Process for producing hydro(chloro)fluorocarbon compounds

Abstract

A process is provided which includes contacting a haloalkane reactant with a fluorination agent in the liquid phase, in the presence of a catalyst, under conditions which are free of or substantially free of a superacid, to produce a product stream including a haloalkane product, preferably a hydro(chloro)fluorocarbon.

Description

TITLE OF THE INVENTIONPROCESS FOR PRODUCING HYDRO(CHLORO)FLUOROCARBON COMPOUNDSCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Patent Application No. 63 / 662,877, filed June 21, 2024, the disclosure of which is incorporated herein by reference in its entirety.FIELD OF THE INVENTION

[0002] The present invention is directed to processes for producing hydro(chloro)fluorocarbon compounds in the absence of a superacid.BACKGROUND OF THE INVENTION

[0003] The fluorocarbon industry has been working for the past few decades to find replacement refrigerants for the ozone depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) being phased out as a result of the Montreal Protocol. The solution for many applications has been the commercialization of hydrofluorocarbon (HFC) compounds for use as refrigerants, solvents, fire extinguishing agents, foam blowing agents and propellants. In addition to ozone depleting concerns, global warming is another environmental concern in many of these applications. Thus, there is a need for compositions that meet both low ozone depletion standards as well as having low global warming potentials.

[0004] Hydro(chloro)fluorocarbons, in particular, are useful in a variety of applications, such as, for example, heat transfer fluids and fire extinguishants. Hydro(chloro)fluorocarbons are also often useful materials for the production of fluoroalkanes, particularly fluoroolefins, particularly HCFOs and HFOs. For example, 1 ,1,1,3,3-pentafluoropropane (CF3CH2CHF2 or HFC-245fa), 3,3-dichloro-1 , 1 , 1- trifluoropropane (CF3CH2CHCI2 or HFC-243fa) and 3-chloro-1 , 1,1,3- tetrafluoropropane (CF3CH2CHFCI or HCFC-244fa), are all starting materials for the production of 1,3, 3, 3-tetrafluoro-1 -propene (CF3CH=CHF or HFO-1234ze).

[0005] Although the preparation of such hydro(chloro)fluorocarbon starting materials has been in commercial practice for several decades, the industry continues to seek improvement in these processes to achieve efficiency and waste reduction. For example, the conventional reactions to produce hydro(chloro)fluorocarbon materials are carried out under superacid conditions in liquid phase fluorination, particularly in the presence of a fluorination agent (e.g., hydrogen fluoride or HF) and superacid comprising MFs, where M is Sb, Ta, and Nb. However, such processes can be extremely corrosive to the reactor materials and hazardous to the environment, thus resulting in increased operation costs and amplified environmental release risks. It would be desirable to provide an improved process for producing such starting materials that minimizes the risks associated with such hazardous and corrosive conditions.SUMMARY OF THE INVENTION

[0006] In one aspect, the present invention relates to a process comprising contacting a haloalkane reactant with a fluorination agent in the liquid phase, in the presence of a catalyst, under conditions which are free of or substantially free of a superacid, to produce a product stream comprising a haloalkane product, preferably a hydro(chloro)fluorocarbon.

[0007] In one aspect, the present invention relates to a process comprising contacting HCC-240fa with a fluorination agent in the liquid phase, in the presence of a catalyst, under conditions which are free of or substantially free of a superacid, to produce a product stream comprising any of HCFC-243fa, HCFC-244a and / or HFC- 245fa.

[0008] In one aspect, the present invention relates to a process comprising contacting HCC-250fb with a fluorination agent in the liquid phase, in the presence of a catalyst, under conditions which are free of or substantially free of a superacid, to produce a product stream comprising HCFC-253fb.

[0009] In one aspect, the present invention relates to a process comprising contacting HCC-230fa with a fluorination agent in the liquid phase, in the presence of a catalyst, under conditions which are free of or substantially free of a superacid, to produce a product stream comprising HFC-236fa.

[0010] In one aspect, the present invention relates to a process comprising contacting HCFC-343jfd with a fluorination agent in the liquid phase, in the presence of a catalyst, under conditions which are free of or substantially free of a superacid, to produce a product stream comprising HCFC-346mdf.DETAILED DESCRIPTION OF THE INVENTION

[0011] The invention provides a process for preparing a haloalkane, and more particularly a hydro(chloro)fluorocarbon.

[0012] 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.

[0013] 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.

[0014] The transitional phrase "consisting essentially of" is used to define a composition, method or apparatus that includes materials, steps, features, components, or elements, in addition to those literally disclosed provided that these additional included materials, steps, features, components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention. The term 'consisting essentially of occupies a middle ground between “comprising” and 'consisting of'. Typically, components of the refrigerant mixtures and the refrigerant mixtures themselves can contain minor amounts (e.g., less than about 0.5 weight percent total) of impurities and / or byproducts (e.g., from the manufacture of the refrigerant components or reclamation of the refrigerant components from other systems) which do not materially affect the novel and basic characteristics of the refrigerant mixture.

[0015] 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 describe such an invention using the terms “consisting essentially of’ or “consisting of.”

[0016] 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.

[0017] Unless otherwise defined, as used herein, the term “about” is understood as within a range of normal tolerance in the art, for example within 2 standard deviations of the mean. “About” can be understood as within 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, 0.05%, or 0.01% of the stated value, preferably as within 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, 0.05%, or 0.01% of the stated value. Unless otherwise clear from the context, all numerical values provided herein are modified by the term “about.”

[0018] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the disclosed compositions, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety, unless a particular passage is cited. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

[0019] In one embodiment, the present invention relates to a process, and more particularly a hydrofluorination process, comprising contacting a haloalkane reactant with a fluorination agent, such as hydrogen fluoride (HF), in the presence of a catalyst and in the absence of or substantially in the absence of a superacid to produce a haloalkane product, and more particularly a hydro(chloro)fluorocarbon.

[0020] In some embodiments, the process further comprises separating the haloalkane product from the product stream as a useful starting material for the production of various types of fluorochemicals, such as HCFOs and HFOs, such as E / Z-HFO-1234ze.

[0021] In some embodiments, the process further comprises recovery and recycling of unreacted haloalkane reactant to the feed stream.

[0022] In one embodiment, the haloalkane reactant preferably comprises at least one hydrochloro(fluoro)carbon, and more particularly a hydrochlorocarbon or hydrochlorofluorocarbon. More particularly, in some embodiments, the haloalkane reactant is represented by the formula R1CH2R2, where R1and R2are the same or different and is each independently a halogenated or partially halogenated C1 to C4 compound, optionally branched, preferably where R2is one of (i) CHxC -x, where x is an integer from 0 to 2; (ii) CHxFyC -x-y, where x is 0 or 1 and y is 1 or 2; or (iii) CHxCI2-xCF3, where x is 0 or 1 .

[0023] In one embodiment, the hydrochloro(fluoro)carbon reactants are compounds having carbon, hydrogen, chlorine and optionally fluorine, including but not limited to 1 ,1 ,1 ,3,3-pentachloropropane (HCC-240fa, CCI3CH2CHCI2); 1 ,1 , 1 ,3- tetrachloropropane (HCC-250fb, CCI3CH2CH2CI); 1 ,1 ,1 ,3,3,3-hexachloropropane (HCC-230fa, CCI3CH2CCI3); 1 , 1 ,1 ,3-trichloro-4,4,4-trifluorobut-1-ene (HCFC-343jfd, CCI3CH2CHCICF3) and the like.

[0024] In some embodiments, the hydrochloro(fluoro)carbon reactants are prepared by an olefin insertion process comprising contacting a haloalkane reactant with an olefin in the presence of a catalyst system to produce a haloalkane insertion product which is utilized as the hydrochloro(fluoro)carbon reactant in the fluorination reactions of the present invention. In some embodiments, the olefin insertion process is preferably carried out at a reduced pressure, such as from about 15 psig to about 50 psig, which results in reduced formation of byproduct telomers, oligomers, dimers and / or other polymeric products. In some embodiments, the reaction mixture comprising the haloalkane insertion product comprises less than about 10 wt.% of byproduct telomers, oligomers, dimers and / or other polymeric products.

[0025] In one embodiment, hydro(chloro)fluorocarbons produced by the process of the present invention, and more particularly by fluorination of the haloalkane reactants, are compounds having carbon, hydrogen, fluorine and optionally chlorine. In some embodiments, the hydro(chloro)fluorocarbon product is represented by the formula CF3CH2R3, where R3is CHxClyFs-x-y, where x is an integer from 0 to 2, and y is an integer from 0 to 2.

[0026] In some embodiments, the hydro(chloro)fluorocarbon products which may be produced by the processes of the present invention include, but are not limited to, 1 ,1 ,1 ,3,3-pentafluoropropane (CFsCH2CHF2 or HFC-245fa); 3,3-dichloro-1 , 1 , 1- trifluoropropane (CF3CH2CHCI2 or HFC-243fa); 3-chloro-1 ,1 ,1 ,3-tetrafluoropropane (CF3CH2CHFCI or HCFC-244fa); 3-chloro-1 , 1 ,1 -trifluoropropane (CF3CH2CH2CI or HCFC-253fb); 1 ,1 ,1 ,3,3,3-hexafluoropropane (CF3CH2CF3 or HFC-236fa); and 2- chloro-1 ,1 ,1 ,4,4,4-hexafluorobutane (CF3CH2CHCICF3 or HCFC-346mdf).

[0027] The processes of the present invention are preferably carried out in the liquid phase.

[0028] The processes of the present invention are preferably carried out in the presence of a catalyst. In some embodiments, the fluorination catalyst for the processes of the present invention is a Lewis acid catalyst, such as a metal halide catalyst, including but not limited to antimony halides, tin halides, thallium halides, iron halides and combinations of two or more. In certain embodiments, metal chlorides and metal fluorides are employed, including but not limited to SbCIs, SbCh, SbFs, SnCk, TaCIs, TiCk, NbCIs, MoCle, NiFs, FeCh, and combinations of two or more of these.

[0029] In some embodiments, examples of liquid phase fluorination catalysts include but are not limited to antimony halide, tin halide, tantalum halide, titanium halide, niobium halide, molybdenum halide, iron halide, fluorinated chrome halide, fluorinated chrome oxide or combinations thereof. In some embodiments, examples of liquid phase fluorination catalysts include but are not limited to SbCIs, SbCIs, SbFs, SnCL, TaCIs, TiCU, NbCIs, MoCle, FeCh, fluorinated species of SbCIs, fluorinated species of SbCIs, fluorinated species of SnCl4, fluorinated species of TaCIs, fluorinated species of TiCU, fluorinated species of NbCIs, fluorinated species ofMoCle, fluorinated species of FeC , or combinations thereof. These catalysts can be readily regenerated by any means known in the art if they become deactivated.

[0030] In one embodiment, the liquid phase fluorination catalyst is selected from SbFs, SnCU, TaCIs, TiCU, NbCIs, and fluorinated species thereof. In another embodiment, the liquid phase fluorination catalyst is selected from SbFs, SnCU, TaCIs, TiCU and / or fluorinated species thereof. In another embodiment the liquid phase fluorination catalyst is SbFs or SbCIs.

[0031] In some embodiments, the fluorination catalyst is MFx, MClx or combinations thereof, where M is a metal and x is an integer from 1 to 5. In some embodiments, the fluorination catalyst is MFxCly, where M is a metal, x+y = 5, and neither x nor y can equal 0. In some embodiments, M comprises a metal selected from Sb, Ta, Nb, Sn, Ti and combinations thereof.

[0032] The fluorination reactions of the present invention are carried out in the absence of or substantially in the absence of a superacid. In some embodiments, The fluorination reactions of the present invention are carried out in the presence of a catalyst and in the absence of or substantially in the absence of a superacid. That is, the present invention relates to a process comprising contacting a haloalkane reactant with a fluorination agent (e.g., HF), in the presence of a catalyst, under conditions which are free of or substantially free of a superacid, in the liquid phase, to produce a hydro(chloro)fluorocarbon.

[0033] As used herein, a superacid is any acid system that is stronger than 100% sulfuric acid and that has an HO (Hammett acidity function) of < -12. See, e.g., Superacid Chemistry, Olah, George A. et al., Wiley (2009). More specifically, as used herein, a superacid or superacid system includes, but is not limited to, an acid of the formula HxFy+MFe, where M is one of Sb, Ta, and Nb, where x = 1, and where y = 0 or where x / y > 1.

[0034] In one embodiment, the fluorination reactions are carried out for a predetermined duration under conditions free of (i.e. , in the absence of) a superacid to form a reaction product comprising a hydro(chloro)fluorocarbon compound, and under conditions selected to avoid the formation of a superacid. For example, the concentrations of the fluorination catalyst (e.g., MFx or MClx, where M is a metal andx is an integer from 1 to 5, or MFxCly, where M is a metal, x+y = 5, and neither x nor y can equal 0), HF, and the haloalkane reactant are selected to avoid the formation of a superacid.

[0035] In one embodiment, the fluorination reactions are carried out for a predetermined duration under conditions substantially free of (i.e. , substantially in the absence of) a superacid to form a reaction product comprising a hydro(chloro)fluorocarbon compound, and under conditions selected to avoid or minimize the formation of a superacid. For example, the concentrations of the fluorination catalyst (e.g., MClx, MFxor MFxCly), HF, and the haloalkane reactant are selected to avoid the formation of a superacid.

[0036] As used herein in terms of the presence of a superacid, “substantially free of” or “substantially in the absence of” means that less than 5 mol% of a superacid is present or formed during the reaction, based on the total metal concentration of the catalyst.

[0037] According to this process, the conversion is between about 80% to about 100%. In some embodiments, about 95% or greater of the haloalkane reactant is converted to the haloalkane product. For example, about 95%, 96%, 97%, 98%, 99%, or 100% of the haloalkane reactant is converted to the haloalkane product.

[0038] According to this process, selectivity of the haloalkane (hydro(chloro)fluorocarbon) is between about 90% to about 95%.

[0039] In some embodiments, in the liquid phase reaction between the haloalkane reactant and HF in the presence of a catalyst and in the absence of or substantially in the absence of a superacid, the haloalkane product is produced in a yield of greater than about 90%, greater than about 91%, greater than about 92%, greater than about 93%, greater than about 94%, greater than about 95%, greater than about 96%, greater than about 97%, greater than about 98%, or greater than about 99%.

[0040] In one embodiment, a molar ratio of organic reactant to HF is from about 1 :1 to about 50:1 , preferably from about 1 :1 to about 30:1.

[0041] In one embodiment, a molar ratio of organic reactant to the catalyst is from about 0.02 to about 1 , preferably from about 0.2 to about 1.

[0042] In one embodiment, a molar ratio of HF to the catalyst is from about 1 :1 to about 5.9:1, preferably from about 1:1 to about 5:1.

[0043] In one embodiment, the reaction may be carried out at a temperature of between about 80°C to about 150°C, or between about 90°C to about 140°C.

[0044] In one embodiment, the reaction is conducted at a pressure of from about 50 psig to about 500 psig, preferably from about 80 psig to about 300 psig. In general, increasing the pressure in the reactor above atmospheric pressure will act to increase the contact time of the reactants in the process. Longer contact times will necessarily increase the degree of conversion in a process, without having to increase temperature.

[0045] Depending on the temperature of the reactor, the product mixture from the reactor will contain varying amounts of unreacted haloalkane feed material and other constituents.

[0046] In some embodiments, the catalyst comprises between about 0.1% and about 20% by weight of the reaction mixture composition. For example, about 1% to about 15%, or about 5% to about 10%, or about 10% to about 15% by weight of the composition. In some embodiments, the catalyst comprises about 8% to about 10% or about 12% to about 15% by weight of the reaction mixture composition.

[0047] In some embodiments, the HF can be present in the reaction mixture composition in an amount of about 40% to about 70% by weight of the composition. For example, about 45% to about 65%, about 50% to about 60%, or about 52% to about 56% by weight of the reaction mixture composition.

[0048] In some embodiments, the reactants can be added together at the same time. In some embodiments, the reactants can be added together sequentially in any order. In some embodiments, the reactants are added sequentially in the following order: (1) catalyst; (2) HF; (3) organic reactant.

[0049] In some embodiments, after addition of the catalyst, the reaction mixture composition is cooled to a temperature of about 0°C to about 20°C, such as about0°C, 5°C, 10°C, 15°C, or about 20°C. In some embodiments, after addition of the catalyst, the reaction mixture composition is cooled to a temperature of about 0°C to about 20°C prior to addition of HF.

[0050] In some embodiments, after addition of HF, the reaction mixture composition is heated to a temperature of about 90°C to about 120°C, or about 100°C to about 110°C, such as about 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, or about 20°C. In some embodiments, the heating is performed for a time of about 30 minutes to about 5 hours or about 30 minutes, 1 hour, 2 hours, 3 hours, 4 hours, or about 5 hours. In some embodiments, the reaction mixture composition is heated to a temperature of about 90°C to about 120°C, or about 100°C to about 110°C for a time of about 30 minutes to about 5 hours. In some embodiments, after addition of HF, the reaction mixture composition is heated to a temperature of about 90°C to about 120°C or about 100°C to about 110°C for a time of about 30 minutes to about 5 hours prior to addition of the haloalkane reactant.

[0051] In some embodiments, after addition of HF, the reaction mixture composition is cooled to a temperature of about 0°C to about 20°C, such as about 0°C, 5°C, 10°C, 15°C, or about 20°C. In some embodiments, after addition of HF, the reaction mixture composition is cooled to a temperature of about 0°C to about 20°C prior to addition of the haloalkane reactant.

[0052] In some embodiments, after addition of HF, the reaction mixture composition is heated to a temperature of about 90°C to about 120°C or about 100°C to about 110°C for a time of about 30 minutes to about 5 hours, followed by cooling to a temperature of about 0°C to about 20°C prior to addition of the haloalkane reactant.

[0053] In some embodiments, after addition of the haloalkane reactant, the reaction mixture composition is heated to a temperature of about 50°C to about 150°C, about 75°C to about 130°C, or about 100°C to about 115°C. In some embodiments, after addition of the haloalkane reactant, the reaction mixture composition is heated to a temperature of about 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, or about 150°C. In some embodiments, after addition of the haloalkane reactant, the reaction mixture composition is heated for a time of about 5hours to about 30 hours or about 15 hours to about 25 hours. In some embodiments, after addition of the haloalkane reactant, the reaction mixture composition is heated for a time of about 5 hours, 10 hours, 15 hours, 20 hours, 24 hours, or about 30 hours. In some embodiments, after addition of the haloalkane reactant, the reaction mixture composition is heated to a temperature of about 50°C to about 150°C, about 75°C to about 130°C, or about 100°C to about 115°C for a time of about 5 hours to about 30 hours or about 15 hours to about 25 hours.

[0054] The specific haloalkane reactant used, as well as the catalyst and reaction conditions used will depend on the desired hydro(chloro)fluorocarbon product. For example, HCFC-243fa, HCFC-244a and / or HFC-245fa may be produced by liquid phase fluorination of HCC-240fa in the presence of a fluorination catalyst and under conditions free of or substantially free of a superacid; HCFC-253fb may be produced by liquid phase fluorination of HCC-250fb in the presence of a fluorination catalyst and under conditions free of or substantially free of a superacid; HFC-236fa may be produced by liquid phase fluorination of HCC-230fa in the presence of a fluorination catalyst and under conditions free of or substantially free of a superacid; or HCFC- 346mdf may be produced by liquid phase fluorination of HCFC-343jfd in the presence of a fluorination catalyst and under conditions free of or substantially free of a superacid.

[0055] The reactor or vessel, distillation columns, feed lines, effluent lines and any other associated units utilized in carrying out any of the process embodiments disclosed herein should be constructed from materials which are resistant to the corrosive effects of hydrogen fluoride, such as nickel and its alloys, including Hastelloy, Monel, and Inconel, or vessels lined with fluoropolymers.

[0056] In one embodiment, the reaction may be conducted in a reaction zone comprising any reaction vessel of appropriate size for the scale for the reaction. In one embodiment, the reaction zone is a reaction vessel comprised of materials which are resistant to corrosion. In one embodiment, these materials comprise alloys, such as nickel-based alloys such as Hastelloy®, nickel-chromium alloys commercially available from Special Metals Corp, under the trademark Inconel® (hereinafter “Inconel®”) or nickel-copper alloys commercially available from Special Metals Corp. (New Hartford, New York) under the trademark Monel®, or vesselshaving fluoropolymers linings. In another embodiment, the reaction vessel may be made of other materials of construction including stainless steels, in particular of the austenitic type, and copper-clad steel.

[0057] In some embodiments, the processes of the present invention are carried out in the same location or facility where one or more of the starting materials (i.e. , haloalkane reactant and / or HF) are made, or proximate locations or facilities where one or more of the starting materials. In some embodiments, proximity of the reactor for processes of the present invention to sources of one or more of the starting materials eliminate the need for storage, handling and / or transportation of the starting material(s). In some embodiments, the haloalkane reactant or HF may be produced in respective reactors at the same site where the processes of the present invention are carried out, and may be stored onsite, if needed, or may be transferred directly from an upstream reactor to a downstream reactor via piping, tubing, etc. which fluidly connects the reactors. In some embodiments, the process is preferably carried out proximate a HF manufacturing site, and / or proximate an HCC-230fa manufacturing site, and / or proximate an HCC-240fa manufacturing site, and / or proximate an HCC-250fb manufacturing site, and / or an HCFC-343jfd manufacturing site.

[0058] In some embodiments, the haloalkane product produced in the liquid phase reaction between the haloalkane reactant and HF in the presence of a catalyst and in the absence of or substantially in the absence of a superacid is isolated or separated from the reaction product stream and / or purified as needed to meet AHRI 700 purity standards. More particularly, the desired hydro(chloro)fluorocarbon product may be separated from any unreacted starting material and any byproducts by conventional techniques such as distillation. The low boiling fraction will typically be the starting halogenated alkane which may be recovered and recycled to the reactor. The unreacted starting materials, particularly the starting halogenated alkane, may be further refined and recycled to the reactor. The separation of the two liquid phases in the reactor may be done at temperatures between the reaction temperature and ambient temperature; cooling the reaction mixture lower than room temperature is usually not necessary.

[0059] The process may further comprise optionally purifying the target hydro(chloro)fluorocarbon compound, such as by adsorption or another conventional purification method known in the art, for example to meet AHRI 700 purity standards.

[0060] In some embodiments, the haloalkane product (e.g., HCFC-243fa, HCFC- 244a, HFC-245fa, HCFC-253fb, HFC-236fa, or HCFC-346mdf) is treated to have a purity of greater than about 90 mol%, 91 mol%, 92 mol%, 93 mol%, 94 mol%, 95 mol%, 96 mol%, 97 mol%, 98 mol%, or greater than about 99 mol%. In some embodiments, the purity is determined by chromatography. In some embodiments, the purity is determined by gas chromatography (GC) analysis.

[0061] The invention will be described in greater detail below by way of specific examples. The following examples are offered for illustrative purposes and are not intended to limit the invention in any manner. Those of skill in the art will readily recognize a variety of non-critical parameters which can be changed or modified to yield essentially the same results.EXAMPLESExample 1

[0062] HCC-240fa is contacted with HF in the liquid phase, in the presence of a Lewis acid catalyst, preferably a metal halide catalyst such as MCls where M is a metal, and in the absence of or substantially in the absence of a superacid, to form a reaction mixture comprising HCFC-243fa. Chlorine is optionally co-fed to the reactor with the HCC-240fa and / or HF. A molar ratio of HCC-240fa to HF is from about 1 to about 15. A molar ratio of HCC-240fa to the MCls is from about 0.02 to about 0.5. A molar ratio of HF to the MCls is from about 5.9 to about 1. The overall concentrations of the fluorination catalyst, HF, and HCC-240fa for the HCC-240fa fluorination reaction are selected to avoid or minimize the formation of a superacid. Less than 5 mol% superacid is present or formed during the reaction based on the total metal concentration of the catalyst. The reaction is carried out at a temperature of between about 80°C to about 150°C. The reaction is conducted at a pressure of from about 50 psig to about 460 psig. The conversion is between about 80% to about 100%. Selectivity of HCFC-243fa is between about 90% to about 95%.

[0063] The reaction mixture comprises HCFC-243fa and one or more additional compounds selected from HFC-245fa, HCFC-244fa, HCFO-E-1233zd, HCFO-Z- 1233zd and a C6 compound.

[0064] The HCFC-243fa is separated from the reaction mixture (e.g., by distillation) and purified as needed to be a suitable starting material for producing an HCFO or HFO, such as E / Z-HFO-1234ze or E / Z-HCFO-1233zd.Example 2

[0065] HCC-240fa is contacted with HF in the liquid phase, in the presence of a Lewis acid catalyst, preferably a metal halide catalyst such as MCls where M is a metal, and in the absence of or substantially in the absence of a superacid, to form a reaction mixture comprising HCFC-244fa. Chlorine is optionally co-fed to the reactor with the HCC-240fa and / or HF. A molar ratio of HCC-240fa to HF is from about 1 to about 20. A molar ratio of HCC-240fa to the MCls is from about 0.02 to about 0.5. A molar ratio of HF to the MCls is from about 5.9 to about 1. The overall concentrations of the fluorination catalyst, HF, and HCC-240fa for the HCC-240fa fluorination reaction are selected to avoid or minimize the formation of a superacid. Less than 5 mol% superacid is present or formed during the reaction based on the total metal concentration of the catalyst. The reaction is carried out at a temperature of between about 80°C to about 150°C. The reaction is conducted at a pressure of from about 50 psig to about 460 psig. The conversion is between about 80% to about 100%. Selectivity of HCFC-244fa is between about 90% to about 95%.

[0066] The reaction mixture comprises HCFC-244fa and one or more additional compounds selected from HFC-243fa, HFC-233da, CF3CHCICFCIH, CF3CHCICHF2, HFO-E-1233zd and HFO-Z-1233zd.

[0067] The HCFC-244fa is separated from the reaction mixture (e.g., by distillation) and purified as needed to be a suitable starting material for producing an HCFO or HFO, such as E / Z-HFO-1234ze or E / Z-HFO-1233zd.Example 3

[0068] HCC-240fa is contacted with HF in the liquid phase, in the presence of a Lewis acid catalyst, preferably a metal halide catalyst such as MCls where M is ametal, and in the absence of or substantially in the absence of a superacid, to form a reaction mixture comprising HFC-245fa. Chlorine is optionally co-fed to the reactor with the HCC-240fa and / or HF. A molar ratio of HCC-240fa to HF is from about 1 to about 30. A molar ratio of HCC-240fa to the MCls is from about 0.02 to about 0.5. A molar ratio of HF to the MCls is from about 5.9 to about 1. The overall concentrations of the fluorination catalyst, HF, and HCC-240fa for the HCC-240fa fluorination reaction are selected to avoid or minimize the formation of a superacid. Less than 5 mol% superacid is present or formed during the reaction based on the total metal concentration of the catalyst. The reaction is carried out at a temperature of between about 80°C to about 150°C. The reaction is conducted at a pressure of from about 50 psig to about 460 psig. The conversion is between about 80% to about 100%. Selectivity of HFC-245fa is between about 90% to about 95%.

[0069] The reaction mixture comprises (i) HFC-245fa, (ii) HFC-243fa, (iii) HFC- 244fa, (iv) one or more compounds selected from HFC-233da, (E)-2,4,5-trichloro- 1 ,1,1 ,6,6,6-hexafluorohex-2-ene, (Z)- 2 , 4 , 5-trichloro- 1 ,1,1 ,6,6,6-hexafluorohex-2- ene, (E)-2-chloro-4-(dichloromethyl)-1 ,1,1 ,5,5,5-hexafluoropent-2-ene, (Z)-2-chloro- 4-(dichloromethyl)-1 ,1,1 ,5,5,5-hexafluoropent-2-ene, (E)-4,5,5-trichloro-1 ,1 ,1 ,6,6,6- hexafluorohex-2-ene, (E)-4-chloro-2-(dichloromethyl)-1,1 ,1 ,5,5,5-hexafluoropent-2- ene, (Z)-4-chloro-2-(dichloromethyl)-1 ,1 ,1 ,5,5,5-hexafluoropent-2-ene, (2Z,4E)-2,5- dichloro-1 ,1,1 ,6,6,6-hexafluorohexa-2,4-diene, (E)-1 ,3-dichloro-5,5,5-trifluoro-2- (trifluoromethyl)pent-l-ene, (Z)-1,3-dichloro-5,5,5-trifluoro-2-(trifluoromethyl)pent-1- ene, (E)-4,5-dichloro-1 , 1 , 1 ,6,6,6-hexafluorohex-2-ene, (E)-4,5,6-trichloro-1 ,1 ,1 ,6,6- pentafluorohex-2-ene, and (v) one or more additional compounds selected from HFC-143a, HFC-1225zc, HFC-236fa, HFO-E / Z-1234ze, HCFC-22, CFC-12, HCFC- 142b, HCFC-133a, HCFC-1224, HCFC-235fa, HCFO-Z-1233zd, HCFC-235da, HCFC-123, HCFC-141b, HCFC-234fb, HCFC-1223xd, HCC-20, HCFC-224aa, CFC- 1213xa, HCFC-233da, and HCFC-223aa, or one or more additional compounds selected from the group consisting of HFO-E-1234ze, HFC-338mf, HFC-356mff, HFO-1234ze(Z), HFO-1234zc, HFC-347 isomer, HCFC-133a, HCFC-244bb, HCFC- 235fa, HCFO-Z-1326mxz, HCFO-1224yd, HCFO-E-1233zd, HCFO-1224zc, HCC- 160, HCFC-244, HCFO-1335, HCFC-123, HCFC-123a, HCFO-Z-1233zd, HBFO- 1233zd(Br), CFO-1214ya, HCC-30, CFC-113, HCFO-1223xd, HCO-1130a and HCO-1130.

[0070] The HFC-245fa is separated from the reaction mixture (e.g., by distillation) and purified as needed to be a suitable starting material for producing an HCFO or HFO, such as E / Z-HFO-1234ze or E / Z-HFO-1233zd.Example 4

[0071] HCC-250fb is contacted with HF in the liquid phase, in the presence of a Lewis acid catalyst, preferably a metal halide catalyst such as MCls where M is a metal, and in the absence of or substantially in the absence of a superacid, to form a reaction mixture comprising HCFC-253fb. Chlorine is optionally co-fed to the reactor with the HCC-250fb and / or HF. A molar ratio of HCC-250fb to HF is from about 1 to about 20. A molar ratio of HCC-250fb to the MCls is from about 0.02 to about 0.4. A molar ratio of HF to the MCls is from about 5.9 to about 1. The overall concentrations of the fluorination catalyst, HF, and HCC-250fb for the HCC-250fb fluorination reaction are selected to avoid or minimize the formation of a superacid. Less than 5 mol% superacid is present or formed during the reaction based on the total metal concentration of the catalyst. The reaction is carried out at a temperature of between about 50 °C to about 140°C. The reaction is conducted at a pressure of from about 50 psig to about 400 psig. The conversion is between about 80% to about 100%. Selectivity of HCFC-253fb is between about 90% to about 95%.

[0072] The reaction mixture comprises HCFC-253fb and one or more additional compounds.

[0073] The HCFC-253fb is separated from the reaction mixture (e.g., by distillation) and purified as needed to be a suitable starting material for producing an HCFO or HFO, such as HFO-1243zf.Example 5

[0074] HCC-230fa is contacted with HF in the liquid phase, in the presence of a Lewis acid catalyst, preferably a metal halide catalyst such as MCls where M is a metal, and in the absence of or substantially in the absence of a superacid, to form a reaction mixture comprising HFC-236fa. Chlorine is optionally co-fed to the reactor with the HCC-240fa and / or HF. A molar ratio of HCC-230fa to HF is from about 1 to about 30. A molar ratio of HCC-230fa to the MCls is from about 0.02 to about 0.5. A molar ratio of HF to the MCls is from about 5.9 to about 1. The overallconcentrations of the fluorination catalyst, HF, and HCC-230fa for the HCC-230fa fluorination reaction are selected to avoid or minimize the formation of a superacid. Less than 5 mol% superacid is present or formed during the reaction based on the total metal concentration of the catalyst. The reaction is carried out at a temperature of between about 80°C to about 150°C. The reaction is conducted at a pressure of from about 80 psig to about 460 psig. The conversion is between about 80% to about 100%. Selectivity of HFC-236fa is between about 80% to about 95%.

[0075] The reaction mixture comprises HFC-236fa and one or more additional compounds selected from HFC-143a, HFO-1225zc, HFC-152a, HFO-E-1234ze, HFO-Z-1234ze, HCFC-22, HFC-245fa, HFC-142b, HFC-133a, HFO-1224 isomers, HFC-235fa, HFC-243db, HFC-243db, HCFO-E-1233zd, HCFO-Z-1233zd, HFC-123, HFC-141b, HCC-30, CFC-113, HFC-234fb, HCFO-Z-1233xd, HCFO-E-1233xd, HFC-234bb, HCC-20, HFC-140, HFC-224aa and HFO-1213xa.

[0076] The HFC-236fa is separated from the reaction mixture (e.g., by distillation) and purified as needed to be a suitable starting material for producing an HCFO or HFO, such as E / Z-HFO-1234ze.Example 6

[0077] HCFC-343jfd is contacted with HF in the liquid phase, in the presence of a Lewis acid catalyst, preferably a metal halide catalyst such as MCls where M is a metal, and in the absence of or substantially in the absence of a superacid, to form a reaction mixture comprising HCFC-346mdf. Chlorine is optionally co-fed to the reactor with the HCC-240fa and / or HF. A molar ratio of HCFC-343jfd to HF is from about 1 to about 15. A molar ratio of HCFC-343jfd to the MCh is from about 0.02 to about 0.3. A molar ratio of HF to the MCls is from about 5.9 to about 1. The overall concentrations of the fluorination catalyst, HF, and HCFC-343jfd for the HCFC-343jfd fluorination reaction are selected to avoid or minimize the formation of a superacid. Less than 5 mol% superacid is present or formed during the reaction based on the total metal concentration of the catalyst. The reaction is carried out at a temperature of between about 50°C to about 150°C. The reaction is conducted at a pressure of from about 50 psig to about 150 psig. The conversion is between about 80% to about 100%. Selectivity of HCFC-346mdf is between about 80% to about 95%.

[0078] The reaction mixture comprises HCFC-346mdf and one or more additional compounds selected from HFO-E-1336mzz, HFO-Z-1336mzz, HFC-347mef, HFO- 1336ft, HFC-345ldf, HFO-1335mzz, HFC-344kfd, HFC-343jfd, HFO-1333azd and H FC- 133a.

[0079] The HCFC-346mdf is separated from the reaction mixture (e.g., by distillation) and purified as needed to be a suitable starting material for producing an HCFO or HFO, such as E / Z-HFO-1336mzz.OTHER EMBODIMENTS

[0080] Embodiment 1 . A process comprising contacting a haloalkane reactant with a fluorination agent in the liquid phase, in the presence of a catalyst, under conditions which are free of or substantially free of a superacid, to produce a product stream comprising a haloalkane product, preferably a hydro(chloro)fluorocarbon.

[0081] Embodiment 2. The process of Embodiment 1 , wherein said haloalkane reactant is an alkane substituted with at least one halogen selected from the group consisting of F, Cl, and combinations thereof.

[0082] Embodiment 3. The process of any of Embodiments 1 to 2, wherein the haloalkane reactant is selected from the group consisting of hydrochlorocarbons and hydrochlorofluorocarbons.

[0083] Embodiment 4. The process of any of Embodiments 1 to 3, wherein the haloalkane reactant is represented by the formula R1CH2R2, where R1and R2are the same or different and is each independently a halogenated or partially halogenated C1 to C4 compound, optionally branched, preferably where R2is one of (i) CHxC -x, where x is an integer from 0 to 2; (ii) CHxFyC -x-y, where x is 0 or 1 and y is 1 or 2; or (iii) CHxCI2-xCF3, where x is 0 or 1.

[0084] Embodiment 5. The process of any of Embodiments 1 to 4, wherein the haloalkane reactant is selected from the group consisting of 1 , 1 ,1 , 3,3- pentachloropropane (HCC-240fa, CCI3CH2CHCI2); 1 ,1 ,1 ,3-tetrachloropropane (HCC- 250fb, CCI3CH2CH2CI); 1 , 1 ,1 ,3,3,3-hexachloropropane (HCC-230fa, CCI3CH2CCI3); 1 ,1 ,1 , 3-trich loro-4 , 4, 4-trifl uorobut- 1 -ene (HCFC-343jfd, CCI3CH2CHCICF3).

[0085] Embodiment 6. The process of any of Embodiments 1 to 5, wherein the haloalkane product comprises at least one hydro(chloro)fluorocarbon.

[0086] Embodiment 7. The process of any of Embodiments 1 to 6, wherein the haloalkane product is represented by the formula CF3CH2R3, where R3is CHxClyFs-x-y, where x is an integer from 0 to 2, and y is an integer from 0 to 2.

[0087] Embodiment 8. The process of any of Embodiments 1 to 7, wherein the haloalkane product is selected from the group consisting of 1 ,1 , 1 ,3, 3- pentafluoropropane (CFsCH2CHF2 or HFC-245fa); 3,3-dichloro-1 , 1 , 1- trifluoropropane (CF3CH2CHCI2 or HFC-243fa); 3-chloro-1 ,1 ,1 ,3-tetrafluoropropane (CF3CH2CHFCI or HCFC-244fa); 3-chloro-1 , 1 ,1 -trifluoropropane (CF3CH2CH2CI or HCFC-253fb); 1 ,1 ,1 ,3,3,3-hexafluoropropane (CF3CH2CF3 or HFC-236fa); and 2- chloro-1 ,1 ,1 ,4,4,4-hexafluorobutane (CF3CH2CHCICF3 or HCFC-346mdf).

[0088] Embodiment 9. The process of any of Embodiments 1 to 8, wherein the catalyst comprises a Lewis acid catalyst, preferably a metal halide catalyst, and more preferably a catalyst which is (i) selected from one of MFXor MClx, where M is a metal and x is an integer from 1 to 5, or (ii) MFxCly, where M is a metal, x+y = 5, and neither x nor y can equal 0. In some embodiments, M comprises a metal selected from Sb, Ta, Nb, Sn, Ti and combinations thereof.

[0089] Embodiment 10. The process of any of Embodiments 1 to 9, wherein concentrations of the fluorination agent, catalyst and haloalkane reactant are selected to prevent or minimize the formation of a superacid.

[0090] Embodiment 11. The process of any of Embodiments 1 to 10, wherein less than 5 mol% of a superacid is present or formed during the reaction based on the total metal concentration of the catalyst.

[0091] Embodiment 12. The process of any of Embodiments 1 to 11 , wherein the haloalkane reactant is HCC-240fa and the haloalkane product is HCFC-243fa.

[0092] Embodiment 13. The process of Embodiment 12, wherein a composition produced by the process comprises the HCFC-243fa, and one or more additional compounds selected from the group consisting of HFC-245fa, HCFC-244fa, HCFO- E-1233zd, HCFO-Z-1233zd and a C6 compound.

[0093] Embodiment 14. The process of any of Embodiments 1 to 11 , wherein the haloalkane reactant is HCC-240fa and the haloalkane product is HCFC-244fa.

[0094] Embodiment 15. The process of Embodiment 14, wherein a composition produced by the process comprises the HCFC-244fa, and one or more additional compounds selected from the group consisting of HFC-243fa, HFC-233da, CF3CHCICFCIH, CF3CHCICHF2, HFO-E-1233zd and HFO-Z-1233zd.

[0095] Embodiment 16. The process of any of Embodiments 1 to 11 , wherein the haloalkane reactant is HCC-240fa and the haloalkane product is HFC-245fa.

[0096] Embodiment 17. The process of Embodiment 16, wherein a composition produced by the process comprises the (i) HFC-245a, (ii) HFC-243fa, (iii) HFC- 244fa, (iv) one or more compounds selected from 233da, (E)-2,4,5-trichloro- 1 ,1,1 ,6,6,6-hexafluorohex-2-ene, (Z)- 2 , 4 , 5-trichloro- 1 ,1,1 ,6,6,6-hexafluorohex-2- ene, (E)-2-chloro-4-(dichloromethyl)-1 ,1,1 ,5,5,5-hexafluoropent-2-ene, (Z)-2-chloro- 4-(dichloromethyl)-1 ,1,1 ,5,5,5-hexafluoropent-2-ene, (E)-4,5,5-trichloro-1 ,1 ,1 ,6,6,6- hexafluorohex-2-ene, (E)-4-chloro-2-(dichloromethyl)-1,1 ,1 ,5,5,5-hexafluoropent-2- ene, (Z)-4-chloro-2-(dichloromethyl)-1 ,1 ,1 ,5,5,5-hexafluoropent-2-ene, (2Z,4E)-2,5- dichloro-1 ,1,1 ,6,6,6-hexafluorohexa-2,4-diene, (E)-1 ,3-dichloro-5,5,5-trifluoro-2- (trifluoromethyl)pent-l-ene, (Z)-1,3-dichloro-5,5,5-trifluoro-2-(trifluoromethyl)pent-1- ene, (E)-4,5-dichloro-1 , 1 , 1 ,6,6,6-hexafluorohex-2-ene, (E)-4,5,6-trichloro-1 ,1 ,1 ,6,6- pentafluorohex-2-ene, and (v) and one or more additional compounds selected from the group consisting of HFC-143a, HFC-1225zc, HFC-236fa, HFO-E / Z-1234ze, HCFC-22, CFC-12, HCFC-142b, HCFC-133a, HCFC-1224, HCFC-235fa, HCFO-Z- 1233zd, HCFC-235da, HCFC-123, HCFC-141b, HCFC-234fb, HCFC-1223xd, HCC- 20, HCFC-224aa, CFC-1213xa, HCFC-233da, and HCFC-223aa, or one or more additional compounds selected from the group consisting of HFO-E-1234ze, HFC- 338mf, HFC-356mff, HFO-1234ze(Z), HFO-1234zc, HFC-347 isomer, HCFC-133a, HCFC-244bb, HCFC-235fa, HCFO-Z-1326mxz, HCFO-1224yd, HCFO-E-1233zd, HCFO-1224zc, HCC-160, HCFC-244, HCFO-1335, HCFC-123, HCFC-123a, HCFO- Z-1233zd, HBFO-1233zd (Br), CFO-1214ya, HCC-30, CFC-113, HCFO-1223xd, HCO-1130a and HCO-1130.

[0097] Embodiment 18. The process of any of Embodiments 1 to 11 , wherein the haloalkane reactant is HCC-250fb and the haloalkane product is HCFC-253fb.

[0098] Embodiment 19. The process of Embodiment 18, wherein a composition produced by the process comprises the HCFC-253fb, and one or more additional compounds.

[0099] Embodiment 20. The process of any of Embodiments 1 to 11 , wherein the haloalkane reactant is HCC-230fa and the haloalkane product is HFC-236fa.

[0100] Embodiment 21. The process of Embodiment 20, wherein a composition produced by the process comprises the HFC-236fa, and one or more additional compounds selected from the group consisting of HFC-143a, HFO-1225zc, HFC- 152a, HFO-E-1234ze, HFO-Z-1234ze, HCFC-22, HFC-245fa, HFC-142b, HFC-133a, HFO-1224 isomers, HFC-235fa, HFC-243db, HFC-243db, HCFO-E-1233zd, HCFO- Z-1233zd, HFC-123, HFC-141 b, HCC-30, CFC-113, HFC-234fb, HCFO-Z-1233xd, HCFO-E-1233xd, HFC-234bb, HCC-20, HFC-140, HFC-224aa and HFO-1213xa.

[0101] Embodiment 22. The process of any of Embodiments 1 to 11 , wherein the haloalkane reactant is HCFC-343jfd and the haloalkane product is HCFC-346mdf.

[0102] Embodiment 23. The process of Embodiment 22, wherein a composition produced by the process comprises the HCFC-346mdf, and one or more additional compounds selected from the group consisting of HFO-E-1336mzz, HFO-Z- 1336mzz, HFC-347mef, HFO- 1336ft, HFC-345ldf, HFO-1335mzz, HFC-344kfd, HFC-343jfd, HFO-1333azd and H FC- 133a.

[0103] It will be appreciated by those skilled in the art that changes could be made to the embodiments described above without departing from the broad inventive concept thereof. It is understood, therefore, that this invention is not limited to the particular embodiments disclosed, but it is intended to cover modifications within the spirit and scope of the present invention as defined by the appended claims.

Claims

CLAIMSWhat is claimed is:1 . A process comprising contacting a haloalkane reactant with a fluorination agent in the liquid phase, in the presence of a catalyst, under conditions which are free of or substantially free of a superacid, to produce a product stream comprising a haloalkane product, preferably a hydro(chloro)fluorocarbon.

2. The process of claim 1 , wherein said haloalkane reactant is an alkane substituted with at least one halogen selected from the group consisting of F, Cl, and combinations thereof.

3. The process of any of claims 1 to 2, wherein the haloalkane reactant is selected from the group consisting of hydrochlorocarbons and hydrochlorofluorocarbons.

4. The process of any of claims 1 to 3, wherein the haloalkane reactant is represented by the formula R1CH2R2, where R1and R2are the same or different and is each independently a halogenated or partially halogenated C1 to C4 compound, optionally branched, preferably where R2is one of (i) CHxC -x, where x is an integer from 0 to 2; (ii) CHxFyC -x-y, where x is 0 or 1 and y is 1 or 2; or (iii) CHxCh-xCFs, where x is 0 or 1.

5. The process of any of claims 1 to 4, wherein the haloalkane reactant is selected from the group consisting of 1 ,1 ,1 ,3,3-pentachloropropane (HCC-240fa, CCI3CH2CHCI2); 1 ,1 ,1 ,3-tetrachloropropane (HCC-250fb, CCI3CH2CH2CI);1 ,1 ,1 ,3,3,3-hexachloropropane (HCC-230fa, CCI3CH2CCI3); 1 ,1 ,1 ,3-trichloro- 4,4,4-trifluorobut-1-ene (HCFC-343jfd, CCI3CH2CHCICF3).

6. The process of any of claims 1 to 5, wherein the haloalkane product comprises at least one hydro(chloro)fluorocarbon.

7. The process of any of claims 1 to 6, wherein the haloalkane product is represented by the formula CF3CH2R3, where R3is CHxClyFs-x-y, where x is an integer from 0 to 2, and y is an integer from 0 to 2.

8. The process of any of claims 1 to 7, wherein the haloalkane product is selected from the group consisting of 1 ,1 ,1 ,3,3-pentafluoropropane (CFsCH2CHF2 or HFC-245fa); 3, 3-dichloro-1 , 1 ,1 -trifluoropropane (CF3CH2CHCI2 or HFC-243fa);3-chloro-1 ,1 ,1 ,3-tetrafluoropropane (CF3CH2CHFCI or HCFC-244fa); 3-chloro- 1 , 1 ,1 -trifluoropropane (CF3CH2CH2CI or HCFC-253fb); 1 ,1 , 1 ,3, 3, 3- hexafluoropropane (CF3CH2CF3 or HFC-236fa); and 2-chloro-1 , 1 ,1 , 4,4,4- hexafluorobutane (CF3CH2CHCICF3 or HCFC-346mdf).

9. The process of any of claims 1 to 8, wherein the catalyst comprises a Lewis acid catalyst, preferably a metal halide catalyst, and more preferably a catalyst which is (i) selected from the group consisting of MFx, MClx and combinations thereof, where M is a metal and x is an integer from 1 to 5, or (ii) MFxCly, where M is a metal, x+y = 5, and neither x nor y can equal 0.

10. The process of claim 9, wherein M comprises a metal selected from the group consisting of Sb, Ta, Nb, Sn, Ti and combinations thereof.

11. The process of any of claims 1 to 10, wherein concentrations of the fluorination agent, catalyst and haloalkane reactant are selected to prevent or minimize the formation of a superacid.

12. The process of any of claims 1 to 11 , wherein less than 5 mol% of a superacid is present or formed during the reaction based on the total metal concentration of the catalyst.

13. The process of any of claims 1 to 12, wherein the haloalkane reactant is HCC- 240fa and the haloalkane product is HCFC-243fa.

14. The process of claim 13, wherein a composition produced by the process comprises the HCFC-243fa, and one or more additional compounds selected from the group consisting of HFC-245fa, HCFC-244fa, HCFO-E-1233zd, HCFO-Z-1233zd and a C6 compound.

15. The process of any of claims 1 to 12, wherein the haloalkane reactant is HCC- 240fa and the haloalkane product is HCFC-244fa.

16. The process of claim 15, wherein a composition produced by the process comprises the HCFC-244fa, and one or more additional compounds selected from the group consisting of HFC-243fa, HFC-233da, CF3CHCICFCIH, CF3CHCICHF2, HFO-E-1233zd and HFO-Z-1233zd.

17. The process of any of claims 1 to 12, wherein the haloalkane reactant is HCC- 240fa and the haloalkane product is HFC-245fa.

18. The process of claim 17, wherein a composition produced by the process comprises (i) the HFC-245a, (ii) HFC-243fa, (iii) HFC-244fa, (iv) one or more compounds selected from HFC-233da, (E)-2,4,5-trichloro-1 , 1 , 1 ,6,6,6- hexafluorohex-2-ene, (Z)- 2,4,5-trichloro-1,1 ,1 ,6,6,6-hexafluorohex-2-ene, (E)- 2-chloro-4-(dichloromethyl)-1 ,1 ,1,5,5,5-hexafluoropent-2-ene, (Z)-2-chloro-4- (dichloromethyl)-l ,1,1 ,5,5,5-hexafluoropent-2-ene, (E)-4,5,5-trichloro-1,1 ,1 ,6,6,6-hexafluorohex-2-ene, (E)-4-chloro-2-(dichloromethyl)-1 , 1 , 1 ,5,5,5- hexafluoropent-2-ene, (Z)-4-chloro-2-(dichloromethyl)-1 ,1,1 ,5,5,5- hexafluoropent-2-ene, (2Z,4E)-2,5-dichloro-1,1 ,1 ,6,6,6-hexafluorohexa-2,4- diene, (E)-1 ,3-dichloro-5,5,5-trifluoro-2-(trifluoromethyl)pent-1-ene, (Z)-1 ,3- dichloro-5,5,5-trifluoro-2-(trifluoromethyl)pent-1-ene, (E)-4,5-dichloro- 1,1 ,1 ,6,6,6-hexafluorohex-2-ene, (E)-4,5,6-trichloro-1 ,1 ,1 ,6,6-pentafluorohex-2- ene, and (v) and one or more additional compounds selected from the group consisting of HFC-143a, HFC-1225zc, HFC-236fa, HFO-E / Z-1234ze, HCFC-22, CFC-12, HCFC-142b, HCFC-133a, HCFC-1224, HCFC-235fa, HCFO-Z- 1233zd, HCFC-235da, HCFC-123, HCFC-141 b, HCFC-234fb, HCFC-1223xd, HCC-20, HCFC-224aa, CFC-1213xa, HCFC-233da, and HCFC-223aa, or one or more additional compounds selected from the group consisting of HFO-E- 1234ze, HFC-338mf, HFC-356mff, HFO-1234ze(Z), HFO-1234zc, H FC-347 isomer, HCFC-133a, HCFC-244bb, HCFC-235fa, HCFO-Z-1326mxz, HCFO- 1224yd, HCFO-E-1233zd, HCFO-1224zc, HCC-160, HCFC-244, HCFO-1335, HCFC-123, HCFC-123a, HCFO-Z-1233zd, HBFO-1233zd (Br), CFO-1214ya, HCC-30, CFC-113, HCFO-1223xd, HCO-1130a and HCO-1130.

19. The process of any of claims 1 to 12, wherein the haloalkane reactant is HCC- 250fb and the haloalkane product is HCFC-253fb.

20. The process of claim 19, wherein a composition produced by the process comprises the HCFC-253fb, and one or more additional compounds.

21. The process of any of claims 1 to 12, wherein the haloalkane reactant is HCC- 230fa and the haloalkane product is HFC-236fa.

22. The process of claim 21 , wherein a composition produced by the process comprises the HFC-236fa, and one or more additional compounds selected from the group consisting of HFC-143a, HFO-1225zc, HFC-152a, HFO-E- 1234ze, HFO-Z-1234ze, HCFC-22, HFC-245fa, HFC-142b, HFC-133a, HFO- 1224 isomers, HFC-235fa, HFC-243db, HFC-243db, HCFO-E-1233zd, HCFO- Z-1233zd, HFC-123, HFC-141b, HCC-30, CFC-113, HFC-234fb, HCFO-Z- 1233xd, HCFO-E-1233xd, HFC-234bb, HCC-20, HFC-140, HFC-224aa and HFO-1213xa.

23. The process of any of claims 1 to 12, wherein the haloalkane reactant is HCFC- 343jfd and the haloalkane product is HCFC-346mdf.

24. The process of claim 23, wherein a composition produced by the process comprises the HCFC-346mdf, and one or more additional compounds selected from the group consisting of HFO-E-1336mzz, HFO-Z-1336mzz, HFC-347mef, HFO-1336ft, HFC-345ldf, HFO-1335mzz, HFC-344kfd, HFC-343jfd, HFO- 1333azd and HFC-133a.