Co-production of 1,1,1-trifluoropropene (1243ZF) and E-1,1,1,4,4,4-hexafluoro-2-butene (E-1336MZZ)

Abstract

The present invention relates to a process for the co-production of 1,1,1-trifluoropropene (HFO-1243zf) and E-1,1,1,4,4,4-hexafluoro-2-butene (E-1336mzz).

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims priority to U.S. Provisional Application No. 63 / 441,970, filed January 30, 2023, the disclosure of which is incorporated herein by reference in its entirety. [Background technology]

[0002] Over the past several decades, many industries have been working to find alternatives to ozone-depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs). CFCs and HCFCs have been used in a wide range of applications, including as aerosol propellants, refrigerants, cleaning agents, blowing agents for thermoplastic and thermoset foams, heat transfer media, immersion fluids for electronics, gaseous dielectrics, fire extinguishing and suppression agents, power cycle working fluids, polymerization media, particulate removal fluids, carrier fluids, buffing abrasives, and displacement drying agents. In their search for replacements for these versatile compounds, many industries have turned to the use of hydrofluorocarbons (HFCs), and more recently, hydrochlorofluoroolefins (HCFOs) and hydrofluoroolefins (HFOs), which have lower global warming potentials (GWPs), as well as C3-C6 hydro(chloro)fluoroolefins, which have higher boiling points that make them particularly suitable for the electronics industry.

[0003] Many hydrochlorofluoroolefins (HCFOs) and hydrofluoroolefins (HFOs) with lower global warming potentials (GWP) are prepared from precursor materials, including, but not limited to, 1,1,1-trifluoropropene (TPY), HFO-1243zf, or 1243zf. HFO-1243zf is also useful as a monomer for telomerization, copolymerization, and the production of other compounds, including, but not limited to, fluorosilicones and pharmaceuticals. Therefore, there remains a need for more effective and efficient methods of producing and using hydrochlorofluoroolefins (HCFOs) and hydrofluoroolefins (HFOs), whether as monomers or intermediate compounds for the production of hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs), hydrochlorofluoroolefins (HCFOs), and hydrofluoroolefins (HFOs).

[0004] Processes for producing C3-C6 hydro(chloro)fluoroolefins generally involve the use of precursor or intermediate compounds such as trifluoropropene (HFO-1243zf), which are either commercially available or can be produced in a two-step process according to the following reaction scheme: Step 1: CCl4 + H2C = CH2 (ethylene) → CCl3CH2CH2Cl (HCC-250fb) (l) Process 2: CCl3CH2CH2Cl+HF→CF3CHCH2(1243zf)(g) Generally, steps 1 and 2 are carried out in separate reactors, requiring separation of HCC-250fb prior to fluorination.

[0005] The 1243zf intermediate is also used to produce (E / Z)-l,l,l,-4,4,4-hexafluorobut-2-ene ((E / Z)-HFO-1336mzz), which is suitable for use as a working fluid in heat transfer systems including, but not limited to, air conditioners (e.g., automotive air conditioners), freezers, refrigerators, heat pumps, chillers (e.g., water chillers, flooded evaporator chillers, direct expansion chillers, centrifugal chillers), walk-in chillers, high temperature heat pumps, mobile chillers, mobile air conditioning units, immersion cooling systems, data center cooling systems, and combinations thereof, and as a component of compositions for heat transfer, refrigeration, high temperature heat pumps, immersion cooling systems, organic Rankine cycles, fire extinguishing / suppression agents, propellants, foam blowing agents, solvents, and / or cleaning fluids.

[0006] One reaction scheme for producing HFO-1336mzz involves four process steps and separate reactors. Step 1: CCl4 + ethylene → CCl3CH2CH2Cl (250fb)(l) Process 2: 250fb+HF→1243zf(g) Step 3: CCl4 + 1243zf → 2,4,4,4-tetrachloro-1,1,1-trifluorobutane (343jfd)(l)

[0007] [ka] Step 4: 343jfd + HF → (E)-1,1,1,4,4,4-hexafiolobut-2-ene (E-1336mzz)g).

[0008] It would be advantageous if the process for producing (E)-1,1,1,4,4,4-hexafluorobut-2-ene (E-1336mzz) could be simplified to reduce investment costs and increase process efficiency (time and yield) without the capital expenditure and time loss incurred in the four-step process. Summary of the Invention [Means for solving the problem]

[0009] The present invention provides a simplified process for the co-production of 1,1,1-trifluoropropene (HFO-1243zf) and E-1,1,1,4,4,4-hexafluoro-2-butene (E-1336mzz).

[0010] The present invention provides a process in which a 250fb and 343jfd feed stream is contacted with HF in a catalytic reaction zone to co-produce 1,1,1-trifluoropropene (HFO-1243zf) and E-1,1,1,4,4,4-hexafluoro-2-butene (E-1336mzz).

[0011] The present invention provides an integrated process using a co-feed that is fluorinated in a single vessel to co-produce 1243zf and E-HFO-1336mzz according to the following reaction scheme: Step 1: CCl4 + H2C = CH2 (ethylene) → CCl3CH2CH2Cl (HCC-250fb) (l) Step 2: CCl4 + 1243zf → 2,4,4,4-tetrachloro-1,1,1-trifluorobutane (343jfd)(l) Step 3: 250fb + 343jfd + HF → (E)-1,1,1,4,4,4-hexafluorobut-2-ene (E-1336mzz) + 1,1,1-trifluoropropene (HFO-1243zf) (g).

[0012] The present invention provides a process for producing E-1,1,1,4,4,4-hexafluoro-2-butene (E-1336mzz) from the co-feed in a single reactor by co-producing 250fb and 343jfd, forming 250fb and 343jfd feed streams, and contacting the feed streams with hydrogen fluoride in the presence of a catalyst.

[0013] The present invention provides a process for forming 1,1,1-trifluoropropene (HFO-1243zf) and E-1,1,1,4,4,4-hexafluoro-2-butene (E-1336mzz) by contacting an HCC with an HCFO compound in the vapor phase in the presence of a catalyst, wherein the HCFO comprises 2,4,4,4-tetrachloro-1,1,1-trifluorobutane (343jfd) and the HCC comprises CClCHCHCl (HCC-250fb).

[0014] The present invention relates to a method for producing a fluorocarbon polymer comprising the steps of (1) 1,1,1-trifluoropropene (HFO-1243zf) and E-1,1,1,4,4,4-hexafluoro-2-butene (E-HFO-1336mzz) or (2) 2,4,4,4-tetrachloro-1,1,1-trifluorobutane (343jfd), CClCHCHCl (HCC-250fb), 1,1,1-trifluoropropene (HFO-1243zf), and 2,4,4,4-tetrachloro-1,1,1-trifluorobutane (343jfd). f) and E-1,1,1,4,4,4-hexafluoro-2-butene (E-1336mzz), and optionally at least one additional member selected from 346mdf, 253fb, 1242zf, 1336ft, 356mff, Z-1326mxz, 1233xf, E-1233zd, 252da, 1241 isomers, and 1333azd.

[0015] The present invention relates to (1) a composition comprising one of 1,1,1-trifluoropropene (HFO-1243zf) and E-1,1,1,4,4,4-hexafluoro-2-butene (E-HFO-1336mzz), and optionally at least one additional member selected from 346mdf, 253fb, 1242zf, 1336ft, 356mff, Z-1326mxz, 1233xf, E-1233zd, Z-1336mxx, 252da, 1241 isomers, and 1333azd.

[0016] The present invention relates to a composition comprising 2,4,4,4-tetrachloro-1,1,1-trifluorobutane (343jfd), CCl3CH2CH2Cl (HCC-250fb), and HF.

[0017] 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. Methods and materials for use in the present invention are described herein; other suitable methods and materials known in the art can also be used. The materials, methods, and examples are illustrative only and are not intended to be limiting. All publications, patent applications, patents, sequences, database entries, and other references mentioned herein are incorporated herein by reference in their entirety. In case of conflict, the present specification, including definitions, will control. [Brief explanation of the drawings]

[0018] [Figure 1] 1 illustrates a flow process of an embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0019] Although HFCs do not contribute to the depletion of the stratospheric ozone layer, they are of concern because they contribute to the "greenhouse effect," i.e., global warming. Because of their contribution to global warming, HFCs are coming under increasing scrutiny, and their widespread use may be restricted in the future. Thus, there is a need for hydrofluoroolefins, such as 1,1,1,4,4,4-hexafluoro-2-butene (CFCH=CHCF, HFO-1336mzz), that are suitable for use as working fluids in heat transfer systems, including, but not limited to, air conditioners (e.g., automotive air conditioners), freezers, refrigerators, heat pumps, chillers (e.g., water chillers, flooded evaporator chillers, direct expansion chillers, centrifugal chillers), walk-in chillers, high temperature heat pumps, mobile chillers, mobile air conditioning units, immersion cooling systems, data center cooling systems, and combinations thereof, and as components of compositions for heat transfer, refrigeration, high temperature heat pumps, immersion cooling systems, organic Rankine cycles, fire extinguishing / suppression agents, propellants, foam blowing agents, solvents, and / or cleaning fluids, and that have high efficiency and thermal stability that meet both goals. Similarly, there is a need for simplified processes for producing HFO-1243zf, a key intermediate for producing HFO-1336mzz, as well as many other HFC, HFO and HCFO products.

[0020] definition It should be readily understood that where applicants have defined an invention or a portion thereof with open-ended terms such as "comprising," the description should (unless expressly stated otherwise) be construed to also include inventions that use the terms "consisting essentially of" or "consisting of."

[0021] As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that includes a list of elements is not necessarily limited to only those elements, but may include other elements not expressly listed or inherent in such process, method, article, or apparatus. Furthermore, unless expressly stated to the contrary, "or" refers to an inclusive "or," not an exclusive "or." For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or absent), A is false (or absent) and B is true (or present), and both A and B are true (or present).

[0022] The transitional phrase "consisting of" excludes any unspecified element, step, or ingredient. In the context of a claim, such a phrase closes the claim to including materials other than those recited, except for impurities normally accompanying the materials. When the phrase "consisting of" appears within a clause in the body of a claim rather than immediately following the preamble, the phrase limits only the elements set forth in that clause and does not exclude other elements from the claim as a whole.

[0023] The transitional phrase "consisting essentially of" is used to define compositions, methods, and compositions that include materials, steps, mechanisms, ingredients, or elements in addition to those literally disclosed, provided that these additionally included materials, steps, mechanisms, components, or elements do not materially affect the basic and novel characteristics of the claimed invention, particularly the mechanism of action for achieving any desired result of the inventive process. The term "consisting essentially of" has a meaning intermediate between "comprising" and "consisting of."

[0024] Additionally, the use of "a" or "an" is used 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 interpreted to include one or at least one, and the singular also includes the plural unless it is clear that a different meaning is intended.

[0025] As used herein, the term "about" is meant to account for variation due to experimental error (e.g., plus or minus about 10% of the stated value). All measurements reported herein are understood to be modified by the term "about," unless otherwise specified, regardless of whether the term "about" is explicitly used.

[0026] When an amount, concentration, or other value or parameter is given as either a range, a preferred range, or a list of upper and / or lower preferred values, this is to be understood as specifically disclosing all ranges formed from any pairing of any upper range value or preferred upper value and any lower range value or preferred lower value, whether or not the ranges are separately disclosed. When a range of numerical values ​​is recited herein, unless otherwise indicated, the range is intended to include its endpoints, and to include all integers and fractions within the range.

[0027] Global warming potential (GWP) is an index used to estimate the relative global warming contribution resulting from the atmospheric emission of one kilogram of a particular greenhouse gas compared to the emission of one kilogram of carbon dioxide. GWP can be calculated for various time horizons and indicates the impact of a given gas over its atmospheric lifetime. GWP over a 100-year time horizon is the commonly referenced value.

[0028] As used herein, "absence of HF" means that there is no constant flow of HF during the reaction, but does not exclude the use of HF to activate the catalyst prior to the reaction.

[0029] As used herein, organophosphines and organophosphorus are used interchangeably and can include primary, secondary, and tertiary phosphines.

[0030] The compounds described herein can be asymmetric (e.g., having one or more stereocenters). Unless otherwise specified, all stereoisomers, such as enantiomers and diastereomers, are intended. Cis / trans and / or E / Z geometric isomers of the compounds of the present invention are described and may be isolated as a mixture of isomers or as separated isomeric forms.

[0031] Chemicals, Abbreviations, and Acronyms

[0032] [Table 1]

[0033] As shown in Figure 1, HCC-250fb and HCFC-343jfd streams fed to reactor 5 are produced separately, each involving the reaction of a hydro(halo)carbon, e.g., CCl, with an alkene or fluoroalkene, e.g., ethylene and 1,1,1-trifluoropropene, produced in separate (distinct) reactors 1 and 3, where HCC-250fb and HCFC-343jfd are formed, respectively. The HCC-250fb and HCFC-343jfd product streams are separated into feed streams 2 and 4, respectively, using conventional techniques and introduced into common reactor 5. Reactor 5 contains, for example, a CrO catalyst (not shown), where HCC-250fb, HCFC-343jfd, and hydrogen fluoride (HF) contact the catalyst to hydrofluorinate and convert HCC-250fb and HCFC-343jfd to HFO-1243zf and HFO-E-1336mzz. Suitable Cr2O3 catalysts include, but are not limited to, JM 62-2 (a chromium catalyst available from Johnson Matthey), LV (a chromium catalyst available from The Chemours Company), JM-62-3 (a chromium catalyst available from Johnson Matthey), and Newport Chrome (a chromium catalyst available from Chemours). The chromium catalyst is preferably activated prior to use by heating the catalyst to 350-400°C under a nitrogen flow for a period of time, followed by further heating under a HF and nitrogen or air flow for a period of time. HFO-E-1336mzz is separated and removed for purification. HFO-1243zf is also separated and recycled to reactor 3 via recycle stream 6.

[0034] Flow 2 250fb (CCl3CH2CH2Cl, GC purity 100%) was purchased from Chemours Although commercially available from U.S. Patent Application Publication Nos. 4,605,802, 5,705,779, and 20110237843A1, paragraphs

[0023] -

[0027] ; and 2019 / 0233353A1, paragraphs

[0018] -

[0022] ,

[0031] -

[0033] ,

[0037] ,

[0040] ,

[0045] -

[0056] , and

[0114] , the entire disclosures of each of which are incorporated herein by reference, in some embodiments, CClCHCHCl can be prepared by the addition reaction of ethylene with carbon tetrachloride (CCl), either in the vapor phase or the liquid phase, to produce 1,1,1,3-tetrachloropropane (HCC-250fb).

[0035] In some embodiments, CClCHCHCl can be prepared in reactor 1 by conducting a reaction according to the process described in paragraphs

[0018] to

[0022] ,

[0031] to

[0033] ,

[0037] ,

[0040] ,

[0045] to

[0056] , and

[0114] of U.S. Patent Publication No. 2019 / 0233353 A1, the disclosures of which are incorporated herein by reference in their entireties.

[0036] In some embodiments, CCl3CH2CH2Cl (250fb) is prepared by contacting carbon tetrachloride (CCl4), ethylene (CH2=CH2), and a metal-ligand catalyst formed from a metal selected from the group consisting of, for example, Fe, Co, Ni, Cu, Mo, Cr, and Mn. In one embodiment, iron metals, including but not limited to, iron powder, iron wire, iron screen, or iron shavings, form an organophosphine (organophosphorus) compound.

[0037] In certain embodiments, CCl3CH2CH2Cl(250fb) can be prepared according to the process described in U.S. Pat. No. 4,605,802, where the reaction is carried out by adding carbon tetrachloride, phosphite, and iron powder at about 70° C. to 140° C. and about 25 to 500 psig (0.17 to 3.45 MPa), and where the iron powder is used at greater than about 0.001 moles per mole of carbon tetrachloride, the disclosure of which is incorporated herein by reference in its entirety.

[0038] In certain embodiments, CCl3CH2CH2Cl(250fb) can also be prepared according to the process described in US Pat. No. 5,705,779, which is incorporated herein by reference.

[0039] In certain embodiments, CCl3CH2CH2Cl(250fb) can be prepared according to the process described in Example 6 of U.S. Pat. No. 4,605,802, which is incorporated herein by reference. In some embodiments, the phosphine ligand can be an alkyl phosphine or an aryl phosphine, including, but not limited to, triphenylphosphine, tributylphosphine, and the like. In one embodiment, the phosphine ligand comprises triphenylphosphine, e.g., triphenylphosphate. In another embodiment, the phosphine ligand consists essentially of triphenylphosphine, e.g., triphenylphosphate. In another embodiment, the phosphine ligand consists of triphenylphosphine, e.g., triphenylphosphate.

[0040] In one embodiment, the CCl4 / ethylene reaction may be carried out at an elevated temperature. In another embodiment, the CCl4 / ethylene reaction may be carried out at a temperature of about 50°C to 250°C. In another embodiment, the CCl4 / ethylene reaction may be carried out at a temperature of about 100°C to 200°C. In another embodiment, the CCl4 / ethylene reaction may be carried out at a temperature of about 120°C to 180°C. In another embodiment, the CCl4 / ethylene reaction may be carried out at a temperature of about 130°C to 170°C.

[0041] In some embodiments of the present invention, the reaction in reactor 1 comprises a metal-catalyzed olefin insertion process, comprising inserting an olefin into a haloalkane reactant using a metal selected from, for example, Fe, Co, Ni, Cu, Mo, Cr, and Mn, and a ligand to obtain a desired product, such as a haloalkane insertion product. Specifically, some embodiments relate to iron and trialkylphosphine catalyst systems with high conversion and selectivity for olefin insertion of haloalkanes.

[0042] In certain embodiments, the metallic iron component of the catalyst can be derived from any source of iron component (including a combination of sources), and can be iron powder, iron wire, iron sieve, or iron scrap.

[0043] In some embodiments, the organophosphorus ligand may be an alkyl phosphate or an aryl phosphate, including, but not limited to, triphenyl phosphate, tributyl phosphate, etc. In one embodiment, the phosphate ligand comprises triphenyl phosphate. In another embodiment, the phosphate ligand consists essentially of triphenyl phosphate. In another embodiment, the phosphate ligand consists of triphenyl phosphate (TPP) in the presence of metallic iron and a phosphine, including tributyl phosphate (TBP), as a liquid phase process.

[0044] In one embodiment, each component of the iron and phosphine catalyst system has a specific concentration relative to the moles of olefinic reactant used. Thus, in some embodiments, the ratio of moles of halocarbon reactant to moles of olefin is about 3:1 to 1:1. In another embodiment, the molar ratio of moles of halocarbon reactant to moles of olefin is about 2.25:1 to 1:1. In another embodiment, the molar ratio of moles of halocarbon reactant to moles of olefin is about 2:1 to 1:1.

[0045] In one embodiment, the ratio of moles of iron to moles of olefin is about 0.01:1 to 0.1:1. In another embodiment, the molar ratio of iron to olefin is about 0.03:1 to 0.06:1. In another embodiment, the molar ratio of iron to olefin is about 0.07:1 to 0.1:1.

[0046] In another embodiment, the number of moles of phosphine ligand can be measured relative to the number of moles of olefin present in the reaction system. For example, in one embodiment, the molar ratio of phosphine ligand to olefin can be about 0.01:1 to 0.04:1. In another embodiment, the molar ratio of phosphine ligand to olefin can be about 0.02:1 to 0.06:1. For example, the molar ratio of phosphine ligand to olefin can be 0.023:1, while in another example, the molar ratio of phosphine ligand to olefin can be 0.046:1.

[0047] In one embodiment, CCl and CH in the presence of iron and an alkyl or aryl phosphine 2= The reaction of CH2 can be carried out at elevated temperatures. In another embodiment, the reaction can be carried out at a temperature of about 50°C to 250°C. In another embodiment, the reaction can be carried out at a temperature of about 75°C to 150°C. In another embodiment, the reaction can be carried out at a temperature of about 100°C to 200°C.

[0048] In certain embodiments, the reaction of CCl4 and CH2=CH2 in the presence of iron and an alkyl or aryl phosphine can be carried out at a temperature between one of 50°C, 60°C, 70°C, 80°C, 90°C and one of 110°C, 120°C, 130°C, 140°C, 150°C, 160°C.

[0049] In certain embodiments, the reaction of CCl4 with CH2=CH2 in the presence of iron and an alkyl or aryl phosphate can be carried out in reactor 1 at a pressure in the reaction zone of the reactor of about 0 psig to 200 psig (0 MPa to 1.4 MPa). In other embodiments, the pressure in the reaction zone can be about 30 psig to 180 psig (0.21 to 1.2 MPa). In certain embodiments, the pressure in the reaction zone of reactor 1 may be operated at a pressure between one of 10 psig, 20 psig, 30 psig, 40 psig, 50 psig, 60 psig, 70 psig, 80 psig and one of 100 psig, 110 psig, 120 psig, 130 psig, 140 psig, 150 psig, 160 psig, 170 psig, 180 psig, 190 psig, and 200 psig (one of 0.1 MPa, 0.14 MPa, 0.21 MPa, 0.28 MPa, 0.34 MPa, 0.41 MPa, 0.48 MPa, 0.55 MPa, and 0.69 MPa, 0.76 MPa, 0.83 MPa, 0.90 MPa, 0.97 MPa, 1.0 MPa, 1.1 MPa, 1.2 MPa, 1.2 MPa, 1.3 MPa, and 1.4 MPa). In other embodiments, the pressure in reactor 1 can be greater than 0 to less than 1 atm, 1 atm, 2 atm, 3 atm, 4 atm, 5 atm, 6 atm, 7 atm, 8 atm, up to about 15 atm or less.

[0050] In certain embodiments, the reaction of CCl4 and CH2=CH2 in the presence of iron and an alkyl or aryl phosphate is carried out at a temperature between one of 50°C, 60°C, 70°C, 80°C, 90°C and one of 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, and at one of 10 psig, 20 psig, 30 psig, 40 psig, 50 psig, 60 psig, 70 psig, 80 psig and one of 100 psig, 110 psig, 120 psig, 130 psig, 140 psig , 150 psig, 160 psig, 170 psig, 180 psig, 190 psig and 200 psig (0.1 MPa, 0.14 MPa, 0.21 MPa, 0.28 MPa, 0.34 MPa, 0.41 MPa, 0.48 MPa, 0.55 MPa, and one of 0.69 MPa, 0.76 MPa, 0.83 MPa, 0.90 MPa, 0.97 MPa, 1.0 MPa, 1.1 MPa, 1.2 MPa, 1.2 MPa, 1.3 MPa and 1.4 MPa).

[0051] Flow 4 In some embodiments, CF3CHClCH2CCl3 (HCFC-343jfd) is produced in reactor 3 according to the process described in paragraphs

[0032] -

[0042] of U.S. Patent Application Publication No. 20190077733, the disclosure of which is incorporated herein by reference in its entirety, which describes a process comprising contacting carbon tetrachloride with 1,1,1-trifluoropropene (HFO-1243zf) in the presence of a catalyst comprising an organophosphorus compound and a metal.

[0052] In one embodiment, CF3CHClCHCl2CCl3 (HCFC-343jfd) is prepared in reactor 3 according to the process described in paragraphs

[0017] -

[0020] and paragraphs

[0032] -

[0044] of U.S. Patent Publication No. 20190077733, the disclosure of which is incorporated herein by reference in its entirety. In some embodiments, carbon tetrachloride and 3,3,3-trifluoropropene are contacted with a metal catalyst and a phosphorus compound, wherein the metal comprises one of iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), molybdenum (Mo), chromium (Cr), and manganese (Mn), and the phosphorus compound comprises one of phosphate ester, phosphoric acid amide, phosphonic acid, phosphonic acid ester, phosphinic acid, phosphinic acid ester, phosphine oxide, phosphine imide, phosphonium salt, phospholene, phosphite, phosphonate, phosphinite, and phosphine.

[0053] In some embodiments, the organophosphorus compound is selected from the group comprising, consisting essentially of, or consisting of phosphates, diphosphates, triphosphates, and trialkylphosphates, hi some embodiments, the organophosphorus compound is tributylphosphate.

[0054] In some embodiments, CF3CHClCH2CCl3 (343jfd) is produced by contacting carbon tetrachloride with 3,3,3-trifluoropropene in the presence of an organophosphorus compound and a catalyst selected from Fe, Co, Ni, Cu, Mo, Cr, and Mn. In some embodiments, the metal is Fe.

[0055] In some embodiments, CF3CHClCH2CCl3 (343jfd) is produced by contacting carbon tetrachloride with 3,3,3-trifluoropropene at a temperature of about 100°C to about 120°C.

[0056] In some embodiments, reacting carbon tetrachloride in a liquid phase with 3,3,3-trifluoropropene in the presence of a catalyst comprising an organophosphorus compound and a metal to produce CFCHClCHClCHCl (343jfd) is carried out at a temperature of about 90° C. to about 130° C., about 100° C. to about 120° C., or about 105° C. to about 115° C. In some embodiments, reacting carbon tetrachloride in a liquid phase with 3,3,3-trifluoropropene in the presence of a catalyst comprising an organophosphorus compound and a metal to produce CFCHClCHClCHCl (343jfd) is carried out at a temperature of about 90° C., 95° C., 100° C., 105° C., 110° C., 115° C., 120° C., 125° C., or about 130° C.

[0057] In some embodiments, the organophosphorus compound is selected from the group consisting of phosphate esters, phosphoric acid amides, phosphonic acids, phosphonate esters, phosphinic acids, phosphinate esters, phosphine oxides, phosphine imides, phosphonium salts, phospholenes, phosphites, phosphonates, phosphinites, and phosphines. In some embodiments, the organophosphorus compound is selected from phosphates, diphosphates, triphosphates, and trialkylphosphates.

[0058] In some embodiments, the organophosphorus compound is a phosphate, diphosphate, triphosphate, or trialkylphosphate. In some embodiments, the organophosphorus compound is tributylphosphate.

[0059] In some embodiments, the metal of the catalyst for producing 343jfd is selected from the group consisting of Fe, Co, Ni, Cu, Mo, Cr, and Mn, hi some embodiments, the metal is Fe.

[0060] In some embodiments, the preparation of 343jfd is carried out at a temperature of about 100°C to about 120°C.

[0061] In some embodiments, the molar ratio of CCl4 to 1,1,1-trifluoropropene (HFO-1243zf) is greater than 1:1, including, but not limited to, 1.5:1, 2:1, 2.5:1, 3:1, and all values ​​and ranges therebetween.

[0062] In some embodiments, at least a portion of the HFO-1243zf is fed from common reactor 5 and, more specifically, is separated and recycled to reactor 3 via recycle stream 6, where it is contacted with CCl4 to form HCFC-343jfd.

[0063] Reactor 5 In some embodiments, the 250fb:343jfd feed molar ratio to reactor 5 is selected from one of 9:11 to 11:9, 0.45 to 0.55, and 0.55 to 0.45.

[0064] In a particular embodiment, the molar ratio of 250fb:343jfd is about 1:1.

[0065] In certain embodiments, the conversion of CCl3CH2CH2Cl and / or 1,1,3-trichloro-4,4,4-trifluorobut-1-ene in reactor 5 is one of at least 95%, at least 96%, at least 98%, at least 99%, and 100%.

[0066] In certain embodiments, the product mixture of reactor 5 comprises HFO-1234z, HFO-E-1336mzz, and optionally one or more of 346mdf, 253fb, 1242zf, 1336ft, 356mff, Z-1326mxz, 1233xf, E-1233zd, 252da, 1241 isomers, and 1333azd.

[0067] In certain embodiments, the HFO-1234zf in the product mixture of reactor 5 comprises about 45 mole percent, about 50 mole percent, about 55 mole percent, between 40 mole percent and 60 mole percent, between 40 mole percent and 55 mole percent, or between 45 mole percent and 55 mole percent.

[0068] In certain embodiments, the HFO-E-1336mzz in the product mixture of reactor 5 comprises about 45 mole percent, about 50 mole percent, about 55 mole percent, between 40 mole percent and 60 mole percent, between 40 mole percent and 55 mole percent, or between 45 mole percent and 55 mole percent.

[0069] In certain embodiments, HFO-Z-1336mzz in the product mixture is less than 1 mole percent, 0.9 mole percent, 0.8 mole percent, 0.7 mole percent, 0.6 mole percent, 0.5 mole percent, 0.4 mole percent, 0.3 mole percent, 0.2 mole percent, 0.1 mole percent, 0.3, 0.4, 0.5, 0.6, or 0.7 mole percent but less than 1 mole percent, greater than 0 mole percent to less than 1 mole percent, 0.1, 0.2, Including all ranges and values ​​from 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9 to 1.0 mole percent, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9 mole percent, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9 mole percent, 0.3, 0.4, 0.5, 0.6 or 0.7 to 0.8 or 0.9 mole percent, 0.3, 0.4, 0.5, or 0.6 to 0.7, 0.8 or 0.9 mole percent, and >0 to <1 mole percent.

[0070] In certain embodiments, E-HFO-1336mzz and HFO-1243zf are each isolated from the product mixture.

[0071] In certain embodiments disclosed herein, the E-HFO-1336mzz from the product mixture is processed for use as at least part of the working fluid in heat transfer systems including, but not limited to, air conditioners (e.g., automotive air conditioners), freezers, refrigerators, heat pumps, chillers (e.g., water chillers, flooded evaporator chillers, direct expansion chillers, centrifugal chillers), walk in chillers, high temperature heat pumps, mobile chillers, mobile air conditioning units, immersion cooling systems, data center cooling systems, and combinations thereof, as well as a component of compositions for heat transfer, refrigeration, high temperature heat pumps, immersion cooling systems, organic Rankine cycles, fire extinguishing / suppression agents, propellants, foam blowing agents, solvents, and / or cleaning fluids.

[0072] In certain embodiments disclosed herein, E-HFO-1336mzz, alone or in blends, is used as a working fluid in heat transfer systems including, but not limited to, air conditioners (e.g., automotive air conditioners), freezers, refrigerators, heat pumps, chillers (e.g., water chillers, flooded evaporator chillers, direct expansion chillers, centrifugal chillers), walk-in chillers, high temperature heat pumps, mobile chillers, mobile air conditioning units, immersion cooling systems, data center cooling systems, and combinations thereof, as well as a component of compositions for heat transfer, refrigeration, high temperature heat pumps, immersion cooling systems, organic Rankine cycles, fire extinguishing / suppression, propellants, foam blowing agents, solvents, and / or cleaning fluids.

[0073] In certain embodiments disclosed herein, the product mixture E-HFO-1336mzz is used as a working fluid in a heat exchanger, thereby producing a cooled working fluid. [Example]

[0074] The present disclosure is further defined in the following examples. It should be understood that these examples, while showing preferred embodiments, are provided for illustrative purposes only. From the above discussion and these examples, those skilled in the art can ascertain preferred features and make various changes and modifications to adapt to various uses and conditions without departing from the spirit and scope thereof.

[0075] Example 1: Preparation of compound 343jfd 3,3,3-Trifluoropropene (66 g, 0.68 mol) was added to a mixture of carbon tetrachloride (158 g, 1.0 mol), Fe powder (1.12 g, 0.02 mol), and tributyl phosphate (2.66 g, 0.01 mol) in a 400 mL Hastelloy reactor. The reactor was heated to 110 °C for 3 h. 217 g of the mixture was transferred to a container and analyzed by GC (100% TFP conversion, 88% selectivity to 343 jfd). The same reaction was repeated twice, and all three batches of material were combined. Subsequent fractionation yielded 299 g of 98.5% pure CCl3CH2CHClCF3 (343 jfd). CCl3CH2CHClCF3: bp 92-94 °C / 140 Torr. 1 H NMR(CDCl3,400MHz)δ 4.52(1H,qdd,J1=J2=6.9Hz,J3=1.8Hz),3.44(1H,dd,J1=16.0Hz,J2=1.9Hz),3.26(1H,dd,J1=16.0Hz,J2=7.6Hz); 19 F NMR(CDCl3,376MHz)δ-74.85(3F,d,J=6.9Hz);MS(EI):213(M + -Cl).

[0076] Example 2: Example of co-production of 1234zf and E-1336mzz: The reactor was a 0.5 inch (1.27 cm) OD Inconel® pipe, 10 inches (25.4 cm) long, 0.35 inch (0.89 cm) wall thickness, packed with 6 cc of JM 62-3 Cr2O3 catalyst obtained from Johnson Matthey PLC. The reactor was heated to high temperature and the reaction was carried out in the gas phase.

[0077] A 1:1 molar mixture of 250fb and 343jfd was fed to the reactor with HF via a vaporizer controlled at 180°C via an ISCO pump at 0.15 mL / hr or 0.3 mL / hr. The reaction pressure was 0-50 psig (0-0.345 MPa). The reactor effluent was analyzed online using an Agilent® 7890GC / 5971 MS. The conditions are summarized in Table 1 below. (Note: CT is contact time (seconds).) The results are shown in Table 2 below. The conversion of both 250fb and 343jfd was 100% in all samples.

[0078] [Table 2]

[0079] [Table 3]

[0080] The unknown components include at least one of the following components: 346mdf, 253fb, 1242zf, 1336ft, 356mff, Z-1326mxz, 1233xf, E-1233zd, 252da, 1241 isomer, and 1333azd.

[0081] The data in Table 1 show that 1243zf and E-1336mzz can be co-produced over a chromium catalyst with the product stream containing HFO-1243zf, E / Z-HFO-1336mzz, and CFCFHCHCF, heptafluorobutane (HFC-347mef).

[0082] Other embodiments Process embodiment 1 comprises contacting CClCHCHCl (HCC-250fb) and CClCHCHClCF (343jfd) with a catalyst in the presence of hydrogen fluoride (HF) in a reaction zone of a reactor; and producing a product mixture comprising at least 1,1,1-trifluoropropene (HFO-1243zf), E-1,1,1,4,4,4-hexafluoro-2-butene (E-1336mzz), and hydrogen chloride.

[0083] Process embodiment 2 includes process embodiment 1 and includes first producing a CClCHCHCl (HCC-250fb) component in a first reaction zone of a reactor, and first producing a CClCHCHClCF (343jfd) component in a second reaction zone of the reactor, isolating CClCHCHCl (HCC-250fb) and CClCHCHClCF (343jfd), respectively, and using CClCHCHCHCl (HCC-250fb) and CClCHCHClCF (343jfd) as feeds to embodiment 1.

[0084] Composition embodiment 1 containing CCl3CH2CH2Cl (HCC-250fb) and CCl3CH2CHClCF3 (343jfd).

[0085] Composition embodiment 1, wherein the ratio of 250fb:343jfdmole is 0.5:1 to 2:1.

[0086] Composition embodiment 2, which is a product mixture of 1,1,1-trifluoropropene (HFO-1243zf) and E-1,1,1,4,4,4-hexafluoro-2-butene (E-1336mzz).

[0087] Composition embodiment 2, comprising at least one of 253fb, 1242zf, 1336ft, 356mff, Z-1326mxz, 1233xf, E-1233zd, 252da, 1241 isomers, and 1333azd.

[0088] Composition embodiment 2, comprising at least two of 346mdf, 253fb, 1242zf, 1336ft, 356mff, Z-1326mxz, 1233xf, E-1233zd, 252da, 1241 isomer, and 1333azd.

[0089] Composition embodiment 2, comprising more than three of 346mdf, 253fb, 1242zf, 1336ft, 356mff, Z-1326mxz, 1233xf, E-1233zd, 252da, 1241 isomer, and 1333azd.

[0090] Composition embodiment 2 further comprises at least one heptafluorobutane isomer.

[0091] Process Embodiment 3 includes the use of E-HFO-1336mzz produced from Process Embodiment 1 as a working fluid in heat transfer systems including, but not limited to, air conditioners (e.g., automotive air conditioners), freezers, refrigerators, heat pumps, chillers (e.g., water chillers, flooded evaporator chillers, direct expansion chillers, centrifugal chillers), walk-in chillers, high temperature heat pumps, mobile chillers, mobile air conditioning units, immersion cooling systems, data center cooling systems, and combinations thereof, and as a component of compositions for heat transfer, refrigeration, high temperature heat pumps, immersion cooling systems, organic Rankine cycles, fire extinguishing / suppression, propellants, foam blowing agents, solvents, and / or cleaning fluids.

[0092] The process of an embodiment, wherein HCC-250fb and / or 343jfd are produced in the liquid phase.

[0093] A process of an embodiment wherein the liquid phase reaction is carried out at a temperature between 200°C and 400°C.

[0094] The process of the embodiment, wherein the molar ratio of HCC-250fb:343jfd is 0.1:0.9 to 0.9:0.1.

[0095] A process of an embodiment, wherein the molar ratio of 1,1,1-trifluoropropene (HFO-1243zf):E-1,1,1,4,4,4-hexafluoro-2-butene (E-1336mzz) is 0.1:0.9 to 0.9:0.1.

[0096] While the present invention has been described in conjunction with its detailed description, it should be understood that the foregoing description is intended to illustrate, but not limit, the scope of the invention, which is defined by the scope of the appended claims. Other aspects, advantages, and modifications are within the scope of the following claims. It should be understood by those skilled in the art to which this invention pertains that any of the features described herein with respect to any particular aspect and / or embodiment of the invention may be combined with any one or more of the other features of any other aspect and / or embodiment of the invention described herein, modified as appropriate to ensure compatibility of the combination. Such combinations are considered to be part of the invention contemplated by this disclosure.

Claims

1. CCl ３ CH ２ CH ２ Cl (HCC-250fb) and CCl ３ CH ２ CHClCF ３ (343jfd) in a molar ratio of 250fb:343jfd of from 0.05:0.95 to 0.95:0.

05.

2. 2. The composition of claim 1, wherein the 250fb:343jfd molar ratio is from 0.3:0.7 to 0.7:0.

3.

3. A composition comprising 1,1,1-trifluoropropene (HFO-1243zf) and E-1,1,1,4,4,4-hexafluoro-2-butene (E-1336mzz).

4. 4. The composition of claim 3, further comprising at least one of 346mdf, 253fb, 1242zf, 1336ft, 356mff, Z-1326mxz, 1233xf, E-1233zd, 252da, 1241 isomers, and 1333azd.

5. 4. The composition of claim 3, further comprising at least two of 346mdf, 253fb, 1242zf, 1336ft, 356mff, Z-1326mxz, 1233xf, E-1233zd, 252da, 1241 isomers, and 1333azd.

6. 4. The composition of claim 3, further comprising more than three of: 346mdf, 253fb, 1242zf, 1336ft, 356mff, Z-1326mxz, 1233xf, E-1233zd, 252da, 1241 isomer, 1333azd.

7. The composition of any one of claims 3 to 6, further comprising at least one heptafluorobutane isomer.

8. A process comprising: (a) In the reaction zone of a reactor, CCl is reacted with HCl in the presence of hydrogen fluoride (HF). ３ CH ２ CH ２ Cl(HCFC-250fb) and CCl ３ CH ２ CHClCF ３ contacting (343jfd) with a catalyst; and (b) producing a product mixture comprising at least 1,1,1-trifluoropropene (HFO-1243zf), E-1,1,1,4,4,4-hexafluoro-2-butene (E-1336mzz), and hydrogen chloride.

9. 9. The process of claim 8, wherein the reactor is a single reactor.

10. 9. The process of claim 8, wherein the contacting occurs in the gas phase.

11. 9. The process of claim 8, wherein the contacting is carried out at a temperature of from 275°C to 350°C.

12. 9. The process of claim 8, wherein the contact time is from 1 to 120 seconds.

13. 9. The process of claim 8, wherein the contacting is carried out at a pressure from atmospheric pressure to 300 psi.

14. 9. The process of claim 8, wherein the contacting is carried out at a temperature of from 275°C to 350°C and a pressure of from 50 to 200 psi.

15. 9. The process of claim 8, wherein the contacting is carried out at a temperature of from 275°C to 350°C, a pressure of from 60 to 180 psi, and a contact time of from 3 to 30 seconds.

16. (i) dissolving the CCl in a liquid phase ３ CH ２ CH ２ Cl(HCFC-250fb); (ii) In a liquid phase, ３ CH ２ CHClCF ３ (343jfd) component, and (iii) the CCl ３ CH ２ CH ２ Cl(HCFC-250fb) and CCl ３ CH ２ CHClCF ３ (343jfd) component, and (iv) said CCl ３ CH ２ CH ２ Cl(HCFC-250fb) and CCl ３ CH ２ CHClCF ３ (343jfd) as a feed to (a).

17. (i) and (ii) are reacted in separate reaction zones with CCl in the presence of a catalyst. ４ with ethylene and 1,1,1-trifluoropropene, respectively.

18. 20. The process of claim 17, wherein the catalysts in (i) and (ii) each comprise a phosphine catalyst.

19. 18. The process of claim 17, wherein the catalysts of (i) and (ii) are chemically similar.

20. 18. The process of claim 17, wherein the catalyst comprises one of iron powder, iron wire, iron sieve, iron filings, or a combination thereof.

21. 21. The process of claim 20, wherein the catalyst comprises one of an alkyl or aryl phosphine and a metal.

22. 17. The process of claim 16, wherein the contacting in (a) is conducted at a temperature of 200 to 400°C.

23. (a) said feed is CCl ３ CH ２ CH ２ Cl (HCFC-250fb): CCl ３ CH ２ CHClCF ３ 17. The process of claim 16, comprising (343jfd) in a molar ratio of 0.1:0.9 to 0.9:0.

1.

24. 17. The process of claim 16, wherein the product mixture of (b) comprises 1,1,1-trifluoropropene (HFO-1243zf) and E-1,1,1,4,4,4-hexafluoro-2-butene (E-1336mzz) in a molar ratio of from 0.1:0.9 to 0.9:0.

1.

25. 18. The process of claim 17, comprising isolating at least the 1,1,1-trifluoropropene (HFO-1243zf), E-1,1,1,4,4,4-hexafluoro-2-butene (E-1336mzz), and HCl of the product mixture.

26. 26. The process of claim 25, comprising isolating 1,1,1-trifluoropropene (HFO-1243zf).

27. The process of claim 25, comprising the E-1,1,1,4,4,4-hexafluoro-2-butene (E-1336mzz), the E-1,1,1,4,4,4-hexafluoro-2-butene (E-1336mzz).

28. 26. The process of claim 25, comprising recycling the 1,1,1-trifluoropropene (HFO-1243zf).

29. 26. The process of claim 25, wherein the 1,1,1-trifluoropropene (HFO-1243zf) is recycled as HFO-1243zf feed for step (ii).

30. 9. The process of claim 8, wherein the HFO-1243zf comprises at least one of a fresh component stream and a recycled component stream.

31. 17. The process of claim 16, wherein (i) and (ii) are carried out in the presence of a catalyst.

32. 32. The process of claim 31 , wherein the catalyst comprises a phosphine catalyst system.

33. 32. The process of claim 31, wherein the catalysts are chemically similar.

34. 32. The process of claim 31 , wherein the catalyst comprises one of iron powder, iron wire, iron sieve, iron filings, or a combination thereof.

35. 32. The process of claim 31 , wherein the catalyst comprises one of an alkyl or aryl phosphine and a metal.

36. 36. The process of claim 35, wherein the metal comprises one of iron powder, iron wire, iron sieve, iron scrap, or a combination thereof.

37. 1. A process comprising isolating E-HFO-1336mzz from a product mixture obtained from the cofluorination of HCC-250fb and HCFC-343jfd, and using the isolated E-HFO-1336mzz as at least a portion of a working fluid in a heat exchanger, thereby producing a cooled working fluid.

38. 1. An integrated system for the co-production of 1,1,1-trifluoropropene (1243zf) and E-1,1,1,4,4,4-hexafluoro-2-butene (E-1336mzz), comprising: (a) a first reaction zone in which 250fb is produced; (b) a second reaction zone in which 343jfd is produced, wherein the first reaction zone and the second reaction zone are isolated from each other; (c) a third reaction zone in which the 250fb and 343jfd are co-fed with a catalyst in the presence of hydrogen fluoride (HF) to produce a product mixture comprising at least 1,1,1-trifluoropropene (HFO-1243zf), E-1,1,1,4,4,4-hexafluoro-2-butene (E-1336mzz), and hydrogen chloride.

39. 40. The system of claim 38, wherein the first reaction zone and the second reaction zone comprise a catalyst.

40. 40. The system of claim 39, wherein the catalyst in the first reaction zone comprises a metal organophosphorus complex.

41. 40. The apparatus of claim 39, wherein the catalyst in the second reaction zone comprises a metal-organophosphorus compound complex.

42. 41. The system of any one of claims 39 to 40, wherein the metal is selected from Fe, Co, Ni, Cu, Mo, Cr, and Mn.

43. 41. The system of any one of claims 39 to 40, wherein the organophosphorus compound is an organophosphorus compound selected from phosphates, diphosphates, triphosphates, and trialkylphosphates. In some embodiments, the organophosphorus compound is tributyl phosphate.

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