Purification of e-1,1,1,4,4,4-hexafluoro-2-butene by adsorption

Abstract

         A process for removing at least one impurity from a mixture comprising E-1,1,1,4,4,4-hexafluoro-2-butene and said impurity, wherein the process comprises: contacting the at least one removing agent, wherein the removing agent is water or comprises at least one adsorbent to reduce the concentration of the at least one impurity.

Description

TITLEPURIFICATION OF E-1,1,1,4,4,4-HEXAFLUORO-2-BUTENE BY ADSORPTIONFIELD[1] This invention relates to methods for removing impurities in fluorinated organic compounds, especially methods for removing unsaturated impurities included in fluorinated olefins, and even more particularly to methods for removing impurities included in E-1,1,1,4,4,4-hexafluoro-2-butene.BACKGROUND [2] Certain hydrofluoroolefins (HFOs), such as tetrafluoropropenes (including 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf), and 1,3,3,3-tetrafluoro-1-propene (HFO-1234ze)) and hexafluorobutenes, such as Z- and E-1,1,1,4,4,4-hexafluoro-2-butene (Z- and E-HFO-1336mzz, respectively) are known to be effective for use in refrigerants, heat transfer media, propellants, foaming agents, blowing agents, gaseous dielectrics, sterilant carriers, polymerization media, particulate removal fluids, carrier fluids, buffing abrasive agents, displacement drying agents and power cycle working fluids.[3] Unlike most chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs), most HFOs pose no threat to the ozone layer. HFOs have also been shown to be low global warming compounds with low toxicity and, hence, can meet increasingly stringent requirements. Accordingly, compositions containing these hydrofluoroolefins are among leading materials being developed for use in many of the aforementioned applications.[4] Processes for making fluoroolefins, can lead to the generation of undesirable by-products, that is, impurities, in the final product, which are difficult to remove.[5] For example, one common method for removing impurities is via distillation. However, this method of removal is made difficult if the boiling point of the impurity is close to that of the desired fluoroolefin product or if substance interactions bring otherwise dissimilar boiling compounds close together (for example azeotropes). Further, even after distillation, it is still possible that small quantities of undesirable impurities will remain.[6] As a result, there is a need to identify impurities generated in the process of making fluoroolefin, e.g., E-HFO-1336mzz and methods for removing these impurities.SUMMARY[7] E-HFO-1336mzz may be produced, for example, by reaction of chlorinated hydro(fluoro)carbons, such CF3CHClCH2CCl3 (HCFC-343jfd) or CF3CHClCH2CF3 (HCFC-346mdf) or CCl3CHClCH2CCl3 (HCC-340jfd) or CCl2=CClCH=CCl2 (HCO-2320az) in liquid or gas phase with HF; or by isomerization of Z-HFO-1336mzz. Such processes are disclosed, for example, in US 10,479,745; US 10,611,709; US2021 / 0188743; WO 2020 / 206247; and WO 2020 / 206335. Undesired impurities include fluorinated and chlorinated compounds that can be difficult to remove by conventional distillation. This invention finds certain methods are useful for removing such impurities.[8] Applicants have found specific impurities can be removed from E-1336mzz by selecting removing agents. The removing agent may be an adsorbent chosen from molecular sieves, alumina, high surface nickel, silica gel and activated carbon or combinations of two or more thereof.[9] In certain embodiments, the removing agent is an adsorbent and the adsorbent is alumina. Optionally, the alumina is loaded with sodium oxide.

[10] In some embodiments, the adsorbent is activated carbon.

[11] In one embodiment, washing with water is found to remove particular impurities from E-1336mzz.

[12] The impurity may be chosen from 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene (HFIB), vinyl chloride, 2-chloro-3,3,3-trifluoropropene, 1,1,3,3,3-pentafluoro-2-methyl-1-propene, 2-chloro-1,1-difluoroethylene, 1,1-dichloro-1,4,4,4-tetrafluoro-2-butene , E-1,1,1,2,4,4,4-heptafluorobut-2-ene, Z-1,1,1,4,4,4-hexafluoro-2-butene, 1-chloro-3,3,3-trifluoropropene, 2-chloro-1,1,1-trifluoroethane, and 2,2-dichloro-1,1,1-trifluoroethane.DETAILED DESCRIPTIONDEFINITIONS

[13] The present invention relates to purifying compositions comprising E-1336mzz and certain impurities. The compounds disclosed herein are defined in Table 1.Table 1. CompoundsCompoundChemical formulaChemical nameE-1327mzyE-CF3CF=CHCF3E-1,1,1,2,4,4,4-heptafluorobut-2-eneZ-1327mzyZ-CF3CF=CHCF3Z-1,1,1,2,4,4,4-heptafluorobut-2-eneE-1336mzzE-CF3CH=CHCF3E-1,1,1,4,4,4-hexafluoro-2-butene356mffCF3CH2CH2CF31,1,1,4,4,4-hexafluorobutane1122CF2=CHCl2-chloro-1,1-difluoroethylene1345cmCF3(CH3)C=CF21,1,3,3,3-pentafluoro-2-methyl-1-propene1334mzzCF3CH═CHCFCl21,1-dichloro-1,4,4,4-tetrafluoro-2-buteneZ-1336mzzZ-CF3CH=CHCF3Z-1,1,1,4,4,4-hexafluoro-2-butene133aCF3CH2Cl2-chloro-1,1,1-trifluoroethane1140CH2=CHClvinyl chloride (monomer), "VCM"1233xfCF3CCl=CH22-chloro-3,3,3-trifluoropropene1233zdE- and / or Z-CF3CH=CHClE- and / or Z-1-chloro-3,3,3-trifluoropropene1112CClF=CClF1,2-dichloro-1,2-difluoroethylene123CF3CHCl22,2-dichloro-1,1,1-trifluoroethaneHFIBCH2=C(CF3)23,3,3-Trifluoro-2-(trifluoromethyl)-1-propene343jfdCCl3CH2CHClCF31,1,1,3-tetrachloro-4,4,4-trifluorobutane340jfdCCl3CHClCH2CCl31,1,1,2,4,4,4-heptachlorobutane346mdfCF3CH2CHClCF32-chloro-1,1,1,4,4,4-hexafluorobutane2320azCCl2=CClCH=CCl21,1,2,4,4-pentachlorobuta-1,3-diene 

[14] The present invention relates to purifying compositions comprising E-1336mzz and certain impurities. The compounds disclosed herein are defined in Table 1. The term recited under the column “Compound” may be used herein.DESCRIPTION

[15] The present invention relates to purifying compositions comprising E-1336mzz and certain impurities.

[16] The present disclosure provides a process comprising: contacting a mixture comprising E-1,1,1,4,4,4-hexafluoro-2-butene and at least one impurity chosen from 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene (HFIB), vinyl chloride, 2-chloro-3,3,3-trifluoropropene, 1,1,3,3,3-pentafluoro-2-methyl-1-propene, 2-chloro-1,1-difluoroethylene, 1,1-dichloro-1,4,4,4-tetrafluoro-2-butene , E-1,1,1,2,4,4,4-heptafluorobut-2-ene, Z-1,1,1,4,4,4-hexafluoro-2-butene, 2-chloro-3,3,3-trifluoropropene, 2-chloro-1,1,1-trifluoroethane, and 2,2-dichloro-1,1,1-trifluoroethane with a removing agent, which can be water or an adsorbent, wherein the adsorbent is chosen from molecular sieves, alumina, high surface nickel, silica gel and activated carbon or combinations of two or more thereof. The alumina can be an alumina loaded with alkali metal oxide, such as sodium oxide (Na2O).

[17] The mixture to be treated typically comprises at least 98% or at least 99% or at least 99.5% or at least 99.8% or at least 99.9% of E-1336mzz, based on the total weight of said mixture.

[18] The process of contacting may be performed by simply combining the mixture comprising E-1336mzz and at least one impurity with a removing agent in any suitable vessel at any suitable temperature and pressure. Conveniently the contacting step may be performed at room temperature in a suitable vessel such as a cylinder. It should be recognized that the boiling point of E-1336mzz is about 7.4°C. In certain embodiments, the removing agent is an adsorbent. When the removing agent is an adsorbent, the contacting step may be performed by flowing the mixture comprising E-1336mzz through an adsorption bed containing the adsorbent as a continuous process.

[19] In one embodiment, the mixture comprising E-1336mzz and 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene (HFIB). In one embodiment, the mixture comprises E-1336mzz and vinyl chloride. In one embodiment, the mixture comprises E-1336mzz and 2-chloro-3,3,3-trifluoropropene. In one embodiment, the mixture comprises E-1336mzz and 1,1,3,3,3-pentafluoro-2-methyl-1-propene. In one embodiment, the mixture comprises E-1336mzz and 2-chloro-1,1-difluoroethylene. In one embodiment, the mixture comprises E-1336mzz and 1,1-dichloro-1,4,4,4-tetrafluoro-2-butene. In one embodiment, the mixture comprises E-1336mzz and E-1,1,1,2,4,4,4-heptafluorobut-2-ene. In one embodiment, the mixture comprises E-1336mzz and vinyl chloride. In one embodiment, the mixture comprises E-1336mzz and Z-1,1,1,4,4,4-hexafluoro-2-butene. In one embodiment, the mixture comprises E-1336mzz and 2-chloro-3,3,3-trifluoropropene. In one embodiment, the mixture comprises E-1336mzz and 2-chloro-1,1,1-trifluoroethane. In one embodiment, the mixture comprises E-1336mzz and 2,2-dichloro-1,1,1-trifluoroethane.

[20] In one embodiment, the process comprising: contacting a mixture comprising E-1,1,1,4,4,4-hexafluoro-2-butene and at least one impurity chosen from 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene , vinyl chloride, 2-chloro-3,3,3-trifluoropropene, 1,1,3,3,3-pentafluoro-2-methyl-1-propene, 2-chloro-1,1-difluoroethylene, 1,1-dichloro-1,4,4,4-tetrafluoro-2-butene, E-1,1,1,2,4,4,4-heptafluorobut-2-ene, Z-1,1,1,4,4,4-hexafluoro-2-butene, 2-chloro-3,3,3-trifluoropropene, 2-chloro-1,1,1-trifluoroethane, and 2,2-dichloro-1,1,1-trifluoroethane with a removing agent, which is water. In one embodiment, the removing agent is water and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene (HFIB).

[21] In one embodiment, the process comprising: contacting a mixture comprising E-1,1,1,4,4,4-hexafluoro-2-butene and at least one impurity chosen from 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene (HFIB), vinyl chloride, 2-chloro-3,3,3-trifluoropropene, 1,1,3,3,3-pentafluoro-2-methyl-1-propene, 2-chloro-1,1-difluoroethylene, 1,1-dichloro-1,4,4,4-tetrafluoro-2-butene, E-1,1,1,2,4,4,4-heptafluorobut-2-ene, Z-1,1,1,4,4,4-hexafluoro-2-butene, 2-chloro-3,3,3-trifluoropropene, 2-chloro-1,1,1-trifluoroethane, and 2,2-dichloro-1,1,1-trifluoroethane with a removing agent, which is an adsorbent. In one embodiment, the adsorbent comprises molecular sieves. In one embodiment, the adsorbent comprises alumina. In one embodiment, the adsorbent comprises high surface nickel. In one embodiment, the adsorbent comprises silica gel. In one embodiment, the adsorbent comprises activated carbon.

[22] In one embodiment, the adsorbent comprises molecular sieves, wherein the molecular sieves are chosen from 4A, 5A and 13X.

[23] In one embodiment, the adsorbent comprises molecular sieves, wherein the molecular sieves are chosen from 4A, 5A and 13X, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene (HFIB).

[24] In one embodiment, the adsorbent comprises molecular sieves, wherein the molecular sieves are chosen from 4A, 5A and 13X, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene (HFIB).

[25] In one embodiment, the adsorbent comprises molecular sieves, wherein the molecular sieves are chosen from 4A, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene (HFIB).

[26] In one embodiment, the adsorbent comprises molecular sieves, wherein the molecular sieves are chosen from 5A, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and vinyl chloride.

[27] In one embodiment, the adsorbent comprises molecular sieves, wherein the molecular sieves are chosen from 4A, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and vinyl chloride.

[28] In one embodiment, the adsorbent comprises molecular sieves, wherein the molecular sieves are chosen from 5A, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and vinyl chloride.

[29] In one embodiment, the adsorbent comprises molecular sieves, wherein the molecular sieves are chosen from 4A, 5A and 13X, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2-chloro-3,3,3-trifluoropropene.

[30] In one embodiment, the adsorbent comprises molecular sieves, wherein the molecular sieves are chosen from 4A, 5A and 13X, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 1,1,3,3,3-pentafluoro-2-methyl-1-propene.

[31] In one embodiment, the adsorbent comprises molecular sieves, wherein the molecular sieves are chosen from 4A, 5A and 13X, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2-chloro-1,1-difluoroethylene.

[32] In one embodiment, the adsorbent comprises molecular sieves, wherein the molecular sieves are chosen from 4A, 5A and 13X, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 1,1-dichloro-1,4,4,4-tetrafluoro-2-butene.

[33] In one embodiment, the adsorbent comprises molecular sieves, wherein the molecular sieves are chosen from 4A, 5A and 13X, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and E-1,1,1,2,4,4,4-heptafluorobut-2-ene.

[34] In one embodiment, the adsorbent comprises molecular sieves, wherein the molecular sieves are chosen from 4A, 5A and 13X, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and Z-1,1,1,4,4,4-hexafluoro-2-butene.

[35] In one embodiment, the adsorbent comprises molecular sieves, wherein the molecular sieves are chosen from 4A, 5A and 13X, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2-chloro-3,3,3-trifluoropropene.

[36] In one embodiment, the adsorbent comprises molecular sieves, wherein the molecular sieves are chosen from 4A, 5A and 13X, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2-chloro-1,1,1-trifluoroethane.

[37] In one embodiment, the adsorbent comprises molecular sieves, wherein the molecular sieves is 13X, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2-chloro-1,1,1-trifluoroethane.

[38] In one embodiment, the adsorbent comprises molecular sieves, wherein the molecular sieves are chosen from 4A, 5A and 13X, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2,2-dichloro-1,1,1-trifluoroethane.

[39] In one embodiment the molecular sieves comprise molecular sieve 4A. In one embodiment the molecular sieves comprise molecular sieve 5A. In one embodiment the molecular sieves comprise molecular sieve 13X.

[40] In one embodiment, the adsorbent comprises alumina, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene.

[41] In one embodiment, the adsorbent comprises alumina, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and vinyl chloride.

[42] In one embodiment, the adsorbent comprises alumina, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2-chloro-3,3,3-trifluoropropene.

[43] In one embodiment, the adsorbent comprises alumina, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 1,1,3,3,3-pentafluoro-2-methyl-1-propene.

[44] In one embodiment, the adsorbent comprises alumina, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2-chloro-1,1-difluoroethylene.

[45] In one embodiment, the adsorbent comprises alumina, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 1,1-dichloro-1,4,4,4-tetrafluoro-2-butene.

[46] In one embodiment, the adsorbent comprises alumina, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and E-1,1,1,2,4,4,4-heptafluorobut-2-ene.

[47] In one embodiment, the adsorbent comprises alumina, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and Z-1,1,1,4,4,4-hexafluoro-2-butene.

[48] In one embodiment, the adsorbent comprises alumina, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2-chloro-3,3,3-trifluoropropene.

[49] In one embodiment, the adsorbent comprises alumina, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2-chloro-1,1,1-trifluoroethane.

[50] In one embodiment, the adsorbent comprises alumina, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2,2-dichloro-1,1,1-trifluoroethane.

[51] In one embodiment, the adsorbent comprises alumina loaded with sodium oxide, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene (HFIB).

[52] In one embodiment, the adsorbent comprises alumina loaded with sodium oxide, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and vinyl chloride.

[53] In one embodiment, the adsorbent comprises alumina loaded with sodium oxide, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2-chloro-3,3,3-trifluoropropene.

[54] In one embodiment, the adsorbent comprises alumina loaded with sodium oxide, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 1,1,3,3,3-pentafluoro-2-methyl-1-propene.

[55] In one embodiment, the adsorbent comprises alumina loaded with sodium oxide, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2-chloro-1,1-difluoroethylene.

[56] In one embodiment, the adsorbent comprises alumina loaded with sodium oxide, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 1,1-dichloro-1,4,4,4-tetrafluoro-2-butene.

[57] In one embodiment, the adsorbent comprises alumina loaded with sodium oxide, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and E-1,1,1,2,4,4,4-heptafluorobut-2-ene.

[58] In one embodiment, the adsorbent comprises alumina loaded with sodium oxide, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and Z-1,1,1,4,4,4-hexafluoro-2-butene.

[59] In one embodiment, the adsorbent comprises alumina loaded with sodium oxide, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2-chloro-3,3,3-trifluoropropene.

[60] In one embodiment, the adsorbent comprises alumina loaded with sodium oxide, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2-chloro-1,1,1-trifluoroethane.

[61] In one embodiment, the adsorbent comprises alumina loaded with sodium oxide, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2,2-dichloro-1,1,1-trifluoroethane.

[62] In one embodiment, the adsorbent comprises high surface area nickel, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene (HFIB).

[63] In one embodiment, the adsorbent comprises high surface area nickel, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and vinyl chloride.

[64] In one embodiment, the adsorbent comprises high surface area nickel, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2-chloro-3,3,3-trifluoropropene.

[65] In one embodiment, the adsorbent comprises high surface area nickel, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 1,1,3,3,3-pentafluoro-2-methyl-1-propene.

[66] In one embodiment, the adsorbent comprises high surface area nickel, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2-chloro-1,1-difluoroethylene.

[67] In one embodiment, the adsorbent comprises high surface area nickel, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 1,1-dichloro-1,4,4,4-tetrafluoro-2-butene.

[68] In one embodiment, the adsorbent comprises high surface area nickel, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and E-1,1,1,2,4,4,4-heptafluorobut-2-ene.

[69] In one embodiment, the adsorbent comprises high surface area nickel, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and Z-1,1,1,4,4,4-hexafluoro-2-butene.

[70] In one embodiment, the adsorbent comprises high surface area nickel, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2-chloro-3,3,3-trifluoropropene.

[71] In one embodiment, the adsorbent comprises high surface area nickel, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2-chloro-1,1,1-trifluoroethane.

[72] In one embodiment, the adsorbent comprises high surface area nickel, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2,2-dichloro-1,1,1-trifluoroethane.

[73] In one embodiment, the adsorbent comprises silica gel, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene (HFIB).

[74] In one embodiment, the adsorbent comprises silica gel, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and vinyl chloride.

[75] In one embodiment, the adsorbent comprises silica gel, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2-chloro-3,3,3-trifluoropropene.

[76] In one embodiment, the adsorbent comprises silica gel, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 1,1,3,3,3-pentafluoro-2-methyl-1-propene.

[77] In one embodiment, the adsorbent comprises silica gel, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2-chloro-1,1-difluoroethylene.

[78] In one embodiment, the adsorbent comprises silica gel, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 1,1-dichloro-1,4,4,4-tetrafluoro-2-butene.

[79] In one embodiment, the adsorbent comprises silica gel, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and E-1,1,1,2,4,4,4-heptafluorobut-2-ene.

[80] In one embodiment, the adsorbent comprises silica gel, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and Z-1,1,1,4,4,4-hexafluoro-2-butene.

[81] In one embodiment, the adsorbent comprises silica gel, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2-chloro-3,3,3-trifluoropropene.

[82] In one embodiment, the adsorbent comprises silica gel, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2-chloro-1,1,1-trifluoroethane.

[83] In one embodiment, the adsorbent comprises silica gel, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2,2-dichloro-1,1,1-trifluoroethane.

[84] In one embodiment, the adsorbent comprises silica gel, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene .

[85] In one embodiment, the adsorbent comprises silica gel, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and vinyl chloride.

[86] In one embodiment, the adsorbent comprises silica gel, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2-chloro-3,3,3-trifluoropropene.

[87] In one embodiment, the adsorbent comprises silica gel, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 1,1,3,3,3-pentafluoro-2-methyl-1-propene.

[88] In one embodiment, the adsorbent comprises silica gel, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2-chloro-1,1-difluoroethylene.

[89] In one embodiment, the adsorbent comprises silica gel, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 1,1-dichloro-1,4,4,4-tetrafluoro-2-butene.

[90] In one embodiment, the adsorbent comprises silica gel, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and E-1,1,1,2,4,4,4-heptafluorobut-2-ene.

[91] In one embodiment, the adsorbent comprises silica gel, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and Z-1,1,1,4,4,4-hexafluoro-2-butene.

[92] In one embodiment, the adsorbent comprises silica gel, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2-chloro-3,3,3-trifluoropropene.

[93] In one embodiment, the adsorbent comprises silica gel, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2-chloro-1,1,1-trifluoroethane.

[94] In one embodiment, the adsorbent comprises silica gel, and the mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2,2-dichloro-1,1,1-trifluoroethane.

[95] The amount of removing agent can be any amount suitable to achieve the desired reduction in the impurities present in the mixture comprising E-1336mzz.

[96] When the removing agent is water, the ratio of the mixture to the removing agent is typically in the range of 0.01:1 to 2:1, preferably 0.05:1 to 1:1, more preferably 0.1:1 to 0.8:1.

[97] When the removing agent is an adsorbent, the ratio of the mixture to the adsorbent is typically in the range of 50:1 to 1:1, preferably 30:1 to 2:1, more preferably 20:1 to 3:1.

[98] At temperature ranging from -30°C to 50°C, preferably -20°C to 40°C, with pressure at the vapor pressure of E-1336mzz or pressure above such vapor pressure.

[99] Removing impurities from a mixture where the mixture has a purity of at least 98% or at least 99% or at least 99.5% or at least 99.8% or at least 99.9% of E-1336mzz can be particularly difficult using distillation methods. In particular, with respect to certain impurities such as HFIB and VCM and 133a, it is desirable to have very low concentrations. In certain embodiments, the process provides a product comprising E-1336mzz and less than 0.3% or less than 0.25% or less than 0.20% or less than 0.15% of HFIB. In certain embodiments, the process provides a product comprising E-1336mzz and less than 0.001% or less than 0.0005% or less than 0.0001 or less than 0.00005% or less than 0.00001% or non-detectable concentration of VCM. For clarity, non-detectable or “ND”, means less than less than 0.00001% or less than 0.1 ppm. In certain embodiments, the process provides a product comprising E-1336mzz and less than 0.02% or less than 0.01% of 133a.

[100] In another embodiment of this invention is provided a composition comprising at least 99% of E-1336mzz and 0.20% or less of HFIB. In another embodiment of this invention is provided a composition comprising at least 99.8% of E-1336mzz and 0.20% or less of HFIB. In another embodiment of this invention is provided a composition comprising at least 99.9% of E-1336mzz and 0.20% or less of HFIB.

[101] In another embodiment of this invention is provided a composition comprising at least 99% of E-1336mzz and less than 0.0005% (5 ppm) of VCM. In another embodiment of this invention is provided a composition comprising at least 99.8% of E-1336mzz and less than 0.0005% (5 ppm) of VCM. In another embodiment of this invention is provided a composition comprising at least 99.9% of E-1336mzz and less than 0.0005% (5 ppm) of VCM.

[102] In another embodiment of this invention is provided a composition comprising at least 99% of E-1336mzz and less than 0.0001% (1 ppm) of VCM. In another embodiment of this invention is provided a composition comprising at least 99.8% of E-1336mzz and less than 0.0001% (1 ppm) of VCM. In another embodiment of this invention is provided a composition comprising at least 99.9% of E-1336mzz and less than 0.0001% (1 ppm) of VCM.

[103] In another embodiment of this invention is provided a composition comprising at least 99% of E-1336mzz and less than 0.00005% (0.5 ppm) of VCM. In another embodiment of this invention is provided a composition comprising at least 99.8% of E-1336mzz and less than 0.00005% (0.5 ppm) of VCM. In another embodiment of this invention is provided a composition comprising at least 99.9% of E-1336mzz and less than 0.00005% (0.5 ppm) of VCM.

[104] In another embodiment of this invention is provided a composition comprising at least 99% of E-1336mzz and less than 0.00005% (0.1 ppm) of VCM. In another embodiment of this invention is provided a composition comprising at least 99.8% of E-1336mzz and less than 0.00001% (0.1 ppm) of VCM. In another embodiment of this invention is provided a composition comprising at least 99.9% of E-1336mzz and less than 0.00001% (0.1 ppm) of VCM.

[105] In another embodiment of this invention is provided a composition comprising at least 99% of E-1336mzz and less than 0.02% (200 ppm) of 133a. In another embodiment of this invention is provided a composition comprising at least 99.8% of E-1336mzz and less than 0.02% (200 ppm) of 133a. In another embodiment of this invention is provided a composition comprising at least 99.9% of E-1336mzz and less than 0.02% (200 ppm) of 133a. In another embodiment of this invention is provided a composition comprising at least 99% of E-1336mzz and less than 0.01% (100 ppm) of 133a. In another embodiment of this invention is provided a composition comprising at least 99.8% of E-1336mzz and less than 0.01% (100 ppm) of 133a. In another embodiment of this invention is provided a composition comprising at least 99.9% of E-1336mzz and less than 0.01% (100 ppm) of 133a.EXAMPLES

[106] Removing impurities from a mixture where the mixture has a purity of at least 98% or at least 99% or at least 99.5% or at least 99.8% or at least 99.9% of E-1336mzz can be particularly difficult using distillation methods. In particular, with respect to certain impurities such as HFIB and VCM, it is desirable to have very low concentrations. In certain embodiments, the process provides a product comprising E-1336mzz and less than 0.3% or less than 0.25% or less than 0.20% or less than 0.15% of HFIB. In certain embodiments, the process provides a product comprising E-1336mzz and less than 0.001% or less than 0.0005% or less than 0.0001 or less than 0.00005% or less than 0.00001% or non-detectable concentration (less than 0.1 ppm) of VCM.

[107] Materials. Molecular sieves (13X, 4A and 5A), silica gel, and alumina are commercially available, from multiple suppliers. HF-200XP alumina is available from BASF. E474 NI is a high surface area nickel, available from BASF. Carbon adsorbents are also commercially available from multiple suppliers, including Calgon Carbon Corporation (BPL AC, CocoPlus AC, CPG-LF AC, OVC AC), Osaka Gas Chemicals Co. Ltd. (Shirasagi AC), and General Carbon Corp. (Sulfursorb 12).Example 1. Reduction of HFIB concentration in E-1336mzz.

[108] In this Example, it was found that certain removing agents selectively removed HFIB from E-1336mzz to reduce the HFIB concentration.Example 1a. HFIB reduction in E-1336mzz

[109] A sample of E-1336mzz containing 0.2285% of HFIB was prepared. The desired amount of this E-1336mzz-HFIB mixture is loaded into a cylinder preloaded with a removing agent as recited in Table 2a, at the recited weight. As illustrated in Table 2a, the removing agents tested were molecular sieves, alumina, high surface nickel, silica gel, activated carbon and water. The mixtures were shaken well then maintained at room temperature for the times recited in Table 2a. The liquid phase of E-1336mzz in the test cylinder was analyzed by GC-MS-FID. The sample loaded with water was analyzed in the same manner, and it will be recognized the cylinder is “reversed”, wherein the organic layer is the heaver layer at bottom. Samples for GC analyses were pulled using a gas tight syringe and injected into GC.The results are presented in GC FID area%. Table 2a. Reduction of HFIB in E1336mzz with various removing agentsRemoving AgentTime, hoursHFIB concentrationHFIB removedRemoving Agent / E1336 weight ratioMol sieve 13X2.50.2257%0.0028%10 / 50230.2148%0.0137%Mol Sieve 4A10.2185%0.0100%10 / 50Mol Sieve 5A1.60.2133%0.0152%10 / 50720.2099%0.0186%HF200XP alumina50.2038%0.0247%10 / 50240.1960%0.0325%E474 Ni2.80.1903%0.0382%10 / 50720.1689%0.0596%Silica Gel10.2029%0.0256%10 / 50670.2014%0.0271%Water1.50.2187%0.0098%200 / 30700.21%0.0181% 

[110] As can be seen from Table 2a, all removing agents were effective at reducing the concentration of HFIB as illustrated by percent of HFIB removed.

[111] Example 1b. HFIB reduction in E-1336mzz using Activated Carbon (removing agent)

[112] Samples of E-1336mzz containing 0.1566% of HFIB were mixed with the commercially available activated carbons for use as removing agent (adsorbent) as recited in Table 2b, at the recited weight ratios in a carbon steel cylinder which was pre-loaded with a activated carbon. The mixtures were shaken well then maintained at room temperature for the times recited in Table 2b. The liquid phase of E-1336mzz in the test cylinder was analyzed by GC-MS-FID. The results are presented in GC-FID area%. Table 2b. Reduction of HFIB in E-1336mzz with various activated carbonsAdsorbentTime, hoursHFIB concentrationHFIB removedAdsorbent / E1336 weight ratioCoco plus AC1.50.1090%0.0476%10 / 50240.1040%0.0526%CPG-LF AC3.50.1091%0.0475%10 / 50240.1129%0.0437%OVC AC2.50.1019%0.0547%10 / 50230.0948%0.0618%Shirasagi AC10.1188%0.0378%10 / 50220.1092%0.0474%Sulfursorb 121.50.1142%0.0424%10 / 50220.1073%0.0493%BPL AC10.1121%0.0445%10 / 50240.1055%0.0511% 

[113] As can be seen from Table 1b, each of the carbons tested was effective at reducing the concentration of HFIB as illustrated by percent of HFIB removed. In comparing the results of Tables 1a and 1b, the activated carbons were more efficient in adsorbing HFIB.Example 2. VCM removal by adsorption of Molecular Sieves

[114] For each molecular sieve adsorbent (removing agent), 50 g of E-1336mzz containing various impurities, including vinyl chloride (“VCM”), was mixed with 5 g of the molecular sieves in a dried cylinder. The mixture was shaken well then maintained at room temperature. The molecular sieves used in this test were all pre-dried at 320°C under He flow for 16 hours. Then liquid phase of E-1336mzz in the test cylinder was analyzed by GC-MS-FID at 2 hours, 24 hours and a few days after E-1336mzz was mixed with the molecular sieves. The result of GC analysis of starting material and material after loaded with molecular sieves are listed in Tables 3a, 3b and 3c, below using GC-FID area%. Table 3a. Adsorbent = Molecular Sieves 4A, treatment for 2 hours,24 hours, 4 daysComponentStarting material2 hours24 hours4 daysE-1327mzy0.00420%0.00410%0.00410%0.00420%E-1336mzz99.97490%99.97630%99.97680%99.97790%1345cm0.00040%0.00040%0.00040%0.00040%Z-1336mzz0.00280%0.00220%0.00230%0.00230%VCM0.00092%0.00059%0.00023%0.00009%1233xf0.01130%0.01090%0.01060%0.01100% Table 3b. Adsorbent (removing agent) = Molecular Sieves 5A, treatment for 2 hours, 24 hours, 4 daysComponentStarting material2 hours24 hours4 daysE-1327mzy0.00420%0.00420%0.00420%0.00420%E-1336mzz99.97490%99.97790%99.97700%99.97830%1345cm0.00040%0.00040%0.00030%0.00030%Z-1336mzz0.00280%0.00230%0.00240%0.00250%VCM0.00092%0.00003%0.00003%0.00006%1233xf0.01130%0.01120%0.01110%0.01110% Table 3c. Adsorbent = Molecular Sieves 13X, treatment for 2 hours,24 hours, 7 daysComponentStarting material2 hours24 hours7 daysE-1327mzy0.00420%0.00420%0.00420%0.00400%E-1336mzz99.97490%99.97490%99.98360%99.98310%1345cm0.00040%0.00040%0.00020%0.00020%Z-1336mzz0.00280%0.00280%0.00032%0.00018%VCM0.00092%0.00092%0.00040%0.00031%1233xf0.01130%0.01130%0.00780%0.00740% 

[115] As can be seen from Tables 3a, 3b, and 3c, the GC results show VCM was efficiently reduced by molecular sieves 4A, 5A and 13X when used as adsorbents / removing agents. Molecular sieve 13X also reduced Z-1336mzz and 1233xf from E-1336mzz.Example 3. HCFC-133a removal from E-1336mzz by adsorption using molecular sieves

[116] In this Example, it was found that certain adsorbents can be used as removing agents to selectively adsorb HCFC-133a from E-1336mzz to reduce the HCFC-133a concentration.

[117] For each molecular sieve adsorbent, 50 g of E-1336mzz containing HCFC-133a and other impurities was mixed with 5 g molecular sieves in a dried cylinder, the mixture was shaken well then maintained at room temperature. The molecular sieves used in this test were all pre-dried at 320°C under He flow for 16 hours. Then liquid phase of E-1336mzz in the test cylinder was analyzed by GC-MS-FID at 2 hours and 24 hours after E-1336mzz was mixed with molecular sieves. The result of GC analysis of starting material and material after loaded with mol sieves are listed in Tables 4a, 4b, and 4c, below using GC-FID area%.Table 4a. Adsorbent = Molecular Sieves 13X, treatment for 2 hours, 24 hours ComponentStarting material2 hours24 hoursE-1327mzy0.0042%0.0044%0.0045%E-1336mzz99.8513%99.9470%99.9601%356mff0.0009%0.0007%0.0005%11220.0005%0.0004%0.0003%1345cm0.0066%0.0042%0.0038%1334mzz0.0003%0.0004%0.0004%Z-1336mzz0.0796%0.0205%0.0094%133a0.0218%0.0091%0.0079%VCM0.0002%0.0004%0.0003%1233xf0.0104%0.0080%0.0081%1233zd0.0036%0.0034%0.0034%11120.0005%0.0005%0.0005%1230.0012%0.0007%0.0008%Table 4b. Adsorbent = Molecular Sieves 5A, treatment for 2 hours, 24 hours ComponentStarting material2 hours24 hoursE-1327mzy0.0042%0.0045%0.0044%E-1336mzz99.8513%99.8586%99.8667%356mff0.0009%0.0012%0.0012%11220.0005%NDND1345cm0.0066%0.0077%0.0068%1334mzz0.0003%NDNDZ-1336mzz0.0796%0.0893%0.0865%133a0.0218%0.0222%0.0187%VCM0.0002%NDND1233xf0.0104%0.0111%0.0109%1233zd0.0036%0.0035%0.0030%11120.0005%0.0006%0.0005%1230.0012%0.0014%0.0012% Table 4c. Adsorbent = Molecular Sieves 4A, treatment for 2 hours, 24 hours ComponentStarting material2 hours24 hoursE-1327mzy0.0042%0.0042%0.0045%E-1336mzz99.8513%99.8694%99.8618%356mff0.0009%0.0013%0.0013%11220.0005%0.0005%0.0005%1345cm0.0066%0.0073%0.0077%1334mzz0.0003%0.0005%0.0004%Z-1336mzz0.0796%0.0812%0.0854%133a0.0218%0.0200%0.0218%VCM0.0002%0.0003%0.0001%1233xf0.0104%0.0102%0.0108%1233zd0.0036%0.0035%0.0037%11120.0005%0.0005%0.0005%1230.0012%0.0012%0.0013% 

[118] As can be seen from Table 4a, the GC results showed molecular sieve 13X can be used as a removing agent to efficiently reduce HCFC-133a, Z-1336mzz and 1233xf. As can be seen from Table 4b, molecular sieve 5A also reduced VCM, 1334mzz and 1122 from E-1336mzz when used as an adsorbent (removing agent).

[119] It can be seen that 13X molecular sieves are preferred over 4A and 5A sieves to reduce concentrations of 133a.Example 4. Purification of E-1336mzz by adsorption using Alumina with and without Na2O

[120] Several types of alumina were used as removing agents (adsorbents). For each alumina adsorbent, 50 g of E-1336mzz containing impurities was mixed with 5 g alumina adsorbent in a dried cylinder. The mixture was shaken well then maintained at room temperature. The liquid phase of E-1336mzz in the test cylinder was analyzed by GC-MS-FID at 2 hours and 24 hours after E-1336mzz was mixed with adsorbent. The result of GC analysis of starting material and material after loaded with alumina are listed in Tables 5a, 5b, 5c and 5d, below using GC-FID area%.Table 5a. Adsorbent = JM Puraspec™ 6259, Na2O / Al2O3, treatment for 2 hours, 24 hours ComponentStarting material2 hours24 hoursE-1327mzy0.0042%0.0042%0.0043%E-1336mzz99.8513%99.9480%99.9635%356mff0.0009%0.0010%0.0005%11220.0005%0.0004%0.0004%1345cm0.0066%0.0038%0.0036%1334mzz0.0003%0.0004%0.0004%Z-1336mzz0.0796%0.0148%0.0077%133a0.0218%0.0079%0.0070%VCM0.0002%0.0003%0.0002%1233xf0.0104%0.0076%0.0077%1233zd0.0036%0.0033%0.0033%11120.0005%0.0005%0.0006%1230.0012%0.0007%0.0007%Table 5b. Adsorbent = BASF CL 750, Na2O / Al2O3, treatment for 2 hours,24 hours ComponentStarting material2 hours24 hoursE-1327mzy0.0042%0.0039%0.0027%E-1336mzz99.8513%99.8814%99.8717%356mff0.0009%0.0011%0.0012%11220.0005%0.0005%0.0005%1345cm0.0066%0.0069%0.0074%1334mzz0.0003%0.0004%0.0005%Z-1336mzz0.0796%0.0744%0.0792%133a0.0218%0.0162%0.0204%VCM0.0002%0.0004%0.0004%1233xf0.0104%0.0097%0.0105%1233zd0.0036%0.0034%0.0036%11120.0005%0.0004%0.0002%1230.0012%0.0011%0.0010% Table 5c. Adsorbent = JM Puraspec™ 3110 Na2O / Al2O3, treatment for24.5 hours ComponentStarting material24.5 hoursE-1327mzy0.0042%0.0024%E-1336mzz99.8513%99.8637%356mff0.0009%0.0012%11220.0005%0.0004%1345cm0.0066%0.0075%1334mzz0.0003%0.0005%Z-1336mzz0.0796%0.0865%133a0.0218%0.0210%VCM0.0002%0.0003%1233xf0.0104%0.0109%1233zd0.0036%0.0038%11120.0005%0.0004%1230.0012%0.0013% Table 5d. Adsorbent = BASF CL 850 Al2O3, treatment for 2 hours, 24 hoursComponentStarting material2 hours24 hoursE-1327mzy0.0042%0.0051%0.0041%E-1336mzz99.8513%99.9516%99.9774%356mff0.0009%0.0006%0.0001%11220.0005%0.0005%0.0003%1345cm0.0066%0.0030%0.0011%1334mzz0.0003%0.0007%0.0004%Z-1336mzz0.0796%0.0155%0.0023%133a0.0218%0.0087%0.0038%VCM0.0002%0.0004%0.0002%1233xf0.0104%0.0083%0.0062%1233zd0.0036%0.0040%0.0032%11120.0005%0.0010%0.0005%1230.0012%0.0006%0.0004% 

[121] Note to Tables 5a-5d: Z-1327mzy was present as shoulder peak to the right side of E-1336mzz. In each treatment (after 2 hours, after 24 hours and after 24.5 hours), the size of the Z-1327mzy shoulder peak was visibly reduced.

[122] As can be seen from Tables 5a, 5b, 5c and 5d, the GC results showed alumina adsorbents are efficient as removing agents in reducing concentrations of 1327mzy, 1345cm, Z-1336mzz, HCFC-133a, HCFO-1233xf and HCFC-123 in the E-1336mzz samples. CLAIMSWhat is claimed is:1. A process for removing impurities from a fluoroolefin mixture comprising E-1,1,1,4,4,4-hexafluoro-2-butene, wherein the process comprises contacting the fluoroolefin mixture with a removing agent to reduce the concentration of one or more of impurities chosen from 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene (HFIB), vinyl chloride, 2-chloro-3,3,3-trifluoropropene, 1,1,3,3,3-pentafluoro-2-methyl-1-propene, 2-chloro-1,1-difluoroethylene, 1,1-dichloro-1,4,4,4-tetrafluoro-2-butene, E-1,1,1,2,4,4,4-heptafluorobut-2-ene, Z-1,1,1,4,4,4-hexafluoro-2-butene, 1-chloro-3,3,3-trifluoropropene, 2-chloro-1,1,1-trifluoroethane, and 2,2-dichloro-1,1,1-trifluoroethane.2. The process of claim 1 wherein the removing agent is water.3. The process of claim 2 wherein the fluoroolefin mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene.4. The process of claim 1 wherein the removing agent comprises at least one adsorbent.5. The process of claim 4 wherein the at least one adsorbent is selected from the group consisting of molecular sieves, alumina, alumina loaded with alkali oxide, high surface area nickel, silica gel and activated carbon.6. The process of claim 4 wherein the at least one adsorbent comprises molecular sieves.7. The process of claim 6 wherein the molecular sieves are chosen from one or more of 4A, 5A and 13X.8. The process of claim 4 wherein the at least one adsorbent comprises alumina.9. The process of claim 4 wherein the at least one adsorbent comprises alumina loaded with alkali oxide.10. The process of claim 4 wherein the at least one adsorbent comprises high surface area nickel.11. The process of claim 4 wherein the at least one adsorbent comprises silica gel.12. The process of claim 4 wherein the at least one adsorbent comprises activated carbon.13. The process of claim 7 wherein the molecular sieve is 4A.14. The process of claim 7 wherein the molecular sieve is 5A.15. The process of claim 7 wherein the molecular sieve is 13X.16. The process of any of claims 4-15 wherein the one or more of impurities comprises 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene (HFIB).17. The process of any of claims 4-15 wherein the one or more of impurities comprises vinyl chloride.18. The process of any of claims 4-15, wherein the one or more of impurities comprises 2-chloro-3,3,3-trifluoropropene.19. The process of any of claims 4-15, wherein the one or more of impurities comprises 1,1,3,3,3-pentafluoro-2-methyl-1-propene.20. The process of claim 1 wherein the one or more of impurities comprises 2-chloro-1,1-difluoroethylene.21. The process of any of claims 4-15 wherein the one or more of impurities comprises 1,1-dichloro-1,4,4,4-tetrafluoro-2-butene.22. The process of any of claims 4-15 wherein the one or more of impurities comprises E-1,1,1,2,4,4,4-heptafluorobut-2-ene.23. The process of any of claims 4-15 wherein the one or more of impurities comprises Z-1,1,1,4,4,4-hexafluoro-2-butene.24. The process of any of claims 4-15 wherein the one or more of impurities comprises 2-chloro-3,3,3-trifluoropropene.25. The process of any of claims 4-15 wherein the one or more of impurities comprises 2-chloro-1,1,1-trifluoroethane.26. The process of any of claims 4-15 wherein the one or more of impurities comprises 2,2-dichloro-1,1,1-trifluoroethane.27. The process of claim 8 wherein the fluoroolefin mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene.28. The process of claim 9 wherein the fluoroolefin mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene.29. The process of claim 10 wherein the fluoroolefin mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene.30. The process of claim 11 wherein the fluoroolefin mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene.31. The process of claim 12 wherein the fluoroolefin mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene.32. The process of claim 8 wherein the fluoroolefin mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2-chloro-3,3,3-trifluoropropene.33. The process of claim 8 wherein the fluoroolefin mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2-chloro-1,1,1-trifluoroethane.34. The process of claim 8 wherein the fluoroolefin mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2-chloro-3,3,3-trifluoropropene and 2-chloro-1,1,1-trifluoroethane.35. The process of claim 9 wherein the fluoroolefin mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2-chloro-3,3,3-trifluoropropene.36. The process of claim 9 wherein the fluoroolefin mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2-chloro-1,1,1-trifluoroethane.37. The process of claim 9 wherein the fluoroolefin mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2-chloro-3,3,3-trifluoropropene and 2-chloro-1,1,1-trifluoroethane.38. The process of claim 13 wherein the fluoroolefin mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and vinyl chloride.39. The process of claim 14 wherein the fluoroolefin mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and vinyl chloride.40. The process of claim 15 wherein the fluoroolefin mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2-chloro-1,1,1-trifluoroethane.41. The process of any of claims 1-40 wherein the amount of E-1,1,1,4,4,4-hexafluoro-2-butene in said mixture is at least 98 wt % based on the total weight of said mixture.42. A composition comprising at least 99% of E-1336mzz and 0.20% or less of 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene.43. A composition comprising at least 99% of E-1,1,1,4,4,4-hexafluoro-2-butene and less than 0.0005% (5 ppm) of vinyl chloride.44. A composition comprising at least 99% of E-1,1,1,4,4,4-hexafluoro-2-butene and less than 0.02% (200 ppm) of 2-chloro-1,1,1-trifluoroethane. ABSTRACTA process for removing at least one impurity from a mixture comprising E-1,1,1,4,4,4-hexafluoro-2-butene and said impurity, wherein the process comprises: contacting the at least one removing agent, wherein the removing agent is water or comprises at least one adsorbent to reduce the concentration of the at least one impurity.

Claims

1. A process for removing impurities from a fluoroolefin mixture comprising E-1,1,1,4,4,4-hexafluoro-2-butene, wherein the process comprises contacting the fluoroolefin mixture with a removing agent to reduce the concentration of one or more of impurities chosen from 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene (HFIB), vinyl chloride, 2-chloro-3,3,3-trifluoropropene, 1,1,3,3,3-pentafluoro-2-methyl-1-propene, 2-chloro-1,1-difluoroethylene, 1,1-dichloro-1,4,4,4-tetrafluoro-2-butene, E-1,1,1,2,4,4,4-heptafluorobut-2-ene, Z-1,1,1,4,4,4-hexafluoro-2-butene, 1-chloro-3,3,3-trifluoropropene, 2-chloro-1,1,1-trifluoroethane, and 2,2-dichloro-1,1,1-trifluoroethane. 2. The process of claim 1 wherein the removing agent is water. 3. The process of claim 2 wherein the fluoroolefin mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene. 4. The process of claim 1 wherein the removing agent comprises at least one adsorbent. 5. The process of claim 4 wherein the at least one adsorbent is selected from the group consisting of molecular sieves, alumina, alumina loaded with alkali oxide, high surface area nickel, silica gel and activated carbon.  6. The process of claim 4 wherein the at least one adsorbent comprises molecular sieves.  7. The process of claim 6 wherein the molecular sieves are chosen from one or more of 4A, 5A and 13X.  8. The process of claim 4 wherein the at least one adsorbent comprises alumina. 9. The process of claim 4 wherein the at least one adsorbent comprises alumina loaded with alkali oxide. 10. The process of claim 4 wherein the at least one adsorbent comprises high surface area nickel.  11. The process of claim 4 wherein the at least one adsorbent comprises silica gel. 12. The process of claim 4 wherein the at least one adsorbent comprises activated carbon.  13. The process of claim 7 wherein the molecular sieve is 4A. 14. The process of claim 7 wherein the molecular sieve is 5A. 15. The process of claim 7 wherein the molecular sieve is 13X. 16. The process of any of claims 4-15 wherein the one or more of impurities comprises 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene (HFIB). 17. The process of any of claims 4-15 wherein the one or more of impurities comprises vinyl chloride. 18. The process of any of claims 4-15, wherein the one or more of impurities comprises 2-chloro-3,3,3-trifluoropropene. 19. The process of any of claims 4-15, wherein the one or more of impurities comprises 1,1,3,3,3-pentafluoro-2-methyl-1-propene. 20. The process of claim 1 wherein the one or more of impurities comprises 2-chloro-1,1-difluoroethylene. 21. The process of any of claims 4-15 wherein the one or more of impurities comprises 1,1-dichloro-1,4,4,4-tetrafluoro-2-butene. 22. The process of any of claims 4-15 wherein the one or more of impurities comprises E-1,1,1,2,4,4,4-heptafluorobut-2-ene. 23. The process of any of claims 4-15 wherein the one or more of impurities comprises Z-1,1,1,4,4,4-hexafluoro-2-butene. 24. The process of any of claims 4-15 wherein the one or more of impurities comprises 2-chloro-3,3,3-trifluoropropene. 25. The process of any of claims 4-15 wherein the one or more of impurities comprises 2-chloro-1,1,1-trifluoroethane. 26. The process of any of claims 4-15 wherein the one or more of impurities comprises 2,2-dichloro-1,1,1-trifluoroethane. 27. The process of claim 8 wherein the fluoroolefin mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene. 28. The process of claim 9 wherein the fluoroolefin mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene. 29. The process of claim 10 wherein the fluoroolefin mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene. 30. The process of claim 11 wherein the fluoroolefin mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene. 31. The process of claim 12 wherein the fluoroolefin mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene. 32. The process of claim 8 wherein the fluoroolefin mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2-chloro-3,3,3-trifluoropropene. 33. The process of claim 8 wherein the fluoroolefin mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2-chloro-1,1,1-trifluoroethane. 34. The process of claim 8 wherein the fluoroolefin mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2-chloro-3,3,3-trifluoropropene and 2-chloro-1,1,1-trifluoroethane. 35. The process of claim 9 wherein the fluoroolefin mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2-chloro-3,3,3-trifluoropropene. 36. The process of claim 9 wherein the fluoroolefin mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2-chloro-1,1,1-trifluoroethane. 37. The process of claim 9 wherein the fluoroolefin mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2-chloro-3,3,3-trifluoropropene and 2-chloro-1,1,1-trifluoroethane. 38. The process of claim 13 wherein the fluoroolefin mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and vinyl chloride. 39. The process of claim 14 wherein the fluoroolefin mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and vinyl chloride. 40. The process of claim 15 wherein the fluoroolefin mixture comprises E-1,1,1,4,4,4-hexafluoro-2-butene and 2-chloro-1,1,1-trifluoroethane. 41. The process of any of claims 1-40 wherein the amount of E-1,1,1,4,4,4-hexafluoro-2-butene in said mixture is at least 98 wt % based on the total weight of said mixture. 42. A composition comprising at least 99% of E-1336mzz and 0.20% or less of 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene. 43. A composition comprising at least 99% of E-1,1,1,4,4,4-hexafluoro-2-butene and less than 0.0005% (5 ppm) of vinyl chloride. 44. A composition comprising at least 99% of E-1,1,1,4,4,4-hexafluoro-2-butene and less than 0.02% (200 ppm) of 2-chloro-1,1,1-trifluoroethane.