WO2025160037A2

WO2025160037A2 - Process for the preparation of e-isomer of 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (hfo-153-10mczz; cf3cf2ch=chc2cf3)

Info

Publication number: WO2025160037A2
Application number: PCT/US2025/012351
Authority: WO
Inventors: Xuehui Sun; Viacheslav A. Petrov; Andrew Jackson
Original assignee: Chemours Co FC LLC
Current assignee: Chemours Co FC LLC
Priority date: 2024-01-22
Filing date: 2025-01-21
Publication date: 2025-07-31
Anticipated expiration: 2026-07-22
Also published as: WO2025160037A3

Abstract

A process is disclosed for (i) producing E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (E-HFO-153-10mczz) from Z-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (Z-HFO-153-10mczz), comprising the steps of (a) providing a starting material comprising Z-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, (b) contacting the starting material with a suitable catalyst in a reaction zone to produce E-HFO-153-10mczz; and optionally, (c) recovering the E-HFO-153-10mczz. The process may be performed in the vapor phase or in the liquid phase and as a batch process or as a continuous process.

Description

PROCESS FOR THE PREPARATION OF E-ISOMER OF 1, 1,1, 2, 2, 5, 5, 6,6,6- DECAFLUORO-3-HEXENE (HFO-153-10mczz; CF3CF2CH=CHCF₂CF3)

FIELD

[0001] The present disclosure relates to processes for the catalytic isomerization of Z-1 , 1 , 1 ,2,2,5,5,6,6,6-decafluoro-3-hexene to produce E-1 ,1 ,1 , 2, 2, 5, 5, 6,6,6- decafluoro-3-hexene.

BACKGROUND

[0002] The perpetual uncertainty in energy supplies and prices and a growing public awareness of the environmental impacts from the extraction, transportation and use of fossil fuels are motivating a renewed interest in low temperature heat utilization (i.e. heat at temperatures lower than about 300°C). Such heat may be extracted from various commercial, industrial or natural sources. Elevation of the temperature of available heat through high temperature mechanical compression heat pumps (HTHPs) to meet heating requirements and conversion of the available heat to mechanical or electrical power through Organic Rankine Cycles (ORCs) are two promising approaches for the utilization of low temperature heat.

[0003] HTHPs and ORCs require the use of working fluids. Working fluids with high global warming potentials (GWPs) currently in common use for HTHPs and ORCs (e.g. HFC-245fa) have been under increasing scrutiny culminating in the landmark HFC amendment to the Montreal Protocol recently agreed upon in Kigali, Rwanda. Clearly, there is an increasing need for more environmentally sustainable working fluids for HTHPs and ORCs, especially given that environmental sustainability is a primary motivation for low temperature heat utilization. More specifically, there is a need for low GWP working fluids with boiling points higher than about 50°C that are particularly suitable for conversion of heat available at temperatures approaching or exceeding 200°C to power and for heating at temperatures approaching 200°C from heat available at lower temperatures. Even more specifically, a low GWP working fluid with a boiling point close to that of ethanol (78.4°C) could be advantageous as a replacement of ethanol in ORC systems for heavy duty vehicles (e.g. trucks) especially in Europe. Such a fluid could also be used as a solvent and as a heat transfer fluid for various applications, including immersion cooling and phase change cooling (e.g. of electronics, including data center cooling).

[0004] The E-isomer of 1,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene (HFO-153- 10mczz; CF3CF2CH=CHCF2CF3) is a candidate for immersion cooling having an attractive boiling point of 47°C.

[0005] In certain processes, HFO-153-10mczz may be produced as a mixture of E- and Z- isomers. The Z-isomer has a higher boiling point of 70.5-71.5°C and poorer dielectric properties compared to E-isomer. Thus, it is desirable to convert the Z-isomer to the E-isomer of HFO-153-10mczz.

SUMMARY

[0006] Disclosed herein is a process to produce the E-isomer of HFO-153- 10mczz (E-1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene ) by isomerization of the Z- isomer of HFO-153-1 Omczz (Z-1 , 1 , 1 ,2,2,5,5,6,6,6-decafluoro-3-hexene).

[0007] Z-HFO-153-10mczz can be isomerized to E-HFO-153-1 Omczz by contacting with a suitable catalyst. The isomerization can be performed in the liquid phase or in the vapor phase. The isomerization process can be performed as a batch process or as a continuous process. The process may be supplemented by the step of recovering the E-1 ,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (E-isomer of HFO-153-1 Omczz).

[0008] The foregoing the following description are exemplary and explanatory only and are not restrictive of the invention as defined in the appended claims.

DESCRIPTION

[0009] Before addressing details of embodiments described below, some terms are defined or clarified.

[0010] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. 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).

[0011] Also, use of “a” or “an” are employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

[0012] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. 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. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety, unless a particular passage is cited. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

[0013] When an amount, concentration, or other value or parameter is given as either a range, preferred range or a list of upper preferable values and/or lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. If, alternatively, relative terms, such as “less than”, “greater than” and the like are used to define an amount, concentration, or other value or parameter, the value recited is excluded. [0014] 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene or HFO-153-10mczz or 153-

10mczz (each of which may be used herein interchangeably and are synonymous) may exist as one of two configurational isomers, E or Z, wherein E is the transisomer and Z is the cis isomer. HFO-153-10mczz or 153-10mczz as used herein refers to the isomers, E-HFO-153-10mczz or Z-HFO-153-10mczz, as well as any combinations or mixtures of such isomers.

[0015] E-1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene or E-HFO-153-10mczz or E-

153-10mczz are used interchangeably and are synonymous herein and all refer to the trans isomer of 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene.

[0016] Z-1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene or Z-HFO-153-10mczz or Z-

153-10mczz are used interchangeably and are synonymous herein and all refer to the cis isomer of 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene.

[0017] The present disclosure provides a process to isomerize Z-153-10mczz to form E-153-10mczz. The process comprises contacting Z-153-10mczz with a suitable catalyst in a reaction zone to produce a product comprising E-153-10mczz. This isomerization process can be carried out in the liquid phase or vapor phase in a continuous, semi-continuous or batch operation.

[0018] In processes to prepare HFO-153-10mczz, a mixture of the Z- and E- isomers may be produced. Z-153-10mczz may be separated from the mixture, for example, by distillation. Z-153-10mczz produced in any method may serve as starting material for the process disclosed herein. A mixture E-153-10mczz and Z- 153-10mczz may also serve as starting material for the process disclosed herein.

[0019] In one embodiment, there is provided a process for the isomerization of Z- 153-10mczz to E-153-10mczz with a suitable catalyst in a reaction zone in the liquid phase.

[0020] A suitable catalyst for use in the liquid phase isomerization process may be a Lewis acid, including, for example, a metal halide. A metal halide may be a Group I HA, Group IVA metal halide, a Group VB metal halide, or combinations of two or more thereof.

[0021] Non-exclusive examples of liquid phase isomerization catalysts include boron halide, aluminum halide, antimony halide, tin halide, tantalum halide, titanium halide, niobium halide, molybdenum halide, iron halide, fluorinated chrome halide, or combinations thereof. Halides include fluoride, chloride, bromide, iodide. Specific non-exclusive examples of liquid phase isomerization catalysts contain AICI3, SbCh, SbCh, SbFs, SnCU, TaCIs, TaFs, TiCU, NbCIs, NbFs, MoCle, FeC , a fluorinated species of SbCIs, a fluorinated species of SbCh, a fluorinated species of SnCl4, a fluorinated species of TaCIs, a fluorinated species of TiCU, a fluorinated species of NbCIs, a fluorinated species of MoCle, a fluorinated species of AICI3 or a fluorinated species of FeCh, or combinations thereof. By “fluorinated species” of a metal chloride, is meant herein that one or more of the chlorine atoms in a metal chloride are replaced by fluorine atoms.

[0022] In certain embodiments, the liquid phase isomerization catalyst contains MCIs-nFn, wherein M = Sb, Ta, Nb where n = 0-5. A catalyst containing MCIs-nF_n, includes MCh-nFn or MCIs-nFn supported on AIF3 or carbon, where n=0-5. In one embodiment the catalyst is antimony pentafluoride. In one embodiment the catalyst is tantalum pentafluoride.

[0023] In one embodiment a suitable catalyst for a liquid phase isomerization process comprises antimony. In particular a suitable catalyst comprises SbCls-nF_n, wherein n = 0, or n = 1 , or n = 2, or n = 3, or n = 4, or n = 5. In certain embodiments the suitable catalyst is or comprises SbCh.

[0024] In another embodiment a suitable catalyst for a liquid phase isomerization process comprises tantalum. In particular a suitable catalyst comprises TaCIs-nFn, wherein n = 0, or n = 1 , or n = 2, or n = 3, or n = 4, or n = 5. In certain embodiments the suitable catalyst is or comprises TaCIs.

[0025] In certain embodiments, the liquid phase isomerization catalyst is or contains AIZ3, where each Z is independently Br, F or Cl. In certain embodiments, each Z is independently Br, F or Cl, provided that Z cannot be entirely F.

[0026] In a particular embodiment, AIZ3 has the formula AIXxFy (mixed aluminum halide) and is an aluminum chlorofluoride or an aluminum bromofluoride (X = Cl, Br), where the total number of atoms of halide, x plus y equals 3, where x ranges from about 0.05 to 2.95 and y ranges from about 2.95 to 0.05. Details of aluminum chlorofluoride catalyst preparation are disclosed in U.S. Pat. No. 5,162,594, which is incorporated herein by reference. [0027] Optionally, a liquid phase process may be performed in the presence of

HF.

[0028] The temperature employed in the reaction zone of a liquid phase isomerization process (“reaction temperature”) typically ranges from about -20°C to about 200°C. In some embodiments, the temperature in the reaction zone ranges from about 50°C to about 150°C or from about 100°C to about 130°C. In some embodiments, the reaction temperature ranges from about 100°C to about 130°C. In some embodiments, the reaction temperature is about ambient, i.e. , room temperature.

[0029] When the liquid phase catalyst is SbFs, the temperature in the reaction zone is preferably in the range of from 0°C to 150°C. When the liquid phase catalyst has the formula, AIXxFy (where X = Cl, Br, x and y are defined above), the temperature in the reaction zone is preferably in the range of from -20°C to 150°C.

[0030] The reaction pressure for the liquid phase isomerization process can be subatmospheric, atmospheric or superatmospheric. In some embodiments, the reaction pressure is near atmospheric. Typical pressure is from about atmospheric (101 kPa) to about 700 psig (4.8 MPa).

[0031] In one embodiment, there is provided a process for the isomerization of Z- 153-10mczz to E-153-10mczz with a suitable catalyst in a reaction zone in the vapor phase.

[0032] A suitable catalyst for use in the vapor phase may be, for example, in the form of pellets, powders or granules. The form of such catalysts is not critical. Suitable catalysts are described above. For example, a suitable catalyst for use in the vapor phase contains chromium, aluminum, zinc, activated carbon or a combination of two or more thereof. In one embodiment, a suitable catalyst comprises or is chromium oxyfluoride.

[0033] In a particular embodiment, a suitable catalyst for use in the vapor phase comprises or is chromium oxyfluoride. In another embodiment, a suitable catalyst comprises or is aluminum oxyfluoride. In another embodiment, a suitable catalyst comprises or is activated carbon. In another embodiment, a suitable catalyst comprises zinc or zinc oxide. [0034] In one embodiment a suitable catalyst for a vapor phase isomerization process comprises or is a metal oxide. The metal may be a transition metal such as chromium, nickel, aluminum, zinc or a combination of two or more thereof. For example, the metal may be a combination of chromium and nickel or chromium and aluminum or chromium and zinc or nickel and aluminum or nickel and zinc or aluminum and zinc. The metal may include other transition metal such as cobalt.

[0035] In one embodiment a suitable catalyst for a vapor phase isomerization process comprises or is a metal oxide. The metal may be a transition metal such as chromium or the metal may be aluminum or a combination thereof. Other metals may be cobalt, zinc, including other transition metals.

[0036] The metal oxide is typically treated with HF or other fluorinated compounds by methods known in the art.

[0037] In some embodiments of this invention, the suitable catalyst comprises a metal-modified chromium oxide or a metal-modified chromium oxyfluoride. Typically, a metal-modified chromium oxide catalyst or a metal-modified chromium oxyfluoride catalyst is used in a gas phase isomerization process. In some embodiments of this invention, such metal is selected from the group consisting of magnesium (e.g. magnesium fluoride), Group VI IB metals (e.g., manganese), Group I II B metals (e.g., lanthanum), and zinc. In use, such metals are normally present as halides (e.g., fluorides), as oxides and/or as oxyhalides. In some embodiments of this invention, these metals are supported on chromium oxide or chromium oxyfluoride or alumina or alumina oxyfluoride or zinc oxide or activated carbon or a combination of two or more thereof.

[0038] In certain embodiments the catalyst comprises chromium oxyfluoride and alumina, wherein the catalyst comprises less than 40% by weight alumina or less than 30% by weight alumina or less than 20% by weight alumina or less than 10% by weight alumina or less than 5% by weight alumina or less than 1% by weight alumina. The catalyst comprising chromium oxyfluoride may be a modified catalyst and further comprise aluminum, magnesium, a Group VI I B metal (e.g., manganese), a Group 111 B metal (e.g., lanthanum), zinc, or combinations of two or more thereof.

[0039] In certain embodiments, the catalyst comprises aluminum oxyfluoride. An aluminum oxyfluoride catalyst may be supported or non-supported. An aluminum oxyfluoride catalyst may contain a metal such as Cr, Ni, Zn, Ti, V, Zr, Mo, Ge, Sn, Pb, Mg.

[0040] In certain embodiments the vapor phase catalyst comprises an aluminum halide. The aluminum halide may have the formula AIXxFy (mixed aluminum halide, wherein X = Cl, Br), where the total number of atoms of halide, x plus y equals 3, where x ranges from about 0.05 to 2.95 and y ranges from about 2.95 to 0.05.

[0041] Optionally the vapor phase isomerization process may be performed in the presence of hydrogen, HF, or HCI.

[0042] The temperature employed in the reaction zone of a vapor phase isomerization process (“reaction temperature”) typically ranges from about 100°C to about 500°C. In some embodiments, the temperature employed in the reaction zone ranges from about 150°C to about 400°C or from about 150°C to about 350°C or from about 250°C to about 300°C for the fluorinated oxide catalysts.

[0043] In some embodiments, the temperature employed in the reaction zone ranges from about 200°C to about 350°C for the aluminum oxyfluoride catalysts.

[0044] The reaction zone pressure for a vapor phase isomerization process can be subatmospheric, atmospheric or superatmospheric. In some embodiments of the invention, the reaction zone pressure can be up to 200 psig (1.4 MPa). In some embodiments of the invention, the reaction zone pressure is near atmospheric. In some embodiments of the invention, the pressure is from about atmospheric (101 kPa) to about 250 psig (1.72 MPa).

[0045] The present invention provides a process to convert a composition comprising Z-HFO-153-10mczz to a composition comprising E-HFO-153-10mczz by contacting the composition comprising Z-HFO-153-10mczz with a suitable catalyst in the liquid phase or in the vapor phase at a suitable contact time. The contact time may vary widely depending on the degree of conversion desired. It will be understood, that contact time in the reaction zone is reduced by increasing the flow rate of the starting material into the reaction zone.

[0046] In one embodiment of a liquid phase isomerization process, the contact time may be from about 1 second to about 24 hours. In one embodiment of a liquid phase isomerization process as disclosed herein, the process is a continuous process with a contact time from about 1 second to about 6 hours.

[0047] In one embodiment of a vapor phase isomerization process, the contact time may be from about 1 second to about 120 seconds, or from about 5 second to about 90 seconds or from about 10 seconds to about 75 seconds or from about 20 seconds to about 60 seconds.

[0048] The present invention provides an isomerization process to convert a composition comprising Z-HFO-153-10mczz to a composition comprising E-HFO- 153-10mczz by contacting the composition comprising Z-HFO-153-10mczz with a suitable catalyst in the liquid phase or in the vapor phase in a batch or continuous process.

[0049] In an embodiment, the isomerization process is conducted in a continuous process in the vapor phase or in the liquid phase. In one embodiment, the isomerization process is conducted in a continuous process in the vapor phase. In one embodiment, the isomerization process is conducted in a continuous process in the liquid phase.

[0050] In an embodiment, the isomerization process is conducted in a batch process in the vapor phase or in the liquid phase. In one embodiment, the isomerization process is conducted in a batch process in the vapor phase. In one embodiment, the isomerization process is conducted in a batch process in the liquid phase.

[0051] In certain embodiments of a continuous process, the starting material is Z- 153-10mczz or a mixture of Z-153-10mczz and E-153-10mczz. In one embodiment, the starting material is Z-153-10mczz. In one embodiment, the starting material is a composition comprising Z-153-10mczz. In one embodiment, the starting material comprises Z-153-10mczz and E-153-10mczz.

[0052] In the process of this invention, the starting material passes through a reaction vessel containing the catalyst. The reaction vessel can be any time of closed vessel such as, for example, a metal tube. In a vapor phase process, the reaction vessel may be packed with the catalyst to form the reaction zone. [0053] In certain embodiments, the conditions of the reacting step, including the choice of catalyst, vapor phase or liquid phase, temperature, pressure, contact time, batch or continuous are selected to obtain E-1 ,1 ,1,2,2,5,5,6,6,6-decafluoro-3-hexene at a selectivity of at least 50% or at least 80% or at least 85%, or at least 90%, or at least 95%.

[0054] In some embodiments of this invention, isomerization yield of E-153- 10mczz is at least 90 mole %. In some embodiments of this invention, isomerization yield of E-153-10mczz is at least 50% or at least 80% or at least 85%, or at least 90%, or at least 95% or at least 99 mole %.

[0055] There is further provided a composition comprising E-153-10mczz. In one embodiment, the composition comprises at least 50% or at least 80% or at least 85%, or at least 90%, or at least 95% or at least 99 mole % E-153-10mczz. In certain embodiments, the composition comprises a mixture of E-153-10mczz and Z- 153-10mczz, wherein the ratio of Z-153-10mczz to E-153-10mczz is less than 10 or less than 5 and is preferably less than 1.

[0056] In certain embodiments the composition comprising E-153-10mczz, the composition comprises Z-153-10mczz, and at least one of CeF , C6H3F9, 3-chloro- 1 ,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (HCFO-152-10mcxz, “152-10mcxz”). It should be understood that 152-10mcxz represents the Z-isomer, the E-isomer or mixture of the Z- and E-isomers. In one embodiment, the composition comprising

[0057] In one embodiment, the composition comprising E-153-10mczz and Z- 153-10mczz comprises Z-152-10mcxz or E-152-10mcxz. In one embodiment, the composition comprising E-153-10mczz and Z-153-10mczz comprises Z-152-10mcxz. In one embodiment, the composition comprising E-153-10mczz and Z-153-10mczz comprises E-152-10mcxz. In one embodiment, the composition comprising E-153- 10mczz and Z-153-10mczz comprises Z-152-10mcxz and E-152-10mcxz.

[0058] In certain embodiments, there is provided a composition comprising E- 153-10mczz and Z-153-10mczz, wherein the ratio of the Z-isomer to the E-isomer is less than 10 or less than 5 or less than 1. Preferably, the ratio of the Z-isomer to the E-isomer is less than 0.5 or less than 0.1. [0059] In one embodiment, upon completion of a batch-wise or continuous isomerization process, the E-153-10mczz can be recovered through any conventional process, including for example, fractional distillation. In another embodiment, upon completion of a batch-wise or continuous hydrogenation process, the E-153-10mczz is of sufficient purity to not require further purification steps.

[0060] In certain embodiments, there is unreacted Z-153-10mczz in the product. In one such embodiment, unreacted Z-153-10mczz can be separated from the product and recycled to the reaction zone for the production of additional E-153- 10mczz.

[0061] The reaction vessel (reactors), distillation columns, and their associated feed lines, effluent lines, and associated units used in applying the processes of embodiments of this invention should be constructed of materials resistant to corrosion. Typical materials of construction include stainless steels, in particular of the austenitic type, the well-known high nickel alloys, such as Monel™ nickel-copper alloys, Hastelloy™ nickel-based alloys and, Inconel™ nickel-chromium alloys, and copper-clad steel.

EXAMPLES

Example 1

[0062] Liquid Phase Isomerization of Z/E-153-10mczz to E-153-10mczz using SbFs

[0063] Catalyst, SbFs, 2 g, was placed into a Teflon® bottle to which was added 10 g of 153-10mczz (ratio E-/Z-isomers 96.4:3.0, purity 99.4%, (0.4% of C2FSCH=CH2 and 0.2 % C2F5CH2CH2C2F5). The bottle was sealed and agitated to mix the contents at ambient temperature for 5 hours. The product mixture was poured on ice, an organic layer was separated, dried over magnesium sulfate to give 9.7 g of material, which was analyzed by ¹⁹F and ¹H NMR. Based on NMR analysis isolated material contained E-isomer of HFO-153-10mczz (99.5 %) and 0.5% of C2F5CH2CH2C2F5. Neither the Z-isomer of HFO-153-10mczz or C2FsCH=CH2 were detectable. Example 2

[0064] Liquid Phase Isomerization of Z/E-153-10mczz to E-153-10mczz using SbFs

[0065] SbFs (3g) was placed in 3-neck flask equipped with dry ice condenser, thermocouple well, addition funnel, and magnetic stir bar. The Z-isomer of 153- 10mczz (bp 70.5-71.5°C), purity 95%, remainder of material was C2F5CH2CH2C2F5), 20 g, was added slowly using addition funnel over a 30-minute period. The addition resulted in mildly exothermic reaction and internal temperature rose to 35°C. The product mixture was agitated at ambient temperature for 5 hours and was diluted with cold water (300 ml) to remove SbFs. The organic layer was separated, dried over MgSCM and filtered cold to give 18 g of material, which according ¹⁹F and ¹H NMR was identified as E-isomer of 153-10mczz (purity 95%, remainder of material was C2F5CH2CH2C2F5).

Example 3

[0066] Production of Z- and E-153-10mczz using CFO-151-10mcxx and Nickel Catalyst

[0067] Nickel catalyst, 5 ml, in the form of 1/8” pellets, (BASF E474 TR, BASF, Ludwigshafen, Germany) was loaded into a 1 inches Monel reactor tube and the catalyst was activated by H2 at 250°C for 8 hours. CFO-151-10mcxx (C2FSCCI=CCIC2FS) was fed to the reactor. Then the reaction was run at conditions in Table 1 and the product mixture is provided in Table 2.

TABLE 1. REACTION CONDITIONS - EXAMPLE 3 TABLE 2. PRODUCT COMPOSITION - EXAMPLE 3

[0068] As can be seen from Table 2, the majority of the 153-10mczz product using nickel catalyst is the Z-isomer.

Example 4

[0069] Production of Z- and E-153-10mczz using CFO-151-10mcxx, Nickel Catalyst and Isomerization using a Fluorinated Alumina Catalyst

[0070] The process of Example 3 was repeated, except using a fluorinated alumina catalyst, 7 ml, downstream of the nickel catalyst in the form of 1/8” pellets.

Operating conditions and the product mixture is provided in Table 3 and 4, respectively.

TABLE 3. REACTION CONDITIONS - EXAMPLE 4 TABLE 4. PRODUCT COMPOSITION - EXAMPLE 4

[0071] As can be seen in Table 4, with addition of the fluorinated alumina catalyst downstream from the nickel catalyst, the Z/E ratio of 153-10mczz is reduced significantly which indicated the significant amount of Z-isomer of 153-10mczz produced in hydrogenation has been isomerized to E-153-10mczz with presence of fluorinated alumina oxide.

Claims

CLAIMS What is claimed is:

1. A process for isomerizing Z-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene to E-

1.1.1.2.2.5.5.6.6.6-decafluoro-3-hexene comprising:

(a) providing a starting material comprising Z-1 ,1 ,1,2,2,5,5,6,6,6-decafluoro- 3-hexene;

(b) contacting the starting material with a suitable catalyst in a reaction zone to produce a product comprising E-1 ,1 ,1,2,2,5,5,6,6,6-decafluoro-3- hexene; and optionally,

(c) recovering the E-1,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene.

2. The process of claim 1 wherein the contacting step is performed in the liquid phase.

3. The process of claim 1 wherein the contacting step is performed in the vapor phase.

4. The process of any of claims 1-3 further comprising recovering the E-

1.1.1.2.2.5.5.6.6.6-decafluoro-3-hexene.

5. The process of claim 2 wherein a suitable catalyst is a Lewis acid, metal halide, or combinations of two or more thereof.

6. The process of claim 5 wherein a suitable catalyst is a metal halide.

7. The process of claim 6 wherein a suitable catalyst includes aluminum halide, antimony halide, tin halide, tantalum halide, titanium halide, niobium halide, molybdenum halide, iron halide, fluorinated chrome halide, or combinations thereof.

8. The process of claim 7 wherein a suitable catalyst contains AlCb, SbCb, SbCb, SbFs, SnCL, TaCb, TiCL, NbCb, MoCb, FeCb, a fluorinated species of SbCb, a fluorinated species of SbCb, a fluorinated species of SnCL, a fluorinated species of TaCb, a fluorinated species of TiCL, a fluorinated species of NbCb, a fluorinated species of MoCb, a fluorinated species of FeCb, or combinations thereof.

9. The process of claim 8 wherein a suitable catalyst contains MCls-nFn, wherein M = Sb or Ta and n = 0-5.

10. The process of claim 9 wherein the catalyst is antimony pentafluoride.

11. The process of claim 9 wherein the catalyst is tantalum pentafluoride.

12. The process of claim 7 wherein a suitable catalyst contains AIZs, wherein Z is one or more of Br, F or Cl.

13. The process of claim 12 wherein AIZ3 has the formula AIXxFy, where X = Cl, Br and the total number of atoms of halide, x plus y equals 3.

14. The process of claim 13, wherein X = Cl and x ranges from about 0.05 to 2.95 and y ranges from about 2.95 to 0.05.

15. The process of any of claims 5-14 wherein the temperature of the reaction zone is in the range of about -20°C to about 200°C.

16. The process of claim 15 wherein the wherein the temperature of the reaction zone is in the range of about 50°C to about 150°C.

17. The process of claim 16 wherein the wherein the temperature of the reaction zone is in the range of about 100°C to about 130°C.

18. The process of claim 10, wherein the temperature in the reaction zone is in the range of from 0°C to 150°C.

18. The process of claim 13, wherein the temperature in the reaction zone is in the range of from -20°C to 150°C.

19. The process of any of claims 5-18, wherein the contact time is from about 1 second to about 24 hours.

20. The process of claim 19, wherein the contact time is from about 1 second to about 6 hours.

21. The process of claim 3 wherein HF is present.

22. The process of claim 3 wherein a suitable catalyst comprises a fluorinated metal or a fluorinated metal oxide.

23. The process of claim 22 wherein the metal is chromium or nickel, aluminum, zinc or combination of two or more thereof.

23. The process of claim 23 wherein the metal is chromium.

24. The process of claim 23 wherein the metal is nickel.

25. The process of claim wherein the metal is aluminum.

26. The process of claim 23 wherein the metal is zinc.

27. The process of any of claims 22-26, wherein the temperature in the reaction zone is in the range from about 100°C to about 500°C.

28. The process of claim 27 wherein the temperature in the reaction zone is in the range from about 150°C to about 400°C.

29. The process of claim 28 wherein the temperature in the reaction zone is in the range from about 250°C to about 300°C.

30. The process of claim 1 wherein the process is a batch process.

31. The process of claim 1 wherein the process is a continuous process.

32. The process of claim 2 wherein the process is a batch process.

33. The process of claim 2 wherein the process is a continuous process.

34. The process of claim 3 wherein the process is a batch process.

35. The process of claim 3 wherein the process is a continuous process.

36. The process of claim 1 wherein the starting material is Z-153-10mczz.

37. The process of claim 1 wherein the starting material further comprises E-

1.1.1.2.2.5.5.6.6.6-decafluoro-3-hexene.

38. The process of any of claims 1-37, wherein there is unreacted Z-

1.1.1.2.2.5.5.6.6.6-decafluoro-3-hexene in the product, and wherein such unreacted Z-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene is separated from the product and recycled to the reaction zone.

39. A composition comprising E-1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene, Z- 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene, and at least one of CeF , C6H3F9, and 3-chloro-1 , 1 , 1 ,2,2,5,5,6,6,6-decafluoro-3-hexene.

40. The composition of claim 39, wherein the ratio of the Z-isomer to the E-isomer of 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene is less than 10.

41. The composition of claim 39, wherein the ratio of the Z-isomer to the E-isomer of 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene is less than 10.

42. The composition of claim 39, wherein the ratio of the Z-isomer to the E-isomer of 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene is less than 1.

43. The composition of any of claims 39-42, wherein the composition comprises 3- chloro-1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene.

44. The composition of claim 39, wherein the composition comprises at least 50% or at least 80% or at least 85%, or at least 90%, or at least 95% or at least 99 mole % E-1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene.