Process for preparation of fluoroolefins by catalytic hydrofluorination of hydrochlorohydrocarbons or hydrochloroalkenes

Abstract

Provided is a process for the preparation of 2-chloro-3, 3, 3-trifluoropropene (HCFO-1233xf) by contacting 1, 1, 2, 3-tetrachloro-1-propene (HCO-1230xa) and HF in the presence of a zinc doped alumina catalyst at a suitable temperature and in a suitable molar ratio of HCO-1230xa: HF. Also provided herein is a process for the preparation of 3, 3, 3-trifluoropropene (HFO-1243zf) by contacting 1, 1, 1, 3-tetrachloropropane (HCC-250fb) and HF in the presence of a zinc doped alumina catalyst at a suitable temperature and in a suitable molar ratio of HCC-250fb: HF.

Description

[0001] Cross-references to related applications

[0002] This application claims the benefit of priority to U.S. Provisional Application 63 / 565,058, filed March 14, 2024, the disclosure of which is incorporated herein by reference in its entirety. Technical Field

[0003] This invention relates to methods for preparing hydrofluoroolefins (HFO) and / or hydrochlorofluoroolefins (HCFO) from hydrochloroolefins (HCO) or hydrochlorocarbons (HCC), and compositions thereof. Background Technology

[0004] For decades, the fluorocarbon industry has been striving to find alternative refrigerants to ozone-depleting chlorofluorocarbons (CFCs) and HCFCs, which are being phased out under the Montreal Protocol. Solutions for many applications involve the commercialization of hydrofluorocarbon (HFC) compounds used as refrigerants, solvents, fire extinguishing agents, foaming agents, and propellants. These currently most widely used new compounds, such as HFC refrigerants, HFC-134a, and HFC-125, have zero ozone depletion potential (ODP) and are therefore unaffected by the current Montreal Protocol phase-out provisions. In addition to ozone depletion, global warming is another environmental concern for many of these applications. According to the UN IPCC Fifth Assessment Report (AR5), HFC refrigerants such as HFC-134a and HFC-125 have global warming potentials (GWPs) of 1,300 and 3,170, respectively.

[0005] This regulatory environment is constantly evolving, and the characteristics taken into consideration are no longer limited to ODP and GWP. More specifically, there is a need for refrigerant compositions that not only meet low ODP standards and have low global warming potential, but also exhibit low or no flammability, provide excellent performance in a variety 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 hydrofluoroolefins, such as 2,3,3,3-tetrafluoropropene (HFO-1234yf) are such new type refrigerants. Chlorofluoroolefins (CFOs) such as 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) and HFOs such as 3,3,3-trifluoropropene (HFO-1243zf) are useful intermediates for producing HFO-1234yf. Some processes for producing HCFO-1233xf from 1,1,2,3-tetrachloro-1-propene (HCO-1230xa) and HFO-1243zf from 1,1,1,3-tetrachloropropane (HCC-250fb) involve the use of metal oxide catalysts, such as chromium oxide catalysts. Although chromium oxide catalysts are highly efficient, they are expensive, have limited availability, and can be environmentally toxic. Thus, there is a need for alternative processes that are more cost effective and more environmentally friendly. The present invention provides such alternative processes, namely, innovative processes for converting HCC or HCO starting materials to HFOs and / or HCFOs, and more specifically, for converting HCO-1230xa to HCFO-1233xf and HCC-250fb to HFO-1243zf. SUMMARY

[0008] In some embodiments, the present invention relates to a process for preparing a hydrofluoroolefin (HFO) and / or a hydrochlorofluoroolefin (HCFO) from a hydrochlorocarbon (HCC) or a hydrochloroolefin (HCO). Generally, the process comprises hydrofluorinating the HCC or HCO under conditions suitable to produce a product stream comprising the HFO and / or HCFO product, and optionally, a reaction intermediate, and optionally, unreacted starting material. More specifically, the process comprises hydrofluorinating the HCC or HCO with an effective amount of hydrogen fluoride (HF) in the presence of a catalyst, preferably a metal-doped catalyst, under conditions suitable to produce a product stream comprising the HFO and / or HCFO product.

[0009] In one embodiment, the HCO starting material used in the process of the present invention is HCO-1230xa.

[0010] In one embodiment, the HFO and / or HCFO produced by the process of the present invention comprises one or more compounds selected from the group consisting of HCFO-1233xf, HFO-1234yf, HFO-1243zf, and HCFO-1232xf.

[0011] In one embodiment, the HCO starting material used in the process of the present invention is HCO-1230xa, and the product stream produced by the process comprises HCFO-1233xf.

[0012] In some embodiments, the present application relates to a process for producing HCFO-1233xf from HCO-1230xa in the presence of a catalyst.

[0013] Certain embodiments of the present application disclosed herein relate to a gas phase process for converting, preferably selectively converting, HCO-1230xa to HCFO-1233xf by hydrofluorination in the presence of a catalyst.

[0014] One embodiment of the present application disclosed herein relates to a composition comprising, consisting essentially of, or consisting of HCFO-1233xf and at least one additional compound selected from the group consisting of HFO-1243zf, HFO-1234yf, HCFC-244bb, HCFO-1232xf, HCO-1230xa, C6H2F8, C6H3F7, C6H3ClF6 isomers, CO-1110, C6H2ClF7 isomers, and C6H3Cl2F7.

[0015] One embodiment of the present application disclosed herein relates to a composition comprising, consisting essentially of, or consisting of HCFO-1233xf and HCFC-244bb and at least one additional compound selected from the group consisting of HFO-1243zf, HFO-1234yf, HCFO-1232xf, HCO-1230xa, C6H2F8, C6H3F7, C6H3ClF6 isomers, CO-1110, C6H2ClF7 isomers, and C6H3Cl2F7.

[0016] Another embodiment of the present application disclosed herein relates to a composition comprising, consisting essentially of, or consisting of HCFO-1233xf, HCFC-244bb, HFO-1234yf and at least one additional compound selected from the group consisting of HFO-1243zf, HCFO-1232xf, HCO-1230xa, C6H2F8, C6H3F7, C6H3ClF6 isomers, CO-1110, C6H2ClF7 isomers, and C6H3Cl2F7.

[0017] Another embodiment of the application disclosed herein relates to a composition comprising, consisting essentially of, or consisting of HCFO-1233xf and at least two additional compounds selected from the group consisting of HFO-1243zf, HFO-1234yf, HCFC-244bb, HCFO-1232xf, HCO-1230xa, C6H2F8, C6H3F7, C6H3ClF6 isomers, CO-1110, C6H2ClF7 isomers, and C6H3Cl2F7.

[0018] One embodiment of the application disclosed herein relates to a composition comprising, consisting essentially of, or consisting of HCFO-1233xf and at least one additional compound selected from the group consisting of HFO-1243zf, HFO-1234yf, HCFC-244bb, HCFO-1232xf, HCO-1230xa, C6H2F8, C6H3F7, C6H3ClF6 isomers, CO-1110, C6H2ClF7 isomers, and C6H3Cl2F7, wherein the total amount of additional compounds is about 10% or less based on the total amount of the composition.

[0019] In one embodiment, the HCC starting material used in the process of the application is HCC-250fb.

[0020] In one embodiment, the HCC starting material used in the process of the application is HCC-250fb, and the product stream produced by the process comprises HFO-1243zf.

[0021] In some embodiments, the application relates to a process for producing HFO-1243zf from HCC-250fb in the presence of a catalyst.

[0022] Certain embodiments of the application disclosed herein relate to a gas phase process for converting, preferably selectively converting, HCC-250fb to HFO-1243zf by hydrofluorination in the presence of a catalyst.

[0023] One embodiment of the application disclosed herein relates to a composition comprising, consisting essentially of, or consisting of HFO-1243zf and at least one additional compound selected from the group consisting of HCFO-1233xf, HCFC-253fb, HCC-250fb, HCFO-1242zf, and HCFO-1241 isomers.

[0024] 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 application belongs. If there is a conflict between the definitions in the specification and those in the patent specification, the definitions in the specification control. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present application, suitable methods and materials are described below. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 A system according to one embodiment of the present application is illustrated.

[0026] The foregoing summary and the following detailed description and accompanying drawings are illustrative and are not intended to be limiting on the application as defined in the appended claims. Other features and benefits of any one or more embodiments will become apparent from the following detailed description, the drawings and the claims. DETAILED DESCRIPTION

[0027] Before addressing the details of the embodiments described herein, certain terms are defined or clarified as follows.

[0028] As used herein, the term "hydro(halo)alkane" means a molecule containing hydrogen, carbon, and optionally fluorine and / or chlorine and / or bromine and / or iodine and no carbon-carbon double bonds (halogen - fluorine, chlorine, bromine, iodine). Examples are described throughout this specification. The term hydro(halo)alkane includes both alkanes and halo-substituted alkanes.

[0029] As used herein, the term "hydrochloroalkene" means an unsaturated organic compound consisting of hydrogen, chlorine, and carbon.

[0030] As used herein, the term "hydrofluoroalkene" means an unsaturated organic compound consisting of hydrogen, fluorine, and carbon.

[0031] As used herein, the term "hydrochlorofluoroalkene" means an unsaturated organic compound consisting of hydrogen, chlorine, fluorine, and carbon.

[0032] As used herein, the term "hydrochlorocarbon" means a saturated organic compound consisting of hydrogen, chlorine, and carbon.

[0033] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” “contains,” “containing,” or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but can include other elements not expressly listed or inherent to such process, method, article, or apparatus. Further, unless expressly stated to the contrary, “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).

[0034] The transitional phrase “consisting essentially of’ is used to define compositions, methods, processes, or the like that include substantially all the materials, steps, features, components, or elements of any process, composition, method, or the like that is disclosed, with the proviso that any additional materials, steps, features, components, or elements do not materially affect the basic and novel characteristics of the claimed invention, especially the action of any process that is intended to be embraced by the invention. The term “consisting essentially of’ occupies a position intermediate between “comprising” and “consisting of.”

[0035] The transitional phrase “consisting of’ excludes any element, step, or ingredient not specified. If there is an open term such as “comprising” in the claim, then the claim is not limited to exclude material that is not recited in the claim. When the phrase “consisting of’ appears in the body of a claim, it should be interpreted to limit the claim to the elements recited in the clause. Other elements are not excluded as a general matter unless the claim is drafted to be so limited.

[0036] Where an applicant has defined the invention or a portion thereof with the term “comprising” a description should be readily understood not to be limited to that which follows the term “comprising” (unless otherwise indicated) and that the description should be interpreted to also include the terms “consisting essentially of’ or “consisting of.”

[0037] Further, the use of “a” or “an” is employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the application. This description should be read to include one, or at least one and the singular also includes the plural, unless it is indicated elsewhere.

[0038] When a range, preferably range or a list of preferred upper and / or lower values is given, it is understood that all ranges formed from any pair of an upper limit or preferred value and any lower limit or preferred value, whether or not the ranges are explicitly disclosed, are expressly disclosed. Whenever a numerical range is given, unless otherwise stated, the range is intended to include both the endpoints and all integers and fractions within the range, unless otherwise indicated.

[0039] As used herein, GC / FID peak area is related to the amount of compound present as a proportion of the total area of all detected peaks. FID area % can be converted to mole % using a calculated or measured response factor. See https: / / www.chromatographytoday.com / news / gc-mdgc / 32 / breaking-news / what-is-a-response-factor / 31169.

[0040] As used herein, the term“about” is intended to indicate an amount that is reasonably close to a stated value (e.g., plus or minus about 10%— ±1%, ±2%, ±3%,... ±10% of the indicated value, or between ±1% of the indicated value and ±10% of the indicated value, and all ranges therebetween). Unless otherwise stated, all measurements reported herein are understood to be modified by the term“about,” whether the term is explicitly used or not.

[0041] Compounds referred to in the present disclosure can be represented by codes, chemical structures, and / or chemical names based on fluorine-containing compound nomenclature conventions. For convenience and reference, selected compounds with codes, structures, and chemical names are provided in Table 1.

[0042] Table 1

[0043]

[0044] Some of the compounds present in the compositions of the present application can exist in different configurational or stereoisomeric forms. The present application is intended to include all single configurational isomers, single stereoisomers, or any combination or mixture of them. Single isomers or multiple isomers of the same compound can be used in any ratio.

[0045] In some embodiments, the present application relates to a process for preparing HFO and / or HCFO from a starting material selected from HCO or HCC. Generally, the process comprises hydrofluorinating HCO or HCC under conditions suitable to produce a product stream comprising HFO and / or HCFO products, and optionally reaction intermediates, and optionally unreacted starting material. More specifically, the process comprises hydrofluorinating HCO or HCC with an effective amount of hydrogen fluoride (HF) in the presence of a catalyst, preferably a metal-doped catalyst, more preferably a metal-doped alumina catalyst, most preferably a zinc-doped alumina catalyst, under conditions suitable to produce a product stream comprising HFO and / or HCFO products.

[0046] In one embodiment, the starting material for the process of the present application is HCO-1230xa or HCC-250fb.

[0047] In one embodiment, the HFO and / or HCFO produced by the process of the present application comprises one or more compounds selected from HCFO-1233xf, HFO-1234yf, HFO-1243zf, and HCFO-1232xf.

[0048] In one embodiment, the HCO for the process of the present application is HCO-1230xa, and the product stream produced by the process comprises HCFO-1233xf.

[0049] In some embodiments, the present application relates to a process for producing HCFO-1233xf from HCO-1230xa in the presence of a catalyst.

[0050] Certain embodiments of the present application disclosed herein relate to a gas phase process for converting HCO-1230xa to HCFO-1233xf by hydrofluorination in the presence of a catalyst.

[0051] Another embodiment disclosed herein relates to a process for converting a starting material selected from HCO and HCC to HFO and / or HCFO with hydrogen fluoride in the presence of a metal-doped alumina catalyst, wherein the doping metal comprises zinc.

[0052] In one embodiment, the HCC for the process of the present application is HCC-250fb, and the product stream produced by the process comprises HFO-1243zf.

[0053] In some embodiments, the present application relates to a process for producing HFO-1243zf from HCC-250fb in the presence of a catalyst.

[0054] Certain embodiments of the application disclosed herein relate to a gas phase process for converting HCC-250fb to HFO-1243zf by hydrofluorination in the presence of a catalyst.

[0055] One skilled in the art will appreciate that while certain aspects of the application disclosed herein can refer to specific embodiments in which the starting material is HCO-1230xa and the product comprises HCFO-1233xf or specific embodiments in which the starting material is HCC-250fb and the product comprises HFO-1243zf, the application has broader applicability to produce HFO and / or HCFO by hydrofluorinating HCO or HCC in the presence of a metal-doped alumina catalyst, and thus the parameters disclosed herein (e.g., reaction pressure, temperature, molar ratio, etc.) are not limited to specific embodiments in which HCO-1230xa is converted to HCFO-1233xf or HCC-250fb is converted to HFO-1243zf by hydrofluorination.

[0056] In some embodiments, the hydrofluorination catalyst that can be used to convert HCO (e.g., HCO-1230xa) or HCC (e.g., HCC-250fb) to HCFO (e.g., HCFO-1233xf) and / or HFO (e.g., HFO-1234yf and / or HFO-1243zf) comprises a Group IIB metal and / or a Group IIIA metal, and more specifically a Group IIB metal and a Group IIIA metal.

[0057] In some embodiments, the catalyst comprises a metal-doped aluminum oxide.

[0058] In preferred embodiments, the catalyst comprises a zinc (Zn) and aluminum (Al) compound.

[0059] In one embodiment, the Zn is doped into the alumina. In some embodiments, the catalyst comprises a zinc-doped aluminum oxide.

[0060] In some embodiments, the catalyst comprises an aluminum oxide doped with a zinc compound. For example, the catalyst can comprise an aluminum oxide doped with a zinc compound selected from the group consisting of a zinc halide, a zinc oxide, zinc hydroxide, zinc acetate, and the like, and combinations thereof.

[0061] In one embodiment, the catalyst comprises about 99 wt% to about 90 wt% alumina and about 1 wt% to about 8 wt% zinc or a zinc compound. In one embodiment, the catalyst is 2.5% Zn / Al203.

[0062] If the catalyst becomes deactivated, the catalyst can be readily regenerated by any means known in the art.

[0063] Another embodiment disclosed herein relates to a process for converting HCO-1230xa to HCFO-1233xf in the presence of a metal-doped alumina catalyst, preferably in the gas phase, wherein the doping metal preferably comprises zinc or a zinc compound.

[0064] Another embodiment disclosed herein relates to a process for converting HCC-250fb to HFO-1243zf in the presence of a metal-doped alumina catalyst, preferably in the gas phase, wherein the doping metal preferably comprises zinc or a zinc compound.

[0065] Optionally, in some embodiments, the catalyst can be pre-treated (pre-activated) with HF or a HF / N2mixture. This pre-treatment can be accomplished, for example, by placing the catalyst in a suitable vessel, and thereafter passing HF through the catalyst at an elevated temperature. In one embodiment, such a vessel can be the reactor used to carry out the hydrofluorination reaction. In one embodiment, the pre-treatment temperature is from about 100°C to about 500°C, or from about 150°C to about 450°C, preferably about 450°C.

[0066] In certain embodiments, the contacting / reaction of the starting material (e.g., HCO-1230xa or HCC-250fb) and HF is carried out in a catalyst-packed reactor or reaction zone that is heated to or maintained at a temperature in the range of from about 150°C to about 400°C, from about 200°C to about 350°C, from about 250°C to about 325°C, or from about 280°C to about 330°C, and all ranges (including endpoints) therebetween. In some embodiments, the temperature of the hydrofluorination reaction is selected from one of the following: about 150°C, about 155°C, about 160°C, about 165°C, about 170°C, about 175°C, about 185°C, about 195°C, about 200°C, about 205°C, about 210°C, about 215°C, about 220°C, about 225°C, about 230°C, about 235°C, about 240°C, about 245°C, about 250°C, about 255°C, about 260°C, about 265°C, about 270°C, about 275°C, about 280°C, about 285°C, about 290°C, about 295°C, about 300°C, about 305°C, about 310°C, about 315°C, about 320°C, about 325°C, about 330°C, or about 335°C, about 345°C, about 350°C, about 355°C, about 360°C, about 365°C, about 370°C, about 375°C, about 380°C, about 385°C, about 390°C, about 395°C, and about 400°C, and all values and ranges therebetween and within about 150°C to about 400°C.

[0067] In certain catalytic gas phase embodiments, the contacting of the starting material (preferably HCO-1230xa or HCC-250fb) with HF is carried out at a temperature range between the following two limits:

[0068] a. about 150°C equals 150°C ± 150°C 1% ± 150°C 2%, ± 150°C 3%, ± 150°C 4%, ± 150°C 5%, ± 150°C 6%, ± 150°C 7%, ± 150°C 8%, ± 150°C 9%, or ± 150°C 10%,

[0069] b. about 200°C equals 200°C ± 200°C 1% ± 200°C 2%, ± 200°C 3%, ± 200°C 4%, ± 200°C 5%, ± 200°C 6%, ± 200°C 7%, ± 200°C 8%, ± 200°C 9%, or ± 200°C 10%,

[0070] c. about 240°C equals 240°C ± 240°C 1% ± 240°C 2%, ± 240°C 3%, ± 240°C 4%, ± 240°C 5%, ± 240°C 6%, ± 240°C 7%, ± 240°C 8%, ± 240°C 9%, or ± 240°C 10%,

[0071] d. about 280°C equals 280°C ± 280°C 1% ± 280°C 2%, ± 280°C 3%, ± 280°C 4%, ± 280°C 5%, ± 280°C 6%, ± 280°C 7%, ± 280°C 8%, ± 280°C 9%, or ± 280°C 10%,

[0072] e. about 300°C equals 300°C ± 330°C 1% ± 330°C 2%, ± 330°C 3%, ± 330°C 4%, ± 330°C 5%, ± 330°C 6%, ± 330°C 7%, ± 330°C 8%, ± 330°C 9%, or ± 330°C 10%,

[0073] f. about 350°C equals 200°C ± 350°C 1% ± 350°C 2%, ± 350°C 3%, ± 350°C 4%, ± 350°C 5%, ± 350°C 6%, ± 350°C 7%, ± 350°C 8%, ± 350°C 9%, or ± 350°C 10%,

[0074] g. about 400°C equals 400°C ± 400°C 1% ± 400°C 2%, ± 400°C 3%, ± 400°C 4%, ± 400°C 5%, ± 400°C 6%, ± 400°C 7%, ± 400°C 8%, ± 400°C 9%, or ± 400°C 10%.

[0075] One embodiment of the present application relates to a process for contacting HCO-1230xa and HF in the presence of a catalyst, preferably a metal-doped alumina catalyst, at a sufficient temperature to produce HCFO-1233xf.

[0076] Certain embodiments of the present application disclosed herein relate to a gas phase process for selectively converting HCO-1230xa to HCFO-1233xf in the presence of HF in the presence of a catalyst, preferably a metal-doped alumina catalyst, at a temperature in the range of 150 °C to 400 °C.

[0077] One embodiment of the present application relates to a process for contacting HCC-250fb and HF in the presence of a catalyst, preferably a metal-doped alumina catalyst, at a sufficient temperature to produce HFO-1243zf.

[0078] Certain embodiments of the present application disclosed herein relate to a gas phase process for selectively converting HCC-250fb to HFO-1243zf in the presence of HF in the presence of a catalyst, preferably a metal-doped alumina catalyst, at a temperature in the range of 150 °C to 400 °C.

[0079] In certain embodiments, contacting of the starting material (e.g., HCO-1230xa or HCC-250fb) with HF to produce certain HCFOs and / or HFOs is conducted at a pressure less than atmospheric pressure, including but not limited to about 0 psig to about 100 psig.

[0080] In some embodiments, the reaction pressure for the gas phase catalytic hydrofluorination of HCO-1230xa to produce HCFO-1233xf or HCC-250fb to produce HFO-1243zf is between about 0 psig and about 100 psig.

[0081] In certain embodiments, contacting of the HCO (e.g., HCO-1230xa) or HCC (e.g., HCC-250fb) with HF is conducted at a HF:organics molar ratio in the range of between about 5: 1 and about 40: 1, or between about 5: 1 and about 30: 1, or between about 10: 1 and about 20: 1, and all ratios therebetween.

[0082] In some embodiments, the HF:organics molar ratio, and more specifically the HF:HCO-1230xa ratio for the gas phase catalytic hydrofluorination of HCO-1230xa to produce HCFO-1233xf, or the HF:HCC-250fb ratio for the gas phase catalytic hydrofluorination of HCC-250fb to produce HFO-1243zf, is in the range between about 5: 1 and about 40: 1, or between about 5: 1 and about 30: 1, or between about 10: 1 and about 20: 1, and all ratios therebetween.

[0083] In some catalytic gas phase embodiments of the present application, the conversion of HCO-1230xa to HCFO-1233xf or the conversion of HCC-250fb to HFO-1243zf in the presence of HF is in the range between about 90% and about 100%. Another embodiment disclosed herein relates to a method of selectively converting HCO-1230xa to greater than about 90% HCFO-1233xf. Another embodiment disclosed herein relates to a method of selectively converting HCC-250fb to greater than about 90% HFO-1243zf. An embodiment of the present application relates to a method of contacting HCO-1230xa and HF at a sufficient temperature to produce greater than about 90% HCFO-1233xf. An embodiment of the present application relates to a method of contacting HCC-250fb and HF at a sufficient temperature to produce greater than about 90% HFO-1243zf.

[0084] In some embodiments of the present application, the reaction of the starting material with HF is conducted in a reactor or reaction zone heated to or maintained at a temperature of about 150°C to about 400°C, or between about 200°C and about 350°C, and at a pressure of between about 0 psig and about 100 psig, in the presence of a catalyst, preferably a zinc-doped alumina catalyst, at a HF:HCO molar ratio of between about 5: 1 and about 40: 1, or about 5: 1 to about 30: 1, to produce one or more HCFOs and / or HFOs in a preferred amount of about 90% or greater.

[0085] In some embodiments of the present application, the reaction of HCO-1230xa with HF is conducted in a reactor or reaction zone heated to or maintained at a temperature of about 150°C to about 400°C, or between about 200°C and about 350°C, and at a pressure of between about 0 psig and about 100 psig, in the presence of a catalyst, preferably a zinc-doped alumina catalyst, at a HF:HCO-1230xa molar ratio of between about 5: 1 and about 40: 1, or about 5: 1 to about 30: 1, to produce HCFO-1233xf in a preferred amount of about 90% or greater.

[0086] In some embodiments of the application, the reaction of HCC-250fb with HF is conducted in a reactor or reaction zone heated to or maintained at a temperature of from about 150 °C to about 400 °C, or between about 200 °C and about 350 °C, and at a pressure of between about 0 psig and about 100 psig, in the presence of a catalyst, preferably a zinc-doped alumina catalyst, at a HF:HCC-250fb molar ratio of between about 5: 1 and about 40: 1, or about 5: 1 to about 30: 1, to produce HFO-1243zf in an amount of preferably about 90% or greater.

[0087] One embodiment disclosed herein relates to a gas phase hydrofluorination process to produce one or more HCFO and / or HFO by contacting a starting material in the presence of a catalyst, preferably a zinc-doped alumina catalyst, at a temperature of from about 150 °C to about 400 °C, or between about 200 °C and about 350 °C, and at a pressure of between about 0 psig and about 100 psig, at a HF:organic molar ratio of between about 5: 1 and about 40: 1, or about 5: 1 to about 30: 1, wherein the conversion of HCO or HCC to HCFO and / or HFO in the presence of HF is about 90% or greater.

[0088] One embodiment disclosed herein relates to a gas phase hydrofluorination process to produce HCFO-1233xf by contacting HCO-1230xa and HF in the presence of a catalyst, preferably a zinc-doped alumina catalyst, at a temperature of from about 150 °C to about 400 °C, or between about 200 °C and about 350 °C, and at a pressure of between about 0 psig and about 100 psig, at a HF:HCO-1230xa molar ratio of between about 5: 1 and about 40: 1, or about 5: 1 to about 30: 1, wherein the conversion of HCO-1230xa to HCFO-1233xf in the presence of HF is about 90% or greater.

[0089] One embodiment disclosed herein relates to a gas phase hydrofluorination process to produce HFO-1243zf by contacting HCC-250fb and HF in the presence of a catalyst, preferably a zinc-doped alumina catalyst, at a temperature of from about 150 °C to about 400 °C, or between about 200 °C and about 350 °C, and at a pressure of between about 0 psig and about 100 psig, at a HF:HCC-250fb molar ratio of between about 5: 1 and about 40: 1, or about 5: 1 to about 30: 1, wherein the conversion of HCC-250fb to HFO-1243zf in the presence of HF is about 90% or greater.

[0090] Figure 1One embodiment is illustrated using system 100 to convert HCOs such as HCO-1230xa to HCFOs such as HCFO-1233xf and / or HCCs such as HCC-250fb to HFOs such as HFO-1243zf. The starting material (e.g., HCO-1230xa or HCC-250fb) feed flows from line 102 and is transported by pump 104 to and through optional vaporizer 110, where the organic feed is optionally heated to about 200°C with a nitrogen stream, and exits vaporizer 110 through line 114 to be combined with HF feed 112 in mixer 116 (or, instead of mixer 116, the organic feed and HF lines can be connected directly to reactor 120 through valves and combined therein). The combined organic / HF feed is fed to heated reactor 120 having a catalyst bed (optionally containing a suitable inert packing) at a temperature suitable for the hydrofluorination of HCOs such as HCO-1230xa or HCCs such as HCC-250fb using any system suitable for heating, control, and regulation of temperature in the range between about room temperature and 700°C. The product mixture from reactor 120 exits through line 124 or is optionally transferred through line 124 to and through a processing system 130, e.g., a scrubber (via a scrubbing fluid 132), a distillation column (not shown), etc., to purify and recover at least one HFO and / or HCFO in line 134, preferably to purify and recover at least one of HCFO-1232xf and / or HCFO-1233xf in line 134 or to purify and recover at least HFO-1243zf in line 134.

[0091] A reactor suitable for liquid phase reactions or gas phase reactions can be used. Preferably, a reactor suitable for gas phase reactions is used. In the gas phase, a heated reactor is used and the reactor is provided with suitable thermal control. Many reactor configurations are possible, including packed bed tubes or column reactors, optionally containing a suitable inert packing, such as Monel ™ or Hastelloy ™ nickel alloy shavings or billets, or other materials inert to halide species. For example, HCl and HF, which allow for efficient mixing of the starting materials.

[0092] The reactor configuration, whether containing a suitable packing or not containing any packing, can be operated in batch, semi-batch, or continuous mode. In addition to the reactors disclosed herein, preheaters and vaporizers, heat exchangers, feed and effluent lines, units related to mass transfer, contact vessels (pre-mixers), distillation columns, and valves related to the reactors, heat exchangers, vessels, columns, and units used in the processes of the various embodiments disclosed herein should be constructed of corrosion resistant materials.

[0093] One embodiment of the application disclosed herein relates to a composition comprising, consisting essentially of, or consisting of HCFO-1233xf and at least one additional compound selected from HFO-1243zf, HFO-1234yf, HCFC-244bb, HCFO-1232xf, HCO-1230xa, C6H2F8, C6H3F7, C6H3ClF6 isomers, CO-1110, C6H2ClF7 isomers, and C6H3Cl2F7, or two or more of the additional compounds.

[0094] One embodiment of the application disclosed herein relates to a composition comprising, consisting essentially of, or consisting of HCFO-1233xf and HCFC-244bb and at least one additional compound selected from HFO-1243zf, HFO-1234yf, HCFO-1232xf, HCO-1230xa, C6H2F8, C6H3F7, C6H3ClF6 isomers, CO-1110, C6H2ClF7 isomers, and C6H3Cl2F7, or two or more of the additional compounds.

[0095] Another embodiment of the application disclosed herein relates to a composition comprising, consisting essentially of, or consisting of HCFO-1233xf, HCFC-244bb, HFO-1234yf and at least one additional compound selected from HFO-1243zf, HCFO-1232xf, HCO-1230xa, C6H2F8, C6H3F7, C6H3ClF6 isomers, CO-1110, C6H2ClF7 isomers, and C6H3Cl2F7, or two or more of the additional compounds.

[0096] One embodiment disclosed herein relates to a composition comprising, consisting essentially of, or consisting of HCFO-1233xf and at least one additional compound selected from HFO-1243zf, HFO-1234yf, HCFC-244bb, HCFO-1232xf, HCO-1230xa, C6H2F8, C6H3F7, C6H3ClF6 isomers, CO-1110, C6H2ClF7 isomers, and C6H3Cl2F7, wherein the total amount of the additional compound(s) is about 10% or less based on the total amount of the composition.

[0097] One embodiment of the application disclosed herein relates to a composition comprising, consisting essentially of, or consisting of HFO-1243zf and at least one additional compound selected from the group consisting of HCFO-1233xf, HCFC-253fb, HCC-250fb, HCFO-1242zf, and HCFO-1241 isomers.

[0098] The following examples are provided to illustrate certain aspects of the application and should not limit the scope of the claims appended hereto.

[0099] Examples

[0100] Example 1 : Preparation of 2.5% Zn / AI2O3 catalyst

[0101] 2.5% Zn / Al203catalyst was prepared by soaking 24 g of Al203in an aqueous solution containing 2.73 g of zinc nitrate hexahydrate in 19.22 g of deionized water. The mixture was left in a vacuum oven at 110 °C overnight to remove water, and the dried catalyst contained 2.5 wt% of zinc.

[0102] Example 2: Hydrofluorination of 1230xa to 1233xf using 2.5% Zn / AI2O3 catalyst

[0103] 2.5% Zn / Al203catalyst was prepared by soaking Al203in an aqueous solution containing an appropriate amount of zinc salt. Excess water was removed by placing the sample in a vacuum oven at 110 °C. 6 ml of prepared 2.5% Zn / Al203catalyst of 12-20 mesh was loaded into a 12 inch long Inconel (0.5 inch OD) tube reactor. The catalyst was activated by HF starting from 150 °C to 450 °C. HCO-1230xa was fed by pump and vaporized at 200 °C with N2through a vaporizer and then mixed with HF and flowed through the reactor with the catalyst bed. The HCO-1230xa-HF reaction was tested under the conditions listed in Table 2 below. The reactor effluent was analyzed by GC-MS-FID and showed that HCFO-1233xf was produced at high concentrations under various conditions (see, e.g., Table 3).

[0104] Table 2

[0105]

[0106] Table 3: Detailed GC analysis at 240°C with a HF / organics ratio of 10.4:1

[0107]

[0108] Example 3: Hydrofluorination of 250fb to 1243zf using 2.5% Zn / AI2O3 catalyst

[0109] A 4 ml 2.5% Zn / Al203catalyst was loaded into a 12 inch long Inconel (0.5 inch OD) tube reactor. The catalyst was activated by HF starting at 150°C to 450°C. HCC-250fb was fed by pump and vaporized at 200°C with N2through a vaporizer and then mixed with HF and flowed through the reactor with the catalyst bed. The HCC250fb-HF reaction was tested under the conditions listed in Table 4 below. The reactor effluent was analyzed by GC-MS-FID and showed production of HFO-1243zf in high concentration at various conditions.

[0110] Table 4

[0111]

[0112] Other embodiments

[0113] Embodiment 1. A method of converting a starting material selected from a hydrochloroolefin and a hydrochlorocarbon to one or more hydrofluoroolefins and / or hydrochlorofluoroolefins, the method comprising contacting the starting material with hydrogen fluoride in the presence of a metal-doped alumina catalyst.

[0114] Embodiment 2. The method of embodiment 1, wherein the doping metal is zinc and / or a zinc compound.

[0115] Embodiment 3. The method of embodiment 2, wherein the catalyst comprises 1 to 8 weight percent zinc as a zinc and / or zinc compound.

[0116] Embodiment 4. The method of any one of embodiments 1 to 3, wherein the hydrochloroolefin is 1,1,2,3-tetrachloro-1-propene (HCO-1230xa).

[0117] Embodiment 5. The method of any one of embodiments 1 to 4, wherein the hydrochlorofluoroolefin produced by the method is 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf).

[0118] Embodiment 6. The method of any one of embodiments 1 to 5, wherein the product stream of the method comprises HCFO-1233xf and at least one additional compound selected from HFO-1243zf, HFO-1234yf, HCFC-244bb, HCFO-1232xf, HCO-1230xa, C6H2F8, C6H3F7, C6H3ClF6isomers, CO-1110, C6H2ClF7isomers, and C6H3Cl2F7.

[0119] Embodiment 7. The process according to any one of embodiments 1 to 3, wherein the hydrochlorocarbon is 1,1,1,3-tetrachloropropane (HCC-250fb).

[0120] Embodiment 8. The process according to any one of embodiments 1 to 3 and 7, wherein the hydrofluoroolefin produced by the process is 3,3,3-trifluoropropene (HFO-1243zf).

[0121] Embodiment 9. The process according to any one of embodiments 1 to 3 and 7 to 8, wherein the product stream of the process comprises HFO-1243zf and at least one additional compound selected from HCFO-1233xf, HCFC-253fb, HCC-250fb, HCFO-1242zf, and HCFO-1241 isomers.

[0122] Embodiment 10. The process according to any one of embodiments 1 to 9, wherein the selectivity of the one or more hydrofluoroolefins and / or hydrochlorofluoroolefins is greater than about 90%.

[0123] Embodiment 11. The process according to any one of embodiments 1 to 0, wherein the hydrogen fluoride: starting material molar ratio is in the range of between about 5: 1 and about 40: 1, preferably about 5: 1 and about 30: 1, more preferably about 10: 1 and about 20: 1.

[0124] Embodiment 12. The process according to any one of embodiments 1 to 11, wherein the reaction zone for contacting the starting material with hydrogen fluoride is heated to a temperature in the range of between about 150 °C and about 400 °C, preferably between about 200 °C to about 350 °C.

[0125] Embodiment 13. A process comprising contacting HCO-1230xa and HF in a reaction zone containing a zinc-doped alumina catalyst and producing HCFO-1233xf.

[0126] Embodiment 14. The process according to embodiment 13, wherein the reaction zone is heated to a temperature of about 150 °C to about 400 °C, preferably about 200 °C to about 350 °C.

[0127] Embodiment 15. A process for producing HCFO-1233xf comprising contacting HCO-1230xa and HF in a reaction zone heated to a temperature of about 150 °C to about 400 °C, preferably about 200 °C to about 350 °C, wherein the reaction zone contains a zinc-doped alumina.

[0128] Embodiment 16. The process of any one of embodiments 13 to 15, wherein the selectivity to HCFO-1233xf is greater than about 90%.

[0129] Embodiment 17. The process of any one of embodiments 13 to 16, wherein the hydrogen fluoride:HCO-1230xa molar ratio is in a range between about 5: 1 and about 40: 1, preferably about 5: 1 and about 30: 1, more preferably about 10: 1 and about 20: 1.

[0130] Embodiment 18. A process comprising contacting HCC-250fb and HF in a reaction zone containing a zinc-doped alumina catalyst and producing HFO-1243zf.

[0131] Embodiment 19. The process of embodiment 18, wherein the reaction zone is heated to a temperature of about 150°C to about 400°C, preferably about 200°C to about 350°C.

[0132] Embodiment 20. A process for producing HFO-1243zf comprising contacting HCC-250fb and HF in a reaction zone heated to a temperature of about 150°C to about 400°C, preferably about 200°C to about 350°C, wherein the reaction zone contains a zinc-doped alumina.

[0133] Embodiment 21. The process of any one of embodiments 18 to 20, wherein the selectivity to HFO-1243zf is greater than about 90%.

[0134] Embodiment 22. The process of any one of embodiments 18 to 21, wherein the hydrogen fluoride:HCC-250fb molar ratio is in a range between about 5: 1 and about 40: 1, preferably about 5: 1 and about 30: 1, more preferably about 10: 1 and about 20: 1.

[0135] Embodiment 23. The process of any one of embodiments 1 to 22, wherein the process is conducted in the gas phase.

[0136] Embodiment 24. The process of any one of embodiments 1 to 23, wherein the process is conducted at a pressure between about 0 psig and about 100 psig.

[0137] Embodiment 25. A gas phase process to produce HCFO-1233xf, the process contacting HCO-1230xa and HF in the presence of a catalyst comprising zinc and aluminum compounds at a temperature of about 150°C to about 400°C, preferably about 200°C to about 350°C, at a molar ratio of HF:HCO-1230xa of about 5: 1 to about 40: 1, preferably about 5: 1 to about 30: 1, and at a pressure of between about 0 psig and about 100 psig.

[0138] Embodiment 26. A gas phase process to produce HFO-1243zf, the process contacting HCC-250fb and HF in the presence of a catalyst comprising zinc and aluminum compounds at a temperature of about 150°C to about 400°C, preferably about 200°C to about 350°C, at a molar ratio of HF:HCC-250fb of about 5: 1 to about 40: 1, preferably about 5: 1 to about 30: 1, and at a pressure of between about 0 psig and about 100 psig.

[0139] Embodiment 27. The gas phase process according to any one of embodiments 25 to 26, wherein the catalyst comprises zinc-doped aluminum oxide.

[0140] Embodiment 28. A composition comprising HCFO-1233xf and at least one additional compound selected from the group consisting of HFO-1243zf, HFO-1234yf, HCFC-244bb, HCFO-1232xf, HCO-1230xa, C6H2F8, C6H3F7, C6H3ClF6 isomers, CO-1110, C6H2ClF7 isomers, and C6H3Cl2F7.

[0141] Embodiment 29. A composition comprising HCFO-1233xf and HCFC-244bb and at least one additional compound selected from the group consisting of HFO-1243zf, HFO-1234yf, HCFO-1232xf, HCO-1230xa, C6H2F8, C6H3F7, C6H3ClF6 isomers, CO-1110, C6H2ClF7 isomers, and C6H3Cl2F7.

[0142] Embodiment 30. A composition comprising HCFO-1233xf, HFO-1234yf, and HCFC-244bb and at least one additional compound selected from the group consisting of HFO-1243zf, HCFO-1232xf, HCO-1230xa, C6H2F8, C6H3F7, C6H3ClF6 isomers, CO-1110, C6H2ClF7 isomers, and C6H3Cl2F7.

[0143] Embodiment 31. A composition comprising HFO-1243zf and at least one additional compound selected from the group consisting of HCFO-1233xf, HCFC-253fb, HCC-250fb, HCFO-1242zf, and HCFO-1241 isomers.

[0144] While certain aspects, embodiments, and principles have been described above, it is understood that the description is illustrative only and is not limiting on the application or the appended claims. The various aspects, embodiments, and principles described above can be used alone or in combination with one another.

Claims

1. A method for converting a starting material selected from hydrochloroolefins and hydrochlorohydrocarbons into one or more hydrofluoroolefins and / or hydrochlorofluoroolefins, the method comprising contacting the starting material with hydrogen fluoride in the presence of a metal-doped alumina catalyst.

2. The method according to claim 1, wherein the doped metal is zinc and / or a zinc compound.

3. The method of claim 2, wherein the catalyst comprises 1% to 8% by weight of zinc as zinc and / or zinc compounds.

4. The method according to any one of claims 1 to 3, wherein the hydrochloroolefin is 1,1,2,3-tetrachloro-1-propene (HCO-1230xa).

5. The method according to any one of claims 1 to 4, wherein the hydrochlorofluoroolefin produced by the method is 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf).

6. The method according to any one of claims 1 to 5, wherein the product stream of the method comprises HCFO-1233xf and at least one additional compound selected from HFO-1243zf, HFO-1234yf, HCFC-244bb, HCFO-1232xf, HCO-1230xa, C6H2F8, C6H3F7, C6H3ClF6 isomer, CO-1110, C6H2ClF7 isomer and C6H3Cl2F7.

7. The method according to any one of claims 1 to 3, wherein the hydrochlorohydrocarbon is 1,1,1,3-tetrachloropropane (HCC-250fb).

8. The method according to any one of claims 1 to 3 and 7, wherein the hydrofluoroolefin produced by the method is 3,3,3-trifluoropropylene (HFO-1243zf).

9. The method according to any one of claims 1 to 3 and 7 to 8, wherein the product stream of the method comprises HFO-1243zf and at least one additional compound selected from HCFO-1233xf, HCFC-253fb, HCC-250fb, HCFO-1242zf and HCFO-1241 isomers.

10. The method according to any one of claims 1 to 9, wherein the selectivity of the one or more hydrofluoroolefins and / or hydrochlorofluoroolefins is greater than about 90%.

11. The method according to any one of claims 1 to 0, wherein the molar ratio of hydrogen fluoride to starting material is in the range of about 5:1 and about 40:1, preferably about 5:1 and about 30:1, more preferably about 10:1 and about 20:

1.

12. The method according to any one of claims 1 to 11, wherein the reaction zone used to contact the starting material with hydrogen fluoride is heated to a temperature in the range of about 150°C and about 400°C, preferably between about 200°C and about 350°C.

13. A method comprising contacting HCO-1230xa and HF in a reaction zone containing a zinc-doped alumina catalyst to produce HCFO-1233xf.

14. The method of claim 13, wherein the reaction zone is heated to a temperature of about 150°C to about 400°C, preferably about 200°C to about 350°C.

15. A method for producing HCFO-1233xf, the method comprising contacting HCO-1230xa and HF in a reaction zone heated to a temperature of about 150°C to about 400°C, preferably about 200°C to about 350°C, wherein the reaction zone contains zinc-doped alumina.

16. The method according to any one of claims 13 to 15, wherein the selectivity of HCFO-1233xf is greater than about 90%.

17. The method according to any one of claims 13 to 16, wherein the molar ratio of hydrogen fluoride to HCO-1230xa is in the range of about 5:1 and about 40:1, preferably about 5:1 and about 30:1, more preferably about 10:1 and about 20:

1.

18. A method comprising contacting HCC-250fb and HF in a reaction zone containing a zinc-doped alumina catalyst to produce HFO-1243zf.

19. The method of claim 18, wherein the reaction zone is heated to a temperature of about 150°C to about 400°C, preferably about 200°C to about 350°C.

20. A method for producing HFO-1243zf, the method comprising contacting HCC-250fb and HF in a reaction zone heated to a temperature of about 150°C to about 400°C, preferably about 200°C to about 350°C, wherein the reaction zone contains zinc-doped alumina.

21. The method according to any one of claims 18 to 20, wherein the selectivity of HFO-1243zf is greater than about 90%.

22. The method according to any one of claims 18 to 21, wherein the hydrogen fluoride:HCC-250fb molar ratio is in the range of about 5:1 and about 40:1, preferably about 5:1 and about 30:1, more preferably about 10:1 and about 20:

1.

23. The method according to any one of claims 1 to 22, wherein the method is carried out in the gas phase.

24. The method according to any one of claims 1 to 23, wherein the method is performed at a pressure between about 0 psig and about 100 psig.

25. A gas-phase method for producing HCFO-1233xf, wherein the method involves contacting HCO-1230xa and HF at a molar ratio of about 5:1 to about 40:1, preferably about 5:1 to about 30:1, in the presence of a catalyst comprising zinc and aluminum compounds, at a temperature of about 150°C to about 400°C, preferably about 200°C to about 350°C, and at a pressure between about 0 psig and about 100 psig.

26. A gas-phase method for producing HFO-1243zf, wherein the method involves contacting HCC-250fb and HF at a molar ratio of about 5:1 to about 40:1, preferably about 5:1 to about 30:1, in the presence of a catalyst comprising zinc and aluminum compounds, at a temperature of about 150°C to about 400°C, preferably about 200°C to about 350°C, and at a pressure between about 0 psig and about 100 psig.

27. The gas-phase method according to any one of claims 25 to 26, wherein the catalyst comprises zinc-doped aluminum oxide.

28. A composition comprising HCFO-1233xf and at least one additional compound selected from the group consisting of HFO-1243zf, HFO-1234yf, HCFC-244bb, HCFO-1232xf, HCO-1230xa, C6H2F8, C6H3F7, C6H3ClF6 isomer, CO-1110, C6H2ClF7 isomer and C6H3Cl2F7.

29. A composition comprising HCFO-1233xf and HCFC-244bb, and at least one additional compound selected from the group consisting of HFO-1243zf, HFO-1234yf, HCFO-1232xf, HCO-1230xa, C6H2F8, C6H3F7, C6H3ClF6 isomer, CO-1110, C6H2ClF7 isomer, and C6H3Cl2F7.

30. A composition comprising HCFO-1233xf, HFO-1234yf, and HCFC-244bb, and at least one additional compound selected from the group consisting of HFO-1243zf, HCFO-1232xf, HCO-1230xa, C6H2F8, C6H3F7, C6H3ClF6 isomer, CO-1110, C6H2ClF7 isomer, and C6H3Cl2F7.

31. A composition comprising HFO-1243zf and at least one additional compound selected from the group consisting of HCFO-1233xf, HCFC-253fb, HCC-250fb, HCFO-1242zf and HCFO-1241 isomers.

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