Compositions and methods for synthesizing 3,3,4,4,4-pentafluoro-1-butene

Abstract

The present application relates to compositions comprising 3,3,4,4,4-pentafluoro-1-butene (HFO-1345zf, CF3CF2CH=CH2), methods of making such compositions, and uses thereof.

Description

Technical Field

[0001] This application relates to compositions containing fluorinated compounds, methods for preparing such compositions, and uses thereof, particularly 3,3,4,4,4-pentafluoro-1-butene (HFO-1345zf, CF3CF2CH=CH2). Background Technology

[0002] Increased public awareness of the environmental impacts of fossil fuel extraction, transportation, and use is prompting a shift towards new forms of environmental sustainability, exemplified by regulations and reductions in atmospheric CO2 equivalent emissions. In particular, new environmental regulations for refrigerants have forced the refrigeration and air conditioning industry to seek new refrigerants with low global warming potential (GWP). For both existing and new applications in thermal management, alternative refrigerants with low GWP and ozone depletion potential (ODP) will need to comply with these new regulations.

[0003] Certain hydrofluoroolefins, such as 3,3,4,4,4-pentafluoro-1-butene (HFO-1345zf, CF3CF2CH=CH2) and E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (E-C2F5CH=CHC2F5, E-HFO-153-10mczz), satisfy both objectives. Specifically, 3,3,4,4,4-pentafluoro-1-butene can be used in heat transfer, etching gas, cleaning solvent, and dielectric gas applications, while E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene can be used in heat transfer fluid applications (e.g., immersion cooling systems, data center cooling systems, or thermal management solutions for EV batteries), dielectric liquids, and cleaning solvents. Therefore, there is a need to develop new methods and intermediate compositions for the preparation of 3,3,4,4,4-pentafluoro-1-butene (HFO-1345zf, CF3CF2CH=CH2) and E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene. Furthermore, intermediates generated in the preparation of HFO-1345zf, such as the tetrafluorobutene isomer (HCFO-1344 isomer), are also promising low-GWP candidates for use in heat transfer, dielectric liquids, and cleaning solvents. Summary of the Invention

[0004] This invention relates to compositions comprising 3,3,4,4,4-pentafluoro-1-butene (HFO-1345zf, CF3CF2CH=CH2), methods for preparing such compositions, and uses thereof.

[0005] The present invention provides a method for preparing HFO-1345zf, the method comprising contacting 2,2,4-trichloro-1,1,1-trifluorobutane (HCFC-353maf, CH2ClCH2CCl2CF3) with HF in a reactor in the presence of a fluorination catalyst to obtain a process mixture containing HFO-1345zf.

[0006] In some embodiments, the method is typically carried out at a temperature of about 250°C to 450°C and a pressure of about 0 psig to 200 psig. Preferably, the temperature is in the range of about 300°C to about 380°C.

[0007] Preferably, the pressure is in the range of about 30 psig to 180 psig, or about 40 psig to 150 psig, or about 60 psig to 120 psig.

[0008] The present invention also provides a composition comprising HFO-1345zf and at least one additional compound selected from 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), dichlorotrifluorobutene isomer (HCFO-1343 isomer), chlorotetrafluorobutene isomer (HCFO-1344 isomer), chloropentafluorobutane isomer (HCFC-355 isomer), 1,1,1,4,4,4-hexafluorobutane (HFC-356mff), and chlorotrifluorobutene isomer (HCFO-1344 isomer). The compositions include 1,1,1-trifluoroethane (HFO-1353 isomer), 1,1,1-trifluoroethane (HFC-143a), trifluoromethane (HFC-23), chlorotrifluoromethane (CFC-13), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,3,3,3-tetrafluoropropene (HFO-1234ze), 2-chloro-1,1,1,3,3,3-hexafluoro-2-butene (HCFO-1326mxz), heptafluorobutene isomer (HFO-1327 isomer), 2,2,3,3,3-pentafluoropropanal, and 2,2,4-trichloro-1,1,1-trifluorobutane (353maf). This composition can be prepared by the methods disclosed herein.

[0009] The present invention also provides compositions comprising 3,3,4,4,4-pentafluoro-1-butene (HFO-1345zf, CF3CF2CH=CH2) and 2,3,3,4,4,4-hexafluoro-1-butene (HFO-1336yf).

[0010] The present invention also provides a composition comprising 3,3,4,4,4-pentafluoro-1-butene (HFO-1345zf, CF3CF2CH=CH2) and 1,3,3,4,4,4-hexafluoro-1-butene (HFO-1336ze). Attached Figure Description

[0011] Figure 1 A flowchart is provided for a method for preparing 3,3,4,4,4-pentafluoro-1-butene according to one embodiment of the present invention. Detailed Implementation

[0012] This invention broadly relates to compositions comprising 3,3,4,4,4-pentafluoro-1-butene (HFO-1345zf, CF3CF2CH=CH2), methods for preparing such compositions, and uses thereof. General terms

[0013] Compounds may be referred to herein by their compound name (e.g., 3,3,4,4,4-pentafluoro-1-butene) or ASHRAE name (e.g., 1345zf) or chemical formula (e.g., CF3CF2CH=CH2), and optionally begin with "CFC", "HCFC", "HFC", "CFO", "HCFO" or "HFO", meaning "chlorofluorocarbon", "hydrochlorofluorocarbon", "hydrofluorocarbon", "chlorofluoroolefin", "hydrochlorofluoroolefin" or "hydrofluoroolefin". The absence of a prefix does not change the meaning of the compound.

[0014] The term "isomer" is used to refer to one having the chemical formula stated above. or A variety of compounds are identified using standard analytical techniques (GC and GC-mass spectrometry). Isomers may comprise one or more compounds having the stated chemical formula, such as straight-chain, branched, and cyclic compounds. Alternatively, isomers may comprise unsaturated compounds (having double bonds) or cyclic compounds having the same chemical formula or multiple degrees of unsaturation (two or more double bonds), or combinations thereof.

[0015] Furthermore, for compounds with unsaturation (double bonds), the compound may have "E-" and "Z-" isomers. If neither "E-" nor "Z-" is identified, the disclosed compound may contain one or both isomers. Specific isomers are identified as "E-" or "Z-". For example, HFO-1336mzz may contain one or both of E-HFO-1336mzz and Z-HFO-1336mzz, while specific isomers are identified as "E-HFO-1336mzz" and "Z-HFO-1336mzz".

[0016] As used herein, the terms “comprising,” “including,” “having,” or any other variations thereof are intended to cover non-exclusive inclusion. For example, a composition, process, method, article of manufacture, 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 composition, process, method, article of manufacture, or apparatus. Furthermore, unless expressly stated otherwise, “or” refers to an inclusive or non-exclusive or. For example, conditions A or B satisfy one of the following: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); and both A and B are true (or exist).

[0017] The transitional phrase "composed of..." does not include any unspecified elements, steps, or components. If in a claim, it will not include protection for materials other than those described, except for impurities typically associated with them. When the phrase "composed of..." appears in a clause of the body of a claim, rather than immediately following the preamble, it only limits the elements described in that clause; other elements as a whole are not excluded from the claim.

[0018] The transitional phrase "consistently composed of..." is used to define compositions or methods that include materials, steps, features, components, or elements in addition to those disclosed in the literature, provided that these additionally included materials, steps, features, components, or elements do not significantly affect one or more essential and novel features of the invention protected by the claims, particularly the mode of action for achieving the desired results of any of the methods of the invention. The term "consistently composed of..." occupies an intermediate position between "comprising" and "composed of...".

[0019] Where the applicant has defined the invention or a part thereof using open-ended terms such as “comprising”, it should be readily understood (unless otherwise stated) that the description should be interpreted as also including inventions using terms such as “substantially composed of” or “composed of”.

[0020] Furthermore, the terms "an" or "a" are used to describe the elements and components described herein. This is for convenience only and to give a general meaning to the scope of the invention. The description should be understood to include one or at least one, and the singular includes the plural, unless it is obvious that it means otherwise.

[0021] Wherever a range of values ​​is listed herein, the range is intended to include its endpoints, as well as all integers and fractions within that range, unless otherwise indicated. When a range is defined, it is not intended to limit the scope of the invention to the specific values ​​listed. Furthermore, all ranges described herein are intended to include not only the particular range specifically described, but also any combination of values ​​therein, including the stated minimum and maximum values.

[0022] As used herein, the term "compound" means all stereoisomers, geometric isomers, tautomers, and isotopes that include the structure or chemical described. Unless otherwise stated, compounds identified herein by name or structure as a particular tautomer are intended to include other tautomers.

[0023] As used in this article, the term "fluorinated catalyst" refers to a substance that accelerates a chemical reaction but is not consumed by the reaction; therefore, it can be recovered without undergoing a chemical change at the end of the reaction.

[0024] When quantities, concentrations, or other values ​​or parameters are given as a list of ranges, preferred ranges, or preferred upper and / or preferred lower limits, it should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred value and any lower or preferred value, regardless of whether the range is disclosed individually. Wherever a numerical range is listed herein, the range is intended to include its endpoints, as well as all integers and fractions within that range, unless otherwise indicated.

[0025] As used herein, in some embodiments, the term “about” may be quantified to represent a specified value of ±1%, ±2%, ±3%, up to and including ±10%, and all integers and fractions therebetween. Method Description

[0026] This invention describes a method for preparing a mixture or composition comprising, consisting of, or substantially consisting of 3,3,4,4,4-pentafluoro-1-butene (HFO-1345zf, CF3CF2CH=CH2) and one or more other compounds.

[0027] In one embodiment, the present invention provides a method for preparing HFO-1345zf, the method comprising HCFC-353maf and HF in a reactor in the presence of a fluorination catalyst.

[0028] This invention provides a method for preparing HFO-1345zf, the method comprising contacting HCFC-353maf with HF in a reactor in the presence of a fluorination catalyst to obtain a process mixture containing HFO-1345zf, wherein the method is carried out at a temperature of about 250°C to 450°C and a pressure of about 0 psig to 200 psig. Preferably, the temperature is in the range of about 300°C to about 380°C, such as about 320°C. Preferably, the pressure is in the range of about 30 psig to 180 psig, or about 40 psig to 150 psig, or about 60 psig to 120 psig, such as about 80 psig.

[0029] The method of the present invention is preferably carried out in the presence of an oxygen-containing gas, which may be co-fed with the starting material 353maf and / or HF. The oxygen-containing gas may be, for example, air.

[0030] In this invention, it has been found particularly advantageous to contact HCFC-353maf with HF at a temperature of about 250°C-450°C in the presence of a fluorination catalyst. At lower temperatures (300°C), oxygen is less effective at removing carbon deposits from the catalyst, leading to faster deactivation. Higher temperatures increase the fluorination rate of the catalyst, also causing catalyst deactivation.

[0031] In one embodiment, the composition comprising HFO-1345zf is produced in one step by fluorinating HCFC-353maf. More specifically, the method comprises fluorinating HCFC-353maf by reacting it with HF in the presence of a fluorinating catalyst, preferably a fluorinating catalyst, to produce a process mixture comprising HFO-1345zf. This process mixture comprises, consists of, or is substantially composed of HFO-1345zf, which is or can be used to produce other compounds, including but not limited to 3,5,5-trichloro-1,1,1,2,2,6,6,6-octafluorohexane (HCFC-548mafd, CF3CF2CHClCH2CCl2CF3) and subsequently E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (E-HFO-153-10mczz, E-CF3CF2CH=CHCF2CF3). Fluorination catalyst

[0032] The fluorination catalyst used in the method of the present invention comprises one or more metals, metal oxides, metal oxyfluorides, or metal fluorides. Metal oxide catalysts preferably form metal (oxy)fluorides exhibiting Lewis acid characteristics. Examples of metals suitable for fluorination catalysts are selected from one or more metals selected from Al, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, La, and Ce.

[0033] In some embodiments, the fluorination catalyst comprises one or more of Al, Zr, Cr, Co, Ni, and Zn.

[0034] In one embodiment, the fluorination catalyst comprises chromium or aluminum. In another embodiment, the fluorination catalyst comprises chromium or aluminum and one or more of Zn, Zr, Co, and Ni.

[0035] Certain metal oxide or metal fluoride fluorination catalysts may contain one or more additional metals selected from the group consisting of Li, Na, K, Ca, Mg, and Cs. The additional metals may be present in small amounts (e.g., less than 2000 ppm, less than 1000 ppm, less than 500 ppm, less than 100 ppm, or less than 10 ppm).

[0036] In some embodiments, the fluorination catalyst comprises aluminum. Aluminum may be present in the form of aluminum oxide, aluminum fluoride, or aluminum oxyfluoride. In some embodiments, the fluorination catalyst comprises Al and also comprises one or more of Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, La, and Ce. In some embodiments, the fluorination catalyst comprises Al and one or more of Zn, Zr, Cr, Co, and Ni.

[0037] In some embodiments, the fluorination catalyst comprises chromium. Chromium may be present in the form of chromium oxide, chromium chloride, chromium fluoride, or chromium oxyfluoride. Chromium may be in the form of Cr(III), such as Cr₂O₃. In some embodiments, the fluorination catalyst comprises Cr and also comprises one or more of Al, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, La, and Ce. In some embodiments, the fluorination catalyst comprises Cr and one or more of Zn, Zr, Co, and Ni.

[0038] In one embodiment, the fluorination catalyst comprises Cr₂O₃. In one embodiment, the fluorination catalyst comprises Cr₂O₃ and one or more of Zn, Zr, Co, K, Na, and Ni. In one embodiment, the fluorination catalyst comprises Cr₂O₃ and Zn. In one embodiment, the fluorination catalyst comprises Cr₂O₃ and Co. In one embodiment, the fluorination catalyst comprises Cr₂O₃ and Ni. In one embodiment, the fluorination catalyst comprises Cr₂O₃ and Zr.

[0039] In one embodiment, the fluorination catalyst comprises Cr2O3 and at least one of Zn, Zr, Co, and Ni, wherein the amount of Zn, Zr, Co, and / or Ni is in the range of about 100 ppm to about 10 wt% based on the weight of Cr2O3. In one embodiment, the fluorination catalyst comprises Cr2O3 and Zn, wherein the amount of Zn is in the range of about 100 ppm to about 10 wt% based on the weight of Cr2O3. In one embodiment, the fluorination catalyst comprises Cr2O3 and Zr, wherein the amount of Zr is in the range of about 100 ppm to about 10 wt% based on the weight of Cr2O3. In one embodiment, the fluorination catalyst comprises Cr2O3 and Co, wherein the amount of Co is in the range of about 100 ppm to about 10 wt% based on the weight of Cr2O3. In one embodiment, the fluorination catalyst comprises Cr2O3 and Ni, wherein the amount of Ni is in the range of about 100 ppm to about 10 wt% based on the weight of Cr2O3.

[0040] In one embodiment, the fluorination catalyst comprises Al₂O₃. In one embodiment, the fluorination catalyst comprises Al₂O₃ and one or more of Zn, Zr, Cr, Co, and Ni. In one embodiment, the fluorination catalyst comprises Al₂O₃ and Zn. In one embodiment, the fluorination catalyst comprises Al₂O₃ and Zr. In one embodiment, the fluorination catalyst comprises Al₂O₃ and Cr. In one embodiment, the fluorination catalyst comprises Al₂O₃ and Co. In one embodiment, the fluorination catalyst comprises Al₂O₃ and Ni.

[0041] In one embodiment, the fluorination catalyst comprises Al2O3 and at least one of Zn, Zr, Cr, Co, and Ni, wherein the amounts of Zn, Zr, Cr, Co, and / or Ni are in the range of about 100 ppm to about 10 wt% based on the weight of Al2O3. In one embodiment, the fluorination catalyst comprises Al2O3 and Zn, wherein the amount of Zn is in the range of about 100 ppm to about 10 wt% based on the weight of Al2O3. In one embodiment, the fluorination catalyst comprises Al2O3 and Zr, wherein the amount of Zr is in the range of about 100 ppm to about 10 wt% based on the weight of Al2O3. In one embodiment, the fluorination catalyst comprises Al2O3 and Cr, wherein the amount of Cr is in the range of about 100 ppm to about 10 wt% based on the weight of Al2O3. In one embodiment, the fluorination catalyst comprises Al2O3 and Co, wherein the amount of Co is in the range of about 100 ppm to about 10 wt% based on the weight of Al2O3. In one embodiment, the fluorination catalyst comprises Al2O3 and Ni, wherein the amount of Ni is in the range of about 100 ppm to about 10% by weight based on the weight of Al2O3.

[0042] The fluorination catalyst can be on a support (“supported”), unsupported, or a mixture of support and fluorination catalyst. If a support is present, suitable supports include AlF3, alumina, fluorinated alumina, or activated carbon. In one embodiment, the fluorination catalyst comprises chromium oxide and alumina.

[0043] Fluorination catalysts may comprise metal oxides or metal halide oxides supported on chromium oxide or aluminum oxide, such as oxides of zinc, iron, magnesium, or nickel. Fluorination catalysts may comprise metal oxides / halides / halogen oxides or mixtures of metal oxides / halides / halogen oxides supported on carbon, wherein the metal is selected from one or more of Al, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, La, and Ce.

[0044] In one embodiment, the fluorination catalyst is a chromium-based catalyst, such as chromium oxide (Cr₂O₃) or fluorinated chromium oxide, or chromium chloride, or chromium fluoride. The catalyst may be unsupported or supported on a carrier, such as activated carbon, graphite, fluorinated graphite, or fluorinated alumina. The chromium fluorination catalyst can be used alone or in the presence of a co-catalyst selected from nickel, cobalt, manganese, potassium, sodium, or zinc. In one embodiment, optionally, the chromium fluorination catalyst is high-surface-area chromium oxide, or chromium / nickel fluorinated alumina supported (Cr / Ni / AlF₃), or carbon-supported chromium halide, the preparation of which is reported in European Patent EP486333. In another embodiment, the fluorination catalyst is a fluorinated Gillette green catalyst.

[0045] In one embodiment, the fluorination catalyst comprises Al2O3. In one embodiment, the fluorination catalyst comprises Al2O3 and one or more of Zn, Zr, Cr, Co, and Ni. In one embodiment, the fluorination catalyst comprises Al2O3 and Zn, or Al2O3 and Cr, or Al2O3 and Co, or Al2O3 and Ni, or Al2O3 and Zr.

[0046] In one embodiment, the fluorination catalyst comprises chromium supported on AlF3, alumina, fluorinated alumina, or activated carbon. In another embodiment, the fluorination catalyst comprises chromium supported on alumina.

[0047] In one embodiment, the fluorination catalyst comprises zinc supported on AlF3, alumina, fluorinated alumina, or activated carbon. In another embodiment, the fluorination catalyst comprises zinc supported on alumina.

[0048] The physical shape of the fluorinated catalyst is not critical and may include, for example, pellets, extrusions, powders, or granules.

[0049] In one embodiment, the fluorinated catalyst is shaped into forms such as granules or pellets of Al, Zr, Cr, or Co. A variety of methods known in the art can be used, which are suitable for providing, for example, packed beds of catalyst in a flow reactor.

[0050] In one embodiment, the method includes activating the fluorination catalyst in a pre-fluorination treatment prior to contacting HCFC-353maf with HF in the presence of a catalyst. When the catalyst is shaped into a single form, the activation of the fluorination catalyst preferably takes place on the final shape of the catalyst. It should be understood that although the term "fluorination catalyst" is used to refer to metal oxides (including Cr2O3 and Al2O3) and metal halides (including CrCl3, CrF3), metal oxides can undergo a pre-fluorination step to generate an active catalyst in situ.

[0051] In one embodiment, the catalyst is prefluorinated prior to use by passing HF (with or without an inert diluent such as nitrogen) through the catalyst at a temperature ranging from about 250°C to 450°C.

[0052] In one particular embodiment, the fluorination catalyst comprises chromium, and the fluorination catalyst is activated prior to use by a procedure in which, in one embodiment of the prefluorination treatment, the procedure includes heating the fluorination catalyst to a temperature of 350°C to 400°C for a period of time under a nitrogen stream, and then heating the fluorination catalyst for another period of time under a stream of HF and nitrogen or air.

[0053] After a period of use, the activity of a fluorination catalyst may decrease. When this occurs, the fluorination catalyst can be regenerated, a process that involves treating the catalyst with oxygen or air at elevated temperatures. This regeneration step removes most of the organic components from the process mixture. Reaction conditions

[0054] In one embodiment, a suitable temperature for the reaction of HCFC-353maf with HF is from about 250°C to about 450°C, preferably from about 300°C to about 380°C. The temperature range is set to advantageously protect the catalyst from deactivation. It has been found that operation outside this range results in more rapid catalyst deactivation. For example, it is believed that at lower temperatures, carbonaceous compound deposits remain on the catalyst surface. Additionally, at higher temperatures, the catalyst is more readily fluorinated in a manner that similarly leads to catalyst deactivation. Therefore, a balance must be found to address the deactivation of the fluorinated catalyst from carbonaceous compound deposits and fluorination of the fluorinated catalyst.

[0055] In one embodiment, a suitable pressure for the reaction of HCFC-353maf with HF is about 0 psig to 200 psig, preferably about 30 psig to 180 psig, or about 40 psig to 150 psig, or about 60 psig to 120 psig. The pressure range is set to achieve the desired conversion and product selectivity, as well as to enhance the separation and recovery of the HCl component from the process mixture. At lower pressures, HCl recovery becomes more complex or expensive. Additionally, at higher pressures, the catalyst deactivation rate has been found to increase. Furthermore, pressure also affects the reaction rate, product selectivity, and productivity.

[0056] In the method of the present invention, preferably, the molar ratio of HF to HCFC-353maf is from about 3:1 to about 50:1, more preferably from about 10:1 to about 45:1, and more preferably from 15:1 to 40:1. Higher ratios are undesirable for the overall efficiency of the method and also affect temperature, pressure, and contact time. Lower ratios affect productivity (conversion rate, selectivity, and yield).

[0057] The method of the present invention includes contacting HCFC-353maf (CF3CCI2CH2CH2CI) with hydrogen fluoride (HF) in a reactor in the presence of a fluorination catalyst to produce a process mixture comprising HFO-1345zf and HCl. Optionally, a certain amount of oxygen is added in this method. The amount of oxygen added is in the range of about 0 mol% to about 10 mol% based on the organic feed entering the contact step. The organic feed comprises 353maf. Optionally, the organic feed further comprises an intermediate recycled from a separation method.

[0058] Preferably, the amount of oxygen added in the method of the present invention is greater than 0% and less than 10 mol%, such as about 0.2 mol% to about 5 mol%, or about 1 mol%. The amount of oxygen added in the method (such as in the range of about 0.2 mol% to about 5 mol%) improves the lifetime of the fluorination catalyst. In the absence of added oxygen, the rate of catalyst deactivation increases. It is also important to avoid adding too much oxygen in the method. Higher oxygen concentrations, specifically greater than 15 mol%, result in lower yields because of increased formation of oxygen-containing byproducts. In addition, higher oxygen concentrations pose a flammability risk.

[0059] The method of the present invention includes contacting HCFC-353maf (CF3CCI2CH2CH2CI) with hydrogen fluoride (HF) in the presence of a fluorination catalyst to produce a process mixture comprising HFO-1345zf and HCl. The contact time can be selected from a range of contact times, such as from as low as about 1 second to 180 seconds. In one embodiment, the contact time is 5 seconds to 120 seconds, 5 seconds to 60 seconds, or 10 seconds to 25 seconds, such as about 15 seconds. It should be understood that shorter contact times reduce the conversion of the starting material HCFC-353maf. However, longer contact times may be undesirable because, for a given set of reaction conditions, it may increase the formation of byproducts (lower yield, selectivity).

[0060] Preferably, the fluorination reaction is carried out in the gas phase. However, those skilled in the art will understand that the fluorination of HCFC-353maf can alternatively be carried out in the liquid phase.

[0061] In one embodiment, the HCFC-353maf starting material can be premixed with HF and then introduced into the reactor to form a process mixture comprising HFO-1345zf and HCl. In another embodiment, HF may not contact HCFC-353maf until both have been introduced into the reactor. In yet another embodiment, HCFC-353maf can be mixed with a recycled organic feed stream before being introduced into the reactor.

[0062] In some embodiments, the reaction of HCFC-353maf produces an effluent stream containing a process mixture or composition comprising HFO-1345zf and HCl.

[0063] In some embodiments, this step can be carried out in a reactor or reaction zone operating in batch, semi-batch, semi-continuous, or continuous mode to produce a reaction mixture containing 1345zf. The effluent stream from the reactor or reaction zone contains a reaction mixture containing HFO-1345zf and HCl.

[0064] For the reaction of HCFC-353maf with HF, the process mixture comprises HFO-1345zf and HCl, and may further contain excess HF, as well as optional reaction byproducts and intermediates. These reaction byproducts and intermediates may include one or more of the following: 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), dichlorotrifluorobutene isomer (HCFO-1343 isomer), tetrafluorobutene isomer (HCFO-1344 isomer), pentafluorobutene isomer (HCFO-1335 isomer), pentafluorobutane isomer (HCFC-355 isomer), 1,1,1,4,4,4-hexafluorobutane (HFC-356mff), and trifluorobutene isomer (HCFO-1353 isomer). The following are isomers of the following: pentafluorobutene (HFO-1345 isomer), 1,1,1-trifluoroethane (HFC-143a), trifluoromethane (HFC-23), chlorotrifluoromethane (CFC-13), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,3,3,3-tetrafluoropropene (HFO-1234ze), 2-chloro-1,1,1,3,3,3-hexafluoro-2-butene (HCFO-1326mxz), heptafluorobutene isomer (HFO-1327 isomer), hexafluorobutene isomer (HFO-1336 isomer), 2,2,3,3,3-pentafluoropropanal, and HCFC-353maf.

[0065] The process mixture may contain additional components such as unreacted starting materials, HCFC-353maf (CF3CCI2CH2CH2CI), reaction intermediates, and reaction byproducts. In one embodiment, the reaction intermediate comprises HCFO-1343 isomer, HFO-1344 isomer, or a mixture of two or more of them.

[0066] In one embodiment, the reaction intermediate comprises the HCFO-1343 isomer.

[0067] In one embodiment, the reaction intermediate comprises the HCFO-1344 isomer.

[0068] In one embodiment, the reaction intermediate comprises a mixture of HCFO-1343 isomer and HCFO-1344 isomer.

[0069] In any embodiment in which the reaction intermediate comprises an HCFO-1343 isomer, the HCFO-1343 isomer comprises one or more of the following: E-2,4-dichloro-1,1,1-trifluoro-2-butene (E-HCFO-1343mxz), 3,3-dichloro-4,4,4-trifluoro-1-butene (HCFO-1343maz), and Z-2,4-dichloro-1,1,1-trifluoro-2-butene (Z-HCFO-1343mxz).

[0070] In any embodiment in which the reaction intermediate comprises an HCFO-1344 isomer, the HCFO-1344 isomer comprises one or more of the following: Z-4-chloro-1,1,1,2-tetrafluoro-2-butene (Z-HCFO-1344myz), E-4-chloro-1,1,1,2-tetrafluoro-2-butene (E-HCFO-1344myz), Z-2-chloro-1,1,1,4-tetrafluoro-2-butene (Z-HCFO-1344myz), and Z-2-chloro-1,1,1,4-tetrafluoro-2-butene (Z-HCFO-1344myz). O-1344mxz), E-2-chloro-1,1,1,4-tetrafluoro-2-butene (E-HCFO-1344mxz), 3-chloro-3,4,4,4-tetrafluoro-1-butene (HCFO-1344fzb), E-2-chloro-1,1,1,3-tetrafluoro-2-butene (E-HCFO-1344mxy) and Z-2-chloro-1,1,1,3-tetrafluoro-2-butene (Z-HCFO-1344mxy).

[0071] In one embodiment, the reaction byproducts and intermediates comprise the HCFO-1335 isomer. In certain embodiments in which the reaction byproducts and intermediates comprise the HCFO-1335 isomer, the HCFO-1335 isomer comprises one or more of the following: E-1-chloro-3,3,4,4,4-pentafluoro-1-butene (E-HCFO-1335dz), E-1-chloro-1,1,4,4,4-pentafluoro-2-butene (E-HCFO-1335lzz), Z-1-chloro-1,1,4,4,4-pentafluoro-2-butene (Z-HCFO-1335lzz), and E-2-chloro-1,1,1,4,4-pentafluoro-2-butene (E-HCFO-1335mxz).

[0072] In one embodiment, the reaction byproducts and intermediates comprise the HCFC-335 isomer. In certain embodiments in which the reaction byproducts and intermediates comprise the HCFC-355 isomer, the HCFC-355 isomer comprises 4-chloro-1,1,1,2,2-pentafluorobutane (HCFC-355of).

[0073] In one embodiment, the reaction byproducts and intermediates comprise the HCFO-1353 isomer. In certain embodiments in which the reaction byproducts and intermediates comprise the HCFO-1353 isomer, the HCFO-1353 isomer comprises 3-chloro-4,4,4-trifluoro-2-butene (HCFO-1353mxz).

[0074] In one embodiment, the reaction byproducts and intermediates comprise the HCFO-1345 isomer. In certain embodiments in which the reaction byproducts and intermediates comprise the HCFO-1345 isomer, the HCFO-1345 isomer comprises 1,1,4,4,4-pentafluoro-2-butene (HFO-1345mzz).

[0075] In one embodiment, the reaction byproducts and intermediates comprise the HFO-1336 isomer. In certain embodiments in which the reaction byproducts and intermediates comprise the HFO-1336 isomer, the HFO-1336 isomer comprises one or more of the following: E-1,1,1,4,4,4-hexafluoro-2-butene (E-HFO-1336mzz), Z-1,1,1,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz), 2,3,3,4,4,4-hexafluoro-1-butene (HFO-1336yf), and 1,3,3,4,4,4-hexafluoro-1-butene (HFO-1336ze).

[0076] Any reaction byproducts, i.e., additional components of the process mixture other than HFO-1336ze and HFO-1336yf, may optionally be removed from the recycling stream and returned to the reaction vessel. Advantageously, when the process mixture contains any of HF, HCFC-353maf, and intermediates (HCFO-1343 and / or HCFO-1344), the method includes separating HF, HCFC-353maf, and intermediates from the process mixture and recycling each of these into a process for contact with the fluorinated catalyst.

[0077] In one embodiment, the method of the present invention includes reacting 353maf with an excess of HF (HF to 353maf in a ratio of about 3:1 to about 50:1, preferably about 10:1 to about 45:1, more preferably 15:1 to 40:1). In one embodiment, the catalyst comprises chromium oxide (Cr2O3) and is dried and partially fluorinated with HF prior to use. The operating temperature is about 300°C to about 380°C, and the operating pressure is about 0 psig to about 200 psig. The method further includes adding about 0.2 mol% to about 5 mol% or 0.5 mol% to 2 mol% oxygen (based on the 353maf feed) to the feed to maintain / increase catalyst lifetime. In one embodiment, in a continuous process, the reactor is periodically shut down to regenerate the catalyst. Shutdowns may occur annually, every 6 months, every 30 days, every 20 days, or every 15 days, such as every 18 days. The reactor has a heat transfer system to achieve and maintain the target operating temperature.

[0078] Specific conditions for temperature, pressure, HF:organic ratio, oxygen concentration, and contact time are provided, with the organic content at 353 mg / L. It has been found that operating outside these conditions presents limiting disadvantages. These disadvantages include catalyst deactivation, increased difficulty in recovering the product, increased byproducts (yield loss, selectivity loss), lower conversion rates, and the need for one or more larger reactors.

[0079] After leaving the reactor, the process mixture containing HFO-1345zf and HCl undergoes distillation to remove HCl. Since this method uses excess HF, the process mixture further contains unreacted HF. The unreacted HF in the process mixture is then preferably recovered and recycled back to the reactor. The process mixture may further contain intermediates. The intermediates may contain HCFO-1343 isomers, HCFO-1344 isomers, or mixtures thereof. In one embodiment, the intermediate contains the HCFO-1343 isomer. In another embodiment, the intermediate contains the HCFO-1344 isomer. In yet another embodiment, the intermediate contains a mixture of the HCFO-1343 and HCFO-1344 isomers. The intermediates and unreacted HCFC-353maf can be recovered and recycled back to the reactor.

[0080] In one embodiment, HF can be recovered. HF recovery may include a combination of distillation and / or liquid-liquid phase separation. When the process mixture contains residual acid, the residual acid can be removed from the process mixture by distillation, absorption by Al2O3, or absorption into an aqueous medium optionally containing a base and neutralized by a base (such as alkali metal hydroxides, including but not limited to KOH), thereby providing a neutralized aqueous medium. After the acid is removed from the process mixture, the neutralized aqueous medium can be dried, for example, using a molecular sieve, if desired. The dried HFO-1345zf can undergo final distillation to provide a usable purified product containing HFO-1345zf.

[0081] The equipment used in the method of this invention includes a feeding system, storage tanks, reactors, distillation columns, etc. Carbon steel is acceptable for the feeding system and storage tanks at ambient temperatures. The high-temperature parts of the reactor and equipment (including the HCl tower) are preferably made of alloys such as Inconel or Hastelloy. Some equipment may be lined with PTFE.

[0082] In one embodiment of the method of the present invention, a reaction system is provided, comprising a reactor and a purification system. The reaction system includes a feed to introduce reactants into the reactor. The feed includes a fresh reactant 353maf feed, a recycled intermediate, recycled 353maf, a fresh reactant HF feed, and a recycled HF feed. The fresh reactant HF feed and the recycled HF feed may be combined in a single HF feed to be introduced into the reactor. A fluorination catalyst feed is also present to introduce the fluorination catalyst into the reactor, such as from a catalyst bed.

[0083] The reactor process stream, i.e., the process mixture, exits the reactor. The process mixture can then proceed through mechanisms used to separate the catalyst from the reaction products. The process mixture then passes through a heat exchanger before entering the purification system.

[0084] In one embodiment, the present invention provides a composition comprising HFO-1345zf and one or more other compounds selected from the following: HCFO-1233xf, HCFO-1233zd, HCFO-1343 isomer, HCFO-1344 isomer, HCFO-1335 isomer, HCFO-1353 isomer, HFO-1345 isomer, HFO-1336 isomer, HCFC-355 isomer, HFC-356mff, HFC-143a, HFC-23, CFC-13, HFO-1234yf, HFO-1234ze, HCFO-1326mxz, HFO-1327 isomer, 2,2,3,3,3-pentafluoropropionaldehyde, and HFC-353maf. In some embodiments, the HCFO-1343 isomer includes one or more of the following: E-HCFO-1343mxz, HCFO-1343maz, and Z-HCFO-1343mxz. In some embodiments, the HCFO-1344 isomer includes one or more of the following: Z-HCFO-1344myz, E-HCFO-1344myz, Z-HCFO-1344mxz, E-HCFO-1344mxz, HCFO-1344fzb, E-HCFO-1344mxy, and Z-HCFO-1344mxy. In some embodiments, the HCFO-1335 isomer includes one or more of the following: E-HCFO-1335dz, E-HCFO-1335lzz, Z-HCFO-1335lzz, and E-HCFO-1335mxz. In some embodiments, the HCFC-355 isomer includes HCFC-355of. In some embodiments, the HCFO-1353 isomer includes HCFO-1353mxz. In some embodiments, the HFO-1345 isomer includes HFO-1345mzz. In some embodiments, the HFO-1336 isomer includes one or more of the following: E-HFO-1336mzz, Z-HFO-1336mzz, HFO-1336yf, and HFO-1336ze.

[0085] The purification system includes a distillation column, an absorber, a scrubber, and a dryer.

[0086] The products of the reaction from the method of the present invention can be purified in a series of additional steps.

[0087] In one embodiment of the method of the invention, the process mixture is cooled, such as by passing it through a heat exchanger, and then treated in a distillation column to remove HCl (the reaction product), thereby providing a process stream with reduced HCl. Since the method uses excess HF, the process stream with reduced HCl further contains unreacted HF.

[0088] After HCl removal, HF can be removed in a distillation column or phase separation. Since HF is a reactant in this method, the removed HF is recycled as a recirculating HF feed to the contact steps of the method. HF removal for recycling can include a combination of distillation and liquid-liquid phase separation.

[0089] In addition to HCl and HF, the process mixture may also contain residual acid. After removing HCl and HF, the residual acid can be removed from the process mixture by absorption with Al₂O₃, or by absorption into an aqueous medium optionally containing an alkali (such as alkali metal hydroxides, including but not limited to KOH) in an absorber. After removal of the residual acid, a washed process mixture is provided.

[0090] The washed process mixture may contain intermediates, wherein the intermediates may contain HCFO-1343 isomers, HCFO-1344 isomers, or mixtures thereof. Intermediates containing HCFO-1343 isomers, HCFO-1344 isomers, or mixtures thereof may also be removed, for example by distillation, and recycled back to the reactor.

[0091] After removing residual acid and intermediates, a washed and distilled process mixture is provided. The washed and distilled process mixture is then dried by passing it through a desiccant. The desiccant may be, for example, a molecular sieve, thus providing a dried process mixture. The dried process mixture is distilled using one or more distillation columns to provide a purified product containing 1345 zf. The purified product may contain greater than 95%, greater than 98%, greater than 99%, or greater than 99.5% of 1345 zf. The purified product is suitable for storage or use.

[0092] The purified product can be used to manufacture other fluorinated compounds, including, for example, 3,5,5-trichloro-1,1,1,2,2,6,6,6-octafluorohexane (HCFC-548mafd) and E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (HFO-153-10mczz). Composition

[0093] The present invention further provides a composition comprising HFO-1345zf and one or more other compounds selected from 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), dichlorotrifluorobutene isomer (HCFO-1343 isomer), tetrafluorobutene isomer (HCFO-1344 isomer), pentafluorobutene isomer (HCFO-1335 isomer), hexafluorobutene isomer (HFO-1336 isomer), pentafluorobutene isomer (HFO-1345 isomer), pentafluorobutane isomer (HCFC-355 isomer), and trifluorobutene isomer (HCFO-135). 3 isomers), 1,1,1,4,4,4-hexafluorobutane (HFC-356mff), 1,1,1-trifluoroethane (HFC-143a), trifluoromethane (HFC-23), chlorotrifluoromethane (CFC-13), heptafluorobutane isomer (HFC-347 isomer), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,3,3,3-tetrafluoropropene (HFO-1234ze), 2-chloro-1,1,1,3,3,3-hexafluoro-2-butene (HCFO-1326mxz), heptafluorobutene isomer (HFO-1327 isomer), 2,2,3,3,3-pentafluoropropanal and 2,2,4-trichloro-1,1,1-trifluorobutane (353maf).

[0094] In some embodiments, the HCFO-1343 isomer is one or more of the following: E-2,4-dichloro-1,1,1-trifluoro-2-butene (E-HCFO-1343mxz), 3,3-dichloro-4,4,4-trifluoro-1-butene (HCFO-1343maz), and Z-2,4-dichloro-1,1,1-trifluoro-2-butene (Z-HCFO-1343mxz).

[0095] In some embodiments, the HCFO-1344 isomer is one or more of the following: Z-4-chloro-1,1,1,2-tetrafluoro-2-butene (Z-HCFO-1344myz), E-4-chloro-1,1,1,2-tetrafluoro-2-butene (E-HCFO-1344myz), and Z-2-chloro-1,1,1,4-tetrafluoro-2-butene (Z-HCFO-1344mxz). E-2-chloro-1,1,1,4-tetrafluoro-2-butene (E-HCFO-1344mxz), 3-chloro-3,4,4,4-tetrafluoro-1-butene (HCFO-1344fzb), E-2-chloro-1,1,1,3-tetrafluoro-2-butene (E-HCFO-1344mxy) and Z-2-chloro-1,1,1,3-tetrafluoro-2-butene (Z-HCFO-1344mxy).

[0096] In some embodiments, the HCFO-1335 isomer is one or more of the following: E-1-chloro-3,3,4,4,4-pentafluoro-1-butene (E-HCFO-1335dz), E-1-chloro-1,1,4,4,4-pentafluoro-2-butene (E-HCFO-1335lzz), Z-1-chloro-1,1,4,4,4-pentafluoro-2-butene (Z-HCFO-1335lzz), and E-2-chloro-1,1,1,4,4-pentafluoro-2-butene (E-HCFO-1335mxz).

[0097] In some embodiments, the HFO-1336 isomer is one or more of the following: E-1,1,1,4,4,4-hexafluoro-2-butene (E-HFO-1336mzz), Z-1,1,1,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz), 2,3,3,4,4,4-hexafluoro-1-butene (HFO-1336yf), and 1,3,3,4,4,4-hexafluoro-1-butene (HFO-1336ze).

[0098] In some embodiments, the HFO-1345 isomer comprises 1,1,4,4,4-pentafluoro-2-butene.

[0099] In some embodiments, the HCFC-355 isomer comprises 4-chloro-1,1,1,2,2-pentafluorobutane (HCFC-355of).

[0100] In some embodiments, the HCFO-1353 isomer comprises 3-chloro-4,4,4-trifluoro-2-butene (HCFO-1353mxz).

[0101] The structures of these compounds are provided in Table 1. Table 1

[0102]

[0103]

[0104] In one embodiment, the composition comprises HFO-1345zf and one or more of the following isomers: tetrafluorobutene, dichlorotrifluorobutene, and pentafluorobutene. In one embodiment, the composition comprises HFO-1345zf and one or more of the following isomers: tetrafluorobutene, trichlorotrifluorobutene, and pentafluorobutene. In one embodiment, the composition comprises HFO-1345zf and one or more of the following isomers: tetrafluorobutene and dichlorotrifluorobutene. In one embodiment, the composition comprises HFO-1345zf and one or more of the following isomers: tetrafluorobutene and pentafluorobutene.

[0105] Compositions comprising 3,3,4,4,4-pentafluoro-1-butene (HFO-1345zf) and one or more other compounds as defined herein can be purified, such as by distillation, absorption, and washing, to remove undesirable compounds. The purified product, such as an intermediate, can be used to produce 3,5,5-trichloro-1,1,1,2,2,6,6,6-octafluorohexane (HCFC-548mafd). Attached Figure Description

[0106] Figure 1 A flowchart of a method for preparing 3,3,4,4,4-pentafluoro-1-butene according to one embodiment of the present invention is provided. Figure 1 The present invention provides a process system 100, which includes a reactor system 101 and a purification system 102. In the reactor system 101, reactant 353maf feed 103, fresh reactant HF feed 104, and recycle HF feed stream 105 are mixed into a single feed stream 106 and fed through a series of heat exchangers (107a, 107b, and 107c) and introduced into the reactor 109 as feed stream 108. Heat exchanger 107a evaporates feed stream 106. Heat exchanger 107b is a process-to-process heat exchanger in which the stream from heat exchanger 107a is heated using heat from reactor process stream 110. The heated feed stream from heat exchanger 107b proceeds through preheater heat exchanger 107c to provide reactor feed stream 108.

[0107] The reactor feed stream 108 enters a tubular reactor 109 containing a solid fluorination catalyst (not shown). The feed stream 108 reacts in the reactor 109 in the presence of the solid fluorination catalyst in a gas-phase reaction to produce the reactor process stream 110.

[0108] The reactor process stream 110 passes through heat exchanger 107b, thereby cooling the stream 110 and providing process stream 111. Process stream 111 is further cooled by passing through heat exchanger 112, providing process stream 113, which enters purification system 102.

[0109] The purification system 102 includes a distillation column, an absorber, a scrubber, and a dryer.

[0110] In HCl distillation column 114, process feed stream 113 is distilled to remove HCl generated in reactor 109. HCl is removed at the top of the column via stream 115. Then, the distilled stream 116 enters HF distillation column 117, where HF is removed. A recycle stream containing HF 118 is removed from column 117. A portion of stream 118 is mixed with reactant HCFC-353maf feed 103 and fresh reactant HF feed 104 as a recycle HF feed stream 105. A purge stream 119 containing HF is removed from stream 118.

[0111] Following the HCl and HF distillation columns, process stream 120 enters absorber 121. Water is fed into absorber 121 as stream 122. HF solution in water is removed from absorber 121 as stream 123. In a process step of washing stream 124 with alkali via scrubber 126, such as using an aqueous solution of KOH, the treated stream 124 from absorber 121 is recycled through column 125. Used KOH solution 127 is removed from scrubber 126 and column 125. The washed process stream is removed from column 125 as stream 128 and then dried by passing it through desiccant column 129. The desiccant may be, for example, a molecular sieve. The dried process stream 130 exits desiccant column 129 for further purification.

[0112] The dried process stream 130 enters a low-boiling-point distillation column 131, where low-boiling-point substances are removed from the top of the column and pass through a condenser as stream 132. Process stream 133 flows from the low-boiling-point distillation column 131 into a distillation column 134, from which high-boiling-point substances are purged as stream 136, and a product stream 135 containing 1345 zf is provided. Product stream 135 containing 1345 zf can be stored in tank 137 for future or immediate use in the manufacture of other fluorinated compounds, including, for example, 3,5,5-trichloro-1,1,1,2,2,6,6,6-octafluorohexane (HCFC-548mafd) and E-1,1,1,2,2,5,5,6,6,6-decafluorohex-3-ene (HFO-153-10mczz).

[0113] Pumps, such as those illustrated by feed streams 103, 104, and 105, are used to introduce and / or circulate materials (reactants, intermediates, products) through reaction system 100. Heat exchangers, such as those illustrated at 107a-d, are used to manage the temperature through reaction system 100.

[0114] Figure 1 Additional components not shown may include purge lines, heat exchangers, pumps, and vacuum equipment for the distillation column.

[0115] 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 pertains. In case of any conflict, this specification and its included definitions shall prevail. Although methods and materials similar to or equivalent to those described herein may be used in the practice or testing of embodiments of the invention, suitable methods and materials are described below. Furthermore, materials, methods, and examples are illustrative only and are not intended to be limiting.

[0116] The following examples are provided to illustrate certain aspects of the invention and should not limit the scope of the appended claims. Example

[0117] In the following embodiments, the letter "T" represents temperature; the letter "P" represents pressure. All temperatures are provided in degrees Celsius (°C).

[0118] Unless otherwise stated, all analyses of the products in the following examples were performed using GC / MS FID, and the results are reported as GC FID area %. Example 1

[0119] 4 cc of chromium oxide catalyst (12 / 20 mesh) was added to an Inconel (0.5-inch OD) tubular reactor. The reaction was run by feeding 353 maf of liquid into a heated chamber where the liquid was vaporized and mixed with HF and N2. The process mixture was then passed through the reactor. A portion of the reactor effluent was passed through a series of valves and analyzed by GC-FID-MS. A portion of the reactor effluent was also passed through an alkaline scrubber, dried with a desiccant, and collected in a dry ice-acetone cold trap. The collected material was then analyzed by NMR to obtain the HFO-1345zf composition listed in Table 2. Table 2

[0120] Example 2

[0121] 6 cc of 2.5 wt% zinc-impregnated alumina catalyst (12 / 20 mesh) was added to an Inconel (0.5 inch OD) tubular reactor. The reaction was run by feeding liquid HCFC-353maf (“feed”) into a heated chamber where it was vaporized and mixed with HF and N2. The process mixture was then passed through the reactor, which was heated from 285°C to 325°C. A portion of the reactor effluent was passed through a series of valves and analyzed by GCMS. Conditions are provided in Table 3. Five GC analyses were performed for each set of conditions in Table 3. These results (average of 5 GC analyses, area %) are provided in Table 4. Table 3

[0122] Table 4

[0123] Example 3

[0124] Add 6 cc of 12-20 mesh 20% CrCl3 / C catalyst to an Inconel (0.5-inch OD) tubular reactor. Activate the catalyst with HF, starting at 150°C and ending at 450°C. HCFC-353maf is pumped in and passed through a vaporizer at 150°C with 4.6 sccm of N2, then mixed with HF. Reaction test conditions are provided in Table 5 below. The process mixture flows through the reactor containing the catalyst. A portion of the reactor effluent is passed through a GC sample loop and analyzed by GC-MS-FID. GC (FID) results (area %) are provided in Table 6. Table 5

[0125] Table 6

[0126] Example 3a

[0127] In Example 3, it was found that the amount of HFO-1345zf formed decreased over time at 270°C, as shown in Table 7 below. After operating at 270°C for 10 hours, the organic feed was stopped. Air regeneration of the catalyst was used under the conditions shown in Table 8 below. After air regeneration, tests were resumed at 315°C and 335°C, with air co-feeding. The GC (FID, area %) results at 315°C and 335°C are provided in Table 9. The results in Table 10 show that at 335°C, the catalyst activity was well maintained with air co-feeding. Table 7

[0128] Table 8

[0129]

[0130] Table 9

[0131] Table 10

[0132] Example 4

[0133] 6 cc of 12-20 mesh 6% zinc-doped chromium oxide (Cr2O3) was added to an Inconel (0.5-inch OD) tubular reactor. The catalyst was activated with HF, starting at 150°C and ending at 450°C. 353 maf was pumped in and passed through a vaporizer with 4.6 sccm of N2 at 150°C, then mixed with HF. The molar ratio of HF to 353 maf was 28.91:1. Reaction test conditions are provided in Table 11 below. The process mixture was passed through the reactor containing the catalyst. A portion of the reactor effluent was passed through a GC sample loop and analyzed by GC / MS (FID). GC results are provided in Table 12. The products from this example were collected, and the GC analyses are shown in Table 13. Table 11

[0134] Table 12

[0135] Table 13

[0136] Example 5

[0137] The method of Example 4 was repeated at 315°C, 325°C, and 335°C with air co-feed. The conditions are provided in Table 14. The GC (FID, area %) analysis results in Table 15 show that the catalyst activity is stable under air co-feed conditions. Table 14

[0138] Table 15

[0139] Example 6

[0140] The methods of Examples 4 and 5 were repeated using a lower HCFC-353maf molar ratio of 20:1. When the HCFC-353maf molar ratio was 29:1, catalyst deactivation was observed to be faster than in previous tests. The conditions are provided in Table 16. The GC analysis results in Table 17 show that when the HCFC-353maf molar ratio was 29:1, catalyst deactivation was observed to be faster than in previous tests. Table 16

[0141] Table 17

[0142] Example 7

[0143] The catalyst from Example 6 was regenerated by air treatment, and then a recovery test was performed at 335°C with a molar ratio of 29:1 for HCFC-353maf. Conditions are provided in Table 18. GC (FID, area %) analysis results in Table 19 show that the catalyst activity was restored and the catalyst remained stable. Table 18

[0144] Table 19

[0145] Example 8

[0146] In a 1" Hastelloy C tubular reactor, a chromium oxide catalyst was loaded and activated by HF treatment. Then, 353 maf and HF were fed at a molar ratio of 1:20 under 80 psig pressure, with a co-feed of 0.2 mol%–0.4 mol% O2 over a temperature range of 340–350 °C for approximately 22 seconds. The product was washed with a caustic alkali solution, collected, and analyzed by GC. The results of the GC analysis are provided in Table 20. Table 20

[0147]

[0148] The product was further distilled and purified by GC-MS-TCD analysis, which revealed additional byproducts as shown in Table 21. Table 21

[0149]

[0150] The structures of the intermediate compounds were further identified by NMR analysis of the distillate collected at 65 °C. The analytical results and structures of the identified intermediates are provided in Table 22. Table 22

[0151]

Claims

1. A method for preparing 3,3,4,4,4-pentafluoro-1-butene, the method comprising contacting 2,2,4-trichloro-1,1,1-trifluorobutane with an excess of HF in the presence of a fluorination catalyst to obtain a process mixture comprising 3,3,4,4,4-pentafluoro-1-butene, wherein the method is carried out at a temperature of about 250°C to 450°C and a pressure of about 0 psig to 200 psig.

2. The method of claim 1, wherein the temperature is in the range of about 300°C to about 380°C.

3. The method according to claim 1 or claim 2, wherein the pressure is in the range of about 30 psig to about 180 psig, about 40 psig to 150 psig, or about 60 psig to 120 psig.

4. The method according to any one of claims 1 to 3, wherein the fluorination catalyst comprises one or more metals, metal oxides, metal fluorides, metal chlorides, or metal fluorides.

5. The method according to claim 4, wherein the fluorination catalyst is a metal oxide, the metal oxide is converted into a metal (oxy) fluoride during activation, and the metal (oxy) fluoride has Lewis acid characteristics.

6. The method of claim 1, wherein the metal oxide comprises chromium, aluminum, cobalt, or zinc.

7. The method according to claim 1, wherein the fluorination catalyst comprises one or more metals selected from Al, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, La and Ce.

8. The method according to claim 7, wherein the fluorination catalyst comprises one or more of Al, Zr, Cr, Co, Ni and Zn.

9. The method of claim 8, wherein the fluorination catalyst comprises chromium or aluminum.

10. The method of claim 8, wherein the fluorination catalyst comprises chromium or aluminum and one or more of Zn, Zr, Co and Ni.

11. The method of claim 4, wherein the fluorination catalyst comprises a metal oxide or a metal fluoride, and contains one or more additional metals selected from the group consisting of Li, Na, K, Ca, Mg and Cs.

12. The method of claim 11, wherein the additional metal is present in an amount of less than 2000 ppm, less than 1000 ppm, less than 500 ppm, less than 100 ppm, or less than 10 ppm.

13. The method of claim 9, wherein the fluorination catalyst comprises aluminum.

14. The method of claim 13, wherein the aluminum is present in the form of aluminum oxide, aluminum fluoride, or aluminum oxyfluoride.

15. The method of claim 13, wherein the fluorination catalyst further comprises one or more of Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, La and Ce.

16. The method of claim 15, wherein the fluorination catalyst comprises one or more of Zn, Zr, Cr, Co and Ni.

17. The method of claim 13, wherein the fluorination catalyst comprises Al2O3.

18. The method of claim 17, wherein the fluorination catalyst comprises Al2O3 and one or more of Zn, Zr, Cr, Co and Ni.

19. The method of claim 18, wherein the fluorination catalyst comprises Al2O3 and Zn, or Al2O3 and Cr, or Al2O3 and Co, or Al2O3 and Ni, or Al2O3 and Zr.

20. The method of claim 9, wherein the fluorination catalyst comprises chromium.

21. The method of claim 20, wherein chromium is present in the form of chromium oxide, chromium chloride, chromium fluoride, or chromium oxyfluoride.

22. The method of claim 21, wherein the fluorination catalyst further comprises one or more of Al, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, La and Ce.

23. The method of claim 20, wherein the fluorination catalyst comprises Cr2O3.

24. The method of claim 20, wherein the fluorination catalyst comprises Cr2O3 and one or more of Zn, Zr, Co and Ni.

25. The method of claim 24, wherein the fluorination catalyst comprises Cr2O3 and Zn, or Cr2O3 and Co, or Cr2O3 and Ni, or Cr2O3 and Zr.

26. The method of claim 20, wherein the catalyst comprises chromium supported on AlF3, alumina, fluorinated alumina, or activated carbon.

27. The method of claim 26, wherein the catalyst comprises chromium supported on alumina.

28. The method of claim 8, wherein the catalyst comprises zinc supported on AlF3, alumina, fluorinated alumina, or activated carbon.

29. The method of claim 28, wherein the catalyst comprises zinc supported on alumina.

30. The method according to any one of claims 1 to 29, the method further comprising a pre-fluorination treatment prior to contacting HCFC-353maf with HF in a reactor in the presence of the fluorination catalyst, wherein the pre-fluorination treatment comprises passing HF through the catalyst with or without an inert diluent such as nitrogen at a temperature in the range of about 250°C to 450°C.

31. The method according to any one of claims 1 to 30, the method further comprising regenerating the fluorinated catalyst after the activity of the catalyst decreases, wherein the regeneration step comprises treating the catalyst with oxygen or air at an elevated temperature, under which most of the organic material is removed.

32. The method according to any one of claims 1 to 31, wherein the method is carried out at a molar ratio of HF to HCFC-353maf of about 3:1 to about 50:

1.

33. The method of claim 20, wherein the molar ratio of HF to HCFC-353maf is about 10:1 to about 45:1 or 15:1 to 40:

1.

34. The method according to any one of claims 1 to 33, the method further comprising adding oxygen-containing gas into the method.

35. The method of claim 34, wherein the amount of oxygen added to the method from the oxygen-containing gas is greater than 0 mol% and less than 10 mol%.

36. The method of claim 34, wherein the amount of oxygen added to the method from the oxygen-containing gas is about 0.2 mol% to about 5 mol%, or about 1 mol.

37. The method according to any one of claims 1 to 36, wherein the process mixture comprising 3,3,4,4,4-pentafluoro-1-butene further comprises unreacted HF, and the unreacted HF is recovered and recycled back into the method.

38. The method according to any one of claims 1 to 37, wherein the process mixture comprises an intermediate and unreacted 353maf, and the unreacted 353maf and the intermediate are recovered and recycled back into the method.

39. The method of claim 38, wherein the intermediate comprises an HCFO-1343 isomer, an HCFO-1344 isomer, or a mixture thereof.

40. A composition comprising 3,3,4,4,4-pentafluoro-1-butene and at least one additional compound selected from: 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), dichlorotrifluorobutene isomer (HCFO-1343 isomer), tetrafluorobutylene isomer (HCFO-1344 isomer), pentafluorobutylene isomer (HCFO-1335 isomer), trifluorobutylene isomer (HCFO-1353 isomer), hexafluorobutylene isomer (HFO-1336 isomer), pentafluorobutylene isomer (HFO-1345 isomer), pentafluorobutane isomer (HCFC- The following are listed: 355 isomer), 1,1,1,4,4,4-hexafluorobutane (HFC-356mff), 1,1,1-trifluoroethane (HFC-143a), trifluoromethane (HFC-23), chlorotrifluoromethane (CFC-13), heptafluorobutane isomer (HFC-347 isomer), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,3,3,3-tetrafluoropropene (HFO-1234ze), 2-chloro-1,1,1,3,3,3-hexafluoro-2-butene (HCFO-1326mxz), heptafluorobutene isomer (HFO-1327 isomer), 2,2,3,3,3-pentafluoropropanal, and 2,2,4-trichloro-1,1,1-trifluorobutane (353maf).

41. The composition of claim 40, wherein the composition comprises one or more of a tetrafluorobutylene isomer, a dichlorotrifluorobutylene isomer, and a pentafluorobutylene isomer.

42. The composition of claim 41, wherein the composition comprises a tetrafluorobutylene isomer.

43. The composition according to claim 42, wherein the tetrafluorobutene isomer is one or more of the following: Z-4-chloro-1,1,1,2-tetrafluoro-2-butene (Z-HCFO-1344myz), E-4-chloro-1,1,1,2-tetrafluoro-2-butene (E-HCFO-1344myz), Z-2-chloro-1,1,1,4-tetrafluoro-2-butene (Z-HCFO-1344m (xz), E-2-chloro-1,1,1,4-tetrafluoro-2-butene (E-HCFO-1344mxz), 3-chloro-3,4,4,4-tetrafluoro-1-butene (HCFO-1344fzb), E-2-chloro-1,1,1,3-tetrafluoro-2-butene (E-HCFO-1344mxy) or Z-2-chloro-1,1,1,3-tetrafluoro-2-butene (Z-HCFO-1344mxy).

44. The composition of claim 41, wherein the composition comprises a dichlorotrifluorobutene isomer.

45. The composition according to claim 44, wherein the dichlorotrifluorobutene isomer is one or more of the following: E-2,4-dichloro-1,1,1-trifluoro-2-butene (E-HCFO-1343mxz), 3,3-dichloro-4,4,4-trifluoro-1-butene (HCFO-1343maz), and Z-2,4-dichloro-1,1,1-trifluoro-2-butene (Z-HCFO-1343mxz).

46. ​​The composition of claim 41, wherein the composition comprises a chloropentafluorobutene isomer.

47. The composition according to claim 46, wherein the chloropentafluorobutene isomer is one or more of the following: E-1-chloro-3,3,4,4,4-pentafluoro-1-butene (E-HCFO-1335dz), E-1-chloro-1,1,4,4,4-pentafluoro-2-butene (E-HCFO-1335lzz), Z-1-chloro-1,1,4,4,4-pentafluoro-2-butene (Z-HCFO-1335lzz), and E-2-chloro-1,1,1,4,4-pentafluoro-2-butene (E-HCFO-1335mxz).

48. The composition of claim 41, wherein the composition comprises two or more of dichlorotrifluorobutene isomers, chlorotetrafluorobutene isomers, and chloropentafluorobutene isomers.

49. The composition of claim 41, wherein the composition comprises at least one dichlorotrifluorobutene isomer and a chlorotetrafluorobutene isomer.

50. The composition of claim 41, wherein the composition comprises a dichlorotrifluorobutene isomer and a chloropentafluorobutene isomer.

51. The composition according to claim 41, wherein the composition comprises a tetrafluorobutylene isomer and a pentafluorobutylene isomer.

52. The composition according to claim 41, wherein the composition comprises a dichlorotrifluorobutene isomer, a chlorotetrafluorobutene isomer, and a chloropentafluorobutene isomer.

53. The composition of claim 40, wherein the composition comprises a hexafluorobutene isomer.

54. The composition according to claim 53, wherein the hexafluorobutene isomer is one or more of the following: E-1,1,1,4,4,4-hexafluoro-2-butene (E-HFO-1336mzz), Z-1,1,1,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz), 2,3,3,4,4,4-hexafluoro-1-butene (HFO-1336yf) and 1,3,3,4,4,4-hexafluoro-1-butene (HFO-1336ze).

55. The composition of claim 40, wherein the composition comprises the HCFO-1353 isomer.

56. The composition of claim 55, wherein the HCFO-1353 isomer comprises HCFO-1353mxz.

57. The composition of claim 40, wherein the composition comprises 1,3,3,4,4,4-hexafluoro-1-butene (HFO-1336ze) and at least one other compound selected from: 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 1-chloro-3,3,3-trifluoropropene (1233zd), Z-4-chloro-1,1,1,2-tetrafluoro-2-butene (Z-HCFO-1344myz), E-4-chloro-1,1,1,2-tetrafluoro-2-butene (E-HCFO-1344myz), Z-2-chloro-1,1,1,4-tetrafluoro-2-butene (Z-HCFO-1344mxz), E-2-chloro- 1,1,1,4-Tetrafluoro-2-butene (E-HCFO-1344mxz), 3-Chloro-3,4,4,4-Tetrafluoro-1-butene (HCFO-1344fzb), E-2-Chloro-1,1,1,3-Tetrafluoro-2-butene (E-HCFO-1344mxy), Z-2-Chloro-1,1,1,3-Tetrafluoro-2-butene (Z-HCFO-1344mxy), E-1-Chloro-3,3,4,4,4-Pentafluoro-1-butene (E-HCFO-1335dz), E-1-Chloro-1,1,4,4,4-Pentafluoro-2-butene (E-HCFO-1335lzz), Z-1-Chloro-1,1,4,4,4-Pentafluoro-2-butene (Z-H CFO-1335lzz), E-2-chloro-1,1,1,4,4-pentafluoro-2-butene (E-HCFO-1335mxz), E-2,4-dichloro-1,1,1-trifluoro-2-butene (E-HCFO-1343mxz), 3,3-dichloro-4,4,4-trifluoro-1-butene (HCFO-1343maz), Z-2,4-dichloro-1,1,1-trifluoro-2-butene (Z-HCFO-1343mxz), 4-chloro-1,1,1,2,2-pentafluorobutane (HCFC-355of), 1,1,1,4,4,4-hexafluorobutane (HFC-356mff), 3-chloro-4,4,4-trifluoro-2-butene (HCF O-1353mxz), 1,1,4,4,4-pentafluoro-2-butene (HFO-1345mzz), 1,1,1-trifluoroethane (HFC-143a), trifluoromethane (HFC-23), chlorotrifluoromethane (CFC-13), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,3,3,3-tetrafluoropropene (HFO-1234ze), 2-chloro-1,1,1,3,3,3-hexafluoro-2-butene (HCFO-1326mxz), heptafluorobutene isomer (HFO-1327 isomer), E-1,1,1,4,4,4-hexafluoro-2-butene (E-HFO-1336mzz), Z-1,1,1,4,44-Hexafluoro-2-butene (Z-HFO-1336mzz), 2,3,3,4,4,4-hexafluoro-1-butene (HFO-1336yf), 1,3,3,4,4,4-hexafluoro-1-butene (HFO-1336ze), 2,2,3,3,3-pentafluoropropanal, and 2,2,4-trichloro-1,1,1-trifluorobutane (HCFC-353maf).

58. The composition of claim 40, wherein the composition comprises 2,3,3,4,4,4-hexafluoro-1-butene (HFO-1336yf) and at least one other compound selected from: 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 1-chloro-3,3,3-trifluoropropene (1233zd), dichlorotrifluorobutene isomer (HCFO-1343 isomer), tetrafluorobutylene isomer (HCFO-1344 isomer), pentafluorobutylene isomer (HCFO-1335 isomer), pentafluorobutane isomer (HCFC-355 isomer), 1,1,1,4,4,4-hexafluorobutane (HFC-356mff), 3-chloro-4,4 4-Trifluoro-2-butene (HCFO-1353mxz), 1,1,4,4,4-pentafluoro-2-butene (HFO-1345mzz), 1,1,1-trifluoroethane (HFC-143a), trifluoromethane (HFC-23), chlorotrifluoromethane (CFC-13), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,3,3,3-tetrafluoropropene (HFO-1234ze), 2-chloro-1,1,1,3,3,3-hexafluoro-2-butene (HCFO-1326mxz), heptafluorobutene isomer (HFO-1327 isomer), 2,2,3,3,3-pentafluoropropanal and 2,2,4-trichloro-1,1,1-trifluorobutane (353maf).

59. The composition of claim 40, wherein the composition comprises 1,1,4,4,4-pentafluoro-2-butene (HFO-1345mzz).

60. The composition according to claim 40, wherein the composition is prepared by the method according to any one of claims 1 to 39.

61. Use of the composition according to any one of claims 40 to 59 in heat transfer applications.

62. Use of the composition according to any one of claims 40 to 59 as a dielectric liquid.

63. Use of the composition according to any one of claims 40 to 59 as a cleaning solvent.

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