High purity fluoroolefin composition and impurity removal method

Abstract

The present invention relates to a process for producing, blending, charging, replacing and packaging fluorine-containing olefin compositions free of oxygen and oxidizing components and / or free of oligomer inhibitors and / or moisture.

Description

Background Art

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority under 35 U.S.C. 119(e) to U.S. Provisional Patent Application No. 63 / 344,859, filed on May 23, 2022, entitled “HIGH PURITY FLUOROOLEFIN COMPOSITIONS–IMPURITY REMOVAL,” the entire contents of which are hereby incorporated by reference. Technical Field

[0003] The present invention relates to high purity HFO and / or HFC containing components and blends substantially free of oxygen or oxidizing components (with or without oligomeric or polymeric inhibitors), and methods of producing, blending, charging, replacing and packaging the same. Background Art

[0005] Tetrafluoropropenes, such as HFO-1234yf and HFO-1234ze, are stable molecules under refrigeration use conditions, such as HFC-125, HFC-134a, HFC-134, HFC-23, HCFOs such as E-HCFO-1233zd, Z-HCFO-1233zd, and HFOs such as E-HFO-1336mzz and Z-HFO-1336mzz, any of which can be blended with HFO-1234yf and / or HFO-Z / E-1234ze and used as heat transfer / refrigerant materials. However, fluoroolefins such as HFO-1234yf can oligomerize or homopolymerize during use, during storage, and / or in the presence of air under harsh conditions. One solution is to use inhibitors such as terpenes, terpenoids, terpinenes, linear unsaturated hydrocarbons, and phenolic compounds, as disclosed in each of U.S. Patent Publication Nos. US20210108119 and US20210040368, the disclosures of each of which are hereby incorporated by reference in their entirety. In addition, ethane, propane, cyclopropane, propylene, butane, butene, isobutane, isobutylene, 2-methylbutane, m-xylene, o-xylene or p-xylene, (α)-methylstyrene, 2-methyl-α-methylstyrene (α,2-dimethylstyrene), 3-methyl-α-methylstyrene (α,3-dimethylstyrene) and 4-methyl-α-methylstyrene (α,4-dimethylstyrene) or a mixture of two or more thereof, in an effective amount, generally less than 0.5 wt%, also inhibits oligomerization or homopolymerization, as described, for example, in a patent application filed on March 18, 2022, entitled “HYDROCARBON ADDITIVES FOR 1234YF AND HFC COMPOSITIONS, METHODS FOR THEIR PRODUCTION, STORAGE AND USE”. The present invention is disclosed in U.S. Provisional Application No. 63 / 321118, entitled “HYDROCARBON ADDITIVES FOR 1234YF COMPOSITION AND METHODS FOR THEIR PRODUCTION, STORAGE AND USAGE”, and U.S. Provisional Application No. 63 / 321120, filed on March 18, 2022, entitled “HYDROCARBON ADDITIVES FOR 1234YF COMPOSITION AND METHODS FOR THEIR PRODUCTION, STORAGE AND USAGE”, the disclosures of each of which are hereby incorporated by reference in their entirety.The inhibitors disclosed in U.S. Patent Publication Nos. US20210108119 and US20210040368 effectively react with oxygen and / or act as chain transfer agents to terminate oligomer / polymer chain growth and limit the amount of oligomer / polymer byproducts to at most 0.03 wt % or 300 ppm, or at most 200 ppm, or preferably at most 100 ppm. However, the presence of inhibitors may also reduce the purity of the refrigerant entering the refrigerant system. Therefore, it is desirable to remove oxygen contaminants and moisture before or during loading, blending, recycling and packaging of these heat transfer / refrigerant materials, as well as from HFO-1234yf and / or HFO-Z / E-1234ze, or other HFO, HCFO, HFC, HCC, HCFC and carbon dioxide (CO2) components, 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, any oligomeric or polymeric inhibitors of HFO-1132a and HFO-Z / E-1132 components (sometimes collectively referred to herein as "inhibitors" or "inhibitors"), or any other additional refrigerant components (alone or in blends) to provide high purity HFO and / or HFC-containing compositions. Summary of the invention

[0006] Disclosed herein are high purity, substantially oxygen-free fluoroolefin-containing compositions comprising at least 2,3,3,3-tetrafluoropropene, and methods of producing, providing, blending, charging, replacing, and packaging the high purity, substantially oxygen-free 2,3,3,3-tetrafluoropropene-containing heat transfer / refrigerant compositions and feeds.

[0007] Disclosed herein are methods for reducing the oxygen level in a composition of fluoroolefins comprising at least 2,3,3,3-tetrafluoropropene to a level below about 10 ppm, or to a level below about 5 ppm.

[0008] Disclosed herein are 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 producing, blending and packaging the same.

[0009] Disclosed herein are techniques for determining, removing / eliminating, or reducing / minimizing contaminants (e.g., oxygen, oxidizing compounds, and / or oligomer inhibitors or polymer inhibitors) present in compositions of fluoroolefins from stored heat transfer / refrigerant compositions (e.g., tanks, containers, or tanks filled with at least one HFO component, either alone or blended with other HFO, HCFO, HFC, HCC, or HCFC components, whether fresh, recovered, or unrecovered / used / spent).

[0010] Disclosed herein are techniques for improving the stability of compositions containing high purity fluoroolefins by analyzing an unstabilized pure or oligomer / polymer-inhibited stabilized HFO, HCFO, HFC, HCC or HCFC component, composition or blend, optionally containing carbon dioxide (CO2), contacting the component or composition with a compound that is effective to reduce the oxygen level of the unstabilized pure or oligomer / polymer-inhibited stabilized HFO, HFCO, HFC, HCC or HCFC component, composition or blend to at most about 10 ppm, preferably at most about 5 ppm, and optionally analyzing the substantially oxygen-free component, composition and blend. Sources of the component, composition or blend include, but are not limited to, process streams, refrigerant circuits and equipment, and storage vessels such as tanks, containers or boxes.

[0011] Disclosed herein are high purity, substantially inhibitor-free, and optionally moisture-free fluoroolefin-containing components, compositions, and blends comprising at least 2,3,3,3-tetrafluoropropene, and methods of producing such components, compositions, and blends, and methods of using the high purity, substantially inhibitor-free, and optionally moisture-free fluoroolefin-containing components, compositions, and blends in refrigerant / heat transfer equipment.

[0012] Also disclosed are compositions containing high purity, substantially moisture-free, oligomer / polymer inhibitor-free and / or oxygen-free fluoroolefins, and methods for producing and charging refrigerant equipment using the compositions containing the high purity, substantially moisture-free, oligomer / polymer inhibitor-free and / or oxygen-free fluoroolefins.

[0013] Also disclosed herein is 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 an oxidizing compound.

[0014] Disclosed herein are methods of contacting a composition of fluorinated olefins comprising at least 2,3,3,3-tetrafluoropropene with a compound suitable for removing at least one of oxygen and an oxidizing compound without cleaving the CF bonds connected to the double bonds of the 2,3,3,3-tetrafluoropropene.

[0015] Disclosed herein are methods for contacting a fluoroolefin-containing composition comprising at least 2,3,3,3-tetrafluoropropene with a compound useful for removing oligomer inhibitors or polymer inhibitors, and eliminating or reducing moisture in a stabilized fluoroolefin-containing composition comprising at least 2,3,3,3-tetrafluoropropene.

[0016] Disclosed herein is a process for blending a substantially oxygen-free fluoroolefin-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.

[0017] Disclosed herein are storage vessels, tanks, and boxes 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 the group consisting 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.

[0018] Disclosed herein are storage vessels, tanks and boxes filled under pressure 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 the group consisting of 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.

[0019] Disclosed herein are methods for preparing and charging refrigerant equipment using compositions containing high purity, substantially moisture-free, oligomer / polymer inhibitor-free, and oxygen-free fluoroolefins.

[0020] Disclosed herein are methods of preparing and charging refrigerant equipment using compositions containing high purity, substantially moisture-free, and oligomer / polymer inhibitor-free fluoroolefins.

[0021] Also disclosed herein is a method for producing a composition containing high purity fluoroolefins by contacting an inhibitor-stabilized fluoroolefin composition with an absorbent bed to remove the inhibitors and their oxidation products. The inhibitor-free fluoroolefin composition can be loaded into a refrigerant system or further treated with a reducing metal oxide to reduce or remove oxygen and / or oxidation compounds to form a high purity fluoroolefin suitable for production, blending, charging, replacement and packaging of compositions containing substantially oxygen-free fluoroolefins such as HFO-1234yf. Absorbents such as silica gel or mineral oil can be used to remove or wash inhibitors, especially terpenes, and their oxidation products to ensure high purity HFO-1234yf enters the refrigerant equipment and / or system, and other materials such as molecular sieves, carbon, activated carbon, alumina, diatomaceous earth can be used.

[0022] Disclosed herein is a technique for improving the stability of high purity fluoroolefin-containing compositions by removing / eliminating or reducing contaminants (e.g., oxygen and oxidizing compounds or oligomer inhibitors or polymer inhibitors). The supply source of the fluoroolefin-containing composition to be treated includes, but is not limited to, refrigerant equipment, refrigerant circuits, storage vessels (e.g., containers, tanks, or tanks) filled with at least one high purity HFO and HCFO, either alone or in a blend, which is subsequently contacted with a reducing metal oxide to reduce or eliminate oxygen present in the high purity fluoroolefin-containing composition.

[0023] Disclosed herein are techniques for removing / eliminating or reducing contaminants (e.g., oxygen and oxidation compounds or oligomer inhibitors or polymer inhibitors) in compositions containing fluoroolefins collected in storage vessels (e.g., containers, tanks, tanks) filled with at least one HFO and HFCO compound, either alone or blended with HFO, HFCO, HFC, HCC, HCFC to be recycled and / or recovered.

[0024] Disclosed herein is a technique for improving the stability of a stabilized fluoroolefin-containing composition (e.g., 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) by contacting the composition with a reducing metal oxide to reduce or eliminate oxygen.

[0025] Disclosed herein are methods for contacting a composition of fluorinated olefins (e.g., HFO-1234yf alone or in combination with HFO-Z / E-1234ze) with a reducing metal oxide to reduce or eliminate oxygen, and optionally blending the substantially oxygen-free HFO-1234yf or HFO-1234yf / -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.

[0026] Disclosed herein are methods for: (1) contacting a composition of fluoroolefins (e.g., HFO-1234yf, alone or in combination with HFO-Z / E-1234ze) with a reducing metal oxide to reduce or eliminate oxygen and form a substantially oxygen-free stream of HFO-1234yf, alone or in combination with HFO-Z / E-1234ze; (2) 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; A 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 that is contacted with a reducing metal oxide to reduce or eliminate oxygen and form substantially oxygen-free HFO-1234yf alone and / or a blend of substantially oxygen-free HFO-1234yf with substantially oxygen-free HFO-Z / E-1234ze and / or (1); or a blend of (1) and (2).

[0027] Disclosed herein are techniques for improving the stability of compositions of fluoroolefins by contacting an unstabilized or stabilized supply of HFO-1234yf, which may be from a high purity or recycled source ("recycled" refrigerant, which results from processing spent / used refrigerant to remove impurities and / or reconstituted to comply with ASHRAE), either 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. The source includes, but is not limited to, a storage vessel (e.g., container, tank or tank) filled with (1) 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, which HFO-1234yf and HFO-Z / E-1234ze may be from a high purity or recycled source, each stabilized or unstabilized, having at least one inhibitor effective to react with oxygen and / or act as a chain transfer agent to terminate oligomeric / polymer chain growth of HFO-1234yf.

[0028] Disclosed herein is a technique for improving the stability of compositions of fluoroolefins by contacting an unstabilized or stabilized supply of HFO-1234yf and HFO-Z / E-1234ze (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 HFO-1234yf and HFO-Z / E-1234ze supply may be from a high purity (fresh source) or recycled source ("recycled" refrigerant, which results from processing spent refrigerant to remove impurities and / or reconstituted to comply with ASHRAE). The source includes, but is not limited to, a storage vessel, such as a container, tank or box, filled with (1) 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.

[0029] Disclosed herein are systems and methods for using a deoxygenation tower containing a 0 or low valent transition metal or reduced transition metal oxide that is effective to reduce oxygen levels to below about 10 ppm to about 0 ppm, and all values ​​therebetween. The transition metals include Cu, Ti, V, Mn, Fe, Co, Zn, Ni, and Pd, and the oxygen removal is performed without cleavage of the C-F bonds of at least the HFO-1234yf fluoroolefin component of the composition for loading, charging, blending, and packaging of the product.

[0030] In one embodiment, 2,3,3,3-tetrafluoropropene (HFO-1234yf) (containing 0 wt % to 100 wt % HFO-1234yf and 0.01 wt % to 99.9 wt % HFO-Z / E-1234ze), alone or in combination with (Z / E)-1,1,1,3-tetrafluoropropene (HFO-Z / E-1234ze, R-1234ze, or 1234ze), is passed through silica or other suitable material such as a deionized water column. The invention also provides a bed of methyl styrene (methyl styrene, ...

[0031] 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 a deaerator.

[0032] In one embodiment, 2,3,3,3-tetrafluoropropene (HFO-1234yf) (containing from greater than 0 wt % to 100 wt % HFO-1234yf and from 0.01 wt % to 99.9 wt % HFO-Z / E-1234ze), alone or in combination with (Z / E)-1,1,1,3-tetrafluoropropene (HFO-Z / E-1234ze, R-1234ze or 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 to about 5 ppm or less, including to 0 ppm and all values ​​and ranges therebetween. DETAILED DESCRIPTION

[0033] As used herein, the terms "comprises," "including," "having," or any other variation thereof, are intended to encompass non-exclusive inclusions. For example, a composition, process, method, article, or apparatus that includes a list of elements need not be limited to only those elements, but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus. In addition, unless expressly indicated to the contrary, "or" refers to an inclusive or and not an exclusive or. For example, a condition A or B satisfies one of the following conditions: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), and both A and B are true (or exist).

[0034] The transitional phrase "consisting of" excludes any unspecified elements, steps, or ingredients. If in a claim, protection is not included for materials other than those recited, except for impurities normally associated therewith. When the phrase "consisting of" appears in a clause in the body of a claim, rather than immediately following the preamble, it limits only the elements recited in that clause; other elements are not excluded from the claim as a whole.

[0035] The transitional phrase "consisting essentially of" is used to define a composition or method that includes materials, steps, features, components, or elements in addition to those disclosed in the document, provided that these additionally included materials, steps, features, components, or elements significantly affect the basic and novel characteristics of the claimed invention, especially the mode of action to achieve any of the desired results of the method of the invention. The term "consisting essentially of" occupies an intermediate position between "comprising" and "consisting of."

[0036] Where the applicant has defined an invention or a portion thereof using open-ended terms such as “comprising,” it should be readily understood that (unless otherwise indicated) the description should be interpreted as also including such inventions using the terms “consisting essentially of” or “consisting of.”

[0037] In addition, the use of "a" or "an" is used to describe elements and components described herein. This is for convenience only and to give a general sense of the scope of the invention. The description should be understood to include one or at least one, and the singular also includes the plural, unless it is obvious that there is another meaning. The AHRI 2019 standard for refrigerant specifications sets maximum contents of air and non-condensable components for single refrigerants (e.g., 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)), e.g., about 1.5 volume % at 25°C, equivalent to about 0.315 volume % of oxygen (about 21% of air), or about 3150 ppm. Such high oxygen content leads to oligomerization / polymerization of HFO-1234yf and other fluoroolefins during storage and use, despite AHRI standards, wherein the oxygen content may also increase during storage, charging, use, recycling and reuse.

[0038] The present invention relates to products and processes for producing compositions and blends containing high purity HFO-1234yf fluoroolefins wherein the oxygen content is at most 5 ppm, 6 ppm, 7 ppm, 8 ppm, 9 ppm or 10 ppm 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 to be blended with HFO-1234yf and / or HFO-Z / E-1234ze, even those refrigerants where the AHRI does not set the non-condensable limit at 1.5 volume percent.

[0039] Oxygen contaminants are removed by contacting the HFO-1234yf and / or HFO-Z / E-1234ze components to be blended, or the stream of any additional HFO, HCFO, HFC, HCC or HCFC components, with a compound that removes oxygen contaminants without cleaving the C-F bonds in fluoroolefins such as 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0040] Deoxygenation agents suitable for removing or reducing oxygen from a mixture of fluorinated olefins at room temperature (e.g., 20° C. to 30° C.) include, but are not limited to, oxides of 0-valent or low-valent transition metals, and reduced transition metals, wherein the transition metal is selected from the group consisting of Cu, Ti, V, Mn, Fe, Co, Zn, Ni, and Pd. Oxides of 0-valent or low-valent transition metals and reduced transition metals are commercially available or can be prepared by heating transition metal oxides in a vessel (such as a tube or a tower) at elevated temperatures (e.g., 100° C. to 300° C.) in the presence of a reducing agent such as hydrogen. Examples of metal oxides suitable for reduction in this manner include CuO, TiO2, V2O5, Mn2O3, Fe2O3, Co3O4, ZnO, NiO, and PdO. Other deoxygenation agents include solutions of ascorbate, NaHSO3, Na2SO3, Na2S2O5, Na2S2O3, Na2S2O4, polyhydroxybenzene compounds such as pyrogallol; Ti(III) salts, Cr(II) salts, Sn(II) salts, Fe(II) salts; nitrites and hypophosphites. Oxygen removal from the fluoroolefin composition may be performed by passing the fluoroolefin composition through a tower or bed of deoxygenation agents at 20°C to 30°C. In embodiments where oxygen removal is effected by a solution of ascorbate, the treated fluoroolefin-containing composition is preferably dried by passing through a bed or tube containing a desiccant such as CaSO4, CaCl2, Na2SO4, MgSO4, silica gel, or molecular sieves.

[0041] Although some metals / metal oxides are known as oxygen scavengers, based on the technical literature, these compounds are generally very reactive towards fluoroolefins. The metals / metal oxides present in known oxygen scavengers have been used to cleave C-F bonds to form more stable metal fluoride bonds. Cleavage of C-F bonds in fluoroolefins (C=CF) 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 by reference. Surprisingly, certain reduced metal oxides of Cu, Ti, V, Mn, Fe, Co, Zn, Ni and Pd perform the intended oxygen removal function but do not cleave C-F bonds in 2,3,3,3-tetrafluoropropene or other fluoroolefins.

[0042] Metal-fluorine bonds (e.g., Cu-F about 431 kJ / mol) are more stable than metal-oxygen (e.g., Cu-O about 343 kJ / mol) bonds, so there is an energetic driving force for the reaction of the metal oxide (the product of oxygen scavenging) with the organofluorine compound. Therefore, it is unexpected and non-obvious that materials used to scrub oxygen from inert gases (Ar, N2), hydrocarbons, and conventional olefins (ethylene, propylene) can remove oxygen contaminants from 2,3,3,3-tetrafluoropropene without significant degradation of the organofluorine compound.

[0043] Representative additional HFO, HFCO, HFC, HCC, HCFC components include, but are not limited to, those listed in Table 1 below.

[0044] Table 1

[0045] Some of the compounds in Table 1 exist as different configurational isomers or stereoisomers. Where a specific isomer is not specified, the present invention is intended to include all single configurational isomers, single stereoisomers, single geometric forms, or any combination thereof in any proportion. For example, the name HFO-Z / E-1234ze is intended to include E-HFO-HFO1234ze (HFO-1234ze (E)) isomers, Z-HFO-1234ze (HFO-1234ze (Z)) isomers, and mixtures of E and Z isomers of HFO-1234ze.

[0046]

[0047]

[0048] One embodiment of the invention disclosed herein involves contacting a feed of fluorinated olefins (e.g., HFO-1234yf and / or HFO-1234ze) having an oxygen content of 100 ppm to about 5000 ppm with a metal oxide at a temperature sufficient to reduce or remove oxygen without cleaving the C-F bonds of HFO-1234yf (e.g., 20° C. to 30° C.), and recovering HFO-1234yf and / or HFO-Z / E-1234ze that is substantially free of oxygen.

[0049] The fluoroolefin-containing feedstock treated in the present invention comprises one or more hydrofluorocarbon compounds meeting the AHRI standard, wherein the total amount of air and other non-condensable impurities may promote oligomerization / polymerization of the fluoroolefin component, such as HFO-1234yf.

[0050] In another embodiment of the invention disclosed herein, the substantially oxygen-free HFO-1234yf and / or HFO-Z / E-1234ze is packaged under pressure in a storage vessel.

[0051] In another embodiment of the invention disclosed herein, substantially oxygen-free HFO-1234yf and / or HFO-Z / E-1234ze are mixed with HFO-1243zf, Z-HFO-1336mzz, E-HFO-1336mzz, HFO-Z / E-1327mz, HCFO-1122, HCFO-Z / E-1122a, HFO-1123, HCFO-Z / E-1233 zd, HCFO-Z / E-1224yd, HFO-1132a and at least one of 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 has been reduced or removed).

[0052] The present invention also relates to removing stabilizers from fluoroolefin compositions to produce high-purity HFO-1234yf and / or HFO-Z / E-1234ze compositions, as well as any additional HFO, HFCO, HFC, HCC or HCFC components. U.S. Patent Publication Nos. US2021 / 0108119 and US2021 / 0040368 disclose the addition of oligomer or polymer inhibitors to HFO-1234yf and / or HFO-Z / E-1234ze compositions and blends, and the disclosures of each of these patents are hereby incorporated herein by reference in their entirety. Although these stabilizer compounds effectively react with oxygen and / or act as chain transfer agents to terminate polymer chain growth such as HFO-1234yf, their presence also reduces the purity of the refrigerant entering the refrigerant system. In order to restore the stabilized composition to the desired high purity, it is necessary to remove the stabilizer. Contacting the stabilized HFO-1234yf composition with silica or mineral oil removes the stabilizer, as well as any water that may be present, and produces a composition containing high purity HFO-1234yf and / or HFO-1234ze.

[0053] In certain embodiments disclosed herein, the inhibitory stabilizers that are added or removed include, but are not limited to, d-limonene and alpha-terpinene having the following structures:

[0054]

[0055] In another embodiment disclosed herein, the inhibitory stabilizers include, but are not limited to, alpha-tocopherol, butylated hydroxytoluene, 4-methoxyphenol, and benzene-1,4-diol.

[0056] In another embodiment disclosed herein, the inhibitory stabilizer includes at least two inhibitors, such as in pairs, including but not limited to limonene, pinene, terpinene, ethane, propane, cyclopropane, propylene, butane, butene, isobutane and isobutylene.

[0057] In another embodiment disclosed herein, the inhibitory stabilizer includes, but is not limited to, limonene and propane, or pinene and propane.

[0058] 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).

[0059] In one embodiment disclosed herein, HFO-1234yf alone or including at least one of HFC-32, HFC-125, HFC-134a, and carbon dioxide includes one of d-limonene and alpha-terpinene.

[0060] In another embodiment disclosed herein, HFO-1234yf and HFO-Z / E-1234ze include one of d-limonene and alpha-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-1 122a, HFO-1123, HFO-Z / E-1233zd, HFO-1224yd, HFO-Z / E-1132, HFO-1132a, HCFO-1112, HF O-E-1225ye, HFO-Z-1225ye, HFO-1234zc, HFO-Z / E-1234ye, HFO-1234yc, HFO-1225zc and HFC 152a.

[0061] definition

[0062] As used herein, a refrigerant is a compound or mixture of compounds used as a heat transfer fluid in a cycle wherein the fluid undergoes a phase change from liquid to gas and back to liquid.

[0063] As used herein, a refrigeration circuit can be part of a mobile or fixed heat transfer system that is fixed in place during operation. A fixed heat transfer system can be located within, attached to, or otherwise associated with a building or any free-standing device located outside a door (such as a soft drink vending machine). These fixed applications may include, but are not limited to, fixed air conditioning units and heat pumps; refrigerators; high temperature heat pumps; and residential, commercial, or industrial air conditioning systems (including residential heat pumps). In fixed refrigeration applications, the disclosed stabilized or purified compositions or blends can be used in a variety of equipment, including commercial, industrial, or residential refrigerators and freezers; ice machines; self-contained coolers and freezers; flooded evaporator refrigerators; direct expansion refrigerators; walk-in and reach-in coolers and freezers; and combined systems. In some embodiments, the disclosed compositions can be used in supermarket refrigeration systems. Additionally, fixed applications can utilize a secondary loop system in which a secondary fluid is cooled by a primary refrigerant, and the secondary fluid is then pumped to a remote location to provide a cooling effect at the remote location.

[0064] A heat transfer medium, such as a refrigerant (also referred to herein as a heat transfer fluid, heat transfer composition, or heat transfer fluid composition or refrigerant composition) is a working fluid used to carry heat from a heat source to a heat sink.

[0065] As used herein, the term "lubricant" means any material added to a composition or compressor (and in contact with any heat transfer composition used within any heat transfer system) that provides lubricity to the compressor to help prevent parts from seizing.

[0066] 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 the oil return of the compressor. In some embodiments, the composition is used with a system lubricant to reduce the viscosity of the oil-rich phase.

[0067] As used herein, the phrase "substantially free of inhibitors" means that the inhibitor content is about 10 ppm or less, including 0 ppm, preferably about 5 ppm or less, including 0 ppm, and all values ​​and ranges therebetween.

[0068] As used herein, the phrase "free of moisture" 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.

[0069] As used herein, the phrase "oxygen-free" means that the oxygen content is about 10 ppm or less, including 0 ppm, preferably about 5 ppm or less, including 0 ppm, and all values ​​and ranges therebetween.

[0070] By "inhibitor" is meant at least one compound according to the invention which reduces, if not eliminates, the conversion of hydrofluoroolefins to oligomers or polymers. Although oligomerization or homopolymerization reactions can be accelerated by relatively high temperatures, such reactions can also occur under ambient conditions, depending on the concentration and type of initiator (e.g., contaminant). The inhibitor can act as a free radical inhibitor or chain transfer agent and does not affect the refrigeration performance or compatibility of the composition with refrigerant oils and equipment (e.g., resins used in seals). The stabilized composition can be used in cooling / heating systems and as a replacement for existing refrigerants with higher global warming potential.

[0071] As used herein, the term fluoroolefins describes unsaturated compounds comprising carbon atoms, fluorine atoms and optional hydrogen atoms. As used herein, the term chlorofluoroolefins describes unsaturated compounds comprising carbon atoms, chlorine atoms, fluorine atoms and optional 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.

[0072] As used herein, the phrase "effective amount" refers to an amount of an inhibitor of the present invention that, when added to a composition comprising at least one fluoroolefin, prevents oligomerization or polymerization of the fluoroolefin and does not degrade performance, for example, when used in a cooling device, compared to a composition without the inhibitor. For cooling devices, such an effective amount of the inhibitor can be determined by testing under the conditions of standard test ASHRAE 97-2007 (RA 2017).

[0073] In one embodiment of the invention, HFO-1234yf from a storage vessel without any inhibitors is first analyzed using known techniques such as GC-MS to determine the composition and optional oxygen content. In one embodiment, the oxygen content is generally from about 100 ppm to about 5000 ppm or more. Suitable techniques for analyzing oxygen content include, but are not limited to, infrared sensors, UV sensors, NIR sensors, ion migration or plasma chromatography, gas chromatography, refractometers, mass spectrometers, high temperature thick film sensors, thin film field effect sensors, Pellistor sensors, Taguchi sensors, and quartz microbalance sensors as disclosed in U.S. Patent Application Publication No. 2008 / 0069177 (the entire disclosure of which is incorporated herein by reference, particularly from column 3, line 42 to column 8, line 15). The HFO-1234yf is then contacted with a reducing metal oxide under ambient conditions to remove or reduce any oxygen present, and is again tested as described above. The substantially oxygen-free HFO-1234yf, for example, 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 in storage vessels as pure 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 ​​therebetween.

[0074] In another embodiment of the present invention, HFO-1234yf compositions containing oligomerization or polymerization inhibitors (including but not limited to limonene, pinene and terpinene and their oxidation products) are optionally analyzed using known techniques to determine the composition of the ingredients, as well as the identification of the inhibitors, and optionally determine the oxygen content. Suitable oxygen analyzers include but are not limited to infrared sensors, UV sensors, NIR sensors, ion migration or plasma chromatography, gas chromatography, refractometers, mass spectrometers, high temperature thick film sensors, thin film field effect sensors, Pellistor sensors, Taguchi sensors and quartz microbalance sensors. Thereafter, the composition contacts a bed of silica gel, which removes the inhibitors and any moisture that may be present. The composition can be tested again to verify that the inhibitors and any moisture have been removed, and if acceptable, used as a source of pure HFO-1234yf, which can then be loaded into refrigeration equipment. Optionally, once the inhibitors and moisture have been removed, the composition can be further contacted with a reducing metal oxide to reduce or remove any oxygen that may be present, and then optionally analyzed again to determine the oxygen content.

[0075] In certain embodiments, sources of HFO-1234yf and / or HFO-1234ze supply include, but are not limited to, feed streams or storage vessels, such as containers, tanks, or tanks, and sources of other HFO, HCFO, HFC, HCC, HCFC components may similarly include, but are not limited to, feed streams or storage vessels of any design suitable for storing HFO, HCFO, HFC, HCC, and HCFC.

[0076] In certain embodiments of the present invention, substantially oxygen-free HFO-1234yf and HFC-32 are blended. Difluoromethane (HFC-32 or R-32) is commercially available or can be prepared by methods known in the art, such as by dechlorofluorination of dichloromethane. In either case, HFC-32 will be treated to have an oxygen content of less than about 10 ppm, preferably less than about 5 ppm.

[0077] In one embodiment, the HFC-32 component of the composition of the present invention comprises HFC-32 having a purity of greater than 99 weight percent, greater than 99.5 weight percent, and in some cases greater than 99.5 weight percent to 99.98 weight percent, and after contacting the reducing metal oxide, the oxygen content of the HFC-32 is less than 10 ppm, less than 5 ppm, and all values ​​therebetween.

[0078] In another specific embodiment, the HFC-32 component includes greater than 99.99% by weight HFC-32, and after contacting the metal oxide, the oxygen content of the HFC-32 will be 10 ppm or less, 5 ppm or less, and all values ​​therebetween. In one embodiment, the HFC-32 component also includes at least one additional compound selected from the group consisting of 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), and each is treated to have an oxygen content of less than about 10 ppm, less than about 5 ppm, and all values ​​therebetween.

[0079] In a specific embodiment, the inhibitor-containing composition may contain:

[0080] about 31 weight percent HFO-1234yf and about 69 weight percent HFC-32; or

[0081] About 65 weight percent HFO-1234yf and about 35 weight percent HFC-32; or

[0082] About 78.5 wt % HFO-1234yf and about 21.5 wt % HFC-32.

[0083] In another embodiment, the inhibitor-containing composition may contain:

[0084] from about 20 wt % to about 40 wt % HFO-1234yf; or

[0085] from about 28 wt % to about 32 wt % HFO-1234yf; or

[0086] from about 30 wt % to about 32 wt % HFO-1234yf; or

[0087] From about 62 wt % to about 65 wt % HFO-1234yf; or

[0088] From about 76 wt % to about 80 wt % HFO-1234yf.

[0089] In one embodiment, the inhibitor and / or moisture-free HFO-1234yf includes a specific weight ratio of HFC-134a or HFC-32. The amount of HFC-134a can range from about 25 wt % to about 75 wt %, from about 30 wt % to about 60 wt %, and in some cases from about 30 wt % to about 50 wt %. The HFO-1234yf blend or composition includes,

[0090] a. about 14 wt% HFC-134a; or

[0091] b. about 25.7 wt % HFC-134a; or

[0092] c. about 25 wt % to 45 wt % HFC-134a; or

[0093] d. about 25 wt % to 44 wt % HFC-134a; or

[0094] e. about 30 wt % HFC-125, about 14 wt % HFC-134a; or

[0095] f. about 36 wt% HFC-32, and about 6 wt% CO2; or

[0096] g. from about 28 wt % to about 32 wt % HFC-32; or

[0097] h. About 68 to 72 weight percent HFC-32.

[0098] In some embodiments, the optional other components (also referred to herein as additives) included in the fluoroolefin feeds, components, compositions, or blends disclosed herein may include one or more components selected from the group consisting of lubricants, dyes (including UV dyes), solubilizers, compatibilizers, stabilizers, tracers, perfluoropolyethers, antiwear agents, extreme pressure agents, corrosion and oxidation inhibitors, metal surface energy reducing agents, 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 optional other components fit into one or more of these categories and may have qualities that enable them to achieve one or more performance characteristics themselves.

[0099] In some embodiments, one or more additives are present in a relatively small amount relative to the overall composition. In some embodiments, the amount of additive concentration in the disclosed composition is less than about 0.1 % by weight of the total composition to as much as about 10 % by weight, preferably about 5 % by weight of the total composition. In some embodiments of the present invention, additive is present in the disclosed composition with an amount between about 0.1 % by weight to about 3.5 % by weight of the total composition. The additive component selected for the disclosed composition is selected based on practicality and / or each equipment component or system requirements.

[0100] In some embodiments, the lubricant is a mineral oil lubricant. In some embodiments, the mineral oil lubricant is selected from the group consisting of: paraffins (including straight carbon chain saturated hydrocarbons, branched carbon chain saturated hydrocarbons, and mixtures thereof), cycloalkanes (including saturated cyclic and ring structures), aromatics (those having unsaturated hydrocarbons containing one or more rings, wherein one or more rings are characterized by alternating carbon-carbon double bonds) and non-hydrocarbons (those molecules containing atoms such as sulfur, nitrogen, oxygen, and mixtures thereof), and mixtures and combinations thereof.

[0101] Some embodiments may contain one or more synthetic lubricants. In some embodiments, the synthetic lubricant is selected from: alkyl substituted aromatics (such as benzene or naphthalene substituted with linear, branched, or a mixture of linear and branched alkyl groups, generally referred to as alkylbenzenes), synthetic paraffins and cycloalkanes, poly (alpha olefins), polyethylene glycols (including polyalkylene glycols), dibasic acid esters, polyesters, neopentyl esters, polyvinyl ethers (PVE), silicones, silicate esters, fluorinated compounds, phosphate esters, polycarbonates, and mixtures thereof, meaning mixtures of any of the lubricants disclosed in this paragraph.

[0102] The lubricant disclosed herein may be a commercially available lubricant. For example, the lubricant may be a paraffinic mineral oil sold by BVA Oils as BVM 100N; 1GS, 3GS and Cycloparaffinic mineral oil sold by 5GS; marketed by Pennzoil under the trademark 372LT, a naphthenic mineral oil sold by Calumet Lubricants under the trademark RO-30 is a naphthenic mineral oil sold by Shrieve Chemicals under the trademark 75. 150 and 500; and branched alkylbenzenes sold by Nippon Oil as HAB 22; and by Castrol in the United Kingdom under the trademark 100 sold as polyol esters (POE); polyalkylene glycols (PAGs) such as RL-488A available from Dow (Dow Chemical, Midland, Michigan, USA), and mixtures thereof, meaning mixtures of any lubricant disclosed in this paragraph.

[0103] Lubricants for use in the present invention can be designed for use with hydrofluorocarbon refrigerants and are miscible with the compositions disclosed herein under compression refrigeration and air conditioning equipment operating conditions. In some embodiments, the lubricant is selected by considering the given compressor requirements and the environment to which the lubricant will be exposed.

[0104] In compositions of the present invention that include a lubricant, the lubricant is present in an amount of less than 5.0 wt % relative to the total composition. In other embodiments, the amount of lubricant is from about 0.1 wt % to 3.5 wt % of the total composition.

[0105] In one embodiment of the invention, a refrigerant containing HFO-1234yf from a storage supply or existing system is treated to improve the purity of the refrigerant by removing any oligomer inhibitors and at least one of moisture and oxygen, and then loaded into refrigerant equipment, including but not limited to commercial, industrial or residential refrigerators and freezers; ice machines; self-contained coolers and freezers; flooded evaporator refrigerators; direct expansion refrigerators; walk-in and reach-in coolers and freezers; and combination systems. In some embodiments, the disclosed compositions can be used in supermarket refrigeration systems. Additionally, stationary applications can utilize a secondary loop system in which a secondary fluid is cooled by a primary refrigerant, and the secondary fluid is then pumped to a remote location to provide a cooling effect at the remote location.

[0106] Containers for storing high purity HFO-1234yf and / or HFO-E / Z-1234ze, or blends with at least one additional HFO, HCFO, HFC, HCC, HCFC, and carbon dioxide (CO2) may be constructed of any suitable material and design capable of sealing the composition therein while maintaining both the gas phase and the liquid phase. Examples of suitable containers include pressure vessels such as cans, filling cylinders, and secondary filling cylinders. The container may be constructed of any suitable material such as carbon steel, manganese steel, chromium-molybdenum steel, and other low alloy steels, stainless steel, and in some cases aluminum alloys. The container may include a pierceable top or valve suitable for dispensing flammable substances.

[0107] In certain embodiments of the present invention, (1) the refrigerant equipment includes at least one refrigerant filled with HFO-1234yf and / or HFO-Z / E-1234ze that is substantially free of oxygen (e.g., containing less than 10 ppm to 0 ppm of oxygen, or less than 5 ppm to 0 ppm of oxygen, optionally containing at least one selected from the group consisting of HFC-125, HFC-134a, HFC-134, HFC 152a, HFC-23, HCFO-Z / E-1233zd and HFO-Z / E-1336mzz) of additional components of substantially oxygen-free components; (2) the refrigerant equipment includes a refrigerant circuit filled with about 0.1 wt % to about 99.9 wt % of HFO-1234yf and about 0.1 wt % to about 99.9 wt % of HFO-Z / E-1234ze, which contains less than 5 ppm to 0 ppm of oligomer inhibitors, optionally comprising at least one component including HFC-125, HFC-134a, HFC-134, HFC % to about 99.9 wt % of HFO-1234yf and about 0.1 wt % to about 99.9 wt % of HFO-Z / E-1234ze, optionally containing at least one additional component including 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, and being substantially free of inhibitors and / or moisture and / or oxygen.

[0108] In certain embodiments of the present invention, the storage vessel is filled with (1) pressurized HFO-1234yf and / or HFO-Z / E-1234ze that is substantially free of oxygen, preferably HFO-1234yf and HFO-Z / E-1234ze containing less than 10 ppm, less than 5 ppm to 0 ppm and all values ​​therebetween, optionally comprising at least one selected from the group consisting of HFC-125, HFC-134a, HFC-134, HFC (2) from about 0.1% to about 99.9% HFO-1234yf and from about 0.1% to about 99.9% HFO-Z / E-1234ze (with less than 5 ppm to 0 ppm oligomer inhibitor), optionally containing at least one additional component comprising HFC-125, HFC-134a, HFC-134 ... 152a, HFC-23, HFO-Z / E-1132, HFO-1132a, HCFO-Z / E-1233zd and HFO-Z / E-1336mzz: and (3) from about 0.1% to about 99.9% HFO-1234yf and from about 0.1% to about 99.9% HFO-Z / E-1234ze, optionally comprising at least one additional component, the additional component comprising 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, and being substantially free of inhibitors and / or moisture and / or oxygen means that the composition contains less than about 10 ppm, preferably less than about 5 ppm, of inhibitors and / or moisture and / or oxygen, respectively.

[0109] In other embodiments of the invention, the substantially inhibitor-free and / or moisture-free and / or oxygen-free fluoroolefin compositions are used for cooling and / or heating in heat transfer systems including, but not limited to, air conditioners, freezers, refrigerators, heat pumps, water-cooled chillers, flooded evaporator refrigerators, direct expansion refrigerators, walk-in coolers, mobile refrigerators, mobile air conditioning units, dehumidifiers, and combinations thereof.

[0110] Example

[0111] Example 1 to Example 4

[0112] To Inconel The reactor was filled with 8cc of CuO on Al2O3 (40 wt%) in a (0.5 inch OD, 15 inch long, 0.34 wall thickness). The catalyst was cooled to 175°C with 50 sccm H2 / N2 (50% H2) in a Lindberg furnace for 8 hours. After the reactor was cooled to room temperature, CF3CF=CH2 (HFO-1234yf) containing air at different concentrations was fed at 10 sccm to 20 sccm (standard cubic centimeters per minute). During the run, the air concentration was measured by GC and showed that the O2 concentration was less than 5 ppm.

[0113]

[0114] Example 5 to Example 10

[0115] 30 g HFO-1234yf containing various concentrations of d-limonene was passed through 20 g silica gel (200 mesh) or 50 mL mineral oil. GC showed that the residual inhibitor content was less than 5 ppm.

[0116]

[0117] Other Implementations

[0118] Method embodiment 1 of the present invention comprises:

[0119] a) contacting a fluoroolefin feed containing at least HFO-1234yf and an oxygen content of up to about 5000 ppm with a reducing metal oxide at a temperature sufficient to reduce or remove oxygen from the fluoroolefin feed without cleaving the C-F bonds of at least one fluoroolefin; and

[0120] b) recovering a substantially oxygen-free fluoroolefin product, wherein the metal oxide comprises as the metal at least one of the following: Cu, Ti, V, Mn, Fe, Co, Zn, Ni and Pd,

[0121] And the temperature is room temperature.

[0122] Method embodiment 2 of the present invention comprises:

[0123] a) 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; and

[0124] b) recovering a fluoroolefin product substantially free of oligomer / polymer inhibitors.

[0125] In process embodiment 2, the fluoroolefin feed has an inhibitor content of up to 5 wt %, and silica gel is used to remove the inhibitor to less than 5 ppm.

[0126] Method embodiment 2 also includes,

[0127] c) 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 bonds of the fluoroolefin; and

[0128] d) recovering a fluoroolefin feed substantially free of oxygen and free of inhibitors.

[0129] Process Embodiments 1 and 2 wherein the temperature is from 20°C to 30°C; or the fluoroolefin feed has an oxygen content of from 100 ppm to about 5000 ppm; or the fluoroolefin product has an oxygen content of up to about 5 ppm oxygen.

[0130] Process Embodiments 1 and 2 wherein the temperature is from 20°C to 30°C, the fluoroolefin feed has an oxygen content of from 100 ppm to about 5000 pp, and the fluoroolefin product has an oxygen content of up to about 5 ppm oxygen.

[0131] Process embodiment 3, wherein the feed of process embodiment 2 comprises:

[0132] i. HFO-1234yf; or

[0133] ii.HFO-Z / E-1234ze; or

[0134] iii. A mixture of HFO-1234yf and HFO-Z / E-1234ze.

[0135] Process Embodiment 1 or 2 or 3 wherein at least one additional HFO, HCFO, HFC, HCFC and carbon dioxide (CO2) component is blended with the substantially oxygen-free product.

[0136] Method embodiment 2 or 3, wherein the oligomer / polymer inhibitor includes at least one oligomer / polymer inhibitor, which includes at least one of ethane, propane, cyclopropane, propylene, butane, butene, isobutane, isobutylene, meta-xylene, o-xylene or para-xylene, (α)-methylstyrene, 2-methyl-α-methylstyrene (α, 2-dimethylstyrene), 3-methyl-α-methylstyrene (α, 3-dimethylstyrene) and 4-methyl-α-methylstyrene (α, 4-dimethylstyrene) and a mixture of two or more of the inhibitors.

[0137] Process Embodiment 1 or 2 or 3 wherein at least one additional component suitable for heat transfer is blended with the substantially oxygen-free product and is at least one selected from the group consisting of HFC-125, HFC-134a, HFC-134, HFC-227ea, HCC-23, CHFO-1233zd(E / Z) and HFO-ZE-1336mzz.

[0138] Process Embodiment 1 or 2 or 3 wherein at least one additional substantially oxygen-free component is blended with the product.

[0139] Process Embodiment 1, 2 or 3, further comprising determining the oxygen content of the at least one fluoroolefin feed.

[0140] Process Embodiment 1, 2 or 3, wherein the feed comprises additional components, the additional components comprising:

[0141] 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 HCC-40,

[0142] At least one of 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.

[0143] Process embodiment 4 of the present invention provides a process comprising: passing a fluoroolefin composition through a tower containing a reduced metal oxide, wherein the reduced metal oxide comprises as a metal at least one of the following: Cu, Ti, V, Mn, Fe, Co, Zn, Ni and Pd, the fluoroolefin composition comprising one of the following: HFO-1234yf; HFO-Z / E-1234ze; and a mixture of HFO-1234yf and HFO-Z / E-1234ze; operating the tower at ambient temperature to remove and / or reduce the oxygen in the fluoroolefin composition to at most 10 ppm, preferably at most 5 ppm, without cleaving the CF bonds of the fluoroolefin; and, recovering the fluoroolefin containing less than 10 ppm of oxygen, preferably less than 5 ppm of oxygen.

[0144] Process embodiment 4 of the present invention utilizes a fluoroolefin feed 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, which is optionally treated using a tower containing a reducing metal oxide operating at ambient temperature to provide HFC-125, HFC-134a, HFC-134, HFC-23, HCFO-Z / E-1233zd and HFO-Z / E-1336mzz components that are substantially free of oxygen; and optionally blended with i) or ii) or iii).

[0145] Pressurized supply source embodiment 1 of the present application provides a pressure container filled with a refrigerant, which includes a pierceable top or valve suitable for dispensing the refrigerant, and the refrigerant comprises at least one of the following: HFO-1234yf substantially free of oxygen; HFO-Z / E-1234ze substantially free of oxygen; and a mixture of HFO-1234yf and HFO-Z / E-1234ze containing less than 10 ppm to 0 ppm of oxygen, preferably less than 5 ppm to 0 ppm of oxygen.

[0146] The pressurized supply source embodiment 2 of the present application comprises the refrigerant of the pressurized supply source embodiment 1 and an additional refrigerant component, which additional refrigerant component is substantially free of oxygen and comprises HFC-125, or HFC-134a, or HFC-134, or HFC-23, or HCFO-Z / E-1233zd, or HFO-Z / E-1336mzz, each containing less than 10 ppm to 0 ppm of oxygen, preferably less than 5 ppm to 0 ppm of oxygen.

[0147] Refrigerant equipment embodiment 1 of the present invention comprises at least one refrigerant circuit pressurized with 0.1 wt % to about 99.9 wt % HFO-1234yf and about 0.1 wt % to about 99.9 wt % HFO-Z / E-1234ze, the refrigerant circuit containing less than 5 ppm to 0 ppm of oligomer inhibitor, optionally comprising at least one additional component selected from the group consisting of HFC-125, HFC-134a, HFC-134, HFC-23, E-HCFO-1233zd, Z-HCFO-1233zd, E-HFO-1336mzz and Z-HFO-1336mzz.

[0148] Refrigerant equipment embodiment 2 of the present invention comprises at least one refrigerant circuit pressurized with a composition comprising from about 0.1 wt % to about 99.9 wt % HFO-Z / E-1234yf and from about 0.1 wt % to about 99.9 wt % HFO-Z / E-1234ze, optionally comprising at least one additional component selected from the group consisting of 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.

[0149] Process embodiment 5 of the present invention provides a process comprising: passing a fluoroolefin composition containing at least HFO-1234yf and optionally an oligomer / polymer inhibitor through one of the following:

[0150] a) silica gel or mineral oil at a temperature sufficient to remove any inhibitors; and

[0151] b) a column containing a reducing metal oxide, wherein the metal oxide comprises as metal at least one of the following: Cu, Ti, V, Mn, Fe, Co, Zn, Ni and Pd, and operating the column at ambient temperature to remove and / or reduce oxygen in the fluoroolefin composition to at most 10 ppm, preferably at most 5 ppm, without cleaving the C-F bonds of the fluoroolefin, and

[0152] c) recovering a fluoroolefin comprising HFO-1234yf, the fluoroolefin containing less than 10 ppm oxygen, preferably less than 5 ppm oxygen and less than 5 ppm of at least one of an oligomer inhibitor.

[0153] Packaging embodiment 1 of the present invention provides packaging of the product of method embodiment 1, 2, 3, 4 or 5.

[0154] Process Embodiments 1, 2, 3, 4 or 5, wherein the feed comprises unrecovered refrigerant, stored refrigerant, fresh refrigerant or recycled refrigerant, each of which may have an oxygen content of up to about 5000 ppm.

[0155] Process embodiment 6 of the present invention comprises adding the substantially inhibitor-free and / or moisture-free and / or oxygen-free fluoroolefin of process embodiment 1, 2, 3, 4 or 5 to a refrigerant plant.

[0156] Process embodiment 7 of the present invention comprises using a heat transfer apparatus with a substantially inhibitor-free and / or moisture-free and / or oxygen-free fluoroolefin of process embodiment 1, 2, 3, 4 or 5 for cooling or heating.

[0157] Heating and cooling embodiments of the present invention include using the inhibitor-free and / or moisture-free and / or oxygen-free fluoroolefin product of Embodiment 1, 2, 3, 4 or 5 in air conditioners, freezers, refrigerators, heat pumps, water-cooled chillers, flooded evaporator refrigerators, direct expansion refrigerators, walk-in coolers, mobile refrigerators, mobile air conditioning units, dehumidifiers, and combinations thereof.

[0158] Although certain aspects, embodiments and principles have been described above, it should be understood that this description is exemplary only and not limiting of the present invention or the appended claims. The aforementioned various aspects, embodiments and principles can be used alone or in combination with each other.

Claims

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

2. The method 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. The method according to claim 1 , wherein the temperature is room temperature.

4. A method comprising: a) contacting an oxyfluoroolefin feed comprising at least one tetrafluoropropylene 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; and b) recovering a fluoroolefin product substantially free of oligomer / polymer inhibitors, said product having an oligomer / polymer inhibitor content of less than 10 ppm.

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

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

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

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

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

10. The process of any one of claims 1 to 9, wherein the fluoroolefin product has an oxygen content of up to about 5 ppm oxygen.

11. The method according to any one of claims 1 to 10, wherein the at least one tetrafluoropropylene comprises one of the following: i.HFO-1234yf; ii. HFO-Z / E-1234ze; and iii. A mixture of HFO-1234yf and HFO-Z / E-1234ze.

12. The process according to any one of claims 1 to 11, wherein at least one additional HFO, HCFO, HFC, HCC, HCFC, and carbon dioxide (CO2) component is blended with the fluoroolefin feed comprising at least HFO-1234yf.

13. The method of claim 4, wherein the oligomer / polymer inhibitor comprises at least one oligomer / polymer inhibitor comprising at least one material selected from the group consisting of ethane, propane, cyclopropane, propylene, butane, butylene, isobutane, isobutylene, m-xylene, o-xylene, p-xylene, (α)-methylstyrene, 2-methyl-α-methylstyrene (α, 2-dimethylstyrene), 3-methyl-α-methylstyrene (α, 3-dimethylstyrene) and 4-methyl-α-methylstyrene (α, 4-dimethylstyrene) and mixtures of two or more thereof.

14. The method of claim 12, wherein the 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. The method according to claim 14, further comprising: c) prior to blending, contacting the at least one additional component with a reducing metal oxide to reduce the oxygen concentration to less than 5 ppm to produce an additional component substantially free of oxygen; as well as d) recovering the additional component which is substantially free of oxygen.

16. The method of claim 14 further comprising blending the substantially oxygen-free fluoroolefin product containing at least HFO-1234yf with an additional component that is substantially free of oxygen.

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

18. The method of 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, an ion mobility or plasma chromatograph, a gas chromatograph, a refractometer, a mass spectrometer, a high temperature thick film sensor, a thin film field effect sensor, and a Pellistor sensor.

19. The process according to any one of claims 1 and 4, wherein the fluoroolefin feed comprises an additional component selected from the group consisting of: 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.

20. The method of claim 2, wherein the contacting reduces the oxygen concentration to 5 ppm or less, including 0.

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

22. The process of claim 21 wherein the fluoroolefin composition passed 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 of claim 22, wherein the at least one additional component is present in an amount up to 1 wt%.

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

25. The method according to claim 10, further comprising: a) treating at least one additional component comprising one of HFC-125, HFC-134a, HFC-134, HFC 152a, HFC-23, HCFO-Z / E-1233zd, and HFO-Z / E-1336mzz using a reduced metal oxide-containing column operated at ambient temperature to provide a HFC-125, HFC-134a, HFC-134, HFC-23, HFC 152a, HCFO-Z / E-1233zd, and HFO-Z / E-1336mzz component that is substantially free of oxygen, The component has an oxygen content of about 10 ppm or less; as well as b) blending one of (i) to (iii) with said at least one of said substantially oxygen-free HFC-125, HFC-134a, HFC-134, HFC152a, HFC-23, HCFO-Z / E-1233zd and HFO-Z / E-1336mzz components.

26. A pressure container filled with a refrigerant, the pressure container comprising a pierceable top or valve suitable for dispensing the refrigerant, the refrigerant comprising at least one of: HFO-1234yf substantially free of oxygen; 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.

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

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

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

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

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

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

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

34. The process of claim 31 wherein at least one additional component comprising one of HFC-125, HFC-134a, HFC-134, HFC152a, HFC-23, HCFO-Z / E-1233zd, and HFO-Z / E-1336mzz is contacted with a tower operating at ambient temperature containing a reduced metal oxide to provide HFC-125, HFC-134a, HFC-134, HFC-23, HCFO-Z / E-1233zd, and HFO-Z / E-1336mzz substantially free of oxygen. 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, the fluoroolefin containing less than 10 ppm, preferably less than 5 ppm, of at least one of oxygen and less than 5 ppm of an oligomer inhibitor.

35. The method of claim 31 further comprising the step of packaging the blend of claim 31.

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

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

38. The method of any one of claims 32 to 34, further comprising filling at least one of a pressurized tank, tank or container.

39. The process of any one of claims 1, 11, 15, 19, 21, 25 or 31 wherein one of the feed and the fluoroolefin composition comprises unrecovered refrigerant.

40. The process of any one of claims 1, 11, 15, 19, 21, 25 or 31 wherein one of the feed and the fluoroolefin composition comprises a storage refrigerant.

41. The process of any one of claims 1, 11, 15, 19, 21, 25 or 31 wherein one of the feed and the fluoroolefin composition comprises fresh refrigerant.

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

43. A method comprising: a) contacting an unrecovered fluoroolefin feedstock comprising at least one tetrafluoropropene compound with a reducing metal oxide at a temperature sufficient to reduce or remove oxygen from said fluoroolefin feedstock without cleaving the C-F bonds of said at least one tetrafluoropropene; and b) recovering a substantially oxygen-free fluoroolefin product.

44. The process of claim 41, wherein the unrecovered tetrafluoropropylene feed comprises one of: HFO-1234yf; HFO-Z / E-1234ze; and A mixture of HFO-1234yf and HFO-Z / E-1234ze.

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