Improved process for preparing 3,3,3-trifluoroprop-1-ene

Abstract

To provide hydrofluoroolefins that can be employed in a wide range of applications, including their use as refrigerants, solvents, foam expansion agents, cleaning agents, aerosol propellants, dielectrics, fire extinguishants, and power cycle working fluids.SOLUTION: A method of preparing a mixture of 3,3,3-trifluoropropene (HFO-1243zf) and 2-chloro-3,3,3-trifluoropropene (HFO-1233xf) comprises reacting a mixture of 3-chloro-1,1,1-trifluoropropane (HCFC-253fb) and 1,1,1-trifluoro-2,3-dichloropropane (HFC-243db) with a base in an aqueous solvent component, in the absence of a phase transfer catalyst, where the aqueous solvent component contains no organic solvent.SELECTED DRAWING: None

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims the benefit of U.S. Provisional Application No. 62 / 469,668 (filed March 10, 2017), the entire disclosure of which is incorporated herein by reference.

[0002] FIELD OF THE INVENTION This application relates to the preparation of 3,3,3-trifluoroprop-1-ene from 3-chloro-1,1,1-trifluoropropane in the presence of a base (e.g., aqueous base) in an aqueous solvent component. The process provided herein is carried out in the absence of a phase transfer catalyst. [Background technology]

[0003] Hydrofluoroolefins (HFOs), which have low ozone depletion potential and low global warming potential, are considered candidates for replacing saturated CFCs (chlorofluorocarbons) and HCFCs (hydrochlorofluorocarbons). HFOs can be used in a wide range of applications, including their use as refrigerants, solvents, foam blowing agents, cleaning agents, aerosol propellants, dielectrics, fire extinguishing agents, and power cycle working fluids. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] U.S. Provisional Application No. 62 / 469,668 Summary of the Invention [Means for solving the problem]

[0005] The present disclosure provides a dehydrohalogenation process in the absence of an organic solvent containing a phase transfer catalyst and a dehydrohalogenation catalyst. Accordingly, the present application provides a process for preparing 3,3,3-trifluoroprop-1-ene, comprising reacting 3-chloro-1,1,1-trifluoropropane with a base in an aqueous solvent component, the reaction being carried out in the absence of a phase transfer catalyst. In some embodiments, the aqueous solvent component comprises 0 to 40 wt. % organic solvent. In some embodiments, the aqueous solvent component does not comprise an organic solvent (i.e., the process is carried out in the absence of an organic solvent).

[0006] In another aspect, the present application further provides a process for preparing a mixture of 3,3,3-trifluoroprop-1-ene (HFO-1243zf) and 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), comprising reacting a mixture of 3-chloro-1,1,1-trifluoropropane (HCFC-253fb) and 1,1,1-trifluoro-2,3-dichloropropane (HCFC-243db) with a base in an aqueous solvent component, wherein the reaction is carried out in the absence of a phase transfer catalyst. In some embodiments, the aqueous solvent component comprises 0-40% organic solvent. In some embodiments, the aqueous solvent component does not comprise an organic solvent (i.e., the process is carried out in the absence of an organic solvent).

[0007] 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. 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. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety, unless a specific passage is cited. In case of conflict, the present specification, including definitions, will control. Furthermore, the materials, methods, and examples are illustrative only and are not intended to be limiting. DETAILED DESCRIPTION OF THE INVENTION

[0008] Historically, phase transfer catalysts (PTCs) have been used to prepare HFOs. While PTCs accelerate the reaction, they also pose environmental concerns due to the need to dispose of these spent catalysts. Furthermore, the use of phase transfer catalysts increases the cost of the dehydrohalogenation reaction, as well as adding complexity and cost to the process workup step because the catalyst must be separated from the organic and aqueous phases.

[0009] Because these can be expensive, eliminating the use of phase transfer catalysts and organic solvent components reduces the cost of these dehydrohalogenation reactions. Additionally, their elimination can make waste disposal easier and less expensive. Furthermore, elimination of phase transfer catalysts can simplify the dehydrohalogenation reaction by reducing the need to recycle and recover catalysts from the process. Finally, because catalysts lower the activation energy of the dehydrohalogenation reaction, there is a high tendency for the dehydrochlorination products to decompose, wasting starting materials. Eliminating phase transfer catalysts in the dehydrohalogenation reaction can reduce this risk. Therefore, to reduce the cost and complexity of the process, there is a need to carry out the dehydrohalogenation reaction in the absence of phase transfer catalysts and organic solvent components.

[0010] The foregoing general description and the following detailed description are exemplary and explanatory only and are not limiting of the invention as defined in the appended claims. Other features and advantages of any one or more of the embodiments will become apparent from the following detailed description and claims.

[0011] Definitions and Abbreviations As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that includes a list of elements is not necessarily limited to those elements, but may include other elements not expressly listed or inherent in such process, method, article, or apparatus. Furthermore, unless expressly stated to the contrary, "or" refers to an inclusive or, not an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or absent), A is false (or absent) and B is true (or present), and both A and B are true (or present).

[0012] Additionally, the use of "a" or "an" is employed to describe elements and components described herein. This is merely for convenience and to give a general sense of the scope of the invention. This description should be interpreted to include one or at least one, and the singular also includes the plural unless it is clear that a different meaning is intended.

[0013] When an amount, concentration, or other value or parameter is given as a range, a preferred range, or a list of upper and / or lower preferred values, these are to be understood as specifically disclosing all ranges formed from any pairing of any upper range value or preferred upper value and any lower range value or preferred lower value, whether or not the ranges are separately disclosed. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints, and to include all integers and fractions within the range.

[0014] As used herein, "consisting essentially of" is used to define compositions, methods, and compositions that include materials, steps, features, components, or elements in addition to those literally disclosed, provided that these additionally included materials, steps, features, components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention, particularly the mechanism of action for achieving any desired result of the inventive process. The terms "consists essentially of" or "consisting essentially of" occupy a middle ground between "comprising" and "consisting of."

[0015] As used herein, the term "alkyl," alone or in combination, includes cyclic or acyclic, and straight-chain or branched alkyl groups, such as methyl, ethyl, n-propyl, i-propyl, or different isomers thereof. For example, an alkyl group may contain 1 to 10 carbon atoms. An alkyl group may be a lower alkyl containing 1 to 6 carbon atoms.

[0016] As defined herein, "aryl," whether used alone or in combination, means an aromatic ring containing 6, 10, 14, or 18 ring carbon atoms. Examples include phenyl, α-naphthyl, β-naphthyl, anthracenyl, and the like.

[0017] By using the term "arylalkyl," it is meant that an alkyl group, as defined herein, is attached to the main chain at one end and to an aryl group at the other end. Examples include benzyl, phenethyl, phenpropyl, and the like.

[0018] The term "heterocyclic," used alone or in combination, refers to an aromatic, partially aromatic, partially saturated, or saturated monocyclic, bicyclic, or tricyclic ring system containing 3 to 14 ring atoms, where one, two, or three of the ring atoms are independently selected from nitrogen, oxygen, and sulfur, and the remaining ring atoms are carbon atoms. A heterocycle may be a fully heteroaromatic or partially heteroaromatic compound, where one of the rings fused to the heterocycle is aromatic. Thus, as used herein, heterocycle includes heteroaromatic compounds. In addition, a heterocycle may contain one or more double bonds, either between two carbons, two nitrogen atoms, or between a nitrogen atom and a carbon atom. The designation aza, oxa, or thio before a heterocyclyl defines that at least a nitrogen, oxygen, or sulfur atom, respectively, is present as a ring atom. The nitrogen atom of a heterocyclic compound may be a basic nitrogen atom. The nitrogen or sulfur atom of a heterocyclic compound may be optionally oxidized to the corresponding N-oxide, S-oxide, or S,S-dioxide. When a heteroaryl is substituted with a hydroxy group, the corresponding tautomer is also included. Representative heterocycles include piperidyl, pyrrolidinyl, piperazinyl, morpholinyl, tetrahydrofuryl, thiomorpholinyl, thiazolidinyl, 1,3-dioxolanyl, 1,4-dioxanyl, tetrahydrothiophenyl, and tetrahydrothiopyranyl. Pyrazinyl, thienyl, isothiazolyl, oxazolyl, pyrazolyl, furanyl, pyrrolyl, 1,2,4-thiadiazolyl, pyridazinyl, quinoxalinyl, phthalazinyl, imidazo[1,2-a]pyridine, imidazo[2,1-b]thiazolyl, benzofuranyl, azaindolyl, benzimidazolyl, benzothienyl, thienopyridyl, thienopyrimidyl, pyrrolopyridyl, imidazopyridyl , benzazindolyl, 1,2,4-triazinyl, benzothiazolyl, imidazolyl, indolyl, indolizinyl, isoxazolyl, isoquinolinyl, isothiazolyl, oxadiazolyl, pyrazinyl, pyridazinyl, pyrazolyl, pyridyl, pyrimidinyl, pyrrolyl, quinazolinyl, quinolinyl, 1,3,4-thiadiazolyl, thiazolyl, thienyl, and triazolyl.

[0019] The term "halogen" means fluoro, chloro, bromo, and iodo.

[0020] As used herein, the term "dehydrohalogenation" refers to a process in which hydrogen and a halogen, such as Cl, Br, or I, on adjacent carbons in a molecule are removed to form the corresponding olefin.

[0021] As used herein, the term "dehydrochlorination" refers to a process in which hydrogen and chlorine on adjacent carbons in a molecule are removed to form the corresponding olefin.

[0022] The term "aqueous solvent" refers to a solvent consisting of water or a mixture of one or more solvents mixed with water. In some embodiments, water is the sole solvent. However, aqueous solvents may also include water mixed with polar solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1,3-butanediol, 1,2-butanediol, acetonitrile, acetaldehyde, acetone, ethylene glycol, propylene glycol, tetrahydrofuran, triethylene glycol, 1,3-propanediol, glycerol, 1,4 dioxane, and the like.

[0023] As defined herein, the term "mixing" refers to the process of stirring the reactants (e.g., 3-chloro-1,1,1-trifluoropropane and base) at a specific mixing power of, for example, about 0.1 to 50 horsepower per 1000 gallons of reaction mixture (e.g., aqueous reaction mixture). The stirring (i.e., mixing) can be carried out, for example, by mechanical means (e.g., a stir bar or shaker such that the reactants are substantially thoroughly mixed with one another under conditions sufficient to dehydrohalogenate 3-chloro-1,1,1-trifluoropropane to produce 3,3,3-trifluoroprop-1-ene), and by other means known in the art or described herein.

[0024] Thus, in some embodiments, mixing is provided by a mechanical agitator. However, mixing power input can alternatively be provided by other methods. These methods are well known in the industry and include using mixing provided by bubbles from a gas added to the container, or using mixing generated within the container by vaporization of a liquid. Mixing can also be provided by drawing liquid from the container to a pump and returning the liquid to the container. A static mixer, rotor-stator head, or other device intended to mix the contents can be present in the liquid circulation path to provide additional mixing power input. Mixing can be provided by a single method or a combination of two or more methods.

[0025] In some embodiments, the reactor agitates the reaction mixture (e.g., 3-chloro-1,1,1-trifluoropropane and base, and, if present, amine) by providing power to an agitator to stir the liquid in the tank. The power input is calculated based on a combination of several parameters, including the geometry of the vessel, the design of the baffles, the design of the impeller, if any, and the speed at which the impeller rotates. This calculation can be performed by one of ordinary skill in the art. In the process described herein, to maximize yield, in one embodiment, the base is mixed together to create small bubbles and a high interfacial layer surface area. An autoclave reactor is an example of a reactor capable of achieving the horsepower per gallon of liquid specified above. In one embodiment, about 0.1 to about 50 horsepower per 1000 gallons of liquid is applied to the agitator, causing the agitator to agitate the reaction mixture, while in another embodiment, about 0.5 to about 40 horsepower per 1000 gallons of liquid is applied to the agitator, causing the agitator to agitate the reaction mixture, and in yet another embodiment, about 1 to about 35 horsepower per 1000 gallons of liquid is applied to the agitator, causing the agitator to agitate the reaction mixture.

[0026] As used herein, "caustic" means a base that can dissociate when placed in water. Examples include alkali metal oxides, hydroxides, or amides, such as sodium or potassium oxide, or sodium or potassium hydroxide, or sodium or potassium amide, or alkaline earth metal hydroxides, alkaline earth metal oxides or amides, alkali metal carbonates, or alkali metal phosphates, or alkali metal carboxylates.

[0027] In one embodiment, the reaction process is carried out in the presence of a base that can dissociate when placed in water. Examples include metal oxides, hydroxides, amides, carbonates, phosphates, or carboxylates. However, as defined, the term "base" excludes amines, including ammonia. Unless otherwise stated, the term "amine" includes ammonia.

[0028] As used herein, the term "metal" in the terms metal hydroxide base, metal carbonate base, metal phosphate base, or metal fluoride base means an alkali metal or alkaline earth metal.

[0029] As used herein, the term "alkali metal hydroxide" refers to a compound or mixture of compounds selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide. In some embodiments, the alkali metal hydroxide is sodium hydroxide.

[0030] As used herein, the term "alkali metal amide" means a compound or mixture of compounds selected from the group consisting of lithium amide, sodium amide, potassium amide, rubidium amide, and cesium amide.

[0031] As used herein, the term "alkaline earth metal hydroxide" means a compound or mixture of compounds selected from the group consisting of beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide.

[0032] As used herein, the term "alkaline earth metal amide" means a compound or mixture of compounds selected from the group consisting of beryllium amide, magnesium amide, calcium amide, strontium amide, and barium amide.

[0033] As used herein, the term "alkali metal carbonate" means a compound or mixture of compounds selected from the group consisting of lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, and cesium carbonate.

[0034] As used herein, the term "alkaline earth metal carbonate" means a compound or mixture of compounds selected from the group consisting of beryllium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, and barium carbonate.

[0035] As used herein, the term "alkali metal oxide" means a compound or mixture of compounds selected from the group consisting of lithium oxide, sodium oxide, potassium oxide, rubidium oxide, and cesium oxide.

[0036] As used herein, the term "alkaline earth metal oxide" means a compound or mixture of compounds selected from the group consisting of beryllium oxide, magnesium oxide, calcium oxide, strontium oxide, and barium oxide.

[0037] As used herein, the term "alkali metal phosphate" means a compound or mixture of compounds selected from the group consisting of lithium phosphate, sodium phosphate, potassium phosphate, rubidium phosphate, and cesium phosphate.

[0038] As used herein, the term "alkaline earth metal phosphate" means a compound or mixture of compounds selected from the group consisting of beryllium phosphate, magnesium phosphate, calcium phosphate, strontium phosphate, and barium phosphate.

[0039] In one embodiment, an amine or ammonia is further present. In one embodiment, the dehydrohalogenation reaction is carried out in the presence of the above-mentioned base and an amine of formula R1R2R3N, where R1, R2, and R3 are as defined above. The alkyl, heterocyclic, aryl, aralkyl, and heterocyclic alkyl groups of R1, R2, and R3 can be substituted or unsubstituted. As used herein, a substituted alkyl group, a substituted heterocyclic group, a substituted aryl group, a substituted aralkyl group, or a substituted heterocyclic alkyl group means that one or more hydrogen atoms on a carbon atom have been replaced with a functional group such as a hydroxyl group, an alkoxy group, a halogen, or an amino group. The amine, as defined herein, can be an aliphatic amine, an aromatic amine, a heterocyclic amine, or a mixture thereof. In some embodiments, the amine is an aliphatic amine.

[0040] In some embodiments, when present, the amine can be a primary amine, a secondary amine, a tertiary amine, or a mixture thereof. In some embodiments, the amine is a primary unsubstituted alkylamine of formula RNH, where R is C-C. 16 In some embodiments, the amine is a primary unsubstituted alkylamine of formula RNH, where R is a C-C unsubstituted alkyl group. Primary unsubstituted alkylamines include methylamine, ethylamine, propylamine, isopropylamine, butylamine, sec-butylamine, tert-butylamine, amylamine, isoamylamine, tert-amylamine, hexylamine, and mixtures thereof.

[0041] In some embodiments, when present, the amine is a secondary unsubstituted alkylamine of formula R1R2NH, where each R1 and R2 is independently a C1-C6 unsubstituted alkyl group. In some embodiments, the amine is a secondary unsubstituted alkylamine of formula R1R2NH, where each R is independently a C1-C3 unsubstituted alkyl group. Examples of secondary unsubstituted alkylamines include dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, di-sec-butylamine, diamylamine, dihexylamine, and mixtures thereof.

[0042] In some embodiments, the amine is a tertiary unsubstituted alkylamine of formula R1R2R3N, where each R1, R2, and R3 is independently a C1-C6 unsubstituted alkyl group. In some embodiments, when present, the amine is a tertiary unsubstituted alkylamine of formula R1R2R3N, where each R1, R2, and R3 is independently a C1-C3 unsubstituted alkyl group. Tertiary unsubstituted alkylamines include trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, trihexylamine, N,N-dimethylethylamine, N,N-dimethylpropylamine, N,N-dimethylbutylamine, and mixtures thereof.

[0043] In other embodiments, if present, the amine is selected from the group consisting of methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, dipropylamine, diisopropylamine, tripropylamine, butylamine, sec-butylamine, tert-butylamine, dibutylamine, tributylamine, di-sec-butylamine, amylamine, isoamylamine, tert-amylamine, dimethylamine, trimethylamine, hexylamine, dihexylamine, trihexylamine, 1,1,3,3-tetramethylbutylamine), N,N-dimethylethylamine, N,N-dimethylpropylamine, N,N-dimethylbutylamine, and mixtures thereof.

[0044] In other embodiments, the amine has one, two, or three substituted alkyl groups thereon, which may be the same or different, and in which one or more hydrogens on the carbon atom are replaced with a hydroxyl group. Examples of such amines include ethanolamine (HNCHCHOH), diethanolamine, triethanolamine, tris(hydroxymethyl)aminomethane ((HOCH)CNH), 2-(methylamino)ethanol (CHNHCHCHOH), 2-(ethylamino)ethanol (CHCHNHCHCHOH), 2-(propylamino)ethanol (CHCHCHNHCHCHOH), 2-(isopropylamino)ethanol ((CH)CHNHCHCHOH), 2-(butylamino)ethanol (CH(C 2-(tert-butylamino)ethanol ((CH)CNHCHCHOH), triisopropanolamine ([CHCH(OH)CH]N), N,N-dimethylethanolamine (HOCHCHN(CH)), 1-dimethylamino-2-propanol ((CH)NCHCH(OH)CH), 3-dimethylamino-1-propanol ((CH)N(CH)OH), 2-amino-2-methyl-1-propanol ((CH)C(NH)CHOH), and mixtures thereof.

[0045] In still other embodiments, one of R1, R2, and R3 of the amine has a C1-C6 substituted alkyl group thereon, where one or more hydrogens on the carbon atom are replaced with a hydroxyl group, and the remaining groups are replaced with hydrogen and C1-C6 alkyl groups. 16Examples of such amines include ethanolamine (HNCHCHOH), tris(hydroxymethyl)aminomethane ((HOCH)CNH), 2-(methylamino)ethanol (CHNHCHCHOH), 2-(ethylamino)ethanol (CHCHNHCHCHOH), 2-(propylamino)ethanol (CHCHCHNHCHCHOH), 2-(isopropylamino)ethanol ((CH)CHNHCHCHOH), and 2-(butylamino)ethanol. (CH3(CH2)3NHCH2CH2OH), 2-(tert-butylamino)ethanol ((CH3)3CNHCH2CH2OH), N,N-dimethylethanolamine (HOCH2CH2N(CH3)2), 1-dimethylamino-2-propanol ((CH3)2NCH2CH(OH)CH3), 3-dimethylamino-1-propanol ((CH3)2N(CH2)3OH), 2-amino-2-methyl-1-propanol ((CH3)2C(NH2)CH2OH), and mixtures thereof. In some embodiments, the R1, R2, and R3 groups of at least one amine are C1-C6 substituted alkyl groups, where one or more hydrogens on a carbon atom are replaced by an amino group and the remaining groups are replaced by hydrogen and C1-C6 substituted alkyl groups. 16 unsubstituted alkyl groups. Examples of such amines include 3-(dimethylamino)propylamine ((CH3)2N(CH2)3NH2), 3-(diethylamino)propylamine ((C2H5)2N(CH2)3NH2), and mixtures thereof.

[0046] In some embodiments, when present, the amine is a polyamine. Examples of polyamines include ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,4-diaminobutane, 1,3-diaminopentane, 1,5-diaminopentane, 1,6-diaminohexane, 2-methyl-1,5-pentanediamine, spermidine (N-(3-aminopropyl)butane-1,4-diamine), spermine (N,N'-bis(3-aminopropyl)butane-1,4-diamine), diethylenetriamine, triethylenetetramine, and mixtures thereof.

[0047] In some embodiments, the amine, when present, is a heterocyclic amine. Examples of heterocyclic amines include pyrrolidine, pyrroline (including 1-pyrroline, 2-pyrroline, and 3-pyrroline), piperidine, piperazine, morpholine, imidazole, pyrazole, pyridine, pyrimidine, pyridazine, pyrazine, pyridine, bipyridine (including 2,2'-bipyridine, 4,4'-bipyridine, 2,3'-bipyridine, and 3,4'-bipyridine, etc.), and mixtures thereof.

[0048] In other embodiments, the amine, when present, is hydrazine (NHNH), a hydrazine derivative such as an alkylhydrazine or arylhydrazine or aralkylhydrazine, etc., and mixtures thereof. Examples of hydrazine derivatives include methylhydrazine (CHNHNH), 1,1-dimethylhydrazine ((CH)NNH), 1,2-dimethylhydrazine (CHNHNHCH), phenylhydrazine, 2,4-dinitrophenylhydrazine, and mixtures thereof.

[0049] In some embodiments, the amine, when present, is an aromatic amine. Examples of aromatic amines include aniline, o-toluidine, m-toluidine, p-toluidine, xylidine, 2,4,6-trimethylaniline, o-anisidine, m-anisidine, p-anisidine, N-methylaniline, N,N-dimethylaniline, N-ethylaniline, N,N-diethylaniline, and mixtures thereof.

[0050] In one embodiment, mixtures of any of the above amines may also be used in the present disclosure.

[0051] In some embodiments, the amine, when present, is selected from the group consisting of heterocyclic amines, hydrazines, and derivatives thereof, and mixtures thereof. In some embodiments, the amine is a heterocyclic amine, and mixtures thereof.

[0052] In one embodiment, one of R1, R2, and R3 is hydrogen, and the other of R1, R2, and R3 is independently lower alkyl. In one embodiment, R2 and R3 can be the same or different. In another embodiment, R1, R2, and R3 are the same as or different from hydrogen and are other than hydrogen. For example, R1, R2, and R3 are independently lower alkyl. In yet another embodiment, R1 is phenyl, alkyl, pyridine, or alkyl-substituted pyridine, and R2 and R3 are as defined above. In another embodiment, the amine is hydrazine.

[0053] In one embodiment, the amine, when present, is a trialkyl or dialkyl amine, and preferred amines are trialkyl amines.

[0054] It should be noted that all combinations and permutations of R1, R2 and R3 are contemplated.

[0055] In one embodiment, the molar ratio of amine to halofluoroalkane, if present, ranges from about 0.02 to about 3. In one embodiment, the molar ratio ranges from about 0.05 to about 0.5, and in another embodiment, the molar ratio ranges from about 0.05 to about 0.25.

[0056] Additionally, in one embodiment, the molar ratio of amine to base, if present, ranges from about 0.05 to about 3, in another embodiment from about 0.05 to about 1, and in yet a further embodiment from about 0.05 to about 0.5.

[0057] As described herein, the process of the present application is carried out in the absence of a catalyst. As used herein, the term "catalyst" refers to a substance that accelerates a chemical reaction but is not consumed by the reaction, and thus can be recovered chemically unchanged at the end of the reaction. A phase transfer catalyst is a heterogeneous catalyst that promotes the transfer of reactants from one phase to another phase where the reaction occurs. For example, a phase transfer catalyst is a catalyst that promotes the transfer of ionic compounds into an organic phase, e.g., from an aqueous phase. When water is used as a solvent, the aqueous or inorganic phase exists as a result of a base (e.g., an alkali metal hydroxide), and the organic phase exists as a result of a (chloro)fluorocarbon. The phase transfer catalyst promotes the reaction of these different components. Various phase transfer catalysts can function in different ways, but their mechanism of action does not determine their usefulness in the present invention, as long as they promote the dehydrohalogenation reaction. For example, the process provided herein may be carried out in the absence of an ionic or neutral phase transfer catalyst. In some embodiments, the processes provided herein are carried out in the absence of a phase transfer catalyst selected from the group consisting of crown ethers, onium salts, cryptands, and polyalkylene glycols and derivatives thereof (e.g., fluorinated derivatives thereof). In some embodiments, the processes provided herein are carried out in the absence of a phase transfer catalyst as provided in International Patent Application No. PCT / US2016 / 050918, the disclosure of which is incorporated herein by reference in its entirety.

[0058] Derivatives of the above crown ethers are also considered phase transfer catalysts and are excluded, such as dibenzyl-18-crown-6, dicyclohexanyl-18-crown-6, dibenzyl-24-crown-8, and dibenzyl-12-crown-4. Other compounds similar to crown ethers that differ by the replacement of one or more of the oxygen atoms with other types of donor atoms, particularly N or S, are also excluded. Fluorinated derivatives, such as compounds in which one or more of the hydrogen atoms are replaced by fluorine, are also excluded.

[0059] Cryptands are another class of compounds that are excluded. These are three-dimensional polymacrocyclic chelators formed by linking bridgehead structures with chains containing appropriately spaced donor atoms. The donor atoms in the bridges can all be O, N, or S, or the compounds can be mixed-donor macrocycles in which the bridge strands contain a combination of such donor atoms. Cryptands that contain bicyclic molecules resulting from linking nitrogen bridgeheads with chains of (--OCH2CH2--) groups are excluded, for example, [2.2.2-cryptand (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane, available under the trade names Kryptand 222 and Kryptofix 222).

[0060] Any type of onium salt, including quaternary phosphonium salts and quaternary ammonium salts, useful as catalysts is excluded. Specific examples of such phosphonium salts and quaternary ammonium salts that are excluded include tetramethylammonium chloride, tetramethylammonium bromide, benzyltriethylammonium chloride, methyltrioctylammonium chloride (commercially available under the trade names Aliquat 336 and Adogen 464), tetra-n-butylammonium chloride, tetra-n-butylammonium bromide, tetra-n-butylammonium hydroxide sulfate, tetra-n-butylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium chloride, triphenylmethylphosphonium bromide, triphenylmethylphosphonium chloride, and benzyltriethylammonium chloride.

[0061] Other onium salts that exhibit high temperature stability (e.g., up to about 200°C), such as 4-dialkylaminopyridinium salts, tetraphenyllarsonium chloride, bis[tris(dimethylamino)phosphine]iminium chloride, and tetrakis[tris(dimethylamino)phosphineimino]phosphonium chloride, are also excluded.

[0062] Also excluded are polyalkylene glycol compounds useful as phase transfer catalysts, such as those of formula R 6 O(R 5 O) m R 7 A polyalkylene glycol compound represented by the formula: 5 is C1~C 10 is an alkylene group, and R 6 and R 7 each independently represents H, C1 to C 10 alkyl groups, aryl groups (i.e., aromatic groups containing 6, 10, or 14 ring carbon atoms, or heteroaryl groups containing 5 to 14 ring atoms and 1 to 3 heteroatoms selected from N, O, and S, with the remaining ring atoms being carbon atoms, e.g., phenyl, naphthyl, or pyridinyl), or arylalkyl groups (e.g., benzyl or C 1~10Also excluded are polyalkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, diisopropylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, and tetramethylene glycol; monoalkyl glycol ethers of such glycols such as monomethyl, monoethyl, monopropyl, and monobutyl ethers; dialkyl ethers of such glycols such as tetraethylene glycol dimethyl ether and pentaethylene glycol dimethyl ether; phenyl ethers; benzyl ethers; and polyalkylene glycols such as polyethylene glycol (average molecular weight about 300) and polyethylene glycol (average molecular weight about 400); and dialkyl (e.g., dimethyl, dipropyl, dibutyl) ethers of such polyalkylene glycols.

[0063] The following abbreviations may be used throughout this application: CFCs: Chlorofluorocarbons HFO: Hydrofluoroolefin HCFC: Hydrochlorofluorocarbon HFO-1243zf (i.e., 1243zf): 3,3,3-trifluoroprop-1-ene HFO-1234yf (i.e., 1234yf): 2,3,3,3-tetrafluoroprop-1-ene HCFC-243db: 1,1,1-trifluoro-2,3-dichloropropane HCFC-244bb: 2-chloro-1,1,1,2-tetrafluoropropane HCFC-253fb (i.e., 253fb): 3-chloro-1,1,1-trifluoropropane HCFO-1233xf (i.e., 1233xf): 2-chloro-3,3,3-trifluoroprop-1-ene HFC-254fb: (i.e., 254fb): 1,1,1,3-tetrafluoropropane HFC-245cb: 1,1,1,2,2-pentafluoropropane PTC: Phase transfer catalyst psig: pounds per square inch gauge RPM: Revolutions per minute

[0064] Process for preparing 3,3,3-trifluoroprop-1-ene Accordingly, the present application provides a process for preparing 3,3,3-trifluoroprop-1-ene (i.e., "HFO-1243zf" or "1243zf"), which comprises reacting 3-chloro-1,1,1-trifluoropropane (i.e., "HCFC-253fb" or "253fb") with a base, wherein the reaction is carried out in the absence of a phase transfer catalyst. A schematic representation of the process provided herein is shown in Scheme 1 below.

[0065] [ka]

[0066] Because phase transfer catalysts (e.g., dehydrohalogenation catalysts such as dehydrochlorination acid catalysts) are not used in the processes described herein, the cost of the reaction is minimized because these catalysts can be expensive. These catalysts must be separated from the product, are difficult to dispose of, and add additional expense to the catalyst system. The processes provided herein, which are carried out in the absence of a catalyst, do not have this additional expense. Furthermore, the elimination of phase transfer catalysts simplifies the dehydrohalogenation reaction by reducing the need to recycle and recover these catalysts from the process. Finally, because catalysts lower the activation energy of the dehydrohalogenation reaction and the dehydrohalogenation products are more prone to decomposition, wasting starting materials, the elimination of phase transfer catalysts in the dehydrohalogenation reaction reduces this risk.

[0067] In some embodiments, the reaction is carried out in the absence of a phase transfer catalyst. In some embodiments, the reaction is carried out in an aqueous solvent component. In some embodiments, the reaction is carried out in the absence of a phase transfer catalyst in an aqueous solvent component. In some embodiments, the reaction is carried out in water in the absence of a phase transfer catalyst.

[0068] In some embodiments, the reaction is carried out in the absence of a phase transfer catalyst, and the aqueous solvent component comprises 0-40 wt% organic solvent. In some embodiments, the reaction is carried out in the absence of a phase transfer catalyst, and the aqueous solvent component comprises 0-30 wt% organic solvent. In some embodiments, the reaction is carried out in the absence of a phase transfer catalyst, and the aqueous solvent component comprises 0-20 wt% organic solvent. In some embodiments, the reaction is carried out in the absence of a phase transfer catalyst, and the aqueous solvent component comprises 0-10 wt% organic solvent. In some embodiments, the reaction is carried out in the absence of a phase transfer catalyst, and the aqueous solvent component does not comprise an organic solvent. In some embodiments, the reaction is carried out in the absence of a phase transfer catalyst and an organic solvent component selected from an aliphatic alcohol, such as methanol, ethanol, n-propanol, isopropanol, or butanol.

[0069] In some embodiments, the reaction is carried out as a liquid phase reaction, hi some embodiments, the reaction is carried out in the presence of water.

[0070] Representative bases useful in the processes provided herein include metal bases such as metal oxides (e.g., alkali metal oxides or alkaline earth metal oxides), metal hydroxides (e.g., alkali metal hydroxides or alkaline earth metal hydroxides), metal amides (e.g., alkali metal amides or alkaline earth metal amides), metal carbonates (e.g., alkali metal carbonates or alkaline earth metal carbonates), or metal phosphates (e.g., alkali metal phosphates or alkaline earth metal phosphates). In some embodiments, the metal base is a transition metal base (e.g., zinc hydroxide). Representative metals included in the metal bases provided herein include, but are not limited to, sodium, potassium, lithium, cesium, calcium, zinc, and the like.

[0071] In some embodiments, the base is an alkali metal hydroxide.

[0072] In some embodiments, the base is mixed with water to form an aqueous base (e.g., an aqueous base suspension) or an aqueous base solution. In some embodiments, the base is an aqueous base.

[0073] In some embodiments, the base is a metal hydroxide base, a metal carbonate base, a metal phosphate base, or a metal fluoride base.

[0074] In some embodiments, the base is an alkali metal hydroxide base, an alkaline earth metal hydroxide base, an alkali metal carbonate base, an alkali metal phosphate base, or an alkali metal fluoride base.

[0075] In some embodiments, the base is an alkali metal hydroxide base.

[0076] In some embodiments, the base is NaOH, KOH, LiOH, CsOH, Ca(OH), Zn(OH), NaCO, KCO, KPO, NaPO, KF, or CsF.

[0077] Preferably, the base is KOH or NaOH.

[0078] In some embodiments, the base is NaOH.

[0079] In some embodiments, the base is KOH.

[0080] In some embodiments, the base is aqueous NaOH.

[0081] In some embodiments, the base is aqueous KOH.

[0082] In some embodiments, about 0.5 to about 10 molar equivalents of base are used based on 1 molar equivalent of 3-chloro-1,1,1-trifluoropropane. In some embodiments, about 1 to about 2 molar equivalents of base are used based on 1 molar equivalent of 3-chloro-1,1,1-trifluoropropane. In some embodiments, about 0.01 to about 5 molar equivalents of base are used based on 1 molar equivalent of 3-chloro-1,1,1-trifluoropropane. In some embodiments, about 0.02 to about 4 molar equivalents of base are used based on 1 molar equivalent of 3-chloro-1,1,1-trifluoropropane. In some embodiments, about 0.02 to about 2 molar equivalents of base are used based on 1 molar equivalent of 3-chloro-1,1,1-trifluoropropane. In some embodiments, about 0.05 to about 1.5 molar equivalents of base are used based on 1 molar equivalent of 3-chloro-1,1,1-trifluoropropane.

[0083] In some embodiments, the reaction is carried out at a temperature of about 20°C to about 100°C, e.g., about 20°C to about 100°C, about 20°C to about 80°C, about 20°C to about 60°C, about 20°C to about 40°C, about 20°C to about 30°C, about 30°C to about 100°C, about 30°C to about 80°C, about 30°C to about 60°C, about 30°C to about 40°C, about 40°C to about 100°C, about 40°C to about 80°C, about 40°C to about 60°C, about 60°C to about 100°C, about 60°C to about 80°C, or about 80°C to about 100°C.

[0084] In some embodiments, the reaction is carried out at a temperature of about 35°C to about 80°C.

[0085] In some embodiments, the reaction is carried out at a temperature of about 35°C to about 65°C.

[0086] In some embodiments, the reaction is carried out at a temperature of about 55°C to about 65°C.

[0087] In some embodiments, the reaction is carried out at a temperature of about 30°C to about 40°C.

[0088] In some embodiments, the reaction is carried out at a pressure of about -10 psig to about 500 psig. In some embodiments, the reaction is carried out at a pressure of about -10 psig to about 230 psig, e.g., -10 psig to about 230 psig, -10 psig to about 150 psig, -10 psig to about 125 psig, -10 psig to about 100 psig, -10 psig to about 75 psig, -10 psig to about 50 psig, -10 psig to about 25 psig, -10 psig to about 0 psig, 0 psig to about 150 psig, 0 psig to about 125 psig, 0 psig to about 100 psig, 0 psig to about 75 psig, 0 psig to about 50 psig, or 0 psig to about 25 psig. The pressure is typically 25 psig to about 150 psig, 25 psig to about 125 psig, 25 psig to about 100 psig, 25 psig to about 75 psig, 25 psig to about 50 psig, 50 psig to about 150 psig, 50 psig to about 125 psig, 50 psig to about 100 psig, 50 psig to about 75 psig, 75 psig to about 150 psig, 75 psig to about 125 psig, 75 psig to about 100 psig, 100 psig to about 150 psig, 100 psig to about 125 psig, or 125 psig to about 150 psig.

[0089] In some embodiments, the reaction is carried out at a pressure of from about 5 psig to about 230 psig.

[0090] In some embodiments, the reaction is carried out at a pressure of from about 5 psig to about 150 psig.

[0091] In some embodiments, the reaction includes combining 3-chloro-1,1,1-trifluoropropane and a base at a power of about 0.1 to about 50 horsepower per 1000 gallons of reaction mixture, e.g., about 0.1 to about 50, about 0.1 to about 40, about 0.1 to about 30, about 0.1 to about 20, about 0.1 to about 10, about 0.1 to about 1, about 1 to about 50, about 1 to about 40, about 1 to about 30, about 1 to about 20, about 1 to about 10, about 10 to about 50, about 10 to about 40, about 10 to about 30, about 10 to about 20, about 20 to about 50, about 20 to about 40, about 20 to about 30, about 30 to about 50, about 30 to about 40, or about 40 to about 50 horsepower per 1000 gallons of reaction mixture.

[0092] In some embodiments, the reaction comprises agitating 3-chloro-1,1,1-trifluoropropane and a base at a mixing power of about 0.5 to about 40 horsepower per 1000 gallons of reaction mixture.

[0093] In some embodiments, the reaction comprises agitating 3-chloro-1,1,1-trifluoropropane and a base at a mixing power of about 1 to about 35 horsepower per 1000 gallons of reaction mixture.

[0094] In some embodiments, the reaction is carried out at a temperature of about 35° C. to about 80° C. and a pressure of about 5 psig to about 230 psig.

[0095] In some embodiments, the reaction is carried out at a temperature of about 55° C. to about 80° C. and a pressure of about 5 psig to about 230 psig.

[0096] In some embodiments, the reaction is carried out at a temperature of about 35° C. to about 80° C. and a pressure of about 5 psig to about 150 psig.

[0097] In some embodiments, the reaction is carried out at a temperature of about 30° C. to about 80° C. and a pressure of about 5 psig to about 150 psig.

[0098] The present application further provides a process for preparing 3,3,3-trifluoroprop-1-ene, comprising reacting 3-chloro-1,1,1-trifluoropropane with aqueous NaOH, wherein the reaction is carried out at a temperature of about 35° C. to about 80° C. and a pressure of about 5 psig to about 150 psig, and wherein the reaction is carried out in the absence of a phase transfer catalyst and an organic solvent component.

[0099] In some embodiments, the reaction is carried out at a pressure of from about 5 psig to about 150 psig.

[0100] In some embodiments, 3-chloro-1,1,1-trifluoropropane is prepared by reacting 1,1,1,3-tetrachloropropane with hydrofluoric acid. In some embodiments, 3-chloro-1,1,1-trifluoropropane is produced as a by-product, intermediate, or by-product during the process of preparing HFO-1243zf.

[0101] In some embodiments, 3-chloro-1,1,1-trifluoropropane is prepared by reacting 1,1,1-trifluoropropane with Cl 2 .

[0102] The processes described herein may be carried out in the presence of an inert gas, such as He, Ar, or N, in the presence or absence of an amine. In some embodiments, an inert gas is co-fed with the starting materials into the reactor.

[0103] In one embodiment, the processes described herein, with or without the presence of an amine, are carried out in the liquid phase in an aqueous solvent using well-known chemical engineering methods, such as a continuous process, a batch process, a semi-continuous process, or a combination thereof.

[0104] Under the conditions described, and in all cases of continuous, batch, or semi-continuous operation, the reaction is completed relatively quickly after initiation. In one embodiment, a reaction time of up to about 4 hours is sufficient. For example, in one embodiment, the reaction time ranges from about 1 to about 120 minutes, while in another embodiment, the reaction time ranges from about 3 to about 60 minutes, and in yet another embodiment, the reaction time ranges from about 5 to about 30 minutes.

[0105] The 3,3,3-trifluoroprop-1-ene is isolated using separation techniques well known in the art, such as distillation, chromatography, extraction, etc. In some embodiments, the 3,3,3-trifluoroprop-1-ene can be isolated by distillation directly from the reaction vessel.

[0106] 3,3,3-Trifluoroprop-1-ene can be used to prepare additional compounds, including HFO-1234yf, which are useful in a variety of applications. Thus, in some embodiments, the process further comprises reacting 3,3,3-trifluoroprop-1-ene with chlorine to make 2,3-dichloro-1,1,1-trifluoropropane (HCFC-243db), which is subsequently dehydrochlorinated to form 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), which is subsequently reacted with HF to form 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb), and finally dehydrochlorinated to form 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0107] In some embodiments, the present application further provides chlorinating 3,3,3-trifluoropropene to form 1,1,1-trifluoro-2,3-dichloropropane (HCFC-243db). In some embodiments, chlorinating comprises reacting with chlorine or HCl / oxygen.

[0108] In some embodiments, the process for preparing HCFC-243db is that disclosed in International Patent Publication No. 2015095497, which is incorporated herein by reference in its entirety.

[0109] Thus, in some embodiments, the process further comprises contacting 3,3,3-trifluoropropene with chlorine in the liquid phase, in the absence or presence of a catalyst, with or without exposure to ultraviolet light, to form 1,1,1-trifluoro-2,3-dichloropropane (HCFC-243db).

[0110] In some embodiments, the catalyst comprises at least one metal halide, wherein the metal is a metal from Groups 13, 14, or 15 of the periodic table, a transition metal, or a combination thereof. In some embodiments, the metal halide is supported on activated carbon. In some embodiments, the activated carbon is acid-washed or caustic-washed. In some embodiments, the metal is nickel, chromium, iron, scandium, yttrium, lanthanum, titanium, zirconium, hafnium, vanadium, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, cobalt, palladium, copper, zinc, tantalum, aluminum, tin, or lead. In some embodiments, the metal halide is a nickel halide, an iron halide, or a chromium halide. In some embodiments, the halide is a chloride. In some embodiments, the metal halide is a nickel chloride, an iron halide, or a chromium halide.

[0111] In some embodiments, the chlorination occurs in the vapor phase with or without a catalyst. In some embodiments, the chlorination is carried out at a temperature ranging from about 80° C. to about 200° C., a pressure ranging from about 10 psig to about 100 psig, and a molar ratio of 3,3,3-trifluoropropene to chlorine gas ranging from about 1:0.02 to about 1:1.

[0112] The present application further provides a process for preparing 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), comprising dehydrochlorinating 1,1,1-trifluoro-2,3-dichloropropane (HCFC-243db) to form 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf).

[0113] The present application also provides a process for preparing 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), comprising reacting 1,1,1-trifluoro-2,3-dichloropropane (HCFC-243db) with a caustic to form 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf).

[0114] In some embodiments, the process for preparing HCFO-1233xf is that disclosed in International Patent Publication No. 2012115957, which is incorporated herein by reference in its entirety.

[0115] Thus, in some embodiments, the process further comprises contacting 1,1,1-trifluoro-2,3-dichloropropane (HCFC-243db) with a catalyst in a reaction zone to produce a product mixture comprising 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), wherein the catalyst is supported on carbon and M is K, Na, or Cs, and Y is F, Cl, or Br. In some embodiments, the carbon is activated carbon. In some embodiments, the carbon is acid-washed activated carbon. In some embodiments, M is K and Y is F or Cl.

[0116] In some embodiments, the temperature in the reaction zone is from about 140°C to about 400°C. In some embodiments, the temperature in the reaction zone is from about 150°C to about 250°C. In some embodiments, the temperature in the reaction zone is from about 175°C to about 225°C.

[0117] In some embodiments, the product selectivity to 2-chloro-3,3,3-trifluoropropene is at least 90 mole %. In some embodiments, the product selectivity to 2-chloro-3,3,3-trifluoropropene is at least 95 mole %. In some embodiments, the dehydrochlorination selectivity to 2-chloro-3,3,3-trifluoropropene is at least 90 mole %.

[0118] In some embodiments, the process for preparing HCFO-1233xf is that disclosed in U.S. Patent Application No. 20120215035, which is incorporated herein by reference in its entirety.

[0119] Thus, in some embodiments, the process further comprises reacting 1,1,1-trifluoro-2,3-dichloropropane (HCFC-243db) with a catalyst in the reaction zone to produce a product mixture comprising 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf).

[0120] In some embodiments, the process further comprises contacting 1,1,1-trifluoro-2,3-dichloropropane (HCFC-243db) with a chromium oxyfluoride catalyst in a reaction zone to produce a product mixture comprising 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf).

[0121] In some embodiments, the process is carried out in the presence of HF. In some embodiments, the molar ratio of HF to 2-chloro-3,3,3-trifluoropropene in the reaction zone is less than or equal to 0.9.

[0122] In some embodiments, the temperature in the reaction zone is from about 200°C to about 500°C. In some embodiments, the temperature in the reaction zone is from about 275°C to about 450°C.

[0123] In some embodiments, the product selectivity to 2-chloro-3,3,3-trifluoropropene is at least 90 mole %. In some embodiments, the dehydrochlorination selectivity to 2-chloro-3,3,3-trifluoropropene is at least 95 mole %.

[0124] The present application further provides a process for preparing 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb), comprising hydrofluorinating 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) with HF to form 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb).

[0125] In some embodiments, the process for preparing HCFC-244bb is that disclosed in U.S. Patent Application No. 20140275648, which is incorporated herein by reference in its entirety.

[0126] Thus, in some embodiments, the process further comprises contacting 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) with HF in the presence of a fluorination catalyst in a plurality of reaction zones under conditions effective to produce a composition comprising 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) and less than about 2 wt. % 1,1,1,2,2-pentafluoropropane (HFC-245cb).

[0127] In some embodiments, the composition produced comprises less than about 1 wt% HFC-245cb. In some embodiments, the composition produced further comprises less than about 5 wt% unreacted HCFO-1233xf. In some embodiments, the composition produced further comprises less than about 2 wt% unreacted HCFO-1233xf.

[0128] In some embodiments, greater than about 95% of the HCFO-1233xf is converted to HCFC-244bb. In some embodiments, greater than about 98% of the HCFO-1233xf is converted to HCFC-244bb.

[0129] In some embodiments, the multiple reaction zones comprise multiple reactors operated in series. In some embodiments, the multiple reactors comprise at least a first and a second reactor operated in series.

[0130] In some embodiments, the fluorination catalyst is selected from the group consisting of Lewis acids, transition metal halides, transition metal oxides, Group IVb metal halides, Group Vb metal halides, or combinations thereof. In some embodiments, the fluorination catalyst is selected from the group consisting of SbCl, SbCl, SbF, SnCl, TaCl, TiCl, NbCl, MoCl, FeCl, fluorinated species of SbCl, fluorinated species of SnCl, fluorinated species of TaCl, fluorinated species of TiCl, fluorinated species of NbCl, fluorinated species of MoCl, fluorinated species of FeCl, or combinations thereof.

[0131] In some embodiments, the fluorination catalyst is the same or different in each of the multiple reaction zones.

[0132] In another embodiment, the process comprises: a) contacting, in a first reaction zone, feedstock 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) with HF and a first fluorination catalyst under conditions effective to produce a first composition comprising unreacted HCFO-1233xf, a first amount of 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb), and a first amount of 1,1,1,2,2-pentafluoropropane (HFC-245cb); and b) contacting, in a second reaction zone, the first composition with a second fluorination catalyst under conditions to produce a second composition, the second composition comprising HCFC-244bb, and less than about 5% by weight of HCFO-1233xf, and less than about 2% by weight of HFC-245cb, relative to the feedstock HCFO-1233xf.

[0133] In some embodiments, the second reaction zone is comprised of one or more reactors operated in series. In some embodiments, the first and second reaction zones each comprise a CSTR reactor. In some embodiments, the first composition further comprises a carryover first fluorination catalyst that is removed from the first composition prior to contacting the second reaction zone. In some embodiments, the first and second fluorination catalysts each comprise a fluorinated SbCl species.

[0134] The present application further provides a process for preparing 2,3,3,3-tetrafluoropropene (HFO-1234yf), comprising hydrofluorinating 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) with HF to form 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0135] The present application also provides a process for preparing 2,3,3,3-tetrafluoropropene (HFO-1234yf), which comprises dehydrochlorinating 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) to form 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0136] The present application further provides a process for preparing 2,3,3,3-tetrafluoropropene (HFO-1234yf), comprising reacting 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) with a caustic to form 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0137] In some embodiments, the process for preparing HFO-1234yf is that disclosed in U.S. Patent Application No. 20140350309, which is incorporated herein by reference in its entirety.

[0138] Thus, in some embodiments, the process further comprises: (a) removing impurities from the reactor such that the reactor is substantially free of impurities; and (b) providing a starting composition comprising 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) in the reactor under conditions effective to produce a final composition comprising 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0139] In some embodiments, the impurities in the reactor are selected from the group consisting of metal halides, metal oxides, and carbonaceous materials, hi some embodiments, the metal halides include halides of Ni, Cr, Fe, Mo, Nb, Cu, and Co.

[0140] In some embodiments, the step of removing impurities from the reactor comprises introducing a reducing agent into the reactor under conditions effective to convert any metal halides or metal oxides to metallic metals.

[0141] In some embodiments, the reducing agent is H, NH, CO, C-C 12 hydrocarbons, and combinations thereof.

[0142] In some embodiments, the step of removing impurities from the reactor comprises introducing an oxidant into the reactor under conditions effective to combust and remove carbonaceous material within the reactor.

[0143] In some embodiments, the oxidizing agent is selected from the group consisting of HO, CO, O, air, O, Cl, N0, and combinations thereof. In some embodiments, the oxidizing agent comprises oxygen.

[0144] In some embodiments, removing impurities from the reactor comprises physically removing carbonaceous material, metal oxides, and metal halides from the reactor, hi some embodiments, physically removing carbonaceous material, metal oxides, and metal halides from the reactor is selected from the group consisting of electropolishing, mechanical polishing, hydraulic polishing, and combinations thereof.

[0145] In some embodiments, the selectivity to 2,3,3,3-tetrafluoropropene is at least 90% or greater.

[0146] In some embodiments, the processes provided herein further include (a) providing a starting composition comprising 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) in a reactor that is substantially free of impurities, and (b) contacting the starting composition in the reactor under conditions effective to produce a final composition comprising 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0147] In some embodiments, the selectivity to 2,3,3,3-tetrafluoropropene is at least 90% or greater.

[0148] In some embodiments, the process for preparing HFO-1234yf is that disclosed in U.S. Patent Application No. 20140303409, which is incorporated herein by reference in its entirety.

[0149] Thus, in some embodiments, the process further comprises: (i) providing a composition comprising 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb); (ii) reducing the level of HF in the composition so that it is substantially free of HF; and (iii) contacting the starting composition with a dehydrochlorination catalyst to produce a final composition comprising 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0150] In some embodiments, the level of HF is reduced in the composition such that HF ​​is present in the composition in an amount less than about 500 ppm. In some embodiments, the level of HF is reduced in the composition such that HF ​​is present in the composition in an amount less than about 50 ppm. In some embodiments, reducing the HF level of the composition includes distilling the HF, passing the composition through a scrubber, or passing the composition over a solid adsorbent.

[0151] In some embodiments, the solid adsorbent is selected from the group consisting of alumina, calcium carbonate, sodium carbonate, and sodium aluminate.

[0152] The present application further provides a process comprising: (i) providing a starting composition comprising 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) that is substantially free of HF; and (ii) contacting the starting composition with a dehydrochlorination catalyst to produce a final composition comprising 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0153] In some embodiments, HF is present in the composition in an amount less than about 500 ppm. In some embodiments, HF is present in the composition in an amount less than about 50 ppm.

[0154] In some embodiments, contacting the starting composition with the dehydrochlorination catalyst occurs in the vapor phase. In some embodiments, contacting the starting composition with the dehydrochlorination catalyst occurs in the liquid phase.

[0155] In some embodiments, the catalyst is selected from the group consisting of: (i) one or more metal halides, (ii) one or more metal halide oxides, (iii) one or more zero-valent metals / metal alloys, and (iv) combinations of two or more of these.

[0156] In some embodiments, the dehydrochlorination occurs in the gas phase.

[0157] In some embodiments, the intermediate products in each step can be purified before being reacted in the next step to remove impurities in the 1234yf produced in the final step to achieve a desired purity, for example, >99.5 wt%. Purification techniques known in the art, such as distillation, extraction, decantation, and adsorption, can be used. Those skilled in the art will appreciate that impurities that are advantageous to remove before the final reaction step to make 1234yf can form or react with substances that have a similar boiling point as 1234yf.

[0158] In some embodiments, the processes provided herein further include substantially isolating 3,3,3-trifluoroprop-1-ene (i.e., 1243zf). "Substantially isolated" means that the compound is at least partially or substantially separated from the environment in which it was formed or detected. Partial separation can include, for example, a composition enriched in the compounds provided herein. Substantial separation can include a composition containing at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95%, at least about 97%, or at least about 99% by weight of the compounds provided herein, or salts thereof. Methods for isolating compounds are routine in the art.

[0159] In some embodiments, the processes provided herein further include substantially isolating (e.g., purifying) the 3,3,3-trifluoroprop-1-ene via distillation. In some embodiments, the process includes substantially separating the 3,3,3-trifluoroprop-1-ene by removing one or more additional components of the reaction mixture (e.g., 253fb, 1233xf, 254fb, or any combination thereof). In some embodiments, one or more additional components of the reaction mixture are removed by distillation.

[0160] use The processes provided herein are useful for preparing 3,3,3-trifluoroprop-1-ene (HFO-1234zf), a compound that may be useful in silicon production, used as a hydraulic fluid or as an intermediate to produce 2,3,3,3-tetrafluoroprop-1-ene (HFO-1234yf). HFO-1234yf is useful in a variety of applications, such as a refrigerant, for use in high temperature heat pumps, organic Rankine cycles, fire extinguishing / suppression agents, propellants, foam foams, solvents, and / or cleaning fluids.

[0161] composition The present application further provides compositions comprising one or more primary components (e.g., 3,3,3-trifluoroprop-1-ene, 3-chloro-1,1,1-trifluoropropane, or a mixture thereof) in combination with one or more additional compounds. In some embodiments, the compositions are prepared according to one or more processes described herein.

[0162] The additional compounds of the compositions described herein may provide improved solubility for the active ingredient in the polymer component of the aerosol or foam. For refrigerant applications, such as those in air conditioning, heat pumps, refrigeration, and power cycles (e.g., organic Rankine cycles), the additional compounds may also improve solubility in refrigeration lubricants, such as mineral oil, alkylbenzenes, synthetic paraffins, synthetic naphthenes, poly(alpha)olefins, polyol esters (POEs), polyalkylene glycols (PAGs), polyvinyl ethers (PVEs), or perfluoropolyethers (PFPEs), or mixtures thereof. Furthermore, the presence of the additional compounds in a sample of 3,3,3-trifluoroprop-1-ene, 3-chloro-1,1,1-trifluoropropane, or a mixture thereof, may be used to identify the process by which one or more of the major components were produced.

[0163] Therefore, the present application i) 3-chloro-1,1,1-trifluoropropane (253fb), and ii) one or more additional compounds selected from the group consisting of 3,3,3-trifluoroprop-1-ene (1243zf), 2-chloro-3,3,3-trifluoropropene (1233xf), 1,1,1,3-tetrafluoropropane (254fb), and 1,1,1-trifluoro-2,3-dichloropropane (243db).

[0164] In some embodiments, the composition comprises: i) 3-chloro-1,1,1-trifluoropropane (253fb), and ii) one or more additional compounds selected from the group consisting of 3,3,3-trifluoroprop-1-ene (1243zf), 2-chloro-3,3,3-trifluoropropene (1233xf), 1,1,1,3-tetrafluoropropane (254fb), and 1,1,1-trifluoro-2,3-dichloropropane (243db).

[0165] In some embodiments, the compositions provided herein are substantially free of a catalyst (e.g., a phase transfer catalyst) described herein.

[0166] In some embodiments, the compositions provided herein further comprise a catalyst described herein. In some embodiments, the catalyst is a phase transfer catalyst described herein.

[0167] In some embodiments, the composition comprises about 25 mole percent or less of 3-chloro-1,1,1-trifluoropropane (253fb), e.g., about 20 mole percent or less, about 15 mole percent or less, about 10 mole percent or less, about 5 mole percent or less, about 2 mole percent or less, or about 1 mole percent or less of 3-chloro-1,1,1-trifluoropropane (253fb).

[0168] In some embodiments, the composition comprises about 1 to about 25 mole percent 3-chloro-1,1,1-trifluoropropane.

[0169] In some embodiments, the composition comprises about 1 to about 5 mole percent 3-chloro-1,1,1-trifluoropropane.

[0170] In some embodiments, the composition comprises about 1 to about 2 mole percent 3-chloro-1,1,1-trifluoropropane.

[0171] In some embodiments, the composition comprises about 20 to about 25 mole percent 3-chloro-1,1,1-trifluoropropane.

[0172] In some embodiments, the composition comprises about 23 to about 25 mole percent 3-chloro-1,1,1-trifluoropropane.

[0173] In some embodiments, the composition comprises about 70 mole percent or more of 3,3,3-trifluoroprop-1-ene (1243zf), e.g., about 75 mole percent or more, about 80 mole percent or more, about 85 mole percent or more, about 90 mole percent or more, about 95 mole percent or more, about 96 mole percent or more, about 97 mole percent or more, about 98 mole percent or more, about 99 mole percent or more, about 99.5 mole percent or more, about 99.6 mole percent or more, about 99.7 mole percent or more, about 99.8 mole percent or more, or about 99.9 mole percent or more of 3,3,3-trifluoroprop-1-ene.

[0174] In some embodiments, the composition comprises about 70 to about 80 mole percent 3,3,3-trifluoroprop-1-ene.

[0175] In some embodiments, the composition comprises about 74 to about 76 mole percent 3,3,3-trifluoroprop-1-ene.

[0176] In some embodiments, the composition comprises about 95 to about 99.9 mole percent 3,3,3-trifluoroprop-1-ene.

[0177] In some embodiments, the composition comprises about 98 to about 99 mole percent 3,3,3-trifluoroprop-1-ene.

[0178] In some embodiments, the composition comprises about 25 percent or less 3-chloro-1,1,1-trifluoropropane (253fb) as measured by gas chromatography / mass spectrometry (GC-MS) (e.g., % area under the curve), e.g., about 20 percent or less, about 15 percent or less, about 10 percent or less, about 5 percent or less, about 2 percent or less, or about 1 percent or less 3-chloro-1,1,1-trifluoropropane (253fb) as measured by GC-MS.

[0179] In some embodiments, the composition comprises about 1 to about 25 percent 3-chloro-1,1,1-trifluoropropane as measured by GC-MS.

[0180] In some embodiments, the composition comprises about 1 to about 5 percent 3-chloro-1,1,1-trifluoropropane as measured by GC-MS.

[0181] In some embodiments, the composition comprises about 1 to about 2 percent 3-chloro-1,1,1-trifluoropropane as measured by GC-MS.

[0182] In some embodiments, the composition comprises about 20 to about 25 percent 3-chloro-1,1,1-trifluoropropane as measured by GC-MS.

[0183] In some embodiments, the composition comprises about 23 to about 25 percent 3-chloro-1,1,1-trifluoropropane as measured by GC-MS.

[0184] In some embodiments, the composition comprises about 70 mole percent or more of 3,3,3-trifluoroprop-1-ene (1243zf) as measured by GC-MS, e.g., about 75 percent or more, about 80 percent or more, about 85 percent or more, about 90 percent or more, about 95 percent or more, about 96 percent or more, about 97 percent or more, about 98 percent or more, about 99 percent or more, about 99.5 percent or more, about 99.6 percent or more, about 99.7 percent or more, about 99.8 percent or more, or about 99.9 percent or more of 3,3,3-trifluoroprop-1-ene as measured by GC-MS.

[0185] In some embodiments, the composition comprises about 70 to about 80 percent 3,3,3-trifluoroprop-1-ene as measured by GC-MS.

[0186] In some embodiments, the composition comprises about 74 to about 76 percent 3,3,3-trifluoroprop-1-ene as measured by GC-MS.

[0187] In some embodiments, the composition comprises about 95 to about 99.9 percent 3,3,3-trifluoroprop-1-ene as measured by GC-MS.

[0188] In some embodiments, the composition comprises about 98 to about 99 percent 3,3,3-trifluoroprop-1-ene as measured by GC-MS.

[0189] In some embodiments, the composition comprises about 0.5 mole percent or less of 2-chloro-3,3,3-trifluoropropene (1233xf), e.g., about 0.4 mole percent or less, about 0.3 mole percent or less, about 0.2 mole percent or less, or about 0.1 mole percent or less of 2-chloro-3,3,3-trifluoropropene.

[0190] In some embodiments, the composition comprises about 0.01 to about 0.15 mole percent 2-chloro-3,3,3-trifluoropropene.

[0191] In some embodiments, the composition comprises about 0.05 to about 0.15 mole percent 2-chloro-3,3,3-trifluoropropene.

[0192] In some embodiments, the composition comprises about 0.05 to about 0.2 mole percent 2-chloro-3,3,3-trifluoropropene.

[0193] In some embodiments, the composition comprises about 0.05 to about 0.1 mole percent 2-chloro-3,3,3-trifluoropropene.

[0194] In some embodiments, the composition comprises about 0.05 to about 0.07 mole percent 2-chloro-3,3,3-trifluoropropene.

[0195] In some embodiments, the composition comprises about 0.1 to about 0.2 mole percent 2-chloro-3,3,3-trifluoropropene.

[0196] In some embodiments, the composition comprises about 0.14 to about 0.16 mole percent 2-chloro-3,3,3-trifluoropropene.

[0197] In some embodiments, the composition comprises about 0.1 mole percent or less of 1,1,1,3-tetrafluoropropane (254fb), e.g., 0.075 mole percent or less, 0.05 mole percent or less, 0.025 mole percent or less, or 0.01 mole percent or less of 1,1,1,3-tetrafluoropropane.

[0198] In some embodiments, the composition comprises about 0.01 to about 0.1 mole percent 1,1,1,3-tetrafluoropropane.

[0199] In some embodiments, the composition comprises about 0.01 to about 0.05 mole percent 1,1,1,3-tetrafluoropropane.

[0200] In some embodiments, the composition comprises about 0.01 to about 0.02 mole percent 1,1,1,3-tetrafluoropropane.

[0201] In some embodiments, the composition comprises about 0.5 percent or less of 2-chloro-3,3,3-trifluoropropene (1233xf) as measured by GC-MS, e.g., about 0.4 percent or less, about 0.3 percent or less, about 0.2 percent or less, or about 0.1 percent or less of 2-chloro-3,3,3-trifluoropropene as measured by GC-MS.

[0202] In some embodiments, the composition comprises from about 0.01 to about 0.15 percent 2-chloro-3,3,3-trifluoropropene as measured by GC-MS.

[0203] In some embodiments, the composition comprises about 0.05 to about 0.15 percent 2-chloro-3,3,3-trifluoropropene as measured by GC-MS.

[0204] In some embodiments, the composition comprises about 0.05 to about 0.2 percent 2-chloro-3,3,3-trifluoropropene as measured by GC-MS.

[0205] In some embodiments, the composition comprises about 0.05 to about 0.1 percent 2-chloro-3,3,3-trifluoropropene as measured by GC-MS.

[0206] In some embodiments, the composition comprises about 0.05 to about 0.07 percent 2-chloro-3,3,3-trifluoropropene as measured by GC-MS.

[0207] In some embodiments, the composition comprises about 0.1 to about 0.2 percent 2-chloro-3,3,3-trifluoropropene as measured by GC-MS.

[0208] In some embodiments, the composition comprises about 0.14 to about 0.16 percent 2-chloro-3,3,3-trifluoropropene as measured by GC-MS.

[0209] In some embodiments, the composition contains about 0.1 percent or less 1,1,1,3-tetrafluoropropane (254fb) as measured by GC-MS, e.g., 0.075 percent or less, 0.05 percent or less, 0.025 percent or less, or 0.01 percent or less 1,1,1,3-tetrafluoropropane as measured by GC-MS.

[0210] In some embodiments, the composition comprises about 0.01 to about 0.1 percent 1,1,1,3-tetrafluoropropane as measured by GC-MS.

[0211] In some embodiments, the composition comprises about 0.01 to about 0.05 percent 1,1,1,3-tetrafluoropropane as measured by GC-MS.

[0212] In some embodiments, the composition comprises about 0.01 to about 0.02 percent 1,1,1,3-tetrafluoropropane as measured by GC-MS.

[0213] In some embodiments, the composition comprises 3-chloro-1,1,1-trifluoropropane (253fb), 3,3,3-trifluoroprop-1-ene (1243zf), 1,1,1-trifluoro-2,3-dichloropropane (243db), 2-chloro-3,3,3-trifluoropropene (1233xf).

[0214] In some embodiments, the composition comprises 3-chloro-1,1,1-trifluoropropane (253fb), 3,3,3-trifluoroprop-1-ene (1243zf), 1,1,1,3-tetrafluoropropane (254fb), 2-chloro-3,3,3-trifluoropropene (1233xf).

[0215] In some embodiments, the composition comprises 3-chloro-1,1,1-trifluoropropane (253fb), 3,3,3-trifluoroprop-1-ene (1243zf), and 2-chloro-3,3,3-trifluoropropene (1233xf).

[0216] In some embodiments, the composition comprises 3-chloro-1,1,1-trifluoropropane (253fb) and 1,1,1-trifluoro-2,3-dichloropropane (243db).

[0217] In some embodiments, the composition comprises 3-chloro-1,1,1-trifluoropropane (253fb), 1,1,1-trifluoro-2,3-dichloropropane (243db), and a catalyst. In some embodiments, the catalyst is a phase transfer catalyst described herein.

[0218] In some embodiments, the composition comprises: about 70 to about 80 mole percent 3,3,3-trifluoroprop-1-ene; about 20 to about 25 mole percent 3-chloro-1,1,1-trifluoropropane; about 0.05 to about 0.1 mole percent 2-chloro-3,3,3-trifluoropropene, and about 0.01 to about 0.05 mole percent 1,1,1,3-tetrafluoropropane.

[0219] In some embodiments, the composition comprises: about 74 to about 76 mole percent 3,3,3-trifluoroprop-1-ene; about 23 to about 25 mole percent 3-chloro-1,1,1-trifluoropropane; about 0.05 to about 0.07 mole percent 2-chloro-3,3,3-trifluoropropene, and about 0.01 to 0.02 mole percent 1,1,1,3-tetrafluoropropane.

[0220] In some embodiments, the composition comprises: about 95 to about 99 mole percent 3,3,3-trifluoroprop-1-ene; about 1 to about 2 mole percent 3-chloro-1,1,1-trifluoropropane, and about 0.1 to about 0.2 mole percent 2-chloro-3,3,3-trifluoropropene.

[0221] In some embodiments, the composition comprises: about 98 to about 99 mole percent 3,3,3-trifluoroprop-1-ene; about 1 to about 2 mole percent 3-chloro-1,1,1-trifluoropropane, and about 0.1 to about 0.2 mole percent 2-chloro-3,3,3-trifluoropropene.

[0222] In some embodiments, the composition has a molecular weight of: about 70 to about 80 percent 3,3,3-trifluoroprop-1-ene; about 20 to about 25 percent 3-chloro-1,1,1-trifluoropropane; about 0.05 to about 0.1 percent 2-chloro-3,3,3-trifluoropropene, and about 0.01 to about 0.05 mole percent 1,1,1,3-tetrafluoropropane.

[0223] In some embodiments, the composition has a molecular weight of: about 74 to about 76 percent 3,3,3-trifluoroprop-1-ene; about 23 to about 25 percent 3-chloro-1,1,1-trifluoropropane; about 0.05 to about 0.07 percent 2-chloro-3,3,3-trifluoropropene, and Contains approximately 0.01 to 0.02 percent 1,1,1,3-tetrafluoropropane.

[0224] In some embodiments, the composition has a molecular weight of: about 95 to about 99 percent 3,3,3-trifluoroprop-1-ene; about 1 to about 2 percent 3-chloro-1,1,1-trifluoropropane, and about 0.1 to about 0.2 percent 2-chloro-3,3,3-trifluoropropene.

[0225] In some embodiments, the composition has a molecular weight of: about 98 to about 99 percent 3,3,3-trifluoroprop-1-ene; about 1 to about 2 percent 3-chloro-1,1,1-trifluoropropane, and about 0.1 to about 0.2 percent 2-chloro-3,3,3-trifluoropropene. [Example]

[0226] The present invention can be described in more detail by specific examples. The following examples are provided for illustrative purposes and are not intended to limit the present invention in any way.

[0227] Example 1. Dehydrochlorination of 253FB with NaOH without a phase transfer catalyst in a 400 mL stirred autoclave reactor at 60° C. and 1000 RPM stirring speed A 12 wt% NaOH solution in water (195 g) and 3-chloro-1,1,1-trifluoropropane (i.e., 253fb; 10 g) were charged into a 400 mL autoclave and heated to 60°C. The reaction mixture was stirred at 1000 RPM (estimated equivalent to 10.1 HP per 1000 gallons) at 60°C. The pressure continuously increased from 7 psig to 78 psig over approximately 2.5 hours, indicating the progress of the reaction. After the reactor pressure stabilized, the reaction mixture was stirred for an additional 1.5 hours. The products were analyzed by GC / MS, as shown in Table 1, and the analysis indicated that ∼98.5% of 253fb was converted to 3,3,3-trifluoroprop-1-ene (i.e., 1243zf) without the use of a phase transfer catalyst.

[0228] [Table 1]

[0229] Example 2. Dehydrochlorination of 253FB with NaOH without a phase transfer catalyst in a 400 mL stirred autoclave reactor at 40° C. and 1000 RPM stirring speed A 12 wt% NaOH solution in water (195 g) and 253fb (10 g) were charged into a 400 mL autoclave and heated to 60°C. The reaction mixture was stirred at 1000 rpm (10.1 HP per thousand gallons) at 40°C. The pressure continuously increased from 9 psig to 27 psig over approximately 3.5 hours, indicating the progress of the reaction. The products were analyzed by GC / MS, as shown in Table 2, and the analysis indicated that ∼75.4% of the 253fb was converted to 1243zf without the use of a phase transfer catalyst.

[0230] [Table 2]

[0231] Other embodiments 1. In some embodiments, the present application provides a process for preparing 3,3,3-trifluoroprop-1-ene, comprising reacting 3-chloro-1,1,1-trifluoropropane with a base in an aqueous solvent component, wherein the reaction is carried out in the absence of a phase transfer catalyst, and the aqueous solvent component comprises 0 to 40 wt. % of an organic solvent. 2. The process of embodiment 1, wherein the aqueous solvent component does not include an organic solvent. 3. The process of embodiment 1 or 2, wherein the base is an aqueous base. 4. The process of embodiment 3, wherein the base is a metal hydroxide base, a metal carbonate base, a metal phosphate base, or a metal fluoride base. 5. The process of embodiment 3, wherein the base is NaOH, KOH, LiOH, CsOH, Ca(OH), Zn(OH), NaCO, KCO, KPO, NaPO, KF, or CsF. 6. The process of embodiment 3, wherein the base is KOH or NaOH. 7. The process of embodiment 3, wherein the base is NaOH. 8. The process of any one of embodiments 1 to 7, wherein about 0.01 to about 5 molar equivalents of base are used, based on 1 molar equivalent of 3-chloro-1,1,1-trifluoropropane. 9. The process of any one of embodiments 1 to 8, wherein the reaction is carried out at a temperature of from about 20°C to about 100°C. 10. The process of any one of embodiments 1 to 8, wherein the reaction is carried out at a temperature of from about 35°C to about 80°C. 11. The process of any one of embodiments 1 to 10, wherein the reaction is carried out at a pressure of from about −10 psig to about 500 psig. 12. The process of any one of embodiments 1 to 10, wherein the reaction is carried out at a pressure of from about 5 psig to about 230 psig. 13. The process of any one of embodiments 1 to 10, wherein the reaction is carried out at a pressure of from about 5 psig to about 150 psig. 14. The process of any one of embodiments 1-13, wherein the reacting comprises mixing 3-chloro-1,1,1-trifluoropropane and a base at a mixing power of from about 0.1 to about 50 horsepower per 1000 gallons of reaction mixture. 15. The process of any one of embodiments 1-13, wherein the reacting comprises mixing 3-chloro-1,1,1-trifluoropropane and a base at a mixing power in the range of from about 0.5 horsepower to about 40 horsepower per 1000 gallons of reaction mixture. 16. The process of any one of embodiments 1 to 8, wherein the reaction is carried out at a temperature of from about 35° C. to about 80° C. and a pressure of from about 5 psig to about 230 psig. 17. The process of any one of embodiments 1 to 8, wherein the reaction is carried out at a temperature of from about 35° C. to about 80° C. and a pressure of from about 5 psig to about 150 psig. 18. The process of any one of embodiments 1 to 18, wherein the reaction further comprises an amine. 19. The process of any one of embodiments 1 to 18, wherein 3-chloro-1,1,1-trifluoropropane is prepared by a process comprising reacting 1,1,1,3-tetrachloropropane with hydrofluoric acid. 20. The process of any one of embodiments 1 to 19, further comprising chlorinating 3,3,3-trifluoropropene to form 1,1,1-trifluoro-2,3-dichloropropane (HCFC-243db). 21. The process of embodiment 20, wherein the chlorination comprises reacting with chlorine or HCl / oxygen. 22. The process of any one of embodiments 20-21, comprising dehydrochlorinating 1,1,1-trifluoro-2,3-dichloropropane (HCFC-243db) to form 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf). 23. The process of embodiment 22, comprising reacting 1,1,1-trifluoro-2,3-dichloropropane (HCFC-243db) with a caustic to form 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf). 24. The process of any one of embodiments 22-23, further comprising hydrofluorinating 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) with HF to form 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb). 25. The process of any one of embodiments 22-23, further comprising hydrofluorinating 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) with HF to form 2,3,3,3-tetrafluoropropene (HFO-1234yf). 26. The process of embodiment 24, further comprising dehydrochlorinating 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) to form 2,3,3,3-tetrafluoropropene (HFO-1234yf). 27. The process of embodiment 24, further comprising reacting 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) with a caustic to form 2,3,3,3-tetrafluoropropene (HFO-1234yf). 28. A process for preparing 3,3,3-trifluoroprop-1-ene, comprising reacting 3-chloro-1,1,1-trifluoropropane with aqueous NaOH, wherein the reaction is carried out at a temperature of about 35°C to about 80°C and a pressure of about 5 psig to about 230 psig, and wherein the reaction is carried out in the absence of a phase transfer catalyst and an organic solvent component. 29. The process of embodiment 28, wherein the reaction is carried out at a pressure of from about 5 psig to about 150 psig. 30. The process of embodiment 28 or 29, wherein 3-chloro-1,1,1-trifluoropropane is prepared by reacting 1,1,1,3-tetrachloropropane with hydrofluoric acid. 31. A process for preparing a mixture of 3,3,3-trifluoroprop-1-ene (HFO-1234zf) and 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), comprising reacting a mixture of 3-chloro-1,1,1-trifluoropropane (HCFC-253fb) and 1,1,1-trifluoro-2,3-dichloropropane (HCFC-243db) with a base in an aqueous solvent component, wherein the reaction is carried out in the absence of a phase transfer catalyst, and the aqueous solvent component comprises 0 to 40% organic solvent. 32. The process of embodiment 31, wherein the aqueous solvent component does not contain an organic solvent. 33.i) 3-chloro-1,1,1-trifluoropropane (253fb), and ii) one or more additional compounds selected from the group consisting of 3,3,3-trifluoroprop-1-ene (1243zf), 2-chloro-3,3,3-trifluoropropene (1233xf), 1,1,1,3-tetrafluoropropane (254fb), and 1,1,1-trifluoro-2,3-dichloropropane (243db). 34. The composition of embodiment 33, wherein the composition comprises 3-chloro-1,1,1-trifluoropropane (253fb), 3,3,3-trifluoroprop-1-ene (1243zf), and 2-chloro-3,3,3-trifluoropropene (1233xf). 35. The composition has, when measured by CG-MS: about 95 to about 99 percent 3,3,3-trifluoroprop-1-ene (1243zf); about 1 to about 2 percent 3-chloro-1,1,1-trifluoropropane (253fb), and 35. The composition of embodiment 33 or 34, comprising about 0.1 to about 0.2 percent 2-chloro-3,3,3-trifluoropropene (1233xf). 36. The composition has, when measured by CG-MS: about 98 to about 99 percent 3,3,3-trifluoroprop-1-ene (1243zf); about 1 to about 2 percent 3-chloro-1,1,1-trifluoropropane (253fb), and 35. The composition of embodiment 33 or 34, comprising about 0.1 to about 0.2 percent 2-chloro-3,3,3-trifluoropropene (1233xf). 37. The composition of embodiment 33, wherein the composition comprises 3-chloro-1,1,1-trifluoropropane (253fb), 3,3,3-trifluoroprop-1-ene (1243zf), 1,1,1,3-tetrafluoropropane (254fb), and 2-chloro-3,3,3-trifluoropropene (1233xf). 38. The composition has, when measured by GC-MS: about 70 to about 80 percent 3,3,3-trifluoroprop-1-ene (1243zf); about 20 to about 25 percent 3-chloro-1,1,1-trifluoropropane (253fb); about 0.05 to about 0.1 percent 2-chloro-3,3,3-trifluoropropene (1233xf), and 38. The composition of embodiment 33 or 37, comprising about 0.01 to about 0.05 percent 1,1,1,3-tetrafluoropropane (254fb). 39. The composition has, when measured by GC-MS: about 74 to about 76 mole percent 3,3,3-trifluoroprop-1-ene (1243zf); about 23 to about 25 mole percent 3-chloro-1,1,1-trifluoropropane (253fb); about 0.05 to about 0.07 mole percent 2-chloro-3,3,3-trifluoropropene (1233xf), and 38. The composition of embodiment 33 or 37, comprising about 0.01 to 0.02 mole percent of 1,1,1,3-tetrafluoropropane (254fb). 40. The composition of embodiment 33, wherein the composition comprises 3-chloro-1,1,1-trifluoropropane (253fb), 3,3,3-trifluoroprop-1-ene (1243zf), 1,1,1-trifluoro-2,3-dichloropropane (243db), and 2-chloro-3,3,3-trifluoropropene (1233xf). 41. The composition of embodiment 33, wherein the composition comprises 3-chloro-1,1,1-trifluoropropane (253fb), 1,1,1-trifluoro-2,3-dichloropropane (243db). 42. The composition of any one of embodiments 33-41, wherein the composition further comprises a catalyst. 43. The composition of any one of embodiments 33-41, wherein the composition is substantially free of catalyst.

[0232] While the present invention has been described in conjunction with its detailed description, it should be understood that the foregoing description is intended to illustrate, and not limit, the scope of the invention as defined by the appended claims. Other aspects, advantages, and modifications are within the scope of the following claims. It should be understood by those skilled in the art that the present invention may be combined with any of the features described herein with respect to any particular aspect and / or embodiment of the invention, with one or more of the other features of any other aspect and / or embodiment of the invention described herein, modified as appropriate to ensure compatibility of the combination. Such combinations are considered to be part of the invention contemplated by this disclosure.

Claims

1. 1. A process for preparing a mixture of 3,3,3-trifluoropropene (HFO-1243zf) and 2-chloro-3,3,3-trifluoropropene (HFO-1233xf), the process comprising reacting a mixture of 3-chloro-1,1,1-trifluoropropane (HCFC-253fb) and 1,1,1-trifluoro-2,3-dichloropropane (HFC-243db) with a base in an aqueous solvent component in the absence of a phase transfer catalyst, the aqueous solvent component being free of an organic solvent.

2. providing a first mixture of 3-chloro-1,1,1-trifluoropropane (HCFC-253fb) and 1,1,1-trifluoro-2,3-dichloropropane (HFC-243db); dehydrochlorinating the first mixture in the absence of a phase transfer catalyst and an organic solvent to form a second mixture; recovering a second mixture comprising 3,3,3-trifluoropropene (HFO-1243zf) and 2-chloro-3,3,3-trifluoropropene (HFO-1233xf); optionally isolating 3,3,3-trifluoropropene (HFO-1243zf); A method comprising:

3. 3. The process according to claim 2, characterized in that 2-chloro-3,3,3-trifluoropropene (HFO-1233xf) is removed by distillation.

4. 3. The process according to claim 2, characterized in that the dehydrochlorination is carried out in the presence of a base.

5. 5. The method of claim 4, wherein the base is KOH or NaOH.

6. 6. The method of claim 5, wherein the base is NaOH.

7. 5. The process according to claim 4, wherein 0.01 to 5 molar equivalents of base are used per molar equivalent of 3-chloro-1,1,1-trifluoropropane.

8. 3. The process according to claim 2, characterized in that the dehydrochlorination is carried out at a temperature of from 40°C to 80°C.

9. 3. The process according to claim 2, characterized in that the dehydrochlorination is carried out at a temperature of from 55°C to 65°C.

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