WO2025160040A1 - Purification of 1,1,1,2,2,5,5,6,6,6-decafluorohex-3-ene - Google Patents

Abstract

The invention disclosed herein relates to 1,1,1,2,2,5,5,6,6,6-decafluorohex-3-ene (153-10mczz) purifications techniques using adsorbents and different and novel types of azeotrope, azeotrope-like and near azeotrope compositions containing 1,1,1,2,2,5,5,6,6,6-decafluorohex-3-ene (153-10mczz).

Description

TITLE

PURIFICATION OF 1 ,1,1,2,2,5,5,6,6,6-DECAFLUOROHEX-3-ENE

BACKGROUND OF THE INVENTION

[0001] The perpetual uncertainty in energy supplies and prices and a growing public awareness of the environmental impacts from the extraction, transportation and use of fossil fuels are motivating a renewed interest in low temperature heat utilization (i.e. , heat at temperatures lower than about 300°C). Such heat may be extracted from various commercial, industrial or natural sources. Elevation of the temperature of available heat through high temperature mechanical compression heat pumps (HTHPs) to meet heating requirements and conversion of the available heat to mechanical or electrical power through Organic Rankine Cycles (ORCs) are two promising approaches for the utilization of low temperature heat.

[0002] ORCs and HTHPs require the use of working fluids. Working fluids with high global warming potentials (GWPs) currently in common use for HTHPs and ORCs (e.g., HFC-245fa) have been under increasing scrutiny culminating in the landmark HFC amendment to the Montreal Protocol recently agreed upon in Kigali, Rwanda. There is an increasing need for more environmentally sustainable working fluids for HTHPs and ORCs, especially given that environmental sustainability is a primary motivation for low temperature heat utilization. More specifically, there is a need for low GWP working fluids with boiling points higher than about 50°C that are particularly suitable for conversion of heat available at temperatures approaching or exceeding 20°C to power and for heating at temperatures approaching 200°C from heat available at lower temperatures. Even more specifically, a low GWP working fluid with a boiling point close to that of ethanol (78.4°C) could be advantageous as a replacement of ethanol in ORC systems for heavy duty vehicles (e.g. trucks) especially in Europe. Such a fluid could also be used as a solvent and as a heat transfer fluid for various applications, including immersion cooling and phase change cooling (e.g., of electronics, including data center cooling).

[0003] Fluoroolefins defined by the formula (I) E- or Z-R¹CH=CHR² , wherein R¹ and R² are, independently, Ci to Ce perfluoroalkyl groups and having boiling points greater than 50°C are considered candidates for use as solvents and as heat transfer fluids for various applications, including immersion cooling and phase change cooling (e.g., of electronics, including data center cooling). The product streams containing the E- or Z-R¹CH=CHR² compounds identified in Table 1 of U.S. Patent Publication U.S. 2021/0040368, the disclosure of which is incorporated herein in its entirety, and produced in accordance with, for example, the processes described at ffl][0061]-1J[0071] in U.S. 2021/0040368. Alternative processes are disclosed in WO 2021/119078, WO 2023/164093, and U.S. Provisional Patent Applications, Nos. 63/623,376, 63/623,395, 63/623,381 , 63/623383, and 63/623,642, each of which was filed on January 22, 2024; and U.S. Provisional Patent Applications, Nos. 63/680,330 and 63/680,351 , each of which was filed on August 7, 2024.

[0004] The product streams containing the E- or Z-R¹CH=CHR² compounds produced by the processes disclosed in the previous paragraph, contain impurities arising from production or handling which can negatively impact the toxicity and/or more importantly the performance of the desired product, E- or Z-R¹CH=CHR². These impurities include, but are not limited to ketones, such as acetone, alcohols, such as t-butanol, aldehydes such as isobutyraldehyde (2-methyl-propanal), 1 ,3- dichloro-1 , 1 ,2,2,3-pentafluoropropane (HCFC-225cb) and CeHFg, which are difficult to separate and remove by distillation. Accordingly, there is a need for techniques and processes to effectively and efficiently remove these types of impurities from these high boiling point hydrofluoroolefins stream.

SUMMARY OF THE INVENTION

[0005] The invention disclosed herein relates to 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluorohex- 3-ene (C2F5CH=CHC2F5, HFO-153-10mczz, or simply 153-10mczz) purification techniques which supplement distilled 153-10mczz products streams. Crude 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluorohex-3-ene product streams are initially purified by distillation.

[0006] In one embodiment, a crude 153-10mczz product stream is run through a two-column continuous distillation system. A first column removes low boilers overhead in the distillate, while higher boilers (E-153-10mczz, acetone, CeHsF l, etc. are withdrawn out the bottom of this first column. In certain embodiments, the low boilers comprise one or more of perfluoroethyl iodide (PFEI) and C4F10. Higher boilers comprise E-153-10mczz and, for example, acetone, and C6H3F10L The stream from the bottom of the first column is fed to the middle of a second distillation column, in which 153-10mczz is removed in an overhead stream, and other high boilers such as, for example, CeHsF l and acetone are removed from the bottom of the second column. Acetone has a boiling point of 56°C and should be a high boiler relative to E-153-10mczz (which has a boiling point 51 °C). As a result, the distillate (overhead stream) from the second distillation column should have no acetone theoretically. However, the applicants have unexpectedly found that some acetone remains in the overhead stream with the E-153-10mczz. The amount of acetone remaining in the stream comprising 153-10mczz may be about 1 mol%. In addition, the unexpected formation of an azeotropic or near azeotropic composition in the second distillation column complicates separation. The applicants have determined that additional separation techniques are necessary to provide the E-153-10mczz purity that is necessary for certain end uses.

[0007] The invention disclosed herein comprises providing a first product stream comprising a compound defined by the formula E- or Z-R¹CH=CHR² (Formula I), e.g., E- or Z-1,1,1 ,2,2,5,5,6,6,6-decafluorohex-3-ene (“153-10mczz”) with a first level of impurities including, but not limited to ketones, such as acetone, alcohols, such as t-butanol, aldehydes such as isobutyraldehyde (2-methyl-propanal), and CeHFg, passing the first product stream through a first distillation column to obtained a second product stream having a second level of impurities lower than said first level, and passing said second product stream through one or more adsorbents to obtain a third product stream having a third level of impurities lower than either the first or second level.

[0008] The invention disclosed herein provides a product stream comprising E- 1 ,1,1,2,2,5,5,6,6,6-decafluorohex-3-ene (E-153-10mczz ) with a first level of impurities comprising including as acetone, and CeHFg, passing the impurity ladened product stream through at least one distillation column to obtained a second product stream having a second level of impurities lower than said first level, and passing said second product stream through one of more adsorbents to obtain a third product stream having a third level of impurities lower than either the first or second level. [0009] The invention disclosed herein relates to 1,1,1,2,2,5,5,6,6,6-decafluorohex- 3-ene (153-10mczz) purification techniques using an adsorbent and different types of azeotrope, azeotrope-like and near azeotrope compositions containing E- 1 ,1,1 ,2,2,5,5,6,6,6-decafluorohex-3-ene (E-153-1 Omczz).

[0010] The invention disclosed herein describes different types of 1 ,1,1,2,2,5,5,6,6,6-decafluorohex-3-ene (153-10mczz) azeotrope, azeotrope-like and near azeotrope compositions.

[0011] This disclosure of the present invention relates to compositions comprising or consisting essentially of: (a) E-1 ,1 ,1 ,2,2,5,5,6,6,6-decafluorohex-3-ene (E-153- 10mczz) and (b) a component selected from the group of acetone and 1,3-dichloro- 1 ,1,2,2,3-pentafluoropropane (HCFC-225cb), wherein the component (b) is present in an effective amount to form an azeotrope, azeotrope-like, or near-azeotrope combination with the E-1 ,1 ,1 ,2,2,5,5,6,6,6-decafluorohex-3-ene (E-153-10mczz).

[0012] The present invention disclosed herein relates to azeotrope and near- azeotrope compositions comprising E-1 ,1 ,1,2,2,5,5,6,6,6-decafluorohex-3-ene (E- 153-10mczz) and one of acetone and 1 ,3-dichloro-1,1,2,2,3-pentafluoropropane (HCFC-225cb).

[0013] The present invention disclosed herein relates to processes for preparing and/or using E-153-10mczz/acetone and E-153-10mczz/HCFC-225cb azeotrope or near azeotrope compositions.

[0014] The present invention disclosed herein relates to processes for removing impurities selected from acetone, C3-C4 alcohols comprising isopropanol and butanol, C3-C5 aldehydes comprising butyraldehyde from C4-C14 hydrofluoroolefins E-153-10mczz/acetone and E-153-10mczz/HCFC-225cb azeotrope, azeotrope-like or near azeotrope compositions.

[0015] The present invention disclosed herein relates to processes for purifying hydrofluoroolefins defined by the formula E- or Z- R¹CH=CHR² (Formula I), wherein R¹ and R² are, independently, Ci to Ce perfluoroalkyl groups which hydrofluoroolefins have boiling points greater than 50°C. [0016] The present invention disclosed herein relates to processes for purifying the fluoroolefins of Tables 1 and 2 to a purity of at least about 99.5%, preferably at least about 99.9%.

TABLE 1

TABLE 2

[0017] In one embodiment of the invention a stream containing an impurity ladened hydrofluoroolefin defined by the formula E- or Z-R¹CH=CHR² (Formula I), wherein R¹ and R² are, independently, Ci to Ce perfluoroalkyl groups stream, is treated with an adsorbent and/or azeotrope or near azeotrope composition to remove the impurities.

[0018] In one embodiment disclosed herein an E-153-10mczz product stream upstream of a 1^st distillation column, or a product stream discharged from one of a first or second distillation column is treated with an azeotrope or near azeotrope compositions formed from E-153-10mczz/ acetone or E-153-10mczz/HCFC-225cb. [0019] In another embodiment disclosed herein a E-153-10mczz product stream from one or more distillation columns, is further treated with at least one of a E-153- 10mczz azeotrope or near azeotrope composition and an adsorbent.

[0020] In another embodiment disclosed herein a E-153-10mczz product stream from a distillation column contacts the E-153-10mczz azeotrope or near azeotrope compositions to remove impurities.

[0021] In several embodiments disclosed herein, at least 15%, 20%, 25% acetone in the product stream, and/or at least 15%, 20%, 25%, 30%, 35% t-butanol in the product stream, and/or 15%, 20%, 25%, 30%, 35% 2-methyl-propanal in the sample, and/or 10%, 15%, or 20% CeHFg in the product stream are removed.

[0022] In another embodiment disclosed herein E-153-10mczz product streams contact at least one of an adsorbent and azeotrope or near azeotrope compositions to remove impurities.

[0023] In another embodiment, the present invention discloses herein processes for using E-153-10mczz azeotropes or near azeotrope compositions formed between E-153-10mczz and one of acetone, and E-153-10mczz/HCFC- 225cb to purify 1 ,1,1 ,2,2,5,5,6,6,6-decafluorohex-3-ene.

[0024] In another embodiment, a stream containing 1, 1 ,1 , 2, 2, 5, 5, 6,6,6- decafluorohex-3-ene is brought into contact with an E-153-10mczz azeotrope or near-azeotrope, or with an adsorbent to remove impurities, where the azeotrope is at least one of an E-153-10mczz/acetone, E-153-10mczz/HCFC- 225cb azeotrope or near azeotrope.

[0025] The adsorbent may be chosen from molecular sieves, alumina, high surface nickel, silica gel and activated carbon or combinations of two or more thereof.

[0026] In certain embodiments, the adsorbent is a molecular sieve or activated carbon or a combination thereof.

[0027] In one embodiment, the adsorbent comprises a molecular sieve. The molecular sieve may be one or more of molecular sieve 3A, molecular sieve 4A, molecular sieve 5A, or molecular sieve 13X. The molecular sieve may be one or more of molecular sieve 5A and molecular sieve 13X.

[0028] In certain embodiments, the adsorbent is alumina. Optionally, the alumina is loaded with alkali oxide, such as sodium oxide.

[0029] In another embodiment a process stream comprising 1 , 1 ,1 , 2, 2, 5, 5, 6,6,6- decafluorohex-3-ene is purified by passage through an adsorbent to remove at least one of a ketone or CeHFg. In this embodiment, the adsorbent is a molecular sieve or activated carbon or alumina, optionally wherein the alumina is loaded with sodium oxide or silica gel or a combination or two or more thereof.

[0030] In one embodiment a process stream comprising 1 , 1 ,1 , 2, 2, 5, 5, 6,6,6- decafluorohex-3-ene is passed through an adsorbent to remove a ketone. In this embodiment, the adsorbent is a molecular sieve or activated carbon or alumina, optionally wherein the alumina is loaded with alkali oxide or silica gel or a combination or two or more thereof.

[0031] In one embodiment a process stream comprising 1 , 1 ,1 , 2, 2, 5, 5, 6,6,6- decafluorohex-3-ene is passed through an adsorbent to remove CeHFg. In this embodiment, the adsorbent is a molecular sieve or activated carbon or alumina, optionally wherein the alumina is loaded with alkali oxide or silica gel or a combination or two or more thereof.

[0032] In one embodiment a process stream comprising 1 , 1 ,1 , 2, 2, 5, 5, 6,6,6- decafluorohex-3-ene is passed through an adsorbent to remove a ketone and CeHFg. In this embodiment, the adsorbent is a molecular sieve or activated carbon or alumina, optionally wherein the alumina is loaded with alkali oxide or silica gel or a combination or two or more thereof.

[0033] In one embodiment a process stream comprising 1 , 1 ,1 , 2, 2, 5, 5, 6,6,6- decafluorohex-3-ene is passed through an adsorbent including but not limited to molecular sieve 3A, molecular sieve 4A, molecular sieve 5A, or molecular sieve 13X, and activated carbon.

[0034] The present invention comprises a process to remove an impurity from a process stream comprising 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluorohex-3-ene and the impurity, wherein the process stream is passed through an adsorbent to reduce the concentration of the impurity.

[0035] In one embodiment the process stream is passed through an adsorbent selected from molecular sieve 5A and molecular sieve 13X and the impurity is acetone or C6HF9.

[0036] In one embodiment the process stream is passed through an adsorbent selected from molecular sieve 5A and molecular sieve 13X and the impurity is acetone.

[0037] In one embodiment the process stream is passed through an adsorbent selected from molecular sieve 5A and molecular sieve 13X and the impurity is C₆HF₉.

[0038] In one embodiment the process stream is passed through an adsorbent selected from molecular sieve 5A and molecular sieve 13X and the impurity is acetone and CeHFg.

[0039] In one embodiment the process stream is passed through an adsorbent, wherein the adsorbent is activated carbon, and the impurity is acetone or CeHFg.

[0040] In one embodiment the process stream is passed through an adsorbent, wherein the adsorbent is activated carbon, and the impurity is acetone.

[0041] In one embodiment the process stream is passed through an adsorbent, wherein the adsorbent is activated carbon, and the impurity is CeHFg.

[0042] In one embodiment the process stream is passed through an adsorbent, wherein the adsorbent is activated carbon, and the impurity is acetone and CeHFg.

[0043] The various embodiments of the invention can be used alone or in combinations with each other. The foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as defined in the appended claims. BRIEF SUMMARY OF THE DRAWINGS

[0044] FIGURE 1 is a graphical representation of azeotrope- 1 ike compositions of

1 ,1,1,2,2,5,5,6,6,6-decafluorohex-3-ene (E-153-10mczz) and acetone data at a temperature of about 65.99°C.

[0045] FIGURE 2 is a graphical representation of the Binary VLE of E-153- 10mczz/F225cb at 65.3°C Liquid/Vapor Mole Fraction E-153-10mczz.

[0046] FIGURE 3 is a graphical representation of the Binary VLE of E-153- 10mczz/F225cb @ 30°C for Liquid/Vapor Mole Fraction E-153-10mczz.

[0047] FIGURE 4 is a graphical representation of the Binary VLE of E-153- 10mczz/F225cb @ 95°C for Liquid/Vapor Mole Fraction E-153-10mczz.

[0048] FIGURE 5 depicts a flow chart for purifying the crude 153-10mczz.

DETAILED DESCRIPTION OF THE INVENTION

[0049] The invention disclosed herein products a product stream comprising a compound defined by the formula E- or Z-R¹CH=CHR² (Formula I), e.g., E-

1 ,1,1,2,2,5,5,6,6,6-decafluorohex-3-ene (E-153-10mczz) with a first level of impurities comprising including, but not limited to ketones, such as acetone, alcohols, such as t-butanol, aldehydes such as isobutyraldehyde (2-methyl- propanal), and CeHFg, passing the impurity ladened product stream through at least one distillation column to obtained a second product stream having a second level of impurities lower than said first level, and passing said second product stream through one of more adsorbents to obtain a third product stream having a third level of impurities lower than either the first or second level.

[0050] The invention disclosed herein products a product stream comprising E-

1 ,1,1,2,2,5,5,6,6,6-decafluorohex-3-ene (E-153-10mczz) with a first level of impurities comprising including as acetone, and CeHFg, passing the impurity ladened product stream through at least one distillation column to obtained a second product stream having a second level of impurities lower than said first level, and passing said second product stream through one of more adsorbents to obtain a third product stream having a third level of impurities lower than either the first or second level. [0051] Before addressing details of embodiments described below, some terms are defined or clarified.

[0052] Global warming potential (GWP) is an index for estimating relative global warming contribution due to atmospheric emission of a kilogram of a particular greenhouse gas compared to emission of a kilogram of carbon dioxide. GWP can be calculated for different time horizons showing the effect of atmospheric lifetime for a given gas. The GWP for the 100-year time horizon is commonly the value referenced.

[0053] As used herein the term “Ozone depletion potential” (ODP) is defined in "The Scientific Assessment of Ozone Depletion, 2002, A report of the World Meteorological Association's Global Ozone Research and Monitoring Project," section 1.4.4, pages 1.28 to 1.31 (see first paragraph of this section). ODP represents the extent of ozone depletion in the stratosphere expected from a compound on a mass-for-mass basis relative to fluorotrichloromethane (CFC-11).

[0054] As used herein, “a” or “an” are employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

[0055] As used herein, the term “about” is meant to account for variations due to experimental error (e.g., plus or minus approximately 10% of the indicated value. ±1%, ± 2%, ± 3, ... ±10%). All measurements reported herein are understood to be modified by the term “about,” whether or not the term is explicitly used, unless explicitly stated otherwise.

[0056] When an amount, concentration, or other value or parameter is given as either a range, preferred range or a list of upper preferable values and/or lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. [0057] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.

[0058] Further, unless expressly stated to the contrary, “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).

[0059] As used herein, the term “consisting essentially of” is used to define a composition, method that includes materials, steps, features, components, or elements, in addition to those literally disclosed provided that these additional included materials, steps, features, components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention, especially the mode of action to achieve the desired result of any of the processes of the present invention. The term “consists essentially of’ or “consisting essentially of” occupies a middle ground between “comprising” and “consisting of.”

[0060] As used herein by "azeotrope" composition is meant a constant boiling liquid admixture of two or more substances that behaves as a single substance. One way to characterize an azeotrope composition is that the vapor produced by partial evaporation or distillation of the liquid has the same composition as the liquid from which it was evaporated or distilled, that is, the admixture distills/refluxes without compositional change. Constant boiling compositions are characterized as azeotropic because they exhibit either a maximum or minimum boiling point, as compared with that of the non-azeotropic mixtures of the same components.

Azeotrope compositions are also characterized by a minimum or a maximum in the vapor pressure of the mixture relative to the vapor pressure of the neat components at a constant temperature.

[0061] By "azeotropic" composition is meant a constant boiling liquid admixture of two or more substances that behaves as a single substance. In general, azeotropy is the phenomenon where a composition comprising two or more molecular species such that the relative volatility between any binary pair of components is unity. That is, the composition of a boiling liquid mixture exhibiting azeotropy is identical to the vapor phase that is produced.

[0062] Additionally, the temperature of a boiling mixture exhibiting azeotropy is constant at a constant pressure. A system is azeotropic when it can be distilled (or condensed) without change of composition. The notion of a system that is “azeotrope-like” or exhibiting “near azeotropy” is commonly known as a system close enough to azeotropy such that the compositions of the liquid and vapor phases in phase equilibrium are of very similar compositions such that during a boiling process the boiling temperature only rises to a small degree. Thus, one way to characterize an azeotropic composition is that the vapor produced by partial evaporation or distillation of the liquid has the same composition as the liquid from which it was evaporated or distilled, that is, the admixture distills/refluxes without compositional change. Constant boiling compositions are characterized as azeotropic because they exhibit either a maximum or minimum boiling point, as compared with that of the non-azeotropic mixtures of the same components. Azeotropic compositions are also characterized by a minimum or a maximum in the vapor pressure of the mixture relative to the vapor pressure of the neat components at a constant temperature.

[0063] By "azeotrope-like" composition (sometimes referred to as “nearazeotrope”) is meant a constant boiling, or substantially constant boiling, liquid admixture of two or more substances that behaves as a single substance. One way to characterize an azeotrope- 1 ike composition is that the vapor produced by partial evaporation or distillation of the liquid has substantially the same composition as the liquid from which it was evaporated or distilled, that is, the admixture distills/refluxes without substantial composition change. Another way to characterize an azeotropelike composition is that the bubble point vapor pressure and the dew point vapor pressure of the composition at a particular temperature are substantially the same, for example within 3 percent, as discussed below. Preferably, the terms “azeotropelike composition” and “near-azeotrope composition” shall be understood to mean a composition wherein the difference between the bubble point pressure (“BP”) and dew point pressure (“DP”) of the composition at a particular temperature is less than or equal to 5 percent and 3 percent respectively based upon the bubble point pressure. As used herein, the terms “azeotrope-like composition” and “ near- azeotrope composition” shall be understood to mean a composition wherein the difference between the bubble point pressure (“BP”) and dew point pressure (“DP”) of the composition at a particular temperature is respectively less than or equal to 5 percent based upon the bubble point pressure, i.e., [(BP-VP)/BP]x100= 5 percent for azeotrope-like compositions and less than or equal to 3 percent for near azeotrope compositions. An azeotrope-like composition can also be characterized by the area that is adjacent to the maximum or minimum vapor pressure in a plot of composition vapor pressure at a given temperature as a function of mole fraction of components in the composition.

[0064] For compositions that are azeotropic, there is usually some range of compositions around the azeotrope point that, for a maximum boiling azeotrope, have boiling points at a particular pressure higher than the pure components of the composition at that pressure and have vapor pressures at a particular temperature lower than the pure components of the composition at that temperature, and that, for a minimum boiling azeotrope, have boiling points at a particular pressure lower than the pure components of the composition at that pressure and have vapor pressures at a particular temperature higher than the pure components of the composition at that temperature. Boiling temperatures and vapor pressures above or below that of the pure components are caused by unexpected intermolecular forces between and among the molecules of the compositions, which can be a combination of repulsive and attractive forces such as van der Waals forces and hydrogen bonding.

[0065] It is recognized in the art that both the boiling point and the amount of each component of an azeotrope composition can change when the azeotrope liquid composition is subjected to boiling at different pressures. Thus, an azeotrope composition may be defined in terms of the unique relationship that exists among components or in terms of the exact amounts of each component of the composition characterized by a fixed boiling point at a specific pressure. An azeotrope or azeotrope-like composition of two or more compounds can be characterized by defining compositions characterized by a boiling point at a given pressure, thus providing identifying characteristics without unduly limiting the scope of the invention by a specific numerical composition, which is limited by and is only as accurate as the analytical equipment available. [0066] It is also recognized in this field that when the relative volatility of a system approaches 1.0, the system is defined as forming an azeotrope-like composition. Relative volatility is the ratio of the volatility of a first component to the volatility of a second component. The ratio of the mole fraction of a component in vapor to that in liquid is the volatility of the components. To determine the relative volatility of any two compounds, a method known as the PTx method can be used. In this procedure, the total absolute pressure in a cell of known volume is measured at a constant temperature for various compositions of the two compounds. Use of the PTx Method is described in detail in "Phase Equilibrium in Process Design", Wiley-lnterscience Publisher, 1970, written by Harold R. Null, on pages 124 to 126; hereby incorporated by reference.

[0067] As used herein, a heat transfer medium comprises a composition used to carry heat from a heat source to a heat sink. For example, heat from a body to be cooled to a chiller evaporator or from a chiller condenser to a cooling tower or other configuration where heat can be rejected to the ambient. As used herein, a working fluid or refrigerant comprises a compound or mixture of compounds (e.g., a composition provided herein) that function to transfer heat in a cycle wherein the working fluid undergoes a phase change from a liquid to a gas and back to a liquid in a repeating cycle.

[0068] As used herein chemicals, abbreviations, and acronyms include CFC- chlorofluorocarbon; HCC-hydrochlorocarbon; HFC-hydrofluorocarbon; HCFC- hydrochlorofluorocarbon; HCO-hydrochloroolefin; HFO-hydrofluoroolefin; HCFO- hydrochlorofluoroolefin.

[0069] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, In case of conflict, the present specification, including definitions, will control. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described below. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting. [0070] One purification embodiment of the invention disclosed herein can be practiced with an adsorbent contained in a stationary packed bed through which the process stream whose components need separation are passed. Alternatively, it can be practiced with the adsorbent applied as a countercurrent moving bed; or with a fluidized bed where the sorbent itself is moving. It can be applied with the adsorbent contained as a stationary packed bed, but the process configured as a simulated moving bed, where the point of introduction to the bed of the process stream requiring separation is changed, such as may be effected using appropriate switching valves.

[0071] Molecular sieves, which may be referred to as “Zeolite” is an aluminum silicate mineral matter of micropore, is commonly used as commercial sorbents. The term “molecular sieves” is used for Zeolite, because of the ability to screen molecules based on size exclusion methods. Molecular sieves or Zeolites are commercially available, such as from W. R. Grace & Co., Baltimore, Maryland.

[0072] Other purification embodiments disclosed herein can be practiced with the inventive azeotropic compositions formed between 1, 1 ,1, 2, 2, 5, 5, 6,6,6- decafluorohex-3-ene and acetone or HCFC- 225cb azeotrope or near azeotrope.

[0073] The perfluoroolefins of Formula I, in particular, 1, 1,1, 2, 2, 5, 5, 6,6,6- decafluorohex-3-ene can be obtained by dehydrohalogenating precursor trihydroiodoperfluoroalkane using phase transfer catalysts. Of particular interest is a process using a base and phase transfer catalyst such as polyhydric alcohols. Use of these polyhydric alcohols for dehydrohalogenation halogenated acyclic and cyclic organics was reported in both the technical and patent literature. See for example Kimura et al. in J. Org. Chem., Vol. 47, No. 12, 1982 and Org. Chem., Vol. 48, No. 2, 1983, and U.S. Patent No. 2,322,258. More recently, the fluoroolefins are prepared according to the processes described a, for example, 1J[0061]-1J[0071] of U.S. 2021/0040368 the disclose of which is incorporated herein by reference in its entirety. Alternative processes to prepare the fluoroolefins are disclosed in WO 2021/119078, WO 2023/164093, and U.S. Provisional Patent Applications, Nos. 63/623,376, 63/623,395, 63/623,381, 63/623383, and 63/623,642, each of which was filed on January 22, 2024; and U.S. Provisional Patent Applications, Nos. 63/680,330 and 63/680,351 , each of which was filed on August 7, 2024. [0074] Compounds of Formula I may be prepared by contacting a perfluoroalkyl iodide with a perfluoroalkyltrihydroolefin of the formula R²CH=CH2 to form a trihydroiodoperfluoroalkane of the formula R¹CH2CHIR². This trihydroiodoperfluoroalkane can then be dehydroiodinated to form R¹CH=CHR². Alternatively, the olefin R¹CH=CHR² may be prepared by dehydroiodination of a trihydroiodoperfluoroalkane of the formula R¹CHICH2R² formed in turn by reacting a perfluoroalkyl iodide of the formula R²I with a perfluoroalkyltrihydroolefin of the formula R¹CH=CH₂.

[0075] The dehydroiodination reaction may be conducted in the absence of solvent by adding the trihydroiodoperfluoroalkane to a solid or liquid basic substance. Suitable reaction times for the dehydroiodination reactions are from about 15 minutes to about six hours or more depending on the solubility of the reactants. Typically, the dehydroiodination reaction is rapid and requires about 30 minutes to about three hours for completion.

[0076] The perfluoroalkyl iodide contacts a perfluoroalkyltrihydroolefin in batch mode by combining the reactants in a suitable reaction vessel capable of operating under the autogenous pressure of the reactants and products at reaction temperature. Suitable reaction vessels include fabricated from stainless steels, in particular of the austenitic type, and the well-known high nickel alloys such as Monel® nickel-copper alloys, Hastelloy® nickel-based alloys and Inconel® nickelchromium alloys.

[0077] The reaction may take be conducted in semi-batch mode in which the perfluoroalkyltrihydroolefin reactant is added to the perfluoroalkyl iodide reactant by means of a suitable addition apparatus such as a pump at the reaction temperature.

[0078] The ratio of perfluoroalkyl iodide to perfluoroalkyltrihydroolefin should be between about 1 :1 to about 4:1 , preferably from about 1.5:1 to 2.5:1. Ratios less than 1.5:1 tend to result in large amounts of the 2:1 adduct as reported by Jeanneaux, et. al. in Journal of Fluorine Chemistry, Vol. 4, pages 261-270 (1974).

[0079] Preferred temperatures for contacting the perfluoroalkyl iodide with the perfluoroalkyltrihydroolefin, in the presence or absence of an initiator, are preferably within the range of about 90-300°C, 100°C-250°C, 110°C-220°C, 150°C-300°C., preferably from about 170°C. to about 250°C, and most preferably from about 180°C. to about 230°C. Suitable contact times for the reaction of the perfluoroalkyl iodide with the perfluoroalkyltrihydroolefin are from about 0.5 hour to 18 hours, preferably from about 4 to about 12 hours. (The initiator may be, for example, Al BN, t-butyl peroxide.)

[0080] The trihydroiodoperfluoroalkane prepared by reaction of the perfluoroalkyl iodide with the perfluoroalkyltrihydroolefin may be used directly in the dehydroiodination step or may preferably be recovered and purified by distillation prior to the dehydroiodination step.

[0081] The dehydroiodination step is carried out by contacting the trihydroiodoperfluoroalkane with a basic substance. Suitable basic substances include alkali metal hydroxides (e.g., sodium hydroxide or potassium hydroxide), alkali metal oxide (for example, sodium oxide), alkaline earth metal hydroxides (e.g., calcium hydroxide), alkaline earth metal oxides (e.g., calcium oxide), alkali metal alkoxides (e.g., sodium methoxide or sodium ethoxide), aqueous ammonia, sodium amide, or mixtures of basic substances such as soda lime. Preferred basic substances are sodium hydroxide and potassium hydroxide. The reaction of the trihydroiodoperfluoroalkane with a basic substance may take place in the liquid phase preferably in the presence of a solvent capable of dissolving at least a portion of both reactants. Solvents suitable for the dehydroiodination step include one or more polar organic solvents such as alcohols (e.g., methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and tertiary butanol), nitriles (e.g., acetonitrile, propionitrile, butyronitrile, benzonitrile, or adiponitrile), dimethyl sulfoxide, N,N- dimethylformamide, N,N-dimethylacetamide, or sulfolane. The choice of solvent may depend on the boiling point product and the ease of separation of traces of the solvent from the product during purification. Typically, ethanol or isopropanol are good solvents for the reaction.

[0082] Typically, the dehydroiodination reaction may be carried out by addition of one of the reactants (either the basic substance or the trihydroiodoperfluoroalkane) to the other reactant in a suitable reaction vessel, fabricated from glass, ceramic, or metal and is preferably agitated with an impeller or stirring mechanism.

[0083] Temperatures suitable for the dehydroiodination reaction are from about 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, or 70°C. to about 100°C, preferably from about 20°C, 30°C, 40°C, 50°C, or 60°C to about 70°C or 80°C. The dehydroiodination reaction may be carried out at ambient pressure or at reduced or elevated pressure. Of note are dehydroiodination reactions in which the compound of Formula I is distilled out of the reaction vessel as it is formed.

[0084] Alternatively, the dehydroiodination reaction may be conducted by contacting an aqueous solution of said basic substance with a solution of the trihydroiodoperfluoroalkane in one or more organic solvents of lower polarity such as an alkane (e.g., hexane, heptane, or octane), aromatic hydrocarbon (e.g., toluene), halogenated hydrocarbon (e.g., methylene chloride, chloroform, carbon tetrachloride, or perchloroethylene), or ether (e.g., diethyl ether, methyl tert-butyl ether, tetrahydrofuran, 2-methyl tetrahydrofuran, dioxane, dimethoxyethane, diglyme, or tetraglyme) in the presence of a phase transfer catalyst. Suitable phase transfer catalysts include quaternary ammonium halides (e.g., tetrabutylammonium bromide, tetrabutylammonium hydrosulfate, triethylbenzylammonium chloride, dodecyltrimethylammonium chloride, and tricaprylylmethylammonium chloride), quaternary phosphonium halides (e.g., triphenylmethylphosphonium bromide and tetraphenylphosphonium chloride), or cyclic polyether compounds known in the art as crown ethers (e.g., 18-crown-6 and 15-crown-5).

[0085] In one embodiment 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene may be prepared from 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-iodohexane (CF3CF2CHICH2CF2CF3) by reaction with KOH using a phase transfer catalyst at about 60°C.

[0086] In another embodiment, the synthesis of 1 , 1 , 1 ,2,2,5,5,6,6,6-decafluoro-3- iodohexane may be carried out by reaction of perfluoroethyliodide (CF3CF2I) and 3,3,4,4,4-pentafluoro-1-butene (CF3CF2CH DH2) at about 200° C under autogenous pressure for about 8 hours, as disclosed in U.S. Patent No.8, 049, 046 the disclosure of which is incorporated herein in its entirety.

[0087] Another process for producing 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluorohex-3-ene relies on the reaction of a corresponding iodide or bromide with water solution of KOH or NaOH in the absence of solvent. The reaction is catalyzed by polyethylene glycols (PEG) of various molecular weights and produces a reaction mixture of 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluorohex-3-ene product in yields of 70-90% yield. The reaction is carried out at 20-90°C, optionally with continuous removal of the product from reaction mixture.

[0088] Another process for producing 1,1,1 ,2,2,5,5,6,6,6-decafluorohex-3-ene relies on fluorination of HCFC-548mafd as set forth, for example, in U.S. Provisional Patent Application Nos. 63/623,383 (filed January 22, 2024) and 63/680351 (filed August 7, 2024). Alternative processes are disclosed in WO 2021/119078, WO 2023/164093, and U.S. Provisional Patent Applications, Nos. 63/623,376, 63/623,381, each of which was filed on January 22, 2024.

[0089] For any of the aforementioned process routes to prepare

1.1.1.2.2.5.5.6.6.6-decafluorohex-3-ene, there is provided a process to purify

1.1.1.2.2.5.5.6.6.6-decafluorohex-3-ene by removing at least moisture by passing the 1,1,1 ,2,2,5,5,6,6,6-decafluorohex-3-ene through a molecular sieve. In one embodiment, the 1,1,1 ,2,2,5,5,6,6,6-decafluorohex-3-ene is purified to remove at least moisture by passing the 1 ,1 ,1,2,2,5,5,6,6,6-decafluorohex-3-ene through molecular sieve 3A. In one embodiment, the 1 ,1 ,1,2,2,5,5,6,6,6-decafluorohex-3-ene is purified to remove at least moisture by passing the 1, 1,1 , 2, 2, 5, 5, 6,6,6- decafluorohex-3-ene through molecular sieve 4A. In one embodiment, the

1 ,1,1,2,2,5,5,6,6,6-decafluorohex-3-ene is purified to remove at least moisture by passing the 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluorohex-3-ene through molecular sieve 5A. In one embodiment, the 1,1 ,1 ,2,2,5,5,6,6,6-decafluorohex-3-ene is purified to remove at least moisture by passing the 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluorohex-3-ene through molecular sieve 13X.

EXAMPLES

[0090] For compositions possessing liquid vapor mole fraction <3%, VLE measurements are carried out in a static cell with a volume of 72.6 cm³. Mixtures are prepared by transferring known quantities (either measured by weight, or density) into the evacuated cell. For a binary VLE - the cell temperature is set to the desired value and a known quantity of the first component is added after degassing. Successive vapor pressure measurements are obtained at isothermal conditions by adding incremental amounts of the second component (after degassing) to complete one half of the VLE curve. The other half of the curve is completed by repeating the procedure starting with a fixed amount of the second component in the cell and adding incremental amounts of the first component. The two sets of measurement are carried out to cover the entire composition range (0% - 100%) with some overlap to allow for checking the consistency of results.

[0091] Example 1 : Vapor Liquid Equilibrium (VLE) of E-1, 1,1, 2, 2, 5, 5, 6,6,6- decafluorohex-3-ene/acetone at 65.99 °C.

[0092] FIGURE 1 is a graphical representation of an NRTL fit to the experimental VLE data of 1 ,1,1,2,2,5,5,6,6,6-decafluorohex-3-ene and acetone in Table 3.

TABLE 3

[0093] Example 2: Table 4 represent the VLE of E-1, 1,1, 2, 2, 5, 5, 6,6,6- decafluorohex-3-ene/HCFC-225cb at 30.00°C. Compositions possessing liquid vapor mole fraction<3%.

TABLE 4

[0094] Example 3: Table 5 provides the VLE of E-1, 1,1, 2, 2, 5, 5, 6, 6, 6- decafluorohex-3-ene/HCFC-225cb at 95°C. Compositions possessing liquid vapor mole fraction<3%.

TABLE 5

[0095] Example 4: Table 6 represents Experimental VLE of E-1, 1,1, 2, 2, 5, 5, 6,6,6- decafluorohex-3-ene / HCFC- 225cb at 65.33°C. TABLE 6

[0096] FIGURES 2-4 are respectively a graphical representation for a correlation of the VLE data for E- 153-1 Omczz and F225cb at 65.3°C, 30°C and 95°C. For E- 153-10mczz mole fractions above 0.84, the vapor and liquid compositions for a given pressure are almost the same making further purification by distillation impractical due to azeotropic or near azeotropic behavior.

[0097] In another embodiment between 20%, 25%, 30%, 35%, 40%, 45 %, 50 %, 55%, 60%, 65% and up to about 99.9 acetone, and/or at least between 20%, 25%, 30%, 35%, 40%, 45 %, 50 %, 55%, 60% and up to about 100% t-butanol, and/or between about 20%, 25%, 30%, 35%, 40%, 45 %, 50 %, 55%, 60% and up to about 100% 2-methyl-propanal, and/or 20%, 25%, 30%, 35%, 40%, 45 %, 50 %, 55%, 60% and up to about 87% CeHFg are removed.

[0098] In another embodiment between 20% and one of 25%, 30%, 35%, 40%, 45 %, 50 %, 55%, 60%, 65% and up to about 99.9 acetone, and/or between 20% and one of 25%, 30%, 35%, 40%, 45 %, 50 %, 55%, 60% and up to about 100% t- butanol, and/or between about 20% and one of ,25%, 30%, 35%, 40%, 45 %, 50 %, 55%, 60% and up to about 100% 2-methyl-propanal, and/or between 20% and one of 25%, 30%, 35%, 40%, 45 %, 50 %, 55%, 60% and up to about 87% C₆HF₉ are removed. [0099] In another embodiment between 25% and one of 30%, 35%, 40%, 45 %, 50 %, 55%, 60%, 65% and up to about 99.9 acetone, and/or between 25% and one of 25%, 30%, 35%, 40%, 45 %, 50 %, 55%, 60% and up to about 100% t-butanol, and/or between about 25% and one of 30%, 35%, 40%, 45 %, 50 %, 55%, 60% and up to about 100% 2-methyl-propanal, and/or between 25% and one of 30%, 35%, 40%, 45 %, 50 %, 55%, 60% and up to about 87% CeHFg are removed.

[0100] In another embodiment between 30% and one of 35%, 40%, 45 %, 50 %, 55%, 60%, 65% and up to about 99.9 acetone, and/or between 30% and one of 35%, 40%, 45 %, 50 %, 55%, 60% and up to about 100% t-butanol, and/or between about 30% and one of 35%, , 40%, 45 %, 50 %, 55%, 60% and up to about 100% 2- methyl-propanal, and/or between 30% and one of 35%, 40%, 45 %, 50 %, 55%, 60% and up to about 87% CeHFg are removed.

[0101] In another embodiment between 35% and one of 40%, 45 %, 50 %, 55%, 60%, 65% and up to about 99.9 acetone, and/or between 35% and one of 40%, 45 %, 50 %, 55%, 60% and up to about 100% t-butanol, and/or between about 35% and one of 40%, 45 %, 50 %, 55%, 60% and up to about 100% 2-methyl-propanal, and/or between 30% and one of 35% and one of 40%, 50 %, 55%, 60% and up to about 87% C6HF9 are removed.

E-153-10MCZZ PURIFICATION

[0102] In embodiments disclosed herein, the minimum amount of acetone, and /or t-butanol and/or 2-methyl propanal and/or C6HF9 removed is defined by the differences between the amount between of acetone, and /or t-butanol and/or 2- methyl propanal and/or CeHFg in the starting stream data of Tables 7-15 less the amount of the acetone, and /or t-butanol and/or 2-methyl propanal and/or CeHFg in the treated stream data of Tables 7-15 divided by the amount between of acetone, and /or t-butanol and/or 2-methyl propanal and/or CeHFg in the starting stream.

[0103] Example 5: E-153-10mczz purification by molecular sieve 5A and molecular sieve 13X.

[0104] Both 5A and 13X molecular sieves were dried in a tube furnace at 320°C under lOOsccm N2 purge for 16 hours before use. The composition of E-153-10mczz used in the test was analyzed by GC-MS-FID before testing. 1g molecular sieve was mixed with 10 g 153-10mczz in a sealed dried glass bottle. The mixture was shaken briefly at the beginning and then sat in a hood without agitation. The mixture was analyzed by GC at 2 hours and 24 hours of test. The result of GC analysis before and after testing are listed in Table 7 below which shows impurities such as acetone, t-butanol, 2-methyl-propanal and C6HF9 are all reduced after contact with both molecular sieves. Also, molecular sieve 13X shows higher efficiency in removing these impurities from 153-10mczz.

TABLE 7

[0105] The acetone level using Zeolite 5A decreased by about 30% after two hours and about 50 % after 24 hours. In contrast, Zeolite 13X effect was markedly better by reducing the acetone level by about 83% after two hours and by at least 99% after 24 hours. Levels of t-butanol, 2-methyl-propanal and CeHFg were also reduced by at least 25%.

[0106] Example 6: E-153-10mczz purification by molecular sieve 13X.

[0107] The 13X molecular sieve was dried in a tube furnace at 320°C under 100 seem N2 purge for 16 hours before use. E-153-10mczz used in this test was analyzed by GC-MS-FID before test. 1g molecular sieve 13X was mixed with 50 g E- 153-10mczz in a sealed dried glass bottle. The mixture was shaken briefly at the beginning and then sat in a hood without agitation. The mixture was analyzed by GC at 2 hours and 24 hours of test. The results of GC analysis before and after test are listed in Table 8 below which shows impurities such as acetone, t-butanol, 2-methyl- propanal and C6HF9 are all reduced after contact with 13X. TABLE 8

[0108] Example 7: E-153-10mczz purification by regenerated molecular sieve 13X. The molecular sieve used in Example 3 was recovered and then regenerated in a tube furnace at 185°C for 12hrs with 100 seem N2 purge. 1g of regenerated molecular sieve 13X was mixed with 50g of 153-10mczz in a sealed dried glass bottle. The mixture was shaken briefly at the beginning and then sat in a hood without agitation. The mixture was analyzed by GC at 2 hours and 24 hours of test. The result of GC analysis before and after the test are listed in Table 9 below which shows impurities such as acetone, t-butanol, 2-methyl-propanal and C6HF9 are all reduced after contact with regenerated 13X.

TABLE 9

[0109] Example 8: Crude 153-10mczz purification by regenerated molecular sieve 13X.

[0110] The 13X molecular sieve was dried in a tube furnace at 320°C under lOOsccm N2 purge for 16 hours before use. A crude 153-10mczz sample is used in this test and its composition was analyzed by GC-MS-FID before test. 1g molecular sieve was mixed with 50 g 153-10mczz in a sealed dried glass bottle. The mixture was shaken briefly at the beginning and then sat in a hood without agitation. The mixture was analyzed by GC at 2 hours and 24 hours of test. The result of GC analysis before and after test are listed in Table 10 below which shows impurities such as acetone, t-butanol, 2-methyl-propanal and CeHFg in the crude 153-10mczz are all reduced after contact with 13X.

TABLE 10

[0111] Example 9: 153-10mczz purification by activated carbons.

[0112] Activated carbons Calgon BPL 4X10 and OVC 4X8 used in this test were dried in a tube furnace at 140°C under lOOsccm N2 purge overnight before use. Calgon Sulfusorb 12 4x10 was purged with 100 seem N2 for 2 hr at room temperature, then treated with 100 seem H2 at 350°C for 6 hour and cool it down under H2 before use. 153-10mczz used in this test was analyzed by GC-MS-FID before test. 1g molecular sieve was mixed with 10 g 153-10mczz in a sealed dried glass bottle. The mixture was shaken briefly at the beginning and then sat in a hood without agitation. The mixture was analyzed by GC at 2 hours and 24 hours of test. The result of GC analysis before and after test are listed in Table 11 below which shows impurities such as acetone, t-butanol, 2-methyl-propanal and C6HF9 in the crude 153-10mczz are all reduced after contact with activated carbons.

TABLE 11

[0113] Example 10: 153-10mczz purification Distillation.

[0114] 36 g of 153-10mczz containing 225cb was distilled with a 14-inch distillation column. The multiple distillation cuts were taken during the distillation and analyzed by GC. The 225cb could not be removed from 153-10mczz-E in this distillation as shown below in Table 12.

TABLE 12

[0115] Example 11A. Analysis of acetone concentration relative to E-153- 10mczz in the crude Step 4 product that is fed to the distillation process is provided in Table 13. TABLE 13

[0116] Example 11 B: The starting purity for the Step 4 product fed to the distillation.

[0117] The composition of the feed material for distillation is provided in Table 14.

TABLE 14

[0118] Example 12A and 12B

[0119] A crude product such as batch 25 and 26 above, were run through a two- column continuous distillation system as illustrated in FIGURE 5. A first column removed low boilers overhead in the distillate (PFEI, C4F10) while higher boilers (E- 153-10mczz, acetone, C6H3F10I, etc.) were sent out the bottom of the column. This bottom stream was fed to the middle of a second distillation column, which takes E- 153-10mczz overhead and high boilers (CeHsFwl and theoretically acetone, etc.) out the bottom. Acetone (boiling point 56°C) should be a high boiler relative to E-153- 10mczz (boiling point 51°C). The distilled product stream from the second distillation column should have no acetone, so it was unexpected that acetone was still present in an amount of ~1 mol%. An azeotropic or near azeotropic composition in the second column makes further removal of the acetone exceedingly difficult or impossible as the liquid and the vapor in the column have the same acetone concentration. TABLE 13. DISTILLED STEP 4 PRODUCT

[0120] In view of the unexpected presence of acetone in the product stream after distillation, the product stream is further processed by passing the distilled product stream through at least one of an (1) adsorbent including one of molecular sieve 5A; molecular sieve 13X; carbon, alumina, and (2) an azeotrope or near azeotrope composition to reduce and/or remove at least one impurity. Other Embodiments

[0121] An azeotrope or near azeotrope composition comprising

1 ,1,1,2,2,5,5,6,6,6-decafluorohex-3-ene and acetone. An azeotrope or near azeotrope composition comprising E-1 ,1,1,2,2,5,5,6,6,6-decafluorohex-3-ene and acetone. An azeotrope or near azeotrope composition comprising Z-

1 ,1,1,2,2,5,5,6,6,6-decafluorohex-3-ene and acetone.

[0122] The azeotrope or near azeotrope composition comprising about 52 to 99 mole percent 1,1 ,1,2,2,5,5,6,6,6-decafluorohex-3-ene and 1 mole percent to 48 mole percent acetone at temperatures between 30°C and 95°C. The azeotrope or near azeotrope composition comprising about 52 to 99 mole percent E-1 , 1 , 1 , 2, 2, 5, 5, 6,6,6- decafluorohex-3-ene and 1 mole percent to 48 mole percent acetone at temperatures between 30°C and 95°C.

[0123] The azeotrope or near azeotrope composition comprising 52 to 59 and 98- 99 mole percent 1 ,1 ,1,2,2,5,5,6,6,6-decafluorohex-3-ene at 65.99°C and 29.584- 29.6119 psia. The azeotrope or near azeotrope composition comprising 52 to 59 and 98-99 mole percent E-1 ,1 ,1,2,2,5,5,6,6,6-decafluorohex-3-ene at 65.99°C and 29.584-29.6119 psia.

[0124] The azeotrope or near azeotrope composition comprising 52 to 57 mole percent 1 ,1,1,2,2,5,5,6,6,6-decafluorohex-3-ene at 65.99 °C and 29.584 to 29.6119 psia. The azeotrope or near azeotrope composition comprising 52 to 57 mole percent E-1 ,1 ,1 ,2,2,5,5,6,6,6-decafluorohex-3-ene at 65.99 °C and 29.584 to 29.6119 psia.

[0125] The azeotrope or near azeotrope composition comprising about 72 to 99 mole percent 1,1 ,1,2,2,5,5,6,6,6-decafluorohex-3-ene and 1 mole percent to 28 mole percent acetone at temperatures of 30°C and 95°C and respectively at pressures of between 7.4525 to 7.5121 psia and between 58.3722 and 59.2877. The azeotrope or near azeotrope composition comprising about 72 to 99 mole percent E-

1 ,1,1 ,2,2,5,5,6,6,6-decafluorohex-3-ene and 1 mole percent to 28 mole percent acetone at temperatures of 30°C and 95°C and respectively at pressures of between 7.4525 to 7.5121 psia and between 58.3722 and 59.2877. [0126] An azeotrope or near azeotrope composition comprises 1 , 1 ,1 , 2, 2, 5, 5, 6,6,6- decafluorohex-3-ene and 1 ,1 ,1 ,2,3,3,3-heptafluoropropane. An azeotrope or near azeotrope composition comprising E-1 ,1 ,1 ,2,2,5,5,6,6,6-decafluorohex-3-ene and 1 ,1 ,1 ,2,3,3,3-heptafluoropropane.

[0127] A process of removing at least one of acetone, t-butanol, butyraldehyde or C6HF9 from a process stream comprising 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluorohex-3-ene, comprising contacting the process stream with one or more of: an adsorbent; molecular sieve 5A; molecular sieve 13X; an 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluorohex-3-ene azeotrope or near-azeotrope composition; a 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluorohex-3- ene/acetone azeotrope or near-azeotrope composition; and an azeotrope or near azeotrope composition comprising 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluorohex-3-ene and 1 ,1 ,1 ,2,3,3,3-heptafluoropropane.

[0128] A process of removing at least one of acetone, t-butanol, butyraldehyde of C6HF9 from a process stream comprising E-1 ,1 ,1 ,2,2,5,5,6,6,6-decafluorohex-3-ene, comprising contacting the process stream with one or more of: an adsorbent; molecular sieve 5A; molecular sieve 13X; an azeotropic or near-azeotropic composition comprising E-1 ,1 ,1 ,2,2,5,5,6,6,6-decafluorohex-3-ene; an azeotropic or near-azeotropic composition comprising, consisting essentially of or consisting of E- 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluorohex-3-ene and acetone; and an azeotrope or near azeotrope composition comprising, consisting essentially of or consisting of E- 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluorohex-3-ene and 1 ,1 ,1 ,2,3,3,3-heptafluoropropane.

[0129] A process comprising contacting a product stream comprising a compound defined by the formula E- or Z-R¹CH=CHR² (Formula I), wherein R¹ and R² are, independently, Ci to Ce perfluoroalkyl groups, with at least one of one or more distillation columns, an adsorbent including one of molecular sieve 5A; molecular sieve 13X; carbon, alumina, and an azeotrope or near azeotrope composition to reduce and/or remove at least one impurity, preferably the process stream comprises 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluorohex-3-ene.

[0130] Although certain aspects, embodiments and principals have been described above, it is understood that this description is made only way of example and not as limitation of the scope of the invention or appended claims. The foregoing various aspects, embodiments and principals can be used alone and in combinations with each other.

Claims

What is claimed is:

1. An azeotrope or near azeotrope composition comprising 1, 1,1, 2, 2, 5, 5, 6,6,6- decafluorohex-3-ene and acetone.

2. The azeotrope or near azeotrope composition of claim 1 comprising about 52 to 99 mole percent 1,1 ,1 ,2,2,5,5,6,6,6-decafluorohex-3-ene and 1 mole percent to 48 mole percent acetone at temperatures between 30°C and 95°C.

3. The azeotrope or near azeotrope composition of claim 2 comprising 52 to 59 and 98-99 mole percent 1 ,1 ,1,2,2,5,5,6,6,6-decafluorohex-3-ene at 65.99 °C and 29.584-29.6119 psia.

4. The azeotrope or near azeotrope composition of claim 3 comprising 52 to 57 mole percent 1 ,1,1,2,2,5,5,6,6,6-decafluorohex-3-ene at 65.99°C and 29.584 to 29.6119 psia.

5. The azeotrope or near azeotrope composition of claim 1 comprising about 72 to 99 mole percent 1,1 ,1 ,2,2,5,5,6,6,6-decafluorohex-3-ene and 1 mole percent to 28 mole percent 1,3-dichloro-1 ,1,2,2,3-pentafluoropropane at temperatures of 30°C and 95°C and respectively at pressures of between 7.4525 to 7.5121 psia and between 58.3722 and 59.2877 psia.

6. The azeotrope or near azeotrope composition of claim 1 , comprising E- 1,1 ,1 ,2,2,5,5,6,6,6-decafluorohex-3-ene.

7. An azeotrope or near azeotrope composition comprising 1, 1,1, 2, 2, 5, 5, 6,6,6- decafluorohex-3-ene and 1 ,3-dichloro-1 , 1 ,2,2,3-pentafluoropropane.

8. A process comprising contacting a product stream comprising a compound defined by the formula E- or Z-R¹CH=CHR² (Formula I), wherein R¹ and R² are, independently, Ci to Ce perfluoroalkyl groups, with at least one of an (1) adsorbent and (2) an azeotrope or near azeotrope composition to reduce and/or remove at least one impurity.

9. The process of claim 8 wherein the product stream comprises

1,1 ,1 ,2,2,5,5,6,6,6-decafluorohex-3-ene and at least one impurity.

10. The process of claim 9 wherein the product stream comprises 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluorohex-3-ene and the at least one impurity is one or more of an alcohol, a ketone, an aldehyde or a Ce fluoroalkane, fluoroalkene or fluoroalkyne.

11. The process of claim 9 comprising contacting the product stream with an adsorbent.

12. The process of claim 11 , wherein the adsorbent is molecular sieves, alumina, high surface nickel, silica gel and activated carbon or combinations of two or more thereof.

13. The process of claim 12, wherein the adsorbent is a molecular sieve or activated carbon or a combination thereof.

14. The process of claim 13, wherein the adsorbent is a molecular sieve chosen from one or more of molecular sieve 3A, molecular sieve 4A, molecular sieve 5A, or molecular sieve 13X.

16. The process of claim 11 , wherein the adsorbent comprises alumina or al alumina loaded with alkali oxide.

17. The process of claim 11 wherein the at least one impurity is acetone.

18. The process of claim 11 wherein one of about 20%, 25%, 30%, 35%, 40%, 45%, 50 %, 55%, 60%, 65% or up to about 99.9% of the acetone is removed.

19. The process of claim 11 further comprising contacting the product stream with the azeotrope or near azeotrope composition according to any one of claims 1-7.

20. The process of claim 11 wherein the adsorbent is selected from a molecular sieve or activated carbon.

21. The process of claim 11 wherein the adsorbent is molecular sieve 5A or molecular sieve 13X.

22. The process of claim 11 wherein the adsorbent is activated carbon. 23 The process of any of claims 14-17 wherein one of about 20%, 25%, 30%, 35%, 40%, 45 %, 50 %, 55%, 60%, 65% or up to about 99.9% of the acetone is removed.

24. The process of claim 9 wherein the at least one impurity comprises at least one of acetone, t-butanol, butyraldehyde and CeHFg.

25. The process of claim 9 wherein the at least one impurity comprises acetone, t- butanol, butyraldehyde and CeHFg.

26. The process of claim 9 comprising removing at least 20% of the acetone impurity.

27. The process of claim 9 wherein the azeotrope or near azeotrope comprises the composition of any of claims 1-7.

28. The process of claim 8 comprising contacting the product stream with an absorbent and wherein the azeotrope or near azeotrope composition comprises

1,1 ,1 ,2,2,5,5,6,6,6-decafluorohex-3-ene.

29. The process of removing at least one of acetone, t-butanol, butyraldehyde of C6HF9 from a 1 ,1 ,1,2,2,5,5,6,6,6-decafluorohex-3-ene process stream, comprising contacting the process stream with at least one of: a. an adsorbent; d. an azeotrope or near-azeotrope composition comprising

1.1.1.2.2.5.5.6.6.6-decafluorohex-3-ene; e. an azeotrope or near-azeotrope composition comprising

1.1.1.2.2.5.5.6.6.6-decafluorohex-3-ene and acetone; and f. an azeotrope or near azeotrope composition comprising

1,1 ,1 ,2,2,5,5,6,6,6-decafluorohex-3-ene and 1 ,3-dichloro-1 , 1 ,2,2,3- pentafluoro-propane.

30. The process of claim 29, wherein the adsorbent is molecular sieve or activated carbon or alumina, optionally wherein the alumina is loaded with sodium oxide or silica gel or a combination or two or more thereof.

31. The process of claim 30, wherein the adsorbent is a molecular sieve.

32. The process of claim 31 , wherein the molecular sieve is molecular sieve 3A, molecular sieve 4A, molecular sieve 5A, or molecular sieve 13X.

33. The process of claim 32, wherein the molecular sieve is molecular sieve 5A or molecular sieve 13X.

34. The process of claim 30, wherein the adsorbent is activated carbon.

35. The process of claim 30, wherein the adsorbent is alumina or alumina loaded with sodium oxide.

36. The process of claim 30, wherein the adsorbent is or silica gel.

37. The process of claim 29, wherein the azeotrope or near-azeotrope composition recited in any one of d, e or f, comprises E-1 ,1 ,1 ,2,2,5,5,6,6,6-decafluorohex-3- ene.

38. A composition comprising 1 ,1,1 ,2,2,5,5,6,6,6-decafluorohex-3-ene and at least one impurity selected from acetone, t-butanol, butyraldehyde and CeHFg.

27. The composition of claim 26 wherein acetone is present in an amount between greater than 0 and less than 1 mole percent.

39. The composition of claim 39 wherein acetone is present in an amount of at least one of (a) between greater than 0.001 mole percent and less than 0.01 mole percent; (b) between greater than 0 and less than 0.1 mole percent; (c) between greater than 0 and less than 0.01 mole percent; (d) between greater than 0 and less than 0.001 mole percent; and (e) between greater than 0 and less than 0.001 mole percent.

40. A process comprising treating a product stream from reaction for producing a compound defined by the formula E- or Z-R¹CH=CHR² (Formula I), wherein R¹ and R² are, independently, Ci to Ce perfluoroalkyl groups.

41. The process of claim 40, wherein the product stream is a crude product stream.

42. The process of claim 40, the product stream is subjected to a first distillation before treatment.

43. The process of claim 40, the product stream is subjected to a first and second distillation before treatment.

44. The process of claim 40 wherein the product stream includes at least one impurity.

45. The process of claim 40 wherein the treatment comprises one of an adsorbent and an azeotrope or near azeotrope separation to reduce and/or remove at least one impurity.

46. A process comprising providing a product stream comprising a compound defined by the formula E- or Z-R¹CH=CHR² (Formula I) with a first impurity level, passing the product stream through at least at least one distillation column to obtained a second product stream having a second level of impurities lower than said first level, and passing said second product stream through one of more adsorbents to obtain a third product stream having a third level of impurities lower than either the first or second level, wherein R¹ and R² are, independently, Ci to Ce perfluoroalkyl groups.

47. The process of claim 46, wherein the first impurity level include acetone.

48. The process of claim 47, wherein the first impurity level of acetone is reduced by one of about 20%, 25%, 30%, 35%, 40%, 45 %, 50 %, 55%, 60%, 65% or up to about 99.9% after treatment with the adsorbent.

49. The process of claim 46, wherein the adsorbent is selected from a molecular sieve or activated carbon or a combination thereof.

50. The process of claim 46, wherein the adsorbent is selected from a molecular sieve or activated carbon.

51. A process to remove an impurity from a process stream comprising 1,1 ,1 ,2,2,5,5,6,6,6-decafluorohex-3-ene and the impurity, wherein the process stream is passed through an adsorbent to reduce the concentration of the impurity.

52. The process of claim 51 , wherein the process stream is passed through an adsorbent selected from molecular sieve 5A and molecular sieve 13X and the impurity is acetone or CeHFg. 53 The process of claim 51 , wherein the process stream is passed through an adsorbent selected from molecular sieve 5A and molecular sieve 13X and the impurity is acetone.

53. The process of claim 51 , wherein the process stream is passed through an adsorbent selected from molecular sieve 5A and molecular sieve 13X and the impurity is CeHFg.

54. The process of claim 51 , wherein the process stream is passed through an adsorbent selected from molecular sieve 5A and molecular sieve 13X and the impurity is acetone and CeHFg.

55. The process of claim 51 , wherein the process stream is passed through an adsorbent, wherein the adsorbent is activated carbon, and the impurity is acetone or CeHFg.

56. The process of claim 51 , wherein the process stream is passed through an adsorbent, wherein the adsorbent is activated carbon, and the impurity is acetone.

57. The process of claim 51 , wherein the process stream is passed through an adsorbent, wherein the adsorbent is activated carbon, and the impurity is C₆HF₉.

58. The process of claim 51 , wherein the process stream is passed through an adsorbent, wherein the adsorbent is activated carbon, and the impurity is acetone and CeHFg.