Method for producing 1,1,1-trifluoropropene from the dehydrochlorination of 3-chloro-1,1,1-trifluoropropane

Abstract

The present invention provides a process that increases the reaction rate in the vapor phase and the conversion of 253fb to 1,1,1-trifluoropropene (HFO-1243zf) by using an HCl cofeed.

Description

[Technical Field]

[0001] (Cross-reference of related applications) This application claims priority to U.S. Provisional Patent Application No. 63 / 455,432, filed on 29 March 2023, the entire disclosure of which is incorporated herein by reference.

[0002] (Field of Invention) The present invention relates to a process for converting 3-chloro-1,1,1-trifluoropropane (HCFC-253fb) to 1,1,1-trifluoropropene, wherein 1,1,1-trifluoropropene is a monomer useful for the production of fluorosilicones, useful for the production of trifluoropropene epoxides and 3,3,3-trifluoropropylbenzene, and useful as a feed material for producing hydro(chloro)fluorocarbons and hydrofluoroolefins, such as 2,3,3,3-tetrafluoropropene and 1,1,1,4,4,4-hexafluorobutene. [Background technology]

[0003] Hydrofluoroolefins (HFOs), with their low ozone depletion potential (ODP) and low global warming potential (GWP), are considered alternative candidates to saturated CFCs (chlorofluorocarbons) and HCFCs (hydrochlorofluorocarbons). HFOs can be used in a wide range of applications, including but not limited to refrigerants, solvents, foaming agents, cleaning agents, aerosol propellants, dielectrics, fire extinguishing agents, working fluids, and power cycle working fluids. [Overview of the project]

[0004] The present invention relates to a process for improving the conversion of 3-chloro-1,1,1-trifluoropropane (i.e., "HCFC-253fb" or "253fb") using an activated carbon catalyst by co-supplying HCl.

[0005] The present invention, as disclosed herein, provides a dehalogenation hydrogenation process that increases the dehydrochlorination rate of HCFC-253fb by using HCl as a co-feed. Accordingly, this application provides a process for preparing 3,3,3-trifluoroprop-1-ene (HFO-1243zf), comprising contacting 3-chloro-1,1,1-trifluoropropane (HCFC-253fb) with a co-feed containing HCl in vapor and in the presence of a catalyst to increase the reaction rate and increase the conversion to 1,1,1-trifluoropropene (HFO-1243zf) and the selectivity to HFO-1243zf.

[0006] One embodiment of the present invention disclosed herein relates to a process for catalytically preparing 3,3,3-trifluoroprop-1-ene (i.e., "HFO-1243zf" or "1243zf") by dehydrochlorinating 3-chloro-1,1,1-trifluoropropane (i.e., "HCFC-253fb" or "253fb") by contacting 253fb with an activated carbon catalyst in the presence of hydrogen chloride, as schematically shown below.

[0007] [ka]

[0008] The catalytic dehydrochlorination process of the present invention is carried out in a vapor phase and includes continuous operation. The temperature of the reaction zone is typically 150°C to 380°C.

[0009] The hydrogen chloride dechlorination process of the present invention can be carried out at a pressure above atmospheric pressure, at atmospheric pressure, or below atmospheric pressure.

[0010] The present invention relates to a process that doubles the conversion from HCFC-253fb to HFO-1243zf by using an HCl cosupply.

[0011] The present invention relates to a process that increases the conversion (dehydrochlorination) from HCFC-253fb to HFO-1243zf by using an HCl cofeed.

[0012] The present invention relates to a catalytic process that increases the conversion from HCFC-253fb to HFO-1243zf by using an HCl cofeed.

[0013] The present invention as disclosed herein relates to a process in which HFO-1243zf, produced according to the present invention as disclosed herein, is an intermediate for forming more highly halogenated compounds such as HCFC-243db, HCFO-1233xf, and / or HCFC-244bb intermediates in the production of 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0014] The present invention, as disclosed herein, may be a step in an integrated process for producing more highly halogenated compounds, including but not limited to 2,3-dichloro-1,1,1-trifluoropane (HCFC-243db), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 2-chloro-1,1,1,2-tetrafluoropropene (HCFC-244bb), and 2,3,3,3-tetrafluoropropane (HFO-1234yf).

[0015] The process disclosed herein relates to an integrated process for producing more highly halogenated compounds, starting from the conversion of 3-chloro-1,1,1-trifluoropropane (HCFC-253fb).

[0016] The present invention, as disclosed herein, also relates to compositions comprising 1,1,1-trifluoropropene (HFO-1243zf), 3-chloro-1,1,1-trifluoropropane (HCFC-253fb), 2,3-dichloro-1,1,1-trifluoropropane (HCFC-243db), 1,1,1,2-tetrafluoropropane (HFC-254eb), 1,1,1,3-tetrafluoropropane (HFC-254fb), 2-chloro-1,1,1-trifluoropropene (HCFO-1233xf), 1,2,3-trichloropropene (HCO-1240xd), and 3-chloro-3,3-difluoropropene (HCFO-1242zf) as main or major components. The amount of 1243zf is one of the following based on the total amount of the composition: more than 50 mole percent, more than 60 mole percent, more than 70 mole percent, or more than 80 mole percent.

[0017] The present invention, as disclosed herein, relates to compositions comprising 1,1,1-trifluoropropene (HFO-1243zf), 3-chloro-1,1,1-trifluoropropane (HCFC-253fb), and greater than 0 to 0.2 mol percent of HCFO-1242zf, and / or greater than 0 to 0.2 mol percent of HCFC-243db, and / or greater than 0 to 0.0001 mol percent of HCO-1240xd, and / or greater than 0 to 0.03 mol percent of HFC-254fb, and / or greater than 0 to 0.3 mol percent of HFC-254eb, and / or greater than 0 to 2 mol percent of HCFO-1233xf. Therefore, the total amount of HCFO-1242zf, HCFC-243db, HCO-1240xd, HFC-254fb, and HFC-254eb is greater than 0, about 1 mol percent, about 0.9 mol percent, or about 0.8 mol percent, or about 0.75 mol percent, or greater than 0 to 0.5 mol percent, or greater than 0 to 0.4 mol percent, or greater than 0 to 0.3 mol percent, or greater than 0 to 0.2 mol percent, or at least 0.00001 mol percent, or at least 0.0001 mol percent, or 0.001 mol percent, or 0.01 mol percent, or 0.1 mol percent, but less than 0.3 mol percent, and all values ​​and ranges in between.

[0018] This specification discloses compositions comprising HFO-1243zf, HCFC-253fb, and at least one additional element selected from HCFO-1242zf, HCFC-243db, HCO-1240xd, HFC-254fb, HFC-254eb, and HCFO-1233xf.

[0019] This specification discloses compositions comprising HFO-1243zf and HCFC-253fb, wherein the total amount of HCFO-1242zf, HCFC-243db, HFC-254fb, HFC-254eb, and R1233xf is less than 1 mole percent.

[0020] This specification discloses a composition comprising HFO-1243zf and HCFC-253fb, wherein the total amount of HCFO-1242zf, HCFC-243db, HFC-254fb, HFC-254eb and HCFO-1233xf is less than 3 mole percent or less than 2 mole percent.

[0021] This specification discloses a composition comprising HCFC-253fb, HCl, and optionally a catalyst, wherein the HCl to HCFC-253fb ratio is one of 0.25:1, 0.5:1, 1:1, 1.5:1, 2.0:1, 2.5:1, 5:1, 7.5:1, 10:1, 20:1, 25:1, 30:1, 35:1, 40:1 and 50:1.

[0022] An integrated system for producing a downstream halogenated compound from HCFC-253fb is disclosed herein.

[0023] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, this specification, including definitions, will 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 invention, the preferred methods and materials are described below. Further, the materials, methods, and examples are illustrative only and not intended to be limiting.

Brief Description of the Drawings

[0024] [Figure 1A] Compare the conversion of HCFC-253fb to HFO-1243zf using HCl or N2 co-feed. [Figure 1B] Compare the selectivity to HFO-1243zf in the presence of HCl or N2. [Figure 2A] Provide another comparison of the conversion of HCFC-253fb using HCl or N2 co-feed. [Figure 2B]This provides another comparison of the selectivity for HFO-1243zf in the presence of HCl and N2. [Modes for carrying out the invention]

[0025] The above summary and the following "Modes for Carrying Out the Invention" are merely illustrative and descriptive, and do not limit the invention as defined in the appended claims. Any one or more other features and advantages of the embodiments will become apparent from the following "Modes for Carrying Out the Invention" and claims.

[0026] The present invention relates to a process for improving the conversion of 3-chloro-1,1,1-trifluoropropane (i.e., "HCFC-253fb" or "253fb") by using an HCl cofeed, thereby dehalogenating 3-chloro-1,1,1-trifluoropropane in the presence of a catalyst to 1,1,1-trifluoropropene (HFO-1243zf), which is then used as a feed in a process to produce a more highly halogenated compound.

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

[0028] As used herein, the term "hydrohaloalkane" means a molecule containing hydrogen, carbon, fluorine, and / or chlorine, and / or bromine, and / or iodine, and which does not have a carbon-carbon double bond (halo = fluoro, chloro, bromo, iod). Examples are described throughout this specification.

[0029] The term "dehalogenation" as used herein means the loss of HX from a hydrohaloalkane, where X = F, Cl, Br, I, and H and X are located on adjacent carbon atoms in the hydrohaloalkane. For example, the terms "dehydrofluorination," "dehydrofluorinate," or "dehydrofluorinated" as used herein means the process of removing hydrogen and fluorine from adjacent carbon atoms in a molecule. The terms "dehydrochlorination," "dehydrochlorinate," or "dehydrochlorinated" as used herein mean the process of removing hydrogen and chlorine from adjacent carbon atoms in a molecule.

[0030] As disclosed herein, the conversion of 3-chloro-1,1,1-trifluoropropane is carried out in the vapor phase. Typically, a heated reactor is used. Many reactor configurations are possible, including horizontal or vertical orientation of the reactor, and any downstream reactions can be carried out in a series of reactors operating in non-adiabatic and adiabatic modes.

[0031] In addition to the reactors disclosed herein, heat exchangers, discharge lines, units related to mass transfer, contact vessels (premixers), distillation columns, and feed, material transfer lines 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.

[0032] The term "thermal," as used herein, means relating to or indicating a reactor, process, or conditions within a reaction zone where heat is not intentionally added to or removed from the reaction zone. It will be understood by those skilled in the art that even with the best thermal insulation, some heat may be lost from a reaction zone operating above ambient temperature (or conversely, gained in a reaction zone operating below ambient temperature).

[0033] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” or any other variations thereof are intended to encompass non-exclusive inclusion. For example, a process, method, article, or apparatus containing a list of elements is not necessarily limited to those elements alone, and may also include other elements not expressly listed with or specific to such process, method, article, or apparatus. Furthermore, unless expressly stated otherwise, “or” means an inclusive “or” and not an exclusive “or.” For example, condition A or B satisfies one of the following: 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).

[0034] The transitional phrase "consisting of" excludes any unspecified element, process, or component. In a claim, such a phrase closes the claim to materials other than those listed, excluding impurities normally associated with the materials. If the phrase "consists of" appears within a clause in the body of the claim rather than immediately following the preamble, it limits the elements described within that clause only, and does not exclude other elements from the claim as a whole.

[0035] The transitional phrase "consisting essentially of" is used to define compositions and methods that include materials, processes, features, components, or elements in addition to those literally disclosed, provided that these additionally included materials, processes, features, components, or elements do not substantially affect the fundamental and novel characteristics of the claimed invention, particularly the mechanism of operation for achieving any of the desired results of the processes of the invention. The term "consisting essentially of" has an intermediate meaning between "including" and "consisting of".

[0036] If applicants define an invention or part thereof using non-limiting terms such as "includes," it should be readily understood that (unless otherwise specified) such descriptions should be interpreted to include inventions that essentially consist of or comprise the same term.

[0037] Furthermore, the use of "a" or "an" is used to describe the elements and components described herein. This is done solely for convenience and to give a general sense of the scope of the invention. This description should be interpreted as including one or at least one, and the singular form also includes the plural form unless it is obvious that otherwise.

[0038] The compounds referred to herein may be referred to by code based on fluorochemical nomenclature, chemical structure, and / or chemical name. For convenience and reference, selected compounds with codes, structures, and chemical names are provided in Table 1.

[0039] [Table 1]

[0040] The dehydrochlorination processes disclosed herein are carried out in the presence of hydrogen chloride (HCl) co-supplied to the reactor with a starting material, 3-chloro-1,1,1-trifluoropropane, which can be prepared by hydrofluorication of commercially available 1,138,355-tetrachloropropane (HCC-250fb) as disclosed in U.S. Patent No. 4,138,355, by conventional treatment with antimony trifluoride as disclosed in Henne et al., "Influence of the CF3 Group on an Adjacent Double Bond" (1950), or by the technique described in U.S. Patent No. 4,078,007, and these disclosures are incorporated in whole by reference.

[0041] The dehydrochlorination process disclosed herein is carried out in the vapor phase, for example, in a reactor operating in continuous mode.

[0042] In another embodiment of the present invention, HCFC-253fb and HCl are in contact with each other in a vapor phase where the molar ratio of HCl to HCFC-253fb is in the ranges of 0.25:1 to 40:1, 0.5:1 to 40:1, 1:1 to 20:1, and 1:1 to 5:1.

[0043] In another embodiment of the present invention, HCFC-253fb and HCl are in contact with each other in a vapor phase where the molar ratio of HCl to HCFC-253fb is 0.25:1, 0.5:1, 1:1, 1.25:1, 1.5:1, 2.0:1, 2.5:1, 5:1, 7.5:1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, and 50:1, as well as all values, increments, and ranges in between.

[0044] In another embodiment of the present invention, HCFC-253fb and HCl come into contact with each other within a reaction zone of temperatures in the ranges of 150°C to 350°C, 175°C to 325°C, 200°C to 325°C, 225°C to 275°C, or approximately 150°C, approximately 175°C, approximately 200°C, approximately 225°C, approximately 250°C, approximately 275°C, approximately 300°C, approximately 325°C, approximately 350°C, and all values ​​and temperature ranges in between.

[0045] In another embodiment of the present invention, HCFC-253fb and HCl are 150°C, 160°C, or 170°C-180°C, 160°C, 170°C, or 180°C-190°C, 170°C-200°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, or 240°C-275°C, 150°C-180°C, 160°C-190°C, 170°C-200°C, 170°C-2 Temperatures in the ranges of 25°C, 170°C-250°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, or 240°C-275°C, 175°C, 185°C, 195°C, 205°C, 215°C, 225°C, 235°C, or 245°C-255°C, 175°C-260°C, as well as all values ​​and temperature ranges in between, are in contact with each other within the reaction zone.

[0046] In one embodiment, the process includes: Step 1: Converting 253fb to 1243zf by dehydrochlorination on a catalyst in the vapor phase with a co-supply of HCl; Step 2: Converting 1243zf produced in Step 1 to 243db by reacting it with Cl2 in the vapor phase or liquid phase with or without a catalyst, or by UV irradiation; Step 3: Converting 243db produced in Step 2 to 1233xf in the vapor phase with a catalyst, or in the liquid phase with a caustic alkali, with or without a catalyst; Step 4: Converting 1233xf produced in Step 3 to 244bb by reacting it with HF in the vapor phase with a catalyst, or in the liquid phase with a catalyst; Step 5: Converting 244bb produced in Step 4 to 1234yf in the vapor phase with or without a catalyst, or in the liquid phase with a caustic alkali, a catalyst, or a polar solvent. Optionally, the products from steps 1, 2, 3, and 4 are purified and / or dried before use in the next step.

[0047] In one embodiment of the present invention, the starting organic material to be dehydrochlorinated and HCl are supplied to and / or through a reactor, reaction vessel, or reaction zone under appropriate reaction conditions in the presence of activated carbon, to selectively dehydrochlorinate HCFC-253fb to HFO-1243zf. For example, in one embodiment, HCFC-253fb and HCl can be supplied to reactors, respectively, where they are brought into contact with a catalyst, and then the product mixture containing HFO-1243zf as the main or primary component is discharged through an outlet and purified in a processing unit.

[0048] In one embodiment of the present invention disclosed herein, HFO-1243zf obtained from the HCFC-253fb → HFO-1243zf conversion is subsequently chlorinated according to the following reaction. CF3CH=CH2+Cl2→CF3CHClCH2Cl(HCFC-243db)

[0049] For example, the HFO-1243zf feed is co-supplied to the reactor along with chlorine, and the 1243zf and Cl2 can be catalytically converted by passing them through the catalyst bed contained in the reactor. A product mixture containing HFO-243db can then be removed.

[0050] HFO-1243zf can be chlorinated to HCFC-243db by contacting HFO-1243zf with chlorine in or without a catalyst, as part of an integrated process is disclosed, for example, in U.S. Patent Application Publication No. 20210317055(A1) (this disclosure is incorporated herein by reference in its entirety).

[0051] In one embodiment, the invention disclosed herein is an integrated system using a plurality of reactors, each generally carrying out at least two of the following reactions, one of which includes reaction (1). (1)CF3CH2CH2Cl→CF3CH=CH2(1243zf)+HCl (2)CF3CH=CH2+Cl2→CF3CHClCH2Cl(HCFC-243db) (3)CF3CHClCH2Cl-HCl→CF3CCl=CH2(HCFO-1233xf)+CF3CH=CHCl(1233zd)+HCl (4)CF3CCl=CH2+HF→CF3CFClCH3(244bb) (5)CF3CFClCH3-HCl→CF3CF=CH2(HFO-1234yf)+HCl

[0052] Therefore, according to one aspect of the present disclosure, a process is provided for converting a hydrohaloalkane, which is further processed in an adiabatic reaction zone, to a hydrohalopropene, the process being (a) A step of providing a reaction zone including at least two reactors connected in series, with heat exchangers arranged in sequence and fluid communication between each of the two reactors in series, (b) A step of introducing CF3CH2CH2Cl as a hydrohaloalkane starting material into the first reactor of a series-connected reactor to produce a reaction product containing HFO-1243zf, (c) The reaction product from (b) is passed through a reactor, wherein HFO-1243zf and Cl2 are supplied together, in or out of the presence of a catalyst, to produce HCFC-243db, and the HCFC-243db produced in step (c) is purified by distillation into (1) a vapor phase reactor having a catalyst or into a liquid phase reactor containing present caustic alkali to convert 243db to, for example, HCFO-1233xf, or (2) HCFC-243db is directly introduced into a vapor phase reactor having a catalyst or into a liquid phase reactor containing caustic alkali to convert HCFC-243db to, for example, HCFO-1233xf. (d) A step of purifying and drying HCFO-1233xf from step (c)(1) or (c)(2), and then reacting the purified and dried HCFO-1233xf with HF in the presence of a catalyst to produce HCFC-244bb, (e) A step of converting HCFC-244bb from step (d) to HFO-1234yf by dehydrochlorination, thermally, in the presence of a catalyst, or by reaction with a caustic alkali.

[0053] In certain embodiments, the steps of the reaction process may be carried out in various reactors, with or without stirring, such as adiabatic and non-adiabatic reactors, as well as reactors designed for vapor-liquid phase reactions.

[0054] In some embodiments of the present invention, the conversion of HFC-253fb in the presence of an activated carbon catalyst is at least 30%, at least 35%, at least 45%, at least 50%, at least 55%, at least 60%, at least 70%, at least 75%, at least 80%, and greater than 80%.

[0055] In some embodiments of the present invention, the improved conversion of HFC-253fb in the presence of an activated carbon catalyst using a co-feed of HCl is at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, and at least 100% greater than the conversion of HFC-253fb without a co-feed of HCl.

[0056] In some embodiments of the present invention, improved conversion of HFC-253fb in the presence of a catalyst is obtained by using a co-feed of HCl, and the improvement is at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, and at least 100% greater than the conversion of HFC-253fb without a co-feed of HCl.

[0057] In some embodiments of the present invention, the improved conversion of HFC-253fb using a co-feed of HCl in the presence of a carbon catalyst is at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, and at least 100%, which is better than the conversion of HFC-253fb without a co-feed of HCl.

[0058] In one embodiment of the present invention, the conversion of 253fb in the presence of an HCl cosupply is at least 30% and the selectivity is greater than 98%, or in the presence of a carbon catalyst and an HCl cosupply, it is at least 30% and the selectivity is greater than 98%.

[0059] In one embodiment of the present invention, the conversion of 253fb in the presence of an HCl cosupply is at least one of 35%, 40%, or 45%, with a selectivity greater than 98%, or in the presence of a carbon catalyst and an HCl cosupply, it is at least one of 35%, 40%, or 45%, with a selectivity greater than 98%.

[0060] In one embodiment of the present invention, the conversion of 253fb in the presence of an HCl cosupply is at least 55%, and the selectivity is greater than 98%.

[0061] In one embodiment of the present invention, the conversion of 253fb in the presence of an HCl cosupply is at least 60%, and the selectivity is greater than 98%.

[0062] In one embodiment of the present invention, the conversion of 253fb in the presence of an HCl cosupply is at least 65%, and the selectivity is greater than 98%.

[0063] In one embodiment of the present invention, the conversion of 253fb in the presence of HCl cosupply is at least 70%, and the selectivity is greater than 98%.

[0064] In one embodiment of the present invention, the conversion of 253fb in the presence of an HCl cosupply is at least 75%, and the selectivity is greater than 98%.

[0065] In one embodiment of the present invention, the conversion of 253fb in the presence of an HCl cosupply is at least 80%, and the selectivity is greater than 98%.

[0066] In certain embodiments of the present invention, the conversion of 253fb is at least one of 30%, 35%, 40%, 45%, or more than 50% using an HCl cosupply.

[0067] In certain embodiments of the present invention, the conversion of 253fb is at least more than 60% using an HCl cosupply.

[0068] In certain embodiments of the present invention, the conversion of 253fb is at least more than 70% using an HCl cosupply.

[0069] In certain embodiments of the present invention, the conversion of 253fb is at least more than 80% using an HCl cosupply.

[0070] In certain embodiments of the present invention, the conversion of 253fb is at least more than 90% using an HCl cosupply.

[0071] In certain embodiments of the present invention, the conversion of 253fb using an HCl co-feed is approximately twice that of 253fb using a nitrogen co-feed.

[0072] In certain embodiments of the present invention, the conversion of 253fb using an HCl co-feed is at least about twice that of 253fb using a nitrogen co-feed.

[0073] In certain embodiments of the present invention, the conversion of 253fb using an HCl cosupply is more than twice that of 253fb using a nitrogen cosupply.

[0074] In certain embodiments of the present invention, the activated carbon catalyst used for the dehydrochlorination of HCFC-253fb may be obtained from any of the following sources: wood, peat, coal, coconut shells, bones, lignite, petroleum residues, and sugar. Commercially available carbons that may be used include those sold under the trademarks of Barneby & Sutcliffe®, Darco®, Nucharm, Columbia JXN®, Columbia LCK®, Calgon® PCB, Calgon® BPL, Westvaco®, Norit®, Takeda®, and Barnaby Cheny NB®.

[0075] In certain embodiments of the present invention, the activated carbon includes a three-dimensional matrix porous carbonaceous material. An example is described in U.S. Patent No. 4,978,649, the disclosure of which is incorporated herein by reference in its entirety. In one embodiment of the present invention, the carbon includes a three-dimensional matrix carbonaceous material obtained by introducing a gaseous or vaporized carbon-containing compound (e.g., hydrocarbon) into granules of a large amount of carbonaceous material (e.g., carbon black), decomposing the carbon-containing compound to deposit carbon on the surface of the granules, and treating the resulting material with an activated gas containing vapor to provide a porous carbonaceous material. A carbon-carbon composite material is thus formed.

[0076] In some embodiments of the present invention, carbon is acid-washed activated carbon. Carbon may be in the form of powder, granules, or pellets, and includes, but is not limited to, Carbon COCO Plus (mesh granules, size 6-12 mesh), with a surface area of ​​900 m². 2 / g~1400m 2 It is within the range of / g.

[0077] The above overview and the subsequent "Modes for Carrying Out the Invention" are merely illustrative and descriptive and do not limit the present invention.

[0078] Example 1 8 mL of Calgon Coco Plus activated carbon (8 × 10 mesh size) was placed in a Monel reaction tube (12 inches long × 0.5 inches outer diameter, 0.034 inches wall thickness, 0.43 inches inner diameter). The carbon was dried under N2 purge at 250°C for 2 hours. Next, 3.3 sccm of HCl was supplied to 253 fb at a rate of 0.46 mL / hour (0.00767 mL / min) at atmospheric pressure and 250°C over 12.5 hours. Subsequently, the HCl supply was replaced with 3.5 sccm of N2, and the reaction was carried out over another 12.5 hours. The product flow was analyzed by online GC at 75-minute intervals, and the analysis results are summarized in the table below.

[0079] [Table 2]

[0080] [Table 3]

[0081] The data from Tables 1 and 2 are shown graphically in Figures 1A and 1B. Figure 1A compares the conversion rate to 253fb versus time using HCl and N2 co-feeds, while Figure 1B compares the selectivity to HFO-1243zf using HCl and N2 co-feeds. In each case, using HCl as a co-feed unexpectedly provides a much higher conversion rate. Figure 1B shows a larger and more consistent selectivity to HFO-1243zf when using the HCl co-feed compared to the nitrogen co-feed. In addition to HFO-1243zf, 1242zf, 253fb, 243db, 254fb, 254eb, 1233xf, and optionally 1240xd are detected in the product stream.

[0082] Example 2 Similar to Example 1, 8 mL of Calgon LSI activated carbon (8 × 10 mesh size) was packed into a Monel reaction tube (12 inches long × 0.5 inches outer diameter, 0.034 inches wall thickness, 0.43 inches inner diameter) and dried under N2 purge at 250°C for 2 hours. Then, 6.45 sccm of HCl was supplied to 253fb at atmospheric pressure and 250°C for 24 hours at a rate of 0.6 mL / hour. Subsequently, the HCl supply was replaced with 5.99 sccm of N2 and the process was carried out for another 24 hours. The GC results of the analysis are shown in the graph in Figure 2A, which compares the conversion rate of 253fb against time using HCl and N2 co-feeds, where the conversion rate of 253fb is approximately at least 10% higher when using HCl as a co-feed compared with nitrogen as a co-feed. Figure 2B compares the selectivity for HFO-1243zf using HCl and nitrogen as co-feeds. In addition to HFO-1243zf, 1242zf, 253fb, 243db, 1240xd, 254fb, 254eb, and 1233xf were detected in the product stream.

[0083] Other Embodiments Embodiment A of the process, comprising contacting a catalyst containing a 3-chloro-1,1,1-trifluoropropane (HCFC-253fb) feed, HCl, and activated carbon in a vapor phase to produce 1,1,1-trifluoropropene in a cofeed / feed (HCl:253fb) ratio of 0.25:1 to 50:1, preferably by contacting the catalyst with 3-chloro-1,1,1-trifluoropropane and HCl in a reactor at a temperature of 150°C to about 350°C, more preferably by contacting the catalyst with 3-chloro-1,1,1-trifluoropropane and HCl in a reactor at a temperature of 175°C to about 300°C, or by contacting the catalyst with 3-chloro-1,1,1-trifluoropropane and HCl in a reactor at a temperature of 200°C to about 250°C.

[0084] Embodiment A of the process, wherein the activated carbon has a surface area in the range of 900 m² / g to 1200 m² / g.

[0085] Embodiment A of the process, which is dehydrochlorination and is carried out at a pressure selected from one of the following: a pressure above atmospheric pressure, atmospheric pressure, and a pressure below atmospheric pressure, preferably at atmospheric pressure.

[0086] Embodiment A of the process, wherein the HCl to HCFC-253fb feed ratio is at least one of 0.25:1, 0.5:1, 1:1, 1.5:1, 2.0:1, 2.5:1, 5:1, 7.5:1, 10:1, 20:1, 25:1, 30:1, 35:1, 40:1, and 50:1, and the conversion (dehydrochlorination) of HCFC-253fb is at least one of 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, or 70%.

[0087] Embodiment A of the process, in which the selectivity for HFO-1243zf is at least 98%.

[0088] Process embodiment B, which includes using the composition of process embodiment A.

[0089] Embodiment A of the composition, comprising 1,1,1-trifluoropropene (HFO-1243zf), 3-chloro-1,1,1-trifluoropropane (HCFC-253fb), 2,3-dichloro-1,1,1-trifluoropropane (HCFC-243db), 1,1,1,2-tetrafluoropropane (HFC-254eb), 1,1,1,3-tetrafluoropropane (HFC-254fb), 2-chloro-1,1,1-trifluoropropene (HCFO-1233xf), 1,2,3-trichloropropene ( Embodiment A of the composition comprising HCO-1240xd) and 3-chloro-3,3-difluoropropene (HCFO-1242zf), wherein optionally comprising one of the following based on the total amount of the composition: more than 50 mol percent of 1,1,1-trifluoropropene, more than 60 mol percent of 1,1,1-trifluoropropene, more than 70 mol percent of 1,1,1-trifluoropropene, or more than 80 mol percent of 1,1,1-trifluoropropene.

[0090] Embodiment A of the composition, wherein the additional compounds include at least two of the following: 243db, 1240xd, 254fb, 254eb, and 1233xf.

[0091] Embodiment C of a process for improving the conversion of 3-chloro-1,1,1-trifluoropropane (HCFC-253fb) to 1,1,1-trifluoropropene (HFO-1243zf), comprising improving the conversion of 3-chloro-1,1,1-trifluoropropane (HCFC-253fb) to 1,1,1-trifluoropropene (HFO-1243zf) in the presence of a catalyst by replacing nitrogen as a cofeed with hydrogen chloride (HCl) or by contacting 3-chloro-1,1,1-trifluoropropane (HCFC-253fb) with HCl in the gas phase.

[0092] Embodiment C of the process, where the HCl to HCFC-253fb feed ratio is one of 0.25:1, 0.5:1, 1:1, 1.5:1, 2.0:1, 2.5:1, 5:1, 7.5:1, 10:1, 20:1, 25:1, 30:1, 35:1, 40:1, or 50:1.

[0093] Embodiment D of a process for thermally dehydrochlorinating 3-chloro-1,1,1-trifluoropropane (HCFC-253fb) in the presence of HCl and 1,1,1-trifluoropropene (HFO-1243zf).

[0094] Embodiment E of a process for producing 3-chloro-1,1,1-trifluoropropane (HCFC-253fb) by thermal dehydrochlorination at a temperature below 300°C or below 275°C but above 200°C in the presence of HCl.

[0095] Embodiment F of a process that increases the production of 1,1,1-trifluoropropene (HFO-1243zf) by dehydrochlorinating 3-chloro-1,1,1-trifluoropropane (HCFC-253fb) at a temperature below 300°C or below 275°C but above 200°C, in the presence of hydrogen chloride instead of nitrogen.

[0096] Step 1: Convert 253fb to 1243zf by dehydrochlorination on a catalyst in the vapor phase with a cofeed of HCl. Step 2: Convert the 1243zf produced in Step 1 to 243db by reacting with Cl2 in the vapor phase or liquid phase, with or without a catalyst, or by UV irradiation. Step 3: Convert the 243db produced in Step 2 to 1233xf in the vapor phase with a catalyst, or in the liquid phase with or without a catalyst using a caustic alkali. Embodiment G of the process, comprising: step 4: converting 1233xf prepared in step 3 to 244bb by reacting with HF in the vapor phase with a catalyst or in the liquid phase with a catalyst; step 5: converting 244bb prepared in step 4 to 1234yf in the vapor phase with or without a catalyst, or in the liquid phase with a catalyst or a polar solvent; and optionally purifying and / or drying the products from steps 1, 2, 3 and 4 before use in the next step.

[0097] The HCl to HCFC-253fb feed ratio is one of 0.25:1, 0.5:1, 1:1, 1.5:1, 2.0:1, 2.5:1, 5:1, 7.5:1, 10:1, 20:1, 25:1, 30:1, 35:1, 40:1, or 50:1, and / or the HCl to HCFC-253fb feed ratio is 0.25:1 to 50:1, and / or the catalyst contains activated carbon and uses a co-feed / feed ratio of 0.25:1 to 50:1, and or / or 3-chloro-1,1,1-trifluoropropane and HCl are brought into contact with the catalyst in a reactor at a temperature of 150°C to approximately 350°C, and / or 3-chloro-1,1,1-trifluoropropane and HCl are brought into contact with the catalyst in a reactor at a temperature of 175°C to approximately 300°C, and / or 3-chloro-1,1,1-trifluoropropane and HCl are brought into contact with the catalyst in a reactor at a temperature of 200°C to approximately 250°C, and / or activated carbon is 900 m 2 / g~1200m 2 Process embodiment G having a surface area in the range of / g.

[0098] It contains 1,1,1-trifluoropropene (HFO-1243zf) and 3-chloro-1,1,1-trifluoropropane (HCFC-253fb), a. HCFO-1242zf greater than 0.0 to 0.2 mol percent, b. HCFC-243 dB above 0.0 to 0.2 mol percent, c.0 to 0.0001 mole percent of HCO-1240xd, d.0 to 0.03 mol percent of HFC-254fb, e.0 to 0.3 mol percent of HFC-254eb, Embodiment A of the composition, comprising at least one of HCFO-1233xf in a concentration of f.0 to ~2 mol%.

[0099] 1,1,1-trifluoropropene (HFO-1243zf), 3-chloro-1,1,1-trifluoropropane (HCFC-253fb), and at least, a. HCFO-1242zf greater than 0.0 to 0.2 mol percent, b. HCFC-243 dB above 0.0 to 0.2 mol percent, c.0 to 0.0001 mole percent of HCO-1240xd, d. HFC-254fb greater than 0.0 to 0.03 mol percent, and Embodiment A of the composition, comprising e.0 to 2 mol% of HCFO-1233xf.

[0100] Embodiment A of the composition comprising 1,1,1-trifluoropropene (HFO-1243zf), 3-chloro-1,1,1-trifluoropropane (HCFC-253fb), 2-chloro-1,1,1-trifluoropropene (HCFO-1233xf), and at least two of the following: greater than 0 to 0.2 mol percent of HCFO-1242zf, greater than 0 to 0.2 mol percent of HCFC-243db, greater than 0 to 0.0001 mol percent of HCO-1240xd, and greater than 0 to 0.03 mol percent of HFC-254fb.

[0101] Embodiment A of a system comprising at least a first and second reactor that convert HCFC-253fb to HFO-1243zf and HFO-1243zf to HCFC-243db, or three or more reactors, some or all of which can be operated as adiabatic reactors.

[0102] Embodiment B of the system, comprising a first catalyst-containing reactor and a second catalyst-containing reactor, each having an overhead product outlet and a supply line in fluid communication with a source containing 3-chloro-1,1,1-trifluoropropane (HCFC-253fb) and hydrogen chloride, wherein the supply line is also connected to the first catalyst-containing reactor to supply the 3-chloro-1,1,1-trifluoropropane (HCFC-253fb) and hydrogen chloride to the first catalyst-containing reactor, and the product outlet is associated with the first catalyst-containing reactor in fluid communication with the second catalyst-containing reactor to introduce the reaction between 1,1-trifluoropropene (HFO-1243zf) and a halogen gas.

[0103] In certain embodiments of the present invention, the conversion of catalyst 253fb is at least one of 30%, 35%, 40%, 45%, or more than 50% using an HCl cofeed.

[0104] In certain embodiments of the present invention, the conversion of catalyst 253fb is at least more than 60% using the HCl cofeed.

[0105] In certain embodiments of the present invention, the conversion of catalyst 253fb is at least more than 70% using an HCl cofeed.

[0106] In certain embodiments of the present invention, the conversion of catalyst 253fb is at least more than 80% using the HCl cofeed.

[0107] In certain embodiments of the present invention, the conversion of catalyst 253fb is at least more than 90% when an HCl cofeed is used.

[0108] Embodiment 1A of the process comprises contacting a catalyst containing activated carbon in a vapor phase with a 3-chloro-1,1,1-trifluoropropane (HCFC-253fb) feed and HCl as a co-feed in a co-feed / feed ratio of 0.25:1 to 50:1 to produce 1,1,1-trifluoropropene, wherein optionally the activated carbon has a surface area in the range of 900 m² / g to 1200 m² / g.

[0109] 3-Chloro-1,1,1-trifluoropropane and HCl are brought into contact with a catalyst in a reactor at temperatures between 150°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, 310°C, or 320°C and approximately 350°C, and optionally, 900 m of activated carbon is added. 2 / g~1200m 2 Embodiment 1B of the process having a surface area in the range of / g.

[0110] 3-Chloro-1,1,1-trifluoropropane and HCl are contacted with a catalyst in a reactor at a temperature between 175 °C, 180 °C, 190 °C, 200 °C, 210 °C, 220 °C, 230 °C, 240 °C, 250 °C, 260 °C, 270 °C, 280 °C or 290 °C and about 300 °C, and optionally, the activated carbon has a surface area in the range of 900 m 2 / g to 1200 m 2 / g, Process Embodiment 1C.

[0111] 3-Chloro-1,1,1-trifluoropropane and HCl are contacted with a catalyst in a reactor at a temperature between 200 °C, 210 °C, 220 °C or 230 °C and about 250 °C, and optionally, the activated carbon has a surface area in the range of 900 m 2 / g to 1200 m 2 / g, Process Embodiment 1D.

[0112] The process is dehydrochlorination, and optionally, (1) the pressure is atmospheric pressure, and / or (2) the HCl to HCFC-253fb feed ratio is one of 0.25:1, 0.5:1, 1:1, 1.5:1, 2.0:1, 2.5:1, 5:1, 7.5:1, 10:1, 20:1, 25:1, 30:1, 35:1, 40:1 and 50:1, and / or (3) the conversion of HCFC-253fb is at least one of 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, or 70%, Process Embodiments 1A, 1B, 1C or 1D.

[0113] The HCl to HCFC-253fb feed ratio is one of 0.25:1, 0.5:1, 1:1, 1.5:1, 2.0:1, 2.5:1, 5:1, 7.5:1, 10:1, 20:1, 25:1, 30:1, 35:1, 40:1 and 50:1, and / or the conversion of HCFC-253fb is at least one of 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, or 70%, Process Embodiments 1A, 1B, 1C or 1D.

[0114] The process according to any one of Embodiments 1A, 1B, 1C, or 1D, wherein the selectivity for HFO-1243zf is at least 98%.

[0115] A composition provided by any one of Embodiments 1A, 1B, 1C, or 1D.

[0116] Embodiment 2 of a composition comprising 1,1,1-trifluoropropene (HFO-1243zf), 3-chloro-1,1,1-trifluoropropane (HCFC-253fb), 2,3-dichloro-1,1,1-trifluoropropane (HCFC-243db), 1,1,1,2-tetrafluoropropane (HFC-254eb), 1,1,1,3-tetrafluoropropane (HFC-254fb), 2-chloro-1,1,1-trifluoropropene (HCFO-1233xf), 1,2,3-trichloropropene (HCO-1240xd), and 3-chloro-3,3-difluoropropene (HCFO-1242zf).

[0117] Embodiment 3 of the composition comprising 1,1,1-trifluoropropene, 3-chloro-1,1,1-trifluoropropane, and at least one additional element selected from 2,3-dichloro-1,1,1-trifluoropropane, 1,1,1,2-tetrafluoropropane, 1,1,1,3-tetrafluoropropane, 2-chloro-1,1,1-trifluoropropene, 1,2,3-trichloropropene, and 3-chloro-3,3-difluoropropene.

[0118] Embodiment 2 or 3 of the composition, comprising one or more of the following based on the total amount of the composition: (a) 1,1,1-trifluoropropene in greater than 50 mol percent, (b) 1,1,1-trifluoropropene in greater than 60 mol percent, (c) 1,1,1-trifluoropropene in greater than 70 mol percent, or (d) 1,1,1-trifluoropropene in greater than 80 mol percent, each optionally comprising additional compounds selected from at least two of 243db, 1240xd, 254fb, 254eb, and 1233xf.

[0119] Embodiment 4 of the process, which includes improving the conversion from 3-chloro-1,1,1-trifluoropropane (HCFC-253fb) to 1,1,1-trifluoropropene (HFO-1243zf) and replacing nitrogen as a co-feed with hydrogen chloride (HCl).

[0120] Embodiment 5 of a process that improves the conversion from 3-chloro-1,1,1-trifluoropropane (HCFC-253fb) to 1,1,1-trifluoropropene (HFO-1243zf) in the presence of a catalyst by contacting 3-chloro-1,1,1-trifluoropropane (HCFC-253fb) with HCl in the gas phase.

[0121] Embodiment 4 or 5 of the process, the HCl to HCFC-253fb feed ratio is 0.25:1, 0.5:1, 1:1, 1.5:1, 2.0:1, 2.5:1, 5:1, 7.5:1, 10:1, 20:1, 25:1, 30:1, 35:1, 40:1, or 50:1, or one of 0.25:1 to 50:1, or 0.25:1 to 1.5:1, or 3:1 to 4:1, as well as all values ​​and ranges between them.

[0122] In the above specification, the concept has been described with reference to specific embodiments. However, it will be understood by those skilled in the art that various modifications and changes can be made without departing from the scope of the invention as set forth in the following claims. Accordingly, this specification should be considered illustrative rather than restrictive, and all such modifications are intended to fall within the scope of the invention.

[0123] For clarity, it should be understood that certain features described herein in the context of separate embodiments may also be provided in combination in a single embodiment. Conversely, for brevity, various features described in the context of a single embodiment may also be provided separately or in any partial combination.

Claims

1. A process comprising contacting a catalyst containing activated carbon in a vapor phase with a feed of 3-chloro-1,1,1-trifluoropropane (HCFC-253fb) and HCl as a co-feed in a co-feed / feed ratio of 0.25:1 to 50:1 to produce 1,1,1-trifluoropropene (HFO-1243zf).

2. The process according to claim 1, wherein 3-chloro-1,1,1-trifluoropropane and HCl are in contact with the catalyst in a reactor at a temperature of 150°C to about 350°C.

3. The process according to claim 1, wherein 3-chloro-1,1,1-trifluoropropane and HCl are in contact with the catalyst in a reactor at a temperature of 175°C to about 300°C.

4. The process according to claim 1, wherein 3-chloro-1,1,1-trifluoropropane and HCl are brought into contact with the catalyst in a reactor at a temperature of 200°C to about 250°C.

5. The activated carbon is 900 m ２ / g to 1200m ２ The process according to any one of claims 1 to 4, having a surface area in the range of / g.

6. The process according to claim 5, wherein the process is dehydrochlorination.

7. The process according to claim 6, wherein the dehydrochlorination is carried out at a pressure selected from one of the following: superatmospheric pressure, atmospheric pressure, and subatmospheric pressure.

8. The process according to claim 6, wherein the pressure is a pressure exceeding atmospheric pressure.

9. The process according to claim 6, wherein the HCl to HCFC-253fb feed ratio is one of 0.25:1, 0.5:1, 1:1, 1.5:1, 2.0:1, 2.5:1, 3:1, 4:1, 5:1, 7.5:1, 10:1, 20:1, 25:1, 30:1, 35:1, 40:1, and 50:

1.

10. The process according to claim 7, wherein the conversion of HCFC-253fb is at least one of 30%, 35%, 40%, 45%, 50%, or 55%.

11. The process according to claim 7, wherein the conversion of HCFC-253fb is at least 60%.

12. The process according to claim 7, wherein the conversion of HCFC-253fb is at least 70%.

13. The process according to claim 7, wherein the conversion of HCFC-253fb is at least 65%.

14. The process according to any one of claims 7 to 13, wherein the selectivity for HFO-1243zf is at least 98%.

15. A composition provided by any one of claims 1 to 13.

16. A composition comprising 1,1,1-trifluoropropene (HFO-1243zf), 3-chloro-1,1,1-trifluoropropane (HCFC-253fb), 2,3-dichloro-1,1,1-trifluoropropane (HCFC-243db), 1,1,1,2-tetrafluoropropane (HFC-254eb), 1,1,1,3-tetrafluoropropane (HFC-254fb), 2-chloro-1,1,1-trifluoropropene (HCFO-1233xf), 1,2,3-trichloropropene (HCO-1240xd), and 3-chloro-3,3-difluoropropene (HCFO-1242zf).

17. A composition comprising at least one additional element selected from 1,1,1-trifluoropropene (HFO-1243zf), 3-chloro-1,1,1-trifluoropropane (HCFC-253fb), and 2,3-dichloro-1,1,1-trifluoropropane (HCFC-243db), 1,1,1,2-tetrafluoropropane (HFC-254eb), 1,1,1,3-tetrafluoropropane (HFC-254fb), 2-chloro-1,1,1-trifluoropropene (HCFO-1233xf), 1,2,3-trichloropropene (HCO-1240xd), and 3-chloro-3,3-difluoropropene (HCFO-1242zf).

18. The composition according to claim 17, comprising more than 50 mole percent of 1,1,1-trifluoropropene based on the total amount of the composition.

19. The composition according to claim 17, comprising more than 60 mole percent of 1,1,1-trifluoropropene based on the total amount of the composition.

20. The composition according to claim 17, comprising more than 70 mole percent of 1,1,1-trifluoropropene based on the total amount of the composition.

21. The composition according to claim 17, comprising more than 80 mole percent of 1,1,1-trifluoropropene based on the total amount of the composition.

22. The composition according to any one of claims 16 to 22, wherein the additional compound comprises at least two of 243 db, 1240 x d, 254 fb, 254 eb, and 1233 x f.

23. A process for improving the conversion from 3-chloro-1,1,1-trifluoropropane (HCFC-253fb) to 1,1,1-trifluoropropene (HFO-1243zf), comprising replacing nitrogen as a co-feed with hydrogen chloride (HCl).

24. A process to improve the conversion from 3-chloro-1,1,1-trifluoropropane (HCFC-253fb) to 1,1,1-trifluoropropene (HFO-1243zf) in the presence of a catalyst, by contacting 3-chloro-1,1,1-trifluoropropane (HCFC-253fb) with HCl as a co-feed in the gas phase.

25. The process according to any one of claims 23 to 24, wherein the HCl to HCFC-253fb feed ratio is one of 0.25:1, 0.5:1, 1:1, 1.5:1, 2.0:1, 2.5:1, 5:1, 7.5:1, 10:1, 20:1, 25:1, 30:1, 35:1, 40:1, or 50:

1.

26. The process according to claim 1, wherein the HCl to HCFC-253fb feed ratio is 0.25:1 to 50:

1.

27. The process according to claim 6, wherein HFO-1243zf is halogenated to HCFC-243db, and this is optionally converted to HCFO-1233xf and HFO-1233zd.

28. A composition comprising HCFC-253fb, HCl, and optionally an activated carbon catalyst, wherein the HCl to HCFC-253fb ratio is one of 0.25:1, 0.5:1, 1:1, 1.5:1, 2.0:1, 2.5:1, 5:1, 7.5:1, 10:1, 20:1, 25:1, 30:1, 35:1, 40:1, and 50:

1.

29. The composition according to claim 28, wherein the HCl to HCFC-253fb ratio is 0.25:1 to 1.5:

1.

30. The composition according to claim 28, wherein the HCl to HCFC-253fb ratio is 0.25:1, 3:1, or 4:

1.

31. The composition according to claim 28, wherein the HCl to HCFC-253fb ratio is 1:1, 10:1, 20:1, 25:1, 30:1, 35:1, 40:1, or 50:

1.

32. It is a process, Step 1: Convert 253fb to 1243zf by dehydrochlorination on a catalyst in the vapor phase with HCl cofeed, Step 2: The 1243zf prepared in Step 1 is subjected to Cl in the vapor phase or liquid phase, with or without a catalyst, or by UV irradiation. ２ It reacts and converts to 243 dB, Step 3: The 243 dB produced in Step 2 is converted to 1233 x f in the vapor phase using a catalyst, or in the liquid phase using a caustic alkali, either in the presence or absence of the catalyst. Step 4: The 1233xf prepared in Step 3 is converted to 244bb by reacting it with HF in the gas phase or in the liquid phase using a catalyst. Step 5: Convert the 244bb prepared in Step 4 to 1234yf in the gas phase with or without a catalyst, or in the liquid phase using a caustic alkali, catalyst, or polar solvent, and optionally purify and / or dry the products from Steps 1, 2, 3 and 4 before use in the next step. A process that includes this.

33. The process according to claim 32, wherein the HCl to HCFC-253fb feed ratio is one of 0.25:1, 0.5:1, 1:1, 1.5:1, 2.0:1, 2.5:1, 5:1, 7.5:1, 10:1, 20:1, 25:1, 30:1, 35:1, 40:1, or 50:

1.

34. The process according to claim 32, wherein the HCl to HCFC-253fb feed ratio is 0.25:1 to 50:

1.

35. The process according to claim 32, wherein the catalyst comprises activated carbon and uses a co-feed / feed ratio of 0.25:1 to 50:

1.

36. The process according to claim 32, wherein 3-chloro-1,1,1-trifluoropropane and HCl are brought into contact with the catalyst in a reactor at a temperature of 150°C to about 350°C.

37. The process according to claim 32, wherein 3-chloro-1,1,1-trifluoropropane and HCl are in contact with the catalyst in a reactor at a temperature of 175°C to about 300°C.

38. The process according to claim 32, wherein 3-chloro-1,1,1-trifluoropropane and HCl are brought into contact with the catalyst in a reactor at a temperature of 200°C to about 250°C.

39. The activated carbon is 900 m ２ / g to 1200m ２ The process according to claim 35, having a surface area in the range of / g.

40. The process according to claim 32, wherein steps 1 to 5 form an integrated process.

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