2-chloro-3,3,3-trifluoropropene (1233xf) compositions and methods for making and using those compositions

Abstract

To provide 2-chloro-3,3,3-trifluoropropene (1233xf) compositions useful as a reactive intermediate.SOLUTION: An intermediate feed composition comprises: a) at least 94.6% of 1233xf, based on the total GC area of the composition; b) 243db, 1223xd, and 1-chloro-3,3,3-trifluoropropyne,; c) at least one additional compound selected from 1232xf, 233ab, 233da, 1243zf, 1233zd, 1224yd, and 2-bromo-3,3,3-trifluoropropene; and d) optionally, more than 0% and up to 2% of at least one solvent-soluble dimer, trimer or oligomer of 1233xf.SELECTED DRAWING: None

Description

[Technical field]

[0001] This application claims the benefit of U.S. Application No. 62 / 857,082, filed June 4, 2019. The disclosure of Application No. 62 / 857,082 is incorporated herein by reference.

[0002] FIELD OF THEINVENTION The present invention relates to 2-chloro-3,3,3-trifluoropropene (1233xf) compositions. More particularly, the present invention relates to 2-chloro-3,3,3-trifluoropropene (1233xf) compositions as heat transfer fluids, refrigerants, and reactive intermediates. [Background technology]

[0003] Hydrofluorocarbons (HFCs), such as hydrofluoroolefins, have been disclosed as effective refrigerants, fire extinguishing agents, heat transfer media, propellants, foaming agents, blowing agents, gaseous dielectrics, sterilant carriers, polymerization media, particulate removal fluids, dispersion media, buffing agents, displacement drying agents, and power cycle working fluids. Hydrofluoro-olefins include substituted chlorofluorocarbons and hydrochlorofluorocarbons, which can deplete the Earth's ozone layer. Many hydrofluorocarbons exhibit high global warming potentials (GWPs). However, hydrofluoro-olefins have short atmospheric lifetimes due to their reactive olefinic bonds, and therefore do not contribute to global warming on a large scale. Summary of the Invention [Means for solving the problem]

[0004] In one embodiment, disclosed herein are compositions useful as refrigerants and heat transfer fluids. The compositions disclosed herein can be used as intermediates to produce 1234yf, which can be used as a low GWP refrigerant, heat transfer medium, blowing agent, or solvent. The compositions disclosed herein can also be used as intermediates to produce 244bb, which in turn is a precursor to 1234yf, which can be used as a low GWP refrigerant, heat transfer medium, blowing agent, or solvent. The compositions disclosed herein can further be used as a source of trifluoromethyl groups (-CF3) to produce a wide range of organic compounds, such as pharmaceuticals, agrochemicals, and functional materials (e.g., Journal of Organic Chemistry, 82(9), 4721-4728; 2017); precursors for making 1223xd (e.g., JP2017014160) and precursors for making 1336mzz (e.g., US Patent Application Publication No. 20160023972 and China Patent Application Publication No. 105218297). The disclosures of the above publications are incorporated herein by reference.

[0005] The compositions disclosed herein comprise a) 2-chloro-3,3,3-trifluoropropene (1233xf) and b) 2,3-dichloro-1,1,1-trifluoropropane (243db), 1,2-dichloro-3,3,3-trifluoropropene (1223xd), 2,3-dichloro-3,3-difluoropropene (1232xf), 2,2,3-trichloro-1,1,1-trifluoro-propane (233ab), 2,3,3-trichloro-1,1 , 1-trifluoro-propane (233da), 3,3,3-trifluoropropyne, 1-chloro-3,3,3-trifluoropropyne, 3,3,3-trifluoro-1-propene (1243zf), 1-chloro-3,3,3-trifluoro-1-propene (1233zd), 1-chloro-2,3,3,3-tetrafluoro-1-propene (1224yd), or 2-bromo-3,3,3-trifluoropropene.

[0006] Also disclosed herein, according to any of the preceding embodiments, is a composition, wherein b) comprises 2,3-dichloro-1,1,1-trifluoropropane (243db).

[0007] Also disclosed herein, in accordance with any of the preceding embodiments, is a composition, wherein b) comprises 1-chloro-3,3,3-trifluoropropyne.

[0008] Also disclosed herein, according to any of the preceding embodiments, is a composition, wherein b) comprises 2-bromo-3,3,3-trifluoropropene.

[0009] Also disclosed herein, according to any of the preceding embodiments, is a composition, wherein b) comprises 1,2-dichloro-3,3,3-trifluoropropene (1223xd).

[0010] In another embodiment, disclosed herein is a 2-chloro-3,3,3-trifluoropropene (1233xf) composition produced by contacting 2,3-dichloro-1,1,1-trifluoropropane (243db) in a liquid phase with a base to effect dehydrochlorination to form 2-chloro-3,3,3-trifluoropropene (1233xf).

[0011] According to any of the preceding embodiments, also disclosed herein is a composition, wherein 2,3-dichloro-1,1,1-trifluoropropane (243db) is contacted with a base in the presence of a catalyst.

[0012] Also disclosed herein, in accordance with any of the preceding embodiments, is a composition, wherein 2,3-dichloro-1,1,1-trifluoropropane (243db) is contacted with a base in the absence of a catalyst.

[0013] Also disclosed herein, in accordance with any of the preceding embodiments, is a composition, wherein the base comprises at least one of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, potassium tert-butoxide, calcium oxide, or calcium hydroxide.

[0014] According to any of the foregoing embodiments, also disclosed herein is a composition comprising 2-chloro-3,3,3-trifluoropropene (1233xf) and at least one of 1-chloro-3,3,3-trifluoro-1-propene (1233zd), 2,3-dichloro-1,1,1-trifluoropropane (243db), 1,2-dichloro-3,3,3-trifluoropropene (1223xd), 2,3-dichloro-3,3-difluoropropene (1232xf), 2,2,3-trichloro-1,1,1-trifluoro-propane (233ab), 2,3,3-trichloro-1,1,1-trifluoro-propane (233da), 3,3,3-trifluoropropyne, 1-chloro-3,3,3-trifluoropropyne, or 2-bromo-3,3,3-trifluoropropene.

[0015] In yet another embodiment, also disclosed herein is a 2-chloro-3,3,3-trifluoropropene (1233xf) composition produced by contacting 2,3-dichloro-1,1,1-trifluoropropane (243db) with a dehydrochlorination catalyst in the vapor phase at a temperature and pressure sufficient to effect dehydrochlorination to form 2-chloro-3,3,3-trifluoropropene (1233xf).

[0016] Also disclosed herein, in accordance with any of the preceding embodiments, is a composition, wherein the dehydrochlorination catalyst comprises activated carbon, alumina, chromium oxide, an oxide of a transition metal, or a metal halide.

[0017] Also disclosed herein, according to any of the foregoing embodiments, is a composition comprising 2-chloro-3,3,3-trifluoropropene (1233xf) and at least one of 2,3-dichloro-1,1,1-trifluoropropane (243db), 1,2-dichloro-3,3,3-trifluoropropene (1223xd), 2,3-dichloro-3,3-difluoropropene (1232xf), 2,2,3-trichloro-1,1,1-trifluoro-propane (233ab), 2,3,3-trichloro-1,1,1-trifluoro-propane (233da), 3,3,3-trifluoropropyne, 1-chloro-3,3,3-trifluoropropyne, or 2-bromo-3,3,3-trifluoropropene.

[0018] In yet another embodiment, disclosed herein is a 2-chloro-3,3,3-trifluoropropene (1233xf) composition produced by contacting a compound selected from the group consisting of 1,1,1,2,3-pentachloropropane (HCC-240db), 2,3,3,3-tetrachloropropene (1230xf), 1,1,2,3 tetrachloropropene (HCC-1230xa), 2,3-dichloro-1,1,1-trifluoropropane (243db), and combinations thereof, with a fluorination catalyst in the presence of hydrogen fluoride in the vapor phase at a temperature and pressure sufficient to form 2-chloro-3,3,3-trifluoropropene (1233xf).

[0019] Also disclosed herein, in accordance with any of the preceding embodiments, is a composition, wherein the fluorination catalyst comprises a chromium, aluminum, cobalt, manganese, nickel or iron oxide, hydroxide, halide, oxyhalide, or inorganic salt thereof.

[0020] In yet another embodiment, the method described herein includes the steps of contacting 2-chloro-3,3,3-trifluoropropene (1233xf) with hydrogen fluoride in the presence of a fluorination catalyst at a temperature sufficient to form 2-chloro-1,1,1,2-tetrafluoropropene (244bb) and thermally dehydrochlorinating 2-chloro-2,3,3,3-tetrafluoropropane (244bb) to 1234yf, or the steps of thermally dehydrochlorinating 2-chloro-2,3,3,3-tetrafluoropropane (244b b) with a gas phase dehydrochlorination catalyst to form 2,3,3,3-tetrafluoropropene (1234yf); or contacting 2-chloro-2,3,3,3-tetrafluoropropane (244bb) with a base at a temperature sufficient to effect dehydrochlorination to form 2,3,3,3-tetrafluoropropene (1234yf).

[0021] Also disclosed herein, in accordance with any of the preceding embodiments, is a composition, wherein 2-chloro-3,3,3-trifluoropropene (1233xf) is contacted with hydrogen fluoride in the vapor phase.

[0022] Also disclosed herein, in accordance with any of the preceding embodiments, is a composition, wherein 2-chloro-3,3,3-trifluoropropene (1233xf) is contacted with hydrogen fluoride in the liquid phase.

[0023] According to any of the foregoing embodiments, also disclosed herein is a composition, in the presence of a catalyst, in the vapor phase, where 2-chloro-1,1,1,2-tetrafluoropropene (244bb) is converted to 1234yf.

[0024] According to any of the preceding embodiments, also disclosed herein is a composition, in which 2-chloro-1,1,1,2-tetrafluoropropene (244bb) is converted to 1234yf in the gas phase in the absence of a catalyst.

[0025] According to any of the preceding embodiments, also disclosed herein is a composition, wherein 2-chloro-1,1,1,2-tetrafluoropropene (244bb) is contacted with a base in the liquid phase.

[0026] In yet another embodiment, the present disclosure provides a method for producing 2-chloro-3,3,3-trifluoropropene (1233xf)-containing compositions comprising the steps of contacting any of the aforementioned 2-chloro-3,3,3-trifluoropropene (1233xf)-containing compositions with hydrogen fluoride in the presence of a fluorination catalyst in the vapor phase at a temperature sufficient to form 2-chloro-1,1,1,2-tetrafluoropropene (244bb) and thermally dehydrochlorinating 2-chloro-2,3,3,3-tetrafluoropropane (244bb) to 1234yf, or Also disclosed are 2,3,3,3-tetrafluoropropene (1234yf) compositions produced by contacting propane (244bb) with a vapor phase dehydrochlorination catalyst to dehydrochlorinate to form 2,3,3,3-tetrafluoropropene (1234yf), or by contacting 2-chloro-2,3,3,3-tetrafluoropropane (244bb) with a base at a temperature sufficient to effect dehydrochlorination to form 2,3,3,3-tetrafluoropropene (1234yf).

[0027] Also disclosed herein, in accordance with any of the preceding embodiments, is a composition, wherein 2-chloro-2,3,3,3-tetrafluoropropane (244bb) is contacted with a base in the liquid phase.

[0028] According to any of the foregoing embodiments, also disclosed herein is a composition, in the presence of a catalyst, in the vapor phase, where 2-chloro-1,1,1,2-tetrafluoropropene (244bb) is converted to 1234yf.

[0029] According to any of the preceding embodiments, also disclosed herein is a composition, in which 2-chloro-1,1,1,2-tetrafluoropropene (244bb) is converted to 1234yf in the gas phase in the absence of a catalyst.

[0030] Also disclosed herein, in accordance with any of the preceding embodiments, is a composition further comprising at least one oligomer.

[0031] According to any of the foregoing embodiments, the oligomer comprises:

[0032] [ka] The structure is In the formula, n=0 to 9.

[0033] According to any of the previous embodiments, also disclosed herein is a composition further comprising at least one solvent. Exemplary solvents include at least one of ketones, ethers, amides, sulfones, chlorocarbons, chlorofluorocarbons, hydrochlorocarbons, and hydrochlorofluorocarbons. Also, in one particular embodiment, a solvent capable of dissolving the 1233xf oligomer.

[0034] According to any of the aforementioned embodiments, the solvent comprises at least one member selected from the group consisting of 113a, dichloromethane, acetone, tetrahydrofuran (THF), CHCl3, 1233xf, 244bb, CCl4, 114a, 114, 113, 243db, 250fb, 1230xa, 240db, 1233zd, 1223xd, 1224yd, and 253fb.

[0035] In yet another embodiment, provided herein is a process for producing a 1233xf-containing composition comprising the steps of contacting the 1233xf-containing composition with hydrogen fluoride in the presence of a fluorination catalyst in the vapor phase at a temperature sufficient to form 2-chloro-1,1,1,2-tetrafluoropropene (244bb) and thermally dehydrochlorinating the 2-chloro-2,3,3,3-tetrafluoropropane (244bb) to 1234yf or gas phase desalting the 2-chloro-2,3,3,3-tetrafluoropropane (244bb). Also disclosed are 2,3,3,3-tetrafluoropropene (1234yf) compositions produced by contacting 2-chloro-2,3,3,3-tetrafluoropropane (244bb) with a base at a temperature sufficient to effect dehydrochlorination to form 2,3,3,3-tetrafluoropropene (1234yf).

[0036] The various embodiments can be used alone or in combination with each other. Other features and advantages of the present invention will become apparent from the following more detailed description, taken in conjunction with the accompanying drawings, which illustrate, by way of example, the principles of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0037] The foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention.

[0038] As used herein, "comprises," "comprising," "includes," "including," "has," "having," or any other variation is 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 to such process, method, article, or apparatus. Furthermore, unless expressly stated to the contrary, "or" means inclusive rather than exclusive or exclusive. 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).

[0039] The transitional phrase "consisting of" excludes any element, step, or ingredient not specified. When in a claim, such a phrase excludes the inclusion of materials other than those recited, except for impurities normally accompanying the materials. When the phrase "consisting of" appears within a clause in the body of a claim rather than immediately following the preamble, the phrase is intended to limit only the elements set forth in that clause and does not exclude other elements from the claim as a whole.

[0040] The transitional phrase "consisting essentially of" is used to define compositions, methods, and methods that include materials, steps, features, ingredients, or elements in addition to those literally disclosed, provided that these additionally included materials, steps, features, ingredients, or elements have a substantial effect on the basic and novel characteristics of the claimed invention, particularly the mode of action for achieving any desired result of the inventive process. The term "consisting essentially of" has a meaning intermediate between "comprising" and "consisting of."

[0041] It should be readily understood that where applicants have defined an invention or a portion thereof with open-ended terms such as "comprising," the description should be construed to also include inventions using the terms "consisting essentially of" or "consisting of" (unless otherwise expressly stated).

[0042] Additionally, the use of "a" or "an" is used 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 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.

[0043] The term "selectivity," as used herein, means the ratio, expressed as a percentage, of the moles of desired product to the moles of desired and undesired products.

[0044] The term "yield" as used herein means the ratio of the amount of product produced to the theoretical maximum amount of product, based on the amount of limiting reagent.

[0045] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled 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 merely illustrative and are not intended to be limiting.

[0046] Methods for producing hydrofluoro-olefins (HFOs) from hydrochloro-olefins, hydrochlorofluoro-olefins and hydrochlorofluorocarbon reagents and intermediates are provided. In an exemplary embodiment, 2-chloro-3,3,3-trifluoropropene (1233xf) is produced by dehydrochlorination of 2,3-dichloro-1,1,1-trifluoropropane (243db).

[0047] The techniques of the present invention may be carried out in a reactor suitable for gas phase reactions. The reactor is fabricated from materials that are resistant to the reactants used. The reactor may be constructed from materials that are resistant to the corrosive effects of hydrogen chloride and hydrogen fluoride, such as stainless steel, Hastelloy, Inconel, Monel, gold, or gold wire or quartz. The reaction may be batch, continuous, semi-continuous, or a combination thereof. Suitable reactors include batch reaction vessels and tubular reactors.

[0048] In a first embodiment, as shown in Scheme (1), 2,3-dichloro-1,1,1-trifluoropropane (243db) undergoes dehydrochlorination in the gas phase to form 2-chloro-3,3,3-trifluoropropene (1233xf).

[0049] [ka]

[0050] In one embodiment, the dehydrochlorination is a thermally driven process in the presence of a dehydrochlorination catalyst. Suitable catalysts include activated carbon, alumina, chromium oxide, transition metal oxides, metal halides, and combinations thereof. When a gas phase thermally driven process is employed, the contact time can range from about 10 seconds to about 5 minutes, from about 30 seconds to about 4 minutes, and optionally from about 1 to about 3 minutes. The use of activated carbon and metal halides on a carbon catalyst can provide desirable results and achieve selectivity to form 1233xf of about 90 to about 99%.

[0051] In another embodiment, when an alumina or chromium oxide catalyst is used in the gas phase thermally driven dehydrochlorination process, the selectivity of the reaction towards the structural isomer 1-chloro-3,3,3-trifluoro-1-propene (1233zd) is typically observed over a range of about 50 to about 92%. When using an alumina or chromium oxide catalyst, the formation of 1233zd is suppressed and the selectivity of 1233xf is improved when hydrogen fluoride (HF) is co-injected into the reaction with 243db. The molar ratio of HF / 243db can range from 0.5 to about 5, from about 1 to about 4.5, and in some cases from about 2 to 4. In some embodiments, the selectivity of 1233xf formation can be greater than about 80%, greater than about 92%, or greater than about 95%. Without being bound by any theory or explanation, the selectivity in 1233xf formation can be increased by using HF.

[0052] In a second embodiment, the dehydrochlorination may be carried out in the liquid phase by contacting 243db with a strong base such as sodium hydroxide, potassium hydroxide, potassium tert-butoxide, calcium oxide, or calcium hydroxide. The molar ratio of base to 243db may range from about 0.1 to about 2, from about 0.5 to about 1.75, and in some cases from about 0.75 to about 1.5. The desired results have been obtained by using a base including NaOH. The liquid phase dehydrochlorination may be carried out in the presence or absence of a phase transfer catalyst. In some embodiments, the phase transfer catalyst may include a quaternary ammonium salt, a phosphonium salt, or a crown ether. The amount of phase transfer catalyst may range from about 0.1 to about 3% by weight, from about 0.5 to about 2.5%, and in some cases from about 1 to about 2%. The desired results may be obtained by using a quaternary ammonium.

[0053] Another embodiment relates to a composition comprising at least one oligomer. The oligomer may comprise at least one of one or more of 1233 monomer, 1233 dimer, 1233 trimer, and high molecular weight 1233 oligomer. The composition may be obtained upon conversion of 243db to 1233xf during storage of a 1233xf-containing composition at elevated temperature and exposure to an initiator. Examples of initiators include at least one of Lewis acids and oxidizing agents (e.g., O2 and air). Further embodiments relate to a composition comprising 1233xf and at least one of the aforementioned oligomers. In one aspect of this embodiment, the 1233xf oligomer is selected from the group consisting of the following:

[0054] [ka] It has the structure:

[0055] The oligomeric structures may vary, including non-linear backbones, branched groups, and double bonds present at the terminal, internal, or internal as branches. "n" may range from 0 (dimer) to 9, typically corresponding to n being 3 to 9 or 4 to 9 trimers.

[0056] In another embodiment of the invention, the repeating unit of the oligomer is a telomer:

[0057] [ka] may include.

[0058] In further embodiments, the 1233xf-containing composition can include at least one additional compound selected from the group consisting of 1243zf, 244bb, 1224 isomers (e.g., 1224yd), 1230xa, 1231xf, 1233zd, 1233xfB (2-bromo-3,3,3-trifluoropropene), 1223xd, 1223za, 1232xf, 243db, 3,3,3-trifluoropropyne, 1-chloro-3,3,3-trifluoropropyne, 234bb, 233ab, and 123. In yet further embodiments, the composition can include 1233xf, at least one 1233 oligomer, and at least one additional compound. The amount of oligomer can range from greater than 0 to 2%, from about 0.1% to 1.8%, and in some cases from about 0.2% to 1.5% of the composition. The amount of additional compounds may range from greater than 0 to about 5%, from about 0.1% to about 4%, and in some cases from about 0.2% to about 3% of the composition. The compositions of these embodiments can also be prepared by blending various compounds to obtain the desired composition. The amount of oligomers can be increased by increasing the temperature, exposure to oxidizing agents (e.g., O2 and air), and contact with Lewis acids.

[0059] In one embodiment, the oligomers and 1233xf can be separated by distillation, adsorption, centrifugation, and / or filtration.

[0060] In another embodiment, the oligomers, if present, can be dissolved by contacting the composition containing the oligomers with at least one solvent. In one particular embodiment, precipitated or solid oligomers are dissolved to remove solvated oligomers. Examples of suitable solvents include at least one member selected from the group consisting of 113a, dichloromethane, acetone, THF, CHCl3, 1233xf, 244bb, CCl4, 114a, 114, 113, 243db, 250fb, 1230xa, 240db, 1233zd, 1223xd, 1224yd, and 253fb. While any suitable amount of solvent can be used, the ratio of solvent to oligomers can range from about 3:1 to 200:1, from about 10:1 to about 175:1, and in some cases from about 25:1 to about 150:1. In a further embodiment, a solvent may be used to remove the oligomer from a composition comprising 1233xf, the oligomer, and optionally at least one additional compound.

[0061] In the gas phase dehydrochlorination process, the temperature in the reaction zone may be from about 325° C. to about 450° C. The preferred temperature varies as a function of the catalyst described herein. The pressure used in the gas phase process may range from about atmospheric to about 100 psig. The dehydrochlorination process may be carried out at superatmospheric, atmospheric, or subatmospheric pressures. The contact time of the starting materials with the catalyst may vary widely. Typically, the contact time is from about 10 minutes to about 150 minutes. In some embodiments of the invention, the contact time is from about 20 to about 80 seconds.

[0062] When a liquid phase process is used, the temperature can range from about 20 to about 100° C., from about 25 to 75° C., and in some cases from about 30 to about 70° C. The liquid phase process time can range from about 10 minutes to 4 hours, from about 30 minutes to about 3 hours, and in some cases from about 1 hour to about 2 hours.

[0063] The contacting step may be carried out by methods known in the art. In some embodiments of the invention, the starting materials, optionally with an inert gas, are fed to a reactor containing a catalyst. In some embodiments of the invention, the starting materials, optionally with an inert gas, are passed through a catalyst bed in the reactor. In some embodiments of the invention, the starting materials, optionally with an inert gas, may be mixed with the catalyst in the reactor using stirring or agitation.

[0064] The dehydrochlorination process may be carried out in the presence of an inert gas, such as He, Ar, or N2. In some embodiments of the present invention, an inert gas is co-fed with the starting materials into the reactor. The amount of inert gas may range from about 5 to about 200%, from about 10 to about 150%, and in some cases from about 25 to about 100% of the volume of the organic starting materials.

[0065] In some embodiments, carbon is suitable as a dehydrochlorination catalyst. Carbon used in embodiments of the present invention may be derived from any of the following sources: wood, peat, coal, coconut shells, bones, lignite, petroleum-based residues, and sugar. Commercially available carbon that may be used includes 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™.

[0066] Activated carbon can also include three-dimensional matrix porous carbonaceous materials. Examples are those described in U.S. Pat. No. 4,978,649, incorporated herein by reference. In one embodiment of the present invention, activated carbon is prepared by introducing a gaseous or vaporous carbon-containing compound (e.g., a hydrocarbon) into a granule of a large amount of carbon material (e.g., carbon black), decomposing the carbon-containing compound and depositing carbon on the surface of the granule, and treating the resulting material with an activation gas containing steam to provide a porous carbonaceous material. A carbon-carbon composite material is thus formed.

[0067] Carbon catalyst embodiments include both non-acid washed, acid washed, and caustic washed carbon. In some embodiments, suitable carbon catalysts can be prepared by treating carbon with acids such as HNO3, HCl, HF, H2SO4, HClO4, CH3COOH, and combinations thereof. The acid treatment is typically sufficient to provide carbon containing less than 1000 ppm ash. Some suitable acid treatments of carbon are described in U.S. Pat. No. 5,136,113, incorporated herein by reference. In some embodiments, the activated carbon is dried at an elevated temperature and then soaked in 1-12 wt. % HNO3 with occasional agitation for 8-24 hours. The soaking process can be carried out at temperatures ranging from room temperature to 80° C. The activated carbon is then filtered and washed with deionized water until the pH of the washings is greater than 4.0 or until the pH of the washings does not change. Finally, the activated carbon is dried at an elevated temperature.

[0068] In some embodiments, the carbon is activated carbon. In some embodiments, the carbon is non-acid washed activated carbon. In some embodiments of the present invention, the carbon is acid washed activated carbon. The carbon may be in the form of a powder, granules, pellets, or the like.

[0069] 2-chloro-3,3,3-trifluoropropene (1233xf) may be purified before further use. In some embodiments, 2-chloro-3,3,3-trifluoropropene (1233xf) is purified by distillation. In one embodiment, distillation can be carried out by heating the reaction mixture to a temperature below the boiling point of 2,3-dichloro-1,1,1-trifluoropropane (243db) and above the boiling point of 2-chloro-3,3,3-trifluoropropene (1233xf), which temperature depends on the pressure at which the reaction is carried out. The 1233xf recovered by heating the reaction mixture can be dried by methods known in the art, including one or more of condensing and decanting the aqueous phase, passing the 1233xf phase through a molecular sieve, and removing water from the 1233xf phase as an azeotrope. Unreacted 2,3-dichloro-1,1,1-trifluoropropane (243db) may be recovered and recycled to the reaction to increase yield. The aqueous salt phase can be removed from the unreacted 243db phase by decantation.

[0070] In a third embodiment, 2-chloro-3,3,3-trifluoropropene (HCFC-1233xf) may be produced by the vapor phase fluorination of a chlorocarbon or mixed chlorocarbon feed comprising one or more materials selected from the group of 1,1,1,2,3-pentachlorodipropane (HCC-240db), 2,3,3,3-tetrachloropropene (1230xf), and 1,1,2,3-tetrachloropropene (HCC-1230xa) with hydrogen fluoride to produce a product stream comprising hydrogen fluoride, 2-chloro-3,3,3-trifluoropropene (1233xf), and hydrogen chloride. The yield of 1233xf in the product stream may range from about 80% to about 99.9%, from about 85% to about 99%, and in some cases, from about 88% to about 99%.

[0071] The reaction of the third embodiment may be carried out as a gas phase process. The reactor is charged with a gas phase fluorination catalyst. Any fluorination catalyst known in the art may be used in this process. Suitable catalysts include, but are not limited to, chromium, aluminum, cobalt, manganese, nickel and iron oxides, hydroxides, halides, oxyhalides, inorganic salts thereof, and mixtures thereof. Suitable catalyst combinations for the present invention non-exclusively include Cr2O3, FeCl3 / C, Cr2O3 / Al2O3, Cr2O3 / AlF3, Cr2O3 / carbon, CoCl2 / Cr2O3 / Al2O3, NiCl2 / Cr2O3 / Al2O3, CoCl2 / AlF3, NiCl2 / AlF3, and mixtures thereof. Chromium oxide / aluminum oxide catalysts are described in U.S. Pat. No. 5,155,082, which is incorporated herein by reference. Chromium (III) oxides, such as crystalline chromium oxide or amorphous chromium oxide, are preferred, with amorphous chromium oxide being most preferred. Chromium oxide (Cr2O3) is a commercially available material that can be purchased in a variety of particle sizes. A fluorination catalyst having a purity of at least 98% is preferred. The fluorination catalyst is present in excess, but at least in an amount sufficient to cause the reaction.

[0072] The reactor is preheated to the fluorination reaction temperature while anhydrous HF is fed to the reactor. A stream containing chlorocarbon feedstock, e.g., 1,1,2,3-tetrachloropropene, and optionally a stabilizer, is introduced into the next reactor vessel and maintained at the desired temperature. Any suitable stabilizer can be used, but examples of stabilizers include triethylamine. The amount of stabilizer can be greater than 0 ppm to about 100 ppm, about 10 ppm to 90 ppm, and in some cases about 25 ppm to about 50 ppm. 1,1,2,3 tetrachloropropene (HCC-1230xa) and HF can be fed to the reactor at any convenient temperature and pressure. In a preferred embodiment, either or both of HCC-1230xa and HF are prevaporized or preheated to a temperature of about 30° C. to about 300° C. prior to entering the reactor. In another embodiment, HCC-1230xa and HF are vaporized in the reactor. The HF and HCC-1230xa feeds are then adjusted to the desired molar ratio. The HF to HCC-1230xa molar ratio preferably ranges from about 3:1 to about 100:1, more preferably from about 4:1 to about 50:1, and most preferably from about 5:1 to about 20:1.

[0073] The gas phase fluorination reaction is carried out at a preferred temperature ranging from about 80°C to about 400°C, more preferably from about 100°C to about 350°C, and most preferably from about 200°C to about 330°C. The pressure in the reactor is not critical and can be superatmospheric, atmospheric, or under vacuum. The vacuum pressure can be from about 5 torr (0.0966 psig) to about 760 torr (14.69 psig). During the gas phase fluorination reaction, HCC-1230xa and HF react in the gas phase in the presence of a fluorination catalyst. The reactant vapors are contacted with the fluorination catalyst for about 1 to 120 seconds, or more preferably for about 1 to 20 seconds.

[0074] The above reaction may result in the formation of additional reaction products. In some embodiments, additional reaction products of the reaction include at least one compound selected from the group consisting of 1,2-dichloro-3,3,3-trifluoropropene (1223xd), 2,3-dichloro-3,3-difluoropropene (1232xf), 2,2,3-trichloro-1,1,1-trifluoro-propane (233ab), 2,3,3-trichloro-1,1,1-trifluoro-propane (233da), 3,3,3-trifluoropropyne, 1-chloro-3,3,3-trifluoropropyne, 3,3,3-trifluoro-1-propene (1243zf), 1-chloro-3,3,3-trifluoro-1-propene (1233zd), 1-chloro-2,3,3,3-tetrafluoro-1-propene (1224yd), and 2-bromo-3,3,3-trifluoropropene. 1233XF, 1,2-dichloro-3,3,3-trifluoropropene (1223XD), 2,3-dichloro-3,3-difluoropropene (1232XF), 2,2,3-trichloro-1,1,1-trifluoropropane (233AB), 2,3,3-trichloro-1,1,1-trifluoropropane (233DA), 3,3,3-trifluoropropyne, 1-chloro-3,3,3-trifluoropropyne, 3,3,3-trifluoropropyne, A composition comprising at least one element selected from the group consisting of 1-chloro-3,3,3-trifluoro-1-propene (1243zf), 1-chloro-3,3,3-trifluoro-1-propene (1233zd), 1-chloro-2,3,3,3-tetrafluoro-1-propene (1224yd), and 2-bromo-3,3,3-trifluoropropene can be prepared by blending 1233xf with at least one of the aforementioned elements. In one embodiment of the present invention, the element comprises at least one of 1-chloro-3,3,3-trifluoropropyne, 2-bromo-3,3,3-trifluoropropene, 1-chloro-3,3,3-trifluoro-1-propene (1233zd), 1,2-dichloro-3,3,3-trifluoropropene (1223xd), or 1-chloro-2,3,3,3-tetrafluoro-1-propene (1224yd).The amount of the element in the composition can range from greater than 0% to about 10% by weight, from about 0.01% to about 5% by weight, from about 0.1% to about 2% by weight, and in some cases from about 0.1% to about 100 ppmw.

[0075] Compositions comprising 2-chloro-3,3,3-trifluoropropene (1233xf) can be used in a variety of applications as a thermally conductive material with low global warming potential. Suitable applications include, but are not limited to, heat pipes, refrigeration systems, immersion cooling systems, and cleaning solvents. 2-chloro-3,3,3-trifluoropropene (1233xf) can further be used as a reactive intermediate for the production of additional hydrofluorocarbon compounds, many of which also exhibit low global warming potential.

[0076] The composition comprising 2-chloro-3,3,3-trifluoropropene (1233xf) may be used as an intermediate to form additional fluorinated compounds. In one embodiment, as shown in Scheme (2), 2-chloro-3,3,3-trifluoropropene (1233xf) in the liquid phase is contacted with hydrogen fluoride in the presence of a catalyst to undergo a hydrofluorination reaction to form 2-chloro-1,1,1,2-tetrafluoropropane (244bb).

[0077] [ka]

[0078] In one embodiment, the catalyst is a Lewis acid catalyst such as SbCl, TiCl, SbF, SnCl, SbCl, TaF, or TiF. In one embodiment, the Lewis acid catalyst is SbCl x F 5-xThe selectivity of the reaction is typically in the range of 80-99%, or 90-99%. The yield of the reaction is typically at least 90%. In some embodiments, the yield is greater than 95%, greater than 97%, or greater than 99%. Examples of suitable reaction conditions are described in WO 2007 / 079431, the disclosures of which are incorporated herein by reference.

[0079] Alternatively, the hydrofluorination may be carried out in the gas phase in the presence of a catalyst. Suitable gas phase catalysts include antimony chloride on carbon (SbCl5 / C). The selectivity of the gas phase process may be greater than 95%, greater than 97%, or greater than 98%. Yields of up to about 92% have been observed. Examples of suitable reaction conditions are described in US Patent Application Publication No. 20090182179 A1, the disclosures of which are incorporated herein by reference.

[0080] In one embodiment, 1-chloro-1,1,1,2-tetrafluoropropene (244bb) in the gas phase undergoes a dehydrochlorination reaction to form 2,3,3,3-tetrafluoropropene (1234yf), as shown in Scheme (3).

[0081] [ka]

[0082] The reaction proceeds by thermally dehydrochlorinating 2-chloro-2,3,3,3-tetrafluoropropane (244bb) to 1234yf, or by contacting 2-chloro-2,3,3,3-tetrafluoropropane (244bb) with a gas phase dehydrochlorination catalyst to form 2,3,3,3-tetrafluoropropene (1234yf), or by contacting 2-chloro-2,3,3,3-tetrafluoropropane (244bb) with a base at a temperature sufficient to cause dehydrochlorination to form 2,3,3,3-tetrafluoropropene (1234yf). Examples of suitable process conditions are disclosed in US Patent Application Publication No. 20110270000, China Patent Application Publication No. 103483142, and International Publication No. 2019203318. These disclosures are incorporated herein by reference.

[0083] In one embodiment, the dehydrochlorination is a thermally driven and gas phase process in the presence of a dehydrochlorination catalyst. Suitable catalysts include activated carbon, Pd / C, Pt / C, MgF2, Cr2O3, MgO, FeCl3, CsCl / MgF2, and KCl / C. The selectivity of the reaction may be 80-92%, or 85-90%. The catalyst contact time may range from about 10 seconds to about 5 minutes, from about 30 seconds to about 4 minutes, and optionally from about 1 to about 3 minutes.

[0084] In one embodiment, the dehydrochlorination may be carried out without a catalyst by a pyrolysis route. In one embodiment, the reaction mixture is heated to about 400-500° C. in the absence of oxygen. By "absence of oxygen" it is meant that less than about 100 ppmv of oxygen is present during the dehydrochlorination. Selectivities of greater than 98% may be achieved.

[0085] Alternatively, the dehydrochlorination can be carried out in the liquid phase by contacting 244bb with a strong base, such as sodium hydroxide, potassium hydroxide, potassium tert-butoxide, calcium oxide, or calcium hydroxide, in the presence of a catalyst. Suitable catalysts include transition metals with activated carbon, such as Pt / C. The selectivity of the liquid phase dehydrochlorination can be about 92-96%. In some embodiments, the reaction can be carried out at a temperature of 70°C to 130°C. Examples of suitable reaction conditions and reactant ratios can be found in US Patent Publication No. 20110270000, Chinese Patent Publication No. CN103483142, and WO2019203318, the disclosures of which are incorporated herein by reference.

[0086] In one embodiment, as shown in Scheme (4), 2-chloro-3,3,3-trifluoropropene (1233xf) in the gas phase is contacted with hydrogen fluoride in the presence of a catalyst and undergoes conversion to form 2,3,3,3-tetrafluoropropene (1234yf).

[0087] [ka]

[0088] In one embodiment, the catalyst is a metal halide catalyst, such as fluorinated chromium oxide, fluorinated Al2O3, fluorinated chromium oxide supported on carbon, fluorinated Al2O3 supported on carbon, or a chromium halide. The selectivity of the reaction is typically in the range of 20-90%, about 30-85%, or in some cases about 65-90%. The yield of the reaction is typically at least 90%. In some embodiments, the yield is greater than 95%, greater than 97%, or greater than 99%. Examples of suitable reaction conditions and reactant ratios are disclosed in U.S. Patent Application Publication No. 20120078020 A1, the disclosures of which are incorporated herein by reference.

[0089] 2,3,3,3-tetrafluoropropene (1234yf) may be further purified. In some embodiments, 2,3,3,3-tetrafluoropropene (1234yf) is purified by distillation. In one embodiment, distillation may be performed by cooling the reaction mixture to a temperature below the boiling point of 2,3,3,3-tetrafluoropropene (1234yf) (-29.5°C). Unreacted 1-chloro-1,1,1,2-tetrafluoropropene (244bb) may be recycled to the reaction to increase yield. If 1233xf is fed to the reactor and vaporized before becoming 244bb, oligomers may remain in the vaporizer and cause vaporizer fouling, and a solvent may be used to dissolve the oligomers and remove the oligomers that desorb from the vaporizer. 1233xf oligomers may also accumulate at the bottom of the distillation column during distillation of 1233xf, and a solvent may be used to dissolve the oligomers and remove the oligomers that have desorbed from the distillation packing. To remove the solid polymer from a vessel, such as, but not limited to, a heat exchanger or distillation column, the process fluid containing 1233xf is removed and a solvent is added. The solvent may be held in the vessel or circulated through the vessel. Heat may be applied to increase the temperature to assist in dissolving the polymer. After a period of time sufficient to dissolve the 1233xf polymer, which may be 2 to 12 hours by way of example, the solvent is removed and the process fluid containing 1233xf is reintroduced.

[0090] The following examples are provided to illustrate certain embodiments of the invention and are not intended to limit the scope of the appended claims. EXAMPLES

[0091] Example 1: Dehydrochlorination of 243db to 1233xf with 30% NaOH at 35°C 100g of 243db, 20g of 30wt% NaOH and 0.25g of TBAB were charged to a 400ml autoclave reactor. The reactor was sealed and then heated to 35°C with stirring. After the reactor was stirred at 35°C for 1 hour, 20g of 30wt% NaOH was added to the reactor three times at hourly intervals. After all the NaOH solution was added, it was stirred for another 3 hours at 35°C. The reactor was cooled to room temperature. Organic liquid samples were withdrawn from the dip tube and analyzed by GC-MS-FID using a GASPRO RTx 1 column. The reaction conditions are shown in Table 1 below.

[0092] [Table 1]

[0093] Example 2: Dehydrochlorination of 243db to 1233xf with 30% NaOH at 45°C 100g of 243db, 92g of 30wt% NaOH and 0.5g of TBAB were charged to a 400ml autoclave reactor. The reactor was sealed and then heated to 45°C with stirring. The reactor was stirred at 45°C for 2 hours and cooled to -10°C. The reactor was opened and the organic liquid phase was analyzed by GC-MS-FID using a GasPro RTx1 column. The reaction conditions are shown in Table 2 below.

[0094] [Table 2]

[0095] Example 3: 243db dehydrochlorination to 1233xf with 30% NaOH at 55°C 100g of 243db, 23g of 30wt% NaOH, 4g of water and 0.2g of TBAB were charged to a 400ml autoclave reactor. The reactor was sealed and then heated to 55°C with stirring. After the reactor was stirred at 55°C for 1 hour, 20g of 30wt% NaOH was added to the reactor in three portions at hourly intervals. After all the NaOH solution was added, it was stirred at 55°C for an additional 4 hours. The reactor was cooled to room temperature. Organic liquid samples were withdrawn from the dip tube and analyzed by GC-MS-FID using a GASPRO RTx 1 column. The reaction conditions are shown in Table 3 below.

[0096] [Table 3]

[0097] Example 4 Oligomer Analysis Using GC / MS 100g of 243db, 23g of 30wt% NaOH, 4g of water and 0.2g of TBAB were charged to a 400ml autoclave reactor. The reactor was sealed and then cooled to 0°C with agitation. After the reactor was agitated for 1 hour at 0°C, 20g of 30wt% NaOH was added to the reactor three times at hourly intervals. After all the NaOH solution was added, the reactor contents were agitated for an additional 4 hours at 0°C. The reactor was allowed to reach room temperature. Organic liquid samples were drawn from the dip tube and analyzed by GC-MS-FID using a GASPRO RTx 1 column. The reaction conditions are shown in Table 4 below.

[0098] [Table 4]

[0099] Example 5: Oligomer Analysis Using GC / MS Liquid Chromatography (LC) To a 400 mL Hastelloy lined shaker tube, 100 g of 1233xf and 23 g of HF were added. The tube was heated to 130° C. with shaking for 24 hours. After 24 hours, the tube was cooled to room temperature and an aqueous solution of potassium hydroxide (67.3 g solid KOH dissolved in 200 mL water) was added. The test was repeated at 90° C. and a portion of the organic layer from each test was removed and analyzed separately by GC / MS-FID (RTX column). The GC / MS results are shown in Table 5 as area %. Due to the detection limit of the GCMS system, only low molecular weight oligomeric compounds are shown in Table 5.

[0100] [Table 5]

[0101] LCMS (Agilent 1290 Infinity II with 6520 QTOF, column: Agilent Infinity Lab Poroshell 120 EC-C18 (2.1×50 mm, 2.7 μm)) was used to identify the higher molecular weight telomeric oligomeric compounds. Results are shown in Table 6 as relative area percent, where n=7 is taken as 100%. GC / MS / LC analysis detected telomers with the following repeat units:

[0102] [ka]

[0103] [Table 6]

[0104] Although the present invention has been described with reference to one or more embodiments, it will be understood by those skilled in the art that various changes can be made without departing from the scope of the invention and that equivalents can be substituted for its elements. In addition, many modifications can be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope of the invention. Therefore, it is not intended that the invention be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but the invention is intended to include all embodiments falling within the scope of the appended claims. In addition, all numerical values ​​specified in the detailed description should be interpreted as if both exact and approximate values ​​were explicitly specified.

Claims

1. 1. An intermediate feed composition comprising: a) at least 94.6% 2-chloro-3,3,3-trifluoropropene (1233xf), based on the total GC area of ​​the composition; b) 2,3-dichloro-1,1,1-trifluoropropane (243db), 1,2-dichloro-3,3,3-trifluoropropene (1223xd), and 1-chloro-3,3,3-trifluoropropyne; c) at least one additional compound selected from 2,3-dichloro-3,3-difluoropropene (1232xf), 2,2,3-trichloro-1,1,1-trifluoropropane (233ab), 2,3,3-trichloro-1,1,1-trifluoropropane (233da), 3,3,3-trifluoropropyne, 3,3,3-trifluoro-1-propene (1243zf), 1-chloro-3,3,3-trifluoro-1-propene (1233zd), 1-chloro-2,3,3,3-tetrafluoro-1-propene (1224yd), and 2-bromo-3,3,3-trifluoropropene; d) optionally, greater than 0% to 2% of at least one solvent soluble dimer, trimer or oligomer of 2-chloro-3,3,3-trifluoropropene (1233xf); 23. An intermediate feed composition comprising:

2. The oligomer comprises: 【Chemistry 1】 The structure is The composition of claim 1, wherein n=0-9.

3. Further comprising at least one solvent capable of at least partially dissolving said oligomer in a solvent:oligomer ratio of 3:1 to 200:1, said at least one solvent being optionally selected from 113a, dichloromethane, acetone, THF, CHCl 3 , 1233xf, 244bb, CCl 4 3. The composition of claim 2, comprising at least one member selected from the group consisting of 114a, 114, 113, 243db, 250fb, 1230xa, 240db, 1233zd, 1223xd, 1224yd, and 253fb.

4. The composition of claim 1 comprising a dimer of 2-chloro-3,3,3-trifluoropropene (1233xf).

5. 2. The composition of claim 1 comprising a trimer of 2-chloro-3,3,3-trifluoropropene (1233xf).

6. The composition of claim 1, comprising 0.0019% or more and less than 5.4% of 2,3-dichloro-1,1,1-trifluoropropane (243 db) based on the total GC area of ​​the composition.

7. 10. The composition of claim 1, further comprising a solvent capable of partially dissolving at least one of a dimer, trimer, or oligomer of 2-chloro-3,3,3-trifluoropropene (1233xf).

8. The composition of claim 1, comprising 2,2,3-trichloro-1,1,1-trifluoropropane (233ab).

9. 10. The composition of claim 1 containing up to 2.69% 2,3-dichloro-1,1,1-trifluoropropane (243 db) based on the total GC area of ​​the composition.

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