Method for preparing HFO-1252ZC by dehydrohalogenation reaction of HFC-263FB and HCFC-262FC and composition thereof

Abstract

Provided herein are methods for the preparation of a difluoroolefin, such as 1, 1-difluoropropene (HFO-1252zc). Also provided herein are compositions and uses of difluoroolefins, such as 1, 1-difluoropropene.

Description

Cross-reference to related applications

[0001] This application claims priority to U.S. Provisional Application No. 63 / 527,133, filed July 17, 2023, and U.S. Provisional Application No. 63 / 565,018, filed March 14, 2024, the full disclosure of each of which is incorporated herein by reference. Technical Field

[0002] This invention relates to methods, compositions, and uses for preparing difluoroolefins. Background Technology

[0003] For decades, numerous industries have been searching for 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, expanders for thermoplastic and thermosetting foams, heat transfer media, gaseous dielectrics, fire extinguishing and flame retardants, power circulation working fluids, polymerization media, particulate removal fluids, carrier fluids, polishing abrasives, and displacement desiccants. In the search for replacements for these versatile compounds, many industries have shifted to hydrofluorocarbons (HFCs).

[0004] Although HFCs do not cause stratospheric ozone depletion, they contribute to the "greenhouse effect," or global warming. Because of this contribution, HFCs are under close scrutiny, and their widespread use may be limited in the future.

[0005] This regulatory environment is constantly evolving, and the characteristics taken into consideration are no longer limited to ozone depletion potential (ODP) and global warming potential (GWP). More specifically, there is a need for refrigerant compositions that not only meet low ODP and low GWP standards, but also exhibit low or no flammability, provide excellent performance in a wide range of applications, and meet the standards of evolving regulations.

[0006] There is a need in the art for novel refrigerants that meet evolving regulations and provide heat transfer and refrigerant properties that meet or exceed the efficiency of conventional refrigerants.

[0007] Some fluoropropylenes, such as 1,1-difluoropropylene (HFO-1252zc), are potential novel refrigerants. Effective and efficient methods for preparing 1,1-difluoropropylene (HFO-1252zc) and its intermediates and compositions are still needed. Summary of the Invention

[0008] This invention relates to a method for preparing 1,1-difluoropropylene (CF2=CHCH3, HFO-1252zc).

[0009] Some embodiments involve a method for preparing 1,1-difluoropropene (HFO-1252zc) by the following steps: First, a compound defined by the formula CF2XCY=CH2 (e.g., 3,3,3-trifluoropropene, CF3CH=CH2, HFO-1243zf; 3-chloro-3,3-difluoropropene, CClF2CH=CH2, HCFO-1242zf; 2,3-dichloro-3,3-difluoropropene, CClF2CCl=CH2, HCFO-1232xf) is hydrogenated with hydrogen to produce a compound defined by the formula CF2XCH2CH3, wherein X is as defined above. In the presence or absence of a catalyst, or in the liquid phase in the presence of a strong base, in the presence or absence of a solvent, and in the presence or absence of a phase transfer catalyst, CF₂XCH₂CH₃ undergoes dehydrohalogenation to form a double bond between the C1 and C2 carbons of a halopropane molecule, producing a mixture of products containing HFO-1252zc. Examples of compounds of the formula CF₂XCH₂CH₃ include, but are not limited to, 1,1,1-trifluoropropane (CF₃CH₂CH₃, HFC-263fb) or 1-chloro-1,1-difluoropropane (CF₂ClCH₂CH₃, HCFC-262fc).

[0010] One embodiment of the invention disclosed herein relates to a method for preparing HFO-1252zc from one of HFC-263fb or HCFC-262fc, with or without a catalyst or in the presence of a strong base.

[0011] Another embodiment of the invention disclosed herein relates to a method for converting HCFC-262fc to HFO-1252zc in the presence or absence of a catalyst.

[0012] One embodiment of the invention disclosed herein relates to a method for making / producing a compound defined by the formula CF2XCH2CH3, wherein X is at least one of chlorine, fluorine, bromine, and iodine. The method includes contacting a compound defined by the formula CF2XCH=CH2 with hydrogen gas, wherein X is selected from chlorine, fluorine, bromine, and iodine.

[0013] Some embodiments of the present invention relate to methods for preparing trihalopropanes of the formula CXF2CH2CH3 (where X is one of F, Cl, Br and I, such as HFC-263fb where X=F and HCFC-262fc where X=Cl).

[0014] Another embodiment of the invention disclosed herein relates to a method of contacting compounds (including, but not limited to, HFO-1243zf or HCFO-1242zf) with hydrogen to form HFC-263fb or HCFC-262fc, respectively.

[0015] One embodiment of the present invention relates to a method for preparing trihalopropanes of the formula CF2XCH2CH3 (where X is F, i.e., HFC-263fb).

[0016] Another embodiment of the invention relates to a method for preparing trihalopropanes of the formula CF2XCH2CH3 (where X is chlorine, i.e., HCFC-262fc).

[0017] In some embodiments disclosed herein, the method includes contacting a first compound with hydrogen in a gaseous or liquid phase to produce a first product mixture comprising a second compound, and dehydrohalogenating the second compound to form a second product mixture comprising HFO-1252zc, and optionally recovering any unreacted first compound and / or unreacted second compound and recycling it to produce additional HFO-1252zc.

[0018] One embodiment disclosed herein relates to a method for preparing a compound defined by the formula CXF2CH2CH3 according to any of the following hydrogenation reactions, wherein X is at least one of chlorine, fluorine, bromine, and iodine:

[0019]

[0020]

[0021]

[0022] One embodiment disclosed herein relates to a method for preparing HFC-263fb according to reaction (I).

[0023] One embodiment disclosed herein relates to a method for preparing HCFC-262fc according to reaction (II) or (III).

[0024] In some embodiments disclosed herein, reactions (I), (II) or (III) may be carried out in the gas phase or in the liquid phase in the presence of a catalyst.

[0025] One implementation disclosed herein involves hydrogenating HFO-1243zf in a gaseous or liquid phase.

[0026] One embodiment disclosed herein involves hydrogenating HFO-1243zf in the gas phase at a temperature ranging from about 30°C to about 100°C (including, but not limited to, about 30°C, about 35°C, about 40°C, about 45°C, about 50°C, about 55°C, about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, about 95°C, or about 100°C, and all values ​​and ranges between about 30°C and about 100°C).

[0027] One embodiment disclosed herein involves hydrogenating HFO-1243zf in the liquid phase at a temperature ranging from about 20°C to about 100°C (including, but not limited to, about 20°C, about 25°C, about 30°C, about 35°C, about 40°C, about 45°C, about 50°C, about 55°C, about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, about 95°C, or about 100°C, and all values ​​and ranges between about 20°C and about 100°C).

[0028] One embodiment disclosed herein involves hydrogenating HCFO-1242zf in a gaseous or liquid phase.

[0029] One embodiment disclosed herein involves hydrogenating HCFO-1242zf in the gas phase at a temperature ranging from about 30°C to about 90°C (including, but not limited to, about 30°C, about 35°C, about 40°C, about 45°C, about 50°C, about 55°C, about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, or about 90°C, and all values ​​and ranges between about 30°C and about 90°C).

[0030] One embodiment disclosed herein involves hydrogenating HCFO-1242zf in the liquid phase at a temperature ranging from about 30°C to about 100°C (including, but not limited to, about 30°C, about 35°C, about 40°C, about 45°C, about 50°C, about 55°C, about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, about 95°C, or about 100°C, and all values ​​and ranges between about 30°C and about 100°C).

[0031] One embodiment disclosed herein involves hydrogenating HCFO-1232xf in a gaseous or liquid phase.

[0032] One embodiment disclosed herein involves hydrogenating HCFO-1232xf in the gas phase at a temperature ranging from about 40°C to about 100°C (including, but not limited to, about 40°C, about 45°C, about 50°C, about 55°C, about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, about 95°C, or about 100°C, and all values ​​and ranges between about 40°C and about 100°C).

[0033] One embodiment disclosed herein involves hydrogenating HCFO-1232xf in the liquid phase at a temperature ranging from about 40°C to about 100°C (including, but not limited to, about 40°C, about 45°C, about 50°C, about 55°C, about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, about 95°C, or about 100°C, and all values ​​and ranges between about 40°C and about 100°C).

[0034] In some embodiments disclosed herein, the hydrogenation catalysts for reactions (I), (II), or (III) carried out in the gas or liquid phase include metals selected from iron (Fe), cobalt (Co), nickel (Ni), ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), rhenium (Re), and platinum (Pt).

[0035] In one embodiment, the metal is supported on a support, which includes, for example, alumina, aluminum fluoride, or carbon. In some embodiments, the metal catalyst is supported on carbon, and the carbon support / carrier includes carbon, acid-washed carbon, activated carbon, and / or a three-dimensional matrix carbon-containing material. In one embodiment, the catalyst is Pd / carbon or Pd / Al₂O₃.

[0036] Another embodiment disclosed herein relates to the preparation of HFO-1252zc from compounds defined by the formula CXF2CH2CH3, wherein X is at least one of chlorine, fluorine, bromine, and iodine, including but not limited to HFC-263fb or HCFC-262fc which can be formed by hydrogenating precursor compounds such as HFO-1243zf, HCFO-1232xf, and HCFO-1242zf. HFC-263fb or HCFC-262fc is dehydrohalogenated according to one of the following reactions to form HFO-1252zc:

[0037]

[0038]

[0039] In some embodiments disclosed herein, methods such as preparing HFO-1252zc by reaction (IV) include first preparing HFC-263fb by hydrogenating HFO-1243zf, which may be carried out in the gas phase at a temperature of about 30°C to about 100°C or in the liquid phase at a temperature of about 20°C to about 100°C and produce a product mixture comprising at least HFC-263fb and HFO-1243zf, and then dehydrohalogenating HFC-263fb to form a product mixture comprising HFO-1252zc.

[0040] In some embodiments disclosed herein, methods for preparing HFO-1252zc by reaction (V) include first preparing HCFC-262fc by: hydrogenating HCFO-1232xf in a gas phase at a temperature of about 40°C to about 100°C or in a liquid phase at a temperature of about 40°C to about 100°C, or hydrogenating HCFO-1242zf in a gas phase at a temperature of about 30°C to about 90°C or in a liquid phase at a temperature of about 30°C to about 100°C to form a product mixture containing HCFC-262fc, and then dehydrohalogenating HCFC-262fc to form a product mixture containing HFO-1252zc.

[0041] In some embodiments disclosed herein, the method for preparing HFO-1252zc (e.g., reaction (IV)) includes first preparing HFC-263fb by hydrogenating HFO-1243zf in the presence of a hydrogenation catalyst such as a supported metal selected from Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Re and Pt.

[0042] In some embodiments disclosed herein, the method for preparing HFO-1252zc (e.g., reaction (V)) includes first preparing HCFC-262fc by hydrogenating HCFO-1242zf or HCFO-1232xf in the presence of a hydrogenation catalyst such as a supported metal selected from Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Re and Pt.

[0043] In some embodiments disclosed herein, the method for preparing HFO-1252zc (e.g., reactions (IV) and / or (V)) is carried out in the presence of a partially fluorinated metal oxide catalyst (including, but not limited to, Pd, Pt, Rh, Fe, Co, Ni, Cu, Mo, Cr, Mn, and combinations thereof as alloys or mixtures). In one embodiment, the catalyst may be supported or unsupported, such as Zn-doped chromium oxide. In the presence of a partially fluorinated metal oxide catalyst, the gas phase temperature is in the range of 300°C to 500°C, including 310°C, 320°C, 330°C, 340°C, 350°C, 360°C, 370°C, 380°C, 390°C, 400°C, 410°C, 420°C, 430°C, 440°C, 450°C, 460°C, 470°C, 480°C, 490°C, 500°C, 510°C, 520°C, 530°C, 540°C, and 550°C, and all values ​​and ranges therebetween, including 375°C to 475°C or 350°C to 450°C.

[0044] In some embodiments disclosed herein, the method for preparing HFO-1252zc (e.g., reactions (IV) and / or (V)) is carried out in the gas phase in the presence of an activated carbon-supported catalyst (including, but not limited to, Co, Ni, Cu, Mo, Cr, Mn, and combinations thereof as alloys or mixtures, optionally doped with Zn). The gas-phase temperature in the presence of the activated carbon-supported catalyst is in the range of 150°C to 300°C, including 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, 300°C, 155°C, 165°C, 175°C, 185°C, etc. ℃, 195℃, 205℃, 215℃, 225℃, 235℃, 245℃, 255℃, 265℃, 275℃, 285℃, 295℃, and all values ​​and ranges therebetween, including 150℃, 160℃, 170℃, 180℃, or 190℃ to 220℃, 230℃, 240℃, 250℃, 260℃, 270℃, 280℃, or 290℃.

[0045] In some embodiments, the preparation of HFO-1252zc (e.g., reaction (IV) and / or (V)) is carried out in the presence of a filler material (e.g., an alloy metal filler such as Monel, Hastelloy C) at a temperature in the range of 400°C to 700°C and a pressure in the range of atmospheric pressure to 80 psig. The reaction temperature can be between about 450°C and about 700°C, or between about 500°C and about 650°C, including 450°C, 460°C, 470°C, 480°C, 490°C, 500°C, 510°C, 520°C, 530°C, 540°C, 550°C, 560°C, 570°C, 580°C, 590°C, 600°C, 610°C, 620°C, 630°C, 640°C, 650°C, 660°C, 670°C, 680°C, 690°C and 700°C, preferably 475°C to 675°C.

[0046] In some embodiments, the method for preparing HFO-1252zc (e.g., reactions (IV) and / or (V)) is carried out in the absence of a catalyst or filler material, for example under pyrolysis conditions, at temperatures between about 400°C and about 900°C, or between about 450°C and about 800°C (including 400°C, 410°C, 420°C, 430°C, 440°C, 450°C, 460°C, 470°C, 480°C, 490°C, 50 ... The temperature range is 10℃, 520℃, 530℃, 540℃, 550℃, 560℃, 570℃, 580℃, 590℃, 600℃, 610℃, 620℃, 630℃, 640℃, 650℃, 660℃, 670℃, 680℃, 690℃, 700℃, 710℃, 720℃, 730℃, 740℃ or 750℃ and less than 900℃, or less than 850℃, or less than 800℃, and all values ​​and ranges in between.

[0047] In some embodiments disclosed herein, reactions (IV) and (V) are carried out independently in: (i) a gas phase in the presence of a metal oxide catalyst, (ii) a gas phase in the absence of a catalyst or packing material, (iii) a gas phase in the presence of a metal alloy packing material; (iv) a liquid phase in the presence of a strong base, (v) a liquid phase in the presence of a strong base and with or without an aprotic solvent, or (vi) a liquid phase in the presence of a strong base, with or without an aprotic solvent and with or without a phase transfer catalyst.

[0048] In some of the liquid-phase embodiments disclosed herein, the preparation of HFO-1252zc is carried out in the presence of a tert-butoxide conjugate such as potassium tert-butoxide or sodium tert-butoxide, at a temperature between -30°C and 100°C, in the presence of an aprotic solvent, and with or without a catalyst such as a crown ether. Suitable solvents include, but are not limited to, polar organic solvents such as alcohols (e.g., methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and tert-butanol), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), or methylpyrrolidine (MP).

[0049] In other embodiments, HFO-1252zc is prepared in the gas phase from one of CF3CH2CH3 and CClF2CH2CH3 with or without a catalyst.

[0050] In another embodiment, HFO-1252zc is prepared by dehydrohalogenating HFC-263fb or HCFC-262fc in the liquid phase in the presence of a strong base.

[0051] In another embodiment, HFO-1252zc is prepared by dehydrohalogenating HFC-263fb or HCFC-262fc in the liquid phase in the presence of a tert-butoxide conjugate such as potassium tert-butoxide or sodium tert-butoxide.

[0052] In another embodiment of the invention, the method for preparing HFO-1252zc includes thermally dehydrohalogenating HFC-263fb or HCFC-262fc with or without a catalyst.

[0053] In some embodiments disclosed herein, the method for preparing HFO-1252zc includes dehydrochlorinating HCFC-262fc or dehydrofluorinating HFC-263fb in the gas phase at a temperature selected from about 400°C to about 700°C or about 500°C to about 900°C and at atmospheric pressure and 80 psig pressure.

[0054] In some embodiments, the method disclosed herein includes first hydrogenating a first compound to produce a second compound, and then dehydrohalogenating the second compound to produce HFO-1252zc.

[0055] In some embodiments, the method disclosed herein for preparing HFO-1252zc is an integrated method.

[0056] In some embodiments, the method disclosed herein for preparing HFO-1252zc includes at least two process steps.

[0057] In another embodiment disclosed herein, HFO-1243zf is hydrogenated to HFC-263fb. In another embodiment disclosed herein, HCFO-1242zf or HCFO-1232xf is hydrogenated to HCFC-262fc.

[0058] In another embodiment disclosed herein, the present invention relates to a method for dehydrohalogenating one of HFC-263fb or HCFC-262fc.

[0059] In some embodiments disclosed herein, the defluorination of HFC-263fb to HFO-1252zc and / or the dechlorination of HCFC-262fc to HFO-1252zc are carried out with or without a catalyst.

[0060] In some embodiments disclosed herein, the dehydrofluorination of HFC-263fb and / or the dehydrochlorination of HCFC-262fc are carried out in the absence of a catalyst.

[0061] In some embodiments disclosed herein, the dehydrofluorination of HFC-263fb and / or the dehydrochlorination of HCFC-262fc are carried out in the presence of suitable fillers such as Monel. ™ Or Hastelloy ™ Nickel alloy shavings or wire (wool), or other materials that are inert to HCl and HF and allow for effective mixing of the starting materials.

[0062] In the defluorination and dechlorination reaction embodiments disclosed herein, the reactions are carried out at a temperature selected from the following: (I) between about 300°C and about 500°C, (II) between about 400°C and about 800°C, and (III) between about 500°C and about 800°C, with each of the aforementioned reactions carried out at a pressure range between atmospheric pressure and 80 psig and all values ​​and ranges therebetween.

[0063] In some embodiments, the defluorination of HFC-263fb and / or the dechlorination of HCFC-262fc are carried out at temperatures between about 300°C and about 500°C at pressures between atmospheric pressure and 80 psig and all values ​​and ranges therebetween.

[0064] In some implementations, the defluorination of HFC-263fb and the dechlorination of HCFC-262fc are carried out at temperatures between about 400°C and about 700°C at pressures between atmospheric pressure and 80 psig and all values ​​and ranges therebetween.

[0065] In some embodiments, the defluorination of HFC-263fb and the dechlorination of HCFC-262fc are carried out at temperatures between about 500°C and about 800°C at pressures between atmospheric pressure and 80 psig and all values ​​and ranges therebetween.

[0066] In some embodiments disclosed herein, HFC-263fb or HCFC-262fc is exposed to a sufficient temperature to achieve dehydrohalogenation, wherein the temperature is selected from one of the following:

[0067] Temperatures greater than 300℃, 310℃, 320℃, 330℃, 340℃, 350℃, 360℃, 370℃, 380℃, 390℃, 400℃, 410℃, 420℃, 430℃, 440℃, 450℃, 460℃, 470℃, 480℃, 490℃, and 500℃.

[0068] Greater than 400℃, 410℃, 420℃, 430℃, 440℃, 450℃, 460℃, 470℃, 480℃, 490℃, 500℃, 510℃, 520℃, 530℃, 540℃, 550℃, 560℃, 570℃, 580℃, 590℃, 600℃, 610℃, 620℃, 630℃, 640℃, 650℃, 660℃, 670℃, 680℃, 690℃ and 700℃, 710℃, 720℃, 730℃, 740℃, 750℃, 760℃, 770℃, 780℃, 790℃ and less than about 800℃, or

[0069] Greater than 500℃, 510℃, 520℃, 530℃, 540℃, 550℃, 560℃, 570℃, 580℃, 590℃, 600℃, 610℃, 620℃, 630℃, 640℃, 650℃, 660℃, 670℃, 680℃, 690℃, 700℃ and less than about 750℃.

[0070] In some embodiments, dehydrohalogenation occurs in the absence of a catalyst, in the presence of a metal alloy filler, in the presence of a strong base, or in the presence of supported or unsupported fluorinated transition metal oxides, nickel-based alloys, or nickel-chromium-based alloys (e.g., Inconel). ™ It can be carried out in the presence of a catalyst, or by pyrolysis in a reactor without a catalyst or filler material.

[0071] In some embodiments described herein, the catalytic dehydrohalogenation of hydrofluorocarbons or hydrochlorofluorocarbons to produce hydrofluoroolefins is typically carried out in the gas phase using a dehydrohalogenation catalyst. Suitable dehydrohalogenation catalysts may include, but are not limited to, chromium oxides, fluorinated chromium oxides doped with a metal (e.g., zinc). Other suitable catalysts include, but are not limited to, aluminum fluoride; fluorinated alumina; metals on aluminum fluoride; metals on fluorinated alumina; oxides, fluorides, and fluoride oxides of magnesium, zinc, and mixtures of magnesium and zinc and / or aluminum; lanthanum oxide and fluorinated lanthanum oxide; chromium oxide, fluorinated chromium oxide, and cubic chromium trifluoride; carbon, acid-washed carbon, activated carbon, three-dimensional matrix carbonaceous materials; and metal compounds supported on carbon. The metal compound is an oxide, fluoride, or fluoride oxide of at least one metal selected from the group consisting of sodium, potassium, rubidium, cesium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, chromium, iron, cobalt, rhodium, nickel, copper, and zinc, and mixtures thereof.

[0072] In some embodiments, liquid-phase dehydrohalogenation is carried out in the presence of a strong base, including but not limited to alkali metal conjugates, including but not limited to sodium tert-butoxide (NaOtBu) and potassium tert-butoxide ((CH3)3COK, KOtBu), wherein the alkali metal is a Group 1A metal in the periodic table that does not include hydrogen.

[0073] Some embodiments of the invention disclosed herein relate to compositions comprising, substantially consisting of, or consisting of the following: HFO-1252zc isomers, including at least HFO-1252zc, HFO-1234yf, HFO-1243zf, and HFC-263fb.

[0074] Certain embodiments of the invention disclosed herein relate to compositions comprising, substantially comprising, or consisting of the following: an HFO-1252zc isomer, including at least HFO-1252zc, HFO-1234yf, HFO-1243zf, and HFC-263fb, and at least one additional compound from Table 1 other than HFO-1252zc, HFO-1234yf, HFO-1243zf, and HFC-263fb.

[0075] Some embodiments of the invention disclosed herein relate to compositions comprising, substantially comprising, or consisting of the following: HFO-1252zc isomers, including at least HFO-1252zc, HFO-1261ze (E / Z isomers), HFO-1234yf, HFO-1243zf, and HCFC-262fc.

[0076] Certain embodiments of the invention disclosed herein relate to compositions comprising, substantially comprising, or consisting of HFC-263fb, HCFC-262fc, and / or HFO-1252zc, wherein HFC-263fb, HCFC-262fc, and / or HFO-1252zc are free of or substantially free of Group A fluorinated substances. In one embodiment, as used herein, “Group A fluorinated substance” includes any substance that satisfies the following condition: (i) contains at least one fully fluorinated methyl (-CF3) or methylene (-CF2-) carbon atom (without any H / Cl / Br / I bonded thereto); as well as (ii) It complies with the persistence criteria in soil / sediments and water as set out in Annex XIII (Section 1.1.1) of the EU REACH Regulation (https: / / reachonline.eu / reach / en / annex-xiii-1-1.1-1.1.1.html, accessed 2 May 2023), and the publication of that criterion is cited in Annex XV Restriction Report of 22 March 2023, the publication of which is incorporated herein by reference (https: / / echa.europa.eu / documents / 10162 / f605d4b5-7c17-7414-8823-b49b9fd43aea, accessed 2 May 2023).

[0077] In another implementation, as used herein, “Group A fluorides” includes the Henry's Law constant. < 250Pa*m 3 / mol and Any substance containing at least one fully fluorinated methyl (-CF3) or methylene (-CF2-) carbon atom (without any H / Cl / Br / I attached to it).

[0078] In the implementation plan, Group A fluorinated substances include, but are not limited to, TFA.

[0079] As used herein, the phrase "free of" relating to the presence of Group A fluorinated substances in the compositions of the present invention means that, when measured by gas chromatography with a flame ionization detector, gas chromatography with a mass detector (by analyzing gas or liquid samples), and / or ion chromatography (by analyzing water samples after bubbling a hot fluid through water), the amount of such substances in the composition is sufficiently low to be undetectable, including but not limited to 0%. Such methods are well known to those skilled in the art. As used herein, the phrase "substantially free of" relating to the presence of Group A fluorinated substances in the compositions of the present invention means that, when measured by gas chromatography (GC) techniques, such as gas chromatography (GC) with a flame ionization or electron capture detector, or GC coupled with a mass detector (GC / MS method), by ion chromatography (IC) or ion chromatography-mass spectrometry (IC-MS), or by high-performance liquid chromatography (HPLC) or high-performance liquid chromatography-mass spectrometry (HPLC-MS), the amount of such substances in the composition is >0% by weight and < 5% by weight, or >0% by weight and < 4% by weight, or >0% by weight and < 3% by weight, or >0% by weight and < 2% by weight, or >0% by weight and < 1% by weight, and all values ​​and ranges therebetween. TFA analytical standards can be used for gas chromatography or ion chromatography and are available from sources such as Sigma Aldrich.

[0080] In a preferred embodiment, the degradation products of the compositions according to the invention are free from or substantially free from Group A fluorides. As used herein, the phrase "free from" relating to the formation of Group A fluorides as degradation products of the compositions of the invention means that, when measured by GC techniques (e.g., GC or GC / MS methods with flame ionization or electron capture detectors), by IC or IC-MS techniques, or by HPLC or HPLC-MS techniques, the theoretical molar yield of such substances in the environmental compartments of air, soil / sediment, and water generated during the tropospheric degradation of the composition is sufficiently low to be undetectable, including but not limited to 0%. As used herein, the phrase "substantially free from" relating to the formation of Group A fluorides from the compositions of the invention means that, when measured by GC techniques (e.g., GC or GC / MS methods with flame ionization or electron capture detectors), by IC or IC-MS techniques, or by HPLC or HPLC-MS techniques, the theoretical molar yield of such substances in the environmental compartments of air, soil / sediment, and water generated during the tropospheric degradation of the composition is >0% and < 5%, or >0% and < 4%, or >0% and < 3%, or >0% and < 2%, or >0% and < 1%, and all values ​​and ranges in between.

[0081] Certain embodiments of the invention disclosed herein relate to compositions comprising, substantially comprising, or comprising of HFC-263fb, HCFC-262fc, and / or HFO-1252zc, and further comprising one or more additional members, including hydrofluorocarbons (HFCs), hydrochlorocarbons (HCCs), hydrochlorofluorocarbons (HCFCs), hydrofluoroolefins (HFOs), hydrochlorofluoroolefins (HFCOs), C2-C4 alkanes, C2-C4 olefins, and tert-butoxypropylene. In some embodiments, such compositions are free of or substantially free of Group A fluorinated substances and / or the degradation products of such compositions are free of or substantially free of Group A fluorinated substances as defined herein.

[0082] Certain embodiments of the invention disclosed herein relate to compositions comprising, substantially comprising, or composed of HFC-263fb, HCFC-262fc, and / or HFO-1252zc, and such compositions further comprise one or more additional compounds other than HFC-263fb, HCFC-262fc, and / or HFO-1252zc as identified in Table 1.

[0083] In one embodiment of the invention, a composition is disclosed herein comprising, substantially comprising, or comprising of, one or more additional members, including at least one of HFC-152a, HFC-254fb, HCFO-1233xf, HFO-1243zf, HFC-143a, HFC-245cb, and HCFC-253db, wherein the amount of HFC-263fb is at least one of 50%, 60%, 70%, 80%, 90%, 95%, or 99% of the total amount of the composition, and all values ​​and ranges therebetween, for example, at least between about 95% and less than 100%.

[0084] In one embodiment of the invention, a composition is disclosed herein comprising HFC-263fb and at least one additional member selected from, substantially comprising, or comprising of the following: HFO-1132a, HFC-125, HFC-143a, HFO-1225zc, HFC-152a, HFO-1252ze, HFO-1252yf, HFO-1252zf, and HFO-1252ye.

[0085] Another embodiment of the invention disclosed herein is a composition comprising, substantially comprising, or consisting of, HFC-263fb and one or more additional members or compounds, including at least one of HFC-152a, HFC-254fb, HCFO-1233xf, HFO-1243zf, HFC-143a, HFC-245cb, and HCFC-253db, wherein the amount of the additional member or each additional member comprises one of greater than 0% and less than 0.1%, greater than 0% and less than 0.01%, greater than 0% and less than 0.002%, greater than 0% and less than 0.003%, greater than 0% and less than 0.004%, and greater than 0% and less than 0.005%, and all values ​​and ranges therebetween, provided that the total amount of the composition is 100%.

[0086] Another embodiment of the invention disclosed herein is a composition comprising HFC-263fb and HFO-1252zc and at least one additional member or compound, substantially comprising or comprising thereof, the additional member or compound including at least one of HFC-152a, HFC-254fb, HCFO-1233xf, HFO-1243zf, HFC-143a, HFC-245cb and HCFC-253db, wherein the total amount of the additional member is greater than 0% and less than about 15%, 14%, 13%, 12%, 11%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2% or 1%, and all values ​​and ranges therebetween.

[0087] Another embodiment of the invention disclosed herein is a composition comprising HCFC-262fc and HFO-1252zc and at least one additional member derived from, substantially comprising, or comprising of: methane, ethylene, ethane, HFC-32, HFO-1132a, HCC-40, HCFC-22, HFO-1261ze-E, HFC-263fb, HFO-1252 isomer, HFC-281fa, HCC-30, C4H3ClF4, E-HFO-1251zb, Z-HFO-1251zb, HFO-1252 dimer, wherein the total amount of the additional member is between greater than 0% and less than about 10%, between greater than 0.001% and less than 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, or 1%, and all values ​​and ranges therein.

[0088] One embodiment of the invention disclosed herein is a composition comprising HFO-1252zc and one or more members selected from the group consisting substantially of or comprising of the following: methane, ethylene, ethane, HFC-23, HFC-125, HFC-143a, HFO-1141, propane, propylene, HFO-1234yf, propylene, C3H4F2, HFO-1261ze-E, HFO-1261ze-Z, HFC-263fb, 2-butene, cyclobutene, 2-methyl-1-propene, HFC-272fb, HCFO-1233, HCO-1260, HFC-374, HFO-1345 isomer, HCFO-1251zb-E, HCFO-1 251zb-Z, HFC-32, HFO-1132a, HCC-40, HCFC-22, HFO-1261ze-E, HFC-263fb, HFO-1252 isomer, HFC-281fa, HCC-30, C4H3ClF4 and HFO-1252 dimer, wherein HFO-1252zc exists in amounts greater than 20% or greater than 30% and less than 100%, or between 30% and 99%, or between greater than 30% and less than 99.5%, or between greater than 30% and less than 99.6%, or between greater than 30% and less than 99.7%, or between greater than 30% and less than 99.8%, or between greater than 30% and less than 99.9%, and all values ​​and ranges thereof.

[0089] One embodiment of the invention disclosed herein is a composition comprising HCFC-262fc and one or more compounds selected from the group consisting substantially of or composed of: propane, propylene, HFO-1261ze-E, HFO-1252zc, HFC-272fb, HCFO-1251zb-E, HCFO-1251zb-Z, HCFC-262 isomer, HCFC-252dc, HCO-1250, and HCC-260.

[0090] One embodiment of the invention disclosed herein is a composition comprising HCFC-262fc and one or more compounds selected from the group consisting substantially of or composed of the following: propane, HFO-1243zf, HFO-1252zc, HFO-1261ze-E, HCFO-1242zf, HCFO-1251zb-E, HCFO-1251zb-Z, HCFO-1242 isomer, HCFC-262 isomer, HCFO-1232, HCFC-252 isomer, HCFC-252dc, HCO-1250, and HCC-260.

[0091] One embodiment of the invention disclosed herein is a composition comprising HCFO-1242zf and one or more compounds selected from the group consisting substantially of or consisting of: ethane, HFC-152a, HFO-1243zf, HFO-1252zc, HCFC-253db, HCFC-262fc, HCFO-1242 isomers, and HCFO-1232.

[0092] One embodiment of the invention disclosed herein is a composition comprising HCFO-1242zf and one or more compounds selected from the group consisting substantially of or composed of the following: HFO-1252zc, HCFC-253db, HCFC-262fc, HCFO-1242 isomers, and HCFO-1232.

[0093] One embodiment of the invention disclosed herein is a composition comprising HCFC-262fc, HFO-1252zc and one or more compounds selected from the group consisting substantially of or composed of: propane, propylene, HFO-1261ze-E, HFC-272fb, HCFO-1251 isomer, HCFC-262 isomer, HCFC-252dc, HCO-1250, and HCC-260.

[0094] One embodiment of the invention disclosed herein is a composition comprising HCFC-262fc, HCFO-1242zf and one or more compounds selected from the group consisting substantially of or composed of: propane, HFO-1243zf, HFO-1252zc, HFO-1261, HCFO-1251 isomer, HCFO-1242 isomer, HCFC-262 isomer, HCFO-1232, HCFC-252, HCFC-252dc, HCO-1250, and HCC-260.

[0095] One embodiment of the invention disclosed herein is a composition comprising HCFO-1242zf, HFO-1252zc and one or more compounds selected from the group consisting substantially of or composed of ethane, HFC-152a, HFO-1243zf, HCFC-253db, HCFC-262fc, HCFO-1242 isomers, and HCFO-1232.

[0096] One embodiment of the invention disclosed herein is a composition comprising HCFO-1242zf, HCFC-262fc and one or more compounds selected from the group consisting substantially of or composed of HFO-1252zc, HCFC-253db, HCFO-1242 isomers and HCFO-1232.

[0097] One embodiment of the invention disclosed herein is a composition comprising, substantially comprising, or comprising of at least three members selected from the group consisting of: 1,1-difluoro-1-propene (HFO-1252zc), trifluoromethane (HFC-23), dichloromethane (HCC-30), chlorofluoromethane (HCFC-31), difluoromethane (HFC-32), ethylene, ethane, dichlorofluoromethane (HCFC-22), chloromethane (HCC-40), dichloromethane (HCC-30), methane, 1,1,2,2,2-pentafluoroethane (HFC-125), 1,1,2-trifluoroethane (HFC-143), 1,1,1-trifluoroethane (HFC-143a), 1,1 -Difluoroethane (HFC-152a), 1,1,1,2,2-pentafluoropropane (HFC-245cb), 2-chloro-1,1,1-trifluoropropane (HCFC-253db), 1,1,1,3-tetrafluoropropane (HFC-254fb), 1,1,1-trichloropropane (HCC-260fb), 1,1-dichloro-1-fluoropropane (HCFC-261fc), 1,1-difluoropropane (HFC-272fb), propane (HC-290), tetrafluorobutene (HFO-374), butane (HC-600), propadiene, 2-butene, cyclobutene, 2-methylpropene, 1-chloro-2,2-difluoroethylene (HCFO-1122), 1,2-difluoroethylene (HFO-1132), 1,1-Difluoroethylene (HFO-1132a), fluoroethylene (HFO-1141), ethylene (HO-1150), 1,1,2-trichloro-3,3,3-trifluoropropene (CFO-1213xa), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 3-chloro-3,3-difluoropropene (HCFO-1242zf), 3,3,3-trifluoropropene (HFO-1243zf), E-1-chloro-1-fluoro-1-propene (E-HCFO-1251zb), Z-1-chloro-1-fluoro-1-propene (Z-HCFO-1251z) b) 3-Chloropropene (HCO-1260zf), 3-fluoro-1-propene (E-HFO-1261zf), E-1-fluoro-1-propene (E-1261ze), 1-fluoropropane (HFC-281fa), 1,1-difluoropropane (HFC-272fb), tetrafluorobutane (C4H6F4), HFO-1252-dimer (C6F4H8), propylene (HO-1270), pentafluorobutene (HFO-1345), HFO-1252 isomer, C4H3ClF4, and E / Zt-BuO-CF=CH-CH3, wherein at least one of the three members includes 1-chloro-1,1-difluoropropane (HCFC-262fc) or 1,1,One of the compounds in 1-trifluoropropane (HFC-263fb).

[0098] One embodiment of the invention disclosed herein is a composition comprising an HFO-1252 isomer and at least one of HFO-1252zc, HFC-263fb, or HCFC-262fc, and one or more members selected from the group consisting substantially of or composed of: trifluoromethane (HFC-23), dichloromethane (HCC-30), chlorofluoromethane (HCFC-31), difluoromethane (HFC-32), ethylene, ethane, dichlorofluoromethane (HCFC-22), chloromethane (HCC-40), dichloromethane (HCC-30), methane, 1,1,2,2,2- Pentafluoroethane (HFC-125), 1,1,2-trifluoroethane (HFC-143), 1,1,1-trifluoroethane (HFC-143a), 1,1-difluoroethane (HFC-152a), 1,1,1,2,2-pentafluoropropane (HFC-245cb), 2-chloro-1,1,1-trifluoropropane (HCFC-253db), 1,1,1,3-tetrafluoropropane (HFC-254fb), 1,1,1-trichloropropane (HCC-260fb), 1,1-dichloro-1-fluoropropane (HCFC-261fc), 1,1-difluoropropane (HFC-272fb) Propane (HC-290), tetrafluorobutene (HFO-374), butane (HC-600), propadiene, 2-butene, cyclobutene, 2-methylpropene, 1-chloro-2,2-difluoroethylene (HCFO-1122), 1,2-difluoroethylene (HFO-1132), 1,1-difluoroethylene (HFO-1132a), fluoroethylene (HFO-1141), ethylene (HO-1150), 1,1,2-trichloro-3,3,3-trifluoropropene (CFO-1213xa), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 2,3,3,3-tetrafluoropropene Alkene (HFO-1234yf), 3-chloro-3,3-difluoropropene (HCFO-1242zf), 3,3,3-trifluoropropene (HFO-1243zf), 1,1-difluoro-1-propene (1252zc), E-1-chloro-1-fluoro-1-propene (E-HCFO-1251zb), Z-1-chloro-1-fluoro-1-propene (Z-HCFO-1251zb), 3-chloropropene (HCO-1260zf), 3-fluoro-1-propene (HFO-1261zf), E-1-fluoro-1-propene (E-1261ze), 1-fluoropropane (281fa), 1,1-Difluoropropane (272fb), tetrafluorobutane (C4H6F4), 1252-dimer (C6F4H8), propylene (HO-1270), pentafluorobutene (HFO-1345), and E / Zt-BuO-CF=CH-CH3, wherein HFO-1252zc is present in amounts greater than 20%, greater than 30%, between 30% and 99%, between 30% and 99.5%, between 30% and 99.6%, between 30% and 99.7%, between 30% and 99.8%, or between 30% and 99.9%, and all values ​​and ranges therein, representing a portion of the total composition.

[0099] One embodiment of the invention disclosed herein is a composition comprising HFO-1252zc and one or more additional members selected from the group consisting substantially of or comprising of: trifluoromethane (HFC-23), dichloromethane (HCC-30), chlorofluoromethane (HCFC-31), difluoromethane (HFC-32), ethylene, ethane, dichlorofluoromethane (HCFC-22), chloromethane (HCC-40), dichloromethane (HCC-30), methane, 1,1,2,2,2-pentafluoroethane (HFC-125), 1,1,2-trifluoroethane (HFC-125), etc. -143), 1,1,1-trifluoroethane (HFC-143a), 1,1-difluoroethane (HFC-152a), 1,1,1,2,2-pentafluoropropane (HFC-245cb), 2-chloro-1,1,1-trifluoropropane (HCFC-253db), 1,1,1,3-tetrafluoropropane (HFC-254fb), 1,1,1-trichloropropane (HCC-260fb), 1,1-dichloro-1-fluoropropane (HCFC-261fc), 1,1-difluoropropane (HFC-272fb), propane (HC-290), tetrafluorobutene (HF O-374), butane (HC-600), propylene, 2-butene, cyclobutene, 2-methylpropene, 1-chloro-2,2-difluoroethylene (HCFO-1122), 1,2-difluoroethylene (HFO-1132), 1,1-difluoroethylene (HFO-1132a), vinyl fluoride (HFO-1141), ethylene (HO-1150), 1,1,2-trichloro-3,3,3-trifluoropropylene (CFO-1213xa), 2-chloro-3,3,3-trifluoropropylene (HCFO-1233xf), 2,3,3,3-tetrafluoropropylene (HFO-1234) yf), 3-chloro-3,3-difluoropropene (HCFO-1242zf), 3,3,3-trifluoropropene (HFO-1243zf), 1,1-difluoro-1-propene (1252zc), E-1-chloro-1-fluoro-1-propene (E-HCFO-1251zb), Z-1-chloro-1-fluoro-1-propene (Z-HCFO-1251zb), 3-chloropropene (HCO-1260zf), E-1-fluoro-1-propene (E-HFO-1261ze), 3-fluoro-1-propene (1261zf), 1-fluoropropane (281fa), 1,The composition comprises 1-difluoropropane (272fb), tetrafluorobutane (C4H6F4), 1252-dimer (C6F4H8), propylene (HO-1270), pentafluorobutene (HFO-1345), and E / Zt-BuO-CF=CH-CH3, wherein one of the additional members includes either HCFC-262fc or HFC-263fb, and the additional member is present in an amount greater than 20%, greater than 30%, between 30% and 99%, between 30% and 99.5%, between 30% and 99.6%, between 30% and 99.7%, between 30% and 99.8%, or between 30% and 99.9%, and all values ​​and ranges therein.

[0100] In some embodiments disclosed herein, the composition comprises at least one of HFC-263fb and HCFC-262fc, HFO-1252zc, and one or more additional members selected from, substantially composed of, or composed of: ethylene, HFC-23, HFO-1132a, propane, HFO-1234yf, E-HFO-1261ze, HFC-143a, HCFO-1233, and HFO-374, wherein HFO-1252zc is present in an amount greater than 20%, greater than 30%, between 30% and 99%, between 30% and 99.5%, between 30% and 99.6%, between 30% and 99.7%, between 30% and 99.8%, or between 30% and 99.9%, and all values ​​and ranges thereof, representing a portion of the total composition.

[0101] One embodiment of the invention disclosed herein is a composition comprising HFC-263fb and one or more additional compounds selected from the group consisting substantially of or consisting of: 1,1-difluoroethane (HFC-152a), 1,1,1,3-tetrafluoropropane (HFC-254fb), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), CF3CH=CH2 (HFO-1243zf), 1,1,1-trifluoroethane (HFC-143a), 1,1,1,2,2-pentafluoropropane (HFC-245cb), and 2-chloro-1,1,1-trifluoropropane (HCFC-253db), wherein the total amount of the additional compounds constitutes a portion of the total composition between 0% and 1%, between 0% and 0.5%, between 0% and 0.1%, and all values ​​and ranges therebetween.

[0102] Another embodiment of the invention disclosed herein is a composition comprising HFC-263fb and the remainder of one or more additional compounds selected from the group consisting of, substantially consisting of, or substantially consisting of: 1,1-difluoroethane (HFC-152a), 1,1,1,3-tetrafluoropropane (HFC-254fb), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), CF3CH=CH2 (HFO-1243zf), 1,1,1-trifluoroethane (HFC-143a), 1,1,1,2,2-pentafluoropropane (HFC-245cb), and 2-chloro-1,1,1-trifluoropropane (HCFC-253db), wherein the total amount of the remainder constitutes a portion of the total composition between 0% and 0.5% or between 0% and 0.1%, and all values ​​and ranges therebetween.

[0103] Another embodiment of the invention disclosed herein is a composition comprising, substantially comprising, or comprising HFC-263fb, and the balance comprising one or more compounds selected from the group consisting of: 1,1-difluoroethane (HFC-152a), 1,1,1,3-tetrafluoropropane (HFC-254fb), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), CF3CH=CH2 (HFO-1243zf), 1,1,1-trifluoroethane (HFC-143a), 1,1,1,2,2-pentafluoropropane (HFC-245cb), and HCFC-253db.

[0104] In some embodiments, the feed composition primarily comprises HFC-263fb, and the remainder comprises one or more compounds selected from the group consisting of 1,1-difluoroethane (HFC-152a), 1,1,1,3-tetrafluoropropane (HFC-254fb), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), CF3CH=CH2 (HFO-1243zf), 1,1,1-trifluoroethane (HFC-143a), 1,1,1,2,2-pentafluoropropane (HFC-245cb), and 2-chloro-1,1,1-trifluoropropane (HCFC-253db), preferably at least 99.9% HFC-263fb based on the total amount of the composition.

[0105] In another embodiment disclosed herein, the feed composition primarily comprises HFC-263fb and includes, in a total amount of one or more of the following compounds: 1,1-difluoroethane (HFC-152a), 1,1,1,3-tetrafluoropropane (HFC-254fb), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), CF3CH=CH2 (HFO-1243zf), 1,1,1-trifluoroethane (HFC-143a), 1,1,1,2,2-pentafluoropropane (HFC-245cb), and HCFC-253db, less than about 0.3%, less than about 0.2%, less than about 0.1%, less than about 0.09%, or less than about 0.05%, and all values ​​and ranges therebetween.

[0106] In another embodiment disclosed herein, the HFC-263fb composition is produced by hydrogenation of HFO-1243zf.

[0107] One embodiment of the invention disclosed herein is a composition comprising HCFC-262fc and one or more additional compounds selected from the group consisting substantially of or consisting of: 1,1,1-trifluoropropane (HFC-263fb), 1,1-dichloro-1-fluoropropane (HCFC-261fc), 1,1,1-trichloropropane (HCC-260fb), 3-chloro-3,3-difluoropropene (HCFO-1242zf), 3,3,3-trifluoropropene (HFO-1243zf), and 1,1-difluoropropane (HFC-272fb), chlorofluoropropene (HCFO-1251), dichloropropene (HCFO-1250), and 1,1-difluoro-1-propene (HFO-1252zc), wherein the total amount of the additional compounds is between 0% and less than 1%, between 0% and less than 0.5%, and between 0% and less than 0.1%.

[0108] In some embodiments disclosed herein, the composition is prepared by hydrogenating HFO-1243zf, and the hydrogenated composition is fed into a reactor for the preparation of HFO-1252zc.

[0109] In another embodiment disclosed herein, the feed composition comprises at least about 60% of 1,1,1-trifluoropropane (HFC-263fb) defined by the GC / FID area.

[0110] In some embodiments disclosed herein, the composition is prepared by hydrogenating HCFO-1242zf or HCFO-1232xf, and the hydrogenated composition is fed into a reactor for the preparation of HFO-1252zc.

[0111] In another embodiment disclosed herein, the feed composition comprises at least about 60% of 1-chloro-1,1-difluoropropane (HCFC-262fc) defined by the GC / FID area.

[0112] 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 pertains. In case of any conflict, this specification and its included definitions shall prevail. Although methods and materials similar to or equivalent to those described herein may be used in the practice or testing of embodiments of the invention, suitable methods and materials are described below. Furthermore, materials, methods, and examples are illustrative only and are not intended to be limiting. Detailed Implementation

[0113] The foregoing overview and the following detailed description are exemplary and illustrative only, and do not constitute a limitation on the invention as defined in the appended claims. Further features and benefits of any one or more embodiments will become apparent from the following detailed description and claims.

[0114] This invention relates to methods for preparing HFO-1252zc, HFC-263fb, and / or HCFC-262fc. More specifically, these methods comprise, substantially consist of, or consist of the following steps: preparing a trihalopropane defined by the formula CF2XCH2CH3 (where X is at least one of Cl, F, Br, or I) by hydrogenating a compound defined by the formula CF2XCY=CH2 (e.g., HFO-1243zf, HCFO-1242zf, or HCFO-1232xf) (where X is one of Cl, F, Br, or I, and Y is one of H, Cl, F, Br, or I). In one embodiment, the trihalopropane of the formula CF2XCH2CH3 includes one of HFC-263fb or HCFC-262fc.

[0115] More specifically, the invention disclosed herein relates to methods for preparing HFO-1252zc, HFC-263fb and / or HCFC-262fc according to the following reactions, which can be carried out in the gas phase or liquid phase, preferably in the presence of a catalyst:

[0116] CF3CH=CH2 (HFO-1243zf) + H2 → CF3CH2CH3 (HFC-263fb)(I)

[0117] CClF2CH=CH2 (HCFO-1242zf) + H2 → CClF2CH2CH3 (HCFC-262fc)(II)

[0118] CClF2CCl=CH2 (HCFO-1232xf) + 2H2→ CClF2CH2CH3 + HCl(III)

[0119] HFC-263fb or HCFC-262fc compounds prepared according to hydrogenation reactions (I), (II) or (III) respectively are then dehydrohalogenated to form HFO-1252zc according to the following reactions, which can be carried out in the gas phase or liquid phase with or without a catalyst.

[0120] CF3CH2CH3 → CF2=CHCH3 (HFO-1252zc) + HF(IV)

[0121] CClF2CH2CH3 → CF2=CHCH3 (HFO-1252zc) + HCl(V)

[0122] Before addressing the details of the implementation schemes described herein, certain terms are defined or clarified as follows.

[0123] As used herein, the term "hydrogen (halogenated) alkane" means a molecule containing hydrogen, carbon, and optionally fluorine and / or chlorine and / or bromine and / or iodine, and without a carbon-carbon double bond (halogenated group, fluorine, chlorine, bromine, iodine). Examples are described throughout this specification. The term hydrogen (halogenated) alkane includes both alkanes and halogen-substituted alkanes.

[0124] As used herein, the term “dehydrohalogenation” means the loss of HX from a hydrohalogenated alkane, where X = F, Cl, Br, I, and H and X are located on adjacent carbons in the hydrohalogenated alkane. For example, as used herein, the term “dehydrofluorination” (“dehydrofluorinating” or “dehydrofluorinated”) means the process during which hydrogen and fluorine are removed from adjacent carbons in the molecule; and as used herein, the term “dehydrochlorination” (“dehydrochlorinating” or “dehydrochlorinated”) means the process during which hydrogen and chlorine are removed from adjacent carbons in the molecule.

[0125] As disclosed herein, the conversion of CF3CH2CH3 takes place in the gas phase at temperatures between approximately 300 °C and approximately 800 °C, depending on the presence or absence of a catalyst and / or alloying packing material, and is typically carried out as a continuous process. Many gas-phase reactor configurations are possible, including packed-bed tube or column reactors operating in continuous mode.

[0126] In contrast, liquid-phase reactions typically occur at lower temperatures, such as in the range of -40°C to 100°C, and are usually operated in a batch or semi-batch manner, although liquid-phase operations can be operated by continuously feeding reactants and removing products from the reaction, and are typically equipped with mechanical stirring to ensure homogeneity of the reaction. Liquid-phase reactors can be equipped with suitable stirring devices to increase the contact between fluids and can be operated similarly in batch, semi-batch, and continuous modes. In addition to the reactors disclosed herein, preheaters and vaporizers, heat exchangers, feed and effluent lines, units associated with mass transfer, contact vessels (premixers), distillation columns, and valves associated with reactors, heat exchangers, vessels, columns, and units used in the methods of the various embodiments disclosed herein should be constructed of corrosion-resistant materials.

[0127] As used herein, the terms “comprising,” “including,” “having,” or any other variations thereof are intended to cover non-exclusive inclusion. For example, a process, method, article of manufacture, or apparatus that includes a list of elements is not necessarily limited to those elements, but may include other elements not expressly listed or inherent to such process, method, article of manufacture, or apparatus. Furthermore, unless expressly stated otherwise, “or” refers to an inclusive or non-exclusive or. For example, condition A or B satisfies any of the following conditions: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); and both A and B are true (or exist).

[0128] The transitional phrase "consistently composed of..." is used to define compositions or methods that include materials, steps, features, components, or elements in addition to those disclosed in the literature, provided that these additionally included materials, steps, features, components, or elements do not significantly affect the essential and novel features of the invention protected by the claims, particularly the mode of action of any process in carrying out the invention to achieve the desired result. The term "consistently composed of..." occupies an intermediate position between "comprising" and "composed of...".

[0129] The transitional phrase "composed of..." does not include any unspecified elements, steps, or components. If included in the claims, protection will not be provided for materials other than those described, except for impurities typically associated with them. When the phrase "composed of..." appears in a clause of the body of a claim, rather than immediately following the preamble, it only limits the elements described in that clause; other elements as a whole are not excluded from the claims.

[0130] Where the applicant has defined the invention or a part thereof using open-ended terms such as “comprising”, it should be readily understood (unless otherwise stated) that the description should be interpreted as also including inventions using terms such as “substantially composed of” or “composed of”.

[0131] Furthermore, the terms "an" or "a" are used to describe the elements and components described herein. This is for convenience only and to give a general meaning to the scope of the invention. This description should be understood to include one or at least one, and the singular includes the plural, unless it is obvious that it means otherwise.

[0132] When quantities, concentrations, or other values ​​or parameters are given as a list of ranges, preferred ranges, or preferred upper and / or preferred lower limits, it should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred range value and any lower or preferred range value, regardless of whether the range is disclosed individually. Wherever a numerical range is given herein, the range is intended to include its endpoints, as well as all integers and fractions within that range, unless otherwise indicated.

[0133] As used in this article, the GC / FID peak area is related to the amount of compound present as a proportion of the total area of ​​all detected peaks. The FID area % can be converted to mol% using a calculated or measured response factor, see, for example, https: / / www.chromatographytoday.com / news / gc-mdgc / 32 / breaking-news / what-is-a-response-factor / 31169.

[0134] As used herein, the term “about” is intended to account for variations due to experimental error (e.g., adding or subtracting approximately 10%, ±1%, ±2%, ±3, … ±10% of the indicated value). Unless otherwise expressly stated, all measurements reported herein should be understood to be modified by the term “about”, whether or not the term is explicitly used.

[0135] The compounds mentioned in this disclosure may be represented by codes, chemical structures, and / or chemical names based on the naming conventions for fluorine-containing compounds. For convenience and reference, selected compounds with codes, structures, and chemical names are provided in Table 1.

[0136] Table 1

[0137]

[0138]

[0139]

[0140] Some of the compounds present in the compositions of the present invention as identified in Table 1 may be present as isomers or stereoisomers with different configurations. The present invention is intended to include all isomers of a single configuration, a single stereoisomer, or any combination or mixture thereof. For example, t-BuO-CF=CH-CH3 is intended to represent any combination or mixture of cis isomers (Z), trans isomers (E), or any ratio of two isomers. Single or multiple isomers of the same compound may be used in any proportion.

[0141] In some embodiments, HFC-263fb is prepared by contacting HFO-1243zf with hydrogen in the presence of a metal catalyst. In other embodiments, HCFC-262fc is prepared by contacting HCFO-1232xf or HCFO-1242zf with hydrogen in the presence of a metal catalyst.

[0142] In one embodiment, for hydrogenating HFO-1243zf to HFC-263fb and / or hydrogenating HCFO-1232xf or HCFO-1242zf to HCFC-262fc, the metal is supported on a support, such as Pd supported on alumina, aluminum fluoride, or carbon. In other embodiments, the metal is a Group VIII metal or rhenium. In some embodiments disclosed herein, the hydrogenation catalyst comprises a metal selected from Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, and Pt.

[0143] In some embodiments, the metal catalyst used to hydrogenate HFO-1243zf to HFC-263fb and / or to hydrogenate HCFO-1232xf or HCFO-1242zf to HCFC-262fc is supported on carbon, and the carbon support / carrier includes carbon, acid-washed carbon, activated carbon, or a three-dimensional carbon-containing matrix material. In one embodiment, the catalyst / catalyst used to convert HFO-1243zf to HFC-263fb and / or to convert HCFO-1232xf or HCFO-1242zf to HCFC-262fc is Pd / carbon or Pd / Al2O3.

[0144] In some embodiments, HFC-263fb is prepared by contacting HFO-1243zf in the gas phase with hydrogen in the presence of a metal catalyst at a temperature ranging from about 30°C to about 100°C (including but not limited to about 30°C, about 35°C, about 40°C, about 45°C, about 50°C, about 55°C, about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, about 95°C, or about 100°C, and all values ​​and ranges between about 30°C and about 100°C).

[0145] In some embodiments, HFC-263fb is prepared by contacting HFO-1243zf in the liquid phase with hydrogen in the presence of a metal catalyst at a temperature ranging from about 20°C to about 100°C (including but not limited to about 20°C, about 25°C, about 30°C, about 35°C, about 40°C, about 45°C, about 50°C, about 55°C, about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, about 95°C, or about 100°C, and all values ​​and ranges between about 20°C and about 100°C).

[0146] In some embodiments, HCFC-262fc is prepared by contacting HCFO-1242zf in the gas phase with hydrogen in the presence of a metal catalyst at a temperature ranging from about 30°C to about 90°C (including but not limited to about 30°C, about 35°C, about 40°C, about 45°C, about 50°C, about 55°C, about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, or about 90°C, and all values ​​and ranges between about 30°C and about 90°C).

[0147] In some embodiments, HCFC-262fc is prepared by contacting HCFO-1242zf in the liquid phase with hydrogen in the presence of a metal catalyst at a temperature ranging from about 30°C to about 100°C (including, but not limited to, about 30°C, about 35°C, about 40°C, about 45°C, about 50°C, about 55°C, about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, about 95°C, or about 100°C, and all values ​​and ranges between about 30°C and about 100°C).

[0148] In some embodiments, HCFC-262fc is prepared by contacting HCFO-1232xf in the gas phase with hydrogen in the presence of a metal catalyst at a temperature ranging from about 40°C to about 100°C (including but not limited to about 40°C, about 45°C, about 50°C, about 55°C, about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, about 95°C, or about 100°C, and all values ​​and ranges between about 40°C and about 100°C).

[0149] In some embodiments, HCFC-262fc is prepared by contacting HCFO-1232xf in the liquid phase with hydrogen in the presence of a metal catalyst at a temperature ranging from about 40°C to about 100°C (including but not limited to about 40°C, about 45°C, about 50°C, about 55°C, about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, about 95°C, or about 100°C, and all values ​​and ranges between about 40°C and about 100°C).

[0150] In some embodiments, dehydrohalogenation is carried out as follows: (I) in the absence of a catalyst or (II) such as with a metal alloy filler such as Monel. ™ Or Hastelloy ™ (ii) HF / HCl inert filler materials filled with nickel alloy shavings or wires, or other materials inert to HCl and HF, and (iii) transition metal oxides, nickel-based alloys, or nickel-chromium-based alloys in the presence of supported or unsupported partially fluorinated materials (e.g., Inconel). ™ In the case of a catalyst, the support comprises one of carbon, silicon carbide, or alumina, or (III) such as a metal alloy filler such as Monel. ™ Or Hastelloy ™ Inert filler material filled with nickel alloy shavings or metal wire, or other materials inert to HCl and HF.

[0151] In some embodiments, dehydrohalogenation is carried out in the liquid phase in the presence of a strong base at temperatures below 100°C, below 80°C, below 60°C, below 40°C, or below 20°C but above about 0°C.

[0152] In some implementations, the dehydrohalogenation of HFC-263fb or HCFC-262fc is carried out in the absence of a catalyst.

[0153] In some implementations, the dehydrohalogenation of HFC-263fb or HCFC-262fc is carried out in the absence of both a catalyst and an alloy filler material.

[0154] In some embodiments, the dehydrohalogenation of HFC-263fb or HCFC-262fc is carried out in the absence of a catalyst but in the presence of a packing material.

[0155] In the gas-phase dehydrohalogenation reaction embodiments disclosed herein, the reaction is carried out at a temperature selected from one of about 300°C to about 800°C, about 300°C to about 500°C, about 400°C to about 700°C, about 400°C to about 800°C, or about 500°C to about 750°C.

[0156] In some of the HFC-263fb and / or HCFC-262fc dehydrohalogenation embodiments disclosed herein, the reaction is carried out at a temperature between about 300°C and about 500°C.

[0157] In some implementations, HFC-263fb and / or HCFC-262fc are exposed to temperatures sufficient to achieve dehydrohalogenation in the range of about 400°C to about 700°C.

[0158] In some implementations, the defluorination of HFC-263fb is carried out at a temperature between about 500°C and about 750°C.

[0159] In some embodiments, liquid-phase dehydrohalogenation is carried out in the presence of a strong base conjugate with an alkali metal (including, but not limited to, sodium tert-butoxide (NaOtBu) and potassium tert-butoxide ((CH3)3COK, KOtBu)).

[0160] In some embodiments, dehydrohalogenation, defluorination (e.g., defluorination of HFC-263fb to form HFO-1252zc), or dechlorination (e.g., dechlorination of HCFC-262fc to form HFO-1252zc) is carried out in the gas phase by pyrolysis, preferably in the absence of a catalyst and / or packing material. Preferably, the pyrolysis is carried out at a temperature between about 400°C and about 900°C, or between about 450°C and about 800°C.

[0161] In some embodiments disclosed herein, the composition comprises HFO-1252zc, HCFC-262fc or HFC-263fb and one or more additional members or compounds selected from the group consisting substantially of or comprising the following: methane, ethylene, trifluoromethane (HFC-23), vinyl fluoride (HFO-1141), propane (HC-290), propylene (HO-1270), 2,3,3,3-tetrafluoropropylene (HF). O-1234yf), propylene, propylene, C3H4F2, 3-fluoro-1-propene (HFO-1261), 3-fluoro-1-propene (HFO-1261), 2-butene, 2-butene, cyclobutene, 2-methyl-1-propene, 1,1-difluoropropane (272fb), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 3-chloropropene (HCO-1260zf), C3H4FCl (I) (HCFO-1251 isomer) and C3H4FCl (II) (HCFO-isomer 1251).

[0162] In some embodiments disclosed herein, the composition comprises HFO-1252zc, HFC-263fb and (1) one or more of the following: methane, ethylene, trifluoromethane (HFC-23), vinyl fluoride (HFO-1141), propane (HC-290), propylene (HO-1270), 2,3,3,3-tetrafluoropropene (HFO-1234yf), propylene, propylene, C3H4F2, 3-fluoro-1-propene (HFO-1261), 3-fluoro-1-propene (HFO-1261), 2-butene, cyclobutene, 2-methyl-1-propene, 1,1-difluoropropane, 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 3-chloropropene (HCO-1260zf), C3H4FCl (I) (HCFO-1251-isomer) and C3H4FCl. (II) an additional member or compound of (HCFO-1251-isomer) or (2) at least one additional member selected from HFO-1132a, HFC-125, HFC-143a, HFO-1225zc, HFC-152a, HFO-1252ze, HFO-1252yf, HFO-1252zf and HFO-1252ye, substantially composed of or composed of.

[0163] In some embodiments disclosed herein, the composition comprises at least one of HFO-1252zc, HCFC-262fc, or HFC-263fb, and one or more additional members selected from, substantially composed of, or composed of: methane, ethylene, ethane, HFC-23, HFC-125, HFC-143a, HFO-1141, propane, propylene, HFO-1234yf, propylene, C3H4F2, HFO-1261ze-E, HFO-1261ze-Z, HFC-263fb, 2-butene. Cyclobutene, 2-methyl-1-propene, HFC-272fb, HCFO-1233, HCO-1260, HFC-374, HFO-1345 isomer, HCFO-1251zb-E, HCFO-1251zb-Z, HFC-32, HFO-1132a, HCC-40, HCFC-22, HFO-1261ze-E, HFC-263fb, HFO-1252 isomer, HFC-281fa, HCC-30, C4H3ClF4 and HFO-1252 dimer.

[0164] In some embodiments disclosed herein, the composition comprises at least one of 1,1-difluoropropylene (HFO-1252zc), 1,1,1-trifluoropropane (HFC-263fb), and one or more additional members selected from the group consisting substantially of or comprising of: methane, ethylene, ethane, HFC-23, HFC-125, HFC-143a, HFO-1141, propane, propylene, HFO-1234yf, propylene, C3H4F2, HFO-1261ze-E, HFO-1261ze-Z, HFC-263fb 2-Butene, cyclobutene, 2-methyl-1-propene, HFC-272fb, HCFO-1233, HCO-1260, HFC-374, HFO-1345 isomer, HCFO-1251zb-E, HCFO-1251zb-Z, HFC-32, HFO-1132a, HCC-40, HCFC-22, HFO-1261ze-E, HFC-263fb, HFO-1252 isomer, HFC-281fa, HCC-30, C4H3ClF4 and HFO-1252 dimer.

[0165] In some embodiments disclosed herein, the composition comprises at least one of HFO-1252zc, HCFC-262fc, and HFC-263fb, and one or more additional members selected from the group consisting substantially of or composed of: methane, ethylene, ethane, HFC-23, HFC-125, HFC-143a, HFO-1141, propane, propylene, HFO-1234yf, propylene, C3H4F2, HFO-1261ze-E, HFO-1261ze-Z, HFC-263fb, and 2-butene. Cyclobutene, 2-methyl-1-propene, HFC-272fb, HCFO-1233, HCO-1260, HFC-374, HFO-1345 isomer, HCFO-1251zb-E, HCFO-1251zb-Z, HFC-32, HFO-1132a, HCC-40, HCFC-22, HFO-1261ze-E, HFC-263fb, HFO-1252 isomer, HFC-281fa, HCC-30, C4H3ClF4 and HFO-1252 dimer.

[0166] In some embodiments disclosed herein, the composition comprises at least one of HFO-1252zc, HFC-263fb, and one or more additional members selected from, substantially consisting of, or consisting of: ethylene, trifluoromethane (HFC-23), 1,1-difluoroethylene (HFO-1132a), vinyl fluoride (HFO-1141), 1,1,2,2,2-pentafluoroethane (HFC-125), propane (HC... -290), 1,1,2-trifluoroethane (HFC-143), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,1-difluoroethane (HFC-152a), 3-fluoro-1-propene (HFO-1261zf), 1,1,1-trifluoroethane (HFC-143a), difluoropropane, chlorotrifluoropropene, pentafluorobutene (HFO-1345), and C4H6F4 (HFC-374).

[0167] In certain embodiments disclosed herein, the composition comprises at least one of HFO-1252zc, HCFC-262fc, and HFC-263fb, and one or more additional members selected from, substantially composed of, or composed of: trifluoromethane (HFC-23), dichloromethane (HCC-30), chlorofluoromethane (HCFC-31), difluoromethane (HFC-32), ethylene, ethane, dichlorofluoromethane (HCFC-22), chloromethane (HCC-40), dichloromethane (HCC-30), methane, 1,1,2,2,2-pentafluoroethane (HFC-125), 1,1,2-trifluoroethane (HFC-143), 1,1 1-Trifluoroethane (HFC-143a), 1,1-Difluoroethane (HFC-152a), 1,1,1,2,2-Pentafluoropropane (HFC-245cb), 2-Chloro-1,1,1-Trifluoropropane (HCFC-253db), 1,1,1,3-Tetrafluoropropane (HFC-254fb), 1,1,1-Trichloropropane (HCC-260fb), 1,1-Dichloro-1-fluoropropane (HCFC-261fc), 1,1-Difluoropropane (HFC-272fb), Propane (HC-290), Tetrafluorobutene (HFO-374), Butane (HC-600), Propylene, 2-Butene, Cyclobutene, 2-Methylpropane Alkenes, 1-chloro-2,2-difluoroethylene (HCFO-1122), 1,2-difluoroethylene (HFO-1132), 1,1-difluoroethylene (HFO-1132a), fluoroethylene (HFO-1141), ethylene (HO-1150), 1,1,2-trichloro-3,3,3-trifluoropropylene (CFO-1213xa), 2-chloro-3,3,3-trifluoropropylene (HCFO-1233xf), 2,3,3,3-tetrafluoropropylene (HFO-1234yf), 3-chloro-3,3-difluoropropylene (HCFO-1242zf), 3,3,3-trifluoropropylene (HFO-1243zf), 1,1-difluoro-1-propene Alkene (1252zc), E-1-chloro-1-fluoro-1-propene (E-HCFO-1251zb), Z-1-chloro-1-fluoro-1-propene (Z-HCFO-1251zb), 3-chloropropene (HCO-1260zf), E-1-fluoro-1-propene (E-HFO-1261ze), 3-fluoro-1-propene (1261zf), 1-fluoropropane (281fa), 1,1-difluoropropane (272fb), tetrafluorobutane (C4H6F4), 1252-dimer (C6F4H8), propylene (HO-1270), pentafluorobutene (HFO-1345) and E / Zt-BuO-CF=CH-CH3.

[0168] In some embodiments disclosed herein, the composition comprises, is substantially composed of, or is composed of: 1,1-difluoropropylene (HFO-1252zc), 3,3,3-trifluoropropylene (HFO-1243zf), and one or more members selected from the group consisting of: trifluoromethane (HFC-23), dichloromethane (HCC-30), chlorofluoromethane (HCFC-31), difluoromethane (HFC-32), ethylene, ethane, dichlorofluoromethane (HCFC-22), chloromethane (HCC-40), dichloromethane (HCC-30), methane, 1,1,2,2,2-pentafluoroethane (HFC-125), and 1,1,2-trifluoroethane (HFC-143). 1,1,1-Trifluoroethane (HFC-143a), 1,1-Difluoroethane (HFC-152a), 1,1,1,2,2-Pentafluoropropane (HFC-245cb), 2-Chloro-1,1,1-Trifluoropropane (HCFC-253db), 1,1,1,3-Tetrafluoropropane (HFC-254fb), 1,1,1-Trichloropropane (HCC-260fb), 1,1-Dichloro-1-fluoropropane (HCFC-261fc), 1,1-Difluoropropane (HFC-272fb), Propane (HC-290), Tetrafluorobutene (HFO-374), Butane (HC-600), Propylene, 2-Butene, Cyclobutene, 2-Methylpropene 1-Chloro-2,2-difluoroethylene (HCFO-1122), 1,2-difluoroethylene (HFO-1132), 1,1-difluoroethylene (HFO-1132a), fluoroethylene (HFO-1141), ethylene (HO-1150), 1,1,2-trichloro-3,3,3-trifluoropropylene (CFO-1213xa), 2-chloro-3,3,3-trifluoropropylene (HCFO-1233xf), 2,3,3,3-tetrafluoropropylene (HFO-1234yf), 3-chloro-3,3-difluoropropylene (HCFO-1242zf), E-1-chloro-1-fluoro-1-propene (E-HCFO-1251zb), Z-1-chloro-1-fluoro -1-Propylene (Z-HCFO-1251zb), 3-Chloropropene (HCO-1260zf), 3-Fluoro-1-Propylene (HFO-1261zf), E-1-Fluoro-1-Propylene (E-HFO-1261ze), 1-Fluoropropane (HFC-281fa), 1,1-Difluoropropane (272fb), Tetrafluorobutane (C4H6F4), 1252-Dimer (C6F4H8), Propylene (HO-1270), Pentafluorobutene (HFO-1345), and E / Zt-BuO-CF=CH-CH3, 1,1,1-Trifluoropropane (HFC-263fb), and 1-Chloro-1,1-Difluoropropane (HCFC-262fc).

[0169] In some embodiments disclosed herein, the composition comprises, is substantially composed of, or is composed of, 1,1-difluoropropene (HFO-1252zc), E-1-fluoro-1-propene (E-HFO-1261ze), and one or more members selected from the group consisting of, or substantially composed of, the following: trifluoromethane (HFC-23), dichloromethane (HCC-30), chlorofluoromethane (HCFC-31), difluoromethane (HFC-32), ethylene, ethane, dichlorofluoromethane (HCFC-22), chloromethane (HCC-40), dichloromethane (HCC-30), methane, 1,1,2,2,2-pentafluoroethane (HFC-125), 1,1,2-trifluoroethane (HFC-14). 3) 1,1,1-Trifluoroethane (HFC-143a), 1,1-Difluoroethane (HFC-152a), 1,1,1,2,2-Pentafluoropropane (HFC-245cb), 2-Chloro-1,1,1-Trifluoropropane (HCFC-253db), 1,1,1,3-Tetrafluoropropane (HFC-254fb), 1,1,1-Trichloropropane (HCC-260fb), 1,1-Dichloro-1-fluoropropane (HCFC-261fc), 1,1-Difluoropropane (HFC-272fb), Propane (HC-290), Tetrafluorobutene (HFO-374), Butane (HC-600), Propylene, 2-Butene, Cyclobutene, 2-Methyl Propylene, 1-chloro-2,2-difluoroethylene (HCFO-1122), 1,2-difluoroethylene (HFO-1132), 1,1-difluoroethylene (HFO-1132a), fluoroethylene (HFO-1141), ethylene (HO-1150), 1,1,2-trichloro-3,3,3-trifluoropropylene (CFO-1213xa), 2-chloro-3,3,3-trifluoropropylene (HCFO-1233xf), 2,3,3,3-tetrafluoropropylene (HFO-1234yf), 3-chloro-3,3-difluoropropylene (HCFO-1242zf), 3,3,3-trifluoropropylene (HFO-1243zf), E-1-chloro-1-fluoro-1-propene (E-HCFO-1251zb), Z-1-chloro-1-fluoro-1-propene (Z-HCFO-1251zb), 3-chloropropene (HCO-1260zf), 3-fluoro-1-propene (HFO-1261zf), 1-fluoropropane (HFC-281fa), 1,1-difluoropropane (272fb), tetrafluorobutane (C4H6F4), 1252-dimer (C6F4H8), propylene (HO-1270), pentafluorobutene (HFO-1345), and E / Zt-BuO-CF=CH-CH3, 1,1,1-trifluoropropane (HFC-263fb), and 1-chloro-1,1-difluoropropane (HCFC-262fc).

[0170] In some embodiments disclosed herein, the composition comprises, substantially comprises, or consists of, 1,1-difluoropropene (HFO-1252zc), 3,3,3-trifluoropropene (HFO-1243zf), E-1-fluoro-1-propene (E-HFO-1261ze), and one or more members selected from the group consisting of, substantially comprising, or consisting of: trifluoromethane (HFC-23), dichloromethane (HCC-30), chlorofluoromethane (HCFC-31), difluoromethane (HFC-32), ethylene, ethane, dichlorofluoromethane (HCFC-22), chloromethane (HCC-40), dichloromethane (HCC-30), methane, 1,1,2,2,2-pentafluoroethane (HFC-23). -125), 1,1,2-trifluoroethane (HFC-143), 1,1,1-trifluoroethane (HFC-143a), 1,1-difluoroethane (HFC-152a), 1,1,1,2,2-pentafluoropropane (HFC-245cb), 2-chloro-1,1,1-trifluoropropane (HCFC-253db), 1,1,1,3-tetrafluoropropane (HFC-254fb), 1,1,1-trichloropropane (HCC-260fb), 1,1-dichloro-1-fluoropropane (HCFC-261fc), 1,1-difluoropropane (HFC-272fb), propane (HC-290), tetrafluorobutene (HFO-374), butane (HC -600), propylene, 2-butene, cyclobutene, 2-methylpropene, 1-chloro-2,2-difluoroethylene (HCFO-1122), 1,2-difluoroethylene (HFO-1132), 1,1-difluoroethylene (HFO-1132a), fluoroethylene (HFO-1141), ethylene (HO-1150), 1,1,2-trichloro-3,3,3-trifluoropropene (CFO-1213xa), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 3-chloro-3,3-difluoropropene (HCFO-1242zf), E-1-chloro-1-fluoro-1-propene (E-HCFO-1251zb), Z-1-chloro-1-fluoro-1-propene (Z-HCFO-1251zb), 3-chloropropene (HCO-1260zf), 3-fluoro-1-propene (HFO-1261zf), 1-fluoropropane (HFC-281fa), 1,1-difluoropropane (272fb), tetrafluorobutane (C4H6F4), 1252-dimer (C6F4H8), propylene (HO-1270), pentafluorobutene (HFO-1345), and E / Zt-BuO-CF=CH-CH3, 1,1,1-trifluoropropane (HFC-263fb), and 1-chloro-1,1-difluoropropane (HCFC-262fc).

[0171] In some embodiments disclosed herein, the composition comprises 1,1-difluoropropene (HFO-1252zc), 1-chloro-1,1-difluoropropane (HCFC-262fc), and one or more members selected from the group consisting of, substantially consisting of, or consisting of: trifluoromethane (HFC-23), dichloromethane (HCC-30), chlorofluoromethane (HCFC-31), difluoromethane (HFC-32), ethylene, ethane, dichlorofluoromethane (HCFC-22), chloromethane (HCC-40), dichloromethane (HCC-30), methane, 1,1,2,2,2-pentafluoroethane (HFC-125), 1,1,2-trifluoroethane (HFC-14) 3) 1,1,1-Trifluoroethane (HFC-143a), 1,1-Difluoroethane (HFC-152a), 1,1,1,2,2-Pentafluoropropane (HFC-245cb), 2-Chloro-1,1,1-Trifluoropropane (HCFC-253db), 1,1,1,3-Tetrafluoropropane (HFC-254fb), 1,1,1-Trichloropropane (HCC-260fb), 1,1-Dichloro-1-fluoropropane (HCFC-261fc), 1,1-Difluoropropane (HFC-272fb), Propane (HC-290), Tetrafluorobutene (HFO-374), Butane (HC-600), Propylene, 2-Butene, Cyclobutene, 2-Methyl Propylene, 1-chloro-2,2-difluoroethylene (HCFO-1122), 1,2-difluoroethylene (HFO-1132), 1,1-difluoroethylene (HFO-1132a), fluoroethylene (HFO-1141), ethylene (HO-1150), 1,1,2-trichloro-3,3,3-trifluoropropylene (CFO-1213xa), 2-chloro-3,3,3-trifluoropropylene (HCFO-1233xf), 2,3,3,3-tetrafluoropropylene (HFO-1234yf), 3-chloro-3,3-difluoropropylene (HCFO-1242zf), 3,3,3-trifluoropropylene (HFO-1243zf), E-1-chloro-1-fluoro-1-propene (E-HCFO-1251zb), Z-1-chloro-1-fluoro-1-propene (Z-HCFO-1251zb), 3-chloropropene (HCO-1260zf), 3-fluoro-1-propene (HFO-1261zf), E-1-fluoro-1-propene (E-HFO-1261ze), 1-fluoropropane (HFC-281fa), 1,1-difluoropropane (272fb), tetrafluorobutane (C4H6F4), 1252-dimer (C6F4H8), propylene (HO-1270), pentafluorobutene (HFO-1345), and E / Zt-BuO-CF=CH-CH3 and 1,1,1-trifluoropropane (HFC-263fb).

[0172] In some embodiments disclosed herein, the composition comprises, is substantially composed of, or is composed of, 1,1-difluoropropene (HFO-1252zc), 1,1,1-trifluoropropane (HFC-263fb), and one or more members selected from the group consisting of, substantially composed of, or consisting of: trifluoromethane (HFC-23), dichloromethane (HCC-30), chlorofluoromethane (HCFC-31), difluoromethane (HFC-32), ethylene, ethane, dichlorofluoromethane (HCFC-22), chloromethane (HCC-40), dichloromethane (HCC-30), methane, 1,1,2,2,2-pentafluoroethane (HFC-125), and 1,1,2-trifluoroethane (HFC-143). 1,1,1-Trifluoroethane (HFC-143a), 1,1-Difluoroethane (HFC-152a), 1,1,1,2,2-Pentafluoropropane (HFC-245cb), 2-Chloro-1,1,1-Trifluoropropane (HCFC-253db), 1,1,1,3-Tetrafluoropropane (HFC-254fb), 1,1,1-Trichloropropane (HCC-260fb), 1,1-Dichloro-1-fluoropropane (HCFC-261fc), 1,1-Difluoropropane (HFC-272fb), Propane (HC-290), Tetrafluorobutene (HFO-374), Butane (HC-600), Propylene, 2-Butene, Cyclobutene, 2-Methylpropene, 1-Chloro-2,2-difluoroethylene (HCFO-1122), 1,2-difluoroethylene (HFO-1132), 1,1-difluoroethylene (HFO-1132a), fluoroethylene (HFO-1141), ethylene (HO-1150), 1,1,2-trichloro-3,3,3-trifluoropropene (CFO-1213xa), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 3-chloro-3,3-difluoropropene (HCFO-1242zf), 3,3,3-trifluoropropene (HFO-1243zf), E-1-chloro-1-fluoro-1-propene (E- HCFO-1251zb), Z-1-chloro-1-fluoro-1-propene (Z-HCFO-1251zb), 3-chloropropene (HCO-1260zf), 3-fluoro-1-propene (HFO-1261zf), E-1-fluoro-1-propene (E-HFO-1261ze), 1-fluoropropane (HFC-281fa), 1,1-difluoropropane (272fb), tetrafluorobutane (C4H6F4), 1252-dimer (C6F4H8), propylene (HO-1270), pentafluorobutene (HFO-1345), and E / Zt-BuO-CF=CH-CH3 and 1-chloro-1,1-difluoropropane (HCFC-262fc).

[0173] In some embodiments disclosed herein, the composition comprises at least one of HFO-1252zc, HFC-263fb and one or more additional members selected from, substantially composed of, or composed of: HFO-1243zf, HFO-1234yf, propylene, HFO-1252ye, and HFO-1252yf.

[0174] In some embodiments disclosed herein, the composition comprises at least one of HFO-1252zc and HFC-263fb, HCFC-262fc, and one or more additional members selected from, substantially composed of, or composed of: ethylene, HFC-23, HFO-1132a, propane, HFO-1234yf, HFO-1261, HFC-143a, HCFO-1233, and HFO-374.

[0175] One embodiment of the invention disclosed herein is a composition comprising HCFC-262fc and one or more compounds selected from the group consisting substantially of or consisting of: propane, propylene, HFO-1243zf, HFO-1261, HFO-1252zc, HFC-272fb, HFO-1252zc, HCFO-1251 (I) isomer, HCFO-1242 isomer, HCFO-1251 (II) isomer, HCFC-262 isomer, HCFC-252dc, HCO-1250, and HCC-260.

[0176] One embodiment of the invention disclosed herein is a composition comprising HCFC-262fc and one or more compounds selected from the group consisting substantially of or consisting of: propane, R-1243zf, HFO-1252zc, HFO-1261, HCFO-1242zf, HCFO-1251 (I) isomer, HCFO-1251 (II) isomer, HCFO-1242 isomer, HCFC-262 isomer, HCFO-1232 isomer, HCFC-252, HCFC-252dc, HCO-1250, and HCC-260.

[0177] One embodiment of the invention disclosed herein is a composition comprising HCFO-1242zf and one or more compounds selected from the group consisting substantially of or consisting of: ethane, HFC-152a, HFO-1243zf, HFO-1252zc, HCFC-253db, HCFC-262fc, HCFO-1242 isomers, and HCFO-1232.

[0178] One embodiment of the invention disclosed herein is a composition comprising HCFO-1242zf and one or more compounds selected from the group consisting substantially of or composed of the following: HFO-1252zc, HCFC-253db, HCFC-262fc, HCFO-1242 isomers, and HCFO-1232.

[0179] One embodiment of the invention disclosed herein is a composition comprising HCFC-262fc, HFO-1252zc and one or more compounds selected from the group consisting substantially of or composed of: propane, propylene, HFO-1261, HFO-1252zc, HFC-272fb, HCFO-1251 (I) isomer, HCFO-1251 (II) isomer, HCFC-262 isomer, HCFC-252dc, HCO-1250 and HCC-260.

[0180] One embodiment of the invention disclosed herein is a composition comprising HCFC-262fc, HCFO-1242zf and one or more compounds selected from the group consisting substantially of or composed of: propane, R-1243zf, HFO-1252zc, HFO-1261, HCFO-1251 (I) isomer, HCFO-1251 (II) isomer, HCFO-1242 isomer, HCFC-262 isomer, HCFO-1232, HCFC-252, HCFC-252dc, HCO-1250, and HCC-260.

[0181] One embodiment of the invention disclosed herein is a composition comprising HCFO-1242zf, HFO-1252zc and one or more compounds selected from the group consisting substantially of or composed of ethane, HFC-152a, HFO-1243zf, HCFC-253db, HCFC-262fc, HCFO-1242 isomers, and HCFO-1232.

[0182] One embodiment of the invention disclosed herein is a composition comprising HCFO-1242zf, HCFC-262fc and one or more compounds selected from the group consisting substantially of or composed of HFO-1252zc, HCFC-253db, HCFO-1242 isomers and HCFO-1232.

[0183] In some embodiments disclosed herein, (1) the total amount of the additional compound / member (compounds other than HFC-263fb and HFO-1252zc) is selected from the total amount of the composition as: greater than 0% and less than 0.5%, greater than 0% and less than 0.4%, greater than 0% and less than 0.2%, greater than 0% and less than 0.2%, greater than 0% and less than about 0.1%, or greater than 0% and less than about 0.01%, provided that the total amount of the composition is 100%, and / or (2) the amount of the additional compound / member is selected from the total amount of the composition as: greater than 0% and less than About 0.2%, greater than 0 mol and less than about 0.1 mol, greater than 0% and less than about 0.01%, greater than 0% and less than about 0.001%, or greater than 0% and less than about 0.0001%, and / or (3) the corresponding amount of the additional compound / member is independently selected from the following based on the total amount of the composition: greater than 0% and less than about 0.2%, greater than 0 mol and less than about 0.1 mol, greater than 0% and less than about 0.01%, greater than 0% and less than about 0.001%, or greater than 0% and less than about 0.0001%, provided that the total amount of the composition is 100%.

[0184] In one composition embodiment disclosed herein, the total amount of compounds other than HFC-263fb (i.e., additional compounds) is based on the total amount of the composition and is between greater than 0% and less than about 15% (expressed as a percentage of GC-FID peak area) and in between.

[0185] In other embodiments disclosed herein, the total amount of additional compounds other than HFC-263fb is between and within all values ​​and ranges of one of the following: greater than 0% and less than 15%, 14%, 13%, 12%, 11%, 10%, 9%, 9%, 7%, 6%, 5%, 4%, 3%, 2%, or 1%.

[0186] In other embodiments disclosed herein, the total amount of additional compounds other than HFC-263fb is based on the total amount of the composition and ranges between greater than 0% and less than 0.1%, greater than 0% and less than 0.01%, greater than 0.0001% and less than 0.3%, greater than 0.0001% and less than 0.2%, greater than 0.0001% and less than 0.1%, greater than 0.0001% and less than 0.01%, or greater than 0.0001% and less than 0.001%, and all values ​​and ranges therebetween.

[0187] In some embodiments disclosed herein, the composition comprises (1) HFO-1252zc, (2) one of HFC-263fb or HCFC-262fc, and (3) one or more additional compounds other than HFO-1252zc, HFC-263fb and HCFC-262fc as identified in Table 1, wherein each additional compound is present in an amount between the following based on the total amount of the composition:

[0188] a) Greater than 0% and less than 20%

[0189] b) Greater than 0% and less than 15%

[0190] c) Greater than 0% and less than 10%

[0191] d) Greater than 0% and less than 4%,

[0192] e) Greater than 0% and less than 3%

[0193] f) greater than 0% and less than 2%

[0194] g) greater than 0% and less than 1%,

[0195] h) greater than 0% and less than 0.5%,

[0196] i) greater than 0% and less than 0.1%,

[0197] j) greater than 0% and less than 0.01%,

[0198] k) is greater than 0% and less than 0.005%,

[0199] l) greater than 0.001% and less than 4%,

[0200] m) greater than 0.001% and less than 3%,

[0201] n) is greater than 0.001% and less than 2%.

[0202] o) greater than 0.001% and less than 1%,

[0203] p) greater than 0.001% and less than 0.5%,

[0204] q) greater than 0.001% and less than 0.1%,

[0205] r) greater than 0.001% and less than 0.01%, or

[0206] s) greater than 0.001% and less than 0.005%,

[0207] The conditions are that the total amount of compounds other than HFO-1252zc, HFC-263fb and HCFC-262fc is greater than 0.0001% and less than 15%, greater than 0.0001% and less than 10%, greater than 0.0001% and less than 8%, greater than 0.0001% and less than 7%, greater than 0.0001% and less than 6%, greater than 0.0001% and less than 5%, greater than 0.0001% and less than 4%, greater than 0.0001% and less than 3%, greater than 0.0001% and less than 2%, greater than 0.0001% and less than 1%, greater than 0.0001% and less than 0.5%, or greater than 0.0001% and less than 0.1%.

[0208] In some embodiments disclosed herein, the composition comprises (1) HFO-1252zc; (2) one of HFC-263fb or HCFC-262fc and (3) one or more C2-C6 olefins selected from ethylene, propylene, butene, propylene, and cyclobutene, in amounts based on the total composition of: greater than 15%, greater than 0% and less than 4%, greater than 0% and less than 3%, greater than 0% and less than 2%, greater than 0% and less than 1%, greater than 0% and less than 0.5%, greater than 0% and less than 0.1%, greater than 0% and less than 0.01%, and greater than 0% and less than 0.005%, provided that HFO-1252zc, HFC-263fb, and HCFC- The total amount of compounds other than 262fc is greater than 0.0001% and less than 10% or 15%, greater than 0.0001% and less than 9%, greater than 0.0001% and less than 8%, greater than 0.0001% and less than 7%, greater than 0.0001% and less than 6%, greater than 0.0001% and less than 5%, greater than 0.0001% and less than 4%, greater than 0.0001% and less than 3%, greater than 0.0001% and less than 2%, greater than 0.0001% and less than 1%, greater than 0.0001% and less than 0.5%, or greater than 0.0001% and less than 0.1%.

[0209] In some embodiments disclosed herein, the composition comprises (1) HFO-1252zc and (2) one of HFC-263fb or HCFC-262fc, and is free of or substantially free of Group A fluorinated substances. In some embodiments, the compositions of the present invention comprise, are substantially composed of, or are composed of, one of HFO-1252zc and HFC-263fb or HCFC-262fc, and the degradation products of such compositions are free of or substantially free of Group A fluorinated substances as defined herein.

[0210] Example

[0211] Example 1: Liquid-phase hydrogenation of HFO-1243zf

[0212] 5 g of 0.5% Pd / C was loaded into a 400 ml Hastelloy C shaking tube. The shaking tube was then cooled to -30 °C and evacuated. 40 g of HFO-1243zf was loaded into the shaking tube and heated back to 55 °C. At 55 °C, H2 was slowly added to a pressure of 250 psig. A rapid pressure drop indicated that the reaction was occurring under these conditions. H2 was further added until the pressure in the reactor no longer decreased; approximately 1 g of H2 was added at the end of the reaction. The products of the reaction were analyzed by GC-MS-FID, and the contents are identified in Table 2 below.

[0213] Table 2

[0214]

[0215] Example 2: Hydrogenation of 1243zf to 263fb in the gas phase using 0.5% Pd / Al2O3.

[0216] 5 ml of 0.5% Pd / Al2O3 was loaded into a 12-inch ½" OD Monel reactor. The catalyst was treated with H2 flow at 200°C for 1 hour. The reactor was then heated to 50°C. The HFO-1243zf, H2, and N2 feeds were controlled by a mass flow controller. The reaction test conditions are listed in Table 3 below. The reactor effluent was analyzed by online GC-MS-FID at the times shown in Table 3 below. The results of the analysis are listed in Table 3 below, showing that HFO-1243zf was completely converted to HFC-263fb with >99% selectivity.

[0217] Table 3

[0218]

[0219] Example 3: Hydrogenation of 1243zf to 263fb in the gas phase using 0.04% Pd / Al2O3.

[0220] 4 ml of 0.04% Pd / Al2O3 was loaded into a 12-inch ½" OD Monel reactor. The catalyst was treated with H2 flow at 200°C for 1 hour. The reactor was then heated to 50°C. The HFO-1243zf, H2, and N2 feeds were controlled by a mass flow controller. The reaction test conditions are listed in Table 4 below. The reactor effluent was analyzed by online GC-MS-FID at the times shown in Table 4 below. The results of the analysis are listed in Table 4 below, showing a high conversion of HFO-1243zf to HFC-263fb with selectivity >99%.

[0221] Table 4

[0222]

[0223] Example 4: Hydrogenation of 1242zf to 262fc in the gas phase using 0.02% Pd / Al2O3.

[0224] In a 12-inch ½" OD Monel reactor, 6 ml of 0.02% Pd / Al2O3 was loaded. The catalyst was treated with H2 flow at 200°C for 1 hour. The reactor was then heated to 50°C. The HFO-1243zf, H2, and N2 feeds were controlled by a mass flow controller. The reaction test conditions are listed in Table 5 below. The reactor effluent was analyzed by online GC-MS-FID at the times shown in Tables 6 and 7 below. The results of the analysis are shown in Tables 6 and 7 below, which show a high conversion of HCFO-1242zf to HCFC-262fc, and the selectivity of HCFC-262fc can reach 93%.

[0225] Table 5

[0226]

[0227]

[0228] Table 6: Detailed GC analysis of the products in Example 4 when the reaction time was 6 hours.

[0229]

[0230] Table 7: Detailed GC analysis of the products in Example 4 when the reaction time was 19.5 hours.

[0231]

[0232] Example 5: Liquid-phase hydrogenation of 1242zf

[0233] 0.25 g of 0.5% Pd / C was loaded into a 10 ml Hastelloy C shaking tube. The shaking tube was then cooled to -30 °C and evacuated. 5 g of HCFO-1242zf was added to the shaker and heated back to 65 °C. At 65 °C, H2 was slowly added to a pressure of 300 psig. A rapid pressure drop indicated that the reaction was occurring under these conditions. H2 was further added until the pressure in the reactor no longer decreased. Both the gas and liquid phases of the reaction mixture were analyzed by GC-MS-FID, and the contents are identified in Tables 8 and 9 below.

[0234] Table 8: Gas-phase GC analysis of the reaction mixture from Example 5

[0235]

[0236] Table 9: Liquid phase GC analysis of the reaction mixture from Example 5

[0237]

[0238] Example 6: Dehydrofluorination of 263fb by Zn-doped chromium oxide

[0239] An Inconel (0.5-inch OD) tubular reactor was loaded with 8 ml of 12-20 mesh JM62-3 chromium catalyst. The catalyst was activated with HF from 150°C to 450°C. HFC-263fb was pumped in and passed through a vaporizer with 9 sccm of N2 at 150°C, then mixed with HF. Reaction conditions were determined in Table 10 below. The reaction mixture flowed through the catalyst bed in the reactor. The reactor effluent was passed through an alkaline scrubber and then collected in a sample bag (not shown). The sample in the sample bag was analyzed by GC-MS-FID. The results of the GC analysis are listed in Table 11 below.

[0240] Table 10

[0241]

[0242] Table 11: GC analysis of the product of Example 6 produced at 450°C

[0243]

[0244] Example 7: 263fb pyrolyzes into 1252zc

[0245] HFC-263fb was fed along with N2 into an empty 12-inch ½" OD Monel reactor (without catalyst or packing material) via a pump. The reactor was heated to 630°C and higher under N2 purging. The reaction conditions are listed in Table 12 below. Under each test condition, the reactor effluent was passed through a KOH scrubber and then collected in a Teddlar bag (not shown). The samples were analyzed by GC-MS-FID. The results are listed in Table 13 below.

[0246] Table 12

[0247]

[0248] Table 13: GC analysis of the product generated at 670°C in Example 7

[0249]

[0250] Example 8: Pyrolysis of 263fb into 1252zc using Monel packing

[0251] A 12-inch ½" OD Monel reactor was loaded with 10 ml of Monel distillation packing. The reactor was heated to 500°C under N2 purging. HFC-263fb was fed into the reactor along with N2 via a pump. The reaction conditions are listed in Table 14 below. Under each test condition, the reactor effluent was passed through a KOH scrubber and then collected in a Teddlar bag (not shown). The samples were analyzed by GC-MS-FID. The results of the analysis are listed in Table 15 below.

[0252] Table 14

[0253]

[0254] Table 15: GC analysis of the product generated at 650°C in Example 10

[0255]

[0256] Example 9: Liquid-phase defluorination of hydrogen fluoride HFC-263fb

[0257] At 0 °C, a mixture of CF3-CH2-CH3 (6.2 g, 63 mmol) and KOtBu (7.1 g, 6.3 mmol) in anhydrous DMF (30 mL) was stirred in a 100 mL flask. The reaction was monitored using gas chromatography. After 1 hour, 1.3 g of the product CF2=CH-CH2 (30% conversion, 86% selectivity) was collected in a dry ice trap.

[0258] Example 10: 262fc was pyrolyzed to 1252zc in an empty gold-lined reactor tube.

[0259] HCFC-262fc was fed into an empty 10-inch-long ½" OD gold-lined tubular reactor via a pump. The reaction test conditions are listed in Table 16 below. Under each test condition, the reactor effluent was analyzed by online GC-MS-FID. The results are listed in Table 17.

[0260] Table 16

[0261]

[0262] Table 17 Detailed GC analysis of the products produced at 490℃

[0263]

[0264] Example 11: 262fc was pyrolyzed to 1252zc in an empty Inconel 625 reactor tube.

[0265] HCFC-262fc was fed into an empty 10-inch-long ½" OD Inconel 625 tubular reactor via a pump. The reaction test conditions are listed in Table 18 below. Under each test condition, the reactor effluent was analyzed by online GC-MS-FID. The results are listed in Table 19.

[0266] Table 18

[0267]

[0268]

[0269] Table 19 Detailed GC analysis of the products produced at 490℃

[0270]

[0271] Some of the system, apparatus, and method implementations disclosed herein include the first and second zones of a discrete reactor.

[0272] Some of the system, apparatus, and method embodiments disclosed herein include a first zone and a second zone located in a discrete reactor, wherein one reactor is configured for gas-phase reactions.

[0273] Some of the system, apparatus, and method embodiments disclosed herein include a first zone and a second zone located in a discrete reactor, wherein one reactor is configured for gas-phase reactions, and wherein the gas-phase reactor includes a catalyst, a packing material, or neither.

[0274] Some of the system, apparatus, and method embodiments disclosed herein include a first zone and a second zone defined by discrete reactors, each configured for gas-phase reactions, and the second gas-phase reactor includes a catalyst, a packing material, or neither.

[0275] Some of the system, apparatus, and method embodiments disclosed herein include a first and a second zone of a discrete reactor, wherein the first reactor is configured for liquid-phase reactions involving stirring / mixing. The liquid-phase reactions are preferably carried out in the presence of a solvent (including, but not limited to, polar aprotic solvents such as DMF, DMAc, DMSO, MP, or tert-butanol), with or without a catalyst (such as crown ethers), at temperatures between -40°C and 100°C, between -30°C and 100°C, between -30°C and 90°C, between -40°C and 80°C, between -40°C and 0°C, between -30°C and 60°C, and all values ​​and ranges thereof.

[0276] Some of the system, apparatus, and method embodiments disclosed herein include a first discrete reaction zone and a second discrete reaction zone, a vaporizer for preheating reactant feed, a scrubber for removing inorganic acids, and a distillation system for separating and / or recovering intermediate compounds, products, and facilitating the recycling of recovered compounds.

[0277] Other implementation plans

[0278] Composition embodiment A, comprising, substantially consisting of, or consisting of the following items,

[0279] HFO-1252zc

[0280] HFC-263fb

[0281] At least one of ethylene, propylene, butene, propylene, and cyclobutene, selected from the following:

[0282] At least one of the following: HFC-23, HFC-123, HFC-143a, HFC-152a, HFO-374, HFO-1141, HFO-1234, HFO-1261, HCFO-1233, HCFO-1251, and HFO-1260; and

[0283] Choose one of HFC-23, HFO-1132, HFO-1141, HFC-125, HFC-143a, HFO-1234, HFO-1261, HCFO-1233, HCFO-1251 and HFO-1260.

[0284] Composition embodiment A(1), comprising, substantially consisting of, or consisting of the following items,

[0285] HFO-1252zc

[0286] HFC-263fb

[0287] At least one of ethylene, propylene, butene, propadiene, and cyclobutene, and

[0288] At least one of HFC-23, HFC-123, HFC-143a, HFC-152a, HFO-374, HFO-1141, HFO-1234, HFO-1261, HCFO-1233, HCFO-1251, and HFO-1260; or at least one of HFC-23, HFO-1132, HFO-1141, HFC-125, HFC-143a, HFO-1234, HFO-1261, HCFO-1233, HCFO-1251, and HFO-1260.

[0289] The aforementioned composition embodiments A and A(1) further comprise HFC-23.

[0290] The aforementioned composition embodiments A and A(1) further comprise HC-290.

[0291] The aforementioned composition embodiments A and A(1) further comprise HFO-1150.

[0292] The aforementioned composition embodiments A and A(1) further comprise HCFO-1233.

[0293] The aforementioned composition embodiments A and A(1) further comprise HFO-1234.

[0294] The aforementioned composition embodiments A and A(1) further comprise HFO-1260.

[0295] The aforementioned composition embodiments A and A(1) further comprise HFO-1261.

[0296] The composition comprises either embodiment A or A(1), which further comprises HFC-23 and HFO-1261.

[0297] The aforementioned composition embodiments A and A(1) further comprise HFC-23, HC-290 and HFO-1261.

[0298] The aforementioned composition embodiments A and A(1) further comprise HFC-23, HC-290, HCFO-1233 and HFO-1261.

[0299] The aforementioned composition embodiments A and A(1) further comprise HFC-23, HC-290, HCFO-1233, HFO-1234 and HFO-1261.

[0300] The aforementioned composition embodiments A and A(1) further comprise HFC-23, HC-290, HFO-1150, HCFO-1233, HFO-1234 and HFO-1261.

[0301] The aforementioned composition is either embodiment A or A(1), wherein HCFO-1233 is HCFO-1233xf.

[0302] The aforementioned composition is either embodiment A or A(1), wherein HFO-1234 is HFO-1234yf.

[0303] Each and every of the aforementioned compositions in embodiments A and A(1) wherein the amount of HFO-1252zc is at least one of 30%, 35%, 40%, 50%, 60%, 70%, 80%, and 99% based on the total amount of the composition.

[0304] Composition embodiment B comprises HFC-263fb, HFC-152a, HFC-254fb, HCFO-1233xf, and HCFC-253db.

[0305] The aforementioned composition embodiment B contains more than 60% HFC-263fb.

[0306] The aforementioned composition embodiment B contains more than 70% HFC-263fb.

[0307] Method embodiment A includes hydrogenating a fluoroolefin defined by the formula CF2XCH2=CH, wherein X is at least one of chlorine, fluorine, and combinations thereof, preferably X=F or Cl, as in 3,3,3-trifluoropropene or 1-chloro-1,1-difluoropropene.

[0308] Method embodiment B includes hydrogenating a first compound to produce a first product mixture and dehydrogenating the first product mixture to produce a second product mixture, wherein the first compound is defined by the formula CF2XCY=CH2 (e.g., CF3CH=CH2 (HFO-1243zf), CClF2CH=CH2 (HCFO-1242zf), CClF2CCl=CH2 (HCFO-1232xf)), wherein X is at least one of chlorine, fluorine, bromine, and iodine, and Y is H, Cl, F, Br, or I, and wherein the first product mixture comprises a product compound defined by the formula CF2XCH2CH3 (e.g., CF3CH2CH3, CF2ClCH2CH3), wherein X is one of Cl, F, Br, or I, and the second product mixture comprises 1,1-difluoropropylene (HFO-1252zc).

[0309] Method implementation scheme C includes preparing HFO-1252zc by dehydrohalogenating a compound defined by formula CF2XCH2CH3 in the gas or liquid phase, wherein X is one of Cl, F, Br or I.

[0310] Method embodiment C2 includes preparing HFO-1252zc by dehydrohalogenating a compound defined by formula CF2XCH2CH3 in the gas phase in the presence of a catalyst, in the presence of a metal alloy filler, or in the absence of both a catalyst and a metal alloy filler, wherein X is one of Cl, F, Br, or I.

[0311] Method embodiment C3 includes preparing HFO-1252zc by dehydrohalogenating a compound defined by formula CXF2CHYCH3 in the liquid phase, wherein X is one of Cl, F, Br or I, and Y is H, Cl, F, Br or I.

[0312] In the aforementioned method embodiment C, the dehydrohalogenation is carried out in the gas phase at a temperature selected from one of the following:

[0313] a. Between 300°C and approximately 500°C

[0314] b. Between 400°C and approximately 700°C, or

[0315] c. Between approximately 450°C and approximately 900°C.

[0316] Any of the aforementioned method embodiments C, wherein the dehydrohalogenation is carried out in the gas phase in the presence of a catalyst, said catalyst comprising supported or unsupported fluorinated transition metal oxides, nickel-based alloys, or nickel-chromium-based alloys (e.g., Inconel). ™ The dehalogenation catalyst includes, but is not limited to, nickel-based alloys, nickel-chromium-based alloys, alumina, aluminum fluoride, fluorinated alumina, preferably one of chromium oxide, fluorinated chromium oxide, and cubic chromium trifluoride; alone or supported on carbon, acid-washed carbon, activated carbon, three-dimensional carbon-containing matrix materials; and metal compounds supported on carbon. The metal compound is preferably a transition metal of the periodic table, such as scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and zinc (Zn).

[0317] Method implementation scheme D includes converting CF3CH=CH2 (HFO-1243zf) to CF3CH2CH3 (HFC-263fb), and dehydrofluorinating HFC-263fb to form a product containing CF2=CHCH3 (HFO-1252zc).

[0318] Method implementation scheme E includes preparing CF2=CHCH3 (HFO-1252zc) by first hydrogenating CClF2CH=CH2 to CClF2CH2CH3 (HCFC-262fc) and then dehydrochlorinating HCFC-262fc to prepare HFO-1252zc.

[0319] The aforementioned method implementation scheme D includes preparing CF2=CHCH3(HFO-1252zc) by first hydrogenating CF3CH=CH2(HFO-1243zf) to form CF3CH2CH3(HFC-263fb), and then defluorinating HFC-263fb to prepare HFO-1252zc.

[0320] The aforementioned method implementation scheme D or E, wherein the dehydrohalogenation is carried out with or without a catalyst.

[0321] In embodiments D or E of the aforementioned method, the dehydrohalogenation is carried out in the presence of a catalyst, preferably a supported or unsupported fluorinated or partially fluorinated transition metal oxide, a nickel-based alloy, or a nickel-chromium-based alloy. In one embodiment, the catalyst metal is selected from at least one of scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and zinc (Zn).

[0322] The aforementioned method is implemented in embodiment D or E, wherein dehydrohalogenation is carried out in the liquid phase, preferably in the presence of a conjugated tert-butoxide salt, most preferably an alkali metal tert-butoxide salt selected from sodium tert-butoxide or potassium tert-butoxide.

[0323] The aforementioned method is implemented in scheme D or E, wherein dehydrohalogenation is carried out in the gas phase.

[0324] In each and every method embodiment D or E, the dehydrohalogenation is carried out at a temperature between 300°C and about 900°C or selected from the following:

[0325] a. Between approximately 300°C and approximately 500°C

[0326] b. Between approximately 400°C and approximately 700°C, or

[0327] c. Between approximately 500°C and approximately 900°C.

[0328] Each and every method embodiment B to E, wherein HFO-1252zc accounts for at least one of greater than 15%, 20%, 25%, 30%, 35%, 40%, 50%, 60%, 70% and 80% based on the total amount of the composition.

[0329] A composition formed by each of the above-described methods, embodiments A to E.

[0330] Composition embodiment A' comprises HFC-263fb and two or more additional compounds selected from HFC-152a, HFC-254fb, HCFO-1233xf, HFO-1243zf and HCFC-253db.

[0331] The composition embodiment A' contains at least 99% HFC-263fb.

[0332] The composition embodiment A', wherein the total amount of the additional compound is selected from one of the following: greater than 0% and less than 0.5%, greater than 0% and less than 0.4%, greater than 0% and less than 0.3%, greater than 0% and less than 0.2%, and greater than 0% and less than 0.1%, such that the total amount of the composition is 100%.

[0333] Composition embodiment B' comprises at least one of HFO-1252zc, HFC-263fb, optionally ethylene, propylene, butene, propylene and cyclobutene, optionally at least one of HFC-23, HFC-123, HFC-143a, HFC-152a, HFO-374, HFO-1141, HFO-1234yf, HFO-1261, HCFO-1233, HCFO-1251 and HFO-1260; and optionally one of HFC-23, HFO-1132, HFO-1141, R-125, HFC-143a, HFO-1234yf, HFO-1261, HCFO-1233, HCFO-1251 and HFO-1260.

[0334] Composition embodiment B(1)', comprising,

[0335] HFO-1252zc

[0336] HFC-263fb

[0337] At least one of ethylene, propylene, butene, propadiene, and cyclobutene, and,

[0338] HFC-23, HFC-123, HFC-143a, HFC-152a, HFO-374, HFO-1141, HFO-1234yf, HFO-1261, HCFO-1233, HCFO-1251 and HFO-1260, or at least one of HFC-23, HFO-1132, HFO-1141, HFC-125, HFC-143a, HFO-1234yf, HFO-1261, HCFO-1233, HCFO-1251 and HFO-1260.

[0339] Composition embodiment C' comprises 1,1-difluoropropylene (HFO-1252zc) and one or more members selected from the group consisting of: methane, ethylene, ethane, HFC-23, HFC-125, HFC-143a, HFO-1141, propane, propylene, HFO-1234yf, propylene, C3H4F2, HFO-1261ze-E, HFO-1261ze-Z, HFC-263fb, HCFC-262fc, 2-butene, cyclobutene, and 2-methyl-1-propene. HFC-272fb, HCFC-262fc, HCFO-1233, HCO-1260, HFC-374, HFO-1345 isomer, HCFO-1251zb-E, HCFO-1251zb-Z, HFC-32, HFO-1132a, HCC-40, HCFC-22, HFO-1261ze-E, HFO-1252 isomer, HFC-281fa, HCC-30, C4H3ClF4, HFO-1252 dimer.

[0340] Composition embodiment D' comprises 1,1-difluoropropylene (HFO-1252zc) and one or more members selected from: ethylene (HO-1150), trifluoromethane (HFC-23), 1,1-dichloroethylene (HCO-1132a), fluoroethane (HFC-1141), 1,1,2,2,2-pentafluoroethane (HFC-125), propane (HC-290), 1,1,2-trifluoroethane (HFC-143), 1,1-difluoropropylene (HFO-1252zc), etc. HFO-1252zc), HFO-1234, 1,1-difluoroethane (HFC-152a), 3-fluoro-1-propene (HFO-1261), 1,1,1-trifluoropropane (HCC-263fb), 1,1,1-trichloroethane (HCC-143a), 3-fluoro-1-propene (HFO-1261), HFO-1252 isomer, chloro-3,3,3-trifluoropropene (HCFO-1233), or pentafluorobutene (HFO-374).

[0341] Composition embodiment E' comprises 1,1-difluoropropylene (HFO-1252zc) and one or more members selected from the group consisting of: methane, ethylene, ethane, HFC-23, HFC-125, HFC-143a, HFO-1141, propane, propylene, HFO-1234yf, propylene, C3H4F2, HFO-1261ze-E, HFO-1261ze-Z, HFC-263fb, 2-butene, cyclobutene, 2-methyl-1-propene, HFC-272f b. HCFC-262fc, HCFO-1233, HCO-1260, HFC-374, HFO-1345 isomer, HCFO-1251zb-E, HCFO-1251zb-Z, HFC-32, HFO-1132a, HCC-40, HCFC-22, HFO-1261ze-E, 263fb, HFO-1252 isomer, HFC-281fa, HCC-30, C4H3ClF4, HFO-1252 dimer.

[0342] Composition embodiment F' comprises 1,1-difluoropropene (HFO-1252zc) and 1,1,1-trifluoropropane (HFC-263b), and one or more members selected from ethylene and propane, and additional members selected from HFC-23, HFO-1132a, HFO-1234, HFO-1261, HFC-263fb, HFC-143a, and HFO-1252 isomers.

[0343] Composition embodiment F(1)' comprises 1,1-difluoropropylene (HFO-1252zc) and 1,1,1-trifluoropropane (HFC-263b), and one or more members selected from Table 1 other than 1,1-difluoropropylene (HFO-1252zc) and 1,1,1-trifluoropropane (HFC-263fb).

[0344] Composition embodiment G' comprises 1,1-difluoropropylene (HFO-1252zc), HFO-1261 and HFC-263fb, trifluoromethane (HFC-23), dichloromethane (HCC-30), chlorofluoromethane (HCFC-31), difluoromethane (HFC-32), ethylene, ethane, dichlorofluoromethane (HCFC-22), chloromethane (HCC-40), dichloromethane (HCC-30), methane, 1,1,2,2,2-pentafluoroethane (HFC-125), 1,1,2-trifluoroethane (HFC-143), 1,1,1-trifluoroethane (HFC-143a), and 1,1-difluoroethane. (HFC-152a), 1,1,1,2,2-pentafluoropropane (HFC-245cb), 2-chloro-1,1,1-trifluoropropane (HCFC-253db), 1,1,1,3-tetrafluoropropane (HFC-254fb), 1,1,1-trichloropropane (HCC-260fb), 1,1-dichloro-1-fluoropropane (HCFC-261fc), 1,1-difluoropropane (HFC-272fb), propane (HC-290), tetrafluorobutene (HFO-374), butane (HC-600), propadiene, 2-butene, cyclobutene, 2-methylpropene, 1-chloro-2,2-difluoroethylene (HCFO- 1122), 1,2-difluoroethylene (HFO-1132), 1,1-difluoroethylene (HFO-1132a), fluoroethylene (HFO-1141), ethylene (HO-1150), 1,1,2-trichloro-3,3,3-trifluoropropene (CFO-1213xa), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 3-chloro-3,3-difluoropropene (HCFO-1242zf), 3,3,3-trifluoropropene (HFO-1243zf), 1,1-difluoro-1-propene (1252zc), E-1 One or more of the following: -chloro-1-fluoro-1-propene (E-HCFO-1251zb), Z-1-chloro-1-fluoro-1-propene (Z-HCFO-1251zb), 3-chloropropene (HCO-1260zf), E-1-fluoro-1-propene (E-HFO-1261ze), 3-fluoro-1-propene (1261zf), 1-fluoropropane (281fa), 1,1-difluoropropane (272fb), tetrafluorobutane (C4H6F4), 1252-dimer (C6F4H8), propylene (HO-1270), pentafluorobutene (HFO-1345), and E / Zt-BuO-CF=CH-CH3.

[0345] Composition embodiment H', comprising each and every composition embodiment A to G, wherein the amount of HFO-1252zc is at least one of greater than 10%, 15%, 20%, 30%, 35%, 40%, 50%, 60%, 70%, 80% or 90% based on the total amount of the composition.

[0346] Composition embodiment I' and each and every composition embodiment B' to H', wherein the composition comprises (1) HFO-1252zc, (2) one of HFC-263fb or HCFC-262fc, and (3) one or more additional members comprising compounds other than HFO-1252zc, HFC-263fb and HCFC-262fc as identified in Table 1, which are present in amounts between the following based on the total amount of the composition:

[0347] Greater than 0% and ≤10%,

[0348] Greater than 0% and ≤8%,

[0349] Greater than 0% and less than 4%,

[0350] Greater than 0% and less than 3%,

[0351] Greater than 0% and less than 2%,

[0352] Greater than 0% and less than 1%,

[0353] Greater than 0% and less than 0.5%,

[0354] Greater than 0% and less than 0.1%,

[0355] Greater than 0% and less than 0.01%,

[0356] Greater than 0% and less than 0.005%,

[0357] Greater than 0.001% and less than 4%,

[0358] Greater than 0.001% and less than 3%,

[0359] Greater than 0.001% and less than 2%,

[0360] Greater than 0.001% and less than 1%,

[0361] Greater than 0.001% and less than 0.5%,

[0362] Greater than 0.001% and less than 0.1%,

[0363] Greater than 0.001% and less than 0.01%, or

[0364] Greater than 0.001% and less than 0.005%;

[0365] The conditions are that the total amount of compounds other than HFO-1252zc, HFC-263fb and HCFC-262fc is greater than 0.0001% and less than 15%, greater than 0.0001% and less than 10%, greater than 0.0001% and less than 8%, greater than 0.0001% and less than 7%, greater than 0.0001% and less than 6%, greater than 0.0001% and less than 5%, greater than 0.0001% and less than 4%, greater than 0.0001% and less than 3%, greater than 0.0001% and less than 2%, greater than 0.0001% and less than 1%, greater than 0.0001% and less than 0.5%, or greater than 0.0001% and less than 0.1%.

[0366] The systems and apparatus used in the embodiments of the methods disclosed herein include a first discrete reaction zone and a second discrete reaction zone, a vaporizer for preheating the reactant feed, a scrubber for removing inorganic acids, and a distillation system for separating and / or recovering intermediate compounds, products, and facilitating the recycling of recovered compounds. Optionally, the systems and apparatus used in all embodiments of the methods disclosed herein include a reactant supply device and / or form at least one of CF2XCY=CH2, CF2XCXCH3, CF2XCH2CH3, and / or CF2=CHCH3, wherein X is at least one of Cl, F, Br, or I; and Y is H, Cl, F, Br, or I.

[0367] Claims and embodiments (CE) :

[0368] Claims (CE) 1. A method for preparing a compound defined by the formula CF2XCH2CH3, wherein X is one of Cl, F, Br or I, the method comprising contacting a haloalkene defined by the formula CF2XCY=CH2 with hydrogen to form a first product mixture comprising CF2XCH2CH3, wherein X is as defined above and Y is one of H, Cl, F, Br or I.

[0369] Claim 2. A method for preparing 1,1,1-trifluoropropane (HFC-263fb, CF3CH2CH3), the method comprising contacting 3,3,3-trifluoropropene (HFO-1243zf, CF3CH=CH2) with hydrogen to form a first product mixture comprising HFC-263fb.

[0370] Claim 3. A method for preparing 1-chloro-1,1-difluoropropane (HCFC-262fc, CClF2CH2CH3), the method comprising contacting 3-chloro-3,3-difluoropropene (HCFO-1242zf, CClF2CH=CH2) with hydrogen to form a first product mixture comprising HCFC-262fc.

[0371] Claim 4. A method for preparing 1-chloro-1,1-difluoropropane (HCFC-262fc, CClF2CH2CH3), the method comprising contacting 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf, CClF2CCl=CH2) with hydrogen to form a first product mixture comprising HCFC-262fc.

[0372] Claim 5. The method according to any one of CE 1 to 4, wherein the contact occurs in a liquid phase or a gas phase.

[0373] Claim 6. The method according to CE 5, wherein the catalyst comprises a hydrogenation catalyst selected from alumina, aluminum fluoride, or carbon, of iron (Fe), cobalt (Co), nickel (Ni), ruthenium (Ru), rhodium (Rh), or palladium (Pd).

[0374] Claim 7. A method for preparing 1,1-difluoropropylene (HFO-1252zc, CF2=CHCH3), the method comprising dehydrohalogenating a compound defined by the formula CF2XCH2CH3, wherein X is one of Cl, F, Br or I, to form a product mixture comprising HFO-1252zc.

[0375] Claim 8. A method for preparing 1,1-difluoropropylene (HFO-1252zc, CF2=CHCH3), the method comprising dehydrofluorinating 1,1,1-trifluoropropane (HFC-263fb, CF3CH2CH3) to form a product mixture containing HFO-1252zc.

[0376] Claim 9. A method for preparing 1,1-difluoropropene (HFO-1252zc, CF2=CHCH3), the method comprising dehydrochlorinating 1-chloro-1,1-difluoropropane (HCFC-262fc, CClF2CH2CH3) to form a product mixture containing HFO-1252zc.

[0377] Claim 10. The method according to any one of CE 7 to 9, wherein the dehydrohalogenation, the defluorination, or the dechlorination is carried out in a liquid phase or a gas phase.

[0378] Claim 11. The method according to CE 10, wherein the dehydrohalogenation, the defluorination, or the dechlorination is carried out in the gas phase by pyrolysis.

[0379] Claim 12. The method according to any one of CE 9 to 11, wherein the dehydrochlorination of HCFC-262fc to form HFO-1252zc is carried out in the gas phase by pyrolysis.

[0380] Claim 13. The method according to CE 7, further comprising contacting a (halogenated) olefin comprising one of 3,3,3-trifluoropropene (HFO-1243zf, CF3CH=CH2), 3-chloro-3,3-difluoropropene (HCFO-1242zf, CClF2CH=CH2) or 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf, CClF2CCl=CH2) with hydrogen to form an intermediate mixture comprising the CF2XCH2CH3 compound.

[0381] Claim 14. A method for preparing 1,1-difluoropropylene (HFO-1252zc, CF2=CHCH3), the method comprising:

[0382] a. Contacting a (halogenated) olefin comprising one of 3,3,3-trifluoropropene (HFO-1243zf, CF3CH=CH2), 3-chloro-3,3-difluoropropene (HCFO-1242zf, CClF2CH=CH2), or 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf, CClF2CCl=CH2) with hydrogen to form a first product mixture comprising a compound defined by the formula CF2XCH2CH3, wherein X is one of Cl, F, Br, or I; and

[0383] b. Dehydrohalogenate the CF2XCH2CH3 compound in the first mixture to form a second product mixture containing HFO-1252zc.

[0384] Claim 15. The method according to any one of CE 7 to 14, wherein the dehydrohalogenation is carried out in the gas phase with or without a catalyst or metal alloy filler.

[0385] Claim 16. The method according to any one of CE 7 to 15, wherein the dehydrohalogenation is carried out in the presence of a catalyst comprising a supported or unsupported partially fluorinated transition metal oxide, a nickel-based alloy, or a nickel-chromium-based alloy.

[0386] Claim 17. The method according to any one of CE 7 to 15, wherein the dehydrohalogenation is carried out by pyrolysis in the absence of a catalyst.

[0387] Claim 18. The method according to any one of CE 7 to 14, wherein the dehydrohalogenation is carried out in the liquid phase.

[0388] Claim 19. The method according to any one of CE 7 to 14 and 18, wherein the dehydrohalogenation is carried out in the presence of a strong base, optionally (1) in the presence or absence of a catalyst, and (2) in the presence or absence of an aprotic solvent.

[0389] Claim 20. The method according to CE 19, wherein the base comprises KOtBu.

[0390] Claim 21. The method according to any one of CE 19 to 20, wherein a solvent is present, and said solvent comprises one of dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), methylpyrrolidine (MP) or tert-butanol, optionally in the presence of a catalyst.

[0391] Claim 22. The method according to any one of CE 19 to 21, wherein KOtBu is continuously added to the mixture to be dehydrohalogenated and / or HFO-1252zc is continuously removed.

[0392] Claim 23. The method according to any one of CE 7 to 14 and 18 to 22, wherein the liquid-phase dehydrohalogenation is carried out at a temperature between about -30°C and about 100°C.

[0393] Claim 24. The method according to any one of CE 7 to 17, wherein the dehydrohalogenation is carried out in the gas phase at a temperature selected from the group consisting of:

[0394] a. Between approximately 300°C and approximately 500°C,

[0395] b. Between approximately 400°C and approximately 700°C, or

[0396] c. Between approximately 450°C and approximately 750°C.

[0397] Claim 25. The method according to CE 24, wherein the dehydrohalogenation is carried out in the presence of a catalyst comprising a supported or unsupported partially fluorinated transition metal oxide, a nickel-based or nickel-chromium alloy.

[0398] Claim 26. The method according to CE 24, wherein the dehydrohalogenation is carried out in the absence of a catalyst.

[0399] Claim 27. The method according to any one of CE 7 and 9 to 26, wherein HCFC-262fc is dehydrochlorinated to HFO-1252zc.

[0400] Claim 28. The method according to CE 27, wherein the dehydrochlorination of HCFC-262fc to HFO-1252zc is carried out in a temperature range of about 450°C to about 550°C.

[0401] Claim 29. The method according to any one of CE 27 to 28, wherein the dehydrochlorination of HCFC-262fc to HFO-1252zc is carried out in a pressure range of about 0 psig to about 150 psig.

[0402] Claim 30. The method according to any one of CE 1 to 6 and 13 to 29, wherein contact with hydrogen occurs under hydrogenation conditions.

[0403] Claim 31. The method according to any one of CE 1 to 6 and 13 to 30, wherein hydrogenation is carried out in a liquid phase or a gas phase.

[0404] Claim 32. The method according to any one of CE 1 to 6 and 13 to 31, wherein the hydrogenation is carried out in the presence of a catalyst comprising Pd supported on one of alumina, aluminum fluoride or carbon.

[0405] Claim 33. The method according to any one of CE 7 to 32, wherein the amount of HFO-1252zc is at least one of greater than 10%, 15%, 20%, 25%, 30%, 35%, 40%, 50%, 60%, 70% and 80% based on the total amount of the composition.

[0406] Claim 34. A composition formed by the method according to any one of CE 1 to 33.

[0407] Claim 35. A composition comprising HFC-263fb and two or more additional compounds selected from the group consisting of HFC-143a, HFC-152a, HFC-245cb, HFC-254fb, HCFO-1233xf, and HCFC-253db.

[0408] Claim 36. The composition according to CE 35, wherein the composition contains at least 99% HFC-263fb.

[0409] Claim 37. The composition according to any one of CE 35 to 36, wherein the total amount of the additional compound is selected from one of about 0% to about 0.5%, about 0% to about 0.4%, about 0% to about 0.3%, about 0% to about 0.2%, and about 0% to about 0.1%, and wherein the total amount of the composition is 100%.

[0410] Claim 38. A composition comprising,

[0411] a.HFO-1252zc

[0412] b.HFC-263fb

[0413] c.HFO-1234yf

[0414] d. At least one compound optionally selected from the group consisting of ethylene, propylene, butene, propylene and cyclobutene.

[0415] e. Any one of the following compounds selected from the group consisting of HFC-23, R-123, HFC-143a, HFC-152a, R-272fb, HFO-374, R1141, HFO-1234yf, HFO-1261, HCFO-1233, HCFO-1251, and HFO-1260; and

[0416] f. Any one of the following compounds selected from the group consisting of HFC-23, HFO-1132, HFO-1141, R-125, HFC-143a, HFO-1234yf, HFO-1261, HCFO-1233, HCFO-1251 and HFO-1260.

[0417] Claim 39. The composition according to CE 34, wherein the composition comprises,

[0418] a.HFO-1252zc

[0419] b.HFC-263fb

[0420] c. At least one compound selected from the group consisting of ethylene, propylene, butene, propylene, and cyclobutene, and,

[0421] d. At least one compound selected from the group consisting of HFC-23, R-123, HFC-143a, HFC-152a, R-272fb, HFO-374, R1141, HFO-1234yf, HFO-1261, HCFO-1233, HCFO-1251 and HFO-1260, or at least one of HFC-23, HFO-1132, HFO-1141, R-125, HFC-143a, R-1243zf, HFO-1234yf, HFO-1261, HCFO-1233, HCFO-1251 and HFO-1260.

[0422] Claim 40. A composition comprising 1,1-difluoropropylene (HFO-1252zc) and one or more members selected from the group consisting of: trifluoromethane (HFC-23), dichloromethane (HCC-30), chlorofluoromethane (HCFC-31), difluoromethane (HFC-32), ethylene, ethane, dichlorofluoromethane (HCFC-22), chloromethane (HCC-40), dichloromethane (HCC-30), methane, 1,1,2,2,2-pentafluoroethane (HFC-125), 1,1,2-trifluoroethane (HFC-143), 1,1,1-trifluoroethane (HFC-143a), 1,1- Difluoroethane (HFC-152a), 1,1,1,2,2-pentafluoropropane (HFC-245cb), 2-chloro-1,1,1-trifluoropropane (HCFC-253db), 1,1,1,3-tetrafluoropropane (HFC-254fb), 1,1,1-trichloropropane (HCC-260fb), 1,1-dichloro-1-fluoropropane (HCFC-261fc), 1,1-difluoropropane (HFC-272fb), propane (HC-290), tetrafluorobutene (HFO-374), butane (HC-600), propadiene, 2-butene, cyclobutene, 2-methylpropene, 1-chloro-2,2-difluoroethylene (HCFO-1122). 1,2-Difluoroethylene (HFO-1132), 1,1-Difluoroethylene (HFO-1132a), fluoroethylene (HFO-1141), ethylene (HO-1150), 1,1,2-trichloro-3,3,3-trifluoropropene (CFO-1213xa), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 3-chloro-3,3-difluoropropene (HCFO-1242zf), 3,3,3-trifluoropropene (HFO-1243zf), E-1-chloro-1-fluoro-1-propene (E-HCFO-1251zb), Z-1-chloro-1-fluoro- 1-Propylene (Z-HCFO-1251zb), 3-Chloropropene (HCO-1260zf), 3-Fluoro-1-propene (HFO-1261zf), E-1-Fluoro-1-propene (E-HFO-1261ze), 1-Fluoropropane (HFC-281fa), 1,1-Difluoropropane (272fb), Tetrafluorobutane (C4H6F4), 1252-dimer (C6F4H8), Propylene (HO-1270), Pentafluorobutene (HFO-1345), and E / Zt-BuO-CF=CH-CH3, 1,1,1-Trifluoropropane (HFC-263fb), and 1-Chloro-1,1-Difluoropropane (HCFC-262fc).

[0423] Claim 41. A composition comprising 1,1-difluoropropylene (HFO-1252zc), 3,3,3-trifluoropropylene (HFO-1243zf), and one or more members selected from the group consisting of: trifluoromethane (HFC-23), dichloromethane (HCC-30), chlorofluoromethane (HCFC-31), difluoromethane (HFC-32), ethylene, ethane, dichlorofluoromethane (HCFC-22), chloromethane (HCC-40), dichloromethane (HCC-30), methane, 1,1,2,2,2-pentafluoroethane (HFC-125), 1,1,2-trifluoroethane (HFC-143), 1, 1,1-Trifluoroethane (HFC-143a), 1,1-Difluoroethane (HFC-152a), 1,1,1,2,2-Pentafluoropropane (HFC-245cb), 2-Chloro-1,1,1-Trifluoropropane (HCFC-253db), 1,1,1,3-Tetrafluoropropane (HFC-254fb), 1,1,1-Trichloropropane (HCC-260fb), 1,1-Dichloro-1-fluoropropane (HCFC-261fc), 1,1-Difluoropropane (HFC-272fb), Propane (HC-290), Tetrafluorobutene (HFO-374), Butane (HC-600), Propylene, 2-Butene, Cyclobutene, 2-Methylpropene, 1 -Chloro-2,2-difluoroethylene (HCFO-1122), 1,2-difluoroethylene (HFO-1132), 1,1-difluoroethylene (HFO-1132a), fluoroethylene (HFO-1141), ethylene (HO-1150), 1,1,2-trichloro-3,3,3-trifluoropropylene (CFO-1213xa), 2-chloro-3,3,3-trifluoropropylene (HCFO-1233xf), 2,3,3,3-tetrafluoropropylene (HFO-1234yf), 3-chloro-3,3-difluoropropylene (HCFO-1242zf), E-1-chloro-1-fluoro-1-propene (E-HCFO-1251zb), Z-1-chloro-1-fluoro- 1-Propylene (Z-HCFO-1251zb), 3-Chloropropene (HCO-1260zf), 3-Fluoro-1-propene (HFO-1261zf), E-1-Fluoro-1-propene (E-HFO-1261ze), 1-Fluoropropane (HFC-281fa), 1,1-Difluoropropane (272fb), Tetrafluorobutane (C4H6F4), 1252-dimer (C6F4H8), Propylene (HO-1270), Pentafluorobutene (HFO-1345), and E / Zt-BuO-CF=CH-CH3, 1,1,1-Trifluoropropane (HFC-263fb), and 1-Chloro-1,1-Difluoropropane (HCFC-262fc).

[0424] Claim 42. A composition comprising 1,1-difluoropropylene (HFO-1252zc), E-1-fluoro-1-propylene (E-HFO-1261ze), and one or more members selected from the group consisting of: trifluoromethane (HFC-23), dichloromethane (HCC-30), chlorofluoromethane (HCFC-31), difluoromethane (HFC-32), ethylene, ethane, dichlorofluoromethane (HCFC-22), chloromethane (HCC-40), dichloromethane (HCC-30), methane, 1,1,2,2,2-pentafluoroethane (HFC-125), and 1,1,2-trifluoroethane (HFC-143). 1,1,1-Trifluoroethane (HFC-143a), 1,1-Difluoroethane (HFC-152a), 1,1,1,2,2-Pentafluoropropane (HFC-245cb), 2-Chloro-1,1,1-Trifluoropropane (HCFC-253db), 1,1,1,3-Tetrafluoropropane (HFC-254fb), 1,1,1-Trichloropropane (HCC-260fb), 1,1-Dichloro-1-fluoropropane (HCFC-261fc), 1,1-Difluoropropane (HFC-272fb), Propane (HC-290), Tetrafluorobutene (HFO-374), Butane (HC-600), Propylene, 2-Butene, Cyclobutene, 2-Methylpropene 1-Chloro-2,2-difluoroethylene (HCFO-1122), 1,2-difluoroethylene (HFO-1132), 1,1-difluoroethylene (HFO-1132a), fluoroethylene (HFO-1141), ethylene (HO-1150), 1,1,2-trichloro-3,3,3-trifluoropropylene (CFO-1213xa), 2-chloro-3,3,3-trifluoropropylene (HCFO-1233xf), 2,3,3,3-tetrafluoropropylene (HFO-1234yf), 3-chloro-3,3-difluoropropylene (HCFO-1242zf), 3,3,3-trifluoropropylene (HFO-1243zf), E-1-chloro-1-fluoro-1-propene ( E-HCFO-1251zb), Z-1-chloro-1-fluoro-1-propene (Z-HCFO-1251zb), 3-chloropropene (HCO-1260zf), 3-fluoro-1-propene (HFO-1261zf), 1-fluoropropane (HFC-281fa), 1,1-difluoropropane (272fb), tetrafluorobutane (C4H6F4), 1252-dimer (C6F4H8), propylene (HO-1270), pentafluorobutene (HFO-1345), and E / Zt-BuO-CF=CH-CH3, 1,1,1-trifluoropropane (HFC-263fb), and 1-chloro-1,1-difluoropropane (HCFC-262fc).

[0425] Claim 43. A composition comprising 1,1-difluoropropylene (HFO-1252zc), 3,3,3-trifluoropropylene (HFO-1243zf), E-1-fluoro-1-propene (E-HFO-1261ze), and one or more members selected from the group consisting of: trifluoromethane (HFC-23), dichloromethane (HCC-30), chlorofluoromethane (HCFC-31), difluoromethane (HFC-32), ethylene, ethane, dichlorofluoromethane (HCFC-22), chloromethane (HCC-40), dichloromethane (HCC-30), methane, 1,1,2,2,2-pentafluoroethane (HFC-12). 5) 1,1,2-Trifluoroethane (HFC-143), 1,1,1-Trifluoroethane (HFC-143a), 1,1-Difluoroethane (HFC-152a), 1,1,1,2,2-Pentafluoropropane (HFC-245cb), 2-Chloro-1,1,1-Trifluoropropane (HCFC-253db), 1,1,1,3-Tetrafluoropropane (HFC-254fb), 1,1,1-Trichloropropane (HCC-260fb), 1,1-Dichloro-1-fluoropropane (HCFC-261fc), 1,1-Difluoropropane (HFC-272fb), Propane (HC-290), Tetrafluorobutene (HFO-374), Butane (HC-6) 00), propylene, 2-butene, cyclobutene, 2-methylpropene, 1-chloro-2,2-difluoroethylene (HCFO-1122), 1,2-difluoroethylene (HFO-1132), 1,1-difluoroethylene (HFO-1132a), fluoroethylene (HFO-1141), ethylene (HO-1150), 1,1,2-trichloro-3,3,3-trifluoropropene (CFO-1213xa), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 3-chloro-3,3-difluoropropene (HCFO-1242zf), E-1-chloro-1-fluoro-1-propene ( E-HCFO-1251zb), Z-1-chloro-1-fluoro-1-propene (Z-HCFO-1251zb), 3-chloropropene (HCO-1260zf), 3-fluoro-1-propene (HFO-1261zf), 1-fluoropropane (HFC-281fa), 1,1-difluoropropane (272fb), tetrafluorobutane (C4H6F4), 1252-dimer (C6F4H8), propylene (HO-1270), pentafluorobutene (HFO-1345), and E / Zt-BuO-CF=CH-CH3, 1,1,1-trifluoropropane (HFC-263fb), and 1-chloro-1,1-difluoropropane (HCFC-262fc).

[0426] Claim 44. A composition comprising 1,1-difluoropropene (HFO-1252zc), 1-chloro-1,1-difluoropropane (HCFC-262fc), and one or more members selected from the group consisting of: trifluoromethane (HFC-23), dichloromethane (HCC-30), chlorofluoromethane (HCFC-31), difluoromethane (HFC-32), ethylene, ethane, dichlorofluoromethane (HCFC-22), chloromethane (HCC-40), dichloromethane (HCC-30), methane, 1,1,2,2,2-pentafluoroethane (HFC-125), and 1,1,2-trifluoroethane (HFC-143). 1,1,1-Trifluoroethane (HFC-143a), 1,1-Difluoroethane (HFC-152a), 1,1,1,2,2-Pentafluoropropane (HFC-245cb), 2-Chloro-1,1,1-Trifluoropropane (HCFC-253db), 1,1,1,3-Tetrafluoropropane (HFC-254fb), 1,1,1-Trichloropropane (HCC-260fb), 1,1-Dichloro-1-fluoropropane (HCFC-261fc), 1,1-Difluoropropane (HFC-272fb), Propane (HC-290), Tetrafluorobutene (HFO-374), Butane (HC-600), Propylene, 2-Butene, Cyclobutene, 2-Methylpropene 1-Chloro-2,2-difluoroethylene (HCFO-1122), 1,2-difluoroethylene (HFO-1132), 1,1-difluoroethylene (HFO-1132a), fluoroethylene (HFO-1141), ethylene (HO-1150), 1,1,2-trichloro-3,3,3-trifluoropropylene (CFO-1213xa), 2-chloro-3,3,3-trifluoropropylene (HCFO-1233xf), 2,3,3,3-tetrafluoropropylene (HFO-1234yf), 3-chloro-3,3-difluoropropylene (HCFO-1242zf), 3,3,3-trifluoropropylene (HFO-1243zf), E-1-chloro-1-fluoro-1-propene ( E-HCFO-1251zb), Z-1-chloro-1-fluoro-1-propene (Z-HCFO-1251zb), 3-chloropropene (HCO-1260zf), 3-fluoro-1-propene (HFO-1261zf), E-1-fluoro-1-propene (E-HFO-1261ze), 1-fluoropropane (HFC-281fa), 1,1-difluoropropane (272fb), tetrafluorobutane (C4H6F4), 1252-dimer (C6F4H8), propylene (HO-1270), pentafluorobutene (HFO-1345), and E / Zt-BuO-CF=CH-CH3 and 1,1,1-trifluoropropane (HFC-263fb).

[0427] Claim 45. A composition comprising 1,1-difluoropropylene (HFO-1252zc), 1,1,1-trifluoropropane (HFC-263fb), and one or more members selected from the group consisting of: trifluoromethane (HFC-23), dichloromethane (HCC-30), chlorofluoromethane (HCFC-31), difluoromethane (HFC-32), ethylene, ethane, dichlorofluoromethane (HCFC-22), chloromethane (HCC-40), dichloromethane (HCC-30), methane, 1,1,2,2,2-pentafluoroethane (HFC-125), 1,1,2-trifluoroethane (HFC-143), 1,1 1-Trifluoroethane (HFC-143a), 1,1-Difluoroethane (HFC-152a), 1,1,1,2,2-Pentafluoropropane (HFC-245cb), 2-Chloro-1,1,1-Trifluoropropane (HCFC-253db), 1,1,1,3-Tetrafluoropropane (HFC-254fb), 1,1,1-Trichloropropane (HCC-260fb), 1,1-Dichloro-1-fluoropropane (HCFC-261fc), 1,1-Difluoropropane (HFC-272fb), Propane (HC-290), Tetrafluorobutene (HFO-374), Butane (HC-600), Propylene, 2-Butene, Cyclobutene, 2-Methylpropene, 1- Chloro-2,2-difluoroethylene (HCFO-1122), 1,2-difluoroethylene (HFO-1132), 1,1-difluoroethylene (HFO-1132a), fluoroethylene (HFO-1141), ethylene (HO-1150), 1,1,2-trichloro-3,3,3-trifluoropropylene (CFO-1213xa), 2-chloro-3,3,3-trifluoropropylene (HCFO-1233xf), 2,3,3,3-tetrafluoropropylene (HFO-1234yf), 3-chloro-3,3-difluoropropylene (HCFO-1242zf), 3,3,3-trifluoropropylene (HFO-1243zf), E-1-chloro-1-fluoro-1-propene (E-H CFO-1251zb), Z-1-chloro-1-fluoro-1-propene (Z-HCFO-1251zb), 3-chloropropene (HCO-1260zf), 3-fluoro-1-propene (HFO-1261zf), E-1-fluoro-1-propene (E-HFO-1261ze), 1-fluoropropane (HFC-281fa), 1,1-difluoropropane (272fb), tetrafluorobutane (C4H6F4), 1252-dimer (C6F4H8), propylene (HO-1270), pentafluorobutene (HFO-1345), and E / Zt-BuO-CF=CH-CH3 and 1-chloro-1,1-difluoropropane (HCFC-262fc).

[0428] Claim 46. A composition comprising 1,1-difluoropropylene (HFO-1252zc) and one or more members selected from the group consisting of: ethylene (HO-1150), trifluoromethane (HFC-23), 1,1-dichloroethylene (HCO-1132a), fluoroethane (HFC-1141), 1,1,2,2,2-pentafluoroethane (HFC-125), propane (HC-290), and 1,1,2-trifluoroethane (HFC-14). 3) 1,1-Difluoropropene (HFO-1252zc), HFO-1234, 1,1-Difluoroethane (HFC-152a), 3-fluoro-1-propene (HFO-1261), 1,1,1-trifluoropropane (HCC-263fb), 1,1,1-trichloroethane (HCC-143a), 3-fluoro-1-propene (HFO-1261), HFO-1252, chloro-3,3,3-trifluoropropene (HCFO-1233), and pentafluorobutene (HFO-374).

[0429] Claim 47. A composition comprising 1,1-difluoropropylene (HFO-1252zc) and one or more members selected from the group consisting of ethylene, HFC-23, HFO-1132a, propane, HFO-1234, HFO-1261, HFC-263fb, HFC-143a and HFO-1252 isomers.

[0430] Claim 48. A composition comprising 1,1-difluoropropylene (HFO-1252zc) and 1,1,1-trifluoropropane (HFC-263fb), and one or more members selected from the group consisting of ethylene and propane, and additional members selected from the group consisting of HFC-23, HFO-1132a, HFO-1234, HFO-1261, HFC-263fb, HFC-143a and HFO-1252 isomers.

[0431] Claim 49. A composition comprising 1,1-difluoropropylene (HFO-1252zc), HFO-1261 and HFC-263fb.

[0432] Claim 50. The composition according to any one of CE 34 to 49, wherein the amount of 1,1-difluoropropylene (HFO-1252zc) is at least one of greater than 10%, 15%, 20%, 25%, 30%, 35%, 40%, 50%, 60%, 70% and 80% based on the total amount of the composition.

[0433] Claim 51. The method according to any one of CE 14 to 33, wherein the unreacted (halogenated) olefin of step (a) is recycled.

[0434] Claim 52. The method according to any one of CE 14 to 33, wherein the unreacted CF2XCH2CH3 compound of step (b) is recycled.

[0435] Claim 53. The method according to any one of CE 14 to 33, the method further comprising separating the CF2XCH2CH3 compound from the first product mixture produced by step (a) prior to dehydrohalogenating the CF2XCH2CH3 compound in step (b).

[0436] Claim 54. A system comprising:

[0437] A first discrete reaction zone and a second discrete reaction zone, the first reaction zone being configured to perform hydrogenation in a liquid or gas phase, and the second reaction zone being configured to perform dehydrohalogenation in one of a gas phase containing a catalyst or metal alloy filler, a gas phase without a catalyst or metal alloy filler, or a liquid phase.

[0438] A gasifier, used to preheat the feed to the discrete reaction zone.

[0439] A scrubber, the scrubber being used to remove inorganic acid from one of the first discrete reaction zone and the second discrete reaction zone,

[0440] An optional recirculation line, the recirculation line being used to recycle unreacted feed into the first reaction zone and the second reaction zone, and

[0441] A supply device for containing one or more of 1,1,1-trifluoropropylene, 3-chloro-3,3-difluoropropylene, 2,3-dichloro-3,3-difluoropropylene and hydrogen.

[0442] Claim 55. The system according to CE 54, further comprising one or more distillation systems for separating and / or recovering compounds comprising 1,1,1-trifluoropropane or 1-chloro-1,1-difluoropropane.

[0443] Claim 56. The system according to CE 54, further comprising a flow line for recycling unconverted compounds.

[0444] Claim 57. A composition comprising HCFC-262fc and one or more compounds selected from the group consisting of: (a) propane, propylene, HFO-1261, HFO-1252zc, HFC-272fb, HFO-1252zc, HCFO-1251 (I) isomer, HCFO-1251 (II) isomer, HCFC-262 isomer, HCFC-252dc, HCO-1250 and HCC-260, or (b) HFO-1243zf, HFO-1252zc, HFO-1261, HCFO-1242zf, HCFO-1251 (I) isomer, HCFO-1251 (II) Isomers, HCFO-1242 isomer, HCFC-262 isomer, HCFO-1232, HCFC-252, HCFC-252dc, HCO-1250 and HCC-260.

[0445] Claim 58. A composition comprising HCFO-1242zf and one or more compounds selected from the group consisting of: (a) ethane, HFC-152a, HFO-1243zf, HFO-1252zc, HCFC-253db, HCFC-262fc, HCFO-1242 isomers and HCFO-1232, or (b) HFO-1252zc, HCFC-253db, HCFC-262fc, HCFO-1242 isomers and HCFO-1232.

[0446] Claim 59. A composition comprising HCFC-262fc, HFO-1252zc and one or more compounds selected from the group consisting of: methane, ethylene, ethane, HFC-23, HFC-125, HFC-143a, HFO-1141, propane, propylene, HFO-1234yf, propylene, C3H4F2, HFO-1261ze-E, HFO-1261ze-Z, HFC-263fb, HCFC-262fc, 2-butene, cyclobutene 2-Methyl-1-propene, HFC-272fb, HCFC-262fc, HCFO-1233, HCO-1260, HFC-374, HFO-1345 isomer, HCFO-1251zb-E, HCFO-1251zb-Z, HFC-32, HFO-1132a, HCC-40, HCFC-22, HFO-1261ze-E, HFO-1252 isomer, HFC-281fa, HCC-30, C4H3ClF4, HFO-1252-dimer.

[0447] Claim 60. A composition comprising HCFO-1242zf, HFO-1252zc and one or more compounds selected from the group consisting of ethane, HFC-152a, HFO-1243zf, HCFC-253db, HCFC-262fc, HCFO-1242 isomers and HCFO-1232, or (b) HCFC-253db, HCFO-1242 isomers and HCFO-1232.

[0448] While certain aspects, embodiments, and principles have been described above, it should be understood that this description is exemplary only and not intended to limit the invention or the appended claims. The various aspects, embodiments, and principles described above can be used individually or in combination with each other.

Claims

1. A method for preparing a compound defined by the formula CF2XCH2CH3, the method comprising contacting a haloalkene defined by the formula CF2XCY=CH2 with hydrogen gas to form a first product mixture comprising CF2XCH2CH3. Where X is one of Cl, F, Br or I, and Y is one of H, Cl, F, Br or I.

2. A method for preparing 1,1,1-trifluoropropane (HFC-263fb, CF3CH2CH3), the method comprising contacting 3,3,3-trifluoropropene (HFO-1243zf, CF3CH=CH2) with hydrogen to form a first product mixture comprising HFC-263fb.

3. A method for preparing 1-chloro-1,1-difluoropropane (HCFC-262fc, CClF2CH2CH3), the method comprising contacting 3-chloro-3,3-difluoropropene (HCFO-1242zf, CClF2CH=CH2) with hydrogen to form a first product mixture comprising HCFC-262fc.

4. A method for preparing 1-chloro-1,1-difluoropropane (HCFC-262fc, CClF2CH2CH3), the method comprising contacting 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf, CClF2CCl=CH2) with hydrogen to form a first product mixture comprising HCFC-262fc.

5. The method according to any one of claims 1 to 4, wherein the contact occurs in a liquid phase or a gas phase.

6. The method according to claim 5, wherein the catalyst comprises a hydrogenation catalyst selected from the group consisting of iron (Fe), cobalt (Co) and nickel (Ni), ruthenium (Ru), rhodium (Rh) or palladium (Pd) on alumina, aluminum fluoride or carbon.

7. A method for preparing 1,1-difluoropropylene (HFO-1252zc, CF2=CHCH3), the method comprising dehydrohalogenating a compound defined by the formula CF2XCH2CH3, wherein X is one of Cl, F, Br or I, to form a product mixture containing HFO-1252zc.

8. A method for preparing 1,1-difluoropropylene (HFO-1252zc, CF2=CHCH3), the method comprising dehydrofluorinating 1,1,1-trifluoropropane (HFC-263fb, CF3CH2CH3) to form a product mixture containing HFO-1252zc.

9. A method for preparing 1,1-difluoropropene (HFO-1252zc, CF2=CHCH3), the method comprising dehydrochlorinating 1-chloro-1,1-difluoropropane (HCFC-262fc, CClF2CH2CH3) to form a product mixture containing HFO-1252zc.

10. The method according to any one of claims 7 to 9, wherein the dehydrohalogenation, defluorination, or dechlorination is carried out in a liquid phase or a gas phase.

11. The method of claim 10, wherein the dehydrohalogenation, defluorination, or dechlorination is carried out in the gas phase by pyrolysis.

12. The method of claim 9, wherein the dehydrochlorination of HCFC-262fc to form HFO-1252zc is carried out in the gas phase by pyrolysis.

13. The method of claim 7, further comprising contacting the (halogenated) olefin with hydrogen to form an intermediate mixture comprising the CF2XCH2CH3 compound, wherein the (halogenated) olefin is selected from the group consisting of 3,3,3-trifluoropropene (HFO-1243zf, CF3CH=CH2), 3-chloro-3,3-difluoropropene (HCFO-1242zf, CClF2CH=CH2) and 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf, CClF2CCl=CH2).

14. A method for preparing 1,1-difluoropropylene (HFO-1252zc, CF2=CHCH3), the method comprising: a. To contact a (halogenated) olefin comprising one of 3,3,3-trifluoropropene (HFO-1243zf, CF3CH=CH2), 3-chloro-3,3-difluoropropene (HCFO-1242zf, CClF2CH=CH2) or 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf, CClF2CCl=CH2) with hydrogen to form a first product mixture comprising a compound defined by the formula CF2XCH2CH3, wherein X is one of Cl, F, Br or I; as well as b. Dehydrohalogenate the CF2XCH2CH3 compound in the first product mixture to form a second product mixture containing HFO-1252zc.

15. The method according to any one of claims 7 to 14, wherein the dehydrohalogenation is carried out in the gas phase with or without a catalyst or metal alloy filler.

16. The method according to any one of claims 7 to 15, wherein the dehydrohalogenation is carried out in the presence of a catalyst comprising a supported or unsupported partially fluorinated transition metal oxide, a nickel-based alloy, or a nickel-chromium-based alloy.

17. The method according to any one of claims 7 to 15, wherein the dehydrohalogenation is carried out by pyrolysis in the absence of a catalyst.

18. The method according to any one of claims 7 to 14, wherein the dehydrohalogenation is carried out in the liquid phase.

19. The method according to any one of claims 7 to 14 and 18, wherein the dehydrohalogenation is carried out in the presence of a strong base, optionally (1) in the presence or absence of a catalyst, and (2) in the presence or absence of an aprotic solvent.

20. The method of claim 19, wherein the base comprises KOtBu t-BuOK.

21. The method according to any one of claims 19 to 20, wherein a solvent is present, and said solvent comprises one of dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), methylpyrrolidine (MP), or tert-butanol, optionally in the presence of a catalyst.

22. The method according to any one of claims 19 to 21, wherein KOtBu is continuously added to the mixture to be dehydrohalogenated and / or HFO-1252zc is continuously removed.

23. The method according to any one of claims 7 to 14 and 18 to 22, wherein the liquid-phase dehydrohalogenation is carried out at a temperature between about -30°C and about 100°C.

24. The method according to any one of claims 7 to 17, wherein the dehydrohalogenation is carried out in the gas phase at a temperature selected from the group consisting of: a. Between approximately 300°C and approximately 500°C, b. Between approximately 400°C and approximately 700°C, or c. Between approximately 450°C and approximately 750°C.

25. The method of claim 24, wherein the dehydrohalogenation is carried out in the presence of a catalyst, said catalyst comprising a supported or unsupported partially fluorinated transition metal oxide, a nickel-based or nickel-chromium alloy.

26. The method of claim 24, wherein the dehydrohalogenation is carried out in the absence of a catalyst.

27. The method according to any one of claims 7 and 9 to 26, wherein HCFC-262fc is dehydrochlorinated to HFO-1252zc.

28. The method of claim 27, wherein the dehydrochlorination of HCFC-262fc to HFO-1252zc is carried out in a temperature range of about 450°C to about 550°C.

29. The method according to any one of claims 27 to 28, wherein the dehydrochlorination of HCFC-262fc to HFO-1252zc is carried out in a pressure range of about 0 psig to about 150 psig.

30. The method according to any one of claims 1 to 6 and 13 to 29, wherein contact with hydrogen occurs under hydrogenation conditions.

31. The method according to any one of claims 1 to 6 and 13 to 30, wherein hydrogenation is carried out in the liquid phase or gas phase.

32. The method according to any one of claims 1 to 6 and 13 to 31, wherein the hydrogenation is carried out in the presence of a catalyst comprising Pd supported on one of alumina, aluminum fluoride or carbon.

33. The method according to any one of claims 7 to 32, wherein the amount of HFO-1252zc is at least one of greater than 10%, 15%, 20%, 25%, 30%, 35%, 40%, 50%, 60%, 70% and 80% based on the total amount of the composition.

34. The method according to any one of claims 14 to 33, wherein the unreacted (halogenated) olefin of step (a) is recycled.

35. The method according to any one of claims 14 to 33, wherein the unreacted CF2XCH2CH3 compound from step (b) is recycled.

36. The method according to any one of claims 14 to 33, the method further comprising separating the CF2XCH2CH3 compound from the first product mixture produced by step (a) prior to dehydrohalogenating the CF2XCH2CH3 compound in step (b).

37. A composition formed by the method according to any one of claims 1 to 36.

38. A composition comprising HFC-263fb and one or more additional compounds, preferably two or more additional compounds selected from the group consisting of HFC-143a, HFC-152a, HFC-245cb, HFC-254fb, HCFO-1233xf, and HCFC-253db.

39. The composition of claim 38, wherein the composition contains at least 99% by weight of HFC-263fb.

40. The composition according to any one of claims 38 to 39, wherein the total amount of the additional compound is selected from one of about 0% by weight and about 0.5% by weight, about 0% by weight and about 0.4% by weight, about 0% by weight and about 0.3% by weight, about 0% by weight and about 0.2% by weight, and about 0% by weight and about 0.1% by weight, and based on the total amount of the composition.

41. A composition comprising, a.HFO-1252zc b.HFC-263fb c.HFO-1234yf d. At least one compound optionally selected from the group consisting of ethylene, propylene, butene, propylene and cyclobutene. e. Any one of the following compounds selected from the group consisting of HFC-23, HCFC-123, HFC-143a, HFC-152a, HFC-272fb, HFO-374, HFO-1141, HFO-1234yf, HFO-1261, HCFO-1233, HCFO-1251 and HFO-1260; and f. Any one of the following compounds selected from the group consisting of HFC-23, HFO-1132, HFO-1141, HFC-125, HFC-143a, HFO-1234yf, HFO-1261, HCFO-1233, HCFO-1251 and HFO-1260.

42. The composition of claim 37, wherein the composition comprises, a.HFO-1252zc; b.HFC-263fb; c. At least one compound selected from the group consisting of ethylene, propylene, butene, propylene, and cyclobutene; and d. At least one compound selected from the group consisting of HFC-23, HCFC-123, HFC-143a, HFC-152a, HFC-272fb, HFO-374, HFO-1141, HFO-1234yf, HFO-1261, HCFO-1233, HCFO-1251 and HFO-1260, or at least one compound selected from the group consisting of HFC-23, HFO-1132, HFO-1141, HFC-125, HFC-143a, HFO-1243zf, HFO-1234yf, HFO-1261, HCFO-1233, HCFO-1251 and HFO-1260.

43. A composition comprising 1,1-difluoropropylene (HFO-1252zc) and one or more additional compounds selected from the group consisting of: trifluoromethane (HFC-23), dichloromethane (HCC-30), chlorofluoromethane (HCFC-31), difluoromethane (HFC-32), ethylene, ethane, dichlorofluoromethane (HCFC-22), chloromethane (HCC-40), dichloromethane (HCC-30), methane, 1,1,2,2,2-pentafluoroethane (HFC-125), 1,1,2-trifluoroethane (HFC-143), 1,1,1-trifluoroethane (HFC-143a), 1,1-difluoroethane (HF) C-152a), 1,1,1,2,2-pentafluoropropane (HFC-245cb), 2-chloro-1,1,1-trifluoropropane (HCFC-253db), 1,1,1,3-tetrafluoropropane (HFC-254fb), 1,1,1-trichloropropane (HCC-260fb), 1,1-dichloro-1-fluoropropane (HCFC-261fc), 1,1-difluoropropane (HFC-272fb), propane (HC-290), tetrafluorobutene (HFO-374), butane (HC-600), propadiene, 2-butene, cyclobutene, 2-methylpropene, 1-chloro-2,2-difluoroethylene (HCFO-1122), 1,2-difluoropropane... Vinyl fluoride (HFO-1132), 1,1-difluoroethylene (HFO-1132a), vinyl fluoride (HFO-1141), ethylene (HO-1150), 1,1,2-trichloro-3,3,3-trifluoropropene (CFO-1213xa), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 3-chloro-3,3-difluoropropene (HCFO-1242zf), 3,3,3-trifluoropropene (HFO-1243zf), E-1-chloro-1-fluoro-1-propene (E-HCFO-1251zb), Z-1-chloro-1-fluoro-1-propene Alkenes (Z-HCFO-1251zb), 3-chloropropene (HCO-1260zf), 3-fluoro-1-propene (HFO-1261zf), E-1-fluoro-1-propene (E-HFO-1261ze), 1-fluoropropane (HFC-281fa), 1,1-difluoropropane (272fb), tetrafluorobutane (C4H6F4), 1252-dimer (C6F4H8), propylene (HO-1270), pentafluorobutene (HFO-1345), and E / Zt-BuO-CF=CH-CH3, 1,1,1-trifluoropropane (HFC-263fb), and 1-chloro-1,1-difluoropropane (HCFC-262fc).

44. A composition comprising 1,1-difluoropropene (HFO-1252zc), 3,3,3-trifluoropropene (HFO-1243zf), and one or more additional compounds selected from the group consisting of: trifluoromethane (HFC-23), dichloromethane (HCC-30), chlorofluoromethane (HCFC-31), difluoromethane (HFC-32), ethylene, ethane, dichlorofluoromethane (HCFC-22), chloromethane (HCC-40), dichloromethane (HCC-30), methane, 1,1,2,2,2-pentafluoroethane (HFC-125), 1,1,2-trifluoroethane (HFC-143), 1,1,1-trifluoroethane... Alkane (HFC-143a), 1,1-difluoroethane (HFC-152a), 1,1,1,2,2-pentafluoropropane (HFC-245cb), 2-chloro-1,1,1-trifluoropropane (HCFC-253db), 1,1,1,3-tetrafluoropropane (HFC-254fb), 1,1,1-trichloropropane (HCC-260fb), 1,1-dichloro-1-fluoropropane (HCFC-261fc), 1,1-difluoropropane (HFC-272fb), propane (HC-290), tetrafluorobutene (HFO-374), butane (HC-600), propadiene, 2-butene, cyclobutene, 2-methylpropene, 1-chloro-2, 2-Difluoroethylene (HCFO-1122), 1,2-Difluoroethylene (HFO-1132), 1,1-Difluoroethylene (HFO-1132a), fluoroethylene (HFO-1141), ethylene (HO-1150), 1,1,2-trichloro-3,3,3-trifluoropropene (CFO-1213xa), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 3-chloro-3,3-difluoropropene (HCFO-1242zf), E-1-chloro-1-fluoro-1-propene (E-HCFO-1251zb), Z-1-chloro-1-fluoro-1-propene Alkenes (Z-HCFO-1251zb), 3-chloropropene (HCO-1260zf), 3-fluoro-1-propene (HFO-1261zf), E-1-fluoro-1-propene (E-HFO-1261ze), 1-fluoropropane (HFC-281fa), 1,1-difluoropropane (272fb), tetrafluorobutane (C4H6F4), 1252-dimer (C6F4H8), propylene (HO-1270), pentafluorobutene (HFO-1345), and E / Zt-BuO-CF=CH-CH3, 1,1,1-trifluoropropane (HFC-263fb), and 1-chloro-1,1-difluoropropane (HCFC-262fc).

45. A composition comprising 1,1-difluoropropene (HFO-1252zc), E-1-fluoro-1-propene (E-HFO-1261ze), and one or more additional compounds selected from the group consisting of: trifluoromethane (HFC-23), dichloromethane (HCC-30), chlorofluoromethane (HCFC-31), difluoromethane (HFC-32), ethylene, ethane, dichlorofluoromethane (HCFC-22), chloromethane (HCC-40), dichloromethane (HCC-30), methane, 1,1,2,2,2-pentafluoroethane (HFC-125), 1,1,2-trifluoroethane (HFC-143), 1,1,1-trifluoroethane (HFC-125), 1,1,2-trifluoroethane (HFC-143), 1,1,1-trifluoromethane (HFC-125), 1,1,2-trifluoro ...methane (H Fluoroethane (HFC-143a), 1,1-difluoroethane (HFC-152a), 1,1,1,2,2-pentafluoropropane (HFC-245cb), 2-chloro-1,1,1-trifluoropropane (HCFC-253db), 1,1,1,3-tetrafluoropropane (HFC-254fb), 1,1,1-trichloropropane (HCC-260fb), 1,1-dichloro-1-fluoropropane (HCFC-261fc), 1,1-difluoropropane (HFC-272fb), propane (HC-290), tetrafluorobutene (HFO-374), butane (HC-600), propadiene, 2-butene, cyclobutene, 2-methylpropene, 1-chloro- 2,2-Difluoroethylene (HCFO-1122), 1,2-Difluoroethylene (HFO-1132), 1,1-Difluoroethylene (HFO-1132a), fluoroethylene (HFO-1141), ethylene (HO-1150), 1,1,2-trichloro-3,3,3-trifluoropropylene (CFO-1213xa), 2-chloro-3,3,3-trifluoropropylene (HCFO-1233xf), 2,3,3,3-tetrafluoropropylene (HFO-1234yf), 3-chloro-3,3-difluoropropylene (HCFO-1242zf), 3,3,3-trifluoropropylene (HFO-1243zf), E-1-chloro-1-fluoro-1-propene (E-H CFO-1251zb), Z-1-chloro-1-fluoro-1-propene (Z-HCFO-1251zb), 3-chloropropene (HCO-1260zf), 3-fluoro-1-propene (HFO-1261zf), 1-fluoropropane (HFC-281fa), 1,1-difluoropropane (272fb), tetrafluorobutane (C4H6F4), 1252-dimer (C6F4H8), propylene (HO-1270), pentafluorobutene (HFO-1345), and E / Zt-BuO-CF=CH-CH3, 1,1,1-trifluoropropane (HFC-263fb) and 1-chloro-1,1-difluoropropane (HCFC-262fc).

46. ​​A composition comprising 1,1-difluoropropene (HFO-1252zc), 3,3,3-trifluoropropene (HFO-1243zf), E-1-fluoro-1-propene (E-HFO-1261ze), and one or more additional compounds selected from the group consisting of: trifluoromethane (HFC-23), dichloromethane (HCC-30), chlorofluoromethane (HCFC-31), difluoromethane (HFC-32), ethylene, ethane, dichlorofluoromethane (HCFC-22), chloromethane (HCC-40), dichloromethane (HCC-30), methane, 1,1,2,2,2-pentafluoroethane (HFC-125), 1,1, 2-Trifluoroethane (HFC-143), 1,1,1-Trifluoroethane (HFC-143a), 1,1-Difluoroethane (HFC-152a), 1,1,1,2,2-Pentafluoropropane (HFC-245cb), 2-Chloro-1,1,1-Trifluoropropane (HCFC-253db), 1,1,1,3-Tetrafluoropropane (HFC-254fb), 1,1,1-Trichloropropane (HCC-260fb), 1,1-Dichloro-1-fluoropropane (HCFC-261fc), 1,1-Difluoropropane (HFC-272fb), Propane (HC-290), Tetrafluorobutene (HFO-374), Butane (HC-600), Propane Diene, 2-Butene, Cyclobutene, 2-Methylpropene, 1-Chloro-2,2-Difluoroethylene (HCFO-1122), 1,2-Difluoroethylene (HFO-1132), 1,1-Difluoroethylene (HFO-1132a), Vinyl fluoride (HFO-1141), Ethylene (HO-1150), 1,1,2-Trichloro-3,3,3-Trifluoropropene (CFO-1213xa), 2-Chloro-3,3,3-Trifluoropropene (HCFO-1233xf), 2,3,3,3-Tetrafluoropropene (HFO-1234yf), 3-Chloro-3,3-Difluoropropene (HCFO-1242zf), E-1-Chloro-1-Fluoro-1-Propylene (E-H CFO-1251zb), Z-1-chloro-1-fluoro-1-propene (Z-HCFO-1251zb), 3-chloropropene (HCO-1260zf), 3-fluoro-1-propene (HFO-1261zf), 1-fluoropropane (HFC-281fa), 1,1-difluoropropane (272fb), tetrafluorobutane (C4H6F4), 1252-dimer (C6F4H8), propylene (HO-1270), pentafluorobutene (HFO-1345), and E / Zt-BuO-CF=CH-CH3, 1,1,1-trifluoropropane (HFC-263fb) and 1-chloro-1,1-difluoropropane (HCFC-262fc).

47. A composition comprising 1,1-difluoropropene (HFO-1252zc), 1-chloro-1,1-difluoropropane (HCFC-262fc), and one or more additional compounds selected from the group consisting of: trifluoromethane (HFC-23), dichloromethane (HCC-30), chlorofluoromethane (HCFC-31), difluoromethane (HFC-32), ethylene, ethane, dichlorofluoromethane (HCFC-22), chloromethane (HCC-40), dichloromethane (HCC-30), methane, 1,1,2,2,2-pentafluoroethane (HFC-125), 1,1,2-trifluoroethane (HFC-143), 1,1,1-trifluoropropane (HFC-262fc), etc. Fluoroethane (HFC-143a), 1,1-difluoroethane (HFC-152a), 1,1,1,2,2-pentafluoropropane (HFC-245cb), 2-chloro-1,1,1-trifluoropropane (HCFC-253db), 1,1,1,3-tetrafluoropropane (HFC-254fb), 1,1,1-trichloropropane (HCC-260fb), 1,1-dichloro-1-fluoropropane (HCFC-261fc), 1,1-difluoropropane (HFC-272fb), propane (HC-290), tetrafluorobutene (HFO-374), butane (HC-600), propadiene, 2-butene, cyclobutene, 2-methylpropene, 1-chloro- 2,2-Difluoroethylene (HCFO-1122), 1,2-Difluoroethylene (HFO-1132), 1,1-Difluoroethylene (HFO-1132a), fluoroethylene (HFO-1141), ethylene (HO-1150), 1,1,2-trichloro-3,3,3-trifluoropropylene (CFO-1213xa), 2-chloro-3,3,3-trifluoropropylene (HCFO-1233xf), 2,3,3,3-tetrafluoropropylene (HFO-1234yf), 3-chloro-3,3-difluoropropylene (HCFO-1242zf), 3,3,3-trifluoropropylene (HFO-1243zf), E-1-chloro-1-fluoro-1-propene (E-H CFO-1251zb), Z-1-chloro-1-fluoro-1-propene (Z-HCFO-1251zb), 3-chloropropene (HCO-1260zf), 3-fluoro-1-propene (HFO-1261zf), E-1-fluoro-1-propene (E-HFO-1261ze), 1-fluoropropane (HFC-281fa), 1,1-difluoropropane (272fb), tetrafluorobutane (C4H6F4), 1252-dimer (C6F4H8), propylene (HO-1270), pentafluorobutene (HFO-1345), and E / Zt-BuO-CF=CH-CH3 and 1,1,1-trifluoropropane (HFC-263fb).

48. A composition comprising 1,1-difluoropropene (HFO-1252zc), 1,1,1-trifluoropropane (HFC-263fb), and one or more additional compounds selected from the group consisting of: trifluoromethane (HFC-23), dichloromethane (HCC-30), chlorofluoromethane (HCFC-31), difluoromethane (HFC-32), ethylene, ethane, dichlorofluoromethane (HCFC-22), chloromethane (HCC-40), dichloromethane (HCC-30), methane, 1,1,2,2,2-pentafluoroethane (HFC-125), 1,1,2-trifluoroethane (HFC-143), 1,1,1-trifluoroethane (HFC-143a), 1,1-difluoroethane (HFC-152a), 1,1,1,2,2-pentafluoropropane (HFC-245cb), 2-chloro-1,1,1-trifluoropropane (HCFC-253db), 1,1,1,3-tetrafluoropropane (HFC-254fb), 1,1,1-trichloropropane (HCC-260fb), 1,1-dichloro-1-fluoropropane (HCFC-261fc), 1,1-difluoropropane (HFC-272fb), propane (HC-290), tetrafluorobutene (HFO-374), butane (HC-600), propadiene, 2-butene, cyclobutene, 2-methylpropene, 1-chloro-2,2-difluoropropane -Difluoroethylene (HCFO-1122), 1,2-difluoroethylene (HFO-1132), 1,1-difluoroethylene (HFO-1132a), fluoroethylene (HFO-1141), ethylene (HO-1150), 1,1,2-trichloro-3,3,3-trifluoropropylene (CFO-1213xa), 2-chloro-3,3,3-trifluoropropylene (HCFO-1233xf), 2,3,3,3-tetrafluoropropylene (HFO-1234yf), 3-chloro-3,3-difluoropropylene (HCFO-1242zf), 3,3,3-trifluoropropylene (HFO-1243zf), E-1-chloro-1-fluoro-1-propene (E-HCFO) -1251zb), Z-1-chloro-1-fluoro-1-propene (Z-HCFO-1251zb), 3-chloropropene (HCO-1260zf), 3-fluoro-1-propene (HFO-1261zf), E-1-fluoro-1-propene (E-HFO-1261ze), 1-fluoropropane (HFC-281fa), 1,1-difluoropropane (272fb), tetrafluorobutane (C4H6F4), 1252-dimer (C6F4H8), propylene (HO-1270), pentafluorobutene (HFO-1345), and E / Zt-BuO-CF=CH-CH3 and 1-chloro-1,1-difluoropropane (HCFC-262fc).

49. A composition comprising 1,1-difluoropropylene (HFO-1252zc) and one or more additional compounds belonging to the group consisting of: ethylene (HO-1150), trifluoromethane (HFC-23), 1,1-difluoroethylene (HCO-1132a), fluoroethane (HFC-1141), 1,1,2,2,2-pentafluoroethane (HFC-125), propane (HC-290), 1,1,2-trifluoroethane (HFC-143), 1 1-Difluoropropene (HFO-1252zc), HFO-1234, 1,1-difluoroethane (HFC-152a), 3-fluoro-1-propene (HFO-1261), 1,1,1-trifluoropropane (HCC-263fb), 1,1,1-trichloroethane (HCC-143a), 3-fluoro-1-propene (HFO-1261), HFO-1252, chloro-3,3,3-trifluoropropene (HCFO-1233), and pentafluorobutene (HFO-374).

50. A composition comprising 1,1-difluoropropylene (HFO-1252zc) and one or more additional compounds selected from the group consisting of ethylene, HFC-23, HFO-1132a, propane, HFO-1234, HFO-1261, HFC-263fb, HFC-143a and HFO-1252 isomers.

51. A composition comprising 1,1-difluoropropylene (HFO-1252zc); 1,1,1-trifluoropropane (HFC-263fb); one or more additional compounds selected from the group consisting of ethylene and propane; and one or more additional compounds selected from the group consisting of HFC-23, HFO-1132a, HFO-1234, HFO-1261, HFC-263fb, HFC-143a and HFO-1252 isomers.

52. A composition comprising 1,1-difluoropropylene (HFO-1252zc), HFO-1261 and HFC-263fb.

53. The composition according to any one of claims 37 to 52, wherein the amount of HFO-1252zc is greater than about 10% by weight, or greater than about 15% by weight, or greater than about 20% by weight, or greater than about 25% by weight, or greater than about 30% by weight, or greater than about 35% by weight, or greater than about 40% by weight, or greater than about 50% by weight, or greater than about 60% by weight, or greater than about 70% by weight, or greater than about 80% by weight, based on the total amount of the composition.

54. The composition according to any one of claims 37 to 53, wherein the total amount of said additional compound is between about 0% by weight and about 0.5% by weight, or between about 0% by weight and about 0.4% by weight, or between about 0% by weight and about 0.3% by weight, or between about 0% by weight and about 0.2% by weight, or between about 0% by weight and about 0.1% by weight, based on the total amount of the composition.

55. A system comprising: A first discrete reaction zone and a second discrete reaction zone, the first reaction zone being configured to perform hydrogenation in a liquid or gas phase, and the second reaction zone being configured to perform dehydrohalogenation in one of a gas phase containing a catalyst or metal alloy filler, a gas phase without a catalyst or metal alloy filler, or a liquid phase. A gasifier, used to preheat the feed to the discrete reaction zone. A scrubber, the scrubber being used to remove inorganic acid from one of the first discrete reaction zone and the second discrete reaction zone, An optional recirculation line, the recirculation line being used to recycle unreacted feed into the first reaction zone and the second reaction zone, and A supply device for containing one or more of 1,1,1-trifluoropropylene, 3-chloro-3,3-difluoropropylene, 2,3-dichloro-3,3-difluoropropylene and hydrogen.

56. The system of claim 55, further comprising one or more distillation systems for separating and / or recovering compounds comprising 1,1,1-trifluoropropane or 1-chloro-1,1-difluoropropane.

57. The system according to any one of claims 55 to 56, the system further comprising a flow line for recycling unconverted compounds.

58. A composition comprising HCFC-262fc and one or more compounds selected from the group consisting of: (a) propane, propylene, HFO-1261, HFO-1252zc, HFC-272fb, HFO-1252zc, HCFO-1251 (I) isomer, HCFO-1251 (II) isomer, HCFC-262 isomer, HCFC-252dc, HCO-1250 and HCC-260, or (b) HFO-1243zf, HFO-1252zc, HFO-1261, HCFO-1242zf, HCFO-1251 (I) isomer, HCFO-1251 (II) Isomers, HCFO-1242 isomer, HCFC-262 isomer, HCFO-1232, HCFC-252, HCFC-252dc, HCO-1250 and HCC-260.

59. A composition comprising HCFO-1242zf and one or more compounds selected from the group consisting of: (a) ethane, HFC-152a, HFO-1243zf, HFO-1252zc, HCFC-253db, HCFC-262fc, HCFO-1242 isomers and HCFO-1232, or (b) HFO-1252zc, HCFC-253db, HCFC-262fc, HCFO-1242 isomers and HCFO-1232.

60. A composition comprising HCFC-262fc, HFO-1252zc, and one or more compounds selected from the group consisting of: methane, ethylene, ethane, HFC-23, HFC-125, HFC-143a, HFO-1141, propane, propylene, HFO-1234yf, propylene, C3H4F2, HFO-1261ze-E, HFO-1261ze-Z, HFC-263fb, HCFC-262fc, 2-butene, cyclobutene, 2-methyl- 1-Propylene, HFC-272fb, HCFC-262fc, HCFO-1233, HCO-1260, HFC-374, HFO-1345 isomer, HCFO-1251zb-E, HCFO-1251zb-Z, HFC-32, HFO-1132a, HCC-40, HCFC-22, HFO-1261ze-E, HFO-1252 isomer, HFC-281fa, HCC-30, C4H3ClF4, HFO-1252-dimer.

61. A composition comprising HCFO-1242zf, HFO-1252zc and one or more compounds selected from the group consisting of ethane, HFC-152a, HFO-1243zf, HCFC-253db, HCFC-262fc, HCFO-1242 isomers and HCFO-1232, or (b) HCFC-253db, HCFO-1242 isomers and HCFO-1232.

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