Process for producing z-1,1,1,4,4,4-hexafluoro-2-butene

Abstract

Systems and processes for preparing (Z)-1,1,1,4,4,4-hexafluoro-2-butene are provided. Processes and systems described provide an integrated process starting from perchloroethylene.

Description

TITLE OF THE INVENTIONPROCESS FOR PRODUCING Z-1 ,1,1,4,4,4-HEXAFLUORO-2-BUTENE FIELD

[0001] The present invention relates in general to processes for producing fluorinated olefins. More particularly, this invention relates to processes and systems for making intermediates, useful in the production fluorinated olefins, such as 1 ,1 ,1 ,4,4,4-hexafluoro-2-butene.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 potential (GWP). Replacement refrigerants with low global warming potentials (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] Z-1,1 ,1,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz, 1336mzzZ) can be used as a refrigerant, heat transfer fluid, foam expansion agent, power cycle working fluid, among other uses. It has also, advantageously, been found that Z-HFO- 1336mzz has a low global warming potential (GWP), GWP=32. Thus, fluorobutene compositions comprising Z-HFO-1336mzz may be good candidates for replacing higher GWP saturated compounds such as CFCs (chlorofluorocarbons), HCFCs (hydrochlorofluorocarbons), or HFCs (hydrofluorocarbons) in many uses.

[0004] Processes to prepare Z-HFO-1336mzz are disclosed, for example, in WO 2015 / 120250 A1. WO 2015 / 120250 A 1 discloses Z-HFO-1336mzz can be prepared starting from CFC-113a (1,1 ,1-trichloro-2,2,2-trifluoroethane) in a four-step process. These processes may not operate at full conversion, thus there is an issue to address reaction product from the process steps. It has been also found that intermediates in these processes may contain byproducts that negatively impact downstream processes and equipment in the manufacture of Z-HFO-1336mzz.Thus improved processes are needed for separation and purification of intermediates as well as a need to address unconverted starting materials.

[0005] The present invention addresses these issues.SUMMARY

[0006] The present invention provides a process and systems that are useful in manufacture of HFO-Z-1,1,1,4,4,4-hexafluoro-2-butene (Z-CF3CH=CHCF3, 1336mzzZ).

[0007] In one embodiment of this invention is provided a process to produce 1 ,1 ,2- trichloro-1 ,2,2-trifluoroethane (CFC-113 or 113) from tetrachloroethylene, (PCE). In this embodiment, the process may be performed in the liquid phase or in the vapor phase.

[0008] In one embodiment of this invention is provided a process to produce 1 ,1 ,1- trichloro-2,2,2-trifluoroethane (CFC-113a or 113a) from CFC-113. In this embodiment, the process may be performed as a batch reaction or as a continuous reaction.

[0009] In one embodiment of this invention is provided a process to produce 2,3- dichloro-1 ,1,1,4,4,4-hexafluoro-2-butene (HCFO-1316mxx or 1316mxx) from 1,1,1- trichloro-2,2,2-trifluoroethane (CFC-113a or 113a).

[0010] In one embodiment of this invention is provided a process to produce 2- chloro-1 ,1 ,1,4,4,4-hexafluoro-2-butene (HCFO-1326mxz or 1326mxz) from 2,3- dichloro-1 ,1,1,4,4,4-hexafluoro-2-butene (HCFO-1316mxx or 1316mxx).

[0011] In one embodiment of this invention is provided a process to produce1.1.1.4.4.4-hexafluoro-2-butyne (PFBY) from 2-chloro-1,1 ,1 ,4,4,4-hexafluoro-2- butene (HCFO-1326mxz or 1326mxz).

[0012] In one embodiment of this invention is provided a process to produce HFO- Z-1,1,1,4,4,4-hexafluoro-2-butene (1336mzzZ) from 1,1,1,4,4,4-hexafluoro-2-butyne (PFBY)

[0013] In one embodiment of this invention is provided a process to produce Z-1.1.1.4.4.4-hexafluoro-2-butene comprises (Step 1) producing 1 ,1 ,2-trichloro-1 ,2,2- trifluoroethane (CFC-113 or 113) from tetrachloroethylene, (PCE); (Step 2)producing 1,1 ,1-trichloro-2,2,2-trifluoroethane (CFC-113a or 113a) from CFC-113; (Step 3) producing 2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene (HCFO-1316mxx or 1316mxx) from 1 ,1 ,1-trichloro-2,2,2-trifluoroethane (CFC-113a or 113a); (Step 4) producing 2-chloro-1,1,1 ,4,4,4-hexafluoro-2-butene (HCFO-1326mxz or 1326mxz) from 2,3-dichloro-1,1,1 ,4,4,4-hexafluoro-2-butene (HCFO-1316mxx or 1316mxx); (Step 5) producing 1,1,1 ,4,4,4-hexafluoro-2-butyne (PFBY) from 2-chloro-1 ,1,1 ,4,4,4- hexafluoro-2-butene (HCFO-1326mxz or 1326mxz); and (Step 6) producing Z- 1 ,1 ,1 ,4,4,4-hexafluoro-2-butene (1336mzzZ) from 1,1,1 ,4,4,4-hexafluoro-2-butyne (PFBY).

[0014] Specific embodiments and reaction systems are described in further detail hereinbelow.BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 illustrates a liquid phase reaction system for producing 1 ,1 ,2- trichloro-1 ,2,2-trifluoroethane (CFC-113 or 113) from tetrachloroethylene (PCE) in an embodiment of this invention.

[0016] Figure 2 illustrates a vapor phase reaction system for producing 1,1,2- trichloro-1 ,2,2-trifluoroethane (CFC-113 or 113) from tetrachloroethylene (PCE) in an embodiment of this invention.

[0017] Figure 3 illustrates a reaction system for producing 1 , 1 , 1-trichloro-2,2,2- trifluoroethane (CFC-113a or 113a) from CFC-113 in one embodiment of the present invention.

[0018] Figure 4 illustrates a reaction system for producing 1 , 1 , 1-trichloro-2,2,2- trifluoroethane (CFC-113a or 113a) from CFC-113 in an alternative embodiment of the present invention.

[0019] Figure 5 illustrates a reaction system for producing 2,3-dichloro-1 , 1 , 1 ,4,4,4- hexafluoro-2-butene (HCFO-1316mxx or 1316mxx) from 1 , 1 , 1 -tri ch I oro-2, 2,2- trifluoroethane (CFC-113a or 113a) in one embodiment of the present invention.

[0020] Figure 6 illustrates a reaction system for producing 2-chloro-1 ,1 ,1 ,4,4,4- hexafluoro-2-butene (HCFO-1326mxz or 1326mxz) from 2,3-dichloro-1 , 1 , 1 ,4,4,4- hexafluoro-2-butene (HCFO-1316mxx or 1316mxx) in one embodiment of the present invention.

[0021] Figure 7 illustrates a reaction system for producing 1,1, 1,4,4, 4-hexafluoro- 2-butyne (PFBY) from 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (HCFO-1326mxz or 1326mxz) in one embodiment of the present invention.

[0022] Figure 8 illustrates a reaction system for producing Z-1, 1 ,1 , 4,4,4- hexafluoro-2-butene (1336mzzZ) from 1,1,1,4,4,4-hexafluoro-2-butyne (PFBY) in one embodiment of the present invention.DETAILED DESCRIPTION

[0023] The following detailed description of preferred embodiments of the present invention will be better understood when read in conjunction with the appended drawings. For the purposes of illustrating the invention, there is shown in the drawings embodiments which are presently preferred. It is understood, however, that the invention is not limited to the precise arrangements and instrumentalities shown.

[0024] 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).

[0025] The transitional phrase "consisting of' excludes any element, step, or ingredient 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.

[0026] The transitional phrase "consisting essentially of" is used to define a composition, method that includes materials, steps, features, components, or elements, in addition to those literally disclosed provided that these additional included materials, steps, features, components, or elements do not materially affectthe 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’.

[0027] 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.”

[0028] 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.

[0029] As used herein, the term “about” is meant to account for variations due to experimental error (e.g., plus or minus approximately 10% of the indicated value). All measurements reported herein are understood to be modified by the term “about”, whether or not the term is explicitly used, unless explicitly stated otherwise.

[0030] 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.

[0031] 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.

[0032] As used herein, the term “catalyst”, refers to a substance that speeds up the chemical reaction, but is not consumed by the reaction; thus it can be recovered chemically unchanged at the end of the reaction.

[0033] In Figures 1-8, lines illustrate feeds and process streams connecting the components of the systems illustrated. Although not shown in the Figures, each of the vessels (reactor, distillation column, decanter, neutralizer, absorber, moisture removal vessel) in Figures 1-8 include inlet and outlet ports to permit flow of material through the process lines. The feeds and process streams are denoted as “feed” and “stream”, beginning with the letters “F”, “P” and “S”.

[0034] The present invention provides processes and reaction systems for producing Z-HFO-1336mzz (1336mzzZ) in an efficient manner. The process comprises the following chemical reactions:Step113 + 3 HCIStep 2: 113Step 3: 113a + 2 H2A 1316mxx + 4 HCIStep 4: 1316mxx + H2-> 1326mxz + HCIStep 5: 1326mxz + NaOH -> PFBY + H2O + NaCI StepStep 1

[0035] In Step 1 of the present invention, there is provided a process for the conversion of perchloroethylene (PCE) to 113. In certain embodiments disclosed herein a tetrachloroethylene (PCE) feed composition, preferably comprising PCE and one or more additional compounds selected from CCU, CHCb, trichloroethylene, 1 ,1 ,3-trichloropropene, ethylene, and 1,1,1,3-tetrachloropropane (HCC-250fb) is used in a reaction to produce 113. The tetrachloroethylene (PCE) feed composition can be used in a liquid phase or vapor phase process.

[0036] In one embodiment, the tetrachloroethylene (PCE) feed composition contains >99% by weight PCE based on the total amount of the composition, and one or more additional compounds selected from chloroform, carbon tetrachloride, bromotrichloromethane, bromotrichloroethylene, 1,2-dichloroethane, ethylene, trichloroethylene (TCE), 1,1,3-trichloro-1-propene, and 1,1 ,1,3-tetrachloropropane. The tetrachloroethylene (PCE) feed composition can be used in a liquid phase or vapor phase process.

[0037] In certain embodiments, Step 1 uses a tetrachloroethylene (PCE) feed composition containing >99% by weight PCE, based on the total amount of the composition, and one or more additional compounds selected from chloroform, carbon tetrachloride, ethylene, trichloroethylene (TCE), 1 ,1 ,3-trichloro-1-propene, and 1,1 ,1,3-tetrachloropropane, is used in a reaction to produce 113. In certain embodiments, Step 1 uses a tetrachloroethylene (PCE) feed composition containing >99% by weight PCE, based on the total amount of the composition, and at least two additional compounds selected from 1 ,1 ,1 -trichloroethane, carbon tetrachloride, dichloromethane, and trichloroethylene (TCE), is used in a reaction to produce 113.Step 1 (Liquid Phase)

[0038] In one embodiment of Step 1 of the present invention, there is provided a continuous liquid phase process for the conversion of perchloroethylene (PCE) to 113. In certain embodiments disclosed herein a PCE feed composition contains >99% by weight PCE based on the total amount of the composition, and one or more additional compounds selected from chloroform, carbon tetrachloride, bromotrichloromethane, bromotrichloroethylene, 1,2-dichloroethane, ethylene, trichloroethylene, 1 ,1,3-trichloro-1-propene, and 1 ,1 ,1,3-tetrachloropropane.

[0039] In this liquid phase process, HF, chlorine, and the PCE feed composition are fed through an inlet to a reactor containing a liquid phase fluorination catalyst, wherein the PCE feed composition fed through an inlet to the reactor is material recovered from a downstream distillation column; wherein a portion of the HF is fresh and a portion of the HF is recycled from a downstream decanter; a portion of the chlorine is fresh and a portion of the chlorine is recycled from a downstream absorber, and wherein the recycled chlorine stream is premixed with a composition comprising PCE before feeding to the first reactor as a component of the PCE feed composition.

[0040] Figure 1 illustrates a reaction system designed for a liquid phase process to produce 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113 or 113) from tetrachloroethylene (PCE) in one embodiment of this invention. In Figure 1 , PCE is fluorinated to produce 113 in a reaction step and then separation steps are performed to remove unreacted materials and impurities.

[0041] The following nomenclature denotes the following elements in Figure 1 : A10A - liquid-liquid neutralizer; A11A - absorber; D10A, D11A, D12A, D13A, and D14A - distillation columns; M10A - moisture removal; R10A - fluorination reactor; X10A - decanter; F10A - feed of anhydrous hydrogen fluoride (HF) from outside of the process to fluorination reactor R10A; F11A - feed of chlorine from outside of the process to fluorination reactor R10A; F12A - feed of PCE from outside of the process to absorber A11 A; F13A - feed of neutralizing agent from outside of the process to liquid-liquid neutralizer A10A; S10A - vapor fraction from fluorination reactor R10A; S11A - higher boiling fraction from distillation column D10A; S12A - lower boiling fraction from distillation column D10A; S13A - higher boiling fraction from distillation column D11A; S14A - lower density fraction from decanter X10A; S15A - higher density fraction from decanter X10A; S16A - lower boiling fraction from distillation column D12A; S17A - outlet from absorber A11 A recycled to fluorination reactor R10A; S18A - higher boiling fraction from distillation column D12A; S19A - higher density fraction from liquid-liquid neutralizer A 10A; S20A - outlet from moisture removal M10A fed through an inlet to distillation column D13A; S21A - higher boiling fraction from distillation column D13A; P10A - lower boiling fraction from distillation column D11A removed through an outlet from the process; P11 A - lower density fraction from liquid-liquid neutralizer A10A removed through an outlet from the process; P12A - lower boiling fraction from distillation column D13A removed through an outlet from the process; P13A - lower boiling fraction from distillation column D14A removed through an outlet from the process; and P14A - higher boiling fraction from distillation column D14A removed through an outlet from the process.

[0042] More particularly, in Figure 1 , there is provided a reactor R10A, which is a continuous liquid phase reactor in which a liquid phase fluorination catalyst is suspended in a liquid reaction mixture. Reactor R10A is a continuous liquid phase reactor with catalyst suspended in the liquid reaction mixture. Products of the reaction are lower boiling than the starting materials and are removed through an outlet from the reactor as a vapor through stream S10A.

[0043] In one embodiment, the liquid phase fluorination catalyst is a transition metal catalyst selected from the group consisting of a tantalum catalyst, a niobium catalyst, or a tantalum-niobium catalyst.

[0044] In one embodiment, the liquid phase fluorination catalyst is a transition metal catalyst is selected from the group consisting of tantalum (V) chloride, niobium (V) chloride, niobium (IV) chloride, and combinations of two or more.

[0045] In one embodiment, the liquid phase fluorination catalyst is a fluorination catalyst is a metal halide selected from the group consisting of antimony halides, tin halides, thallium halides, iron halides and combinations of two or more.

[0046] In one embodiment, the liquid phase fluorination catalyst is a metal halide catalyst is selected from the group consisting of SbCb, SbCb, SbFs, SnCU, TiCL, NiFs, FeCb, and combinations of two or more, and preferably the metal halide catalyst is SbCb or SbFs.

[0047] Catalyst concentration the liquid phase fluorination catalyst is not specifically limited and the reaction will progress at reduced, preferred and increased concentrations. Preferred catalyst concentrations are 50 to 90 weight percent of the initial reactor charge.

[0048] The reaction pressure is not specifically limited and will proceed at reduced, preferred and increased pressure. The preferred operating pressure of the reactor is 1 to 2 MPaG. Pressure may be applied above or below the preferred range.

[0049] The reaction temperature is not specifically limited and will proceed at reduced, preferred and increased temperature. The preferred operating temperature of the reactor is 100 to 200°C. Temperatures above or below the preferred range may also be used.

[0050] As shown in Figure 1 , there are five inlets to the reactor: Fresh HF is fed through an inlet to reactor R10A in stream F10A; fresh chlorine is fed through an inlet to reactor R10A in stream F11A. High boiler fraction from distillation column D10A is fed through an inlet to reactor R10A in stream S11A. Stream S11A is composed primarily of 113, for purpose of recycling this starting material. Lower density fraction from decanter X10A is fed through an inlet to reactor R10A in stream S14A. S14A is composed primarily of recycled HF that is returned to reactor R10A. Outlet stream from absorber A11A is fed through an inlet to the reactor in stream S17A. S17A is composed primarily of fresh PCE feed and also contains unreacted chlorine from the reactor.

[0051] The residence time in reactor R10A is defined as the liquid volume in the reactor (cubic meters) divided by the total volumetric flow supplied to the reactor (m3 / h). The residence time is not specifically limited and will proceed at reduced, preferred and increased residence times. The preferred residence time in the reactor is 0.5 to 2 hours. It is also possible to use residence times above or below the preferred range.

[0052] The reaction products obtained in reactor R10A are removed as stream S10A (first reaction product). Stream S10A is fed through an inlet to distillation column D10A. Stream S10A contains HF, HCI, chlorine, and 113 (the desired product). Stream S10A may further comprise organic byproducts from the fluorination reaction. The main products of the fluorination reaction are HCI and 113 are formed as products of the fluorination reaction of PCE with HF (illustrated in Step 1). Thus, the first reaction product comprises HF, HCI, chlorine, and 113 and optionally organic byproducts.

[0053] Distillation column D10A separates the components of stream S10A into lower boiling and higher boiling fractions. The higher boiling fraction is removed through an outlet from distillation column D10A in stream. Stream S11A comprises HF. Stream S11A may further comprise HCI, chlorine, 113 and organic byproducts from the fluorination reaction.

[0054] The lower boiling fraction is removed through an outlet from distillation column D10A in stream S12A. Stream S12A contains HF, HCI, chlorine, 113 and organic byproducts from the fluorination. A majority of the HCI and HF in stream S11A, which is supplied to distillation column D10A is removed through an outlet from the column D10A as a lower boiling fraction stream S12A.

[0055] The preferred operating pressure of distillation column D10A is slightly lower than the preferred operating pressure of the reactor to allow for flow from reactor R10A to distillation column D10A. It is also possible to use pressures in distillation column D10A above or below the preferred range.

[0056] The higher boiling fraction removed through an outlet from distillation column D10A as stream S11A is returned (recycled) to reactor R10A where any HF and chlorine continue to participate in the reaction to produce 113.

[0057] The lower boiling fraction removed through an outlet from distillation column D10A as stream S12A is supplied to distillation column D11A. Distillation column D11A further separates the components from reactor R10A into lower boiling and higher boiling fractions. The higher boiling fraction is removed through an outlet from distillation column D11A in stream S13A. Stream S13A comprises HF, chlorine, 113 and may further comprise organic byproducts from the fluorination. HCI is essentially removed through an outlet from stream S13A. The lower boiling fraction is removed through an outlet from distillation column D11A in stream P10A and is removed through an outlet from the process. Stream P10A contains HCI with only minor concentrations of other components. The preferred operating pressure of distillation column D11A is slightly lower than the preferred operating pressure of distillation column D10A to allow for flow from distillation column D10A to distillation column D11A. It is also possible to use pressures in distillation column D11A above or below the preferred range.

[0058] The higher boiling fraction removed through an outlet from distillation column D11A, stream S13A, is cooled and is optionally supplied to decanter X10A. After cooling, stream S13A may separate into two liquid phases with different mass densities. A lower density fraction is removed through an outlet from decanter X10A in stream S14A. Stream S14A returns to fluorination reactor R10A for continued participation in the reaction to produce 113. Stream S14A comprises primarily HF. Stream S14A may further comprise 113 and organic byproducts from the fluorination reaction in small amounts.

[0059] The higher density fraction removed through an outlet from stream S13A in decanter X10A is stream S15A. Stream S15A is fed through an inlet to distillation column D12A. Stream S15A comprises HF, chlorine, 113 and organic byproducts. Stream S15A contains little HF, which is removed into stream S14A.

[0060] Pressure in decanter X10A is not critical so long as the liquid phases do not vaporize and the preferable range is slightly lower than the preferred pressure of distillation column D11 A to allow for flow between distillation column D11A and decanter X10A. The preferred operating temperature of decanter X10A is -50°C to 0°C. It is also possible to use pressures in decanter X10A above or below the preferred range.

[0061] The higher density fraction removed through an outlet from decanter X10A in stream S15A is fed through an inlet to distillation column D12A. Distillation column D12A separates the components in stream S15A into lower boiling and higher boiling fractions.

[0062] The higher boiling fraction removed through an outlet from distillation column D12A is stream S18A. Stream S18A comprises 113 and organic byproducts from the fluorination reaction with trace amounts of HF and chlorine.

[0063] The lower boiling fraction removed through an outlet from distillation column D12A is stream S16A. Stream S16A contains HF and chlorine with low concentrations of 113 and organic byproducts from the fluorination reaction. The majority of the chlorine and HF supplied to distillation column D12A is removed through an outlet from the column in the lower boiling fraction stream S16A.

[0064] The preferred operating pressure of distillation column D12A is slightly lower than the preferred operating pressure of decanter X10A to allow for flow from decanter X10A to distillation column D12A, but that is not required.

[0065] The pressure of distillation column D12A is not specifically limited and the separations will occur at reduced, preferred and increased pressure. It is also possible to use pressures in distillation column D12A above or below the preferred range.

[0066] The lower boiling fraction removed through an outlet from distillation column D12A in stream S16A is supplied to absorber A11 A. Fresh PCE is provided from outside the process and is fed through an inlet to absorber A11A in stream F12A. Stream S16A comprising chlorine and HF absorb into the PCE fed in stream F12A in absorber A11 A. The product from absorber A11 A is stream S17A, which comprises PCE, HF and chlorine. Stream S17A is removed through an outlet from absorber A11A and is fed through an inlet to reactor R10A as the PCE feed in the reaction of Step 1 to produce 113.

[0067] HF and chlorine contained in stream S17A returned to reactor R10A continue to participate in the fluorination reaction. The preferred operating pressure of absorber A11 A is slightly lower than the preferred operating pressure of distillation column S12A to allow for flow from distillation column D12A to absorber A11A. Thepressure of absorber A10A is not specifically limited and the separation will occur at reduced, preferred and increased pressure. A pump or other motive device is used to feed stream S17A from absorber A11A to reactor R10A. There is not a need to control the temperature in absorber A11 A.

[0068] The higher boiling fraction removed through an outlet from distillation column D12A as stream S18A comprises trace amounts of HF and chlorine that need to be removed. Stream S18A and feed F13A are fed through separate inlets to liquid-liquid neutralizer A10A. Feed F13A comprises a neutralizing agent. The neutralizing agent provided in Feed F13A may be an alkali solution. Liquid-liquid neutralizer A10A may be any device designed to intimately mix and separate the two liquid phases and neutralize the trace amounts of components, where in for this process, the components include HF and chlorine.

[0069] A lower density alkali phase is removed through an outlet from liquid-liquid neutralizer A10A stream P11A. P11A comprising product of neutralizing stream S18A and is then removed through an outlet from the process.

[0070] A higher density organic phase is removed through an outlet from liquidliquid neutralizer A10A in stream S19A. Stream S19A is free of HF and chlorine and contains 113, organic byproducts from the fluorination reaction and water.

[0071] The pressure of liquid-liquid neutralizer A10A is not specifically limited and can operate at reduced, preferred and increased pressure. The preferred operating pressure of liquid-liquid neutralizer A 10A is slightly below the preferred operating pressure of distillation column D12A to allow for flow from distillation column D12A to liquid-liquid neutralizer A10A, but that is not required.

[0072] The preferred operating temperature of liquid-liquid neutralizer A10A is 10°C to 50°C. It is also possible to use temperatures above or below the preferred range.

[0073] The higher density organic phase that is removed through an outlet from the liquid-liquid neutralizer A10A in stream S19A contains water that is preferably removed from stream S19A before further processing. For this purpose, stream S19A is fed through an inlet to moisture removal device M10A. The moisture removal device is typically a fixed bed of desiccant, but other methods could beemployed to remove the moisture from stream S19A. Dry 113 produced in the fluorination reaction is removed through an outlet from moisture removal device M10A as stream S20A. Stream S20A is supplied to distillation column D13A.

[0074] Distillation column D13A separates the components of stream S20A into lower boiling and higher boiling fractions. A higher boiling fraction is removed through an outlet from distillation column D13A in stream S21A. Stream S21A contains 113 and other higher boiling organic byproducts from the fluorination reaction.

[0075] A lower boiling fraction is removed through an outlet from distillation column D13A in stream P12A. Stream P12A contains lower boiling organic byproducts from the fluorination reaction as well as small amounts of 113. Stream P12A is removed through an outlet from the process. Typical lower boiling impurities produced in the fluorination reaction include, but are not limited to, 1,1 -dichloro- 1, 2,2,2- tetrafluoroethane (114A) and 1 ,1-dichloro-2,2,2-trifluoroethane (123).

[0076] The pressure of distillation column D13A is not specifically limited and the separation will occur at reduced, preferred and increased pressure. The preferred operating pressure of distillation column D13A is 0.5 to 1.5 MPaG. It is also possible to use pressures in distillation column D13A above or below the preferred range.

[0077] The higher boiling fraction removed through an outlet from distillation column D13A in stream S21A is fed through an inlet to distillation column D14A. Distillation column D14A separates the components into a lower boiling fraction comprising 113 and a higher boiling fraction.

[0078] The higher boiling fraction is removed through an outlet from distillation column D14A in stream P14A. Stream P14A contains other higher boiling organic byproducts from the fluorination reaction and small amounts of 113. Typical higher boiling impurities produced in the fluorination reaction include, but are not limited to, 1 ,1 ,1,2-tetrachloro-2,2-difluoroethane (112) and 1,1 ,2-trichloro-2,2-difluoroethane (122). Stream P14A is removed through an outlet from the process.

[0079] The lower boiling fraction from distillation column D14A is the desired product from the fluorination reaction, Step 1. Stream P13A removes 113 from process Step 1.

[0080] The preferred operating pressure of distillation column D14A is slightly below the preferred operating pressure of distillation column D13A to allow for flow from distillation column D13A to distillation column D14A, but that is not required. It is also possible to use pressures in distillation column D14A above or below the preferred range.Step 1 (Vapor Phase)

[0081] In one embodiment of Step 1 of the present invention, there is provided a continuous vapor phase process for the conversion of PCE to 113.

[0082] In certain embodiments disclosed herein a composition containing >99% by weight PCE based on the total amount of the composition, and one or more additional compounds selected from chloroform, carbon tetrachloride, bromotrichloromethane, bromotrichloroethylene, 1,2-dichloroethane, ethylene, trichloroethylene, 1 ,1,3-trichloro-1-propene, and 1 ,1 ,1,3-tetrachloropropane is used as a tetrachloroethylene (PCE) feed composition.

[0083] In one embodiment of this vapor phase process, fresh feeds of HF, chlorine and the PCE feed composition are fed through an inlet to a reactor containing a vapor phase fluorination catalyst and the PCE feed composition fed through an inlet to the reactor is material recovered from a downstream distillation column; wherein a portion of the HF is fresh and a portion of the HF is recycled from a downstream decanter; a portion of the chlorine is fresh and a portion of the chlorine is recycled from a downstream absorber, and wherein the recycled chlorine stream is premixed with a composition comprising PCE before feeding to the first reactor as a component of the PCE feed composition. The PCE feed composition may be a tetrachloroethylene (PCE) feed composition comprising >99% by weight PCE based on the total amount of the composition, and one or more additional compounds selected from chloroform, carbon tetrachloride, bromotrichloromethane, bromotrichloroethylene, 1,2-dichloroethane, ethylene, trichloroethylene, 1,1,3- trichloro-1 -propene, and 1 ,1,1,3-tetrachloropropane is used as a tetrachloroethylene (PCE) feed composition.

[0084] In this liquid phase process, HF, chlorine, and the PCE feed composition are fed through an inlet to a reactor containing a liquid phase fluorination catalyst, wherein the PCE feed composition fed through an inlet to the reactor is material recovered from a downstream distillation column; wherein a portion of the HF is fresh and a portion of the HF is recycled from a downstream decanter; a portion of the chlorine is fresh and a portion of the chlorine is recycled from a downstream absorber, and wherein the recycled chlorine stream is premixed with a composition comprising PCE before feeding to the first reactor as a component of the PCE feed composition.

[0085] Figure 2 illustrates a reaction system of a second embodiment designed for a vapor phase process to produce 1,1 ,2-trichloro-1 ,2,2-trifluoroethane (CFC-113 or 113) from tetrachloroethylene (PCE). In Figure 2, PCE is fluorinated to produce 113 in a reaction step and then separation steps are performed to remove unreacted materials and impurities.

[0086] The following nomenclature denotes the following elements in Figure 2: A10B - liquid-liquid neutralizer; D10B, D11 B, D12B, D13B and D14B - distillation columns; M10B - moisture removal; R10B - fluorination reactor; X10B - decanter; F10B - feed of anhydrous hydrogen fluoride (HF) from outside of the process to fluorination reactor R10B; F11B - feed of chlorine from outside of the process to fluorination reactor R10B; F12B - feed of PCE from outside of the process to absorber A11B; F13B - feed of neutralizing agent from outside of the process to liquid-liquid neutralizer A10B; S10B - reaction mixture from fluorination reactor R10B; S11 B - higher boiling fraction from distillation column D10B; S12B - lower boiling fraction from distillation column D10B; S13B - higher boiling fraction from distillation column D11 B; S14B - lower density fraction from decanter X10B; S15B - higher density fraction from decanter X10B; S17B - lower boiling fraction from distillation column D12B; S18B - higher boiling fraction from distillation column D12B; S19B - higher density fraction from absorber A10B; S20B - outlet from moisture removal M10B fed through an inlet to distillation column D13B; S21B - higher boiling fraction from distillation column D13B; P10B - lower boiling fraction from distillation column D11 B removed through an outlet from the process; P11 B - lower density fraction from absorber A10B removed through an outlet from the process; P12B - lower boiling fraction from distillation column D13B removedthrough an outlet from the process; P13B - lower boiling fraction from distillation column D14B removed through an outlet from the process; and P14B - higher boiling fraction from distillation column D14B removed through an outlet from the process.

[0087] More particularly, in Figure 2, reactor R10B is a continuous vapor phase reactor containing solid catalyst. The configuration of reactor R10B may be a single reactor or multiple reactors in series.

[0088] In this embodiment, a reaction mixture (“first reaction mixture”) is produced in reactor 10B. The first reaction mixture is removed through an outlet from reactor R10B as a vapor in stream S10B.

[0089] The reaction pressure in this embodiment is not specifically limited and will proceed at reduced, preferred and increased pressure. The preferred operating pressure of the reactor is 1 to 4 MPaG. It is also possible to apply pressure above or below the preferred range. Reaction at increased pressure is advantageous since increased pressure reduces the size of equipment.

[0090] The reaction temperature is not specifically limited and will proceed at reduced, preferred and increased temperature. The preferred operating temperature of the reactor is 150°C to 400°C. It is also possible to use temperatures above or below the preferred range.

[0091] Referring to Figure 2, there are six inlets to reactor R10B. Through one inlet, fresh HF is fed through an inlet to reactor R10B in stream F10B. Through another inlet, fresh chlorine is fed through an inlet to reactor R10B in stream F11B. Through another inlet fresh PCE is fed through an inlet to reactor R10B in stream F12B. The fresh PCE may be a tetrachloroethylene (PCE) feed composition may comprise >99% by weight PCE based on the total amount of the composition, and one or more additional compounds selected from chloroform, carbon tetrachloride, bromotrichloromethane, bromotrichloroethylene, 1,2-dichloroethane, ethylene, trichloroethylene, 1 ,1,3-trichloro-1-propene, and 1 ,1 ,1,3-tetrachloropropane is used as a tetrachloroethylene (PCE) feed composition.

[0092] Through another inlet , a higher boiler fraction from distillation column D10B is fed through an inlet to reactor R10B in stream S11 B as a recycle stream,wherein distillation column D10B is connected to and is immediately downstream of reactor R10B. Through another inlet, a lower density fraction from decanter X10B is fed through an inlet to reactor R10B in stream S14B as a recycle stream, wherein decanter X1 OB is downstream from distillation column D10B and a second distillation column D11 B. Through another inlet, a lower boiling fraction from distillation column D12B is fed through an inlet to reactor R10B in stream S17B as a recycle stream, wherein distillation column D12B is downstream of distillation columns D10B and D11 B and downstream from decanter X10B. More information on relationship of streams, distillation columns and decanters are provided hereinbelow.

[0093] Stream S11 B comprises intermediate products in the conversion of PCE to 113 from reactor R1 OB. Stream S11 B comprises one or more of 1 , 1 , 1 ,2,2- pentachloro-2-fluoroethane (111), 1 ,1 ,2,2-tetrachloro-1 ,2-difluoroethane (112), and 1 ,1 ,1 ,2-tetrachloro-2,2-difluoroethane (112A). Stream S14B, the lower density fraction from decanter X10B comprises material to be recycled. S14B comprises HF. Stream S17B, the lower boiling fraction from distillation column D12B comprises chlorine to recycle and may further comprise organic byproducts from the fluorination reaction in reactor R10B.

[0094] The residence time in reactor R10B is defined as the empty volume of the reactor (cubic meters) divided by the total volumetric flow supplied to the reactor (m3 / h). The residence time is not specifically limited and will proceed at reduced, preferred and increased residence times. The preferred residence time in reactor R10B is 0.5 to 10 minutes. It is also possible to use residence times above or below the preferred range.

[0095] Stream S10B containing the reaction product from reactor R10B is fed through an inlet to distillation column D10B. Stream S10B contains HF, HCI, chlorine, 113, intermediate reaction products and organic byproducts from the fluorination reaction. Distillation column D10B separates the components of stream S10B into lower boiling and higher boiling fractions. The higher boiling fraction is removed through an outlet from distillation column D10B in stream S11 B. Stream S11 B comprises intermediate reaction products (111 , 112, 112a) and organic byproducts from the fluorination reaction.

[0096] The lower boiling fraction is removed through an outlet from distillation column D10B in stream S12B. Stream S12B contains HF, HCI, chlorine, 113 and other organic byproducts from the fluorination reaction. The majority of the HF, HCI and chlorine supplied to distillation column D10B is removed through an outlet from the column in the lower boiling fraction stream S12B.

[0097] The preferred operating pressure of distillation column D10B is slightly lower than the preferred operating pressure of the reactor to allow for flow from reactor R10B to distillation column D10B. It is also possible to use pressures in distillation column D10B above or below the preferred range.

[0098] The higher boiling fraction removed through an outlet from distillation column D10B in stream S11 B comprising intermediate reaction products (111 , 112, 112a) is returned to reactor R10B through an inlet. Thus, the intermediate reaction products in stream S11 B continue to participate in the reaction to produce 113.

[0099] The lower boiling fraction removed through an outlet from distillation column D10B is fed through an inlet to distillation column D11 B in stream S12B. Distillation column D11B separates the components of stream S12B into lower boiling and higher boiling fractions.

[0100] The higher boiling fraction is removed through an outlet from distillation column D11 B in stream S13B. Stream S13B contains HF, chlorine, 113 and other organic byproducts from the fluorination, with the HCI essentially removed.

[0101] The lower boiling fraction is removed through an outlet from distillation column D11 B in stream P10B and is removed through an outlet from the process. Stream P10B contains HCI with only minor concentrations of other components. Stream P10B may be subjected to treatments to recover the HCI contained therein.

[0102] The preferred operating pressure of distillation column D11 B is slightly lower than the preferred operating pressure of distillation column D10B to allow for flow from distillation column D10B to distillation column D11 B. It is also possible to use pressures in distillation column D11 B above or below the preferred range.

[0103] The higher boiling fraction removed through an outlet from distillation column D11 B, stream S13B, is cooled then supplied to decanter X10B. Cooling may occur by passing through a heat exchanger or by other means provided betweendistillation column D11 B and decanter X1 OB. After cooling, stream S13B is separate into two liquid phases with different mass densities and fed through an inlet to decanter X1 OB.

[0104] The lower density fraction is removed through an outlet from decanter X10B in stream S14B. Stream S14B returns to fluorination reactor R10B to continue to participate in the reaction to produce 113. Stream S14B comprises HF. Stream S14B further comprises lesser amounts of 113 and organic byproducts from the fluorination reaction. Stream S14B is returned (fed) through an inlet to fluorination reactor R10B. Thus, unreacted HF is recycled from the product of reactor R10B so that this HF (recycled HF) can continue to participate in the fluorination reaction to produce 113 in reactor R10B.

[0105] The higher density fraction removed through an outlet from decanter X10B in stream S15B is fed through an inlet to distillation column D12B. Stream S15B contains HF, chlorine, 113 and other organic byproducts with most of the HF removed into stream S14B.

[0106] The pressure in decanter X10B is not important provided the liquid phases do not vaporize and the preferable range is slightly lower than the preferred pressure of distillation column D11 B to allow for flow between distillation column D11 B and decanter X10B. It is also possible to use pressures in decanter X10B above or below the preferred range. The preferred operating temperature of decanter X10B is -50°C to 0°C. It is also possible to use pressures in decanter X10B above or below the preferred range.

[0107] The higher density fraction removed through an outlet from decanter X10B in stream S15B is fed through an inlet to distillation column D12B. Distillation column D12B separates the components of stream S15B into lower boiling and higher boiling fractions.

[0108] The higher boiling fraction of stream S15B is removed through an outlet from distillation column D12B in stream S18B. Stream S18B comprises 113 and organic byproducts from the fluorination reaction. Stream S18B further comprises trace amounts of HF and chlorine.

[0109] The lower boiling fraction of stream S15B is removed through an outlet from distillation column D12B in stream S17B. Stream S17B comprises HF and chlorine. Stream S17B further comprises low concentrations of 113 and organic byproducts from the fluorination reaction. The majority of the chlorine and HF supplied to distillation column D12B is removed through an outlet from distillation column D12B in the lower boiling fraction stream S17B.

[0110] The preferred operating pressure of distillation column D12B is slightly lower than the preferred operating pressure of decanter X10B to allow for flow from decanter X1 OB to distillation column D12B, but that is not required. The pressure of distillation column D12B is not specifically limited and the separations will occur at reduced, preferred and increased pressure. It is also possible to use pressures in distillation column D12B above or below the preferred range.

[0111] The lower boiling fraction comprising HF and chlorine that is removed through an outlet from distillation column D12B in stream S17B is fed through an inlet to fluorination reactor R10B for continued participation in the reaction to produce 113. Thus, both HF and chlorine are recycled.

[0112] The higher boiling fraction from distillation column D12B comprising 113 is removed through an outlet from distillation column D12B in stream S18B. There are trace amounts of HF and chlorine in stream S18B that need to be removed prior to proceeding to use this material in producing 113a in a subsequent step to producing 1336mzzZ.

[0113] Stream S18B is fed through an inlet to liquid-liquid neutralizer A10B.Feed F13B is also fed through an inlet to liquid-liquid neutralizer A10B. Feed F13B comprises a neutralizing agent. The neutralizing agent provided in feed F13B may be an alkali solution. Liquid-liquid neutralizer A10B may be any device designed to intimately mix and separate the two liquid phases and neutralize the trace amounts of components, where in for this process, the components include HF and chlorine.

[0114] The lower density alkali phase produced in liquid-liquid neutralizer A10B is removed through an outlet from liquid-liquid neutralizer A10B in stream P11 B. Thus stream P11 B is removed through an outlet from the process illustrated in Figure 2.

[0115] The higher density organic phase is removed through an outlet from the liquid-liquid neutralizer A1 OB in stream S19B. Stream S19B comprises 113 and organic byproducts from the fluorination reaction and water. Stream S19B is essentially free of HF and chlorine.

[0116] The pressure of liquid-liquid neutralizer A1 OB is not specifically limited and can operate at reduced, preferred and increased pressure. The preferred operating pressure of liquid-liquid neutralizer A 10B is slightly below the preferred operating pressure of distillation column D12B to allow for flow from distillation column D12B to liquid-liquid neutralizer A1 OB, but that is not required. The preferred operating temperature of liquid-liquid neutralizer A1 OB is 10°C to 50°C. It is also possible to use temperatures above or below the preferred range.

[0117] The higher density organic phase that is removed through an outlet from the liquid-liquid neutralizer A1 OB in stream S19B contains water that should be removed from stream S19B before further processing. Stream S19B is fed through an inlet to moisture removal device M10B. The moisture removal device is typically a fixed bed of desiccant, but other methods could be employed to remove the moisture from stream S19B. Dry 113 produced in the fluorination reaction is removed from moisture removal device M10A as stream S20B. Stream S20B is supplied to distillation column D13B.

[0118] Distillation column D13B separates the components of stream S20B into lower boiling and higher boiling fractions. A higher boiling fraction is removed from distillation column D13B in stream S21 B. Stream S21B contains 113 and other higher boiling organic byproducts from the fluorination reaction.

[0119] A lower boiling fraction is removed from distillation column D13B in stream P12B. Stream P12B contains lower boiling organic byproducts from the fluorination reaction as well as small amounts of 113. Stream P12B is removed from the process. Typical lower boiling impurities produced in the fluorination reaction include, but are not limited to, 1,1-dichloro-1 ,2,2,2-tetrafluoroethane (114A) and 1 , 1-dichloro- 2,2,2-trifluoroethane (123).

[0120] The pressure of distillation column D13B is not specifically limited and the separation will occur at reduced, preferred and increased pressure. The preferredoperating pressure of distillation column D13B is 0.5 to 1.5 MPaG. It is also possible to use pressures in distillation column D13B above or below the preferred range.

[0121] The higher boiling fraction removed from distillation column D13B in stream S21 B is fed to distillation column D14B. Distillation column D14B separates the components into a lower boiling fraction comprising 113 and a higher boiling fraction.

[0122] The higher boiling fraction is removed from distillation column D14B in stream P14B. Stream P14B contains other higher boiling organic byproducts from the fluorination reaction and small amounts of 113. Typical higher boiling impurities produced in the fluorination reaction include, but are not limited to, 1 ,1 ,1 ,2- tetrachloro-2,2-difluoroethane (112) and 1 ,1,2-trichloro-2,2-difluoroethane (122). Stream P14B is removed from the process.

[0123] The lower boiling fraction from distillation column D14B is the desired product from the fluorination reaction, Step 1. Stream P13B removes 113, from process Step 1.

[0124] The preferred operating pressure of distillation column D14B is slightly below the preferred operating pressure of distillation column D13B to allow for flow from distillation column D13B to distillation column D14B, but that is not required. It is also possible to use pressures in distillation column D14B above or below the preferred range.

[0125] In certain embodiments disclosed herein for Step 1 , there is produced a composition comprising 113, which composition contains >99% by weight 113 based on the total amount of the composition, and two or more additional compounds selected from CFC-113a, HCFC-123, HCFC-123a, CFC-115, CFC-12, HCFC-124, CFC-114, CFC-1317, CFC-216, CFC-318, CFC-316, CFC-215cb, CFC-214cb. HCFC-122, CFC-112, CFC-112a. CFC-1112a, PCE. The composition comprising 113 may be produced by either the liquid phase or the vapor phase process for Step 1 , as disclosed herein. In the liquid phase process for step 1 , Stream P13A comprises 113. This Stream P13A may then comprise >99% by weight 113 based on the total amount of the composition, and two or more additional compounds selected from CFC-113a, HCFC-123, HCFC-123a, CFC-115, CFC-12, HCFC-124, CFC-114, CFC-1317, CFC-216, CFC-318, CFC-316, CFC-215cb, CFC-214cb.HCFC-122, CFC-112, CFC-112a. CFC-1112a, and PCE. In the vapor phaseprocess for step 1 , Stream P13B comprises 113. This Stream P13B may then comprise >99% by weight 113 based on the total amount of the composition, and two or more additional compounds selected from CFC-113a, HCFC-123, HCFC- 123a, CFC-115, CFC-12, HCFC-124, CFC-114, CFC-1317, CFC-216, CFC-318, CFC-316, CFC-215cb, CFC-214cb. HCFC-122, CFC-112, CFC-112a. CFC-1112a, and PCE.Step 2

[0126] In Step 2 of the present invention, there is provided a process for the conversion of 1,1,2-trichloro-1 ,2,2-trifluoroethane (CFC-113 or 113) to 1 , 1 , 1-trichloro- 2,2,2-trifluoroethane (CFC-113a or 113a). In certain embodiments disclosed herein a 113 feed composition comprises 113. Preferably, the 113 feed composition comprises, consists essentially of or, or consists of CFC-113 and less than about 1% by weight of two or more additional compounds selected from CFC-113a, CFC-114a, HCFC-123, HCFC-123a, CFC-115, CFC-12, HCFC-124, CFC-114, CFC-1317, CFC- 216, CFC-318, CFC-316, CFC-215cb, CFC-214cb. HCFC-122, CFC-112, CFC- 112a. CFC-1112a, and PCE, wherein the total amount of said additional compounds is less than 1 weight % of the total composition.

[0127] The 113 feed composition may be produced by a liquid phase or a vapor phase process as discussed hereinabove. In one embodiment, the 113 feed composition is produced by the liquid phase process as described and presented in Figure 1. In one embodiment, the 113 feed composition is produced by the vapor phase process as described and presented in Figure 2.Step 2 (Batch Process)

[0128] In one embodiment of Step 2 of the present invention, there is provided a batch process of a first embodiment for the conversion (isomerization) of 113 to 113a. This batch process comprises feeding a liquid phase isomerization catalyst and a 113 feed composition to a reactor, operating the reactor at temperature and pressure to convert the 113 to 113a, thus producing a product mixture comprising catalyst, 113 and 113a. The process further comprises separating 113, 113a and catalyst from the product mixture, to produce a separated product comprising 113 and catalyst, and then removing and recovering 113 and catalyst from the separatedproduct. The recovered 113 and the recovered catalyst are recycled to the reactor of the batch process. The process further comprises separating and removing impurities from the product mixture comprising catalyst, 113 and 113a.

[0129] Figure 3 illustrates a reaction system of one embodiment for a system useful for a process for producing 1,1,1-trichloro-2,2,2-trifluoroethane (113a) from 1 , 1 ,2-trich loro- 1 ,2,2-trifluoroethane (113) in an embodiment of Step 2 of the present invention. This embodiment relates to a manner in which isomerization is carried out to produce 113a in a reaction step, then separations are carried out to remove unreacted materials and impurities.

[0130] The following nomenclature denotes the following elements in Figure 3: D21 A and D22A - distillation columns; E20A - partial condenser; T20A - storage tank for unrefined 113A; R20A - isomerization reactor; F20A - feed of 113 from outside of the process to isomerization reactor R20A; F21 A - feed of PCE from outside of the process to distillation column D22A; S20A - reaction vapor from isomerization reactor R20A to partial condenser E20A; S21A - liquid return from partial condenser E20A to isomerization reactor R20A; S22A - liquid reaction mixture withdrawn from reactor R20A at the end of the batch; S23A - continuous feed of reaction mixture to distillation column D21A; S24A - higher boiling fraction from distillation column D21 A; P20A - vent from partial condenser E20A removed through an outlet from process; P21A - lower boiling fraction from distillation column D21 A removed through an outlet from process; P22A - lower boiling fraction from distillation column D22A removed through an outlet from process; and P23A - higher boiling fraction from distillation column D22A removed through an outlet from process.

[0131] Reactor R20A is a batch, agitated, liquid phase reactor with catalyst suspended in the liquid reaction mixture. Reactor 20A is charged with catalyst and a 113 feed composition. The reaction, that is, the isomerization reaction of 113 to 113a occurs in Reactor R20A. After completion of the reaction, agitation is stopped and the catalyst is allowed to settle. The reaction mixture in reactor R20A is transferred from reactor R20A so that reactor R20A can be used for a new batch. The reaction mixture produced in Reactor 20A is withdrawn from Reactor 20A in stream S22A.

[0132] Stream S22A is fed to storage tank T20A. Storage tank T20A is used to collect multiple batches of reaction mixture produced in the isomerization reaction in reactor R20A.

[0133] The preferred reaction batch time in reactor R20A is 6 to 18 hours. It is also possible to use reaction batch times above or below the preferred range.

[0134] Catalyst concentration is not specifically limited and the reaction will progress at reduced, preferred and increased concentrations. Preferred catalyst concentrations are 1 to 5 weight percent of the initial reactor charge. It is also possible to use catalyst concentrations above or below the preferred range.

[0135] The reaction temperature is not specifically limited and will proceed at reduced, preferred and increased temperature. The preferred operating temperature of the reactor is 0°C to 80°C. It is also possible to use temperatures above or below the preferred range.

[0136] The pressure of reactor R20A is normally determined by the vapor pressure of the reaction mixture at the operating temperature of the reactor. The reaction pressure is not specifically limited and will proceed at reduced, preferred and increased pressure. The preferred operating pressure of reactor R20A is 0.01 to 0.05 MPaG. It is also possible to apply pressure above or below the preferred range.

[0137] As shown in Figure 3, there are two inlets to the reactor: Fresh 113 is fed through an inlet to reactor R20A in stream F20A. Stream S21A is composed primarily of 113, for purpose of recycling this material from partial condenser E20A.

[0138] Reactor R20A has an outlet which attaches to partial condenser E20A. Thus vapor from the reaction mixture in reactor R20A is removed through an outlet from reactor R20A through an outlet to stream S20A. Most of the material contained in stream S20A is condensed in partial condenser E20A. The condensed liquid is removed through an outlet from partial condenser E20A and is returned to reactor R20A for continued participation in the reaction to produce 113a in stream S21A. Stream S21A is primarily unreacted 113. Partial condenser E20A has attached a small vent that permits inert materials to be removed in stream P20A. Stream P20A is removed through an outlet from the process and not returned / recycled.

[0139] Storage tank T20A has an outlet that is connected to distillation column D21 A through which is fed stream S23A. Stream S23A is the feed of the reaction mixture from an outlet of storage tank T20A to distillation column D21A. In a second aspect of this embodiment, product mixture from storage tank T20A is fed continuously from an outlet of storage tank T20A to an inlet of distillation column D21A in stream S23A.

[0140] Distillation column D21A separates the components from the reaction mixture of storage tank T20A into lower boiling and higher boiling fractions.

[0141] The lower boiling fraction from distillation column D21A is removed through an outlet from distillation column D21A in stream P21A. Stream P21A comprises 1 ,1-dichloro-1 ,2,2,2-tetrafluoroethane (114a) as a main component. Stream P21A further comprises smaller amounts of 1,1-dichloro-2,2,2-trifluoroethane (123), 113 and 113a. Stream P21A is removed through an outlet in distillation column D21A, and removed from the process.

[0142] The higher boiling fraction is removed through an outlet from distillation column D21A in stream S24A. Stream S24A comprises 113 and 113a.

[0143] The pressure of distillation column D21A is not specifically limited and will separate the components at reduced, preferred and increased pressure. The preferred operating pressure of the distillation column D21A is 0.1 to 0.8 MPaG. It is also possible to use pressures above or below the preferred range.

[0144] The higher boiling fraction of stream S24A that is removed through an outlet from distillation column D21A is fed through an inlet to distillation column D22A. Fresh PCE is fed in feed F21A through an inlet to distillation column D21A. This fresh PCE in feed F21A fed to distillation column D22A is used to reduce the potential of solidification of the higher boiling fraction once removed through an outlet of distillation column D22A in stream P23A.

[0145] Distillation column D22A separates the components of stream S24B into a lower boiling fraction comprising 113a and a higher boiling fraction comprising PCE. The higher boiling fraction is removed om stream P23A through an outlet from distillation column D22A. Stream P23A comprises PCE (as supplied in stream F21 A), organic byproducts of the isomerization reaction as well as small amounts of113 and 113a. The higher boiling fraction in stream P23A is removed through an outlet in distillation column D22A. Stream P23A may be recycled to Step 1 as part of feed F12A or F12B as disclosed hereinabove and as illustrated in Figures 1 and 2, respectively to produce additional 113 product.

[0146] The lower boiling fraction from distillation column D22A is the desired product from this process step, 113a, and is removed through an outlet in distillation column D22A in stream P22A. Thus stream P22A comprises 113a.

[0147] The preferred operating pressure of distillation column D22A is slightly below the preferred operating pressure of distillation column D21 A to allow for flow from distillation column D21A to distillation column D22A. It is also possible to use pressures in distillation column D22A above or below the preferred range.Step 2 (Continuous Process)

[0148] In one embodiment of Step 2 of the present invention, there is provided a continuous process of a second embodiment for the conversion (isomerization) of 113 to 113a. This continuous process comprises feeding a 113 feed composition to a vapor phase reactor containing a catalyst, operating the reactor at temperature and pressure to convert the 113 to 113a, thus producing a reaction mixture comprising 113 and 113a, separating 113 and 113a from the reaction mixture, producing a product comprising 113a, removing and recovering 113, and recycling the recovered 113 to the reactor. The process further comprises separating and removing impurities from the reaction mixture comprising catalyst, 113 and 113a.

[0149] Figure 4 illustrates a reaction system of an alternative embodiment for a system useful for a process for producing 1,1,1-trichloro-2,2,2-trifluoroethane (113a) from 1 , 1 , 2-trich loro- 1 ,2,2-trifluoroethane (113) in an embodiment of Step 2 of the present invention. This second embodiment of Step 2 relates to a manner in which isomerization is carried out to produce 113A in a reaction step, then separations are carried out to remove unreacted materials and impurities.

[0150] The following nomenclature denotes the following elements in Figure 4: D21 B and D22B - distillation columns; R20B - isomerization reactor; F20B - feed of 113 from outside of the process to isomerization reactor R20B; F21 B - feed of PCE from outside of the process to distillation column D22B; S23B - reaction mixtureoutlet from reactor R20B; S24B - higher boiling fraction from distillation column D21 B; P21 B - lower boiling fraction from distillation column D21 B removed through an outlet from the process; P22B - lower boiling fraction from distillation column D22B removed through an outlet from the process; and P23B - higher boiling fraction from distillation column D22B removed through an outlet from the process.

[0151] Reactor R20B is a continuous reactor and contains solid catalyst. The configuration of Reactor 20B may be a single reactor or multiple reactors in series. The reaction mixture is removed through an outlet from the reactor through stream S23B.

[0152] The reaction pressure is not specifically limited and will proceed at reduced, preferred and increased pressure. The preferred operating pressure of the reactor is 0.01 to 0.05 MPaG. It is also possible to apply pressure above or below the preferred range.

[0153] The reaction temperature is not specifically limited and will proceed at reduced, preferred and increased temperature. The preferred operating temperature of the reactor is 10°C to 100°C. It is also possible to use temperatures above or below the preferred range.

[0154] The residence time in the reactor is defined as the empty volume of the reactor (cubic meters) divided by the total volumetric flow supplied to the reactor (m3 / h). The residence time is not specifically limited and will proceed at reduced, preferred and increased residence times. The preferred residence time in reactor R20B is 0.5 to 10 minutes. It is also possible to use residence times above or below the preferred range.

[0155] The reaction mixture in reactor R20B is removed through an outlet from reactor R20B in stream S23B. Stream S23B comprising the reaction mixture is fed to distillation column D21 B. Distillation column D21 B separates the components into lower boiling and higher boiling fractions.

[0156] The lower boiling fraction of distillation column D21 B is removed through an outlet from distillation column D21 B in stream P21B. Stream P21B comprises 1,1- dichloro-1 ,2,2,2-tetrafluoroethane (114a). While 114a is a major component of stream P21 B, stream P21 B further comprises smaller amounts of 1 , 1-dichloro-2,2,2-trifluoroethane (123), 113 and 113a. Stream P21 B is removed through an outlet of distillation column D21 B from the process.

[0157] The higher boiling fraction of distillation column D21B is removed through an outlet from distillation column D21 B in stream S24B. Stream S24B comprises 113 and 113a. These are the major components of stream S24B.

[0158] The pressure of distillation column D21B is not specifically limited and will separate the components at reduced, preferred and increased pressure. The preferred operating pressure of the distillation column D21 B is 0.1 to 0.8 MPaG. It is also possible to use pressures above or below the preferred range.

[0159] The higher boiling fraction of stream S24B that is removed through an outlet from distillation column D21 B is fed through an inlet to distillation column D22B. Fresh PCE is fed in feed F21B through an inlet to distillation column D21B. This fresh PCE in feed F21 B fed to distillation column D22B is used to reduce the potential of solidification of the higher boiling fraction once removed through an outlet of distillation column D22B in stream P23B.

[0160] The higher boiling fraction is removed om stream P23B through an outlet from distillation column D22B. Stream P23B comprises PCE (as supplied in stream F21 B), organic byproducts of the isomerization reaction as well as small amounts of 113 and 113a. The higher boiling fraction in stream P23B is removed through an outlet in distillation column D22B. Stream P23B may be recycled to Step 1 as part of feed F12B or F12B as disclosed hereinabove and as illustrated in Figures 1 and 2, respectively to produce additional 113 product.

[0161] The lower boiling fraction from distillation column D22B is the desired product from this process step, 113a, and is removed through an outlet in distillation column D22B in stream P22B. Thus stream P22B comprises 113a.

[0162] The preferred operating pressure of distillation column D22B is slightly below the preferred operating pressure of distillation column D21 B to allow for flow from distillation column D21 B to distillation column D22B. It is also possible to use pressures in distillation column D22B above or below the preferred range.

[0163] In certain embodiments disclosed herein for Step 2, there is produced a composition comprising 113a, which composition contains no more than 0.5% totalof at least one of 113, 122, 123 and 1122, or no more than 0.2% total of at least one of 113, 122, 123 and 1122, 0.1% total of at least one of 113, 122, 123 and 1122, or 0.05% total of at least one of 113, 122, 123 and 1122, or 0.01% total of at least one of 113, 122, 123 and 1122. The composition comprising 113a may be produced by either the batch or the continuous process for Step 2, as disclosed herein. In the batch process for Step 2, Stream P22A comprises 113. This Stream P22A may then comprise no more than 0.5% total of at least one of 113, 122, 123 and 1122, or no more than 0.2% total of at least one of 113, 122, 123 and 1122, 0.1% total of at least one of 113, 122, 123 and 1122, or 0.05% total of at least one of 113, 122, 123 and 1122, or 0.01% total of at least one of 113, 122, 123 and 1122. In the continuous process for Step 2, Stream P22B comprises 113. This Stream P22B may then comprise no more than 0.5% total of at least one of 113, 122, 123 and 1122, or no more than 0.2% total of at least one of 113, 122, 123 and 1122, 0.1% total of at least one of 113, 122, 123 and 1122, or 0.05% total of at least one of 113, 122, 123 and 1122, or 0.01% total of at least one of 113, 122, 123 and 1122.

[0164] In certain embodiments, the product produced in Step 2 is a composition comprising 113a and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises no more than 0.5 % total of one or more of 122b, 132a, 132b, 142, 142b, 1112, 1112a, and PCE.Step 3 (1316mxx Process)

[0165] In Step 3 of the present invention, there is provided a continuous dimerization process for the conversion of 1,1 ,1-trichloro-2,2,2-trifluoroethane (CFC- 113a or 113a) to 2,3-dichloro-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene (CFO-1316mxx or 1316mxx). This continuous process comprises contacting a 113a feed composition with a catalyst in a reactor wherein the 113a feed composition comprises 113a. Preferably, the 113a feed composition contains no more than 0.5% total of at least one of 113, 122, 123 and 1122, or no more than 0.2% total of at least one of 113, 122, 123 and 1122, 0.1% total of at least one of 113, 122, 123 and 1122, or 0.05% total of at least one of 113, 122, 123 and 1122, or 0.01% total of at least one of 113, 122, 123 and 1122. The feed composition comprising 113a may be produced by either the batch or the continuous process for Step 2, as disclosed herein.

[0166] In one embodiment of Step 3 of the present invention, the dimerization process comprises feeding a 113a feed composition to a reactor, operating the reactor at temperature and pressure to convert the 113a present in the feed composition to 1316mxx, thus producing a product mixture comprising 113a and 1316mxx, separating unreacted 113a from the product mixture to produce a stream comprising 113a and a stream comprising 1316mxx, removing 113a from the stream comprising 113a and recovering 113a from the stream comprising 113a, and recycling the recovered 113a to the reactor. The process further comprises separating and removing impurities from the stream comprising 1316mxx.

[0167] Figure 5 illustrates a reaction system for an embodiment for a process for producing 2,3-dichloro-1 ,1,1,4,4,4-hexafluorobut-2-ene (1316mxx) from 1,1 ,1- trichloro-2,2,2-trifluoroethane (113a) in Step 3 of this invention. This embodiment relates to a manner in which dimerization is carried out to produce 1316mxx in a reaction step, then separations are carried out to remove unreacted materials and impurities.

[0168] The following nomenclature denotes the following elements in Figure 5: A30 - absorber; D30, D31, D32 and D33 - distillation columns; M30 - moisture removal; R30 - reactor; F30 - feed of 113A from outside the process; F31 - feed of hydrogen from outside the process; F32 - feed of water from outside the process; S30 - reaction mixture; S31 - lower boiling fraction from distillation column D30; S32 - vapor fraction from absorber A30; S33 - dry vapor return to reactor R30; S34 - higher boiling fraction from distillation column D30; S35 - lower boiling fraction from distillation column D31; S36 - higher boiling fraction from distillation column D32; S37 - higher boiling fraction from distillation column D31; S38 - higher boiling fraction from distillation column D33; S39 - liquid return to reactor R30; P30 - liquid fraction from absorber A30 removed through an outlet from the process; P31 - lower boiling fraction from distillation column D32 removed through an outlet from the process; P32 - lower boiling fraction from distillation column D33 removed through an outlet from the process; and P33 - fraction of the higher boiling fraction from distillation column D33 removed through an outlet from the process.

[0169] Referring to Figure 5, there is provided reactor R30, which is a continuous vapor phase reactor containing solid catalyst. There are five inlets to reactor R30. These inlets provide for introduction of fresh and recycled materials to reactor R30.

[0170] Stream F30 is provided through an inlet to reactor R30. Stream F30 comprises fresh 113a, such as produced according to the processes illustrated in Figures 3 and 4, from streams P22A and P22B, respectively.

[0171] Stream F31 is provided through an inlet to reactor R30. Stream F31 comprises fresh hydrogen provided from a source external to the reactor.

[0172] Stream S33 is provided through an inlet to reactor R30. Stream S33 is a dried vapor fraction produced downstream from reactor R30 in absorber A30.Stream S33 comprises hydrogen and lower boiling organic byproducts that are recycled and returned to reactor R30. Stream S33 comprises one or more organic byproducts including 1,1,1-trifluoroethane (143a) and 1 , 1 -dichloro-2,2,2- trifluoroethane (123).

[0173] Stream S36 is provided through an inlet to reactor R30. Stream S36 is a higher boiler fraction produced downstream from reactor R30 in distillation column D32. Stream S36 comprises 113a, 113 and organic byproducts from the dimerization reaction that are recycled and returned to reactor R30.

[0174] Stream S39 is provided through an inlet to reactor R30. Stream S39 is a portion of a higher boiler fraction produced downstream from reactor R30 in distillation column D33. Stream S39 comprises 1316mxx, 2,2,3,3-tetrachloro- 1 ,1 ,1,4,4,4-hexafluoroethane (316maa) and other organic byproducts from the dimerization reaction that are recycled and returned to reactor R30.

[0175] The reaction mixture produced in reactor R30 is removed through an outlet from reactor R30 as a vapor through stream S30.

[0176] The reaction pressure in reactor R30 is not specifically limited and will proceed at reduced, preferred and increased pressure. The preferred operating pressure of reactor R30 is 0.5 to 2 MPaG. It is also possible to apply pressure above or below the preferred range. Reaction at increased pressure is advantageous since increased pressure reduces the size of equipment.

[0177] The reaction temperature in reactor R30 is not specifically limited and will proceed at reduced, preferred and increased temperature. The preferred operating temperature of the reactor is 75°C to 200°C. It is also possible to use temperatures above or below the preferred range.

[0178] The residence time in reactor R30 is defined as the empty volume of the reactor (cubic meters) divided by the total volumetric flow supplied to reactor R30 (m3 / h). The residence time is not specifically limited and will proceed at reduced, preferred and increased residence times. The preferred residence time in reactor R30 is 0.2 to 4 minutes. It is also possible to use residence times above or below the preferred range.

[0179] The reaction mixture produced in reactor R30 exits an outlet of reactor R30 as stream S30. Stream S30 is fed through an inlet to distillation column D30. Stream S30 comprises hydrogen, HCI, 113a, 123, 143a, 316maa, 1316mxx and other organic byproducts from the dimerization reaction.

[0180] Distillation column D30 separates the components of the reaction mixture produced in reactor R30 into lower boiling and higher boiling fractions.

[0181] The higher boiling fraction produced in distillation column D30 is removed through an outlet from distillation column D30 in stream S34. Stream S34 contains primarily 113A, 123, 316maa, 1316mxx and other organic byproducts from the dimerization reaction.

[0182] The lower boiling fraction produced in distillation column D30 is removed through an outlet from distillation column D30 in stream S31. Stream S31 contains hydrogen, HCI, 113A, 123, 143A and other organic byproducts from the dimerization reaction. The majority of the hydrogen, HCI and 143a supplied to distillation column D30 is removed through an outlet from distillation column D30 in the lower boiling fraction stream S31.

[0183] The preferred operating pressure of distillation column D30 is slightly lower than the preferred operating pressure of reactor R30 to allow for flow from reactor R30 to distillation column D30. It is also possible to use pressures in distillation column D30 above or below the preferred range.

[0184] The lower boiling fraction removed through an outlet from distillation column D30 is fed through an inlet to absorber A30 in stream S31 . Water is fed through an inlet to absorber A30 in stream F32. HCI contained in stream S31 is absorbed into the water in absorber A30.

[0185] A vapor fraction is removed from absorber A30 through an outlet in stream S32. Stream S32 contains hydrogen, 113a, 123, 143a, other organic byproducts from the dimerization reaction. Stream S32 also contains water introduced to absorber A30 in stream F32. A liquid fraction is removed through an outlet from absorber A30 in stream P30. Stream P30 contains HCI and water with trace dissolved organic components produced in the dimerization reaction.

[0186] The preferred concentration of HCI in water is 10 to 37% by weight. It is also possible to use HCI concentrations below the preferred range. After it is removed through an outlet from absorber A30, stream P30 is removed through an outlet from the process.

[0187] The vapor fraction that is removed through an outlet from absorber A30 in stream S32 contains water that should be removed from stream S32 before returning contents of stream S32 to reactor R30. Stream S32 is supplied to moisture removal device M30 to produce dried stream S33. Moisture removal device M30 is typically a fixed bed of desiccant, but other methods could be employed to remove the moisture from stream S32. Dried stream S33 is removed through an outlet from M30. Stream S33 comprises hydrogen and 113a. Stream S33 is returned (recycled) to reactor R30 for further participation in the reaction to produce 1316mxx.

[0188] The higher boiling fraction removed through an outlet from distillation column D30 in stream S34 is supplied to distillation column D31. Distillation column D31 separates the components of stream S34 into lower boiling and higher boiling fractions.

[0189] The higher boiling fraction from distillation column D31 is removed through an outlet from distillation column D31 in stream S37. Stream S37 contains 316maa, 1316mxx and other organic byproducts from the dimerization reaction.

[0190] The lower boiling fraction from distillation column D31 is removed through an outlet from distillation column D31 in stream S35. Stream S35 contains 113a, 113, 123 and other organic byproducts from the dimerization. Stream S35 is the lower boiling fraction and comprises 113a, 113 and 123 from stream S34 that is fed to distillation column D31.

[0191] Stream S37 is the higher boiling fraction and comprises 316maa and 1316mxx from stream S34 that is fed to distillation column D31.

[0192] The preferred operating pressure of distillation column D31 is 0.1 to 0.4 MPaG. The pressure of distillation column D31 is not specifically limited and the separations will occur at reduced, preferred and increased pressure. It is also possible to use pressures in distillation column D31 above or below the preferred range.

[0193] The lower boiling fraction removed through an outlet from distillation column D31 in stream S35 is fed to through an inlet to distillation column D32. Distillation column D32 separates the components into lower boiling and higher boiling fractions. The higher boiling fraction is removed through an outlet from distillation column D32 in stream S36. Stream S36 comprises 113a. Stream S36 comprises small amounts of 113, 123 and other organic byproducts from the dimerization reaction. The higher boiling fraction is returned to reactor R30 in stream S36 for further participation in the reaction to produce 1316mxx. The lower boiling fraction is removed through an outlet from distillation column D32 in stream P31. Stream P31 contains 123. Stream P31 contains smaller amounts of 113, 113a and other organic byproducts from the dimerization reaction.

[0194] Stream S35 provides 113a and 113 fed to distillation column D32. Stream S36 is removed from distillation column D32 through an outlet from distillation column D32 as a higher boiling fraction.

[0195] The preferred operating pressure of distillation column D32 is slightly lower than the preferred operating pressure of distillation column D31 to allow for flow from distillation column D31 to distillation column D32. The pressure of distillation column D32 is not specifically limited and the separations will occur at reduced, preferred and increased pressure. It is also possible to use pressures in distillation column D32 above or below the preferred range.

[0196] Stream S37, the higher boiling fraction in distillation column D31 is removed through an outlet from distillation column D31 and is fed through an inlet to distillation column D33. Distillation column D33 separates the components of stream S37 into lower boiling and higher boiling fractions. The higher boiling fraction is removed through an outlet from distillation column D33 in stream S38. Stream S38 contains 316maa, 1316mxx and other organic byproducts from the dimerization reaction. The lower boiling fraction is the desired product from this process step. This lower boiling fraction is provides as stream P32 and comprises 1316mxx. Stream P32 is removed through an outlet from distillation column D33 and the process.

[0197] The higher boiling fraction stream from S38 can be returned to reactor R30 in stream S39 for further participation in the reaction to produce 1316mxx. Some or all of stream S38 can also be removed through an outlet from the process in stream P33.

[0198] The preferred operating pressure of distillation column D33 is slightly lower than the preferred operating pressure of distillation column D31 to allow for flow from distillation column D31 to distillation column D33. The pressure of distillation column D33 is not specifically limited and the separations will occur at reduced, preferred and increased pressure. It is also possible to use pressures in distillation column D33 above or below the preferred range.

[0199] A composition comprising 1316mxx produced according to Step 3 is provided in Stream P32. In certain embodiments disclosed herein for Step 3, there is produced a composition comprising 1316mxx, which composition contains no more than 0.5% total of at least one of 113, 122, 123 and 1122, or no more than 0.2% total of at least one of 113, 122, 123 and 1122, 0.1% total of at least one of 113, 122, 123 and 1122, or 0.05% total of at least one of 113, 122, 123 and 1122, or 0.01% total of at least one of 113, 122, 123 and 1122.

[0200] The composition provided in Stream P32, which is a composition comprising 1316mxx produced according to Step 3 of the process disclosed herein may comprise Z-1316mxx or E-1316mxx or a mixture of Z-1316mxx and E-1316mxx. When the composition provided in Step 3 comprises a mixture of Z-1316mxx and E- 1316mxx, the ratio of Z-1316mxx to E-1316mxx (Z / E) is in the range of 1 to 99 or 5to 95 or 10 to 90 or 15 to 85 or 20 to 80 or 25 to 75 or 30 to 70 or 35 to 65 or 40 to 60 or 45 to 55 or 50 to 50 or 55 to 45 or 60 to 40 or 65 to 35 or 70 to 30 or 75 to 25 or 80 to 20 or 85 to 15 or 90 to 10 or 95 to 5 or 99 to 1. The ratio of Z-1316mxx to E- 1316mxx (Z / E) is preferably in the range 10 to 90 or 15 to 85 or 20 to 80 or 25 to 75 or 30 to 70 or 35 to 65 or 40 to 60 or 45 to 55 or 50 to 50 or 55 to 45 or 60 to 40 or 65 to 35 or 70 to 30 or 75 to 25 or 80 to 20 or 85 to 15 or 90 to 10. More preferably, the ratio of Z-1316mxx to E-1316mxx (Z / E) is in the range of 65 or 40 to 60 or 45 to 55 or 50 to 50 or 55 to 45 or 60 to 40 or 65 to 35.Step 4 (1326mxz Process)

[0201] In Step 4 of the present invention, there is provided a continuous process for the hydrodechlorination of 2,3-dichloro-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene (CFO- 1316mxx or 1316mxx) to produce 2-chloro-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene (HCFO- 1326mxz or 1326mxz). This continuous process comprises contacting a 1316mxx feed composition with a catalyst in a reactor wherein the 1316mxx feed composition comprises 1316mxx. Preferably, the 1316mxx feed composition contains no more than 0.5% total of at least one of 113, 122, 123 and 1122, or no more than 0.2% total of at least one of 113, 122, 123 and 1122, 0.1% total of at least one of 113, 122, 123 and 1122, or 0.05% total of at least one of 113, 122, 123 and 1122, or 0.01% total of at least one of 113, 122, 123 and 1122. The feed composition comprising 1316mxx may be produced by either the batch or the continuous process for Step 3, as disclosed herein.

[0202] In one embodiment of Step 4 of the present invention, there is provided a continuous process for the hydrodechlorination of 1316mxx to produce 1326mxz. This process comprises feeding a 1316mxx feed composition and hydrogen to a reactor, operating the reactor at temperature and pressure to convert the 1316mxx to 1326mxz, thus producing a product mixture comprising 1316mxx and 1326mxz, separating unreacted 1316mxx from the product mixture to produce a stream comprising 1316mxx and a stream comprising 1326mxz, removing and recovering 1316mxx from a stream comprising 1316mxx, and recycling the recovered 1316mxx to the reactor. The process further comprises separating and removing impurities from the stream comprising 1326mxz.

[0203] Figure 6 illustrates a reaction system for an embodiment for a process for producing 2-chloro-1,1,1 ,4,4,4-hexafluorobut-2-ene (1326mxz) from 2,3-dichloro- 1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene (1316mxx). The embodiment relates to a manner in which hydrodechlorination is carried out to produce 1316mxx in a reaction step, then separations are carried out to remove unreacted materials and impurities.

[0204] The following nomenclature denotes the following elements in Figure 6: A40 - absorber; D40, D41 and D42 - distillation columns; M40 - moisture removal; R40 - reactor; F40 - feed of 1316mxx from outside the process; F41 - feed of hydrogen from outside the process; F42 - feed of water from outside the process; S40 - reaction mixture; S41 - lower boiling fraction from distillation column D40; S42 - vapor fraction from absorber A40; S43 - dry vapor return to reactor R40; S44 - higher boiling fraction from distillation column D40; S45 - higher boiling fraction from distillation column D41; S46 - higher boiling fraction from distillation column D42; S47 - higher boiling fraction from distillation column D42 returned to reactor R40; P40 - liquid fraction from absorber A40 removed through an outlet from the process; P41 - lower boiling fraction from distillation column D41 removed through an outlet from the process; P42 - lower boiling fraction from distillation column D42 removed through an outlet from the process; and P43 -fraction of the higher boiling fraction from distillation column D42 removed through an outlet from the process..

[0205] Referring to Figure 6, Reactor R40 is a continuous vapor phase reactor containing solid catalyst. There are four inlets to reactor R40. These inlets provide for introduction of fresh and recycled materials to reactor R40

[0206] Stream F40 comprises 1316mxx and is fed from the outside of the reaction system to reactor R40, in stream F40;

[0207] Stream F40 is provided through an inlet to reactor R40. Stream F40 may comprise fresh 1316mxx, such as produced according to the process illustrated in Figure 5, from stream P32.

[0208] Stream F41 is provided through an inlet to reactor R40. Stream F41 comprises fresh hydrogen provided from a source external to the reactor.

[0209] Stream S43 is provided through an inlet to reactor R40. Stream S43 is a dried vapor fraction produced downstream from reactor R40 in absorber A40.Stream S43 comprises hydrogen, 1326mxz and lower boiling organic byproducts from the hydrodechlorination reaction that are recycled and returned to reactor R40.

[0210] Stream S47 is provided through an inlet to reactor R40. Stream S47 is a higher boiler fraction produced downstream from reactor R40 in distillation column D42. Stream S47 comprises 1316mxx and other organic byproducts from the hydrodechlorination reaction that are recycled and returned to reactor R40.

[0211] The reaction mixture is removed through an outlet from reactor R40 as a vapor through stream S40.

[0212] The reaction pressure in reactor R40 is not specifically limited and will proceed at reduced, preferred and increased pressure. The preferred operating pressure of the reactor is 0.5 to 2 MPaG. It is also possible to apply pressure above or below the preferred range. Reaction at increased pressure is advantageous since increased pressure reduces the size of equipment.

[0213] The reaction temperature in reactor R40 is not specifically limited and will proceed at reduced, preferred and increased temperature. The preferred operating temperature of the reactor is 130°C to 250°C. It is also possible to use temperatures above or below the preferred range.

[0214] The residence time in reactor R40 is defined as the empty volume of the reactor (cubic meters) divided by the total volumetric flow supplied to the reactor (m3 / h). The residence time is not specifically limited and will proceed at reduced, preferred and increased residence times. The preferred residence time in reactor R140 is 0.3 to 3 minutes. It is also possible to use residence times above or below the preferred range.

[0215] The reaction mixture produced in reactor R40 is removed through an outlet from reactor R40 as a vapor in stream S40. Stream S40 is fed through an inlet to distillation column D40. Stream S40 contains hydrogen, HCI, 1316mxx, 1326mxz and other organic byproducts from the hydrodechlorination reaction.

[0216] Distillation column D40 separates the components of the reaction mixture produced in reactor R40 into lower boiling and higher boiling fractions.

[0217] The higher boiling fraction produced from distillation column D40 is removed through an outlet from distillation column D40 in stream S44. Stream S44 contains 1316mxx, 1326mxz and organic byproducts from the hydrodechlorination reaction.

[0218] The lower boiling fraction produced from distillation column D40 is removed through an outlet from distillation column D40 in stream S41. Stream S41 contains hydrogen, HCI, 1326mxz and organic byproducts from the hydrodechlorination. The majority of the hydrogen and HCI supplied to distillation column D40 is removed through an outlet from the column in the lower boiling fraction stream S41.

[0219] The preferred operating pressure of distillation column D40 is slightly lower than the preferred operating pressure of reactor R40 to allow for flow from reactor R40 to distillation column D40. It is also possible to use pressures in distillation column D40 above or below the preferred range.

[0220] The lower boiling fraction removed through an outlet from distillation column D40 is supplied to absorber A40 in stream S41. Water is fed through an inlet to absorber A40 in stream F42. HCI contained in stream S41 is absorbed into the water in absorber A40.

[0221] A vapor fraction is removed through an outlet from absorber A40 in stream S42. Stream S42 contains hydrogen, 1326mxz, organic byproducts from the hydrodechlorination reaction and water.

[0222] A liquid fraction removed through an outlet from absorber A40 in stream P40. Stream P40 contains HCI and water. Stream P40 also contains trace dissolved organic compounds.

[0223] The preferred concentration of HCI in water is 10 to 37% by weight. It is also possible to use HCI concentrations below the preferred range. After it is removed through an outlet from absorber A40, stream P40 is removed through an outlet from the process.

[0224] The vapor fraction that is removed through an outlet from absorber A40 in stream S42 contains water that should be removed from stream S42 before returning contents of stream S42 to reactor R40. Stream S42 is supplied to moisture removaldevice M40 to produce dried stream S43. Moisture removal device M40 is typically a fixed bed of desiccant, but other methods could be employed to remove the moisture from stream S42. Dried stream S43 is removed through an outlet from M40. Stream S43 is returned (recycled) to reactor R40 for further participation in the reaction to produce 1326mxz.

[0225] The higher boiling fraction from distillation column D40 is removed through an outlet from distillation column D40 in stream S44. Stream S44 is fed through an inlet to distillation column D41. Distillation column D41 separates the components into lower boiling and higher boiling fractions.

[0226] The higher boiling fraction from distillation column D41 is removed through an outlet from distillation column D41 in stream S45. Stream S45 contains 1316mxx, 1326mxz and organic byproducts from the hydrodechlorination. Stream S45 is fed through an inlet to distillation column D42. Distillation column D41 provides for removing 1316mxx and 1326mxz in the higher boiling fraction stream S45.

[0227] The lower boiling fraction from distillation column D41 is removed through an outlet from distillation column D41 in stream P41. Stream P41 contains 1 ,1 ,1 ,4,4,4-hexafluoro-2-butene (1336mzz), 1 ,1 ,1 ,4,4,4-hexafluorobutane (356mff) and other lower boiling organic byproducts from the hydrodechlorination reaction. Stream P41 is removed through an outlet from distillation column D41 and from the process.

[0228] The preferred operating pressure of distillation column D41 is 0.1 to 0.4 MPaG. The pressure of distillation column D41 is not specifically limited and the separations will occur at reduced, preferred and increased pressure. It is also possible to use pressures in distillation column D41 above or below the preferred range.

[0229] The higher boiling fraction removed through an outlet from distillation column D41 in stream S45 is fed through an inlet to distillation column D42. Distillation column D42 separates the components from stream S45 into lower boiling and higher boiling fractions.

[0230] The higher boiling fraction of distillation column D42is removed through an outlet from distillation column D42 in stream S46. Stream S46 contains 1316mxxwith other organic byproducts from the hydrodechlorination reaction. Stream S46 may be returned to reactor R40 in stream S47 for further participation in the reaction to produce 1326mxz. Some or all of stream S38 can also be removed through an outlet from the process in stream P43.

[0231] The lower boiling fraction distillation column D42 is removed through an outlet from distillation column D42 in stream P42. The lower boiling fraction is the desired product from this process step, 1326mxz, and is removed through an outlet from the process in stream P42.

[0232] The preferred operating pressure of distillation column D42 is slightly lower than the preferred operating pressure of distillation column D41 to allow for flow from distillation column D41 to distillation column D42. The pressure of distillation column D42 is not specifically limited and the separations will occur at reduced, preferred and increased pressure. It is also possible to use pressures in distillation column D42 above or below the preferred range.

[0233] A composition comprising 1326mxz produced according to Step 4 is provided in Stream P42. In certain embodiments disclosed herein for Step 4, there is produced a composition comprising 1326mxz, which composition contains no more than 0.5% total of at least one of 113, 122, 123 and 1122, or no more than 0.2% total of at least one of 113, 122, 123 and 1122, 0.1% total of at least one of 113, 122, 123 and 1122, or 0.05% total of at least one of 113, 122, 123 and 1122, or 0.01% total of at least one of 113, 122, 123 and 1122. In certain embodiments, the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises one or more of 113a, 142b, 143a, 346mdf, 356mff, 1336mzzE, and 1345czf.

[0234] The composition provided in Stream P42, which is a composition comprising 1326mxz produced according to Step 4 of the process disclosed herein may comprise 1326mxzZ or 1326mxzE or a mixture of 1326mxzZ and 1326mxzE.

[0235] In certain embodiments, the product produced in Step 4 comprising 1326mxz comprises a mixture of 1326mxzZ and 1326mxzE. In such embodiments, the ratio of 1326mxzZ to 1326mxzE (Z / E) is in the range of 1 to 99 or 5 to 95 or 10 to 90 or 15 to 85 or 20 to 80 or 25 to 75 or 30 to 70 or 35 to 65 or 40 to 60 or 45 to 55 or 50 to 50 or 55 to 45 or 60 to 40 or 65 to 35 or 70 to 30 or 75 to 25 or 80 to 20 or85 to 15 or 90 to 10 or 95 to 5 or 99 to 1. The ratio of Z-1326mxz to E-1326mxz (Z / E) is preferably in the range 10 to 90 or 15 to 85 or 20 to 80 or 25 to 75 or 30 to 70 or 35 to 65 or 40 to 60 or 45 to 55 or 50 to 50 or 55 to 45 or 60 to 40 or 65 to 35 or 70 to 30 or 75 to 25 or 80 to 20 or 85 to 15 or 90 to 10. More preferably, the ratio of Z-1326mxz to E-1326mxz (Z / E) is in the range of 65 or 40 to 60 or 45 to 55 or 50 to 50 or 55 to 45 or 60 to 40 or 65 to 35.

[0236] In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122, wherein the ratio of Z-1326mxz to E-1326mxz (Z / E) is in the range of 10 to 90 or 15 to 85 or 20 to 80 or 25 to 75 or 30 to 70 or 35 to 65 or 40 to 60 or 45 to 55 or 50 to 50 or 55 to 45 or 60 to 40 or 65 to 35 or 70 to 30 or 75 to 25 or 80 to 20 or 85 to 15 or 90 to 10. In one embodiment the composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122, wherein the ratio of Z-1316mxx to E-1326mxz (Z / E) is in the range of 65 or 40 to 60 or 45 to 55 or 50 to 50 or 55 to 45 or 60 to 40 or 65 to 35.Step 5 (PFBY Process)

[0237] In Step 5 of the present invention, there is provided a continuous process for the dehydrodechlorination of 2-chloro-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene (HCFO- 1326mxz or 1326mxz) to produce 1 ,1 ,1 ,4,4,4-hexafluoro-2-butyne (perfluorobutyne or PFBY). In this process, a 1326mxz feed composition is contacted with a base in the presence of a phase transfer catalyst. The 1326mxz feed composition comprises 1326mxz. Preferably, the 1326mxz feed composition contains no more than 0.5% total of at least one of 113, 122, 123 and 1122, or no more than 0.2% total of at least one of 113, 122, 123 and 1122, 0.1% total of at least one of 113, 122, 123 and 1122, or 0.05% total of at least one of 113, 122, 123 and 1122, or 0.01% total of at least one of 113, 122, 123 and 1122. In certain embodiments, the 1326mxz feed composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises one or more of 113a, 142b, 143a, 346mdf, 356mff, 1336mzzE, and 1345czf. The feed composition comprising 1326mxz may be produced by process for Step 4, as disclosed herein.

[0238] In one embodiment of Step 5 of the present invention, there is provided a continuous process for the conversion of 1326mxz to PFBY. This comprises feeding a 1326mxz feed composition, phase transfer catalyst (PTC), and base to a reactor,operating the reactor at temperature and pressure to convert the 1326mxz to PFBY, thus producing a product mixture comprising 1326mxz and PFBY, and separating unreacted 1326mxz from the product mixture to produce a stream comprising 1326mxz and a stream comprising PFBY, removing and recovering 1326mxz from the stream comprising 1326mxz and recycling the recovered 1326mxz to the reactor. The process further comprises separating and removing impurities from the stream comprising PFBY.

[0239] Figure 7 illustrates a reaction system for an embodiment for a process for producing hexafluoro-2-butyne (PFBY) from 2-chloro-1 , 1 ,1 ,4,4,4-hexafluorobut-2- ene (1326mxz). The embodiment relates to a manner in which dehydrochlorination of 1326mxz is carried out to produce PFBY in a reaction step, then separations are carried out to remove unreacted materials and impurities.

[0240] The following nomenclature denotes the following elements: R50 - dehydrochlorination reactor; D50, D51 , D52 and D53 - distillation columns; X50 - decanter; F50 - feed of 1326mxz from outside the process; F51 - feed of potassium hydroxide or sodium hydroxide solution from outside the process; F52 - feed of phase transfer catalyst (PTC) from outside the process; S50 - vapor portion of the reaction mixture from reactor R50; S51 - lower boiling fraction from distillation column D50; S52 - higher boiling fraction from distillation column D50; S53 - higher boiling fraction from distillation column D51 ; S54 - higher boiling fraction from distillation column D52; S55 - liquid portion of the reaction mixture from reactor R50; S56 - higher density fraction from decanter X50; S57 - portion of stream S55 directly returned to reactor R50; S58 - portion of stream S55 supplied to distillation column D53; S59 - lower boiling fraction from distillation column D53; P50 - lower boiling fraction from distillation column D51 ; P51 - lower boiling fraction from distillation column D52; P52 - lower density fraction from decanter X50; and P53 - higher boiling fraction from distillation column D53.

[0241] Referring to Figure 7, reactor R50 is a continuous stirred tank reactor containing aqueous liquid and organic liquid phases. In reactor R50, 1326mxz is subjected to dehydrochlorination to form PFBY.

[0242] There are seven feeds to reactor R50.

[0243] Stream F50 is provided through an inlet to reactor R50. Stream F50 comprises: 1326mxz.

[0244] Stream F51 is provided through an inlet to reactor R50. Stream F51 comprises a base chosen from potassium hydroxide solution or sodium hydroxide solution.

[0245] Stream F52 is provided through an inlet to reactor R50. Stream F52 a phase transfer catalyst.

[0246] Stream S52 is a higher boiling fraction produced downstream from reactor R50 in distillation column D50. Stream S52 includes 1326mxz, water and other organic byproducts from the dehydrochlorination reaction recycled for further participation in the reaction to produce PFBY.

[0247] Stream S54 is a higher boiling fraction produced downstream from reactor R50 in distillation column D52. Stream S54 includes 1326mxz, water and other organic byproducts from the dehydrochlorination reaction recycled for further participation in the reaction to produce PFBY.

[0248] Stream S57 is the portion of the higher density organic fraction from decanter X50 directly recycled to reactor R50 for further participation in the reaction to produce PFBY. Stream S57 includes 1326mxz, PTC, water and other organic byproducts from the dehydrochlorination reaction.

[0249] Stream S59 is a lower boiling fraction produced downstream from reactor R50 from distillation column D53. Stream S59 includes 1326mxz and other organic byproducts from the dehydrochlorination reaction recycled for further participation in the reaction to produce PFBY.

[0250] The hydrodechlorination reaction produces a reaction mixture comprising a vapor portion and a liquid portion in reactor R50. The vapor portion of the reaction mixture exits reactor R50 through an outlet as stream S50. The liquid portion of the reaction mixture exits reactor R50 through an outlet as stream S55.

[0251] The reaction pressure in reactor R50 is not specifically limited and will proceed at reduced, preferred and increased pressure. The preferred operatingpressure of the reactor is -0.05 to 1.8 MPaG. It is also possible to apply pressure above or below the preferred range.

[0252] The preferred operating temperature of reactor R50 is 0°C to 150°C. It is also possible to use temperatures above or below the preferred range.

[0253] Reaction at increased pressure is advantageous since increased pressure reduces the size of equipment. Reaction at lower pressure and lower temperature is advantageous since reduced pressure improves reaction selectivity.

[0254] The residence time in reactor R50 is defined as the liquid volume in the reactor (m3) divided by the reactor liquid outlet volumetric flow (m3 / h). The preferred residence time in reactor R50 is 0.5 to 5 hours. It is also possible to use residence times above or below the preferred range. Residence time exerts an influence on selectivity to PFBY and can be appropriately adjusted as required to achieve the desired reaction results.

[0255] The reaction mixture in reactor R50 comprises a vapor portion, an aqueous liquid portion and an organic liquid portion.

[0256] The aqueous liquid and organic liquid portions exit reactor R50 through an outlet in stream S55. Stream S55 is supplied to decanter X50. Decanter X50 separates the aqueous liquid and organic liquid portions contained in stream S55 into (1) a lower density, aqueous fraction containing water and salts formed in the dehydrochlorination of 1326mxz and (2) a higher density, organic fraction containing 1326mxz, PTC and other organic byproducts from the dehydrochlorination reaction.

[0257] The lower density, aqueous fraction is removed through an outlet from decanter X50 in stream P52. Stream P52 comprises water and salts. Stream P52 is removed through an outlet of decanter X50 and from the process.

[0258] The higher density, organic fraction is removed through an outlet from decanter X50 in stream S56. Stream S56 comprises 1326mxz, PTC, water and other organic byproducts from the dehydrochlorination reaction.

[0259] The pressure of decanter X50 is not specifically limited and will proceed at reduced, preferred and increased pressure. Pressure is only required to prevent flashing liquid in decanter X50. The preferred operating pressure of decanter X50 is0.2 to 1.0 MPaG. It is also possible to apply pressure above or below the preferred range.

[0260] The temperature of decanter X50 is not specifically limited and will proceed at reduced, preferred and increased temperature. The preferred operating pressure of decanter X50 is 0°C to 50°C. It is also possible to apply pressure above or below the preferred range.

[0261] Stream S56, which is the higher density, organic fraction produced in decanter X50 can be split into two portions, producing streams S57 and S58. One portion of stream S56 may be directly returned (recycled) to reactor R50 in stream557 for further participation in the reaction to produce PFBY. A second (the remaining) portion of stream S56 may be fed to the inlet of distillation column D53 in stream S58. The range of the splits can be 0% up to 100%. If the split is 0%, none of stream S56 is returned to reactor R50. If the split is 100%, all of stream S56 is returned to reactor R50. The range of the split may be adjusted as needed to control the concentration of impurities and PTC in the reaction system.

[0262] Stream S58 is fed through an outlet of decanter X50 to an inlet of distillation column D53. Distillation column D53 separates the components of stream558 into lower boiling and higher boiling fractions.

[0263] The higher boiling fraction produced in distillation column D53 is removed through an outlet from distillation column D53 in stream P53. Stream P53 contains 1326mxz, PTC and other organic byproducts from the dehydrochlorination reaction. The majority of the PTC supplied to distillation column D53 is removed from stream S58 through an outlet from distillation column D53 in the higher boiling fraction stream P53. Stream P53 is removed through an outlet from the process.

[0264] The lower boiling fraction produced in distillation column D53 is removed through an outlet from distillation column D53 in stream S59. Stream S59 contains 1326mxz, water and other organic byproducts from the dehydrochlorination reaction. The majority of 1326mxz supplied to distillation column D53 from stream S58 is removed through an outlet from distillation column D53 in the lower boiling fraction stream S59. Stream S59 is returned to reactor R50 for further participation in the reaction to produce PFBY.

[0265] The preferred operating pressure of distillation column D53 is slightly lower than the preferred operating pressure of decanter X50 to allow for flow from decanter X50 to distillation column D53. It is also possible to use pressures in distillation column D53 above or below the preferred range.

[0266] The vapor portion of the reaction mixture in reactor R50 exits reactor R50 in stream S50. Stream S50 is fed through an inlet to distillation column D50. Stream S50 contains PFBY, 1326mxz, water and other organic byproducts from the dehydrochlorination reaction. Distillation column D50 separates the components from stream S50 into lower boiling and higher boiling fractions.

[0267] The higher boiling fraction produced in distillation column D50 is removed through an outlet from distillation column D50 in stream S52. Stream S52 contains 1326mxz, water and other organic byproducts from the dehydrochlorination reaction. Stream S52 is returned (recycled) to reactor R50 for further participation in the reaction to produce PFBY.

[0268] The lower boiling fraction produced in distillation column D50 is removed through an outlet from distillation column D50 in stream S51. Stream S51 contains PFBY, 1326mxz, water and other organic byproducts from the dehydrochlorination reaction. The majority of the PFBY supplied to distillation column D50 from stream S50 is removed through an outlet from the column in the lower boiling fraction stream S51 .

[0269] The preferred operating pressure of distillation column D50 is slightly lower than the preferred operating pressure of the reactor to allow for flow from reactor R50 to distillation column D50. It is also possible to use pressures in distillation column D50 above or below the preferred range.

[0270] The lower boiling fraction from distillation column D50 in stream S51 is supplied to distillation column D51. Distillation column D51 separates the components into lower boiling and higher boiling fractions.

[0271] The lower boiling fraction is the desired product from this process step, PFBY, and is removed through an outlet from distillation column D51 in stream P50. Thus stream P50 comprises PFBY. The majority of the PFBY supplied to distillation column D51 is removed through an outlet from the column in the lower boilingfraction stream P50. Stream P50 is removed through an outlet from the process.Steam P50 is available for use in Step 6 as described further below.

[0272] The higher boiling fraction produced in distillation column D51 is removed through an outlet from distillation column D51 in stream S53. Stream S53 contains 1326mxz, water and other organic byproducts from the dehydrochlorination reaction. Stream S53 is supplied to distillation column D52.

[0273] The pressure of distillation column D51 is not specifically limited and will proceed at reduced, preferred and increased pressure. The preferred operating pressure of distillation column D51 is 0.1 to 0.5 MPaG. It is also possible to use pressures in distillation column D51 above or below the preferred range.

[0274] The higher boiling fraction produced in distillation column D51 in stream S53 is supplied to distillation column D52. Distillation column D52 separates the components into lower boiling and higher boiling fractions.

[0275] The lower boiling fraction produced in distillation column D52 contains 1 ,1 ,1 ,4,4,4-hexafluoro-but-2-ene (1336mzz), 1326mxz, water and other lower boiling organic byproducts from the dehydrochlorination reaction. The lower boiling fraction exits through an outlet in distillation column D52 in stream P51. Stream P51 is removed through an outlet from the process.

[0276] The higher boiling fraction produced in distillation column D52 is removed through an outlet from distillation column D52 in stream S54. Stream S54 contains 1326mxz, water and other organic byproducts from the dehydrochlorination reaction. Stream S54 is returned to reactor R50 for further participation in the reaction to produce PFBY.

[0277] The preferred operating pressure of distillation column D52 is slightly lower than the preferred operating pressure of distillation column D51 to allow for flow from distillation column D51 to distillation column D52. It is also possible to use pressures in distillation column D50 above or below the preferred range.

[0278] A composition comprising PFBY produced according to Step 5 is provided in Stream P50. In certain embodiments disclosed herein for Step 5, there is produced a composition comprising PFBY, which composition contains no more than 0.5% total of at least one of 113, 122, 123 and 1122, or no more than 0.2% total of atleast one of 113, 122, 123 and 1122, 0.1% total of at least one of 113, 122, 123 and 1122, or 0.05% total of at least one of 113, 122, 123 and 1122, or 0.01% total of at least one of 113, 122, 123 and 1122. In certain embodiments, the composition comprising PFBY produced according to Step 5 further comprises one or more additional compounds chosen from HFC-23, HFC-41, HCFC-132b, HCFC-142b, HFC-143a, HFC-152a, trifluoropropyne, HFC-263fb, HFC-356mff, HCFO-1122, 1326mxzZ, 1326mxzE, 1327mz, 1336mzzE, and trifluoroacetone. The additional compound may be present in an amount of no more than 0.5% or no more than 0.1% or no more than 0.01%.Step 6 (1336mzzZ Process)

[0279] In Step 6 of the present invention, there is provided a process for the hydrogenation of 1 ,1,1,4,4,4-hexafluoro-2-butyne (perfluorobutyne or PFBY) to 1 ,1 ,1 ,4,4,4-hexafluoro-2-butene (HFO-Z-1336mzz or 1336mzzZ). The process comprises contacting a PFBY feed composition and hydrogen with a catalyst. In certain embodiments disclosed herein a PFBY feed composition comprises PFBY. Preferably, the PFBY feed composition contains no more than 0.5% total of at least one of 113, 122, 123 and 1122, or no more than 0.2% total of at least one of 113, 122, 123 and 1122, 0.1% total of at least one of 113, 122, 123 and 1122, or 0.05% total of at least one of 113, 122, 123 and 1122, or 0.01% total of at least one of 113, 122, 123 and 1122. In certain embodiments, the PFBY feed composition comprises PFBY and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises no more than 0.5% of one or more additional compounds chosen from HFC-23, HFC-41 , HCFC-132b, HCFC-142b, HFC-143a, HFC-152a, trifluoropropyne, HFC-263fb, HFC-356mff, HCFO-1122, HCFO-Z-1326mxz, HCFO- E-1326mxz, HFO-1327mz, HFO-E-1336mzz, and trifluoroacetone. The PFBY feed composition may be produced by process for Step 5, as disclosed herein.

[0280] In one embodiment of Step 6 of the present invention, there is provided a hydrogenation process for the conversion of PFBY to 1336mzzZ. This process comprises feeding a PFBY feed composition to a reactor, operating the reactor at temperature and pressure to convert the PFBY to 1336mzzZ, thus producing a product mixture comprising of PFBY and 1336mzzZ, and separating unreacted PFBY from the product mixture to produce a stream comprising PFBY and a streamcomprising 1336mzzZ, , removing and recovering PFBY from the stream comprising PFBY and recycling the recovered PFBY to the reactor. The process further comprises separating and removing impurities from the stream comprising 1336mzzZ.

[0281] Figure 8 illustrates a reaction system for an embodiment for a process for producing (Z)-1,1,1,4,4,4-hexafluorobut-2-ene ((Z)-1336mzz) from hexafluoro-2- butyne (PFBY). The embodiment relates to a manner in which hydrogenation of PFBY is carried out to produce (Z)-1336mzz in a reaction step, then separations are carried out to remove unreacted materials and impurities.

[0282] The following nomenclature denotes the following elements: R60 - hydrogenation reactor; D60, D61 and D62 - distillation columns; F60, F61 - feeds from outside the process; S60 - reaction mixture from reactor R60; S61 - lower boiling fraction from distillation column D60; S62 - higher boiling fraction from distillation column D60; S63 - higher boiling fraction from distillation column D61 ; P60 - lower boiling fraction from distillation column D61 removed through an outlet from process; P61 - lower boiling fraction from distillation column D62 removed through an outlet from process; P62 - higher boiling fraction from distillation column D61 removed through an outlet from process.

[0283] Referring to Figure 8, reactor R60 is a continuous vapor phase reactor containing solid catalyst. There are 3 inlets to reactor R60.

[0284] Stream F60 is provided through an inlet to reactor R60. Stream F60 comprises PFBY. Stream F60 is provided from outside of the reaction system such as from a process as illustrated in Figure 7.

[0285] Stream F61 is provided through an inlet to reactor R60. Stream F61 comprises hydrogen. Stream F61 is provided from outside of the reaction system from the outside is supplied to reactor R60 in stream F61.

[0286] Stream S61 is provided through an inlet to reactor R60. Stream S61 is a low boiling fraction produced downstream from reactor R60 in distillation column D60. Stream S61 includes PFBY, other lower boiling organic byproducts from the hydrogenation reaction and a heat diluent, if used, recycled for further participation in the reaction to produce 1336mzzZ.

[0287] The reactor configuration of reactor R60 may be a single reactor or multiple reactors in series. The reaction mixture (product mixture) exits reactor R60 through an outlet as a vapor in stream S60.

[0288] The reaction pressure in reactor R60 is not specifically limited and will proceed at reduced, preferred and increased pressure. The preferred operating pressure of the reactor is 0 to 2 MPaG. It is also possible to apply pressure above or below the preferred range. Reaction at increased pressure is advantageous since increased pressure reduces the size of equipment.

[0289] The reaction temperature in reactor R60 is not specifically limited and will proceed at reduced, preferred and increased temperature. The preferred operating temperature of the reactor 30°C to 200°C. It is also possible to use temperatures above or below the preferred range. The formation of byproducts can be lowered by the reaction temperature not being unnecessarily high. This is an exothermic reaction and temperatures higher than the above range may occur locally within the reactor or catalyst. A heat diluent may be used to reduce the temperature rise created by the exothermic reaction. The heat diluent can be any inert material compatible with the process.

[0290] The residence time in reactor R60 is defined as the empty volume of the reactor (cubic meters) divided by the total volumetric flow supplied to the reactor (m3 / h). The residence time is not specifically limited and will proceed at reduced, preferred and increased residence times. The preferred residence time in reactor R60 is 5 to 120 seconds. It is also possible to use residence times above or below the preferred range.

[0291] The reaction mixture produced in reactor R60 is a vapor. The reaction mixture exits reactor R60 through an outlet in stream S60. Stream S60, the reaction mixture comprises 1336mzzZ, PFBY and hydrogen.

[0292] Stream S60 is fed through an inlet to distillation column D60.

[0293] Distillation column D60 separates the components stream S60 into lower boiling and higher boiling fractions.

[0294] The lower boiling fraction produced in distillation column D60 is removed through an outlet from distillation column D60 in stream S61. Stream S61 containsPFBY, other lower boiling organic byproducts from the hydrogenation reaction and a heat diluent, if used. The majority of the PFBY supplied to distillation column D60 leaves the column in the lower boiling fraction stream S61. Stream S61 is returned to reactor R60 for continued participation in the reaction to produce PFBY.

[0295] The higher boiling fraction produced in distillation column D60 is removed through an outlet from distillation column D60 in stream S62. Stream S62 contains 1336mzzZ and other higher boiling organic byproducts from the hydrogenation reaction. The majority of 1336mzzZ supplied to distillation column D60 from stream S60 is removed through an outlet from the column in the higher boiling fraction stream S62.

[0296] The preferred operating pressure of distillation column D60 is slightly higher than the preferred operating pressure of reactor R60 to allow for flow from distillation column D60 to reactor R60. It is also possible to use pressures in distillation column D60 above or below the preferred range.

[0297] The high boiling fraction produced in distillation column D60 in stream S62 is fed through an inlet to distillation column D61. Distillation column D61 separates the components of stream S62 into lower boiling and higher boiling fractions.

[0298] The lower boiling fraction produced in distillation column D61 is removed through an outlet from distillation column D61 in stream P60. Stream P60 contains 1336mzzZ, 1,1,1 ,4,4,4-hexafluorobutane (356mff) and other lower boiling organic byproducts from the hydrogenation reaction.

[0299] The higher boiling fraction produced in distillation column D61 is removed through an outlet from distillation column D61 in stream S63. Stream S63 contains (Z)-1336mzz and other higher boiling organic byproducts from the hydrogenation reaction. The majority of the 1336mzzZ supplied to distillation column D61 is removed through an outlet from the column in the higher boiling fraction stream P63.

[0300] The preferred operating pressure of distillation column D61 is slightly lower than the preferred operating pressure of distillation column D60 to allow for flow from distillation column D60 to distillation column D61. It is also possible to use pressures in distillation column D61 above or below the preferred range.

[0301] The high boiling fraction produced in distillation column D61 in stream S63 is fed from an outlet of distillation column D61 to an inlet of distillation column D62. Distillation column D62 separates the components of stream S63 into lower boiling and higher boiling fractions.

[0302] The lower boiling fraction produced in distillation column D62 is the desired product from this process step, 1336mzzZ, and is removed through an outlet from the process in stream P61. The majority of the 1336mzzZ supplied to distillation column D62 is removed through an outlet from the column in the lower boiling fraction stream P61.

[0303] The higher boiling fraction produced in distillation column D62 is removed through an outlet from distillation column D62 in stream P62. Stream P62 contains 1336mzzZ and higher boiling organic byproducts from the hydrogenation reaction.

[0304] The preferred operating pressure of distillation column D62 is slightly lower than the preferred operating pressure of distillation column D61 to allow for flow from distillation column D61 to distillation column D60. It is also possible to use pressures in distillation column D62 above or below the preferred range.

[0305] Without further elaboration, it is believed that one skilled in the art can, using the description and figures herein, utilize the present invention to its fullest extent. After reading this specification, skilled artisans appreciate that other aspects and embodiments are possible without departing from the scope of the invention.

Claims

CLAIMSWhat is claimed is:

1. A process to produce 1 ,1 ,2-trichloro-1,2,2-trifluoroethane (CFC-113 or 113) from a PCE feed composition comprising contacting the PCE feed composition with HF and a catalyst in a liquid phase or a vapor phase process.

2. The process of claim 1 wherein the PCE feed composition comprises PCE and one or more additional compounds selected from CCI4, CHCI3, trichloroethylene, 1,1 ,3-trichloropropene, ethylene, and 1, 1,1,3- tetrachloropropane (HCC-250fb).

3. The process of claim 1 wherein the PCE feed composition comprises >99% by weight PCE based on the total amount of the composition, and one or more additional compounds selected from chloroform, carbon tetrachloride, bromotrichloromethane, bromotrichloroethylene, 1 ,2-dichloroethane, ethylene, trichloroethylene (TCE), 1 , 1 ,3-trichloro-1 -propene, and 1, 1,1,3- tetrachloropropane.

4. The process of claim 1 wherein the PCE feed composition comprises >99% by weight PCE, based on the total amount of the composition, and at least two additional compounds selected from 1,1,1 -trichloroethane, carbon tetrachloride, dichloromethane, and trichloroethylene (TCE).

5. The process of any of claims 1-4, wherein the process is performed in the liquid phase.

6. The process of claim 5 wherein HF, chlorine, and the PCE feed composition are fed through an inlet to a reactor containing a liquid phase fluorination catalyst, wherein the PCE feed composition fed through an inlet to the reactor is material recovered from a downstream distillation column; wherein a portion of the HF is fresh and a portion of the HF is recycled from a downstream decanter; a portion of the chlorine is fresh and a portion of the chlorine is recycled from a downstream absorber, and wherein the recycled chlorine stream is premixed with a composition comprising PCE before feeding to the first reactor as a component of the PCE feed composition.

7. The process of any of claims 1-4, wherein the process is performed in the vapor phase.

8. The process of claim 7 wherein fresh feeds of HF, chlorine and the PCE feed composition are fed through an inlet to a reactor containing a vapor phase fluorination catalyst and the PCE feed composition fed through an inlet to the reactor is material recovered from a downstream distillation column; wherein a portion of the HF is fresh and a portion of the HF is recycled from a downstream decanter; a portion of the chlorine is fresh and a portion of the chlorine is recycled from a downstream absorber, and wherein the recycled chlorine stream is premixed with a composition comprising PCE before feeding to the first reactor as a component of the PCE feed composition.

9. A process to produce 1 ,1 ,1-trichloro-2,2,2-trifluoroethane (CFC-113a or 113a) from a 113 feed composition comprising contacting the 113 feed composition with a catalyst in a batch or a continuous process.

10. The process of claim 9 wherein the 113 feed composition comprises CFC-113 and less than about 1% by weight of two or more additional compounds selected from CFC-113a, CFC-114a, HCFC-123, HCFC-123a, CFC-115, CFC- 12, HCFC-124, CFC-114, CFC-1317, CFC-216, CFC-318, CFC-316, CFC- 215cb, CFC-214cb. HCFC-122, CFC-112, CFC-112a. CFC-1112a, and PCE, wherein the total amount of said additional compounds is less than 1 weight % of the total composition.

11. The process of claim 9 wherein the process is a batch process.

12. The process of claim 11 wherein the process comprises feeding a liquid phase isomerization catalyst and a 113 feed composition to a reactor, operating the reactor at temperature and pressure to convert the 113 to 113a, thus producing a product mixture comprising catalyst, 113 and 113a; separating 113, 113a and catalyst from the product mixture, to produce a separated product comprising 113 and catalyst, and then removing and recovering 113 and catalyst from the separated product; recycling the recovered 113 and the recovered catalyst to the reactor of the batch process.

13. The process of claim 12 further comprising separating and removing impurities from the product mixture comprising catalyst, 113 and 113a.

14. The process of claim 9 wherein the process is a continuous process.

15. The process of claim 14 wherein the process comprises feeding a 113 feed composition to a vapor phase reactor containing a catalyst, operating the reactor at temperature and pressure to convert the 113 to 113a, thus producing a reaction mixture comprising 113 and 113a, separating 113 and 113a from the reaction mixture, producing a product comprising 113a, removing and recovering 113, and recycling the recovered 113 to the reactor.

16. The process of claim 15 further comprising separating and removing impurities from the reaction mixture comprising catalyst, 113 and 113a.

17. A process to produce 2,3-dichloro-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene (HCFO- 1316mxx or 1316mxx) from a 113a feed composition comprising contacting the 113a feed composition with a catalyst in a continuous process.

18. The process of claim 17 wherein the 113a feed composition contains no more than 0.5% total of at least one of 113, 122, 123 and 1122.

19. The process of claim 17 wherein the process comprises feeding a 113a feed composition to a reactor, operating the reactor at temperature and pressure to convert the 113a present in the feed composition to 1316mxx, thus producing a product mixture comprising 113a and 1316mxx, separating unreacted 113a from the product mixture to produce a stream comprising 113a and a stream comprising 1316mxx, removing 113a from the stream comprising 113a and recovering 113a from the stream comprising 113a, and recycling the recovered 113a to the reactor.

20. The process of claim 19 further comprising separating and removing impurities from the stream comprising 1316mx.

21. A process to produce 2-chloro-1 , 1 ,1 , 4,4, 4-hexafluoro-2-butene (HCFO- 1326mxz or 1326mxz) from a 1316mxx feed composition comprising contacting the 1316mxx feed composition with a catalyst in a continuous process.

22. The process of claim 21 wherein the 1316mxx feed composition contains no more than 0.5% total of at least one of 113, 122, 123 and 1122.

23. The process of claim 21 wherein the process comprises feeding a 1316mxx feed composition and hydrogen to a reactor, operating the reactor at temperature and pressure to convert the 1316mxx to 1326mxz, thus producing a product mixture comprising 1316mxx and 1326mxz, separating unreacted 1316mxx from the product mixture to produce a stream comprising 1316mxx and a stream comprising 1326mxz, removing and recovering 1316mxx from a stream comprising 1316mxx, and recycling the recovered 1316mxx to the reactor.

24. The process of claim 23 further comprising separating and removing impurities from the stream comprising 1326mxz.

25. A process to produce 1 ,1 ,1 ,4,4,4-hexafluoro-2-butyne (PFBY) from a 1326mxz feed composition comprising contacting the 1326mxz feed composition with a base in the presence of a phase transfer catalyst.

26. The process of claim 25 wherein the 1326mxz feed composition contains no more than 0.5% total of at least one of 113, 122, 123 and 1122.

27. The process of claim 25 wherein the 1326mxz feed composition comprises 1326mxz and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises one or more of 113a, 142b, 143a, 346mdf, 356mff, E-1336mzz, and 1345czf.

28. The process of claim 25 wherein the process comprises feeding a 1326mxz feed composition, phase transfer catalyst (PTC), and base to a reactor, operating the reactor at temperature and pressure to convert the 1326mxz to PFBY, thus producing a product mixture comprising 1326mxz and PFBY, and separating unreacted 1326mxz from the product mixture to produce a stream comprising 1326mxz and a stream comprising PFBY, removing and recovering 1326mxz from the stream comprising 1326mxz and recycling the recovered1326mxz to the reactor.

29. The process of claim 28 further comprising separating and removing impurities from the stream comprising PFBY.

30. A process to produce Z-1 ,1,1 ,4,4,4-hexafluoro-2-butene from 1,1, 1 ,4, 4, 4- hexafluoro-2-butyne (PFBY) which comprises contacting a PFBY feed composition and hydrogen with a catalyst.

31. The process of claim 30 wherein the PFBY feed composition contains no more than 0.5% total of at least one of 113, 122, 123 and 1122.

32. The process of claim 30 wherein the PFBY feed composition comprises PFBY and no more than 0.5% total of at least one of 113, 122, 123 and 1122 and further comprises no more than 0.5% of one or more additional compounds chosen from HFC-23, HFC-41 , HCFC-132b, HCFC-142b, HFC-143a, HFC- 152a, trifluoropropyne, HFC-263fb, HFC-356mff, HCFO-1122, HCFO-Z- 1326mxz, HCFO-E-1326mxz, HFO-1327mz, HFO-E-1336mzz, and trifluoroacetone.

33. The process of claim 31 wherein the process comprises feeding a PFBY feed composition to a reactor, operating the reactor at temperature and pressure to convert the PFBY to 1336mzzZ, thus producing a product mixture comprising of PFBY and 1336mzzZ, and separating unreacted PFBY from the product mixture to produce a stream comprising PFBY and a stream comprising 1336mzzZ, , removing and recovering PFBY from the stream comprising PFBY and recycling the recovered PFBY to the reactor.

34. The process of claim 33 further comprising separating and removing impurities from the stream comprising 1336mzzZ.

36. A provided a process to produce Z-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene comprises (Step 1) producing 1,1,2-trichloro-1 ,2,2-trifluoroethane (CFC-113 or 113) from tetrachlorothylene, (PCE); (Step 2) producing 1 , 1 , 1 -trichloro-2,2,2- trifluoroethane (CFC-113a or 113a) from CFC-113; (Step 3) producing 2,3- dichloro-1,1 ,1 ,4,4,4-hexafluoro-2-butene (HCFO-1316mxx or 1316mxx) from 1 ,1 ,1-trichloro-2,2,2-trifluoroethane (CFC-113a or 113a); (Step 4) producing 2- chloro-1 ,1 ,1,4,4,4-hexafluoro-2-butene (HCFO-1326mxz or 1326mxz) from 2,3- dichloro-1,1 ,1 ,4,4,4-hexafluoro-2-butene (HCFO-1316mxx or 1316mxx); (Step 5) producing 1,1,1,4,4,4-hexafluoro-2-butyne (PFBY) from 2-chloro-1 , 1 , 1 ,4,4,4- hexafluoro-2-butene (HCFO-1326mxz or 1326mxz); and (Step 6) producing Z- 1 ,1 ,1 ,4,4,4-hexafluoro-2-butene from 1 ,1,1 ,4,4,4-hexafluoro-2-butyne (PFBY).

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