Processes to prepare fluoroolefin compositions and uses thereof

Abstract

The present application relates to compositions comprising E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (E-HFO-153-10mczz, E-CF3CF2CH=CHCF2CF3) processes of preparing such compositions and their use.

Description

TITLE PROCESSES TO PREPARE FLUOROOLEFIN COMPOSITIONS AND USES THEREOF FIELD

[0001] The present invention relates to processes to prepare fluoroolefincompositions comprising E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (E-HFO-153-10mczz) and uses in thermal management applications. BACKGROUND

[0002] A growing public awareness of the environmental impacts from the extraction,transportation and use of fossil fuels are motivating a new environmental sustainability driver in the form of regulations and reduction in output of CO2 equivalence in the atmosphere. In particular, new environmental regulations on refrigerants have forced the refrigeration and air-conditioning industry to look for new refrigerants with low global warming potentials (GWP). Replacement refrigerants with low global warming potential (GWP) and ozone depletion potential (ODP) for both existing and new applications in thermal management segments will need to adhere to these new regulations.

[0003] Certain hydrofluoroolefins, such as E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene(E-C2F5CH=CHC2F5, E-HFO-153-10mczz), are believed to meet both goals. Inparticular, E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene may be useful in heat transfer fluidapplications (e.g., immersion cooling systems, data-center cooling systems or thermal management solution for EV batteries). Accordingly, the present application provides new processes for preparing E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene andcompositions comprising E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene.SUMMARY

[0004] The present invention relates to compositions comprising E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (E-HFO-153-10mczz, E-CF3CF2CH=CHCF2CF3), processes of preparing such compositions and their use.

[0005] The present invention provides a process for preparing E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene comprising contacting 3,5,5-trichloro-1,1,1,2,2,6,6,6- octafluorohexane (HCFC-548mafd, CF3CF2CHClCH2CCl2CF3) with HF in the presenceof a fluorination catalyst in a reactor, to obtain a process mixture comprising E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene.

[0006] In certain embodiments, the process is performed at a temperature of about250-450°C, a pressure of about 0 to 200 psig. Preferably, the temperature is in the range of about 275 to about 380°C. Preferably the pressure is in the range of about 30 to 180 psig or about 40 to 150 psig, or about 60-120 psig.

[0007] The present invention also provides a composition comprising E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (E-HFO-153-10mczz), and at least one additional compound chosen from 2-chloro-1,1,1,2,5,5,6,6,6-nonafluoro-3-hexene (HCFO-153-9mbzz ), 3-chloro-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (HCFO-152- 10mcxz), 2,5-dichloro-1,1,1,6,6,6-hexafluorohexa-2,4-diene (HCFO-2536mxzzx), 2- chloro-1,1,1,5,6,6,6-heptafluorohexa-2,4-diene (HCFO-2537mxzzy), 2,4-dichloro- 1,1,1,5,5,6,6,6-octafluoro-2-hexene (HCFO-1538mxzd), 1,1,1,2,2,3,5,5,6,6,6- undecafluoro-3-hexene (HFO-152-11mcyz), 1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2- hexene (HFO-152-11myz), 2-chloro-1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene (HCFO- 152-10mdz), 2,3,5-trichloro-1,1,1,4,4,6,6,6-octafluoro-2-hexene (HCFO-1528mdcxx), 1- chloro-3,3,4,4,5,5-hexafluoro-2-(trifluoromethyl)cyclopent-1-ene, 1,1,1,4,4,5,5,6,6,6- decafluoro-2-hexene (HFO-153-10mzz), C6F10 isomers, hexafluorobutene isomers (HFO-1336 isomers), C5HF9 isomers, C6F12 isomers,C6HF11 isomers, C5H2F8 isomers, C5HClF8 isomers, C6F8 isomers, C6HF9 isomers, C6ClF9 isomers, 2-chloro-1,1,1,4,4,4- hexafluoro-2-butene (HCFO-1326mxz), 2-chloro-1,1,1,4,4,4-hexafluorobutane (HCFC- 346mdf) and 3,5,5-trichloro-1,1,1,2,2,6,6,6-octafluorohexane (HCFC-548mafd). The composition may be prepared by the process disclosed herein.

[0008] The composition disclosed herein can be used as a refrigerant, heat transferfluid, foam expansion agent, power cycle working fluid, among other uses. It has also, advantageously, been found that the composition has low global warming potential.Thus, a composition comprising E-HFO-153-10mczz may be a good candidate forreplacing higher GWP compounds in many uses.

[0009] In one embodiment, the composition of this invention can be used as aworking fluid in an immersion cooling unit. An immersion cooling unit includes an immersion cell, defining an internal cavity, a heat generating electronic or electrical component positioned in the internal cavity, a working fluid which partially fills the internal cavity and at least partially immerses the heat generating electronic or electrical device, and a condensing coil positioned inside the cavity above the working fluid,wherein the working fluid is a composition comprising E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, and at least one additional compound chosen from 2-chloro-1,1,1,2,5,5,6,6,6- nonafluoro-3-hexene (HCFO-153-9mbzz ), 3-chloro-1,1,1,2,2,5,5,6,6,6-decafluoro-3- hexene (HCFO-152-10mcxz), 2,5-dichloro-1,1,1,6,6,6-hexafluorohexa-2,4-diene (HCFO-2536mxzzx), 2-chloro-1,1,1,5,6,6,6-heptafluorohexa-2,4-diene (HCFO- 2537mxzzy), 2,4-dichloro-1,1,1,5,5,6,6,6-octafluoro-2-hexene (HCFO-1538mxzd), 1,1,1,2,2,3,5,5,6,6,6-undecafluoro-3-hexene (HFO-152-11mcyz), 1,1,1,2,4,4,5,5,6,6,6- undecafluoro-2-hexene (HFO-152-11myz), 2-chloro-1,1,1,4,4,5,5,6,6,6-decafluoro-2- hexene (HCFO-152-10mdz), 2,3,5-trichloro-1,1,1,4,4,6,6,6-octafluoro-2-hexene (HCFO- 1528mdcxx), 1-chloro-3,3,4,4,5,5-hexafluoro-2-(trifluoromethyl)cyclopent-1-ene, 1,1,1,4,4,5,5,6,6,6- decafluoro-2-hexene (HFO-153-10mzz), C6F10 isomer, hexafluorobutene isomers (HFO-1336 isomers), C5HF9 isomer, C6F12 isomers, C6HF11 isomers, C5H2F8 isomer, C5HClF8 isomers, C6F8 isomers, C6HF9 isomers, C6ClF9 isomers, 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (HCFO-1326mxz), 2-chloro- 1,1,1,4,4,4-hexafluorobutane (HCFC-346mdf) and 3,5,5-trichloro-1,1,1,2,2,6,6,6- octafluorohexane (HCFC-548mafd). The composition may be prepared according to the process disclosed herein.

[0010] The structures of such compounds are provided in Table 1.TABLE 1 Name Formula Compound1,1,1,4,4,5,5,6,6,6- decafluoro-2-hexene C2F5CH=CHC2F5 HFO-153-10mzzE-1,1,1,2,2,5,5,6,6,6- exene E-C F CH=CHCE-HFO-153- decafluoro-3-h 2 5 2F510mczz Z-1,1,1,2,2,5,5,6,6,6- decafluoro-3-hexene Z-C2F5CH=CHC2F5 Z-HFO-153-10mczz1,1,1,2,2,3,5,5,6,6,6-undecafluoro-3-hexene CF3CF2CF=CHCF2CF3 HFO-152-11mcyzE-1,1,1,2,2,3,5,5,6,6,6- exene E-CF3CF2CF=CHCF2E-HFO-152-undecafluoro-3-h CF311mcyz E-1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-hexene E-CF3CF=CHCF2CF2CF3 E-HFO-152-11myzZ-1,1,1,2,2,3,5,5,6,6,6-undecafluoro-3-hexene Z-CF3CF2CF=CHCF2CF3 Z-HFO-152-11mcyzZ-1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-hexene Z-CF3CF=CHCF2CF2CF3 Z-HFO-152-11myz3-chloro- 1,1,1,2,2,5,5,6,6,6-CF3CF2CCl=CHCF2CF3HCFO-152-decafluoro-3-hexene10mcxz2-chloro- 1,1,1,4,4,5,5,6,6,6- CF3CCl=CHCF2CF2CF3 HCFO-152-10mdz decafluoro-2-hexene 2-chloro-3,3,3- trifluoropropene CF3CCl=CH2 HCFO-1233xf2,3,3,3- tetrafluoropropene CF3CF=CH2 HFO-1234yf1,3,3,3- tetrafluoropropene CF3CH=CHF HFO-1234zedichloropenta- HCFO-1325 fluorobutene isomers C4HCl2F5isomers 2-chloro-1,1,1,4,4,4- hexafluoro-2-butene CF3CCl=CHCF3 HCFO-1326mxzchloropentafluorobutene rs C H CHCFO-1335 isome 4 2 lF5isomers 1,1,1,4,4-pentafluoro-3- chlorobutene CF3CH=CClCF2H HCFO-1335mxzhexafluorobutene isomers C4H2F6 HFO-1336 isomersName Formula Compound,1,1,4,4,4-hexafluoro-2- butene CF3CH=CHCF3 HFO-1336mzztrichlorotrifluorobuteneCHCFO-1343 isomers 4H3Cl2F3isomers E-1,2-dichloro-4,4,4- trifluoro-2-butene CF3CCl=CHCH2Cl E-HCFO-1343mxzZ-1,2-dichloro-4,4,4- trifluoro-2-butene CF3CCl=CHCH2Cl Z-HCFO-1343mxz,1,4,4,4-pentafluoro-2- butene CF3CH=CHCHF2 HFO-1345mzz,3,4,4,4-pentafluorobut- 1-ene CH2=CHCF2CF3 HFO-1345zfchlorotrifluorobutene H omers CCFO-1353 is 4H4ClF3isomers nonafluoropentene isomers C5HF9 HFO-1429 isomersoctafluoropentene isomers C5H2F8 HFO-1438 isomers2,3,5-trichloro- 1,1,1,4,4,6,6,6- CF3CCl=CClCF2CHClCF3 HCFO-1528mdcxx octafluoro-2-hexene 2,4-dichloro- 1,1,1,5,5,6,6,6- CF3CCl=CHCHClCF2CF3 HCFO-1538mxzd octafluoro-2-hexene chloro- nonafluorohexene C6H3ClF9HCFO-1539isomersisomers2-chloro- 1,1,1,2,5,5,6,6,6- CF3CClF=CHCH2CF2CF3 HCFO-1539mbzz nonafluoro-3-hexene ,5-dichloro-1,1,1,6,6,6- hexafluorohexa-2,4- CF3CCl=CHCH=CClCF3 HCFO-2536mxzzx diene 2-chloro-1,1,1,5,6,6,6- heptafluorohexa-2,4- CF3CCl=CHCH=CFCF3 HCFO-2537mxzzy diene dodecafluorohexane isomers C6H2F12 HFC-53-12 isomerstetrachlorohexa- omers C Cl FHCFO-1416fluoropentene is 5 4 6isomerschlorotrifluoromethane CClF3 CFC-13trifluoromethane CHF3 HFC-23Name Formula Compound1-chloro-1,1,2,2,2- pentafluoroethane CClF2CF3 CFC-1151-chloro-1,2,2,2- tetrafluoroethane CHClFCF3 HCFC-1241,1,1,2,2- pentafluoroethane CF3CHCF2 HFC-1252-chloro-1,1,1- trifluoroethane CF3CH2Cl HCFC-133a1,1,2,2-tetrafluoroethane CHF2CHF2 HFC-1341,1,1-trifluoroethane CF3CH3 HFC-143a1,1,1,2,2,3,3- heptfluoropropane CF3CF2CHF2 HFC-227ca1,1,1,3,3,3- hexafluoropropane CF3CH2CF3 HFC-236fa1,1,1,2,2- pentafluoropropane CF3CF2CH3 HFC-245cb1,1,1,2,2,4,4,4- octafluorobutane CF3CH2CF2CF3 HFC-338mfdichloropenta- fluorobutane isomers C4H3Cl2F5 HCFC-345 isomers2-chloro-1,1,1,4,4,4- hexafluorobutane CF3CH2CHClCF3 HCFC-346mdfheptafluorobutane isomers C4H3F7 HFC-347 isomers2,2,4-trichloro-1,1,1- trifluorobutane CH2ClCH2CCl2CF3 HCFC-353mafchloropentafluorobutane isomers C4H4ClF5 HCFC-355 isomers3,5,5-trichloro- 1,1,1,2,2,6,6,6- CF3CF2CHClCH2CCl2CF3 HCFC-548mafd octafluorohexane C5H2F8 C5H2F8 isomers C5HClF8 C5HClF8 isomers C5HF9 C5HF9 isomers C6ClF11 C6ClF11 isomers C6ClF9 C6ClF9 isomers C6Cl3F7 C6Cl3F7 isomers C6Cl4F6 C6Cl4F6 isomers C6HClF10 C6HClF10 isomersName Formula CompoundC6HClF8 C6HClF8 isomers C6HCl2F9 C6HCl2F9 isomers C6HCl2F7 C6HCl2F7 isomers C6HCl3F8 C6HCl3F8 isomers C6H2ClF9 C6H2ClF9 isomers C6H2ClF7 C6H2ClF7 isomers C6HF11 C6HF11 isomers C6HF9 C6HF9 isomers C6H2F10 C6H2F10 isomers C6H2F8 C6H2F8 isomers C6H4F6 C6H4F6 isomers C6F12 C6F12 isomers C6F10 C6F10 isomers C6F8 C6F8 isomers C6H10 C6H10 isomers C7H5F7 C7H5F7 isomers BRIEF DESCRIPTION OF THE FIGURE

[0011] Figure 1 provides a flow diagram for a process useful to prepare E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene according to an embodiment of this invention. DETAILED DESCRIPTION

[0012] The present invention relates broadly to compositions comprising E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (E-HFO-153-10mczz, E-CF3CF2CH=CHCF2CF3), processes of preparing such compositions and their use. GENERAL TERMS

[0013] Compounds may be referred to herein by the compound name (e.g., E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene) or ASHRAE designation (e.g., E-HFO-153-10mczz, or more simply, E-153-10mczz) or chemical formula (e.g.,CF3CF2CH=CHCF2CF3) and optionally prefaced by “CFC”, “HCFC”, “HFC”, “CFO”, “HCFO”, or “HFO”, meaning “chlorofluorocarbon”, “hydrochlorofluorocarbon”, “hydrofluorocarbon”, “chlorofluoroolefin”, “hydrochlorofluoroolefins”, or“hydrofluoroolefin”. The absence of the preface does not change the meaning of the compound.

[0014] The term “isomers” is used to represent one or more compounds having therecited chemical formula that are identified using standard analytical techniques (GC and GC-mass spectrometry). The isomers may include one or more compounds having the recited chemical formula, such as linear, branched and cyclic compounds). Alternatively, isomers may include unsaturated compounds (having a double bond) or cyclic compounds having the same chemical formula or multiple unsaturations (two or more double bonds) or combinations with cyclic structures.

[0015] More specifically, when a compound is recited as a chemical formula, one ormore isomers having the recited formula are included. For example, the chemical formula “C6HF11” includes compounds having the recited chemical formula (e.g., C6HF11) are included (such as linear, branched and cyclic compounds).

[0016] In addition, with respect to compounds having unsaturation (double bond), thecompound may have “E-“ and “Z-“ isomers. If neither “E-“ nor “Z-“ are identified, the compound disclosed may contain one or both isomers. Specific isomers are identified as “E-“ or “Z-“. For example, HFO-152-11mcyz may include one or both of E-HFO-152- 11mcyz and Z- HFO-152-11mcyz, whereas specific isomers are identified as “E-HFO- 152-11mcyz” and “Z-HFO-152-11mcyz.

[0017] 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 composition, 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 composition, process, method, article, or apparatus. 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).

[0018] The transitional phrase "consisting of" excludes any element, step, oringredient not specified. If in the claim, such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase "consists of" appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.

[0019] The transitional phrase "consisting essentially of" is used to define acomposition, 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 “consisting essentially of” occupies a middle ground between “comprising” and “consisting of”.

[0020] Where applicants have defined an invention or a portion thereof with an open-ended term such as “comprising,” it should be readily understood that (unless otherwise stated) the description should be interpreted to also include such an invention using the terms “consisting essentially of” or “consisting of.”

[0021] Also, use of “a” or “an” are employed to describe elements and componentsdescribed 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.

[0022] 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. It is not intended that the scope of the invention be limited to the specific values recited when defining a range. Moreover, all ranges set forth herein are intended to include not only the particular ranges specifically described, but also any combination of values therein, including the minimum and maximum values recited.

[0023] The term “compound” as used herein is meant to include all stereoisomers,geometric isomers, tautomers, and isotopes of the structures or chemical described. Compounds herein identified by name or structure as one particular tautomeric form are intended to include other tautomeric forms unless otherwise specified.

[0024] When an amount, concentration, or other value or parameter is given as eithera 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.

[0025] As used herein the term “about” in certain embodiments can be quantified tomean ± 1%, ± 2%, ± 3% up to and including ±10% of the stated value, and all whole numbers and fractions therebetween. PROCESS DESCRIPTION

[0026] The present invention describes processes for preparing a mixture or acomposition comprising, consisting of, or consisting essentially of E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene and one or more additional compounds.

[0027] In one embodiment, the present invention provides a process for preparing E-HFO-153-10mczz comprising contacting HCFC-548mafd with HF in the presence of a fluorination catalyst in a reactor.

[0028] The present invention provides a process for preparing E-HFO-153-10mczzcomprising contacting HCFC-548mafd with HF in the presence of a fluorination catalystin a reactor, to obtain a process mixture comprising E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, wherein the process is performed at a temperature of about 250-450°C, a pressure of about 0 to 200 psig. Preferably, the temperature is in the range of about 275 to about 380°C, or such as about 300-380°C. Preferably the pressure is in the range ofHCFC-548mafd with HF are from about 30 to 180 psig or about 40 to 150 psig, or about 60-120 psig, such as about 80 psig.

[0029] The process of the present invention is preferably performed in the presenceof oxygen or an oxygen-containing gas, which may be co-fed with the starting material HCFC-548mafd and / or HF. The oxygen-containing gas may be, for example, air.

[0030] In the present invention, it has been found particularly advantageous toperform the process of contacting HCFC-548mafd with HF in the presence of a fluorination catalyst at a temperature of about 250-450°C. At temperatures lower than this range, when oxygen is added, the oxygen is less effective at removing tar deposits from the catalyst resulting in faster deactivation. Higher temperatures increase the rate of fluorination of the catalyst also deactivating the catalyst and increases formation of side products.

[0031] In one embodiment, a composition comprising E-HFO-153-10mczz isproduced in one step by fluorination of HCFC-548mafd. More particularly, the process comprises fluorination of HCFC-548mafd by reacting with HF, in the presence of afluorination catalyst, to make a product comprising E-HFO-153-10mczz. The productcomprises, consists of, or consists essentially of E-HFO-153-10mczz, which is or can beas a heat transfer fluid in applications such as power cycles, high temperature heat pumps and immersion cooling. Fluorination Catalyst

[0032] The fluorination catalyst used in the process of this invention comprises one ormore metals, metal oxides, metal oxyfluorides or metal fluorides. A metal oxide catalyst preferably forms a metal (oxy)fluoride having Lewis acid character. Examples of metals suitable for use in the fluorination catalyst is chosen from one or more of metals selected from Al, Sc, Y, Ti, Zr, Hf, V Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, La and Ce.

[0033] In certain embodiments, the fluorination catalyst comprises one or more of Al,Zr, Cr, Co and Ni.

[0034] In one embodiment, the fluorination catalyst comprises chromium oraluminum. In one embodiment the fluorination catalyst comprises chromium or aluminum and one or more of Zn, Zr, Co, and Ni.

[0035] Certain metal oxide or metal fluoride fluorination catalysts may contain one ormore additional metals selected from the group consisting of Li, Na, K, Ca, Mg, and Cs. The additional metal may be present in smaller amounts (such in an amount of less than 2000 or less than 1000 or less than 500 or less than 100 or less than 10 ppm).

[0036] In certain embodiments, the fluorination catalyst comprises aluminum. Thealuminum may be present in the form of aluminum oxide, aluminum fluoride or aluminum oxyfluoride. In certain embodiments the fluorination catalyst comprises Al and one or more of Sc, Y, Ti, Zr, Hf, V Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, La and Ce. In certain embodiments the fluorination catalyst comprises Al and one or more of Zn, Zr, Cr, Co, and Ni.

[0037] In certain embodiments, the fluorination catalyst comprises chromium. Thechromium may be present in the form of chromium oxide, chromium chloride, chromium fluoride or chromium oxyfluoride. Chromium may be in the form of Cr(III), such as Cr2O3. In certain embodiments the fluorination catalyst comprises Cr and one or more of Al, Sc, Y, Ti, Zr, Hf, V Nb, Ta, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, La and Ce. In certain embodiments the fluorination catalyst comprises Cr and one or more of Zn, Zr, Co, and Ni.

[0038] In one embodiment, the fluorination catalyst comprises Cr2O3. In oneembodiment, the fluorination catalyst comprises Cr2O3 and one or more of Zn, Zr, Co, K, Na and Ni. In one embodiment, the fluorination catalyst comprises Cr2O3 and Zn. In one embodiment, the fluorination catalyst comprises Cr2O3 and Co. In one embodiment, the fluorination catalyst comprises Cr2O3 and Ni. In one embodiment, the fluorination catalyst comprises Cr2O3 and Zr.

[0039] In one embodiment, the fluorination catalyst comprises Cr2O3 and at least oneof Zn, Zr, Co, and Ni, wherein the amount of Zn, Zr, Co, and / or Ni ranges from about 100 ppm to about 10% by weight, based on weight of Cr2O3. In one embodiment thefluorination catalyst comprises Cr2O3 and Zn wherein the amount of Zn is in the range of from about 100 ppm to about 10% by weight, based on weight of Cr2O3. In one embodiment the fluorination catalyst comprises Cr2O3 and Zn wherein the amount of Zn is in the range of from about 100 ppm to about 10% by weight, based on weight of Cr2O3. In one embodiment the fluorination catalyst comprises Cr2O3 and Co wherein the amount of Co is in the range of from about 100 ppm to about 10% by weight, based on weight of Cr2O3. In one embodiment the fluorination catalyst comprises Cr2O3 and Ni, wherein the amount of Ni is in the range of from about 100 ppm to about 10% by weight, based on weight of Cr2O3.

[0040] In one embodiment, the fluorination catalyst comprises Al2O3. In oneembodiment, the fluorination catalyst comprises Al2O3 and one or more of Zn, Zr, Cr, Co, and Ni. In one embodiment, the fluorination catalyst comprises Al2O3 and Zn. In one embodiment, the fluorination catalyst comprises Al2O3 and Zn. In one embodiment, the fluorination catalyst comprises Al2O3 and Cr. In one embodiment, the fluorination catalyst comprises Al2O3 and Co. In one embodiment, the fluorination catalyst comprises Al2O3 and Ni.

[0041] In one embodiment, he fluorination catalyst comprises Al2O3 and at least oneof Zn, Zr, Cr, Co, and Ni, wherein the amount of Zn, Zr, Cr, Co, and / or Ni ranges from about 100 ppm to about 10% by weight, based on weight of Al2O3. In one embodiment the fluorination catalyst comprises Al2O3 and Zn wherein the amount of Zn is in the range of from about 100 ppm to about 10% by weight, based on weight of Al2O3. In one embodiment the fluorination catalyst comprises Al2O3 and Zr wherein the amount of Zr is in the range of from about 100 ppm to about 10% by weight, based on weight of Al2O3. In one embodiment the fluorination catalyst comprises Al2O3 and Cr wherein the amount of Cr is in the range of from about 100 ppm to about 10% by weight, based on weight of Al2O3. In one embodiment the fluorination catalyst comprises Al2O3 and Co wherein the amount of Co is in the range of from about 100 ppm to about 10% by weight, based on weight of Al2O3. In one embodiment the fluorination catalyst comprises Al2O3 and Ni, wherein the amount of Ni is in the range of from about 100 ppm to about 10% by weight, based on weight of Al2O3.

[0042] The fluorination catalyst may be on a support (“supported”) or unsupported ora mixture of a support with the fluorination catalyst. If a support is present, suitablesupports include AlF3, alumina, fluorinated alumina or activated carbon. The fluorinationcatalyst, for example, may comprise chromium oxide and alumina.

[0043] The fluorination catalyst may comprise a metal oxide or metal oxyhalidessupported on chromia or alumina, for example oxides of zinc, iron, magnesium or nickel.The fluorination catalyst may comprise a metal oxides / halides / oxyhalides, or mixedmetal oxides / halides / oxyhalides supported on carbon, wherein the metal is chosen fromone or more of Al, Sc, Y, Ti, Zr, Hf, V Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni,Pd, Pt, Cu, Ag, Au, Zn, La and Ce.

[0044] In one embodiment, the fluorination catalyst is a chromium-based catalyst,such as chromium oxide (Cr2O3) or fluorinated chromium oxide, which catalyst may either be unsupported, or supported on a support such as activated carbon, graphite, fluoride graphite, or alumina fluoride. The chromium fluorination catalyst may either be used alone, or in the presence of a co-catalyst selected from nickel, cobalt, manganese, potassium, sodium or zinc. In one embodiment, optionally a chromium fluorination catalyst is high surface area chromium oxide, or chromium / nickel on alumina fluoride (Cr / Ni / AlF3), or chromium halide on carbon, the preparation of which is reported in European Patent EP486333. In another embodiment, the fluorination catalyst is fluorinated Guignet’s green catalyst.

[0045] In one embodiment, the fluorination catalyst comprises Al2O3. In oneembodiment, the fluorination catalyst comprises Al2O3 and one or more of Zn, Zr, Cr, Co, and Ni. In one embodiment, the fluorination catalyst comprises Al2O3 and Zn, or Al2O3 and Cr, or Al2O3 and Co, or Al2O3 and Ni, or Al 2O3 and Zr.

[0046] In one embodiment, the fluorination catalyst comprises chromium supportedon AlF3, alumina, fluorinated alumina or activated carbon. In one embodiment, the fluorination catalyst comprises chromium supported on alumina.

[0047] In one embodiment, the fluorination catalyst comprises zinc supported on AlF3,alumina, fluorinated alumina or activated carbon. In one embodiment, the fluorination catalyst comprises zinc supported on alumina.

[0048] The physical shape of the fluorination catalyst is not critical and may, forexample, include pellets, extrudates, powders, or granules.

[0049] In one embodiment, the fluorination catalyst is shaped into a form, such asgranulated, or pressed into pellets. A variety of methods generally known in the art, may be used that are suitable to provide, for example, a packed bed of catalyst in a flow reactor.

[0050] In one embodiment, the process comprises activating the fluorination catalystin a prefluorination treatment prior to contacting HCFC-548mafd with HF in the presence of the catalyst. Activation of the fluorination catalyst is preferably carried outon the final shape of the catalyst; in the event the catalyst is shaped into a form. Itshould be understood that while the term “fluorination catalyst” is used to refer to metal oxides, including Cr2O3 and Al2O3, herein, the metal oxide will undergo the prefluorination step to generate the active catalyst in situ.

[0051] In one embodiment, the catalyst undergoes a prefluorination treatment bypassing HF, with or without an inert diluent such as nitrogen, over the catalyst at a temperature within the range of about 250 to 450°C prior to use.

[0052] In a particular embodiment, the fluorination catalyst comprises chromium andthe fluorination catalyst is activated before use, by a procedure comprising heating the fluorination catalyst to a temperature of from 350°C to 400°C under a flow of nitrogen for a period of time, then heating the fluorination catalyst under a flow of HF and nitrogen or air for an additional period of time in one embodiment of a prefluorination treatment.

[0053] After use for a period of time, the activity of the catalyst may decrease. Whenthis occurs, the catalyst may be regenerated, wherein a regenerating step comprises treating the catalyst with oxygen or air at elevated temperature. Optionally, the catalyst is treated with HF at a temperature in the range of 250°C to 450°C, after the treatment with oxygen before the regenerated catalyst is re-used. The regenerating step isperformed after purging the majority of the organic components from the processmixture, wherein the organic materials comprise 548mafd and / or E-153-10mczz.Reaction conditions

[0054] In one embodiment, suitable temperatures for the process of the reaction ofHCFC-548mafd with HF are from about 250°C to about 450°C, preferably from about 300°C to about 380°C. Temperature ranges are set to advantageously protect the catalyst from deactivation. It has been found that operating at temperatures outside of the recited ranges results in faster deactivation of the catalyst. For example, it is believed at lower temperatures, carbon deposits remain on the surface of the catalyst. In addition, at higher temperatures, the catalyst is more susceptible to becoming fluorinated in a way that also results in catalyst deactivation. Thus, a balance must be found to address fluorination catalyst deactivation from both carbon containing compounds deposits as well as fluorination of the fluorination catalyst.

[0055] In one embodiment, suitable pressures for the process of the reaction ofHCFC-548mafd with HF are from about 0 to 200 psig, preferably from about 30 to 180 psig or about 40 to 150 psig, or about 60-120 psig.. Pressure ranges are set to advantageously protect the catalyst from deactivation and to enhance separation and recovery of HCl component of the product. At lower pressures, the recovery of HCl is more complex. In addition, at higher pressures, it is found that the rate of catalyst deactivation increases.

[0056] In the process of this invention, it is preferred to have a molar ratio of HF toHCFC-548mafd from about 3:1 to about 50:1, preferably from about 10:1 to about 45:1, more preferred, 15:1 to 40:1. Higher ratios are undesired for overall efficiency of the process, and also impact temperature, pressure and contact time. Lower ratios impact productivity (conversion, selectivity, and yield).

[0057] In the process of this invention, comprising contacting HCFC-548mafd withhydrogen fluoride (HF) in a reactor, in the presence of a fluorination catalyst, to producea process mixture comprising E-HFO-153-10mczz and HCl, an amount of oxygen isoptionally added. The oxygen amount added ranges from about 0 to about 10 mole%based on the amount of organic feed to the contacting step. The organic feed comprises HCFC-548mafd. Optionally, the organic feed further comprises intermediates recycled from separation processes such as those described herein. The intermediates may comprise one or more of C6H2ClF9 isomers, C6HClF8 isomers, C6H2Cl2F8 isomers, C6HCl2F7 isomers and C6HCl3F6 isomers.

[0058] Preferably the amount of oxygen added in the process of this invention isgreater than 0% and less than 10 mole%, such as from about 0.2 mole % to about 5 mole%, or about 1 mole%. An amount of oxygen added in the process such as in the range of about 0.2 mole % to about 5 mole%, improves life of the fluorination catalyst. In the absence of added oxygen, the rate of catalyst deactivation increases. It is also important to avoid adding too much oxygen in the process. A higher concentration of oxygen, particularly greater than 15 mole% oxygen results in lower yield as there is an increase in the formation of oxygenated byproducts. In addition, a higher concentration of oxygen presents a flammability risk.

[0059] In the process of this invention, comprising contacting HCFC-548mafd withhydrogen fluoride (HF), in a reactor, in the presence of a fluorination catalyst, a processmixture comprising E-HFO-153-10mczz and HCl, the contact time can be chosen from arange of contact times, such as from as low as about 1 second to 180 seconds. In one embodiment, contact time is from 5 seconds to 120 seconds, or 10-60 seconds or about 15 seconds. It should be appreciated that shorter contact times reduces conversion of the starting material 548mafd. However longer contact times may be undesirable as they may increase formation of byproducts (lower yield, selectivity) for a given set of reaction conditions.

[0060] Preferably, the fluorination reaction is carried out in the vapor phase.However, it will be understood by those skilled in the art that the fluorination of HCFC- 548mafd may, alternatively, be performed in the liquid phase.

[0061] In one embodiment, the HCFC-548mafd starting material may be pre-mixedwith the HF, and then introduced into the reactor. In some embodiments, thefluorination catalyst may optionally also be pre-mixed with the HCFC-548mafd and HF.In another embodiment, the HF may not be contacted with the HCFC-548mafd until both have been introduced into the reactor.

[0062] In some embodiments, the reaction of HCFC-548mafd produces an effluentstream comprising a process mixture or composition comprising E-HFO-153-10mczzand HCl.

[0063] In some embodiments, this step may be conducted in a reactor or reactionzone which is operating in batch, semi-batch, semi-continuous, or continuous modes, toproduce a reaction mixture comprising E-HFO-153-10mczz. An effluent stream of thereactor or reaction zone comprises the reaction mixture comprising E-HFO-153-10mczzand HCl and HF.

[0064] For the reaction of HCFC-548mafd and HF, the process mixture comprises E-HFO-153-10mczz and HCl, and may further contain excess HF, as well as, optionally, reaction byproducts and intermediates. The reaction byproducts may comprise one or more of HCFO-1539mbzz (CF3CFClCH=CHCF2CF3), HCFO-152-10mcxz (CF3CF2CCl=CHCF2CF3), HCFO-2536mxzzx (CF3CCl=CHCH=CClCF3), C6H2ClF9, C6HClF8, C6H2Cl2F8, C6HCl2F7, and C6HCl3F6.

[0065] The process mixture may comprise additional components such as unreactedstarting material, HCFC-548mafd (CF3CF2CHClCH2CCl2CF3) and optionally, intermediates and byproducts formed in the process. The intermediates and byproducts may comprise one or more isomers of HCFO-1539. In one embodiment, the intermediates and byproducts comprise HCFO-1539mbzz. The intermediates and byproducts may further comprise at least one of C6H2ClF9, C6HClF8, C6H2Cl2F8, C6HCl2F7, and C6HCl3F6. Any of the unreacted starting materials, HF and 548mafd, may be optionally separated and recycled for further reaction. Advantageously, when the process mixture comprises any of HF, HCFC-548mafd, intermediates and byproducts, the process comprises separating the HF, HCFC-548mafd, and intermediates from the process mixture and recycling each of these to the process for contacting with the fluorination catalyst. Intermediates and byproducts may comprise one or more isomers of HCFO-1539, C6H2ClF9, C6HClF8, C6H2Cl2F8, C6HCl2F7, or C6HCl3F6.

[0066] In one embodiment, the process of this invention involves reacting 548mafdwith an excess of HF (HF to organic of about 10:1 to about 30:1) in a vapor phasereactor, producing a product stream comprising E-153-10-mczz and HCl. In oneembodiment, the catalyst comprises chrome oxide (Cr2O3). The catalyst is dried and partially fluorinated with HF before use. The operating temperature is about 260°C to about 380°C and the operating pressure is about 0 to about 200 psig. The process further comprising adding 0.5 to 5 mole % oxygen in the feed (based on the feed of 548mafd) to maintain / increase catalyst life. In one embodiment, in a continuous process, the reactor is shut down periodically to regenerate the catalyst. Catalyst regeneration may occur over a span of time from about once every year to once every 5 days. For example, catalyst regeneration may occur once every 30 days or once every 20 days or once every 15 days, such as once every 18 days. The reactor has a heat transfer system to achieve and maintain a target operating temperature.

[0067] Specific conditions of temperature, pressure, HF:organic ratio, oxygenconcentration and contact time are provided, wherein the organic is 548mafd. It has been found that the recited conditions provide limit disadvantages of operating outside of the recited conditions. Disadvantages include one or more of catalyst deactivation, increased difficulties to recover product, increased byproducts (loss of yield, loss of selectivity), lower conversion, need for larger reactor.

[0068] After exiting the reactor, the process mixture comprising E-HFO-153-10mczzand HCl undergoes distillation to remove HCl. The process mixture further comprises unreacted HF as the process uses an excess of HF. The unreacted HF in the process mixture is preferably then recovered and recycled back to the reactor.

[0069] In one embodiment, HF is recovered from the process mixture. HF recoverymay comprise a combination of distillation and liquid-liquid phase separation. When the process mixture comprises residual acids, residual acids may be removed from the process mixture by absorbing by Al2O3 or absorbing into an aqueous medium, which optionally contains dilute base, and neutralizing with dilute base (such as alkali metal hydroxide, including, but not limited to KOH), providing a neutralized stream. Following removal of acids from the process mixture, the neutralized stream is then dried, forexample, using molecular sieves. The dried E-HFO-153-10mczz may undergo a finaldistillation to provide a purified product comprising E-HFO-153-10mczz, available foruse.

[0070] Equipment used in the process of this invention includes feed systems,storage tanks, reactor, distillation columns and the like. Carbon steel may be acceptable for ambient temperature feed systems and storage tanks. The reactor and high temperature portions of the equipment, including the HCl column are preferably constructed of an alloy such as Inconel or Hastelloy. Certain equipment may be lined with PTFE.

[0071] In one embodiment of the process of this invention, there is provided areaction system comprising a reactor and a purification system. The reaction system includes feeds to introduce reactants to the reactor.

[0072] The feeds include a reactant HCFC-548mafd feed, a fresh reactant HF feed,and optionally a feed for recycled intermediates, a feed for recycled 548mafd, and a recycled HF feed. The fresh reactant HF feed and optional recycled HF feed may be combined in a single feed for HF to be introduced to the reactor. There is also a fluorination catalyst feed to introduce the fluorination catalyst to the reactor, such as from a catalyst bed.

[0073] The feeds may further comprise a recycle stream comprising HCFC-548mafdand intermediates and byproducts. The recycle stream may comprise one or more of HFO-1539mbzz (CF3CFClCH=CHCF2CF3), HCFO-152-10mcxz (CF3CF2CCl=CHCF2CF3), HFO-2536mxzzx (CF3CCl=CHCH=CClCF3), C6H2ClF9 isomers. C6HClF8 isomers, C6H2Cl2F8 isomers, C6HCl2F7 isomers and C6HCl3F6 isomers. Intermediates may comprise one or more of C6H2ClF9 isomers. C6HClF8 isomers, C6H2Cl2F8 isomers, C6HCl2F7 isomers and C6HCl3F6 isomers.

[0074] A reactor process mixture exits the reactor. The reactor process mixture mayproceed through a mechanism to separate catalyst from the process mixture in a reaction process mixture. The reaction process mixture proceeds through heat exchangers prior to entering the purification system.

[0075] In one embodiment, the present invention provides a composition comprisingE-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (E-HFO-153-10mczz), and at least one additional compound chosen from 2-chloro-1,1,1,2,5,5,6,6,6-nonafluoro-3-hexene (HCFO-153-9mbzz ), 3-chloro-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (HCFO-152- 10mcxz), 2,5-dichloro-1,1,1,6,6,6-hexafluorohexa-2,4-diene (HCFO-2536mxzzx), 2- chloro-1,1,1,5,6,6,6-heptafluorohexa-2,4-diene (HCFO-2537mxzzy), 2,4-dichloro- 1,1,1,5,5,6,6,6-octafluoro-2-hexene (HCFO-1538mxzd), 1,1,1,2,2,3,5,5,6,6,6- undecafluoro-3-hexene (HFO-152-11mcyz), 1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2- hexene (HFO-152-11myz), 2-chloro-1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene (HCFO- 152-10mdz), 2,3,5-trichloro-1,1,1,4,4,6,6,6-octafluoro-2-hexene (HCFO-1528mdcxx), 1- chloro-3,3,4,4,5,5-hexafluoro-2-(trifluoromethyl)cyclopent-1-ene, 1,1,1,4,4,5,5,6,6,6- decafluoro-2-hexene (HFO-153-10mzz), C6F10 isomers, hexafluorobutene isomers (HFO-1336 isomers), C5HF9 isomers, C6F12 isomers, C6HF11 isomers, C5H2F8 isomers, C5HClF8 isomers, C6F8 isomers, C6HF9 isomers, C6ClF9 isomers, 2-chloro-1,1,1,4,4,4- hexafluoro-2-butene (HCFO-1326mxz), 2-chloro-1,1,1,4,4,4-hexafluorobutane (HCFC- 346mdf) and 3,5,5-trichloro-1,1,1,2,2,6,6,6-octafluorohexane (HCFC-548mafd).

[0076] The purification system comprises distillation columns, absorbers, scrubbersand dryers.

[0077] The products from the reaction of the process of this invention may be purifiedin a series of additional steps.

[0078] In one embodiment of the process of this invention, the process mixture iscooled, such as through heat exchangers and is then treated in distillation columns to remove HCl (a product of the reaction) to provide a process stream with reduced HCl. The process stream with reduced HCl further comprises unreacted HF as the process uses an excess of HF.

[0079] Following removal of HCl, HF may be removed in a distillation column or aphase separation. Since HF is a reactant in the process, the removed HF is preferably recycled to the contacting step of the process as recycled HF feed. HF removal for recycling may comprise a combination of distillation and liquid-liquid phase separation.

[0080] In addition to HCl and HF, the process mixture may comprise residual acids.Residual acids may be removed from the process mixture after removing HCl and HF, by absorbing with Al2O3, or absorbing into an aqueous medium in an absorber, which optionally contains dilute base (such as alkali metal hydroxide, including, but not limited to KOH). Following removal of residual acids, a scrubbed process mixture is provided.

[0081] The scrubbed process mixture may comprise intermediates and byproductsformed during the process. The scrubbed process mixture may comprise one or more HFO-1539mbzz (CF3CFClCH=CHCF2CF3) and HFO-152-10mcdz (CF3CF2CCl=CHCF2CF3) and HFO-2536mxzzx (CF3CCl=CHCH=CClCF3), C6H2ClF9 isomers, C6HClF8 isomers, C6H2Cl2F8 isomers, C6HCl2F7 isomers, and C6HCl3F6 isomers. The intermediates may be also removed, such as by distillation and recycled back to the reactor. The intermediates may comprise one or more of C6H2ClF9 isomers. C6HClF8 isomers, C6H2Cl2F8 isomers, C6HCl2F7 isomers and C6HCl3F6 isomers.

[0082] Following removal of residual acids and intermediates, a scrubbed and distilledprocess mixture is provided. The scrubbed and distilled process mixture is then dried by passing through a drying agent. The drying agent may be, for example, molecular sieves, providing a dried process mixture. The dried process mixture is distilled usingone or more distillation columns to provide a purified product comprising E-HFO-153-10mczz. The purified product may comprise greater than 95% or greater than 98% orgreater than 99% or greater than 99.5% E-HFO-153-10mczz. The purified product maycomprise E-HFO-153-10mczz and at least one additional compound wherein theamount of E-HFO-153-10mczz is at least 99% or at least 99.5%.

[0083] In one embodiment, there is provided a composition comprising E-HFO-153-10mczz and at least one of 2-chloro-1,1,1,2,5,5,6,6,6-nonafluoro-3-hexene (HCFO- 1539mbzz), 1,1,1,2,2,3,5,5,6,6,6-undecafluoro-3-hexene (HFO-152-11mcyz) and Z- 1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-hexene (Z-HFO-152-11myz). This compositionmay comprise at least 99% or at least 99.5% E-HFO-153-10mczz.

[0084] In one embodiment, there is provided a composition comprising E-HFO-153-10mczz and 2-chloro-1,1,1,2,5,5,6,6,6-nonafluoro-3-hexene. This composition maycomprise at least 99% or at least 99.5% E-HFO-153-10mczz.

[0085] In one embodiment, there is provided a composition comprising E-HFO-153-10mczz, 2-chloro-1,1,1,2,5,5,6,6,6-nonafluoro-3-hexene and 1,1,1,2,2,3,5,5,6,6,6- undecafluoro-3-hexene. This composition may comprise at least 99% or at least 99.5% E-HFO-153-10mczz.

[0086] In one embodiment, there is provided a composition comprising E-HFO-153-10mczz, 2-chloro-1,1,1,2,5,5,6,6,6-nonafluoro-3-hexene and Z-1,1,1,2,4,4,5,5,6,6,6- undecafluoro-2-hexene. This composition may comprise at least 99% or at least 99.5% E-HFO-153-10mczz.

[0087] In one embodiment, there is provided a composition comprising E-HFO-153-10mczz and 1,1,1,2,2,3,5,5,6,6,6-undecafluoro-3-hexene. This composition maycomprise at least 99% or at least 99.5% E-HFO-153-10mczz.

[0088] In one embodiment, there is provided a composition comprising E-HFO-153-10mczz and Z-1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-hexene. This composition maycomprise at least 99% or at least 99.5% E-HFO-153-10mczz.

[0089] In one embodiment, there is provided a composition comprising E-HFO-153-10mczz, 1,1,1,2,2,3,5,5,6,6,6-undecafluoro-3-hexene and Z-1,1,1,2,4,4,5,5,6,6,6- undecafluoro-2-hexene. This composition may comprise at least 99% or at least 99.5% E-HFO-153-10mczz.

[0090] In one embodiment, there is provided a composition comprising E-HFO-153-10mczz, 2-chloro-1,1,1,2,5,5,6,6,6-nonafluoro-3-hexene, 1,1,1,2,2,3,5,5,6,6,6- undecafluoro-3-hexene and Z-1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-hexene. Thiscomposition may comprise at least 99% or at least 99.5% E-HFO-153-10mczz.

[0091] The composition comprising E-HFO-153-10mczz and one or more additionalcompounds may be used as a refrigerant. In one embodiment, the composition for useas a refrigerant comprises E-HFO-153-10mczz and at least one of 2-chloro-1,1,1,2,5,5,6,6,6-nonafluoro-3-hexene, 1,1,1,2,2,3,5,5,6,6,6-undecafluoro-3-hexene and Z-1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-hexene.

[0092] The composition comprising E-HFO-153-10mczz and one or more additionalcompounds may be used in a heat transfer application. In one embodiment, thecomposition for use in a heat transfer application comprises E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene and at least one of 2-chloro-1,1,1,2,5,5,6,6,6-nonafluoro-3-hexene, 1,1,1,2,2,3,5,5,6,6,6-undecafluoro-3-hexene and Z-1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2- hexene.

[0093] The composition comprising E-HFO-153-10mczz and one or more additionalcompounds may be used as a foam expansion agent. In one embodiment, thecomposition for use as a foam expansion agent comprises E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene and at least one of 2-chloro-1,1,1,2,5,5,6,6,6-nonafluoro-3-hexene, 1,1,1,2,2,3,5,5,6,6,6-undecafluoro-3-hexene and Z-1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2- hexene.

[0094] The composition comprising E-HFO-153-10mczz and one or more additionalcompounds may be used as a power cycle working fluid. In one embodiment, thecomposition for use as a power cycle working fluid comprises E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene and at least one of 2-chloro-1,1,1,2,5,5,6,6,6-nonafluoro-3-hexene, 1,1,1,2,2,3,5,5,6,6,6-undecafluoro-3-hexene and Z-1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2- hexene.

[0095] In one embodiment, the composition comprising E-HFO-153-10mczz and oneor more additional compounds may be used as a working fluid in an immersion cooling unit. In one embodiment, the composition for use as a working fluid in an immersioncooling unit comprises E-HFO-153-10mczz and at least one of 2-chloro-1,1,1,2,5,5,6,6,6-nonafluoro-3-hexene, 1,1,1,2,2,3,5,5,6,6,6-undecafluoro-3-hexene and Z-1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-hexene.

[0096] In one embodiment, an immersion cooling unit comprises an immersion cell,defining an internal cavity, a heat generating electronic or electrical component positioned in the internal cavity, a working fluid which partially fills the internal cavity and at least partially immerses the heat generating electronic or electrical device, and a condensing coil positioned inside the cavity above the working fluid. In oneembodiment of this invention, the working fluid is a composition comprising E-HFO-153-10mczz, and at least one additional compound chosen from 2-chloro-1,1,1,2,5,5,6,6,6- nonafluoro-3-hexene, 3-chloro-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, 2,5-dichloro- 1,1,1,6,6,6-hexafluorohexa-2,4-diene, 2-chloro-1,1,1,5,6,6,6-heptafluorohexa-2,4-diene, 2,4-dichloro-1,1,1,5,5,6,6,6-octafluoro-2-hexene, 1,1,1,2,2,3,5,5,6,6,6-undecafluoro-3- hexene, 1,1,1,2,2,3,5,5,6,6,6-undecafluoro-3-hexene, 2-chloro-1,1,1,4,4,5,5,6,6,6- decafluoro-2-hexene, 2,3,5-trichloro-1,1,1,4,4,6,6,6-octafluoro-2-hexene, 1-chloro- 3,3,4,4,5,5-hexafluoro-2-(trifluoromethyl)cyclopent-1-ene, 1,1,1,2,2,3,5,5,6,6,6- undecafluoro-3-hexene and 3,5,5-trichloro-1,1,1,2,2,6,6,6-octafluorohexane.

[0097] In one embodiment, the working fluid comprises E-HFO-153-10mczz and atleast one of 2-chloro-1,1,1,2,5,5,6,6,6-nonafluoro-3-hexene (HCFO-1539mbzz), 1,1,1,2,2,3,5,5,6,6,6-undecafluoro-3-hexene (HFO-152-11mcyz) and Z- 1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-hexene (Z-HFO-152-11myz). In one embodiment,the working fluid comprises E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene and 2-chloro-1,1,1,2,5,5,6,6,6-nonafluoro-3-hexene. In one embodiment, the working fluid comprises E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene and 2-chloro-1,1,1,2,5,5,6,6,6-nonafluoro-3- hexene and 1,1,1,2,2,3,5,5,6,6,6-undecafluoro-3-hexene. In one embodiment, theworking fluid comprises E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene and 2-chloro-1,1,1,2,5,5,6,6,6-nonafluoro-3-hexene and Z-1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-hexene. In one embodiment, the working fluid comprises E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene and 1,1,1,2,2,3,5,5,6,6,6-undecafluoro-3-hexene. In oneembodiment, the working fluid comprises E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene andZ-1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-hexene. In one embodiment, the working fluidcomprises E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, 1,1,1,2,2,3,5,5,6,6,6-undecafluoro-3-hexene and Z-1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-hexene. In oneembodiment, the working fluid comprises E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, 2-chloro-1,1,1,2,5,5,6,6,6-nonafluoro-3-hexene, 1,1,1,2,2,3,5,5,6,6,6-undecafluoro-3- hexene and Z-1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-hexene. The working fluid maycomprise at least 99% or at least 99.5% E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene.DESCRIPTION OF THE FIGURE

[0098] Figure 1 provides a flow diagram for a process useful to prepare E-HFO-153-10mczz according to an embodiment of this invention. In Figure 1, there is provided aprocess system 100 which includes reactor system 101 and purification system 102. Inreactor system 101, reactant 548mafd feed 103, fresh reactant HF feed 104 andrecycled HF feed stream 105 are mixed into a single feed stream 106 and fed through aseries of heat exchangers (107a, 107b and 107c) and introduced to reactor 109 in feedstream 108. Heat exchanger 107a vaporizes feed stream 106. Heat exchanger 107b isa process-to-process heat exchanger in which stream from heat exchanger 107a isheated using the heat from reactor process stream 110. The heated feed stream fromheat exchanger 107b proceeds through preheater heat exchanger 107c to providereactor feed stream.

[0099] Reactor feed stream 108 enters tubular reactor 109, which contains solidfluorination catalyst (not shown). Feed stream 108 reacts in reactor 109 in the presenceof solid fluorination catalyst in a vapor phase reaction to produce reactor processstream 110.

[0100] Reactor process stream 110 passes through heat exchanger 107b, thuscooling stream 110 and providing process stream 111. Process stream 111 is furthercooled by passing through heat exchanger 112, providing process stream 113, whichenters purification system 102.

[0101] Purification system 102 comprises distillation columns, absorbers, scrubbers,and dryers.

[0102] Process feed stream 113 is distilled in HCl distillation column 114 to removeHCl generated in reactor 109. HCl is removed overhead in stream 115. Distilled stream116 then enters HF distillation column 117, in which HF is removed. A recycle streamcomprising HF 118 is removed from column 117. A portion of stream 118 is mixed withreactant 548mafd feed 103 and fresh reactant HF feed 104 as recycled HF feed stream105. A purge stream comprising HF 119 is removed from stream 118.

[0103] After HCl and HF distillation columns, process stream 120 enters absorber121. Water is fed to absorber 121 as stream 122. A solution of HF in water is removedfrom absorber 121 in stream 123. Treated stream 124 from absorber 121 is circulatedthrough column 125 in a process step for scrubbing stream 124 with base throughscrubber 126, such as, for example, using an aqueous solution of KOH. Spent KOHsolution 127 is removed from scrubber 126 and column 125. The process streamfollowing scrubbing is removed from column 125 in stream 128, which is then dried bypassing through drying agent column 129. The drying agent may be, for example,molecular sieves. Dried process stream 130 exits drying agent column 129 for furtherpurification.

[0104] Dried process stream 130 enters low boiler distillation column 131 in which lowboilers are removed overhead and pass through a condenser in stream 132. From lowboiler distillation column 131, the process stream 133 passes to distillation column 134,from which high boilers are purged in stream 136 and product stream 135 comprising E-153-10mczz is provided. Product stream 135 comprising E-153-10mczz may be storedin tank 137 for future or immediate use in manufacture of other fluorochemicals or usedin heat transfer applications, such as, for example, in power cycles, high temperature heat pumps and immersion cooling.

[0105] Pumps such as illustrated with feed streams 103, 104 and 105 are used tointroduce and / or circulate materials (reactants, intermediates, products) throughreaction system 100. Heat exchangers such as illustrated at 107a-d are used tomanage temperature through reaction system 100.

[0106] Additional components not shown in Figure 1 may include purge lines, heatexchangers, pumps, and vacuum equipment for distillation columns. Composition and Uses

[0107] In one embodiment of this invention is provided a composition comprising E-HFO-153-10mczz comprising one or more additional compounds. The additional compound may be chosen from 2-chloro-1,1,1,2,5,5,6,6,6-nonafluoro-3-hexene (HCFO- 153-9mbzz ), 3-chloro-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (HCFO-152-10mcxz),2,5-dichloro-1,1,1,6,6,6-hexafluorohexa-2,4-diene (HCFO-2536mxzzx), 2-chloro- 1,1,1,5,6,6,6-heptafluorohexa-2,4-diene (HCFO-2537mxzzy), 2,4-dichloro- 1,1,1,5,5,6,6,6-octafluoro-2-hexene (HCFO-1538mxzd), 1,1,1,2,2,3,5,5,6,6,6- undecafluoro-3-hexene (HFO-152-11mcyz), 1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2- hexene (HFO-152-11myz), 2-chloro-1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene (HCFO- 152-10mdz), 2,3,5-trichloro-1,1,1,4,4,6,6,6-octafluoro-2-hexene (HCFO-1528mdcxx), 1- chloro-3,3,4,4,5,5-hexafluoro-2-(trifluoromethyl)cyclopent-1-ene, 1,1,1,4,4,5,5,6,6,6- decafluoro-2-hexene (HFO-153-10mzz), C6F10 isomers, hexafluorobutene isomers (HFO-1336 isomers), C5HF9 isomers, C6F12 isomers, C6HF11 isomers, C5H2F8 isomers, C5HClF8 isomers, C6F8 isomers, C6HF9 isomers, C6ClF9 isomers, 2-chloro-1,1,1,4,4,4- hexafluoro-2-butene (HCFO-1326mxz), 2-chloro-1,1,1,4,4,4-hexafluorobutane (HCFC- 346mdf) and 3,5,5-trichloro-1,1,1,2,2,6,6,6-octafluorohexane (HCFC-548mafd).

[0108] In one embodiment, the composition disclosed herein can be used as arefrigerant, heat transfer fluid, foam expansion agent, power cycle working fluid, among other uses. In one embodiment, the composition disclosed herein is used as a heat transfer fluid. In one embodiment the use as a heat transfer fluid is in a refrigeration system. In one embodiment the use as a heat transfer fluid is in a high temperature heat pump. In one embodiment the use as a heat transfer fluid is in a power cycle, such as an organic Rankine cycle.

[0109] In one embodiment, the composition of this invention can be used as aworking fluid in an immersion cooling unit including an immersion cell, defining an internal cavity, is provided, wherein an electronic or electrical component is positioned in the internal cavity. In this embodiment, the working fluid partially fills the internal cavity and at least partially immerses the heat generating electronic or electrical device. A condensing coil is positioned inside the cavity above the working fluid.

[0110] In one embodiment of this invention, an immersion cooling unit comprises: animmersion cell, defining an internal cavity; i) an electrical component in the internal cavity; ii) a working fluid partially filling the internal cavity; iii) a condensing coil, positioned in the internal cavity above the electrical component; wherein the working fluid at least partially immerses the electrical component; and wherein the working fluidcomprises, consists essentially of, or consists of a composition comprising E-HFO-153-10mczz and at least one additional compound chosen from 2-chloro-1,1,1,2,5,5,6,6,6-nonafluoro-3-hexene (HCFO-153-9mbzz ), 3-chloro-1,1,1,2,2,5,5,6,6,6-decafluoro-3- hexene (HCFO-152-10mcxz), 2,5-dichloro-1,1,1,6,6,6-hexafluorohexa-2,4-diene (HCFO-2536mxzzx), 2-chloro-1,1,1,5,6,6,6-heptafluorohexa-2,4-diene (HCFO- 2537mxzzy), 2,4-dichloro-1,1,1,5,5,6,6,6-octafluoro-2-hexene (HCFO-1538mxzd), 1,1,1,2,2,3,5,5,6,6,6-undecafluoro-3-hexene (HFO- 152-11mcyz), 1,1,1,2,4,4,5,5,6,6,6- undecafluoro-2-hexene (HFO-152-11myz), 2-chloro-1,1,1,4,4,5,5,6,6,6-decafluoro-2- hexene (HCFO-152-10mdz), 2,3,5-trichloro-1,1,1,4,4,6,6,6-octafluoro-2-hexene (HCFO- 1528mdcxx), 1-chloro-3,3,4,4,5,5-hexafluoro-2-(trifluoromethyl)cyclopent-1-ene, 1,1,1,4,4,5,5,6,6,6- decafluoro-2-hexene (HFO-153-10mzz), C6F10 isomers, hexafluorobutene isomers (HFO-1336 isomers), C5HF9 isomers, C6F12 isomers, C5H2F8 isomers, C5HClF8 isomers, C6F8 isomers, C6HF9 isomers, C6ClF9 isomers, 2-chloro- 1,1,1,4,4,4-hexafluoro-2-butene (HCFO-1326mxz), 2-chloro-1,1,1,4,4,4- hexafluorobutane (HCFC-346mdf) and 3,5,5-trichloro-1,1,1,2,2,6,6,6-octafluorohexane (HCFC-548mafd).

[0111] Unless otherwise defined, all technical and scientific terms used herein havethe 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.

[0112] The following Examples are provided to illustrate certain aspects of theinvention and shall not limit the scope of the appended claims. EXAMPLES

[0113] In the following Examples, the letter “T” designates temperature; the letter “P”designates pressures. All temperatures are provided in degrees Celsius (°C).

[0114] Unless otherwise stated, all analyses for products in the following Exampleswere performed using GC / MS FID and results are reported in GC FID Area%. Example 1. Synthesis of 153-10mczz

[0115] Into an Inconel (0.5 inch OD) tube reactor was added 4 cc of chromium oxidecatalyst (12 / 20 mesh). The reaction was run by feeding liquid HCFC-548mafd into a heated chamber where it vaporized and mixed with HF and N2. The reaction mixture was then allowed to pass through the reactor. Part of the reactor effluent was passed through a series of valves and analyzed by GC / MS. Part of the reactor effluent can also be passed through a caustic scrubber, dried over a desiccant and trap in a dry iceacetone trap. The trapped material is then analyzed by NMR to give E-153-10mczzcomposition listed in Table 2 below. TABLE 2 Chemical Name Compound Chemical Formula mole %E-1,1,1,2,2,5,5,6,6,6- E-153-E-CF CF CH=C82.4878% decafluoro-3-hexene10mczz 3 2 HCF2CF32-chloro-1,1,1,2,5,5,6,6,6- o-3-hexene 1539mbzz C5.8649% nonafluor F3CFClCH=CHCF2CF33-chloro-1,1,1,2,2,5,5,6,6,6-152-12.5736% decafluoro-3-hexene 0mcdz CF3CF2CCl=CHCF2CF32,5-dichloro-1,1,1,6,6,6- exafluorohexa-2,4-diene 252.2272% h36mxzzx CF3CCl=CHCH=CClCF32-chloro-1,1,1,5,6,6,6- ne 2537mxzzy CF CCl=CHCH=CFC1.6498% heptafluorohexa-2,4-die 3 F32,4-dichloro-1,1,1,5,5,6,6,6-1538mxzd CF CCl1.4435% octafluoro-2-hexene 3 =CHCHClCF2CF31,1,1,2,2,3,5,5,6,6,6- 3-hexene 152-11mcyz CF CF1.1631% undecafluoro- 3 2CF=CHCF2CF32-chloro-1,1,1,4,4,5,5,6,6,6-152-10m0.9981% decafluoro-2-hexene dz CF3CCl=CHCF2CF2CF32,3,5-trichloro-1,1,1,4,4,6,6,6-1528mdcxx CF CHClCF CCl=CCl0.9074% octafluoro-2-hexene 3 2 CF31-chloro-3,3,4,4,5,5-hexafluoro- 0.6846% 2-(trifluoromethyl)cyclopent-1- Cyclic-CF2CF2CF2C(CF3)CCl- ene 3,5,5-trichloro-1,1,1,2,2,6,6,6-548mafd CF CF CHClCH0.0000% octafluorohexane 3 2 2CCl2CF3Example 2

[0116] The product produced in Example 1 was purified using methods disclosedherein of including distillation. The composition after purification is provided in Table 3. TABLE 3 Chemical Name Compound Chemical Formula AnalyzedGC area % E-1,1,1,2,2,5,5,6,6,6- E-153-E-CF3CF2CH=CHCF2-CF399.5% decafluoro-3-hexene 10mczz 2-chloro-1,1,1,2,5,5,6,6,6-1539mbzz CF3CFClCH=CHCF2CF3 0.20%nonafluoro-3-hexene 1,1,1,2,2,3,5,5,6,6,6-152-11mcyz CF3CF2CF=CHCF2CF3 0.10%undecafluoro-3-hexene Example 3Hydrofluorination of HCFC-548mafd to E-HFO-153-10mczz, using 4%Zn / Al2O3 catalyst

[0117] 6ml (12-20 mesh) of 4% Zn / Al2O3 catalyst is loaded into a 12 inches longInconel (0.5 inch OD) tube reactor. The catalyst is activated by HF starting from 150°C and raising to 450°C. The reaction of 548mafd-with HF reaction was tested at conditions listed in Table 4 below. HCFC-548mafd was fed by a pump and went through a vaporizer at 200°C with N2 and then is mixed with HF and flow through the reactorwith catalyst bed. The reactor effluent is analyzed by a GC-MS-FID and shows E-HFO-153-10mczz, was produced at high concentration at various conditions. Results are provided in Table 5. TABLE 4 Sample Time T P (psig) 548mafdN2 HF (ml / hr)(sccm) (sccm) 11.25 280 1.3 0.15 3.09 6.132 2.50 280 1.4 0.15 3.09 6.103 3.75 280 1.1 0.15 3.09 6.064 5.00 280 1 0.15 3.09 6.065 6.25 280 0.9 0.15 3.09 6.066 7.50 280 0.9 0.15 3.09 6.13Sample Time T P (psig) 548mafdN2 HF (ml / hr)(sccm) (sccm) 78.75 300 0.9 0.15 3.09 6.178 10.00 300 0.9 0.15 3.09 6.149 11.25 300 0.9 0.15 3.09 6.1610 12.50 315 0.9 0.15 3.09 6.1711 13.75 315 0.9 0.15 3.09 6.1412 15.00 315 0.9 0.15 3.09 6.1013 16.25 330 0.9 0.15 3.09 6.1614 17.50 330 0.9 0.15 3.09 6.1215 18.75 330 0.9 0.15 3.04 6.0516 20.00 345 0.9 0.15 3.02 6.04TABLE 5Sample 548mafd E-153- 1233xf C6H2F8C6H2F8 1539 1539 1539 C6H2ClF7 C6H2ClF7 Other 10mczz isomers isomers isomers isomers isomers isomers compounds GC-FID area% 10.00 67.08 0.00 14.83 6.79 0.00 0.00 0.00 3.08 0.00 8.222 0.00 75.15 0.00 6.88 0.00 0.00 0.00 0.00 4.49 0.00 13.493 2.58 24.69 0.00 11.87 3.27 31.19 4.42 0.33 15.06 4.34 2.254 13.74 17.67 0.04 3.97 1.06 38.50 4.39 1.11 11.41 3.61 4.545 8.67 23.96 0.06 5.65 1.11 37.47 4.24 0.72 10.17 3.34 4.676 7.54 41.82 0.10 3.93 0.77 23.74 2.89 0.68 8.73 3.64 6.277 4.87 48.53 0.11 3.86 0.77 23.61 2.78 0.44 7.33 3.00 4.818 7.12 44.12 0.09 3.79 0.70 24.87 2.91 0.64 7.90 3.29 4.649 2.02 63.96 0.12 2.65 0.59 11.62 1.51 0.21 5.43 2.83 9.2010 2.15 63.92 0.15 2.62 0.58 11.67 1.51 0.22 5.52 2.92 8.9111 2.02 64.68 0.12 2.58 0.00 11.54 2.06 0.22 5.39 2.83 8.6212 0.51 71.56 0.25 1.99 0.00 5.32 1.25 0.15 3.61 2.22 13.2913 0.60 71.03 0.18 1.99 0.39 5.57 0.86 0.18 3.67 2.26 13.4614 0.56 71.43 0.18 1.96 0.39 5.44 0.85 0.18 3.58 2.20 13.4215 0.28 71.09 0.29 2.17 0.32 3.83 0.45 0.30 2.98 1.83 16.75Example 4Production, Purification of E-153-10mczz and analysis of E-153-10mczz product

[0118] In a 1” Hastelloy C tube reactor Cr2O3 catalyst was loaded and activated byHF treatment. Then 548mafd and HF were fed at mol ratio of 1:40 at 30 psig pressure with co-fed of 0.2mol% O2 at a temperature of 320°C with contact time around 13 seconds. The product was scrubbed by a caustic and collected. The crude product was analyzed by GC-MS-FID. The result of GC analysis is provided in Table 6. TABLE 6 Compound FID area%HFC-125 0.0020%CFC-115 0.0032%C6F10 isomers 0.0128%C6F10 isomers 0.0207%C6F10 isomers 0.115%C5HF9 isomers 0.0321%C6F12 isomers 0.0984%Z-152-11mcyz 0.739%E-153-10mczz 82.0%C6HF11 isomers 0.0399%C6HF11 isomers 0.0080%C6HF11 isomers 0.0082%Z-152-11myz 0.0981%C6HF11 isomers 0.0306%C6H2F12 isomers 0.130%C6ClF9 isomers 0.203%C6H2F10 isomers 0.125%C5HClF8 isomers 0.0630%C6H2F10 isomers 0.226%C6HClF10 isomers 1.30%C6HClF10 isomers 0.691%C6H2ClF9 isomers 7.64%C5HF9 isomers 0.152%C6H2ClF9 isomers 0.228%C6H2ClF9 isomers 0.621%C6HClF8 isomers 0.0715%C6H2ClF9 isomers 0.101%C6H2ClF7 isomers 0.194%C6Cl2F10 isomers 0.126%Compound FID area%C6HCl2F9 isomers 0.310%C6HClF10 isomers 0.247%C6HCl2F9 isomers 0.296%C6H2Cl2F8 isomers 0.983%C6Cl2F8 isomers 0.102%C6HCl2F7 isomers 0.169%C6HCl2F7 isomers 0.133%C6HCl2F7 isomers 0.125%C6H2Cl2F6 isomers 0.311%C6HCl3F6 isomers 0.178%Other compounds 2.08%

[0119] This crude E-153-10mczz was purified in a series of distillation columns,absorbers, scrubbers and dryers as described according to Figure 1. The purified product was analyzed by NMR and GC-MS-FID to determine the composition. The composition is provided in Table 7 and Table 8. TABLE 7 NMR analysis Compound Formula Name Mole %E-1,1,1,2,2,5,5,6,6,6- decafluoro-3-hexene E-C2F5CH=CHC2F5 E-153-10mczz 98.6Z-1,1,1,2,2,3,5,5,6,6,6- undecafluoro-3-hexene Z-CF3CF2CF=CHCF2CF3 Z-152-11mcyz 1.22Z-1,1,1,2,4,4,5,5,6,6,6- undecafluoro-2-hexene Z-CF3CF=CHCF2CF2CF3 Z-152-11myz 0.14TABLE 8 GC-MS-FID analysis Compounds FID area%C6F10 isomers 0.0002%C6F10 isomers 0.0009%HFO-1336 isomers 0.0007%C5HF9 isomers 0.0004%C6F12 isomers / C5H2F8 isomers / other 0.0058% compound(s) C6F12 isomers 0.0009%Z-HFO-152-11mcyz 0.8150%E-HFO-153-10mczz 99.0500%Z-HFO-152-11myz 0.0083%C6F10 isomers 0.0040%C6F8 isomers 0.0036%HFO-153-10mzz 0.0069%C6HF9 isomers 0.0095%C6HF9 isomers 0.0008%C6ClF9 isomers 0.0060%C6HF9 isomers 0.0019%C6HF9 isomers 0.0022%HCFO-1326mxz 0.0015%C6HClF10 isomers 0.0009%C6H2ClF9 isomers 0.0004%C5HClF8 isomers 0.0073%C5HClF8 isomers 0.0009%HCFC-346mdf 0.0028%Other compounds 0.0661%

Claims

CLAIMS What is claimed is:

1. A process for preparing E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene comprisingcontacting 3,5,5-trichloro-1,1,1,2,2,6,6,6-octafluorohexane with an excess of HF in the presence of a fluorination catalyst to obtain a process mixture comprising E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, wherein the process is performed at a temperature of about 250-450°C, a pressure of about 0 to 200 psig.

2. The process of claim 1 wherein the temperature is in the range of about 300 to about 380°C.

3. The process of claim 1 or claim 2 wherein the pressure is in the range of about 30 to about 180 psig or about 40 to 150 psig, or about 60-120 psig.

4. The process of any of claims 1-3, wherein the fluorination catalyst comprises one or more metals, metal oxides, metal oxyfluorides, metal chloride or metal fluorides.

5. The process of claim 4 wherein the fluorination catalyst is a metal oxide and the metal oxide forms a metal (oxy)fluoride having Lewis acid character.

6. The process of claim 1 wherein the metal oxide comprises chromium or aluminum or cobalt or zinc.

7. The process of claim 1 wherein the fluorination catalyst comprises one or more of metals selected from Al, Sc, Y, Ti, Zr, Hf, V Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, La and Ce.

8. The process of claim 7 wherein the fluorination catalyst comprises one or more of Al, Zr, Cr, Co, Ni and Zn.

9. The process of claim 8 wherein the fluorination catalyst comprises chromium or aluminum.

10. The process of claim 8 wherein the fluorination catalyst comprises chromium or aluminum and one or more of Zn, Zr, Co, and Ni.

11. The process of claim 4, wherein the fluorination catalyst comprises a metal oxide or metal fluoride and contains one or more additional metals selected from the group consisting of Li, Na, K, Ca, Mg, and Cs.

12. The process of claim 11, wherein the additional metal is present in an amount of less than 2000 or less than 1000 or less than 500 or less than 100 or less than 10 ppm.

13. The process of claim 9, wherein the fluorination catalyst comprises aluminum.

14. The process of claim 13, wherein aluminum is present in the form of aluminum oxide, aluminum fluoride or aluminum oxyfluoride.

15. The process of claim 13, wherein the fluorination catalyst further comprises one or more of Sc, Y, Ti, Zr, Hf, V Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, La and Ce.

16. The process of claim 15, wherein the fluorination catalyst comprises one or more of Zn, Zr, Cr, Co, and Ni.

17. The process of claim 13, wherein the fluorination catalyst comprises Al2O3.

18. The process of claim 17, wherein the fluorination catalyst comprises Al2O3 and one or more of Zn, Zr, Cr, Co, and Ni.

19. The process of claim 18, wherein the fluorination catalyst comprises Al2O3 and Zn, or Al2O3 and Cr, or Al2O3 and Co, or Al2O3 and Ni, or Al 2O3 and Zr.

20. The process of claim 9, wherein the fluorination catalyst comprises chromium.

21. The process of claim 20, wherein chromium is present in the form of chromium oxide, chromium chloride, chromium fluoride or chromium oxyfluoride.

22. The process of claim 21, wherein the fluorination catalyst further comprises one or more of Al, Sc, Y, Ti, Zr, Hf, V Nb, Ta, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, La and Ce.

23. The process of claim 20, wherein the fluorination catalyst comprises Cr2O3.

24. The process of claim 20, wherein the fluorination catalyst comprises Cr2O3 and one or more of Zn, Zr, Co, and Ni.

25. The process of claim 24, wherein the fluorination catalyst comprises Cr2O3 and Zn, or Cr2O3 and Co, or Cr2O3 and Ni, or Cr2O3 and Zr.

26. The process of claim 20 wherein, the catalyst comprises chromium supported on AlF3, alumina, fluorinated alumina or activated carbon.

27. The process of claim 26 wherein the catalyst comprises chromium supported on alumina.

28. The process of claim 8 wherein, the catalyst comprises zinc supported on AlF3, alumina, fluorinated alumina or activated carbon.

29. The process of claim 28 wherein the catalyst comprises zinc supported on alumina.

30. The process of any of claims 1-29 further comprising, a prefluorination treatment prior to contacting HCFC-548mafd with HF in the presence of the fluorination catalyst in a reactor, wherein the prefluorination treatment comprises passing HF, with or without an inert diluent such as nitrogen, over the catalyst at a temperature within the range of about 250 to 450°C.

31. The process of any of claims 1-30 further comprising, regenerating the fluorination catalyst after the catalyst has decreased in activity, wherein a regenerating step comprises treating the catalyst with oxygen or air at elevated temperature in the condition majority organic materials are purged away.

32. The process of claim 31, wherein the organic materials comprise HCFC- 548mafd and / or E-HFO-153-10mczz.

33. The process of any of claims 1-32, wherein the process is performed at a molar ratio of HF to HCFC-548mafd from about 3:1 to about 50:

1.

34. The process of claim 33 wherein the molar ratio of HF to HCFC-548mafd is from about 10:1 to about 45:1, or 15:1 to 40:

1.

35. The process of any of claims 1-34, further comprising adding an oxygen- containing gas to the process.

36. The process of claim 35 wherein the amount of oxygen added to the process from the oxygen-containing gas is greater than greater than 0% and less than 10 mole%.

37. The process of claim 35 wherein the amount of oxygen added to the process from the oxygen-containing gas is from about 0.2 mole % to about 5 mole%, or from about 1 mole%.

38. The process of any of claims 1-37, wherein the process mixture comprising E- 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene further comprises unreacted HF and the unreacted HF is recovered and recycle to the process.

39. The process of any of claims 1-37, wherein the process mixture comprises intermediates and unreacted 548mafd, and the unreacted 548mafd and intermediates are recovered and recycled to the process.

40. The process of claim 39, wherein the intermediates comprise one or more of C6H2ClF9 isomers, C6HClF8 isomers, C6H2Cl2F8 isomers, C6HCl2F7 isomers, and C6HCl3F6 isomers.

41. A composition comprising E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (E-HFO- 153-10mczz), and at least one additional compound chosen from 2-chloro- 1,1,1,2,5,5,6,6,6-nonafluoro-3-hexene (HCFO-153-9mbzz ), 3-chloro- 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (HCFO-152-10mcxz), 2,5-dichloro- 1,1,1,6,6,6-hexafluorohexa-2,4-diene (HCFO-2536mxzzx), 2-chloro- 1,1,1,5,6,6,6-heptafluorohexa-2,4-diene (HCFO-2537mxzzy), 2,4-dichloro- 1,1,1,5,5,6,6,6-octafluoro-2-hexene (HCFO-1538mxzd), 1,1,1,2,2,3,5,5,6,6,6- undecafluoro-3-hexene (HFO-152-11mcyz), 1,1,1,2,4,4,5,5,6,6,6-undecafluoro- 2-hexene (HFO-152-11myz), 2-chloro-1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene (HCFO-152-10mdz), 2,3,5-trichloro-1,1,1,4,4,6,6,6-octafluoro-2-hexene (HCFO- 1528mdcxx), 1-chloro-3,3,4,4,5,5-hexafluoro-2-(trifluoromethyl)cyclopent-1-ene, 1,1,1,4,4,5,5,6,6,6- decafluoro-2-hexene (HFO-153-10mzz), C6F10 isomers, hexafluorobutene isomers (HFO-1336 isomers), C5HF9 isomers, C6F12 isomers, C5H2F8 isomers, C5HClF8 isomers, C6F8 isomers, C6HF9 isomers, C6HF11 isomers, C6ClF9 isomers, 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (HCFO- 1326mxz), 2-chloro-1,1,1,4,4,4-hexafluorobutane (HCFC-346mdf) and 3,5,5- trichloro-1,1,1,2,2,6,6,6-octafluorohexane (HCFC-548mafd).

42. The composition of claim 41, wherein the composition comprises E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene and at least one of 2-chloro- 1,1,1,2,5,5,6,6,6-nonafluoro-3-hexene, 1,1,1,2,2,3,5,5,6,6,6-undecafluoro-3- hexene and Z-1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-hexene.

43. The composition of claim 42, wherein the composition comprises E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene and 2-chloro-1,1,1,2,5,5,6,6,6- nonafluoro-3-hexene.

44. The composition of claim 42, wherein the composition comprises E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, 2-chloro-1,1,1,2,5,5,6,6,6-nonafluoro- 3-hexene and 1,1,1,2,2,3,5,5,6,6,6-undecafluoro-3-hexene.

45. The composition of claim 42, wherein the composition comprises E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, 2-chloro-1,1,1,2,5,5,6,6,6-nonafluoro- 3-hexene and Z-1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-hexene.

46. The composition of claim 42, wherein the composition comprises E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene and 1,1,1,2,2,3,5,5,6,6,6-undecafluoro- 3-hexene.

47. The composition of claim 42, wherein the composition comprises E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, 1,1,1,2,2,3,5,5,6,6,6-undecafluoro-3- hexene and Z-1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-hexene.

48. The composition of claim 42, wherein the composition comprises E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene and Z-1,1,1,2,4,4,5,5,6,6,6- undecafluoro-2-hexene.

49. The composition of claim 42, wherein the composition comprises E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, 2-chloro-1,1,1,2,5,5,6,6,6-nonafluoro- 3-hexene, 1,1,1,2,2,3,5,5,6,6,6-undecafluoro-3-hexene and Z- 1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-hexene.

50. The composition of any of claims 42-49, wherein composition comprises at least 99% or at least 99.5% E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene.

51. The composition of claim 42, wherein the composition comprises HCFC- 548mafd and one or more of C6H2ClF9 isomers, C6HClF8 isomers, C6H2Cl2F8 isomers, C6HCl2F7 isomers, and C6HCl3F6 isomers.

52. The composition of claim 42 prepared according to the process of any of claims 1-40.

53. Use of a composition comprising E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene andat least one of 2-chloro-1,1,1,2,5,5,6,6,6-nonafluoro-3-hexene, 1,1,1,2,2,3,5,5,6,6,6-undecafluoro-3-hexene and Z-1,1,1,2,4,4,5,5,6,6,6- undecafluoro-2-hexene as a refrigerant.

54. Use of a composition comprising E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene andat least one of 2-chloro-1,1,1,2,5,5,6,6,6-nonafluoro-3-hexene, 1,1,1,2,2,3,5,5,6,6,6-undecafluoro-3-hexene and Z-1,1,1,2,4,4,5,5,6,6,6- undecafluoro-2-hexene in a heat transfer application.

55. Use of a composition comprising E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene andat least one of 2-chloro-1,1,1,2,5,5,6,6,6-nonafluoro-3-hexene, 1,1,1,2,2,3,5,5,6,6,6-undecafluoro-3-hexene and Z-1,1,1,2,4,4,5,5,6,6,6- undecafluoro-2-hexene as a foam expansion agent.

56. Use of a composition comprising E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene andat least one of 2-chloro-1,1,1,2,5,5,6,6,6-nonafluoro-3-hexene, 1,1,1,2,2,3,5,5,6,6,6-undecafluoro-3-hexene and Z-1,1,1,2,4,4,5,5,6,6,6- undecafluoro-2-hexene as a power cycle working fluid.

57. An immersion cooling unit comprising an immersion cell, defining an internal cavity, a heat generating electronic or electrical component positioned in the internal cavity, a working fluid which partially fills the internal cavity and at least partially immerses the heat generating electronic or electrical device, and a condensing coil positioned inside the cavity above the working fluid, wherein the working fluid is a composition comprising E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (E-HFO-153-10mczz), and at least one additional compound chosen from 2-chloro-1,1,1,2,5,5,6,6,6-nonafluoro-3-hexene (HCFO-153-9mbzz ), 3- chloro-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (HCFO-152-10mcxz), 2,5- dichloro-1,1,1,6,6,6-hexafluorohexa-2,4-diene (HCFO-2536mxzzx), 2-chloro-1,1,1,5,6,6,6-heptafluorohexa-2,4-diene (HCFO-2537mxzzy), 2,4-dichloro- 1,1,1,5,5,6,6,6-octafluoro-2-hexene (HCFO-1538mxzd), 1,1,1,2,2,3,5,5,6,6,6- undecafluoro-3-hexene (HFO- 152-11mcyz), 1,1,1,2,4,4,5,5,6,6,6-undecafluoro- 2-hexene (HFO-152-11myz), 2-chloro-1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene (HCFO-152-10mdz), 2,3,5-trichloro-1,1,1,4,4,6,6,6-octafluoro-2-hexene (HCFO- 1528mdcxx), 1-chloro-3,3,4,4,5,5-hexafluoro-2-(trifluoromethyl)cyclopent-1-ene, 1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene (HFO-153-10mzz), C6F10 isomers, hexafluorobutene isomers (HFO-1336 isomers), C5HF9 isomers, C6F12 isomers, C6HF11 isomers, C5H2F8 isomers, C5HClF8 isomers, C6F8 isomers, C6HF9 isomers, C6ClF9 isomers, 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (HCFO- 1326mxz), 2-chloro-1,1,1,4,4,4-hexafluorobutane (HCFC-346mdf) and 3,5,5- trichloro-1,1,1,2,2,6,6,6-octafluorohexane (HCFC-548mafd)(HCFC-548mafd).

58. The immersion cooling unit of claim 57, wherein the working fluid comprises E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene and at least one of 2-chloro- 1,1,1,2,5,5,6,6,6-nonafluoro-3-hexene (HCFO-1539mbzz), 1,1,1,2,2,3,5,5,6,6,6- undecafluoro-3-hexene (HFO-152-10mcyz) and Z-1,1,1,2,4,4,5,5,6,6,6- undecafluoro-2-hexene (Z-HFO-152-11myz).

59. The immersion cooling unit of claim 57, wherein the working fluid comprises E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene and 2-chloro-1,1,1,2,5,5,6,6,6- nonafluoro-3-hexene.

60. The immersion cooling unit of claim 57, wherein the working fluid comprises E- 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene and 2-chloro-1,1,1,2,5,5,6,6,6- nonafluoro-3-hexene and 1,1,1,2,2,3,5,5,6,6,6-undecafluoro-3-hexene.

61. The immersion cooling unit of claim 57, wherein the working fluid comprises E- 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene and 2-chloro-1,1,1,2,5,5,6,6,6- nonafluoro-3-hexene and Z-1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-hexene.

61. The immersion cooling unit of claim 57, wherein the working fluid comprises E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene and 1,1,1,2,2,3,5,5,6,6,6-undecafluoro- 3-hexene.

62. The immersion cooling unit of claim 57, wherein the working fluid comprises E- 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene and Z-1,1,1,2,4,4,5,5,6,6,6- undecafluoro-2-hexene.

63. The immersion cooling unit of claim 57, wherein the working fluid comprises E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, 1,1,1,2,2,3,5,5,6,6,6-undecafluoro-3- hexene and Z-1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-hexene.

64. The immersion cooling unit of claim 57, wherein the working fluid comprises E- 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, 2-chloro-1,1,1,2,5,5,6,6,6-nonafluoro- 3-hexene, 1,1,1,2,2,3,5,5,6,6,6-undecafluoro-3-hexene and Z- 1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-hexene.

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