, and all values therebetween.

[0076] In a specific embodiment, the inhibitor-containing composition may contain the following: About 31% by weight of HFO-1234yf and about 69% by weight of HFC-32; or About 65% by weight of HFO-1234yf and about 35% by weight of HFC-32; or About 78.5% by weight of HFO-1234yf and about 21.5% by weight of HFC-32.

[0077] In other specific embodiments, the inhibitor-containing composition may contain the following: About 20 to about 40 weight percent of HFO-1234yf; or About 28 to about 32 weight percent of HFO-1234yf; or About 30 to about 32 weight percent of HFO-1234yf; or From about 62 to about 65 weight percent of HFO-1234yf; or From about 76 to about 80 weight percent of HFO-1234yf.

[0078] In one embodiment, HFO-1234yf that does not contain inhibitors and / or moisture contains HFC-134a or HFC-32 in a specific weight ratio. The amount of HFC-134a can range from about 25 to about 75 weight percent, from about 30 to about 60 weight percent, and in some cases from about 30 to about 50 weight percent. The HFO-1234yf blend or composition a. About 14 weight percent of HFC-134a; or b. About 25.7 weight percent of HFC-134a; or c. From about 25 to 45 weight percent of HFC-134a; or d. From about 25 to 44 weight percent of HFC-134a and; or e. About 30 weight percent of HFC-125, about 14 weight percent of HFC-134a; or f. About 36 weight percent of HFC-32 and about 6 weight percent of CO 2 ; or g. From about 28 to about 32 weight percent of HFC-32; or h. From about 68 to about 72 weight percent of HFC-32.

[0079] In some embodiments, other optional components (also referred to herein as "additives") included in the fluoroolefin feeds, components, compositions, blends disclosed herein can include one or more of the components selected from lubricants, dyes (including UV dyes), solubilizers, cosolvents, stabilizers, tracers, perfluoropolyethers, antiwear agents, extreme pressure agents, corrosion and oxidation inhibitors, metal surface energy reducers, metal surface deactivators, free radical scavengers, foam control agents, viscosity index improvers, pour point depressants, detergents, viscosity modifiers, and mixtures thereof. In fact, many of these other optional components can fit into one or more of these classifications and can themselves have qualities that contribute to the achievement of one or more performance characteristics.

[0080] In some embodiments, one or more additives are present in small amounts relative to the overall composition. In some embodiments, the concentration of the additive(s) in the disclosed composition ranges from less than about 0.1 weight percent to up to about 10 weight percent, preferably about 5 weight percent, of the total composition. In some embodiments of the present invention, the additive is present in the disclosed composition in an amount from about 0.1 weight percent to about 3.5 weight percent of the total composition. The additive component(s) selected for the disclosed composition are selected based on utility and / or the requirements of the individual equipment components or systems.

[0081] In some embodiments, the lubricant is a mineral lubricant. In some embodiments, the mineral lubricant is selected from paraffins (such as straight-chain carbon-chain saturated hydrocarbons, branched-chain carbon saturated hydrocarbons, and mixtures thereof), naphthenes (such as saturated cyclic and ring structures), aromatic compounds (containing unsaturated hydrocarbons having one or more rings characterized by alternating carbon-carbon double bonds), and non-hydrocarbons (such as those containing atoms such as sulfur, nitrogen, oxygen, and mixtures thereof), and mixtures and combinations thereof.

[0082] Some embodiments may contain one or more synthetic lubricating oils. In some embodiments, the synthetic lubricating oil is selected from alkyl group-substituted aromatic compounds (such as benzene or naphthalene substituted with straight-chain, branched-chain alkyl groups or mixtures of straight-chain, branched-chain alkyl groups, often referred to as alkylbenzenes), synthetic paraffins and naphthenes, poly(α-olefins), polyglycols (such as polyalkylene glycols), dibasic acid esters, polyesters, neopentyl esters, polyvinyl ethers (PVE), silicones, silicate esters, fluorides, phosphate esters, polycarbonates, and mixtures thereof (meaning mixtures of any of the lubricants disclosed in this chapter).

[0083] The lubricants disclosed in this specification may be commercially available lubricants. For example, the lubricant may be paraffinic mineral oil sold by BVA Oil as BVM100N, naphthenic mineral oil sold by Crompton Co. under the trade names Suniso® 1GS, Suniso® 3GS and Suniso® 5GS, naphthenic mineral oil sold by Pennzoil under the trade name Sontex® 372LT, naphthenic mineral oil sold by Calumet Lubricants under the trade name Calumet® RO-30, linear alkylbenzene sold by Shrieve Chemicals under the trade names Zerol® 75, Zerol® 150 and Zerol® 500, branched alkylbenzene sold by Nippon Oil as HAB22, polyol ester (POE) sold by Castrol, United Kingdom under the trade name Castrol® 100, polyalkylene glycol (PAG) such as RL-488A of Dow (Dow Chemical, Midland, Michigan), and mixtures thereof (meaning any mixture of the lubricants disclosed in this paragraph).

[0084] The lubricant used with the present invention may be designed for use with hydrofluorocarbon refrigerants and may be compatible with the compositions disclosed herein under the operating conditions of compression cooling devices and air conditioning devices. In some embodiments, the lubricant is selected by considering the requirements of a given compressor and the environment to which the lubricant is exposed.

[0085] In the composition of the present invention containing a lubricant, the lubricant is present in an amount of less than 5.0% by weight of the total composition. In other embodiments, the amount of the lubricant is from about 0.1% to 3.5% by weight of the total composition.

[0086] In one embodiment of the present invention, the purity of the refrigerant is increased by treating HFO-1234yf-containing refrigerant from storage supply or an existing system to remove any oligomer inhibitor and at least one of moisture and oxygen, and then filling refrigerant equipment including, but not limited to, commercial, industrial, or household refrigerators and freezers; ice makers; built-in coolers and freezers; flooded evaporator chillers; direct expansion chillers; walk-in and reach-in coolers and freezers; and combined systems. In some embodiments, the disclosed compositions can be used in supermarket cooling systems. Further, stationary applications may utilize a secondary loop system where a secondary fluid is cooled by a primary refrigerant and then pumped to a remote location to provide a cooling effect at the remote location.

[0087] Containers for storing blends of high purity HFO-1234yf and / or HFO-E / Z-1234ze, or at least one additional HFO, HCFO, HFC, HCC, HCFC, and carbon dioxide (CO 2 ) can be constructed of any suitable material and design capable of sealing the composition therein while maintaining a gas phase and a liquid phase. Examples of suitable containers include pressure vessels such as tanks, filled cylinders, and secondary filled cylinders. The container can be constructed from any suitable material such as carbon steel, manganese steel, chrome-molybdenum steel, particularly low alloy steel, stainless steel, and optionally aluminum alloys in some cases. The container may be provided with a perforated top or valve suitable for dispensing flammable substances.

[0088] In certain embodiments of the present invention, (1) the refrigerant facility includes at least one refrigerant circuit filled with substantially oxygen-free HFO-1234yf and / or HFO-Z / E-1234ze, such as HFO-1234yf and HFO-Z / E-1234ze, containing oxygen of less than 10 ppm to 0 ppm, or less than 5 ppm to 0 ppm, and optionally at least one additional component selected from substantially oxygen-free components including HFC-125, HFC-134a, HFC-134, HFC-152a, HFC-23, HCFO-Z / E-1233zd, and HFO-Z / E-1336mzz; (2) the refrigerant facility includes a refrigerant circuit filled with about 0.1 to about 99.9 wt% of HFO-1234yf, containing an oligomer inhibitor of less than 5 ppm to 0 ppm, and optionally at least one additional component including HFC-125, HFC-134a, HFC-134, HFC-152a, HFC-23, HCFO-Z / E-1233zd, and HFO-Z / E-1336mzz, and about 0.1 to about 99.9 wt% of HFO-Z / E-1234ze; (3) the refrigerant facility includes at least one refrigerant facility substantially free of inhibitors and / or moisture and / or oxygen, including at least one refrigerant circuit filled with about 0.1 to about 99.9 wt% of HFO-1234yf and about 0.1 to about 99.9 wt% of HFO-Z / E-1234ze, optionally including at least one additional component of HFC-125, HFC-134a, HFC-134, HFC-152a, HFC-23, HFC-227ea, HCFO-Z / E-1233zd, HFO-Z / E-1132, HFO-1132a, and HFO-Z / E-1336mzz.

[0089] In certain embodiments of the present invention, the storage container is filled with the following: (1) Pressurized substantially oxygen-free HFO-1234yf and / or HFO-Z / E-1234ze, preferably HFO-1234yf and HFO-Z / E-1234ze, containing less than 10 ppm, less than 5 ppm to 0 ppm of oxygen, and all values in between, optionally containing at least one additional substantially oxygen-free component selected from HFC-125, HFC-134a, HFC-134, HFC-152a, HFC-23, HFC-227ea, HCFO-Z / E-1233zd, and HFO-Z / E-1336mzz; (2) About 0.1 to about 99.9% of HFO-1234yf, about 0.1 to about 99.9% of HFO-Z / E-1234ze, oligomer inhibitor less than 5 ppm to 0 ppm, and optionally containing at least one additional component including HFC-125, HFC-134a, HFC-134, HFC-152a, HFC-23, HCFO-Z / E-1233zd, and HFO-Z / E-1336mzz; (3) About 0.1 to about 99.9% of HFO-1234yf, about 0.1 to about 99.9% of HFO-Z / E-1234ze, and optionally containing at least one additional component including HFC-125, HFC-134a, HFC-134, HFC-152a, HFC-23, HFO-Z / E-1132, HFO-1132a, HCFO-Z / E-1233zd, and HFO-Z / E-1336mzz, substantially free of inhibitor and / or moisture and / or oxygen (meaning that the composition contains less than about 10 ppm, preferably less than about 5 ppm of inhibitor and / or moisture and / or oxygen respectively).

[0090] In other embodiments of the present invention, a fluorinated olefin composition substantially free of inhibitor and / or moisture and / or oxygen includes, but is not limited to, air conditioners, refrigerators, freezers, heat pumps, water chillers, flooded evaporator chillers, direct expansion chillers, walk-in coolers, mobile refrigerators, mobile air conditioning units, dehumidifiers, and combinations thereof, and is used for cooling and / or heating in a heat transfer system.

Examples

[0091] (Examples 1 - 4) An Inconel tube (registered trademark) (outer diameter 0.5 inches, length 15 inches, wall thickness 0.34 inches) is filled with 8 cc of CuO (40 wt%) above. The catalyst is reduced in a Lindberg furnace at 175 °C for 8 hours with 50 sccm of H 2 O 3 / N2 (50% H 2 )). After cooling the reactor to room temperature, CF containing different concentrations of air 2 CF=CH 3 (HFO - 1234yf) is supplied at 10 - 20 sccm (standard cubic centimeters per minute). During the course of operation, the air concentration is measured by GC, indicating that the O 2 concentration is less than 5 ppm. 2

[0092]

Table 2

[0093] (Examples 5 - 10) 30 g of HFO - 1234yf containing various concentrations of d - limonene is passed through 20 g of silica gel (200 mesh) or 50 mL of mineral oil. GC indicates that the residual inhibitor content is less than 5 ppm.

[0094]

Table 3

[0095] Other Embodiments Process Embodiment 1 of the present invention is a) contacting a fluorolefin feed containing at least HFO - 1234yf and an oxygen content of up to about 5000 ppm with a reduced metal oxide at a temperature sufficient to reduce or remove oxygen from the fluorolefin feed without cleaving the C - F bond of at least one fluorolefin; ​b) A step of recovering a substantially oxygen-free fluoroolefin product, wherein the metal oxide contains at least one of Cu, Ti, V, Mn, Fe, Co, Zn, Ni, and Pd as the metal and the temperature is room temperature.

[0096] Process Embodiment 2 of the present invention is a) A step of contacting a fluoroolefin feed and an oligomer / polymer inhibitor with one of silica gel and mineral oil at a temperature sufficient to remove the inhibitor; b) A step of recovering a fluoroolefin product substantially free of oligomer / polymer inhibitor.

[0097] In Process Embodiment 2, the fluoroolefin feed has an inhibitor content of 5 wt% or less, and silica gel is used to remove the inhibitor to less than 5 ppm.

[0098] Process Embodiment 2 further includes c) A step of contacting the inhibitor-free fluoroolefin product of step b) with a reducing metal oxide at a temperature sufficient to reduce or remove oxygen without cleaving the C-F bond of the fluoroolefin; d) A step of recovering a substantially oxygen-free and inhibitor-free fluoroolefin feed.

[0099] In Process Embodiments 1 and 2, the temperature is between 20°C and 30°C; or the fluoroolefin feed has an oxygen content of 100 ppm to about 5000 ppm; or the fluoroolefin product has an oxygen content of at most about 5 ppm.

[0100] In Process Embodiments 1 and 2, the temperature is between 20°C and 30°C, the fluoroolefin feed has an oxygen content between 100 ppm and about 5000 ppm, and the fluoroolefin product has an oxygen content of at most about 5 ppm.

[0101] The feed of Process Embodiment 2 is i. HFO-1234yf; or ii. HFO-Z / E-1234ze; or iii. a mixture of HFO-1234yf and HFO-Z / E-1234ze, Process Embodiment 3.

[0102] At least one additional HFO, HCFO, HFC, HCFC, and carbon dioxide (CO 2 ) component is blended with a substantially oxygen-free product, Process Embodiment 1, or 2, or 3.

[0103] The oligomer / polymer inhibitor includes at least one oligomer / polymer inhibitor including at least one of ethane, propane, cyclopropane, propylene, butane, butene, isobutane, isobutene, meta-, ortho-, or para-xylene, alpha (α)-methylstyrene, 2-methyl-alpha-methylstyrene (α,2-dimethylstyrene), 3-methyl-alpha-methylstyrene (α,3-dimethylstyrene), and 4-methyl-alpha-methylstyrene (α,4-dimethylstyrene), and mixtures of two or more of the above inhibitors, Process Embodiment 2 or 3.

[0104] At least one additional component suitable for heat transfer is blended with a substantially oxygen-free product and is selected from at least one of HFC-125, HFC-134a, HFC-134, HFC-227ea, HCC-23, CHFO-1233zd(E / Z), and HFO-ZE-1336mzz, Process Embodiment 1, or 2, or 3.

[0105] At least one additional substantially oxygen-free component is blended with the product, Process Embodiment 1, or 2, or 3.

[0106] Further including determining the oxygen content of at least one fluoroolefin feed, Process Embodiment 1, or 2, or 3.

[0107] The feed is Process Embodiment 1, or 2, or 3, comprising an additional component comprising HFO-Z / E-1225ye; or HFO-Z / E-1225ye and HFC-32; or HFO-Z / E-1225ye and HFC-134a; or HFC 152a, or HFO-Z / E-1225ye, HFC-134a, and HFC-32; or HFO-Z / E-1225ye and HFC-125; or at least one of HCC-40, HCFC-22, CFC-115, HCFC-124, HCFC-1122, and CFC-1113; or FC-125, HFC-134a, HFC-134, HFC-23, HCFO-Z / E-1233zd, and HFO-Z / E-1336mzz.

[0108] Process Embodiment 4 of the present invention comprises the steps of passing a fluoroolefin composition through a column containing a reduced metal oxide, the reduced metal oxide containing at least one of Cu, Ti, V, Mn, Fe, Co, Zn, Ni, and Pd as the metal, the fluoroolefin composition containing any one of HFO-1234yf; HFO-Z / E-1234ze; and a mixture of HFO-1234yf and HFO-Z / E-1234ze; operating the column at ambient temperature to remove oxygen in the fluoroolefin composition without cleaving the C-F bond of the fluoroolefin and / or reducing it to at most 10 ppm, preferably at most 5 ppm; and recovering a fluoroolefin containing less than 10 ppm of oxygen, preferably less than 5 ppm of oxygen.

[0109] Process Embodiment 4 of the present invention uses a fluoroolefin feedstock further containing one or more of HFC-125, HFC-134a, HFC-134, HFC-152a, HFC-23, HCFO-Z / E-1233zd, and HFO-Z / E-1336mzz, and optionally treats it in a reduced metal oxide-containing column operated at ambient temperature to provide substantially oxygen-free HFC-125, HFC-134a, HFC-134, HFC-23, HCFO-Z / E-1233zd, and HFO-Z / E-1336mzz components; and optionally blends with i), or ii), or iii).

[0110] Embodiment 1 of the pressurized supply of the present application provides a pressure-resistant container filled with a refrigerant, which is adapted to dispense a refrigerant containing at least one of substantially oxygen-free HFO-1234yf; substantially oxygen-free HFO-Z / E-1234ze; and a mixture of HFO-1234yf and HFO-Z / E-1234ze containing oxygen of less than 10 ppm to 0 ppm, preferably less than 5 ppm to 0 ppm, and is provided with a pierceable top or valve.

[0111] Embodiment 2 of the pressurized supply of the present application includes the refrigerant of Embodiment 1 of the pressurized supply and an additional refrigerant component containing substantially no oxygen and containing oxygen of less than 10 ppm to 0 ppm, preferably less than 5 ppm to 0 ppm, respectively, of HFC-125, or HFC-134a, or HFC-134, or HFC-23, or HCFO-Z / E-1233zd, or HFO-Z / E-1336mzz.

[0112] Embodiment 1 of the refrigerant facility of the present invention includes at least one refrigerant circuit pressurized with about 0.1 to about 99.9 wt% of HFO-1234yf and about 0.1 to about 99.9 wt% of HFO-Z / E-1234ze containing an oligomer inhibitor of less than 5 ppm to 0 ppm, optionally including at least one additional component selected from HFC-125, HFC-134a, HFC-134, HFC-23, E-HCFO-1233zd, Z-HCFO-1233zd, E-HFO-1336mzz, and Z-HFO-1336mzz.

[0113] Embodiment 2 of the refrigerant facility of the present invention includes at least one refrigerant circuit pressurized with a composition containing about 0.1 to about 99.9 wt% of HFO-Z / E-1234yf and about 0.1 to about 99.9 wt% of HFO-Z / E-1234ze, optionally including at least one additional component selected from HFC-125, HFC-134a, HFC-134, HFC-152a, HFC-23, HCFO-Z / E-1233zd, and HFO-Z / E-1336mzz, and the composition is substantially free of inhibitors and / or moisture and / or oxygen.

[0114] Process Embodiment 5 of the present invention passes a fluoroolefin composition containing at least HFO-1234yf and optionally an oligomer / polymer inhibitor through a) silica gel or mineral oil at a temperature sufficient to remove any inhibitor; and b) a column containing a reducing metal oxide, wherein the metal oxide contains at least one of Cu, Ti, V, Mn, Fe, Co, Zn, Ni, and Pd as the metal, and the column is operated at ambient temperature to remove oxygen and / or reduce it to at most 10 ppm, preferably at most 5 ppm, in the fluoroolefin composition without cleaving the C-F bond of the fluoroolefin; c) recovering HFO-1234yf-containing fluoroolefin containing at least one of less than 10 ppm of oxygen, preferably less than 5 ppm of oxygen, and less than 5 ppm of oligomer inhibitor.

[0115] Packaging Embodiment 1 of the present invention provides a step of packaging the product of Process Embodiment 1, 2, 3, 4, or 5.

[0116] In Process Embodiment 1, 2, 3, 4, or 5, the feed can include unrecovered refrigerant, stored refrigerant, fresh refrigerant, or recycled refrigerant, each having an oxygen content of up to about 5000 ppm.

[0117] Process Embodiment 6 of the present invention includes a step of filling a refrigeration facility with a fluoroolefin substantially free of inhibitor and / or moisture and / or oxygen of Process Embodiment 1, 2, 3, 4, or 5.

[0118] Process Embodiment 7 of the present invention includes a step of cooling or heating using a heat transfer device with a fluoroolefin substantially free of inhibitor and / or moisture and / or oxygen of Process Embodiment 1, 2, 3, 4, or 5.

[0119] The heating and cooling embodiments of the present invention include using a fluorolefin product that does not contain an inhibitor and / or moisture and / or oxygen of Embodiment 1, 2, 3, 4, or 5 in an air conditioner, refrigerator, freezer, heat pump, water chiller, flooded evaporator chiller, direct expansion chiller, walk-in cooling unit, mobile refrigerator, mobile air conditioning unit, dehumidifier, and combinations thereof.

[0120] While certain aspects, embodiments, and principles have been described above, it is understood that this specification is made for illustrative purposes only and is not intended to limit the scope of the present invention or the appended claims. The various aspects, embodiments, and principles described above may be used alone and in combination with each other.

Claims

1. a) contacting a fluorolefin feed containing oxygen and comprising at least one tetrafluoropropene compound with a reduced metal oxide at a temperature sufficient to reduce or remove oxygen from the fluorolefin feed without cleaving the C-F bond of the at least one tetrafluoropropene; b) recovering a fluorolefin product substantially free of oxygen, the product having an oxygen content of at most about 10 ppm oxygen; A process comprising:

2. The process of claim 1, wherein the reduced metal oxide comprises at least one metal selected from the group consisting of Cu, Ti, V, Mn, Fe, Co, Zn, Ni, and Pd.

3. The process of claim 1, wherein the temperature is room temperature.

4. a) contacting an oxygen-containing fluorolefin feed comprising at least one tetrafluoropropene compound and an oligomer / polymer inhibitor with one of silica gel and mineral oil at a temperature sufficient to reduce or remove the oligomer / polymer inhibitor; b) recovering a fluorolefin product substantially free of oligomer / polymer inhibitor having an oligomer / polymer inhibitor content of less than 10 ppm; A process comprising:

5. The process of claim 4, wherein the fluorolefin feed has an inhibitor content of greater than 10 ppm and up to 5 wt%, and silica gel is used to reduce or remove the inhibitor content.

6. The process of claim 4, wherein the inhibitor content is reduced to less than 5 ppm.

7. c) contacting the fluorolefin product of step b) with a reduced metal oxide at a temperature sufficient to reduce or remove oxygen without cleaving the C-F bond of the at least one tetrafluoropropene; d) recovering a fluorolefin product substantially free of oxygen and free of inhibitor having an oxygen content of less than about 10 ppm; The process of claim 4, further comprising:

8. The process according to any one of claims 1 to 7, wherein the temperature is from 20 °C to 30 °C.

9. The process according to any one of claims 1 to 8, wherein the fluorolefin feed has an oxygen content of from 100 ppm to about 5000 ppm.

10. The process according to any one of claims 1 to 9, wherein the fluorolefin product has an oxygen content of at most about 5 ppm oxygen.

11. wherein said at least one tetrafluoropropene is i. HFO-1234yf; ii. HFO-Z / E-1234ze; and iii. a mixture of HFO-1234yf and HFO-Z / E-1234ze, The process according to any one of claims 1 to 10, comprising one of.

12. At least one additional HFO, HCFO, HFC, HCC, HCFC, and carbon dioxide (CO ２ ) component is blended with the fluoroolefin feedstock comprising at least HFO-1234yf, the process according to any one of claims 1 to 11.

13. The oligomer / polymer inhibitor according to claim 4, comprising at least one oligomer / polymer inhibitor comprising at least one material selected from the group consisting of ethane, propane, cyclopropane, propylene, butane, butene, isobutane, isobutene, meta-xylene, ortho-xylene, para-xylene, alpha (α)-methylstyrene, 2-methyl-alpha-methylstyrene (α,2-dimethylstyrene), 3-methyl-alpha-methylstyrene (α,3-dimethylstyrene), and 4-methyl-alpha-methylstyrene (α,4-dimethylstyrene), and mixtures of two or more thereof.

14. The process according to claim 12, wherein said at least one additional component is a component suitable for heat transfer and is selected from the group consisting of HFC-125, HFC-134a, HFC-134, HFC 152a, HCC-23, CHFO-1233zd(E / Z), and HFO-Z / E-1336mzz.

15. c) contacting said at least one additional component with a reduced metal oxide prior to blending to reduce the oxygen concentration to less than 5 ppm to produce an additional component substantially free of oxygen; d) recovering said additional component substantially free of oxygen, The process according to claim 14, further comprising.

16. The process according to claim 14, further comprising blending said substantially oxygen-free fluorolefin product containing at least HFO-1234yf with a substantially oxygen-free additional component.

17. e) further comprising determining the oxygen content of said at least one fluorolefin feed and said additional component, and of the mixture of said substantially oxygen-free fluorolefin product and said additional component, The process according to any one of claims 1 and 15.

18. The process according to claim 17, wherein the oxygen content is determined using a device selected from the group consisting of an infrared sensor, a UV sensor, a NIR sensor, ion mobility or plasma chromatography, gas chromatography, refractive index measurement, mass spectrometry, a high temperature thick film sensor, a thin film field effect sensor, and a peristatic sensor.

19. The fluoroolefin feedstock is a) HFO-Z / E-1225ye; b) HFO-Z / E-1225ye and HFC-32; c) HFO-Z / E-1225ye and HFC-134a; d) HFO-Z / E-1225ye, HFC-134a, and HFC-32; e) HFO-Z / E-1225ye and HFC-125; f) HFO-Z / E-1225ye and HFC-152a; g) at least one of HCC-40, HCFC-22, CFC-115, HCFC-124, HCFC-1122, and CFC-1113; h) HFC-125, HFC-134a, HFC-134, HFC 152a, HFC-23, HCFO-Z / E-1233zd, and HFO-Z / E-1336mzz; and i) at least one of HFC-125, HFC-134a, HFC-134, HFC 152a, HFC-23, and HFO-1225zc, HCFO-Z / E-1233zd, and HFO-Z / E-1336mzz The process according to any one of claims 1 and 4, comprising an additional component selected from the group consisting of

20. The process according to claim 2, wherein the contacting step reduces the oxygen concentration to 5 ppm or less (including 0).

21. a) a step of passing a fluoroolefin composition through a column containing a reduced metal oxide, wherein the reduced metal oxide contains at least one of Cu, Ti, V, Mn, Fe, Co, Zn, Ni, and Pd as a metal, and the fluoroolefin composition is i. HFO-1234yf; ii. HFO-Z / E-1234ze; and iii. a mixture of HFO-1234yf and HFO-Z / E-1234ze, wherein the step comprises any one of the above; b) operating the column at ambient temperature to remove oxygen in the fluoroolefin composition and / or reduce it to at most 10 ppm, preferably at most 5 ppm, without cleavage of the C-F bond of the fluoroolefin. c) a step of recovering a fluoroolefin containing less than 10 ppm, preferably less than 5 ppm of oxygen; A method comprising.

22. The method according to claim 21, wherein the fluoroolefin composition passing through the column further comprises at least one additional component selected from the group consisting of FC-125, HFC-134a, HFC-134, HFC 152a, HFC-23, HCFO-Z / E-1233zd, and HFO-Z / E-1336mzz.

23. The method according to claim 22, wherein the at least one additional component is present in an amount of up to 1% by weight.

24. The method according to claim 22, wherein the at least one additional component is present in an amount of up to 0.5% by weight.

25. a) Treating at least one additional component containing one of HFC-125, HFC-134a, HFC-134, HFC-152a, HFC-23, HCFO-Z / E-1233zd, and HFO-Z / E-1336mzz with a reducing metal oxide-containing column operated at ambient temperature to provide substantially oxygen-free HFC-125, HFC-134a, HFC-134, HFC-23, HFC-152a, HCFO-Z / E-1233zd, and HFO-Z / E-1336mzz components, wherein the oxygen content of the components is about 10 ppm or less; b) Blending one of (i) to (iii) with the at least one of the substantially oxygen-free HFC-125, HFC-134a, HFC-134, HFC 152a, HFC-23, HCFO-Z / E-1233zd, and HFO-Z / E-1336mzz components; The process according to claim 10, further comprising.

26. A pressure-resistant container filled with a refrigerant, comprising a perforable upper part or valve adapted to dispense the refrigerant, wherein the refrigerant comprises at least one of substantially oxygen-free HFO-1234yf; HFO-Z / E-1234ze; a mixture of HFO-1234yf and HFO-Z / E-1234ze containing oxygen of less than 5 ppm to 0 ppm.

27. The pressure-resistant container according to claim 26, further comprising at least one substantially oxygen-free component selected from HFC-125, HFC-134a, HFC-134, HFC-152a, HFC-23, HCFO-Z / E-1233zd, and HFO-Z / E-1336mzz.

28. At least one refrigerant circuit pressurized with: substantially oxygen-free HFO-1234yf, optionally containing at least one additional component selected from HFC-125, HFC-134a, HFC-134, HFC-23, HCFO-Z / E-1233zd, and HFO-Z / E-1336mzz; HFO-Z / E-1234ze; and a mixture of HFO-1234yf and HFO-Z / E-1234ze containing less than 5 ppm to 0 ppm of oxygen.

29. At least one refrigerant circuit pressurized with: about 0.1 to about 99.9 wt% of HFO-1234yf, optionally containing at least one additional component selected from HFC-125, HFC-134a, HFC-134, HFC-23, E-HCFO-1233zd, Z-HCFO-1233zd, E-HFO-1336mzz, and Z-HFO-1336mzz; and about 0.1 to about 99.9 wt% of HFO-Z / E-1234ze containing less than 5 ppm to 0 ppm of an oligomer inhibitor.

30. At least one refrigerant circuit pressurized with: about 0.1 to about 99.9 wt% of HFO-Z / E-1234yf, optionally containing at least one additional component selected from HFC 152a, HFC-125, HFC-134a, HFC-134, HFC-23, HCFO-Z / E-1233zd, and HFO-Z / E-1336mzz, substantially free of inhibitors, and / or substantially free of moisture, and / or substantially free of oxygen; and about 0.1 to about 99.9 wt% of HFO-Z / E-1234ze.

31. At least HFO-1234yf, and optionally (1) an oligomer / polymer inhibitor and / or (2) a fluorinated olefin composition containing oxygen, a) silica gel or mineral oil at a temperature sufficient to remove said inhibitor; b) A column containing a reducing metal oxide, wherein the metal oxide contains at least one of Cu, Ti, V, Mn, Fe, Co, Zn, Ni, and Pd as the metal, and the column is operated at ambient temperature to remove oxygen in the fluoroolefin composition and / or reduce it to at most 10 ppm, preferably at most 5 ppm, without cleaving the C-F bond of the fluoroolefin, said column, a step of passing through any one of; c) a step of recovering an HFO-1234yf-containing fluoroolefin containing at least one of oxygen less than 10 ppm, preferably less than 5 ppm, and an oligomer inhibitor less than 5 ppm, A method comprising.

32. The method according to claim 31, wherein the fluoroolefin composition comprises at least HFO-1234yf and HFO-Z / E-1234ze.

33. The method according to claim 32, wherein the fluoroolefin composition comprises from about 0.1 to about 99.9% by weight of HFO-1234yf and from about 0.1 to about 99.9% by weight of HFO-Z / E-1234ze.

34. Contacting at least one additional component selected from HFC-125, HFC-134a, HFC-134, HFC-152a, HFC-23, HCFO-Z / E-1233zd, and HFO-Z / E-1336mzz with a column containing a reducing metal oxide operated at ambient temperature to provide substantially oxygen-free HFC-125, HFC-134a, HFC-134, HFC-152a, HFC-23, HCFO-Z / E-1233zd, and HFO-Z / E-1336mzz components, and blending the substantially oxygen-free HFC-125, HFC-134a, HFC-134, HFC-23, HCFO-Z / E-1233zd, and HFO-Z / E-1336mzz additional components with the HFO-1234yf-containing fluoroolefin containing at least one of oxygen less than 10 ppm, preferably less than 5 ppm, and an oligomer inhibitor less than 5 ppm, The method according to claim 31.

35. The method according to claim 31, further comprising a step of packaging the blend according to claim 31.

36. The method according to claim 31, further comprising a step of packaging the composition according to claim 32 or claim 33.

37. The method according to claim 31, further comprising the step of packaging the blend according to claim 34.

38. The method according to any one of claims 32 to 34, further comprising the step of filling at least one of a pressure tank, a canister or a container.

39. The process according to any one of claim 1, claim 11, claim 15, claim 19, claim 21, claim 25 or claim 31, wherein one of the feed and the fluoroolefin composition contains an unrecovered refrigerant.

40. The process according to any one of claim 1, claim 11, claim 15, claim 19, claim 21, claim 25 or claim 31, wherein one of the feed and the fluoroolefin composition contains a stored refrigerant.

41. The process according to any one of claim 1, claim 11, claim 15, claim 19, claim 21, claim 25 or claim 31, wherein one of the feed and the fluoroolefin composition contains a fresh refrigerant.

42. The process according to any one of claim 1, claim 11, claim 15, claim 19, claim 21, claim 25 or claim 31, wherein one of the feed and the fluoroolefin composition contains a recycled refrigerant.

43. A process comprising: a) contacting an unrecovered fluoroolefin feed containing at least one tetrafluoropropene compound with a reduced metal oxide at a temperature sufficient to reduce or remove oxygen from the fluoroolefin feed without cleaving the C-F bond of the at least one tetrafluoropropene; b) recovering a substantially oxygen-free fluoroolefin product. The process comprising.

44. The unrecovered tetrafluoropropene feed is HFO-1234yf, HFO-Z / E-1234ze, and a mixture of HFO-1234yf and HFO-Z / E-1234ze. The process according to claim 41, wherein the process contains any one of the above.

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