WO2024205836A1 - Method for producing 1,1,1-trifluoropropene from the dehydrochlorination of 3-chloro-1,1,1-trifluoropropane - Google Patents

Abstract

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

Description

TITLE OF THE INVENTION

METHOD FOR PRODUCING 1,1,1-TRIFLUOROPROPENE FROM THE DEHYDROCHLORINATION OF 3-CHLORO-1.1.1-TRIFLUOROPROPANE

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Application No. 63/455,432, filed on March 29, 2023, the disclosure of which is herein incorporated by reference in its entirety.

FIELD OF THE INVENTION

[0002] The present invention relates to processes for converting 3-chloro- 1,1,1 - trifluoropropane (HCFC-253fb) to 1,1,1 -trifluoropropene which is a useful monomer for the production of fluorosilicones, useful in the manufacture of trifluoropropene epoxide and 3,3,3-trifluoropropylbenzene, and as a feed material for the producing hydro(chloro)fluorocarbons and hydrofluoroolefins such as 2, 3,3,3- tetrafluoropropene and 1 ,1,1,4,4,4-hexafluorobutene.

BACKGROUND OF THE INVENTION

[0003] Hydrofluoroolefins (HFOs), having low ozone depletion potential (ODP) and low global warming potential (GWP), are regarded as candidates for replacing saturated CFCs (chlorofluorocarbons) and HCFCs (hydrochlorofluorocarbons).

HFOs can be employed in a wide range of applications, including but not limited to, refrigerants, solvents, foam expansion agents, cleaning agents, aerosol propellants, dielectrics, fire extinguishants, working fluids and power cycle working fluids.

SUMMARY OF THE INVENTION

[0004] The present invention relates to a process of enhancing conversion of 3- chloro-1,1,1-trifluoropropane (i.e., “HCFC-253fb” or“253fb”) using an activated carbon catalyst by co-feeding HCI.

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

[0006] One embodiment of the invention disclosed herein relates to a process of 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 the 253fb with an activated carbon catalyst in the presence of hydrogen chloride, schematically shown below.

Scheme 1 .

[0007] The catalytic dehydrochlorination process of the present invention is conducted in the vapor phase, which includes continuous operation. The temperature in the reaction zone is typically from 150° C to 380°C.

[0008] The dehydrochlorination process of the present invention can be conducted at superatmospheric, atmospheric, or subatmospheric pressures.

[0009] The process of the present invention relates to a process which provides a two-fold increase in the conversion of HCFC-253fb to HFO-1243zf by using an HCI co-feed.

[0010] The process of the present invention relates to a process which increases the conversion (dehydrochlorination) of HCFC-253fb to HFO-1243zf by using an HCI co-feed.

[0011] The process of the present invention relates to a catalytic process which increases the conversion of HCFC-253fb to HFO-1243zf by using an HCI co-feed.

[0012] The present invention disclosed herein relates to processes where the HFO-1243zf produced in accordance with the invention disclosed herein is an intermediate for forming higher halogenated compounds such as HCFC-243db, HCFO-1233xf, and/or HCFC-244bb intermediates in the production of 2, 3,3,3- tetrafluoropropene (HFO-1234yf). [0013] The present invention disclosed herein can be one step of an integrated process to produce higher 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 of 2, 3,3,3- tetrafluoropropane (HFO-1234yf).

[0014] The process disclosed herein relates to integrated processes for producing higher halogenated compounds starting from the conversion of 3-chloro-1 , 1 , 1 trifluoropropane (HCFC-253fb).

[0015] The present invention disclosed herein also relate to compositions including

1.1.1 -trifluoropropene (HFO-1243zf) as the main or major component, 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). The amount 1243zf is one of: greater than 50 mole percent based on the total amount of the compositions, greater than 60 mole percent based on the total amount of the compositions, greater than 70 mole percent based on the total amount of the compositions, greater than 80 mole percent based on the total amount of the compositions.

[0016] The present invention disclosed herein relates to compositions including

1.1.1 -trifluoropropene (HFO-1243zf), 3-chloro-1 ,1 ,1-trifluoropropane (HCFC-253fb), and between greater than 0 and 0.2 mole percent HCFO-1242zf, and/or between greater than 0 and 0.2 mole percent HCFC-243db, and/or between greater than 0 and 0.0001 mole percent HCO-1240xd, and/or between greater than 0 and 0.03 mole percent HFC-254fb, and/or between greater than 0 and 0.3 mole percent HFC- 254eb, and/or between greater than 0 and 2 mole percent HCFO-1233xf. Thus, the total amount HCFO-1242zf, HCFC-243db, HCO-1240xd, HFC-254fb, and HFC- 254eb is greater than 0 and: about 1 mole percent, about 0.9 mole percent, or about 0.8 mole percent, or about 0.75 mole percent, or greater than 0 and 0.5 mole percent, or greater than 0 and 0.4 mole percent, or greater than 0 and 0.3 mole percent, or greater than 0 and 0.2 mole percent; or at least 0.00001 mole percent, or at least 0.0001 mole percent, or 0.001 more percent, or 0.01 mole precent or 0.1 mole percent but less than 0.3 mole percent, and all values and ranges therebetween.

[0017] Disclosed herein is a composition including HFO-1243zf, HCFC-253fb and at least one additional member selected from HCFO-1242zf, HCFC-243db, HCO- 1240xd, HFC-254fb, HFC-254eb and HCFO-1233xf.

[0018] Disclosed herein is a composition including HFO-1243zf and HCFC-253fb and the total amount of HCFO-1242zf, HCFC-243db, HFC-254fb, HFC-254eb and R1233xf is less than 1 mole percent.

[0019] Disclosed herein is a composition including HFO-1243zf and HCFC-253fb and 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.

[0020] Disclosed herein is composition comprising HCFC-253fb, HCI and optionally, a catalyst, wherein the HCI: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.

[0021] Disclosed herein is an integrated system for producing downstream halogenated compounds from HCFC-253fb.

[0022] 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, the present 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, 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 THE DRAWINGS

[0023] Figure 1A compares the conversion of HCFC-253fb to HFO-1243zf using HCI or N2 co-feeds.

[0024] Figure 1 B compares the selectivity to HFO-1243zf in the presence of HCI or N2. [0025] Figure 2A provides another comparison of the conversion of HCFC-253fb using HCI or N2 co-feeds.

[0026] Figure 2B provides another comparison of the selectivity to HFO-1243zf in the presence of HCI and N2.

DETAILED DESCRIPTION OF THE INVENTION

[0027] The foregoing summary and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as defined in the appended claims. Other features and benefits of any one or more of the embodiments will be apparent from the following detailed description, and from the claims.

[0028] The present invent relates to a process of enhancing conversion of 3- chloro-1,1,1-trifluoropropane (i.e. , “HCFC-253fb” or “253fb”) by using an HCI co-feed whereby 3-chloro-1,1,1-trifluoropropaneis is dehydrohalogenated to 1,1,1- trifluoropropene (HFO-1243zf), in the presence of a catalyst and the HFO-1243zf is used as a feed in processes for producing higher, halogenated compounds.

[0029] Before addressing details of embodiments described herein, certain terms are defined or clarified as follows.

[0030] The term “hydrohaloalkane,” as used herein means a molecule containing hydrogen, carbon, fluorine and/or chlorine and/or bromine and/or iodine, with no carbon-carbon double bond (halo=fluoro, chloro, bromo, iodo). Examples are described throughout the instant specification.

[0031] The term “dehydrohalogenation,” as used herein, means loss of HX from a hydrohaloalkane, where X=F, Cl, Br, I, where H and X are on adjacent carbons in the hydrohaloalkane. For example, the term “dehydrofluorination,” “dehydrofluorinating” or “dehydrofluorinated,” as used herein, means a process during which hydrogen and fluorine on adjacent carbons in a molecule are removed; the term “dehydrochlorination,” “dehydrochlorinating,” or “dehydrochlorinated,” as used herein, means a process during which hydrogen and chlorine on adjacent carbons in a molecule are removed. [0032] As disclosed herein conversion of 3-chloro-1 ,1 ,1 trifluoropropane is conducted in the vapor phase. Typically a heated reactor is used. A number of reactor configurations are possible including horizontal or vertical orientation of the reactor, and any downstream reactions can be carried in a series of reactors operated in non-adiabatic and adiabatic modes.

[0033] In addition to the reactors disclosed herein, heat exchangers, effluent lines, units associated with mass transfer, contacting vessels (pre-mixers), distillation columns, and feed, material transfer lines and valving associated with reactors, heat exchangers, vessels, columns, and units that are used in the processes of various embodiments disclosed herein should be constructed of materials resistant to corrosion.

[0034] The term “adiabatic,” as used herein means relating to or denoting a reactor or process or condition in a reaction zone in which heat is not intentionally added or removed from the reaction zone. It will be appreciated by those skilled in the art that even with the best insulation, some heat may be lost from reaction zones operating above ambient temperature (or conversely gained for reaction zones operating below ambient temperature).

[0035] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such 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 is true (or present).

[0036] The transitional phrase “consisting of’ excludes any element, step, or ingredient not specified. If in the claim such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase “consists of” appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole. [0037] The transitional phrase “consisting essentially of” is used to define a composition, method that includes materials, steps, features, components, or elements, in addition to those literally disclosed provided that these additional included materials, steps, features, components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention, especially the mode of action to achieve the desired result of any of the processes of the present invention. The term ‘consisting essentially of’ occupies a middle ground between “comprising” and “consisting of.”

[0038] Where applicants have defined an invention or a portion thereof with an open-ended term such as “comprising,” it should be readily understood that (unless otherwise stated) the description should be interpreted to also include such an invention using the terms “consisting essentially of’ or “consisting of.”

[0039] Also, use of “a” or “an” are employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

[0040] Compounds referred to in this disclosure may be referred to by code, based on fluorochemical naming convention, chemical structure and/or chemical name. For convenience and reference, selected compounds with codes, structures and chemical names are provided in Table 1.

TABLE 1

[0041] The dehydrochlorination process disclosed herein is conducted in the presence of hydrogen chloride (HCI) which is co-fed into the reactor with the starting material 3-chloro-1, 1 ,1 -trifluoropropane which is commercially available or can be prepared by hydrofluorination of 1 ,1 ,1 ,3-tetrachloropropane (HCC-250fb) as disclosed in U.S. Patent No. 4,138,355, or by conventional treatment with antimony trifluoride as disclosed Henne et al., “Influence of the CF3 Group on an Adjacent Double Bond” (1950), or techniques described in U.S. Patent No. 4,078,007, the disclosures of which are incorporated by reference in their entireties.

[0042] The dehydrochlorination process disclosed herein is conducted in the vapor phase, in a reactor operating in, for example, a continuous mode.

[0043] In another embodiment of the invention, HCFC-253fb and HCI contact one another in the vapor phase where the molar ratio of HCI to HCFC-253fb ranges from 0.25:1 to 40:1 , 0.5:1 to 40:1, 1:1 to 20:1 and 1 :1 to 5:1.

[0044] In another embodiment of the invention, HCFC-253fb and HCI contact one another in the vapor phase where the molar ratio of HCI 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. and all values, increments and ranges therebetween.

[0045] In another embodiment of the invention, HCFC-253fb and HCI contact one another in a reaction zone at temperatures ranging from between 150°C and 350°C, between 175°C and 325°C, between 200°C and 325°C, between 225°C and 275°C, or at temperatures of about 150°C, about 175°C, about 200°, about 225°C, about 250°C, about 275°C, about 300°C, about 325°C, about 350°C, and all values and temperature ranges therebetween.

[0046] In another embodiment of the invention, HCFC-253fb and HCI contact one another in a reaction zone at temperatures ranging between of 150°C, 160°C, or 170°C and 180°C, between 160°C, 170°C or 180°C and 190°C, between 170°C and 200°C, between 180°C, 190°C, 200°C, 210°C, 220°C, 230°C or 240°C and 275°C, 150°C and 180°C, between 160°C and 190°C, between 170°C and 200°C, between 170°C and 225°C, between 170°C and 250°C, between 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C or 240°C and 275°C, between 175°C, 185°C, 195°C, 205°C, 215°C, 225°C, 235°C or 245°C and 255°C, 175°C and 260°C and all values and temperature ranges therebetween. [0047] In one embodiment, the process comprises Step 1 : 253fb dehydrochlorination over a catalyst in vapor phase with co-Feed of HCI to convert to 1243zf; Step 2 1243zf made from Step 1 reacts with Cl₂ in vapor phase, or liquid phase with a catalyst or without a catalyst, or by UV irradiation to convert to 243db; Step 3: 243db made from step 2 is converted to 1233xf in vapor phase with a catalyst or in liquid phase with a caustic with or without presence of a catalyst; Step 4: 1233xf made from step 3 is converted to 244bb by reacting with HF in vapor phase with a catalyst or in liquid phase with a catalyst; and Step 5: 244bb made from step 4 is converted to 1234yf in vapor phase with or without a catalyst or in liquid phase with a caustic, a catalyst or polar solvent. Optionally the product from Steps 1, 2, 3 and 4 are purified and/or dried before use in the next step.

[0048] In one embodiment of the invention, starting organic materials to be dehydrochlorinated and HCI are fed into and/or through a reactor, reaction vessel or reaction zone, in the presence of activated carbon, under suitable reaction conditions, to selectively dehydrochlorinate HCFC-253fb to HFO-1243zf. For example, in one embodiment, HCFC-253fb and HCI may be respectively fed into a reactor where they contact a catalyst, and then a product mixture comprising HFO- 1243zf as the main or major component is discharged through an outlet for purification in treating units.

[0049] In one embodiment of the invention disclosed herein, the HFO-1243zf from the HCFC-253fb — > HFO-1243zf conversion is subsequently chlorinated in accordance with the following reaction:

CF₃CH=CH₂ + Cl₂ — > CF₃CHCICH₂CI (HCFC-243db)

[0050] For example, an HFO-1243zf feed may be co-fed with chlorine to a reactor and catalytically converted by passing 1243zf and Cl₂ through a catalyst bed contained therein. A product mixture include HFO-243db may be withdrawn.

[0051] HFO-1243zf can be chlorinated to HCFC- 243db by contacting HFO-1243zf with chlorine in the presence or absence of a catalyst as part of an integrated process is disclosed in, for example, U.S. Patent Publication No.

US20210317055A1 , the disclosure of which is incorporated herein by reference in its entirety. [0052] In one embodiment, the invention disclosed herein is an integrated system using multiple reactors, generally each performing at least two of the following reactions, one of which should include reaction (1):

(1) CF3CH2CH2CI -^CF₃CH=CH₂ (1243zf) +HCI

(2) CF₃CH=CH₂+ Cl₂ CF₃CHCICH₂CI (HCFC-243db)

(3) CF₃CHCICH₂CI - HCI CF₃CCI=CH₂(HCFO-1233xf) + CF₃CH=CHCI (1233zd) +HCI

(4) CF₃CCI=CH₂ + HF — > CF₃CFCICH₃ (244bb)

(5) CF₃CFCICH₃ -HCI -^CF₃CF=CH₂(HFO-1234yf) + HCI

[0053] Thus, according to one aspect of the present disclosure, there is provided a process for converting a hydrohaloalkane to a hydrohalopropene which is further processed in an adiabatic reaction zone, which process comprises the steps of:

(a) providing a reaction zone comprising at least two serially connected reactors and having a heat exchanger disposed in sequence and in fluid communication between each two reactors in series;

(b) introducing CF₃CH2CH2CI as an hydrohaloalkane starting material into a first reactor of serially connected reactors and producing a reaction product comprising HFO-1243zf;

(c) passing the reaction product from (b) to a reactor, where HFO-1243zf and CI2 is cofed to produce HCFC-243db, in the presence or absence of a catalyst, wherein the HCFC- 243db produced in step (c) is (1) purified by distillation into a vapor phase reactor with a catalyst, or into a liquid phase reactor containing caustic present to convert 243db into e.g., HCFO- 1233xf, or (2) directly introduced into a vapor phase reactor with a catalyst, or into a liquid phase reactor containing caustic to convert HCFC-243db into e.g., HCFO-1233xf;

(d) 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 and producing HCFC-244bb; and (e) converting HCFC-244bb from step (d) to HFO- 1234yf through a dehydrochlorination, thermally, in the presence of a catalyst, or through reaction with a caustic.

[0054] In certain embodiments steps of the reaction process can be conducted in a variety of reactors, e.g., adiabatic and non-adiabatic reactors, and reactors designed for vapor liquid phase reactions, with or without agitation.

[0055] In several embodiments of the invention conversion of HFC-253fb in the presence of an activated carbon catalyst is at least 30%, is at least 35 %, is at least 45%, is at least 50%, is at least 55%, is at least 60%, is at least 70%, is at least 75%, is at least 80%, and is greater than 80%.

[0056] In several embodiments of the invention improved conversion of HFC-253fb in the presence of an activated carbon catalyst using a co-feed of HCI is at least 10%, is at least 20%%, is at least 30%, is at least 40%, is at least 50%, is at least 60%, is at least 70%, is at least 80%, is at least 90%, is at least 100% and is greater than HFC-253fb conversion without co-feed of HCI.

[0057] In several embodiments of the invention improved conversion of HFC-253fb in the presence of a catalyst is obtained by using a co-feed of HCI where the improvement is at least 10%, is at least 20%%, is at least 30%, is at least 40%, is at least 50%, is at least 60%, is at least 70%, is at least 80%, is at least 90%, is at least 100% and is greater than HFC-253fb conversion without co-feed of HCI.

[0058] In several embodiments of the invention improved conversion of HFC-253fb in the presence of a carbon catalyst and using a co-feed of HCI is at least 10%, is at least 20%%, is at least 30%, is at least 40%, is at least 50%, is at least 60%, is at least 70%, is at least 80%, is at least 90%, is at least 100% and is better than HFC- 253fb conversion without co-feed of HCI.

[0059] In one embodiment of the invention conversion of 253fb in the presence of an HCI co-feed is at least 30% and a selectivity is greater than 98%, or in the presence of a carbon catalyst and an HCI co-feed is at least 30% and a selectivity is greater than 98%.

[0060] In one embodiment of the invention conversion of 253fb in the presence of an HCI co-feed is at least one of 35%, 40% or 45% and a selectivity greater than 98%, or the presence of a carbon catalyst and an HCI co-feed is at least one of 35%, 40% or 45% and a selectivity is greater than 98%.

[0061] In one embodiment of the invention conversion of 253fb in the presence of an HCI co-feed is at least 55% and a selectivity greater than 98%.

[0062] In one embodiment of the invention conversion of 253fb in the presence of an HCI co-feed is at least 60% and a selectivity greater than 98%.

[0063] In one embodiment of the invention conversion of 253fb in the presence of an HCI co-feed is at least 65% and a selectivity greater than 98%.

[0064] In one embodiment of the invention conversion of 253fb in the presence of an HCI co-feed is at least 70% and a selectivity greater than 98%.

[0065] In one embodiment of the invention conversion of 253fb in the presence of an HCI co-feed is at least 75% and a selectivity greater than 98%.

[0066] In one embodiment of the invention conversion of 253fb in the presence of an HCI co-feed is at least 80% and a selectivity greater than 98%.

[0067] In certain embodiments of the invention 253fb conversion is at least one of 30%, 35%, 40%, 45% or 50% greater using an HCI co-feed.

[0068] In certain embodiments of the invention 253fb conversion is at least 60% greater using an HCI co-feed.

[0069] In certain embodiments of the invention 253fb conversion is at least 70% greater using an HCI co-feed.

[0070] In certain embodiments of the invention 253fb conversion is at least 80% greater using an HCI co-feed.

[0071] In certain embodiment of the invention 253fb conversion is at least 90% greater using an HCI co-feed.

[0072] In certain embodiments of the invention 253fb conversion using an HCI cofeed is about twice that of the 253fb conversion using a nitrogen co-feed.

[0073] In certain embodiments of the invention 253fb conversion using an HCI cofeed is at least about twice that of the 253fb conversion using a nitrogen co-feed. [0074] In certain embodiments of the invention 253fb conversion using an HCI cofeed is greater than twice that of the 253fb conversion using a nitrogen co-feed.

[0075] In certain embodiments of the invention the activated carbon catalyst used in the dehydrochlorination of HCFC-253fb may come from any of the following sources: wood, peat, coal, coconut shells, bones, lignite, petroleum-based residues and sugar. Commercially available carbons which may be used include those sold under the following trademarks: Barneby & Sutcliffe™, Darco™, Nucharm, Columbia JXN™, Columbia LCK™, Calgon™ PCB, Calgon™ BPL, Westvaco™, Norit™, Takeda™ and Barnaby Cheny NB™.

[0076] In certain embodiments of the invention the activated carbon includes a three-dimensional matrix porous carbonaceous material. Examples are those described in U.S. Pat. No. 4,978,649, the disclosure of which is incorporated herein by reference in its entirety. In one embodiment of the invention, the carbon includes three-dimensional matrix carbonaceous materials which are obtained by introducing gaseous or vaporous carbon-containing compounds (e.g., hydrocarbons) into a mass of granules of a carbonaceous material (e.g., carbon black); decomposing the carbon-containing compounds to deposit carbon on the surface of the granules; and treating the resulting material with an activator gas comprising steam to provide a porous carbonaceous material. A carbon-carbon composite material is thus formed.

[0077] In some embodiments of this invention, carbon is an acid washed activated carbon. The carbon can be in the form of powder, granules, or pellets, including but not limited to Carbon COCO Plus (mesh granules 6-12 mesh in size) and a surface area ranging from 900 m²/g to 1400 m²/g.

[0078] The foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention.

EXAMPLE 1

[0079] 8 ml Calgon Coco plus activated carbon (8x10 mesh size) was loaded into a Monel reactor tube (12"L x .5" O.D.-.034" wall .43" I.D.). The carbon is dried at 250°C under N2 purge for2hrs. Then 253fb at 0.46ml/hr (0.00767 ml/min). rate was fed with 3.3 seem HCI for 12.5 hrs. at atmospheric pressure at 250°C. Thereafter, the HCI feed was replaced with 3.5 seem N2 and ran for 12.5hrs. The stream of product was analyzed by online GC at intervals of 75 minutes and the result of analysis is tabulated below.

TABLE 1 - HCI

TABLE 2 - N₂

[0080] The data of Table 1 and Table 2 is graphed in Figures 1A and 1B. Figure 1A compares the 253fb conversion rate versus time using co-feeds of HCI and N₂, whereas Figure 1 B compares the selectivity to HFO-1243zf using co-feeds of HCI and N₂. In each case, using HCI as a co-feed unexpectedly provides much higher conversion. Fig. 1B illustrates greater and more consistent selectivity to HFO-1243zf with the HCI co-feed compared with a nitrogen co-feed. In additional to HFO-1243zf, 1242zf, 253fb, 243db, 254fb, 254eb, 1233xf and optionally 1240xd are detected in the product stream. Example 2

[0081] As with Example 1 , a Monel reactor tube (12"L x .5" O.D.-.034" wall .43" I.D.), was filled with 8 ml Calgon LSI activated carbon (8x10 mesh size) and dried at 250°C under N2 purge for 2hrs. HCI was then fed at 6.45 seem with 0.6ml/hr. of 253fb at atmosphere pressure at 250C for 24hrs, after that HCI feed is replaced with 5.99sccm N2 and run for another 24hrs. The GC result of analysis are shown in graphs of Figure 2A which compares the 253fb conversion rate versus time using cofeeds of HCI and N2, where the conversion rate of 253fb is generally at least 10% higher using HCI as a co-feed compared with nitrogen as a co-feed. Fig. 2B compares the selectivity to HFO-1243zf using HCI and nitrogen co-feeds. In additional to HFO-1243zf, 1242zf, 253fb, 243db, 1240xd , 254fb, 254eb and 1233xf are detected in the product stream.

OTHER EMBODIMENTS

[0082] Process embodiment A comprising contacting a 3-chloro-1 , 1 , 1- trifluoropropane (HCFC-253fb) feed, HCI and a catalyst comprising activated carbon in the vapor phase to produce 1 ,1 ,1 -trifluoropropene at a co-feed/feed (HCI:253fb) ratio of between 0.25:1 up to 50:1 , preferably 3-chloro-1 , 1 ,1 -trifluoropropane and HCI contact the catalyst in a reactor at a temperature between 150°C and about 350°C. more preferably 3-chloro- 1 ,1 ,1 -trifluoropropane and HCI contact the catalyst in a reactor at a temperature between 175°C and about 300°C or 3-chloro-1 ,1 ,1- trifluoropropane and HCI contact the catalyst in a reactor at a temperature between 200°C and about 250°C.

[0083] The process embodiment A wherein the activated carbon has a surface area ranging from 900 m2/g to 1200 m2/g.

[0084] The process embodiment A which is a dehydrochlorination and conducted at a pressure selected from one of superatmospheric, atmospheric and subatmospheric pressures, preferably where the pressure is atmospheric.

[0085] The process embodiment A, wherein the HCI: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 the HCFC-253fb conversion (dehydrochlorination) is at least one of 30%, 35%, 40%, 45% 50%, 55%, 60%, 65% or 70%. [0086] The process embodiment A wherein selectivity to HFO-1243zf is at least 98%.

[0087] Process embodiment B comprising using the composition of process embodiment A.

[0088] Composition embodiment A 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), optionally comprising one of greater than 50 mole percent 1,1 ,1- trifluoropropene based on the total amount of the compositions, greater than 60 mole percent 1,1,1 -trifluoropropene based on the total amount of the compositions, greater than 70 mole percent 1 ,1 ,1 -trifluoropropene based on the total amount of the compositions, greater than 80 mole percent 1 ,1 ,1-trifluoropropene based on the total amount of the compositions.

[0089] The composition embodiment A wherein the additional compounds comprise at least two or more of 243db, 1240xd, 254fb, 254eb and1233xf.

[0090] Process embodiment C of improving conversion of 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 (HCI) or enhancing conversion of 3-chloro-1 , 1 ,1 -trifluoropropane (HCFC-253fb) in the presence of a catalyst to 1,1,1-trifluoropropene (HFO-1243zf) by contacting 3-chloro-1 ,1 ,1- trifluoropropane (HCFC-253fb) with HCI in the gas phase.

[0091] The process embodiment C wherein the HCI: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.

[0092] Process embodiment D of thermally dehydrochlorinating 3-chloro-1 ,1 , 1- trifluoropropane (HCFC-253fb) in the presence of HCI and 1,1,1-trifluoropropene (HFO-1243zf). [0093] Process embodiment E of thermally dehydrochlorinating 3-chloro-1 ,1 , 1- trifluoropropane (HCFC-253fb) at a temperature less than 300°C, or less than 275°C but greater than 200°C to produce in the presence of HCI.

[0094] Process embodiment F of increasing the production of 1 ,1 ,1- trifluoropropene (HFO-1243zf) by dehydrochlorinating 3-chloro-1 ,1 ,1-trifluoropropane (HCFC-253fb) in the presence of hydrogen chlorine instead of nitrogen at temperatures less than 300°C, or less than 275°C but greater than 200°C.

[0095] Process embodiment G comprising: Step 1 : 253fb dehydrochlorination over a catalyst in vapor phase with cofeed of HCI to convert to 1243zf; Step 2 1243zf made from Step 1 reacts with Ch in vapor phase, or liquid phase with a catalyst or without a catalyst, or by UV irradiation to convert to 243db; Step 3: 243db made from step 2 is converted to 1233xf in vapor phase with a catalyst or in liquid phase with a caustic with or without presence of a catalyst; Step 4: 1233xf made from step 3 is converted to 244bb by reacting with HF in vapor phase with a catalyst or in liquid phase with a catalyst; Step 5: 244bb made from step 4 is converted to 1234yf in vapor phase with or without a catalyst or in liquid phase with a catalyst or polar solvent, and optionally the product from Steps 1 , 2, 3 and 4 are purified and/or dried before use in the next step.

[0096] The process embodiment G: wherein the HCI: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 HCI:HCFC-253fb feed ratio is between 0.25:1 and 50:1., and/or, wherein the catalyst comprises activated carbon using a co-feed/feed ratio of between 0.25:1 up to 50:1 , and /or wherein 3-chloro-1 ,1 ,1-trifluoropropane and HCI contact the catalyst in a reactor at a temperature between 150°C and about 350°C, and/or 3-chloro- 1 ,1 ,1 -trifluoropropane and HCI contact the catalyst in a reactor at a temperature between 175°C and about 300°C, and/or wherein 3-chloro-1 , 1 , 1- trifluoropropane and HCI contact the catalyst in a reactor at a temperature between 200°C and about 250°C., and/or wherein the activated carbon has a surface area ranging from 900 m²/g to 1200 m²/g.

[0097] Composition embodiment A including 1 ,1 ,1 -trifluoropropene (HFO-1243zf), 3-chloro-1 ,1 ,1-trifluoropropane (HCFC-253fb), and at least one or more of: a. between greater than 0 and 0.2 mole percent HCFO-1242zf, b. between greater than 0 and 0.2 mole percent HCFC-243db, c. between greater than 0 and 0.0001 mole percent HCO-1240xd, d. between greater than 0 and 0.03 mole percent HFC-254fb, e. between greater than 0 and 0.3 mole percent HFC-254eb, f. between greater than 0 and 2 mole percent HCFO-1233xf.

[0098] Composition embodiment A including 1,1,1 -trifluoropropene (HFO-1243zf), 3-chloro-1 ,1,1-trifluoropropane (HCFC-253fb), and at least, a. between greater than 0 and 0.2 mole percent HCFO-1242zf, b. between greater than 0 and 0.2 mole percent HCFC-243db, c. between greater than 0 and 0.0001 mole percent HCO-1240xd, d. between greater than 0 and 0.03 mole percent HFC-254fb, and e. between greater than 0 and 2 mole percent HCFO-1233xf.

[0099] Composition embodiment A including 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, between greater than 0 and 0.2 mole percent HCFO-1242zf, between greater than 0 and 0.2 mole percent HCFC-243db, between greater than 0 and 0.0001 mole percent HCO-1240xd, and between greater than 0 and 0.03 mole percent HFC-254fb.

[0100] A system embodiment A including at least first and second reactors respectively converting HCFC-253fb to HFO-1243zf, and HFO-1243zf to HCFC- 243db, or three or more reactors some or all may be operated as adiabatic reactors.

[0101] A system embodiment B comprising first and second catalyst containing reactors respectively comprising overhead product outlets, feed lines in fluid communication with contained sources of 3-chloro-1 ,1 ,1 -trifluoropropane (HCFC- 253fb) and hydrogen chloride, said feed lines also coupled to said first reactor for feeding said 3-chloro-1 ,1,1-trifluoropropane (HCFC-253fb) and hydrogen chloride to said first catalyst containing reactor, and the product outlet associated said first catalyst containing reactor in fluid communication with said second catalyst containing for introducing for 1,1 -trifluoropropene (HFO-1243zf) reaction with halogen gases. [0102] In certain embodiment of the invention catalytic 253fb conversion is at least one of 30%, 35%, 40%, 45% or 50% greater using an HCI co-feed.

[0103] In certain embodiment of the invention catalytic 253fb conversion is at least 60% greater using an HCI co-feed.

[0104] In certain embodiment of the invention catalytic 253fb conversion is at least 70% greater using an HCI co-feed.

[0105] In certain embodiment of the invention catalytic 253fb conversion is at least 80% greater using an HCI co-feed.

[0106] In certain embodiment of the invention catalytic 253fb conversion is at least 90% greater when using an HCI co-feed.

[0107] Process embodiment 1 A comprising contacting a 3-chloro-1 ,1 ,1- trifluoropropane (HCFC-253fb) feed and HCI as a co-feed with a catalyst comprising activated carbon in the vapor phase to produce 1,1,1 -trifluoropropene at a co- feed/feed ratio of between 0.25:1 up to 50:1, optionally the activated carbon has a surface area ranging from 900 m2/g to 1200 m2/g.

[0108] The process embodiment 1 B, wherein 3-chloro- 1 ,1,1 -trifluoropropane and HCI contact the catalyst in a reactor at a temperature 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 about 350°C, optionally the activated carbon has a surface area ranging from 900 m²/g to 1200 m²/g.

[0109] The process embodiment 1C, wherein 3-chloro-1 ,1,1 -trifluoropropane and HCI contact the 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, optionally the activated carbon has a surface area ranging from 900 m²/g to 1200 m²/g.

[0110] The process embodiment 1D, wherein 3-chloro-1 ,1,1 -trifluoropropane and HCI contact the catalyst in a reactor at a temperature between 200°C, 210°C, 220°C or 230°C and about 250°C, optionally the activated carbon has a surface area ranging from 900 m²/g to 1200 m²/g. [0111] The process embodiments 1 A, 1 B, 1 C or 1 D, wherein the process is a dehydrochlorination, optionally (1) wherein the pressure is atmospheric, and/or (2) wherein the HCI 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) and/or wherein the HCFC-253fb conversion is at least one of 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, or 70%.

[0112] The process embodiments 1A, 1 B, 1C or 1 D, wherein the HCI 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 wherein the HCFC-253fb conversion is at least one of 30%, 35%, 40%, 45% 50%, 55%, 60%, 65%, or 70%.

[0113] The process according to any of embodiments 1A, 1 B, 1C or 1 D wherein selectivity to HFO-1243zf is at least 98%.

[0114] A composition provided by any of embodiments 1A, 1 B, 1C or 1D.

[0115] A composition embodiment 2 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).

[0116] A composition embodiment 3 comprising 1 ,1 ,1 -trifluoropropene, 3-chloro- 1 ,1 ,1 -trifluoropropane, and at least one additional member 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.

[0117] Composition embodiments 2 or 3, wherein comprise one of (a) greater than 50 mole percent 1,1,1 -trifluoropropene based on the total amount of the compositions; (b) greater than 60 mole percent 1,1,1 -trifluoropropene based on the total amount of the compositions; (c) greater than 70 mole percent 1 ,1 ,1- trifluoropropene based on the total amount of the compositions; or (d) greater than 80 mole percent 1,1,1-trifluoropropene based on the total amount of the compositions, each optionally including additional compounds selected from at least two or more of 243db, 1240xd, 254fb, 254eb and1233xf.

[0118] A process embodiment 4 of improving conversion of 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 (HCI).

[0119] A process embodiment 5 of enhancing conversion of 3-chloro-1 ,1 ,1- trifluoropropane (HCFC-253fb) in the presence of a catalyst to 1 ,1 ,1 -trifluoropropene (HFO-1243zf) by contacting 3-chloro-1 , 1 ,1 -trifluoropropane (HCFC-253fb) with HCI in the gas phase.

[0120] Process embodiment 4 or 5 wherein the HCI: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 , or between 0.25:1 and 50:1 , or between 0.25:1 and 1.5:1 , or 3:1 and 4:1 and all values and ranges therebetween.

[0121] In the foregoing specification, the concepts have been described with reference to specific embodiments. However, one of ordinary skill in the art appreciates that various modifications and changes can be made without departing from the scope of the invention as set forth in the claims below. Accordingly, the specification is to be regarded in an illustrative rather than a restrictive sense, and all such modifications are intended to be included within the scope of invention.

[0122] It is to be appreciated that certain features are, for clarity, described herein in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any subcombination.

Claims

CLAIMS We claim:

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

2. The process of claim 1, wherein 3-chloro- 1 ,1 ,1 -trifluoropropane and HCI contact the catalyst in a reactor at a temperature between 150°C and about 350°C.

3. The process of claim 1, wherein 3-chloro- 1,1,1 -trifluoropropane and HCI contact the catalyst in a reactor at a temperature between 175°C and about 300°C.

4. The process of claim 1, wherein 3-chloro- 1 ,1 ,1 -trifluoropropane and HCI contact the catalyst in a reactor at a temperature between 200°C and about 250°C.

5. The process of any of claims 1-4 wherein the activated carbon has a surface area ranging from 900 m²/g to 1200 m²/g.

6. The process of 5 wherein the process is a dehydrochlorination.

7. The process of claim 6 where the dehydrochlorination is conducted at a pressure selected from one of superatmospheric, atmospheric and subatmospheric pressures.

8. The process of claim 6, wherein the pressure is superatmospheric.

9. The process of claim 6, wherein the HCI 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 of claim 7 wherein HCFC-253fb conversion is at least one of 30%,

35%, 40%, 45% 50% or 55%.

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

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

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

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

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

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 1 ,1 ,1 -trifluoropropene (HFO-1243zf), 3-chloro-1 , 1 , 1 - trifluoropropane (HCFC-253fb), and at least one additional member selected from 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 of claim 17 comprising greater than 50 mole percent 1,1,1- trifluoropropene based on the total amount of the compositions.

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

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

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

22. The composition of any one of claims 16-22, wherein the additional compounds comprise at least two or more of 243db, 1240xd, 254fb, 254eb and1233xf.

23. A process of improving conversion of 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 (HCI).

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

25. The process of any one of claims 23-24 wherein the HCI: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 of claim 1 wherein the HCI:HCFC-253fb feed ratio is between 0.25:1 and 50:1.

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

28. A composition comprising HCFC-253fb, HCI and optionally, an activated carbon catalyst, wherein the HCI: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 of claim 28, wherein the HCI:HCFC-253fb ratio is between 0.25:1 and 1.5:1.

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

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

32. A process comprising:

Step 1: 253fb dehydrochlorination over a catalyst in vapor phase with cofeed of HCI to convert to 1243zf;

Step 2: 1243zf made from Step 1 reacts with C in vapor phase, or liquid phase with a catalyst or without a catalyst, or by UV irradiation to convert to 243db;

Step 3: 243db made from step 2 is converted to 1233xf in vapor phase with a catalyst or in liquid phase with a caustic with or without presence of a catalyst;

Step 4: 1233xf made from step 3 is converted to 244bb by reacting with HF in vapor phase with a catalyst or in liquid phase with a catalyst; Step 5: 244bb made from step 4 is converted to 1234yf in vapor phase with or without a catalyst or in liquid phase with a caustic, a catalyst or polar solvent, and optionally the product from Steps 1 , 2, 3 and 4 are purified and/or dried before use in the next step.

33. The process of Claim 32 wherein the HCI: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 of claim 32 wherein the HCI:HCFC-253fb feed ratio is between 0.25:1 and 50:1.

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

36. The process of claim 32 wherein 3-chloro-1 ,1 ,1 -trifluoropropane and HCI contact the catalyst in a reactor at a temperature between 150°C and about 350°C.

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

38. The process of claim 32, wherein 3-chloro-1 ,1,1-trifluoropropane and HCI contact the catalyst in a reactor at a temperature between 200°C and about 250°C.

39. The process of Claim 35 wherein the activated carbon has a surface area ranging from 900 m²/g to 1200 m²/g.

40. The process of claim 32 wherein steps 1-5 form an integrated process.