Process for (HYDRO)chloro(fluoro)carbon recovery

Abstract

A recovery process includes (i) contacting or mixing an effective amount of a treatment reagent with a composition to form a treated composition, the composition including at least one member selected from at least one (hydro)haloalkane, at least one (hydro)chloro(fluoro)carbon, at least one metal, at least one metal salt, at least one organic nitrile redox system, at least one phosphate, at least one phosphine, at least one metal phosphate complex, at least one metal phosphine complex, and combinations thereof; and subjecting the treated composition to separation, such as distillation or fractionation, to recover the at least one (hydro)haloalkane and the at least one (hydro)chloro(fluoro)carbon.

Description

TITLE OF THE INVENTIONPROCESS FOR (HYDRO)CHLORO(FLUORO)CARBON RECOVERYCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Patent Application No. 63 / 662,885, 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 recovering (hydro)chloro(fluoro)carbon compounds from waste or purge streams comprising such compounds, as well as byproduct oligomers, metals, solvents, and the like.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. Certain hydrofluoroolefins (HFOs) and hydrochlorofluoroolefins (HCFOs) are believed to meet both goals.

[0004] Catalyzed reactions of carbon tetrachloride with olefins to form hydrochloro(fluoro)carbon compounds are known in the art. Such hydrochloro(fluoro)carbons include, but are not limited to, 1 ,1 ,1 ,3-tetrachloropropane (CCI3-CH2-CH3, HCC-250fb), 1,1 ,1 ,3,3-pentachloropropane (HCC-240fa, CCI3CH2CHCI2), and 1 ,1,1,3,3,3-hexachloropropane (HCC-230fa, CCI3CH2CCI3). These hydrochloro(fluoro)carbons are often useful materials for the production of fluoroalkanes, particularly hydrofluoroalkanes and more particularly HFCs, andfluoroolefins, particularly HCFOs and HFOs, which are useful as refrigerants, fire extinguishants, heat transfer media, propellants, foaming agents, gaseous dielectrics, sterilant carriers, polymerization media, particulate removal fluids, carrier fluids, buffing abrasive agents, displacement drying agents and power cycle working fluids.

[0005] For example, HCC-250fb is a starting material for the production of 2, 3,3,3- tetrafluoropropene (HFO-1234yf) and (E)-1 ,1 ,1 ,4,4,4-Hexafluorobut-2-ene (E-HFO- 1336mzz). HCC-240fa is a starting material for the production of E / Z-1 , 3,3,3- tetrafluoropropene (E / Z-HFO-1234ze), E / Z-1-chloro-3,3,3-trifluoropropene (E / Z- HFO-1233zd), and / or 1 ,1 , 1 ,3, 3-pentafluoropropane (CF3CH2CHF2 or HFC-245fa), which are thermal management fluids used in a variety of applications. HCC-230fa is a starting material for the production of 1 ,1 ,1 ,3,3,3-hexafluoropropane (HFC- 236fa), which is used as a fire extinguishant.

[0006] The preparation of such hydrochloro(fluoro)carbon starting materials has been in commercial practice for several decades, for example by the reaction of carbon tetrachloride (CCk) with olefins catalyzed by redox systems (Cu or Cu salts and organic nitriles, or Fe or Fe salts and organic phosphine or organic phosphate esters). However, the conventional reactions to produce these starting materials often form various degrees of oligomers as byproducts, such as of the formula CCl3(cH2-CRR’)nCI, where n > 2, and R and R’ are independently H, Cl, or both. The oligomers are purged in the reaction and / or purification process as waste. The purge stream also contains significant amounts of unreacted CCU, reaction products, metals, metal salts, organic nitrile redox systems, phosphates, phosphines, metal phosphate complexes and / or metal phosphine complexes.

[0007] Although it is desirable to recover CCU and the reaction products from the purge stream, the corrosivity of the purge stream makes recovery of these compounds challenging. For example, expensive metal alloy would be required as the material of construction for the recovery equipment in order to minimize the corrosion impact and, in many cases, no suitable metal alloy can be used due to the extreme corrosivity. Thus, the waste or purge stream is typically simply sent for incineration. Either way, the current processes of handling and managing the purge stream lead to increased financial cost and environmental footprint. It would bedesirable to provide an improved process for managing the waste of processes to produce hydrochloro(fluoro)carbon starting materials to achieve efficiency and waste reduction.SUMMARY OF THE INVENTION

[0008] In one aspect, the present invention relates to a recovery process comprising: contacting or mixing an effective amount of a treatment reagent with a composition to form a treated composition, the composition comprising at least one member selected from at least one (hydro)haloalkane, at least one (hydro)chloro(fluoro)carbon, at least one metal, at least one metal salt, at least one organic nitrile redox system, at least one phosphate, at least one phosphine, at least one metal phosphate complex, at least one metal phosphine complex, and combinations thereof; and subjecting the treated composition to separation, such as distillation or fractionation, to recover the at least one (hydro)haloalkane and the at least one (hydro)chloro(fluoro)carbon.

[0009] In one aspect, the present invention relates to a composition comprising: (i) carbon tetrachloride and one or more additional compound selected from dichloromethane (CH2CI2), trichloroethylene (HCC-1120), tetrachloroethene (CC- 1110), chloroform (CHCI3), chloromethane (CH3CI), dichloroethane, trichloroethane, bromodichloromethane, bromochloroethane, dichloroethene, dichloroethane, 1,1,2- trichloroethane, 1,1,1 -trichloroethane, hexachloroethane, E-1 ,2-dichloroethene, Z-1 ,2 dichloroethene and 1 ,1 -dichloroethene, or at least two additional compounds or at least three additional compounds or more; (ii) HCC-230fa and one or more additional compound selected from CCI3CCI2CH2CI, CCI3CHCICH2CI, CCI3CH2CH2CI, CCI2=CH-CCI3, CCI3CH2CCI2CH2CCI3 and CCI3CH2CCI2CH2CCI3; (iii) at least one of metals, metal salts, organic nitrile redox systems, phosphates, phosphines, metal phosphate complexes, metal phosphine complexes, and combinations thereof; and (iv) optionally byproducts including oligomers, dimers, telomers and other polymeric products.

[0010] In one aspect, the present invention relates to a composition comprising: (i) carbon tetrachloride and one or more additional compound selected from dichloromethane (CH2CI2), trichloroethylene (HCC-1120), tetrachloroethene (CC- 1110), chloroform (CHCI3), chloromethane (CH3CI), dichloroethane, trichloroethane,bromodichloromethane, bromochloroethane, dichloroethene, dichloroethane, 1,1,2- trichloroethane, 1,1,1 -trichloroethane, hexachloroethane, E-1 ,2-dichloroethene, Z-1 ,2 dichloroethene and 1 ,1 -dichloroethene, or at least two additional compounds or at least three additional compounds or more; (ii) HCC-240fa and one or more additional compound selected from 1 -chlorobutane; 1 ,2,3-trichloropropene (CHCI=CCI-CH2CI, HCO-1240xd); HCO-1230xd (CHCI=CCI-CHCI2, 1 ,2,3,3-tetrachloropropene);1.1.1.3- tetrachloropropane (CCI3-CH2-CH3, HCC-250fb); 1 ,4 dichlorobutane; 1 ,2- dichloro-cyclobutane, 1 ,1,4,4-tetrachlorobutadiene; 1,1, 3, 4 tetrachlorobutadiene;1.1.1.2.3-pentachloropropane (HCC-240db); 1 , 1 , 3, 3-tetrachloro-1 -propene (CCI2=CH-CHCI2); C5H7CI3 isomer(s) and C4H7CI3 isomer(s); (iii) at least one of metals, metal salts, organic nitrile redox systems, phosphates, phosphines, metal phosphate complexes, metal phosphine complexes, and combinations thereof; and (iv) optionally byproducts including oligomers, dimers, telomers and other polymeric products.

[0011] In one aspect, the present invention relates to a composition comprising: (i) carbon tetrachloride and one or more additional compound selected from dichloromethane (CH2CI2), trichloroethylene (HCC-1120), tetrachloroethene (CC- 1110), chloroform (CHCI3), chloromethane (CH3CI), dichloroethane, trichloroethane, bromodichloromethane, bromochloroethane, dichloroethene, dichloroethane, 1,1,2- trichloroethane, 1,1,1 -trichloroethane, hexachloroethane, E-1 ,2-dichloroethene, Z-1 ,2 dichloroethene and 1 ,1 -dichloroethene, or at least two additional compounds or at least three additional compounds or more; (ii) HCC-250fb and one or more additional compound selected from CCI4; 1 ,1,1 -trichloropropane; dichlorobutane; 1 , 1 ,1 ,2- tetrachloroethane; CCI2=CH-CH2CI; C3H3CI3 isomers; C3H3CI5 and hexachloroethane; (iii) at least one of metals, metal salts, organic nitrile redox systems, phosphates, phosphines, metal phosphate complexes, metal phosphine complexes, and combinations thereof; and (iv) optionally byproducts including oligomers, dimers, telomers and other polymeric products.

[0012] In one aspect, the present invention relates to a composition comprising: (i) carbon tetrachloride and one or more additional compound selected from dichloromethane (CH2CI2), trichloroethylene (HCC-1120), tetrachloroethene (CC- 1110), chloroform (CHCI3), chloromethane (CH3CI), dichloroethane, trichloroethane, bromodichloromethane, bromochloroethane, dichloroethene, dichloroethane, 1,1,2-trichloroethane, 1,1,1 -trichloroethane, hexachloroethane, E-1 ,2-dichloroethene, Z-1 ,2 dichloroethene and 1 ,1 -dichloroethene, or at least two additional compounds or at least three additional compounds or more; (ii) at least two of (a) HCC-230fa and one or more additional compound selected from CCI3CCI2CH2CI, CCI3CHCICH2CI, CCI3CH2CH2CI, CCI2=CH-CCI3, CCI3CH2CCI2CH2CCI3 and CCI3CH2CCI2CH2CCI3; (b) HCC-240fa and one or more additional compound selected from 1-chlorobutane; 1 ,2,3-trichloropropene (CHCI=CCI-CH2CI, HCO- 1240xd); HCO-1230xd (CHCI=CCI-CHCI2, 1 ,2,3,3-tetrachloropropene); 1 , 1 ,1,3- tetrachloropropane (CCI3-CH2-CH3, HCC-250fb); 1 ,4 dichlorobutane; 1 ,2-dichloro- cyclobutane, 1,1 ,4,4-tetrachlorobutadiene; 1 ,1, 3, 4 tetrachlorobutadiene; 1 , 1,1, 2,3- pentachloropropane (HCC-240db); 1,1 ,3,3-tetrachloro-1-propene (CCI2=CH-CHCI2); C5H7CI3 isomer(s) and C4H7CI3 isomer(s); and (c) HCC-250fb and one or more additional compound selected from CCI4; 1,1 ,1 -trichloropropane; dichlorobutane; 1 ,1,1,2-tetrachloroethane; CCI2=CH-CH2CI; C3H3CI3 isomers; C3H3CI5 and hexachloroethane; (iii) at least one of metals, metal salts, organic nitrile redox systems, phosphates, phosphines, metal phosphate complexes, metal phosphine complexes, and combinations thereof; and (iv) optionally byproducts including oligomers, dimers, telomers and other polymeric products.BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

[0013] The following detailed description of preferred embodiments of the present invention will be better understood when read in conjunction with the appended drawing. For the purposes of illustrating the invention, there is shown in the drawing an embodiment which is presently preferred. It is understood, however, that the invention is not limited to the precise arrangements and instrumentalities shown. In the drawings:

[0014] FIG. 1 depicts a treatment and recovery process according to an embodiment of the present invention; and

[0015] FIG. 2 depicts a treatment and recovery process according to another embodiment of the present invention.DETAILED DESCRIPTION OF THE INVENTION

[0016] The invention provides a process for recovering a (hydro)haloalkane and / or a (hydro)chloro(fluoro)carbon from a process stream, such as a purge stream or waste stream.

[0017] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

[0018] 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.

[0019] 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.

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

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

[0022] 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.”

[0023] 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.

[0024] The process of the present invention comprises recovery of (hydro)haloalkanes and / or (hydro)chloro(fluoro)carbons from a process stream, more preferably a waste stream or a purge stream. In some embodiments, the process stream comprises a composition comprising at least one of (hydro)haloalkanes, (hydro)chloro(fluoro)carbons, metals, metal salts, organic nitrile redox systems, phosphates, phosphines, metal phosphate complexes, metal phosphine complexes, and combinations thereof.

[0025] In one embodiment, at least one (hydro)haloalkane such as carbon tetrachloride is present in the process stream. In one embodiment, at least one (hydro)chloro(fluoro)carbon selected from HCC-230fa, HCC-240fa and HCC-250fbis / are present in the process stream. In one embodiment, the process stream further comprises metals (e.g., iron, copper and / or nickel), metal salts (e.g., copper salts, iron salts and / or nickel salts), organic nitrile redox systems (e.g., Cu / organic nitrile) phosphates, phosphines, metal phosphate complexes (e.g., organic phosphate ester complex), and / or metal phosphine complexes.

[0026] In some embodiments, the metals, metal salts, organic nitrile redox systems, phosphates, phosphines, metal phosphate complexes and / or metal phosphine complexes of the process stream may have been included in or generated by a catalyst system utilized in an underlying reaction or reactions to form the process stream. Similarly, in some embodiments, the (hydro)haloalkanes and (hydro)chloro(fluoro)carbon compounds present in the process stream may have been used in (i.e. , as a reactant) or produced by an underlying reaction or reactions to form the process stream. In some embodiments, the process stream further comprises oligomers as byproducts of the underlying reaction or reactions to form the process stream.

[0027] For example, in some embodiments, the process stream may be or have been generated as a result of an olefin insertion process comprising contacting a (hydro)haloalkane reactant with an olefin in the presence of a catalyst system to produce a haloalkane product.

[0028] In some embodiments, (hydro)haloalkanes useful as reactants in the insertion process are of the formula CnHmXp wherein n is an integer from 1 to 200, preferably from 1 to 20, most preferably from 1 to 5, X is a halogen such as fluorine, chlorine, bromine, iodine, or mixtures thereof, and m and p are each independently 0 to 2n+2 provided that m+p=2n+2. In one embodiment, the (hydro)haloalkane reactant is a C1 to C5 compound. In another embodiment, the (hydro)haloalkane reactant is a C1, C2 or C3 compound. In some embodiments, the (hydro)haloalkane reactant is selected from chlorocarbons, chlorofluorocarbons, hydrochlorocarbons and hydrochlorofluorocarbons.

[0029] In one embodiment, chlorocarbons are compounds having only carbon and chlorine, including but not limited to carbon tetrachloride (CCU), perchloroethane (CCI3CCI3), and the like. In one embodiment, the haloalkane reactant is carbontetrachloride, and an amount of unreacted carbon tetrachloride is present in the process stream, and more particularly the waste stream or purge stream.

[0030] In one embodiment, chlorofluorocarbons are compounds having carbon, hydrogen, fluorine, and chlorine, including but not limited to dichlorodifluoromethane (CCI2F2), trichlorofluoroethane (CCI3F), 1 ,1 ,1-trichloro-2,2,2-trifluoroethane (CFC- 113a, CF3CCI3), 1 ,1 ,2-trichloro-1 ,2,2- trifluoroethane (CFC-113, CF2CICFCI2), and the like. In one embodiment, the (hydro)haloalkane reactant is CFC-113a, and an amount of unreacted CFC-113a is present in the process stream, and more particularly the waste stream or purge stream.

[0031] In some embodiments, olefins useful in the reaction which produces the process stream are of the formula CnHyXz wherein n is an integer from 2 to 200, preferably from 2 to 20 and most preferably from 2 to 4, X is a halogen such as fluorine, chlorine, bromine, iodine, or mixtures thereof, and y and z are each independently 0 to 2n provided that y+z=2n.

[0032] In one embodiment, the olefin is an unsaturated hydrocarbon, with at least one double bond, optionally substituted with Cl, F or combinations thereof. In another embodiment, the olefin is selected from vinyl chloride (CH2=CHCI), 3,3,3- trifluoropropene (CF3CH=CH2), vinyl fluoride (CH2=CHF), vinylidene chloride (CH2=CCl2), vinylidene fluoride (CH2=CF2), allyl chloride (CH2=CHCH2CI), and the like. In some embodiments, the olefin is vinyl chloride, vinylidene chloride or 3,3,3- trifluoropropene.

[0033] In one embodiment, the haloalkane insertion product preferably comprises at least one (hydro)chloro(fluro)carbon, and more particularly a hydrochlorocarbon or hydrochlorofluorocarbon. More particularly, in some embodiments, the haloalkane insertion product 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.

[0034] In one embodiment, hydrochlorocarbons produced by the reaction of the haloalkane reactant and olefin are compounds having carbon, hydrogen, and chlorine, including but not limited to chloromethane (CH3CI), methylene chloride(CH2CI2), trichloromethane (CHCb), chloroethane (CH3CH2CI), dichloroethane (CH3CHCI2 or CH2CICH2CI), 1 ,1 ,1 ,3,3-pentachloropropane (HCC-240fa, CCI3CH2CHCI2), 1 ,1 ,1 ,3,3,3-hexachloropropane (HCC-230fa, CCI3CH2CCI3) and the like.

[0035] In one embodiment, hydrochlorofluorocarbons produced by the reaction of the haloalkane reactant and olefin are compounds having carbon, hydrogen, fluorine, and chlorine, including but not limited to chlorodifluoromethane (CHF2CI), dichlorofluoromethane (CHFCI2), chlorofluoromethane (CH2FCI), 2,2-dichloro-1 , 1 , 1 - trifluoroethane (CHCI2CF3), 1 ,2-dichloro-1 ,1 ,2-trifluoroethane (CHFCICCIF2), 2,2- dichloro-1 , 1 ,2-trifluoroethane (CHF2CFCI2), 2-chloro-1 ,1 , 1 ,2-tetrafluoroethane (CHFCICF3), 2,2,4,4-tetrachloro-1 ,1 ,1-trifluorobutane (CF3CCI2CH2CHCI2, HCFC- 343mfn), and the like.

[0036] In one embodiment, oligomers formed as byproducts of such reactions are represented by the formula CCl3(cH2-CRR’)nCI, where n > 2, and R and R’ are independently H, Cl, or both.

[0037] In some embodiments, the catalyst system of the underlying reaction which produces the process stream comprises, consists essentially of or consists of a catalyst and a co-catalyst.

[0038] In some embodiments, the catalysts useful in the present invention include metal ions and neutral metallic species. Suitable catalysts include, for example, but are not limited to, cuprous salts, organometallic cuprous compounds, metallic iron components, metallic nickel components and iron chlorides. Exemplary cuprous salts and organometallic cuprous compounds include, without limitation, cuprous chloride, cuprous bromide, cuprous cyanide, cuprous sulfate, and cuprous phenyl. Exemplary iron species include FeCh and FeC .

[0039] Co-catalysts useful in the present invention include, but are not limited to, organic ligands capable of forming a complex with the catalyst used and capable of bringing the catalyst into solution. In some embodiments, suitable ligands include organic amines, such as, without limitation, tert-butylamine, n-butylamine, secbutylamine, 2-propylamine, benzylamine, tri-n-butylamine, pyridine and combinations thereof. In one embodiment, the preferred organic amine is tert-butylamine.

[0040] Alternatively, the co-catalyst may be a nitrile including, without limitation, acetonitrile, propionitrile, n-butyronitrile, benzonitrile, phenylacetonitrile and combinations thereof. In one embodiment, the preferred nitrile is acetonitrile particularly where the catalyst is a copper containing material. In some embodiments, copper or copper halides may be used in combination with an organic nitrile compound, such as but not limited to acetonitrile or propionitrile.

[0041] As another alternative, the co-catalyst may be an amide including, without limitation, hexamethylphosphoramide (HMPA), dimethylformamide and combinations thereof. In one embodiment, hexamethylphosphoramide is the most preferred amide. Also suitable are combinations of amines, nitriles, amides, phosphines and phosphates.

[0042] The co-catalysts are chelating agents and may also serve as solvents. In some embodiments, a solvent may help dissolve the solid catalyst. When a solvent is used, it preferably serves as the co-catalyst. Useful solvents non-exclusively include nitrile compounds. The catalysts, co-catalysts and solvents useful in the present invention are commercially available.

[0043] In some embodiments, the co-catalyst is a phosphorous containing compound, such as a phosphine ligand, such as an alkylphosphine or arylphosphine, including but not limited to triphenyl phosphine, tributyl phosphine and the like. In one embodiment, the phosphine ligand comprises triphenylphosphine. In another embodiment, the phosphine ligand consists essentially of triphenylphosphine. In another embodiment, the phosphine ligand consists of triphenylphosphine.

[0044] In other embodiments, the catalyst may comprise a phosphorous containing compound, such as a phosphate, such as but not limited to, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, diethyl phosphate, dibutyl phosphate, monophenyl phosphate, monobutyl phosphate, dimethylphenyl phosphate, diethylphenyl phosphate, dimethyethyl phosphate and phenyl ethyl methyl phosphate.

[0045] In one embodiment, these catalysts and co-catalysts form a catalyst system used in the reaction which produces the process stream. In one embodiment of the catalyst system, the catalyst is CuCI and the co-catalyst is acetonitrile (CH3CN), tertbutylamine (t-Bu-NH2), n-butylamine (n-Bu-NH2), sec-butylamine (sec-Bu-NH2),benzyl-amine (benzyl-NH2), ethanol-amine, pyridine or tri-n-butylamine (n-BusN). In another embodiment of the catalyst system, the catalyst is iron powder, or iron wire, and / or ferric chloride and the co-catalyst is HMPA, tributylphosphite((BuO)3P), trichloroethylphosphite((CICH2CH2O)3P), triphenylphosphite((PhO)3P), tributylphosphate, or triphenylphosphate. In another embodiment of the catalyst system, the catalyst system is cuprous chloride / tert-butylamine, cuprous chloride / acetonitrile, iron powder / hexamethylphosphoramide or iron powder / tributylphosphate.

[0046] In one embodiment, the catalysts and co-catalysts of the insertion reaction are present in the process stream produced by the reaction and subsequently subjected to the recovery process of the present invention. In some embodiments, the process stream may be a waste stream or purge stream of a reaction conducted with or without a solvent, wherein the catalyst and co-catalyst are dissolved in the haloalkane reactant to form a homogenous mixture, followed by feeding the mixture to a reaction zone along with the olefin reactant.

[0047] More particularly, an olefin insertion process, e.g., to produce HCC-230fa, HCC-240fa and / or HCC-250fb, produces a product stream which may be subjected to distillation to separate the haloalkane product from the product stream as a useful starting material for the production of various types of fluorochemicals, such as HFCs and HFOs. The process thus further comprises separating the target hydrochloro(fluoro)carbon compound from the reaction product stream.

[0048] More particularly, the desired hydrochloro(fluoro)carbon product may be separated from any unreacted starting material, solvent, and any byproducts (e.g., higher molecular weight oligomers) by conventional techniques, such as distillation. The low boiling fraction will typically be the starting halogenated alkane and the alkene (olefin) which may be recovered and recycled to the reactor.

[0049] The higher boiling fraction will comprise significant amounts of unreacted starting materials, particularly the starting halogenated alkane such as carbon tetrachloride, the target hydrochloro(fluoro)carbon compound (e.g., HCC-230fa, HCC-240fa and / or HCC-250fb), the catalyst, the co-catalyst, the solvent and / or higher boiling (oligomer) byproducts. More particularly, the higher boiling fraction comprises at least one of haloalkanes, (hydro)chloro(fluoro)carbons, metals, metalsalts, organic nitrile redox systems, phosphates, phosphines, metal phosphate complexes, metal phosphine complexes, and the like. In one embodiment, the higher boiling fraction comprises at least one of carbon tetrachloride; at least one hydrochlorocarbon selected from HCC-230fa, HCC-240fa and HCC-250fb; metals (e.g., iron, copper and / or nickel); metal salts (e.g., copper salts, iron salts and / or nickel salts); organic nitrile redox systems (e.g., copper and organic nitrile redox system); phosphates; phosphines; metal phosphate complexes (e.g., organic phosphate ester complex); and / or metal phosphine complexes.

[0050] The higher boiling fraction is referred to herein as the process stream, the purge stream or a distillation heel, which is treated by the recovery process of the present invention.

[0051] In some embodiments, the purge stream is not sent to the recovery process of the present invention directly, but rather is collected and combined with purge streams of other catalyzed processes to make hydrochlorocarbons such as HCC- 230fa, HCC-240fa and HCC-250fb. For example, either onsite or at a remote facility, a plurality of such purge streams are combined to form a waste stream, which constitutes the process stream of the present invention for treatment by the recovery process. In such cases, the process stream (waste stream) comprises a composition comprising the starting halogenated alkane such as carbon tetrachloride, at least two hydrochloro(fluoro)carbon compounds (e.g., HCC-230fa, HCC-240fa and / or HCC-250fb), the catalyst, the co-catalyst, the solvent and / or higher boiling (oligomer) byproducts. More particularly, the process stream (waste stream) comprises at least one of haloalkanes, at least two (hydro)chloro(fluoro)carbons, metals, metal salts, organic nitrile redox systems, phosphates, phosphines, metal phosphate complexes, metal phosphine complexes, and the like. In one embodiment, the process stream (waste stream) comprises at least one of carbon tetrachloride; at least two hydrochlorocarbons selected from HCC-230fa, HCC-240fa and HCC-250fb; metals (e.g., iron, copper and / or nickel); metal salts (e.g., copper salts, iron salts and / or nickel salts); organic nitrile redox systems (e.g., copper / organic nitrile redox system), phosphates; phosphines; metal phosphate complexes (e.g., organic phosphate ester complex); and / or metal phosphine complexes.

[0052] In some embodiments, the process stream comprises a composition comprising:

[0053] (i) carbon tetrachloride and one or more additional compound selected from dichloromethane (CH2CI2), trichloroethylene (HCC-1120), tetrachloroethene (CC- 1110), chloroform (CHCI3), chloromethane (CH3CI), dichloroethane, trichloroethane, bromodichloromethane, bromochloroethane, dichloroethene, dichloroethane, 1,1,2- trichloroethane, 1,1,1 -trichloroethane, hexachloroethane, E-1 ,2-dichloroethene, Z-1 ,2 dichloroethene and 1 ,1 -dichloroethene, or at least two additional compounds or at least three additional compounds or more;

[0054] (ii) HCC-230fa and one or more additional compound selected from CCI3CCI2CH2CI, CCI3CHCICH2CI, CCI3CH2CH2CI, CCI2=CH-CCI3, CCI3CH2CCI2CH2CCI3 and CCI3CH2CCI2CH2CCI3;

[0055] (iii) at least one of metals, metal salts, organic nitrile redox systems, phosphates, phosphines, metal phosphate complexes, metal phosphine complexes, and combinations thereof; and

[0056] (iv) optionally byproducts including oligomers, dimers, telomers and other polymeric products.

[0057] In some embodiments, the process stream, and more particularly the waste stream, comprises a composition comprising HCC-230fa, CCI2=CH-CCI3 (HCO- 1220za), one or more metal salts such as FeC and / or FeCh, and HCI.

[0058] In some embodiments, the process stream comprises a composition comprising:

[0059] (i) carbon tetrachloride and one or more additional compound selected from dichloromethane (CH2CI2), trichloroethylene (HCC-1120), tetrachloroethene (CC- 1110), chloroform (CHCI3), chloromethane (CH3CI), dichloroethane, trichloroethane, bromodichloromethane, bromochloroethane, dichloroethene, dichloroethane, 1,1,2- trichloroethane, 1,1,1 -trichloroethane, hexachloroethane, E-1 ,2-dichloroethene, Z-1 ,2 dichloroethene and 1 ,1 -dichloroethene, or at least two additional compounds or at least three additional compounds or more;

[0060] (ii) HCC-240fa and one or more additional compound selected from 1- chlorobutane; 1 ,2,3-trichloropropene (CHCI=CCI-CH2CI, HCO-1240xd); HCO- 1230xd (CHCI=CCI-CHCI2, 1 ,2,3,3-tetrachloropropene); 1 ,1,1,3-tetrachloropropane (CCI3-CH2-CH3, HCC-250fb); 1,4 dichlorobutane; 1 ,2-dichloro-cyclobutane, 1 , 1,4,4- tetrachlorobutadiene; 1,1 , 3, 4 tetrachlorobutadiene; 1 ,1 ,1 ,2,3-pentachloropropane (HCC-240db); 1 ,1,3,3-tetrachloro-1-propene (CCI2=CH-CHCI2); C5H7CI3 isomer(s) and C4H7CI3 isomer(s);

[0061] (iii) at least one of metals, metal salts, organic nitrile redox systems, phosphates, phosphines, metal phosphate complexes, metal phosphine complexes, and combinations thereof; and

[0062] (iv) optionally byproducts including oligomers, dimers, telomers and other polymeric products.

[0063] In some embodiments, the process stream, and more particularly the waste stream, comprises a composition comprising HCC-240fa, CCI2=CH-CHCI2 (HCO- 1230za), one or more metal salts such as FeC and / or FeCh, and HCI.

[0064] In some embodiments, the process stream comprises a composition comprising:

[0065] (i) carbon tetrachloride and one or more additional compound selected from dichloromethane (CH2CI2), trichloroethylene (HCC-1120), tetrachloroethene (CC- 1110), chloroform (CHCI3), chloromethane (CH3CI), dichloroethane, trichloroethane, bromodichloromethane, bromochloroethane, dichloroethene, dichloroethane, 1,1,2- trichloroethane, 1,1,1 -trichloroethane, hexachloroethane, E-1 ,2-dichloroethene, Z-1 ,2 dichloroethene and 1 ,1 -dichloroethene, or at least two additional compounds or at least three additional compounds or more;

[0066] (ii) HCC-250fb and one or more additional compound selected from CCI4; 1 ,1,1 -trichloropropane; dichlorobutane; 1,1,1,2-tetrachloroethane; CCI2=CH-CH2CI; C3H3CI3 isomers; C3H3CI5 and hexachloroethane;

[0067] (iii) at least one of metals, metal salts, organic nitrile redox systems, phosphates, phosphines, metal phosphate complexes, metal phosphine complexes, and combinations thereof; and

[0068] (iv) optionally byproducts including oligomers, dimers, telomers and other polymeric products.

[0069] In some embodiments, the process stream, and more particularly the waste stream, comprises a composition comprising HCC-250fb, CCI2=CH-CH2CI (HCO- 1240za), one or more metal salts such as FeC and / or FeCh, and HCI.

[0070] In some embodiments, the process stream comprises a composition comprising:

[0071] (i) carbon tetrachloride and one or more additional compound selected from dichloromethane (CH2CI2), trichloroethylene (HCC-1120), tetrachloroethene (CC- 1110), chloroform (CHCI3), chloromethane (CH3CI), dichloroethane, trichloroethane, bromodichloromethane, bromochloroethane, dichloroethene, dichloroethane, 1,1,2- trichloroethane, 1,1,1 -trichloroethane, hexachloroethane, E-1 ,2-dichloroethene, Z-1 ,2 dichloroethene and 1 ,1 -dichloroethene, or at least two additional compounds or at least three additional compounds or more;

[0072] (ii) at least two of (a) HCC-230fa and one or more additional compound selected from CCI3CCI2CH2CI, CCI3CHCICH2CI, CCI3CH2CH2CI, CCI2=CH-CCI3, CCI3CH2CCI2CH2CCI3 and CCI3CH2CCI2CH2CCI3; (b) HCC-240fa and one or more additional compound selected from 1 -chlorobutane; 1,2,3-trichloropropene (CHCI=CCI-CH2CI, HCO-1240xd); HCO-1230xd (CHCI=CCI-CHCI2, 1 , 2,3,3- tetrachloropropene); 1 ,1 ,1,3-tetrachloropropane (CCI3-CH2-CH3, HCC-250fb); 1 ,4 dichlorobutane; 1 ,2-dichloro-cyclobutane, 1 ,1 ,4,4-tetrachlorobutadiene; 1 ,1, 3, 4 tetrachlorobutadiene; 1,1 ,1 ,2,3-pentachloropropane (HCC-240db); 1, 1,3,3- tetrachloro-1-propene (CCI2=CH-CHCI2); C5H7CI3 isomer(s) and C4H7CI3 isomer(s); and (c) HCC-250fb and one or more additional compound selected from CCI4; 1,1 ,1 -trichloropropane; dichlorobutane; 1,1,1,2-tetrachloroethane; CCI2=CH- CH2CI; C3H3CI3 isomers; C3H3CI5 and hexachloroethane;

[0073] (iii) at least one of metals, metal salts, organic nitrile redox systems, phosphates, phosphines, metal phosphate complexes, metal phosphine complexes, and combinations thereof; and

[0074] (iv) optionally byproducts including oligomers, dimers, telomers and other polymeric products.

[0075] In some embodiments, the process stream, and more particularly the waste stream, comprises a composition comprising at least two of (i) HCC-230fa and HCO- 1220za, (ii) HCC-240fa and HCO-1230za, and (iii) HCC-250fb and HCO-1240za, as well as one or more metal salts, such as FeCb and / or FeCh, and HCI.

[0076] In some embodiments, the presence of oligomers, dimers, telomers and other polymeric products in the process stream may be minimized or eliminated, for example, if the haloalkane product is produced according to the applicant’s own process for reduced telomer formation, as set forth in applicant’s U.S. Provisional Application under applicant’s docket no. TS0078-US01-PRV, the entire disclosure of which is incorporated herein by reference.

[0077] In some embodiments, any of the above-described process streams are a result of an olefin insertion process comprising contacting carbon tetrachloride with an olefin in the presence of a catalyst system to produce the haloalkane product.

[0078] In some embodiments, the catalyst or co-catalyst components contribute to corrosiveness of the process stream. More particularly, in some embodiments, the corrosivity of the process stream is due to metal salts, metal halides (for example CuCI2, CuCI, NiCI2, FeCI3, FeCI2) with organic nitrile or organic phosphorus containing compounds (for example, phosphate esters or phosphine), which produce free halides in an acidic environment in the presence of moisture, especially iron metal halides and organic phosphate ester complexes. Organic phosphate ester complexes produce free chloride ions in an acidic environment in the presence of moisture, and FeC is a Lewis acid that can catalyze dehydrochlorination of the (hydro)chloro(fluoro)carbon to release HCI. These substances result in the process stream being corrosive, and this corrosivity is increased at the elevated temperatures required for recovery processes, for instance, distillation separation.

[0079] The process of the present invention reduces or neutralizes the corrosivity of the process stream by use of a treatment reagent, and enables recovery of the unreacted haloalkane starting material (e.g., CCL) and the haloalkane reaction product (e.g., HCC-240fa, HCC-230fa or HFC-250fb).

[0080] More particularly, referring to FIGs. 1 and 2, the process of the present invention comprises optional measurement of the metals concentration of the process stream, such as, for example, the Fe concentration in the stream. In someembodiments, if the metals concentration is above a set threshold (e.g., 1000 ppm), the process stream is then subjected to treatment by a treatment reagent. The metals concentrations may be measured and determined by any suitable methods or equipment known in the art. For example, the metals concentration may be measured, online or offline, by inductively coupled plasma mass spectroscopy (ICP- MS).

[0081] More particularly, the process comprises contacting or adding an effective amount of a treatment reagent with or to the composition of the process stream. The treatment reagent is preferably selected from an alkaline phosphate, an alkaline earth phosphate, an alkaline carbonate, alkaline earth carbonate, an alkaline bicarbonate, an alkaline earth bicarbonate, an alkaline silicate, an alkaline earth silicate, and combinations thereof. In some embodiments, the treatment reagent is preferably an alkaline phosphate, such as but not limited to trisodium phosphate, sodium monohydrogen phosphate, and / or sodium dihydrogenphosphate.

[0082] It will be understood by those skilled in the art that the treatment reagent may be any material selected from an alkaline phosphate, an alkaline earth phosphate, an alkaline carbonate, alkaline earth carbonate, an alkaline bicarbonate, an alkaline earth bicarbonate, an alkaline silicate, an alkaline earth silicate, and combinations thereof, and may be selected based upon the composition of the process stream and more particularly based upon the metals, metal salts, organic nitrile redox systems, phosphates, phosphines, metal phosphate complexes and / or metal phosphine complexes contained in the process stream, since these are the components believed to cause the corrosivity of the process stream.

[0083] As used herein, an “effective amount” of the treatment reagent means an amount that is sufficient to reduce the metals (e.g., Fe) concentration in the process stream to be below about 1000 ppm, preferably below about 500 ppm, more preferably below about 100 ppm.

[0084] In some embodiments, the treatment reagent may be in a solid form or may be an aqueous solution, preferably a concentrated aqueous solution.

[0085] In some embodiments, the process optionally comprises adding a diluting solvent to the process stream, either before or after introduction of the treatment reagent (not shown in FIGs 1 and 2.). Examples of the diluting solvent include, butare not limited to, (hydro)chloro(fluoro)carbons, such as CFC-113a, CCbH, CFC- 113, trichloroethylene, tetrachloroethylene, CCk, HCC-240fa, HCC-250fb and HCC- 230fa. Preferably, the solvent is one of the material used to make the final product, such as CCk, HCC-240fa, HCC-250fb or HCC-230fa.

[0086] In some embodiments, the process comprises passing the process stream through a solids filter before introduction of the treatment reagent for contact or mixing with the process stream (not shown), for removal of waste solids from the process stream. The waste solids may then be sent for destruction as appropriate.

[0087] The treatment reagent reacts with the metals, metal salts, organic nitrile redox systems, phosphates, phosphines, metal phosphate complexes and / or metal phosphine complexes to form insoluble metal phosphates, leading to a neutral or basic environment which does not contribute to corrosivity of the process stream. The insoluble metal phosphate is preferably a solid precipitate. Preferably, a pH of the mixture of the process stream and treatment reagent is maintained to be equal to or greater than 7.

[0088] In some embodiments, as shown in FIGs. 1 and 2, the process further comprises further purification of the treated process stream (treated composition) for solids separation. More particularly, the treated process stream can be further purified, for example by filtration, settling, membrane separation, porous metal separation, centrifuge and the like of the process stream to separate the metal phosphate salts or metal phosphine salts from the treated composition. The filtered waste solids may be sent for destruction as appropriate.

[0089] In some embodiments, as shown in FIGs. 1 and 2, the process further comprises drying of the filtrate, such as by at least one of molecular sieves, zeolites, activated alumina, and the like.

[0090] In some embodiments, as shown in FIGs. 1 and 2, the process further comprises separation of the filtrate, such as by distillation or fractionation, to recover the desired compounds, such as the unreacted starting material and / or the haloalkane product. Any waste (liquid or organic) from the separation process may be sent for destruction as appropriate.

[0091] In some embodiments, as shown in FIG. 2, where the process involves wet treatment of the process stream, the process may include a step of phase separation after the solids separation and prior to drying. The phase separation may be done by, for example, decantation, to separate the aqueous and organic phases. Any aqueous waste from the phase separation process may be sent for destruction as appropriate. Optionally, the separated aqueous waste could be recycled in the process by adding more treatment reagent to it. Any organic waste from the downstream separation process may also be sent for destruction as appropriate.

[0092] In one embodiment, a recovered composition obtained by the process of the present invention comprises at least one (hydro)chloro(fluoro)carbon.

[0093] In one embodiment, a recovered composition obtained by the process of the present invention comprises at least one of carbon tetrachloride, HCC-230fa, HCC-240fa and / or HCC-250fb and combinations thereof.

[0094] In one embodiment, a recovered composition obtained by the process of the present invention comprises at least one of (i) carbon tetrachloride and one or more additional compound selected from dichloromethane (CH2CI2), trichloroethylene (HCC-1120), tetrachloroethene (CC-1110), chloroform (CHCb), chloromethane (CH3CI), dichloroethane, trichloroethane, bromodichloromethane, bromochloroethane, dichloroethene, dichloroethane, 1,1,2-trichloroethane, 1 ,1 ,1- trichloroethane, hexachloroethane, E-1,2-dichloroethene, Z-1,2 dichloroethene and 1 ,1 -dichloroethene, or at least two additional compounds or at least three additional compounds or more; (ii) HCC-230fa and one or more additional compound selected from CCI3CCI2CH2CI, CCI3CHCICH2CI, CCI3CH2CH2CI, CCI2=CH-CCI3, CCI3CH2CCI2CH2CCI3 and CCI3CH2CCI2CH2CCI3; (iii) HCC-240fa and one or more additional compound selected from 1 -chlorobutane; 1,2,3-trichloropropene (CHCI=CCI-CH2CI, HCO-1240xd); HCO-1230xd (CHCI=CCI-CHCI2, 1 , 2,3,3- tetrachloropropene); 1 ,1 ,1,3-tetrachloropropane (CCI3-CH2-CH3, HCC-250fb); 1 ,4 dichlorobutane; 1 ,2-dichloro-cyclobutane, 1 ,1 ,4,4-tetrachlorobutadiene; 1 ,1, 3, 4 tetrachlorobutadiene; 1,1 ,1 ,2,3-pentachloropropane (HCC-240db); 1, 1,3,3- tetrachloro-1-propene (CCI2=CH-CHCI2); C5H7CI3 isomer(s) and C4H7CI3 isomer(s); and (iv) HCC-250fb and one or more additional compound selected fromCCI4; 1,1 ,1 -trichloropropane; dichlorobutane; 1,1,1,2-tetrachloroethane; CCI2=CH- CH2CI; C3H3CI3 isomers; C3H3CI5 and hexachloroethane.

[0095] In some embodiments, the process may comprise a further separation (e.g., further distillation and possibly decantation if an aqueous phase is present) to separate the unreacted starting material (e.g., carbon tetrachloride and the one or more additional compounds) and the haloalkane product (e.g., HCC-230fa and the one or more additional compounds; HCC-240fa and the one or more additional compounds; HCC-250fb and the one or more additional compounds; combinations thereof).

[0096] It will be understood by those skilled in the art that the recovery process of the present invention may be carried out as a stand-alone process on any composition or process stream exhibiting corrosivity due to the presence of, e.g., metals, metal salts, organic nitrile redox systems, phosphates, phosphines, metal phosphate complexes and / or metal phosphine complexes, or may be performed downstream of an olefin insertion process to produce, e.g., HCC-230fa, HCC-240fa and / or HCC-250fb, such as the olefin insertion process described herein. In some embodiments, the recovery process of the present invention may be carried out either onsite (e.g., at the same facility where the process stream is generated) in an integrated manner, such that the distillation heel of the purification process would be sent to the (hydro)chloro(fluoro)carbon recovery system of the present invention. In some embodiments, the recovery process of the present invention may be carried out at a second facility remote from or proximate to the first facility (e.g., a chlorocarbon production site or waste treatment facility).

[0097] The recovery process of the present invention can also be carried out as part of the purification process during hydrochloro(fluoro)carbon production, such as an olefin insertion process to produce, e.g., HCC-230fa, HCC-240fa and / or HCC- 250fb, such as the olefin insertion process described herein.

[0098] For example, in some embodiments, where the recovery process of the present invention is carried out downstream of a process to make HCC-230fa, HCC- 240fa or HCC-250fb, the recovered and purified starting material (carbon tetrachloride) may be recycled to the olefin insertion process, and the recovered and purified hydrochlorocarbon (HCC-230fa, HCC-240fa or HCC-250fb) may be sent,directly or indirectly, to a downstream process where the hydrochlorocarbon is used as a starting material for a further reaction.

[0099] In some embodiments, where the recovery process is a stand-alone process, the recovered and purified starting material (carbon tetrachloride) and the recovered and purified hydrochlorocarbon (HCC-230fa, HCC-240fa or HCC-250fb) may be stored in separate feed or storage tanks, for any appropriate subsequent use.

[0100] In some embodiments, the process stream (i.e. , the waste stream or purge stream) is not treated by the recovery process of the present invention, but rather is incinerated, onsite or offsite, optionally with HCI, HF and / or CO2 recovery.

[0101] Without further elaboration, it is believed that one skilled in the art can, using the description herein, utilize the present invention to its fullest extent. The following specific embodiments are, therefore, to be construed as merely illustrative, and do not constrain the remainder of the disclosure in any way whatsoever.

[0102] 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

[0103] A waste stream from a process of making HCC-240fa contains HCC-240fa (43%), HCC-240db (0.5%), 230fa (4%), CCI3(CH2CHCI)2CI (30%), tributyl phosphate (10%) plus other (hydro)chlorinated carbons. The waste stream is analyzed by ICP, and found to contain 7170 ppm Fe. The pH of the organic is 1. 500 grams of the waste stream is treated with 3.7 g of trisodium phosphate according to the inventive process. A solid (iron phosphate) is formed, and is removed by filtration The pH of the organic is 8. Re-analysis by ICP shows Fe content is below 5 ppm.Example 2

[0104] A waste stream from a process of making HCC-240fa contains HCC-240fa (43%), HCC-240db (0.5%), 230fa (4%), CCI3(CH2CHCI)2CI (30%), tributyl phosphate (10%) plus other (hydro)chlorinated carbons. The waste stream is analyzed by ICP, and found to contain 7170 ppm Fe. The pH of the organic is 1. 500 grams of the waste stream is treated with 5 g of disodium phosphate. A solid (iron phosphate) is formed, and is removed by filtration. The pH of the organic is 8. Reanalysis by ICP shows Fe content is below 5 ppm.OTHER EMBODIMENTS

[0105] Embodiment 1. A recovery process comprising: contacting or mixing an effective amount of a treatment reagent with a composition to form a treated composition, the composition comprising at least one member selected from the group consisting of at least one (hydro)haloalkane, at least one (hydro)chloro(fluoro)carbon, at least one metal, at least one metal salt, at least one organic nitrile redox system, at least one phosphate, at least one phosphine, at least one metal phosphate complex, at least one metal phosphine complex, and combinations thereof; and subjecting the treated composition to separation, such as distillation or fractionation, to recover the at least one (hydro)haloalkane and the at least one (hydro)chloro(fluoro)carbon.

[0106] Embodiment 2. The recovery process of Embodiment 1 , wherein the effective amount is an amount sufficient to reduce a metals concentration of the composition to be below about 1000 ppm, preferably below about 500 ppm, more preferably below about 100 ppm.

[0107] Embodiment 3. The recovery process of any of Embodiments 1 to 2, wherein the treatment reagent is a member selected from the group consisting of an alkaline phosphate, an alkaline earth phosphate, an alkaline carbonate, alkaline earth carbonate, an alkaline bicarbonate, an alkaline earth bicarbonate, an alkaline silicate, an alkaline earth silicate, and combinations thereof, preferably an alkaline phosphate, more preferably trisodium phosphate, sodium monohydrogen phosphate, and / or sodium dihydrogenphosphate.

[0108] Embodiment 4. The recovery process of any of Embodiments 1 to 3, wherein the treatment reagent reacts with at least one of the following: the at least one metal, the at least one metal salt, the at least one organic nitrile redox system, the at least one phosphate, the at least one phosphine, the at least one metal phosphate complex, and / or the at least one metal phosphine complex, and forms an insoluble metal phosphate.

[0109] Embodiment 5. The recovery process of any of Embodiments 1 to 4, wherein the treatment reagent increases a pH of the composition to be 7 or higher.

[0110] Embodiment 6. The recovery process of any of Embodiments 1 to 5, wherein the composition is a process stream or a mixture of process steams.

[0111] Embodiment ?. The recovery process of Embodiment 6, wherein each process stream is a purge stream of a production process.

[0112] Embodiment 8. The recovery process of Embodiment 7, wherein the purge stream is generated from an upstream process comprising contacting the at least one (hydro)haloalkane with an olefin in the presence of a catalyst system to produce the at least one (hydro)chloro(fluoro)carbon.

[0113] Embodiment 9. The recovery process of Embodiment 8, wherein the recovered at least one haloalkane is recycled to the upstream process.

[0114] Embodiment 10. The recovery process of Embodiment 8 or Embodiment 9, wherein the catalyst system of the upstream process comprises at least one member selected from the group consisting of the at least one metal, the at least one metal salt, the at least one organic nitrile redox system, the at least one phosphate, the at least one phosphine, and the at least one metal phosphate complex.

[0115] Embodiment 11. The recovery process of any of Embodiments 1 to 10, wherein the at least one (hydro)chloro(fluoro)carbon is 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) CHxCh-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 , and more preferably is selected from the group consisting of 1 ,1 ,1 ,3-tetrachloropropane (CCI3-CH2-CH3, HCC-250fb),1 ,1 ,1 ,3,3-pentachloropropane (HCC-240fa, CCI3CH2CHCI2), 1 ,1 , 1 ,3, 3, 3- hexachloropropane (HCC-230fa, CCI3CH2CCI3), and combinations thereof.

[0116] Embodiment 12. The recovery process any of Embodiments 1 to 11 , wherein the at least one (hydro)haloalkane comprises CnHmXp wherein n is an integer from 1 to 200, preferably from 1 to 20, most preferably from 1 to 5, X is a halogen such as fluorine, chlorine, bromine, iodine, or mixtures thereof, and m and p are each independently 0 to 2n+2 provided that m+p=2n+2, and more preferably comprises carbon tetrachloride.

[0117] Embodiment 13. The recovery process of any of Embodiments 1 to 12, wherein the composition comprises:(i) carbon tetrachloride and one or more additional compound selected from dichloromethane (CH2CI2), trichloroethylene (HCC-1120), tetrachloroethene (CC-1110), chloroform (CHCI3), chloromethane (CH3CI), dichloroethane, trichloroethane, bromodichloromethane, bromochloroethane, dichloroethene, dichloroethane, 1 ,1 ,2-trichloroethane, 1 ,1 ,1 -trichloroethane, hexachloroethane, E-1 ,2-dichloroethene, Z-1 ,2 dichloroethene and 1 ,1- dichloroethene, or at least two additional compounds or at least three additional compounds or more;(ii) HCC-230fa and one or more additional compound selected from CCI3CCI2CH2CI, CCI3CHCICH2CI, CCI3CH2CH2CI, CCI2=CH-CCI3, CCI3CH2CCI2CH2CCI3 and CCI3CH2CCI2CH2CCI3;(iii) at least one of metals, metal salts, organic nitrile redox systems, phosphates, phosphines, metal phosphate complexes, metal phosphine complexes, and combinations thereof; and(iv) optionally byproducts including oligomers, dimers, telomers and other polymeric products.

[0118] Embodiment 14. The recovery process of any of Embodiments 1 to 12, wherein the composition comprises:(i) carbon tetrachloride and one or more additional compound selected from dichloromethane (CH2CI2), trichloroethylene (HCC-1120), tetrachloroethene (CC-1110), chloroform (CHCI3), chloromethane (CH3CI), dichloroethane,trichloroethane, bromodichloromethane, bromochloroethane, dichloroethene, dichloroethane, 1 ,1 ,2-trichloroethane, 1 ,1 ,1 -trichloroethane, hexachloroethane, E-1 ,2-dichloroethene, Z-1 ,2 dichloroethene and 1 ,1- dichloroethene, or at least two additional compounds or at least three additional compounds or more;(ii) HCC-240fa and one or more additional compound selected from 1- chlorobutane; 1 ,2,3-trichloropropene (CHCI=CCI-CH2CI, HCO-1240xd); HCO- 1230xd (CHCI=CCI-CHCI2, 1 ,2,3,3-tetrachloropropene); 1 , 1 ,1 ,3- tetrachloropropane (CCI3-CH2-CH3, HCC-250fb); 1 ,4 dichlorobutane; 1 ,2- dichloro-cyclobutane, 1 ,1 ,4,4-tetrachlorobutadiene; 1 ,1 , 3, 4 tetrachlorobutadiene; 1 ,1 ,1 ,2,3-pentachloropropane (HCC-240db); 1 , 1 ,3,3- tetrachloro-1 -propene (CCI2=CH-CHCI2); C5H7CI3 isomer(s) and C4H7CI3 isomer(s);(iii) at least one of metals, metal salts, organic nitrile redox systems, phosphates, phosphines, metal phosphate complexes, metal phosphine complexes, and combinations thereof; and(iv) optionally byproducts including oligomers, dimers, telomers and other polymeric products.

[0119] Embodiment 15. The recovery process of any of Embodiments 1 to 12, wherein the composition comprises:(i) carbon tetrachloride and one or more additional compound selected from dichloromethane (CH2CI2), trichloroethylene (HCC-1120), tetrachloroethene (CC-1110), chloroform (CHCI3), chloromethane (CH3CI), dichloroethane, trichloroethane, bromodichloromethane, bromochloroethane, dichloroethene, dichloroethane, 1 ,1 ,2-trichloroethane, 1 ,1 ,1 -trichloroethane, hexachloroethane, E-1 ,2-dichloroethene, Z-1 ,2 dichloroethene and 1 ,1- dichloroethene, or at least two additional compounds or at least three additional compounds or more;(ii) HCC-250fb and one or more additional compound selected from CCI4; 1 ,1 ,1- trichloropropane; dichlorobutane; 1 ,1 ,1 ,2-tetrachloroethane; CCI2=CH-CH2CI; C3H3CI3 isomers; C3H3CI5 and hexachloroethane;(iii) at least one of metals, metal salts, organic nitrile redox systems, phosphates, phosphines, metal phosphate complexes, metal phosphine complexes, and combinations thereof; and(iv) optionally byproducts including oligomers, dimers, telomers and other polymeric products.

[0120] Embodiment 16. The recovery process of any of Embodiments 1 to 12, wherein the composition comprises:(i) carbon tetrachloride and one or more additional compound selected from dichloromethane (CH2CI2), trichloroethylene (HCC-1120), tetrachloroethene (CC-1110), chloroform (CHCI3), chloromethane (CH3CI), dichloroethane, trichloroethane, bromodichloromethane, bromochloroethane, dichloroethene, dichloroethane, 1 ,1 ,2-trichloroethane, 1 ,1 ,1 -trichloroethane, hexachloroethane, E-1 ,2-dichloroethene, Z-1 ,2 dichloroethene and 1 ,1- dichloroethene, or at least two additional compounds or at least three additional compounds or more;(ii) at least two of (a) HCC-230fa and one or more additional compound selected from CCI3CCI2CH2CI, CCI3CHCICH2CI, CCI3CH2CH2CI, CCI2=CH-CCI3, CCI3CH2CCI2CH2CCI3 and CCI3CH2CCI2CH2CCI3; (b) HCC-240fa and one or more additional compound selected from 1 -chlorobutane; 1 ,2,3- trichloropropene (CHCI=CCI-CH2CI, HCO-1240xd); HCO-1230xd (CHCI=CCI- CHCI2, 1 ,2,3,3-tetrachloropropene); 1 ,1 ,1 ,3-tetrachloropropane (CCI3-CH2- CH3, HCC-250fb); 1 ,4 dichlorobutane; 1 ,2-dichloro-cyclobutane, 1 , 1 ,4,4- tetrachlorobutadiene; 1 ,1 , 3, 4 tetrachlorobutadiene; 1 , 1 ,1 , 2,3- pentachloropropane (HCC-240db); 1 ,1 ,3,3-tetrachloro-1-propene (CCI2=CH- CHCI2); C5H7CI3 isomer(s) and C4H7CI3 isomer(s); and (c) HCC-250fb and one or more additional compound selected from CCI4; 1 ,1 ,1 -trichloropropane; dichlorobutane; 1 ,1 ,1 ,2-tetrachloroethane; CCI2=CH-CH2CI; C3H3CI3 isomers; C3H3CI5 and hexachloroethane;(iii) at least one of metals, metal salts, organic nitrile redox systems, phosphates, phosphines, metal phosphate complexes, metal phosphine complexes, and combinations thereof; and(iv) optionally byproducts including oligomers, dimers, telomers and other polymeric products.

[0121] Embodiment 17. The recovery process of any of Embodiments 1 to 12, wherein the composition comprises HCC-230fa, HCO-1220za, one or more metal salts such as FeC and / or FeCh, and HCI.

[0122] Embodiment 18. The recovery process of any of Embodiments 1 to 12, wherein the composition comprises HCC-240fa, HCO-1230za, one or more metal salts such as FeC and / or FeCh, and HCI.

[0123] Embodiment 19. The recovery process of any of Embodiments 1 to 12, wherein the composition comprises HCC-250fb, HCO-1240za, one or more metal salts such as FeC and / or FeCh, and HCI.

[0124] Embodiment 20. The recovery process of any of Embodiments 1 to 12, wherein the composition comprises at least two of (i) HCC-230fa and HCO-1220za, (ii) HCC-240fa and HCO-1230za, and (iii) HCC-250fb and HCO-1240za; one or more metal salts, such as FeC and / or FeCh; and HCI.

[0125] While the invention has been described with reference to one or more embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. In addition, all numerical values identified in the detailed description shall be interpreted as though the precise and approximate values are both expressly identified.

Claims

CLAIMSWhat is claimed is:

1. A recovery process comprising: contacting or mixing an effective amount of a treatment reagent with a composition to form a treated composition, the composition comprising at least one member selected from the group consisting of at least one (hydro)haloalkane, at least one (hydro)chloro(fluoro)carbon, at least one metal, at least one metal salt, at least one organic nitrile redox system, at least one phosphate, at least one phosphine, at least one metal phosphate complex, at least one metal phosphine complex, and combinations thereof; and subjecting the treated composition to separation, such as distillation or fractionation, to recover the at least one (hydro)haloalkane and the at least one (hydro)chloro(fluoro)carbon.

2. The recovery process of claim 1, wherein the effective amount is an amount sufficient to reduce a metals concentration of the composition to be below about 1000 ppm, preferably below about 500 ppm, more preferably below about 100 ppm.

3. The recovery process of any of claims 1 to 2, wherein the treatment reagent is a member selected from the group consisting of an alkaline phosphate, an alkaline earth phosphate, an alkaline carbonate, alkaline earth carbonate, an alkaline bicarbonate, an alkaline earth bicarbonate, an alkaline silicate, an alkaline earth silicate, and combinations thereof, preferably an alkaline phosphate, more preferably trisodium phosphate, sodium monohydrogen phosphate, and / or sodium dihydrogenphosphate.

4. The recovery process of any of claims 1 to 3, wherein the treatment reagent reacts with at least one of the following: the at least one metal, the at least one metal salt, the at least one organic nitrile redox system, the at least one phosphate, the at least one phosphine, the at least one metal phosphate complex, and / or the at least one metal phosphine complex, and forms an insoluble metal phosphate.

5. The recovery process of any of claims 1 to 4, wherein the treatment reagent increases a pH of the composition to be 7 or higher.

6. The recovery process of any of claims 1 to 5, wherein the composition is a process stream or a mixture of process steams.

7. The recovery process of claim 6, wherein each process stream is a purge stream of a production process.

8. The recovery process of claim 7, wherein the purge stream is generated from an upstream process comprising contacting the at least one (hydro)haloalkane with an olefin in the presence of a catalyst system to produce the at least one (hydro)chloro(fluoro)carbon.

9. The recovery process of claim 8, wherein the recovered at least one haloalkane is recycled to the upstream process.

10. The recovery process of claim 8 or claim 9, wherein the catalyst system of the upstream process comprises at least one member selected from the group consisting of the at least one metal, the at least one metal salt, the at least one organic nitrile redox system, the at least one phosphate, the at least one phosphine, and the at least one metal phosphate complex.

11. The recovery process of any of claims 1 to 10, wherein the at least one (hydro)chloro(fluoro)carbon is 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 , and more preferably is selected from the group consisting of 1 ,1 ,1 ,3-tetrachloropropane (CCI3-CH2-CH3, HCC- 250fb), 1 ,1 ,1 ,3,3-pentachloropropane (HCC-240fa, CCI3CH2CHCI2), 1 , 1 ,1 , 3,3,3- hexachloropropane (HCC-230fa, CCI3CH2CCI3), and combinations thereof.

12. The recovery process any of claims 1 to 11 , wherein the at least one (hydro)haloalkane comprises CnHmXp wherein n is an integer from 1 to 200, preferably from 1 to 20, most preferably from 1 to 5, X is a halogen such as fluorine, chlorine, bromine, iodine, or mixtures thereof, and m and p are eachindependently 0 to 2n+2 provided that m+p=2n+2, and more preferably comprises carbon tetrachloride.

13. The recovery process of any of claims 1 to 12, wherein the composition comprises:(i) carbon tetrachloride and one or more additional compound selected from the group consisting of dichloromethane (CH2CI2), trichloroethylene (HCC-1120), tetrachloroethene (CC-1110), chloroform (CHCI3), chloromethane (CH3CI), dichloroethane, trichloroethane, bromodichloromethane, bromochloroethane, dichloroethene, dichloroethane, 1 ,1 ,2-trichloroethane, 1 ,1 ,1 -trichloroethane, hexachloroethane, E-1 ,2-dichloroethene, Z-1 ,2 dichloroethene and 1 ,1- dichloroethene, or at least two additional compounds or at least three additional compounds or more;(ii) HCC-230fa and one or more additional compound selected from the group consisting of CCI3CCI2CH2CI, CCI3CHCICH2CI, CCI3CH2CH2CI, CCI2=CH-CCI3, CCI3CH2CCI2CH2CCI3 and CCI3CH2CCI2CH2CCI3;(iii) at least one component selected from the group consisting of metals, metal salts, organic nitrile redox systems, phosphates, phosphines, metal phosphate complexes, metal phosphine complexes, and combinations thereof; and(iv) optionally byproducts including oligomers, dimers, telomers and other polymeric products.

14. The recovery process of any of claims 1 to 12, wherein the composition comprises:(i) carbon tetrachloride and one or more additional compound selected from the group consisting of dichloromethane (CH2CI2), trichloroethylene (HCC-1120), tetrachloroethene (CC-1110), chloroform (CHCI3), chloromethane (CH3CI), dichloroethane, trichloroethane, bromodichloromethane, bromochloroethane, dichloroethene, dichloroethane, 1 ,1 ,2-trichloroethane, 1 ,1 ,1 -trichloroethane, hexachloroethane, E-1 ,2-dichloroethene, Z-1 ,2 dichloroethene and 1 ,1-dichloroethene, or at least two additional compounds or at least three additional compounds or more;(ii) HCC-240fa and one or more additional compound selected from the group consisting of 1 -chlorobutane; 1 ,2,3-trichloropropene (CHCI=CCI- CH2CI, HCO-1240xd); HCO-1230xd (CHCI=CCI-CHCI2, 1, 2,3,3- tetrachloropropene); 1 ,1,1,3-tetrachloropropane (CCI3-CH2-CH3, HCC- 250fb); 1,4 dichlorobutane; 1,2-dichloro-cyclobutane, 1 , 1 ,4,4- tetrachlorobutadiene; 1 ,1 , 3, 4 tetrachlorobutadiene; 1, 1 ,1 , 2,3- pentachloropropane (HCC-240db); 1 ,1, 3, 3-tetrachloro-1 -propene (CCI2=CH-CHCI2); C5H7CI3 isomer(s) and C4H7CI3 isomer(s);(iii) at least one component selected from the group consisting of metals, metal salts, organic nitrile redox systems, phosphates, phosphines, metal phosphate complexes, metal phosphine complexes, and combinations thereof; and(iv) optionally byproducts including oligomers, dimers, telomers and other polymeric products.

15. The recovery process of any of claims 1 to 12, wherein the composition comprises:(i) carbon tetrachloride and one or more additional compound selected from the group consisting of dichloromethane (CH2CI2), trichloroethylene (HCC-1120), tetrachloroethene (CC-1110), chloroform (CHCI3), chloromethane (CH3CI), dichloroethane, trichloroethane, bromodichloromethane, bromochloroethane, dichloroethene, dichloroethane, 1 ,1,2-trichloroethane, 1,1,1 -trichloroethane, hexachloroethane, E-1,2-dichloroethene, Z-1,2 dichloroethene and 1 ,1- dichloroethene, or at least two additional compounds or at least three additional compounds or more;(ii) HCC-250fb and one or more additional compound selected from the group consisting of CCI4; 1,1,1 -trichloropropane; dichlorobutane; 1, 1,1 ,2- tetrachloroethane; CCI2=CH-CH2CI; C3H3CI3 isomers; C3H3CI5 and hexachloroethane;(iii) at least one component selected from the group consisting of metals, metal salts, organic nitrile redox systems, phosphates, phosphines, metal phosphate complexes, metal phosphine complexes, and combinations thereof; and(iv) optionally byproducts including oligomers, dimers, telomers and other polymeric products.

16. The recovery process of any of claims 1 to 12, wherein the composition comprises:(i) carbon tetrachloride and one or more additional compound selected from the group consisting of dichloromethane (CH2CI2), trichloroethylene (HCC-1120), tetrachloroethene (CC-1110), chloroform (CHCI3), chloromethane (CH3CI), dichloroethane, trichloroethane, bromodichloromethane, bromochloroethane, dichloroethene, dichloroethane, 1 ,1,2-trichloroethane, 1,1,1 -trichloroethane, hexachloroethane, E-1,2-dichloroethene, Z-1,2 dichloroethene and 1 ,1- dichloroethene, or at least two additional compounds or at least three additional compounds or more;(ii) at least two of (a) HCC-230fa and one or more additional compound selected from the group consisting of CCI3CCI2CH2CI, CCI3CHCICH2CI, CCI3CH2CH2CI, CCI2=CH-CCI3, CCI3CH2CCI2CH2CCI3 and CCI3CH2CCI2CH2CCI3; (b) HCC-240fa and one or more additional compound selected from the group consisting of 1 -chlorobutane; 1 ,2,3-trichloropropene (CHCI=CCI-CH2CI, HCO- 1240xd); HCO-1230xd (CHCI=CCI-CHCI2, 1 ,2,3,3-tetrachloropropene); 1,1 ,1,3-tetrachloropropane (CCI3-CH2-CH3, HCC-250fb); 1 ,4 dichlorobutane; 1 ,2-dichloro-cyclobutane, 1 , 1 ,4,4-tetrachlorobutadiene;1,1 , 3, 4 tetrachlorobutadiene; 1,1 ,1 ,2,3-pentachloropropane (HCC- 240db); 1 ,1, 3, 3-tetrachloro-1 -propene (CCI2=CH-CHCI2); C5H7CI3 isomer(s) and C4H7CI3 isomer(s); and (c) HCC-250fb and one or more additional compound selected from the group consisting of CCI4; 1,1 ,1- trichloropropane; dichlorobutane; 1 ,1,1,2-tetrachloroethane; CCI2=CH- CH2CI; C3H3CI3 isomers; C3H3CI5 and hexachloroethane;(iii) at least one component selected from the group consisting of metals, metal salts, organic nitrile redox systems, phosphates, phosphines, metal phosphate complexes, metal phosphine complexes, and combinations thereof; and(iv) optionally byproducts including oligomers, dimers, telomers and other polymeric products.

17. The recovery process of any of claims 1 to 12, wherein the composition comprises HCC-230fa, HCO-1220za, one or more metal salts such as FeC and / or FeCh, and HCI.

18. The recovery process of any of claims 1 to 12, wherein the composition comprises HCC-240fa, HCO-1230za, one or more metal salts such as FeC and / or FeCh, and HCI.

19. The recovery process of any of claims 1 to 12, wherein the composition comprises HCC-250fb, HCO-1240za, one or more metal salts such as FeC and / or FeCh, and HCI.

20. The recovery process of any of claims 1 to 12, wherein the composition comprises at least two of (i) HCC-230fa and HCO-1220za, (ii) HCC-240fa and HCO-1230za, and (iii) HCC-250fb and HCO-1240za; one or more metal salts, such as FeCh and / or FeCh; and HCI.

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