HK1135681A - Processes for the production of fluoropropanes and halopropenes and azeotropic compositions of 2-chloro-3,3,3-trifluoro-1-propene with hf and of 1,1,1,2,2-pentafluoropropane with hf - Google Patents

Description

Process for the preparation of fluoropropanes, halopropenes and azeotropic compositions of 2-chloro-3, 3, 3-trifluoro-1-propene with HF and of 1,1, 1, 2, 2-pentafluoropropane with HF

Technical Field

The invention relates to a method for preparing the following substances: 1,1, 1, 2, 2-pentafluoropropane, 2, 3, 3, 3-tetrafluoro-1-propene, 1,1, 1, 3, 3-pentafluoropropane, 1, 3, 3, 3-tetrafluoro-1-propene, 2-chloro-3, 3, 3-trifluoro-1-propene and/or 1-chloro-3, 3, 3-trifluoro-1-propene.

Background

Due to the Montreal Protocol (Montreal Protocol) regulation of the gradual cessation of the use of ozone depleting chlorofluorocarbons (CFCs) and Hydrochlorofluorocarbons (HCFCs), the industry has been working for the past few decades to find alternative refrigerants. The solution for most refrigerant manufacturers is to commercialize Hydrofluorocarbon (HFC) refrigerants. The new hydrofluorocarbon refrigerants, HFC-134a, which are currently the most widely used, have zero ozone depletion potential and are therefore not affected by the current regulatory phase out due to the montreal protocol. The production of other hydrofluorocarbons for use in the following applications is also of great interest: such as solvents, blowing agents, cleaning agents, aerosol propellants, heat transfer media, dielectrics, fire extinguishing agents, and power cycle working fluids.

There is also considerable interest in developing new refrigerants with the potential to mitigate the global warming phenomenon for the automotive air conditioning market.

1,1, 1, 3, 3-pentafluoropropane (CF)₃CH₂CHF₂Or HFC-245fa) is a refrigerant and blowing agent that can be produced by reacting 1,1, 1, 3, 3-pentachloropropane (CCl)₃CH₂CHCl₂Or HCC-240fa) in the liquid phase (see, e.g., U.S. patent No. 6,291,730).

1,1, 1, 2, 2-pentafluoropropane (CF)₃CF₂CH₃Or HFC-245cb) has been made by the addition of methyl fluoride to tetrafluoroethylene in the presence of antimony pentafluoride as disclosed in us patent 6,184,426.

2, 3, 3, 3-tetrafluoro-1-propene (CF)₃CF＝CH₂Or HFC-1234yf) may be used as a refrigerant and polymer intermediate, which has been catalyzed by chromium oxide₃CF₂CCl₃Such as disclosed in U.S. patent 2,996,555 to Rausch.

1-chloro-3, 3, 3-trifluoro-1-propene (CF)₃CH-CHCl or HCFC-1233zd) are useful as chemical intermediates and may be made by fluorination of HCC-240fa, e.g., in the United statesDisclosed in U.S. Pat. No. 6,013,846.

1, 3, 3, 3-tetrafluoro-1-propene (CF)₃CH ═ CHF or HFC-1234ze) can be used as refrigerants, made by the dehydrofluorination of HFC-245fa using either aqueous or alcoholic solutions of strong bases or using a chromium-containing catalyst in the presence of oxygen at elevated temperatures, as disclosed in U.S. patent 6,124,510, and HCFC-1233zd as disclosed in U.S. patent 5,895,825. HFC-1234ze may also be made from HCC-240fa, as disclosed in U.S. patent 6,111,150.

2-chloro-3, 3, 3-trifluoro-1-propene (CF)₃CCl＝CH₂Or HCFC-1233xf) may be used as intermediates and polymer monomers. HCFC-1233xf is prepared by the dehydrochlorination of 1, 2-dichloro-3, 3, 3-trifluoropropane using potassium hydroxide as described by Haszeldine on pages 2495 to 2504 of the Journal of the chemical Society "(1951).

There is a need for a process for the preparation of compounds from the group HCFC-1233xf, HFC-245fa, HFC-245cb, HFC-1234ze, HCFC-1233zd and HFC-1234yf wherein the other compounds of the group are also made from a common halogenated hydrocarbon feedstock and these compounds can be recovered if desired.

Summary of The Invention

The present invention provides a process for preparing at least one product compound selected from the group consisting of: CF (compact flash)₃CF₂CH₃、CF₃CF＝CH₂And CF₃CCl＝CH₂. The method comprises the following steps: reacting at least one starting material with HF in a reaction zone, optionally in the presence of a fluorination catalyst, the starting material being selected from the group consisting of: from the formula CX₃CHClCH₂Halopropanes represented by X, formula CClX₂CCl＝CH₂Halopropenes of the formula CX₂＝CClCH₂A halopropene represented by X, wherein each X is independently selected from the group consisting of F and Cl, reacted to a compound comprisingHF、HCl、CF₃CF₂CH₃、CF₃CF＝CH₂And CF₃CCl＝CH₂The product mixture of (a), wherein the molar ratio of HF to the total amount of starting materials fed to the reaction zone is at least stoichiometric; and recovering the at least one product compound from the product mixture.

The present invention also provides a process for preparing at least one product compound selected from the group consisting of: CF (compact flash)₃CH₂CHF₂、CF₃CHF and CF₃CH ═ CHCl. The method comprises the following steps: reacting at least one starting material with HF in a reaction zone, optionally in the presence of a fluorination catalyst, the starting material being selected from the group consisting of: from the formula CX₃CHClCH₂Halopropanes represented by X, represented by the formula CX₃CCl＝CH₂Halopropenes of the formula CX₂＝CClCH₂Halopropenes represented by X, wherein each X is independently selected from the group consisting of F and Cl, reacted to form a composition comprising HF, HCl, CF₃CH₂CHF₂、CF₃CHF and CF₃A product mixture of CH ═ CHCl, wherein the molar ratio of HF to the total amount of starting materials fed to the reaction zone is at least stoichiometric; and recovering the at least one product compound from the product mixture.

The present invention also provides a process for preparing at least one product compound selected from the group consisting of: CF (compact flash)₃CF₂CH₃And CF₃CF＝CH₂. The method comprises the following steps: reacting at least one starting material with HF in a reaction zone, optionally in the presence of a fluorination catalyst, the starting material being selected from the group consisting of: from the formula CX₃CHClCH₂Halopropanes represented by X, represented by the formula CX₃CCl＝CH₂Halopropenes of the formula CX₂＝CClCH₂Halopropenes represented by X, wherein each X is independently selected from the group consisting of F and Cl, reacted to form a composition comprising HF, HCl, CF₃CF₂CH₃And CF₃CF＝CH₂The product mixture of (a), wherein the molar ratio of HF to the total amount of starting materials fed to the reaction zone is at least stoichiometric; and recovering the at least one product compound from the product mixture.

The invention also provides azeotropic compositions. Provide a catalyst containing CF₃CCl＝CH₂And HF; wherein HF is present in an effective amount to react with CF₃CCl＝CH₂An azeotropic combination is formed. Providing another composition comprising CF₃CF₂CH₃And HF; wherein HF is present in an effective amount to react with CF₃CF₂CH₃An azeotropic combination is formed.

Detailed Description

As used herein, the term "feedstock" refers to a halopropane or halopropene reacted with Hydrogen Fluoride (HF) in a reaction zone in embodiments of the present invention. As noted above, for certain processes of the present invention, the starting material is selected from the group consisting of: from the formula CX₃CHClCH₂Halopropanes represented by X, formula CClX₂CCl＝CH₂Halopropenes of the formula CX₂＝CClCH₂A halopropene represented by X, wherein each X is independently selected from the group consisting of F and Cl; while for certain other processes of the present invention, the starting material is selected from the group consisting of: from the formula CX₃CHClCH₂Halopropanes represented by X, represented by the formula CX₃CCl＝CH₂Halopropenes of the formula CX₂＝CClCH₂X represents a halopropene, wherein each X is independently selected from the group consisting of F and Cl.

The process of the invention employs a molar ratio of HF to the total amount of starting materials of at least stoichiometry. The stoichiometric ratio is determined by subtracting the weighted average of the number of fluorine substituents in the starting material from the weighted average of the number of fluorine substituents in the desired product. For example, for the reaction of C₃H₃Cl₅Preparation C₃H₃F₅Isomers, HF and C₃H₃Cl₅In a stoichiometric ratio of 51. As another example, for a mixed gas composed of CF₃CCl＝CH₂Preparation of a 1: 1 mixture of HFC-245cb and HFC-1234yf, HF and CF₃CCl＝CH₂The stoichiometric ratio of (A) to (B) is 1.5: 1.

Certain compounds prepared by the process of the present invention may exist in one of two configurational isomers. For example, HFC-1234ze and HCFC-1233zd may each exist as the E-or Z-isomer. HFC-1234ze, as used herein, refers to the isomers E-HFC-1234ze or Z-HFC-1234ze, as well as any combination or mixture of such isomers; as used herein, HCFC-1233zd refers to the isomers E-HCFC-1233zd or Z-HCFC-1233zd, as well as any combination or mixture of such isomers.

As described above, the present invention provides a process that involves the use of at least one starting material to produce a product mixture comprising at least one product compound selected from the group consisting of HFC-245cb, HFC-1234yf and HCFC-1233xf, said starting material being selected from the group consisting of: from the formula CX₃CHClCH₂Halopropanes represented by X, formula CClX₂CCl＝CH₂Halopropenes of the formula CX₂＝CClCH₂And X represents a halogenated propene. Of note are embodiments of the process wherein HFC-1234yf is recovered. Additional HFC-1234yf may be obtained by dehydrofluorination of HFC-245cb in the product mixture. Also of note are embodiments of the process wherein HCFC-1233xf in the product mixture is fluorinated to produce at least one of HFC-1234yf and HFC-245 cb.

The product mixture may also contain HFC-1234 ze. HFC-1234ze can be recovered. The product mixture may also contain HCFC-1233 zd. HFC-1234ze and HFC-245fa may also be obtained by fluorination of HCFC-1233zd in the product mixture.

The product mixture may also contain HFC-245 fa. HFC-245fa can be recovered. HFC-245fa may also be subjected to dehydrofluorination to produce HFC-1234 ze.

The product mixture may also contain HFC-1234 ze. A mixture of HFC-245cb and HFC-1234ze may be recovered and further reacted with HF in the liquid phase in the presence of a fluorination catalyst under fluorination conditions to produce a mixture comprising HFC-245fa and HFC-245 cb. Alternatively, a mixture of HFC-245cb and HFC-1234ze may be recovered and further reacted under dehydrofluorination conditions in the presence of a dehydrofluorination catalyst to produce a mixture comprising HFC-1234ze and HFC-1234 yf.

HFC-245fa, HFC-1234ze and/or HCFC-1233zd may also be present in the product mixture. HFC-245cb, HFC-1234yf and HCFC-1233xf and HFC-245fa (if present), HFC-1234ze (if present) and HCFC-1233zd (if present) in the product mixture may together be further reacted in the liquid phase with HF in the presence of a fluorination catalyst under fluorination conditions to produce a mixture comprising HFC-245fa and HFC-245 cb. The HFC-245fa and HFC-245cb in the mixture may be subjected to dehydrofluorination (either alone or as a mixture) to produce HFC-1234ze and HFC-1234yf which may be recovered. See, for example, U.S. patent application publication US2006/0106263(A1), which is incorporated herein by reference.

HCFC-1233zd and HFC-245fa may also be present in the product mixture. The HCFC-1233xf, HCFC-1233zd and HFC-245fa in the product mixture may be further reacted with HF in the liquid phase under fluorination conditions in the presence of a fluorination catalyst to produce a fluorinated catalyst comprising CF₃CH₂CHF₂And CF₃CF₂CH₃A mixture of (a).

As noted above, the present invention also provides a process involving the use of at least one feedstock selected from the group consisting of HFC-245fa, HFC-1234ze and HCFC-1233zd to produce a product mixture comprising HFC-245fa, HFC-1234ze and HCFC-1233 zd: from the formula CX₃CHClCH₂Halopropanes represented by X, represented by the formula CX₃CCl＝CH₂Halopropenes of the formula CX₂＝CClCH₂And X represents a halogenated propene. Of note are embodiments of the process wherein HFC-1234ze is recovered. Additional HFC-1234ze is obtained by dehydrofluorination of HFC-245fa in the product mixture. And alsoOf note are embodiments of the process wherein HCFC-1233zd in the product mixture is fluorinated to produce at least one of HFC-1234ze and HFC-245 fa.

Also of note is a process wherein HFC-245fa is recovered.

Also of note is a process wherein the product mixture also comprises HFC-1234yf and HFC-1234yf in the product mixture is recovered.

The product mixture may also comprise HFC-245 cb. A mixture of HFC-245cb and HFC-1234ze may be recovered and further reacted with HF in the liquid phase in the presence of a fluorination catalyst under fluorination conditions to produce a mixture comprising HFC-245fa and HFC-245 cb. Alternatively, a mixture of HFC-245cb and HFC-1234ze may be recovered and further reacted under dehydrofluorination conditions in the presence of a dehydrofluorination catalyst to produce a mixture comprising HFC-1234ze and HFC-1234 yf.

HFC-245cb, HFC-1234yf and/or HCFC-1233xf may also be present in the product mixture. The HFC-245fa, HFC-1234ze, and HCFC-1233zd from the product mixture together with HFC-245cb (if present), HFC-1234yf (if present), and HCFC-1233xf (if present) may be further reacted in the liquid phase with HF in the presence of a fluorination catalyst under fluorination conditions to produce a mixture comprising HFC-245fa and HFC-245 cb. The HFC-245fa and HFC-245cb in the mixture may be subjected to dehydrofluorination (either alone or as a mixture) to produce HFC-1234ze and HFC-1234yf which may be recovered. See, for example, U.S. patent application publication US2006/0106263 (A1).

HCFC-1233xf may also be present in the product mixture. The HCFC-1233xf, HCFC-1233zd and HFC-245fa in the product mixture may be further reacted with HF in the liquid phase under fluorination conditions in the presence of a fluorination catalyst to produce a fluorinated catalyst comprising CF₃CH₂CHF₂And CF₃CF₂CH₃A mixture of (a).

As indicated above, the present invention also provides a method involving the use of at least oneA feedstock selected from the group consisting of HFC-245cb and HFC-1234yf to produce a product mixture comprising HFC-245cb and HFC-1234 yf: from the formula CX₃CHClCH₂Halopropanes represented by X, represented by the formula CX₃CCl＝CH₂Halopropenes of the formula CX₂＝CClCH₂And X represents a halogenated propene. Of note are embodiments of the process wherein HCFC-1233xf is used as the starting material.

From the formula CX₃CHClCH₂Suitable halopropane feedstocks represented by X include CCl₃CHClCH₂Cl (HCC-240db) and CF₃CHClCH₂Cl (HCFC-243 db). HCFC-243db is a readily available starting material, commercially available CF₃CH＝CH₂(3, 3, 3-trifluoro-1-propene or HFC-1243 zf).

From the formula CX₃CCl＝CH₂Suitable halopropene starting materials include HCFC-1233 xf. HCFC-1233xf may be prepared by the dehydrochlorination of HCFC-243 db.

Chemical formula CX₂＝CClCH₂Suitable halopropene starting materials represented by X include CCl₂＝CClCH₂Cl。

The reaction may be carried out in the liquid or vapor phase. For the liquid phase embodiments of the present invention, the reaction of the feedstock with HF can be carried out in a liquid phase reactor in batch mode, semi-continuous mode, or continuous mode. In batch mode, the feedstock is blended with HF in an autoclave or other suitable reaction vessel and heated to the desired temperature.

Preferably, the reaction is carried out in semi-batch mode by feeding HF to the liquid phase reactor containing the feedstock, or by feeding the feedstock to the liquid phase reactor containing HF, or by feeding HF to a mixture comprising HF and the reaction product formed by initially heating the feedstock with HF. Alternatively, the HF may be fed to a liquid phase reactor containing a mixture of the starting material and a reaction product formed from the reaction of HF with the starting material. In another embodiment of the liquid phase process, HF and the starting materials can be fed simultaneously in the desired stoichiometric ratio to a reactor containing a mixture of HF and reaction products formed by the reaction of HF with the starting materials.

In the liquid phase reactor, temperatures suitable for reacting HF with the feedstock are from about 80 ℃ to about 180 ℃, preferably from about 100 ℃ to about 150 ℃. Higher temperatures generally result in greater conversion of the feedstock.

Suitable molar ratios of HF to total amount of starting materials fed to the liquid phase reactor are at least stoichiometric and generally range from about 5: 1 to about 100: 1. Of note are embodiments wherein the molar ratio of HF to starting material is from about 8: 1 to about 50: 1.

The reactor pressure in the liquid phase process is not critical. In a batch reaction, the reactor pressure is typically the autogenous pressure of the system at the reaction temperature. In the starting materials and intermediate reaction products, the chlorine substituents are replaced with fluorine to form hydrogen chloride, while the system pressure is increased. In a continuous process, the pressure in the reactor may be set so that the lower boiling products (e.g., HCl, CF) are reacted₃CF＝CH₂、E/Z-CF₃CHF and CF₃CF₂CH₃) Is discharged from the reactor, optionally through a packed column or condenser. In this way, higher boiling intermediates remain in the reactor and volatile products are removed. Typical reactor pressures are about 20 psig (239kPa) to about 1,000 psig (6,994 kPa).

In embodiments of the invention where the reaction is carried out in a liquid phase process, useful catalysts include carbon, AlF₃、BF₃、FeCl_3-aF_a(wherein a is 0 to 3), carbon-supported FeX₃、SbCl_3-aF_a、AsF₃、MCl_5-bF_b(wherein b is 0 to 5 and M is Sb, Nb, Ta or Mo) and M' Cl_4-cF_c(wherein c is 0 to 4, and M' is Sn, Ti, Zr or Hf). A preferred catalyst for the liquid phase process is MCl_5-bF_b(wherein b is 0 to 5, and M is Sb or Nb or Ta).

Preferably, the reaction of HF with the starting material is carried out in the vapor phase. A heated reactor is generally used. A variety of reactor configurations may be employed, including horizontal or vertical orientation of the reactor, and the order of reaction of the feedstock with HF. In one embodiment of the invention, the starting materials may be first vaporized and fed to the reactor in gaseous form.

In another embodiment of the invention, the feedstock may be contacted with HF in a pre-reactor and then reacted in a vapor phase reactor. The prereactor may be empty, but is preferably filled with a suitable packing, for example Monel^TMOr Hastelloy^TMNickel alloy turnings or wool-like fillers, or other materials that do not react with HCl and HF, which can effectively mix the feedstock with HF vapor.

The pre-reactor temperature suitable for this embodiment of the invention is from about 80 ℃ to about 250 ℃, preferably from about 100 ℃ to about 200 ℃. Temperatures above about 100 c can result in partial conversion of the starting material to compounds having a higher degree of fluorination. Higher temperatures result in greater conversion of the feedstock entering the reactor and a higher degree of fluorination of the converted compound. Under these conditions, for example, a mixture of HF and HCFC-243db is converted to a mixture comprising essentially HF, HCl, HCFC-243db, HCFC-244db (CF)₃CHClCH₂F) And mixtures of HCFC-1233 xf.

The degree of fluorination reflects the number of fluorine substituents in the starting material and its fluorinated product in place of the chlorine substituents. For example, HFC-245cb represents a higher degree of fluorination than HCFC-243db, whereas HFC-1234yf represents a higher degree of fluorination than HCFC-1233 xf.

The molar ratio of HF to the total amount of starting materials in the pre-reactor is generally in the range of from about the stoichiometric ratio of HF to the total amount of starting materials to about 50: 1. Preferably, the molar ratio of HF to total amount of feed in the pre-reactor is from about two times to about 30: 1 the stoichiometric ratio of HF to total amount of feed. In one embodiment of the invention, the preferred molar ratio of HF to total amount of feedstock is employed in the pre-reactor and no additional amount of HF is added to the vapor phase reaction zone.

In a preferred embodiment of the invention, the starting materials and HF are vaporized and fed to a prereactor or vapor phase reactor.

Suitable temperatures for the vapor phase reaction of the present invention are from about 120 ℃ to about 500 ℃. Temperatures in the range of about 300 ℃ to about 350 ℃ favor the formation of HFC-1234yf, HFC-245cb, and HCFC-1233 xf. Temperatures in the range of about 350 ℃ to about 450 ℃ are advantageous for the additional formation of HFC-1234ze, HFC-245fa and HCFC-1233 zd. Higher temperatures result in greater conversion of the starting material and greater degree of fluorination of the converted product. If the feedstock is a halopropane, a reactor temperature of about 150 ℃ to about 275 ℃ favors the formation of HCFC-1233xf as the primary product.

Suitable reactor pressures for the vapor phase reactor can range from about 1 to about 30 atmospheres. Pressures of about 15 to about 25 atmospheres may be advantageously employed to facilitate separation of HCl from other reaction products, and suitable reaction times may be about 1 to about 120 seconds, preferably about 5 to about 60 seconds.

The molar ratio of HF to the total amount of feed in the vapor phase reaction is generally in the range of from about the stoichiometric ratio of HF to the total amount of feed to about 50: 1, and preferably from about 10: 1 to about 30: 1.

Preferably, the catalyst is used in a reaction zone where HF reacts with the vapor phase of the feedstock. Fluorination catalysts useful in the vapor phase reaction of the present invention include: carbon; graphite; alumina; fluorided alumina; aluminum fluoride; carbon-supported alumina; carbon-supported aluminum fluoride; fluorinated alumina supported on carbon; magnesium fluoride supported on aluminum fluoride; metals (including elemental metals, metal oxides, metal halides, and/or other metal salts); aluminum fluoride supported metal; fluorided alumina supported metal; alumina-supported metal; and a carbon-supported metal; a mixture of metals.

Metals suitable for use as catalysts (optionally supported on alumina, aluminum fluoride, fluorided alumina or carbon) include chromium, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, manganese, rhenium, scandium, yttrium, lanthanum, titanium, zirconium, and hafnium, copper, silver, gold, zinc and/or metals having atomic numbers from 58 to 71 (i.e., lanthanide metals). Preferably, when a supported catalyst is used, the total metal content of the catalyst is from about 0.1 to about 20 weight percent, based on the total weight of the catalyst; typically from about 0.1 to about 10 weight percent based on the total weight of the catalyst.

Typical fluorination catalysts for the vapor phase reaction of the present invention include: chromium-containing catalysts comprising chromium (III) oxide (Cr)₂O₃)；Cr₂O₃Supporting other metals, e.g. Cr₂O₃Supporting magnesium halide or zinc halide; a carbon-supported chromium (III) halide; a mixture of chromium and magnesium (including elemental metals, metal oxides, metal halides, and/or other metal salts), optionally supported by graphite; and mixtures of chromium and other metals (including elemental metals, metal oxides, metal halides, and/or other metal salts), optionally supported on graphite, alumina, or aluminum halides (e.g., aluminum fluoride).

Chromium-containing catalysts are well known in the art. Such catalysts can be prepared by precipitation or impregnation methods, as generally described by Satterfield in "heterogenous Catalysis in Industrial practice" 2 nd edition, pages 87 to 112 (McGraw-Hill, New York, 1991).

Of note are fluorination catalysts comprising at least one chromium-containing component selected from the group consisting of: crystalline alpha-chromium oxide (wherein from about 0.05 atom% to about 6 atom% of the chromium atoms in the alpha-chromium oxide lattice are replaced by trivalent cobalt atoms) and crystalline alpha-chromium oxide treated with a fluorinating agent (wherein from about 0.05 atom% to about 6 atom% of the chromium atoms in the alpha-chromium oxide lattice are replaced by trivalent cobalt atoms). Such catalysts, including their preparation, are disclosed in U.S. patent application publication US2005/0228202, which is incorporated herein by reference in its entirety.

Optionally, the metal-containing catalyst described above may be pretreated with HF. The method of this pretreatment may be, for example, placing the metal-containing catalyst in a suitable vessel and subsequently passing HF over the metal-containing catalyst. In one embodiment of the invention, such a vessel may be a reactor for carrying out the fluorination reaction of the present invention. Typically, the pretreatment time is from about 15 to about 300 minutes and the pretreatment temperature is from about 200 ℃ to about 450 ℃.

In one embodiment of the invention, the product mixture comprises HFC-245cb, HFC-245fa, HFC-1234yf, HFC-1234ze, HCFC-1233zd and HCFC-1233 xf.

If the product mixture produced by the process of the present invention comprises (i) the product compounds HFC-245cb, HFC-245fa, HFC-1234yf, HFC-1234ze, HCFC-1233zd and HCFC-1233xf, (ii) HF and HCl, (iii) by-products and (iv) unreacted starting materials, separation steps (a) through (e) may be employed to recover the product compounds in such product mixture.

In the separation step (a), the product mixture may be delivered to a distillation column to separate HCl from the product mixture.

In separation step (b), the product mixture obtained by separation step (a) may be delivered to one or more distillation columns to separate the azeotropic composition of HFC-1234yf and HF from the remainder of the product mixture. The azeotropic composition of recovered HFC-1234yf and HF may be further separated into individual components using a procedure similar to that described in U.S. patent application publication US2006/0106263(a1), which is incorporated herein by reference.

In separation step (c), the product mixture obtained by separation step (b) is passed to one or more distillation columns from which HF, HFC-245cb, HFC-1234ze, HCFC-1233xf, HCFC-1233zd and HFC-245fa are recovered from the top of the distillation columns, while higher boiling materials, such as CF, are removed from the bottom of the distillation columns₃CHClCH₂Cl and CF₃CHClCH₂F. The CF may be further separated from other by-products and unreacted starting materials by methods such as distillation₃CHClCH₂Cl and CF₃CHClCH₂F, and can be recycled in the vapor phase fluorination reactor.

In separation step (d), the product mixture comprising HF, HFC-245cb, HFC-1234ze, HCFC-1233xf, HCFC-1233zd and HFC-245fa recovered from the top of the distillation column by separation step (c) may be delivered to one or more distillation columns from which the azeotropic composition HFC-245cb/HF and the azeotropic composition HFC-1234ze/HF are recovered. The recovered HFC-245cb/HF and HFC-1234ze/HF azeotrope compositions can then be further separated into individual components using a process similar to the procedure described in U.S. patent publication US2006/0106263(a 1).

In another embodiment of separation step (d), the product mixture recovered from the top of the distillation column in separation step (c) comprising HF, HFC-245cb, HFC-1234ze, HCFC-1233xf, HCFC-1233zd and HFC-245fa can be recovered for use in the reaction zone of the vapor phase fluorination reactor.

In separation step (e), the product mixture comprising HCFC-1233xf, HCFC-1233zd and HFC-245fa and any HF recovered from the bottom of the distillation column by separation step (d) may be delivered to a distillation column to separate HCFC-1233xf, HCFC-1233zd and HFC-245 fa. HCFC-1233xf may be fluorinated to produce at least one of HFC-245cb and HFC-1234 yf. HCFC-1233zd may be fluorinated to produce at least one of HFC-245fa and HFC-1234 ze.

In the separation step (e), HCFC-1233xf is observed to form an azeotrope with HF when separating HCFC-1233 xf.

As noted above, in certain embodiments of the present invention, the mixture comprising HF, HFC-245cb and HFC-1234ze produced according to the process of the present invention is contacted with additional HF in a liquid phase fluorination reactor, optionally in the presence of a liquid phase fluorination catalyst, to produce a mixture comprising HF, HFC-245cb and HFC-245 fa. The mixture containing HF, HFC-245cb and HFC-245fa is then separated into the individual components using a process similar to the procedure described in U.S. patent publication US2006/0106263 (A1). Fluorination catalysts suitable for these embodiments may be selected from the catalysts described for use in the liquid phase embodiments of the fluorination reactor described herein. In these embodiments, the molar ratio of HF to HFC-245cb and HFC-1234ze, based on the amount of HFC-1234ze in the mixture, is generally from about 5: 1 to about 100: 1, preferably from about 10: 1 to about 40: 1. Temperatures suitable for these embodiments of the present invention range from about 30 ℃ to about 180 ℃, preferably from about 50 ℃ to about 150 ℃. Reactor pressures suitable for these embodiments are typically autogenous pressures at the reactor temperature. The pressure may be in the range of about 1 to about 30 atmospheres.

As noted above, in certain embodiments of the present invention, the mixture comprising HF, HFC-245cb and HFC-1234ze produced according to the process of the present invention may be delivered to a reaction zone comprising a dehydrofluorination catalyst (optionally after removal of HF). Reaction zone conditions are selected to be suitable for the conversion of HFC-245cb to HFC-1234 yf. The products comprising HFC-1234ze and HFC-1234yf removed from the reactor are separated using techniques known in the art. Catalysts suitable for these embodiments of the present invention, as well as suitable operating conditions, are disclosed in U.S. Pat. No. 5,396,000, the teachings of which are incorporated herein by reference. Preferably, the dehydrofluorination catalyst comprises aluminium fluoride or fluorided alumina or trivalent chromium oxide. Reaction temperatures suitable for these embodiments range from about 150 ℃ to about 500 ℃. In these embodiments, the contact time in the reaction zone is generally from about 1 second to about 500 seconds.

As noted above, in certain embodiments of the present invention, a mixture containing HCFC-1233xf, HCFC-1233zd and HFC-245fa prepared according to the process of the present invention is reacted with HF in the presence of a liquid phase fluorination catalyst in a liquid phase fluorination reactor to produce a mixture containing HF, HFC-245cb and HFC-245 fa. The fluorination conditions were similar to those described for the preparation of the above described mixture containing HFC-1234ze and HFC-245 cb. The mixture comprising HF, HFC-245cb and HFC-245fa is then optionally delivered to a distillation column to separate the two pentafluoropropanes and azeotropic HF by using a process similar to the procedure described in U.S. patent application publication No. US2006/0106263(a 1).

As noted above, HFC-245cb produced according to the process of the present invention may be dehydrofluorinated to produce HFC-1234yf, while HFC-245fa produced according to the process of the present invention may be dehydrofluorinated to produce HFC-1234 ze. Typical dehydrofluorination reaction conditions and dehydrofluorination catalysts are disclosed in U.S. Pat. No. 5,396,000, which is incorporated herein by reference. Dehydrofluorination reaction temperatures suitable for the present invention range from about 150 ℃ to about 500 ℃. However, higher temperatures are desirable for the dehydrofluorination reaction of HFC-245 cb. Suitable contact times for these dehydrofluorination reactions are from about 1 second to about 500 seconds. Preferably, the dehydrofluorination catalyst comprises at least one catalyst selected from the group consisting of aluminum fluoride, fluorinated alumina and trivalent chromium oxide.

As noted above, in certain embodiments of the present invention, a mixture containing HFC-245cb, HFC-1234yf, HFC-1234ze, HCFC-1233xf, HCFC-1233zd and HFC-245fa present in a product mixture produced according to the process of the present invention is reacted with HF in a liquid phase fluorination reactor in the presence of a liquid phase fluorination catalyst. The fluorination conditions were similar to those described for the preparation of the above described mixture containing HFC-1234ze and HFC-245 cb. The fluorination catalysts suitable for use in the above-described liquid phase embodiments of the present invention may be selected from those described for use in the liquid phase embodiments of the fluorination reactors described herein.

The amount of HF required for the liquid phase reaction depends on the total amount of HFC-1234yf, HFC-1234ze, HCFC-1233xf and HCFC-1233zd present in the mixture. The molar ratio of HF to the sum of the moles of HFC-1234yf, HFC-1234ze, HCFC-1233xf and E/Z-HCFC-1233zd is generally from about stoichiometric (between 1: 1 to 2: 1) to about 100: 1, and preferably from about 8: 1 to about 50: 1. Temperatures suitable for these embodiments of the present invention are generally in the range of about 30 ℃ to about 180 ℃, preferably in the range of about 50 ℃ to about 150 ℃. HF can then be removed from the resulting pentafluoropropane mixture (i.e., HFC-245cb and HFC-245fa) and then recovered using techniques known in the art to provide a single compound.

In connection with developing a process for separating the single compounds produced by the fluorination reactions of the present invention, it should be noted that HCFC-1233xf may exist as an azeotrope with HF, while HFC-245cb may exist as an azeotrope with HF.

The present invention also provides azeotropic compositions comprising an effective amount of hydrogen fluoride in admixture with HCFC-1233 xf. An effective amount of hydrogen fluoride refers to an amount of hydrogen fluoride that can form an azeotrope when mixed with HCFC-1233 xf.

The invention also provides azeotropic compositions comprising an effective amount of hydrogen fluoride admixed with HFC-245 cb. An effective amount of hydrogen fluoride refers to an amount of hydrogen fluoride that can form an azeotrope when mixed with HFC-245 cb.

As recognized in the art, an azeotropic composition is a mixture of two or more different components. When in the liquid state at a given pressure, the mixture will boil at a substantially constant temperature, which may be above or below the boiling temperature of the individual components, while the vapor component of the mixture is substantially the same as the boiling liquid component.

Thus, a primary feature of an azeotropic composition is that, at a given pressure, the boiling point of the liquid composition is fixed, and the composition of the vapor above the boiling composition is essentially that of the boiling liquid composition (i.e., no fractionation of the liquid composition components occurs). It is also recognized in the art that the boiling points and weight percentages of each component of the azeotropic composition may change when the azeotropic composition boils at different pressures. Thus, an azeotropic composition characterized by a fixed boiling point at a given pressure may be defined by the unique relationship that exists between the components, or the compositional ranges of these components, or the exact weight percentages of each component in the composition. It is also recognized in the art that various azeotropic compositions, including their boiling points at a particular pressure, can be calculated (see, e.g., w.schottky "ind.eng.chem.process des.dev., 1980, 19, 432 to 439). Experimental identification of azeotropic compositions containing the same components can be used to confirm the accuracy and/or modify the accuracy of such calculations at the same or other temperatures and pressures.

In accordance with the present invention, there is provided a composition comprising HCFC-1233xf and HF wherein HF is present in an effective amount to form an azeotropic combination with HCFC-1233 xf. These compositions comprise, by calculation, from about 71 mole% to about 60 mole% HF, and from about 29 mole% to about 40 mole% HCFC-1233xf (the azeotrope thus formed has a boiling point between about 0 ℃ and about 100 ℃ and a boiling pressure between about 14.3 pounds per square inch (98.6kPa) and about 277 pounds per square inch (1907 kPa)).

A composition may be formed that consists essentially of an azeotrope of hydrogen fluoride and HCFC-1233 xf. These compositions include compositions calculated to consist essentially of from about 71 mole% to about 60 mole% HF, and from about 29 mole% to about 40 mole% HCFC-1233xf (the azeotrope so formed has a boiling point between about 0 ℃ and about 100 and a boiling pressure between about 14.3 pounds per square inch (98.6kPa) and about 277 pounds per square inch (1907 kPa)).

After these calculations, it has been experimentally confirmed that azeotropes of HCFC-1233xf with HF can be formed at a variety of temperatures and pressures. For example, it has been found that an azeotrope of HF and HCFC-1233xf at 29.84 deg.C and 45.8 pounds per square inch (315.9kPa) contains essentially about 68.4 mole percent HF and about 31.6 mole percent HCFC-1233 xf. It has been calculated that an azeotrope of HF with HCFC-1233xf at 54.74 c and 96.7 pounds per square inch (666.9kPa) contains essentially about 66.6 mole percent HF and about 33.4 mole percent HCFC-1233 xf. It has been calculated that an azeotrope of HF and HCFC-1233xf at 79.67 deg.c and 186.2 pounds per square inch (1284.1kPa) contains essentially about 63.3 mole% HF and about 36.7 mole% HCFC-1233 xf.

According to calculations based on experiments, azeotropic compositions are provided. The composition comprises from about 71.7 mole% to about 60.2 mole% HF and from about 28.3 mole% to about 39.8 mole% HCFC-1233xf (the azeotrope so formed has a boiling point between about 0 ℃ and about 100 ℃ and a boiling pressure between about 15.1 psig (104.1kPa) and about 306.3 psig (2112.4 kPa)). Also provided are compositions consisting essentially of: about 71.7 mole% to about 60.2 mole% HF, and about 28.3 mole% to about 39.8 mole% HCFC-1233xf (the azeotrope so formed has a boiling point between about 0 ℃ and about 100 ℃ and a boiling pressure between about 15.1 psig (104.1kPa) and about 306.3 psig (2112.4 kPa)).

Azeotropic compositions of HF with HCFC-1233xf may be used as a source of HF to fluorinate other halogenated or unsaturated compounds. Such fluorination reactions may be carried out, for example, in the liquid phase using conventional antimony pentahalide catalysts known in the art, or in the vapor phase using chromium oxide catalysts known in the art. Alternatively, azeotropic compositions of HF and HCFC-1233xf may be used as recycle streams for fluorination reactors in which both the HF and HCFC-1233xf components recycled are available as reactants. For example, as indicated above, HCFC-1233xf may be used as a feedstock for the production of HFC-1234 yf.

According to the present invention, there are also provided compositions. The composition comprises HFC-245cb and HF, wherein the HF is present in an effective amount to form an azeotropic combination with HFC-245 cb. These compositions comprise from about 25.4 mole% to about 39.5 mole% HF, and from about 74.6 mole% to about 60.5 mole% HFC-245cb (the azeotrope thus formed having a boiling point between about-40 ℃ and about 90 ℃ and a boiling pressure between about 5.6 psig (38.6kPa) and about 413.0 psig (2848.3 kPa)) based on calculations based on the experiment.

A composition consisting essentially of an azeotrope of hydrogen fluoride and HFC-245cb can be formed. These combinations include compositions consisting essentially of from about 25.4 mole% to about 39.5 mole% HF, and from about 74.6 mole% to about 60.5 mole% HFC-245cb (the azeotrope so formed having a boiling point between about-40 ℃ and about 90 ℃ and a boiling pressure between about 5.6 psig (38.6kPa) and about 413.0 psig (2848.3 kPa)).

From experimentation and calculations based on the experiments, it has been determined that azeotropes of HFC-245cb and HF can be formed at a variety of temperatures and pressures. For example, it has been calculated that an azeotrope of HF and HFC-245cb at-20 ℃ and 14.7 psig (101.4kPa) contains essentially about 30.2 mole percent HF and about 69.8 mole percent HFC-245 cb. It has been calculated that an azeotrope of HF and HFC-245cb at 0c and 33.2 pounds per square inch (229.0kPa) contains essentially about 33.3 mole percent HF and about 66.7 mole percent HFC-245 cb. It has been found that an azeotrope of HF at 19.87 ℃ and 65.7 pounds per square inch (453.1kPa) with HFC-245cb contains essentially about 36.5 mole percent HF and about 63.5 mole percent HFC-245 cb. It has been calculated that the azeotrope of HF and HFC-245cb at 40 c and 119.4 psig (823.4kPa) contains essentially about 38.6 mole percent HF and about 61.4 mole percent HFC-245 cb. It has been found that an azeotrope of HF and HFC-245cb at 59.65 c and 200.3 psig (1381.4kPa) contains essentially about 39.6 mole percent HF and about 60.4 mole percent HFC-245 cb.

Azeotropic compositions of HF with HFC-245cb can be used as a source of HF to fluorinate other halogenated or unsaturated compounds. Such fluorination reactions may be carried out, for example, in the liquid phase using conventional antimony pentahalide catalysts known in the art, or in the vapor phase using chromium oxide catalysts known in the art. For example, contacting an azeotropic mixture of HF and HFC-245cb with acetylene, optionally in the presence of a catalyst such as carbon, will produce HFC-245cb and HFC-152a (CH) by fluorination of the acetylene₃CHF₂) A mixture of (a). In addition, azeotropic compositions of HF with HFC-245cb can also be used as recycle streams for the fluorination reactor where the recycled HF can be used as a reactant. For example, an azeotropic composition of HF and HFC-245cb may serve as a source of HF by recycling it to the reaction zone of the present invention and then reacting with CX, defined above, of the formula₃CHClCH₂Halopropanes represented by X, formula CClX₂CCl＝CH₂Halopropenes of the formula CX and/or₂＝CClCH₂And contacting the halopropene represented by X.

The reactor, distillation column and its associated feed, effluent and associated components used to carry out the process of the present invention should be constructed of materials resistant to hydrogen fluoride and hydrogen chloride. Typical materials of manufacture well known in the fluorination art include stainless steels, especially austenitic stainless steels, well known high nickel alloys such as Monel^TMNickel-copper alloy, Hastelloy^TMNickel baseAlloys and Inconel^TMNichrome, and copper clad steel.

Without further elaboration, it is believed that one skilled in the art can, using the description herein, utilize the present invention to its fullest extent. The following detailed description is, therefore, to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.

Examples

Preparation of a catalyst containing 98% chromium/2% cobalt

784.30g of Cr (NO)₃)₃[9(H₂O)](1.96 moles) and 11.64g Co (NO)₃)₂[6(H₂O)](0.040 mol) was dissolved in 2000mL of deionized water to prepare a solution. 950mL of 7.4M aqueous ammonia was added dropwise to the solution until the pH reached about 8.5. The slurry was stirred at room temperature overnight and then allowed to evaporate to dryness in air at a temperature of 110-120 ℃. The dried catalyst was then calcined in air at 400 ℃ for 24 hours and used.

General procedure for product analysis

The following general procedure is used to illustrate the method of analyzing the fluorination reaction product. A portion of the total reactor effluent was sampled online for organic product analysis using a gas chromatograph equipped with a mass spectrometer detector. The gas chromatograph utilized a 20 foot (6.1 meter) long x 1/8 inch (0.32 cm) diameter tube containing an inert carbon supportA perfluorinated polyether. Helium flow rate 30 mL/min (5.0X 10)^-7m³In seconds). The gas chromatography conditions were: the temperature was 60 ℃ for an initial holding period of three minutes, and then the temperature was set to rise to 200 ℃ at a rate of 6 ℃/minute.

Illustration of the drawings

243db is CF₃CHClCH₂Cl 244db is CF₃CHClCH₂F

245cb is CF₃CF₂CH₃245fa is CF₃CH₂CHF₂

1234yf is CF₃CF＝CH₂1233xf is CF₃CCl＝CH₂

1233zd is E-and Z-CHCl ═ CHCF₃1234ze is E-and Z-CHF ═ CHCF₃

1243zf is CH₂＝CHCF₃

Examples 1 to 5

CF ₃ CHClCH ₂ Fluorination of Cl

The 98% chromium/2% cobalt catalyst prepared above (21.4g, 15mL, -12 to +20 mesh (1.68 to 0.84mm)) was placed in an Inconel of 5/8' (1.58cm) diameter^TMA nickel alloy reaction tube, said reaction tube heated in a fluidized sand bath. The catalyst was pre-fluorinated with HF as follows. The catalyst was heated, the temperature was raised from 45 ℃ to 175 ℃ over about 1.5 hours, and a nitrogen stream (50 cc/min) was passed during the heating. HF was then added to the reactor at a flow rate of 50 cc/min for 1.3 hours at a temperature of 175 ℃. The reactor nitrogen flow rate was reduced to 20 cc/min and the HF flow rate was increased to 80 cc/min; this flow rate was maintained for 0.3 hour. The reactor temperature was then gradually raised to 400 ℃ over 1 hour. The HF and nitrogen flows were thereafter stopped and the reactor was brought to the desired operating temperature. Then HF vapor and CF₃CHClCH₂Cl begins to flow through the reactor. A portion of the reactor effluent was analyzed by online GC/MS.

Table 1 shows CF catalyzed by 98/2 Cr/Co catalyst₃CHClCH₂Cl fluorineAs a result of the reaction, the reaction is carried out at different operating temperatures and with the indicated HF and CF₃CHClCH₂Cl molar ratio; the analytical data are in GC area%. The nominal volume of the catalyst bed was 15 cc; the Contact Time (CT) was 15 seconds. Example 1 no catalyst was used.

TABLE 1

Fluorination of HCFC-243db

Example numbering	Ratio of HF/243	Temperature of(℃)	1243 zf	243d b	244d b	1234 yf	245c b	1233 xf	1233z d	1234z e	245f a
												1	5/1	140	0.1	88.4	7.4	0	0	3.9	0	0	0
2	10/1	275	0	0.2	0.6	1.3	4.8	90.0	0	0.7	1.0
												3	20/1	325	0	0	0	19.1	11.4	61.7	2.3	3.1	1.9

4	20/1	350	0	0	0	32.2	8.1	45.3	4.7	7.9	0.9
												5	20/1	400	0	0	0	17.9	6.6	36.3	19.7	14.4	3.6

Example 6

In the presence of TaF ₅ In case of (2) CF ₃ CHClCH ₂ Reaction of Cl with HF

To 210mL Hastelloy^TMInto the C-type tube were charged 10.0g (0.0599 mol) of HCFC-243db and 25.4g (0.040 mol) of tantalum pentafluoride. Then 40.0g (2.0 moles) of hydrogen fluoride was added to the tube. The tube was heated to 150 ℃ and held between 149 ℃ and 150 ℃ for eight hours while shaking. The tube was then cooled to room temperature and cooled with 100mL of water. The contents of the tube were poured out and the small organic layer was collected and neutralized. This sample contained 91.1% unconverted HCFC-243 db; GC-MS analysis of the converted product was as follows:

components GC area%

CF₃CF₂CH₃ 39.3

CF₃CH₂CHF₂ 5.5

C₃H₃ClF₄ 9.2

C₃H₃ClF₄ 27.6

CF₃CH₂CH₂Cl 2.9

CF₃CCl₂CH₂F 8.6

CF₃CH₂CHCl₂ 6.9

Claims (32)

1. A process for preparing at least one product compound selected from the group consisting of CF₃CF₂CH₃、CF₃CF＝CH₂And CF₃CCl＝CH₂The method comprising:

reacting at least one starting material with HF in a reaction zone, optionally in the presence of a fluorination catalyst, said starting material being selected from the group consisting of: from the formula CX₃CHClCH₂Halopropanes represented by X, formula CClX₂CCl＝CH₂To representAnd halopropenes of the formula CX₂＝CClCH₂Halopropenes represented by X, wherein each X is independently selected from the group consisting of F and Cl, thereby forming a halogenated propylene comprising HF, HCl, CF₃CF₂CH₃、CF₃CF＝CH₂And CF₃CCl＝CH₂Wherein the molar ratio of HF to the total amount of starting materials fed to the reaction zone is at least stoichiometric; and

recovering the at least one product compound from the product mixture.

2. The process of claim 1 wherein CF₃CF＝CH₂And recovering.

3. The process of claim 2 wherein CF is excluded from the product mixture₃CF₂CH₃Dehydrofluorination to produce additional CF₃CF＝CH₂。

4. The process of claim 1 wherein CF is excluded from the product mixture₃CCl＝CH₂Fluorination to form CF₃CF＝CH₂And CF₃CF₂CH₃At least one of (1).

5. The process of claim 1, wherein the product mixture further comprises CF₃CH ═ CHF; and wherein CF in the product mixture₃CHF is recovered.

6. The process of claim 1, wherein the product mixture further comprises CF₃CH ═ CHCl; and wherein CF is present in the product mixture₃Fluorination of CH ═ CHCl to CF₃CHF and CF₃CH₂CHF₂At least one of (1).

7. The method of claim 1, whereinThe product mixture also contains CF₃CH₂CHF₂(ii) a And wherein CF in the product mixture₃CH₂CHF₂And recovering.

8. The process of claim 1, wherein the product mixture further comprises CF₃CH₂CHF₂(ii) a And wherein CF is present in the product mixture₃CH₂CHF₂Dehydrofluorination to CF₃CH＝CHF。

9. The process of claim 1, wherein the product mixture further comprises CF₃CH ═ CHF; and wherein CF₃CF₂CH₃And CF₃The mixture of CH ═ CHF is recovered and further reacted in the liquid phase with HF under fluorination conditions in the presence of a fluorination catalyst to produce a catalyst comprising CF₃CH₂CHF₂And CF₃CF₂CH₃A mixture of (a).

10. The process of claim 1, wherein the product mixture further comprises CF₃CH ═ CHF; and wherein CF₃CF₂CH₃And CF₃The mixture of CH ═ CHF is recovered and further reacted under dehydrofluorination conditions in the presence of a dehydrofluorination catalyst to produce a catalyst comprising CF₃CHF and CF₃CF＝CH₂A mixture of (a).

11. The process of claim 1, wherein the CF in the product mixture₃CF₂CH₃、CF₃CF＝CH₂And CF₃CCl＝CH₂With CF in the product mixture₃CH₂CHF₂、CF₃CHF and CF₃CH ═ CHCl, if present, is further reacted with HF together in the liquid phase under fluorination conditions in the presence of a fluorination catalyst to produce a catalyst comprising CF₃CH₂CHF₂And CF₃CF₂CH₃A mixture of (a).

12. The method of claim 11, wherein CF is excluded from the mixture₃CH₂CHF₂And CF₃CF₂CH₃Dehydrofluorination to CF₃CHF and CF₃CF＝CH₂Both of them; and wherein CF₃CHF and CF₃CF＝CH₂Are all recovered.

13. The process of claim 1, wherein the product mixture further comprises CF₃CH₂CHF₂And CF₃CH ═ CHCl; and wherein CF in the product mixture₃CCl＝CH₂、CF₃CH₂CHF₂And CF₃CH ═ CHCl is further reacted in the liquid phase with HF under fluorination conditions in the presence of a fluorination catalyst to produce a catalyst comprising CF₃CH₂CHF₂And CF₃CF₂CH₃A mixture of (a).

14. The process of claim 1 wherein the starting materials are reacted in the vapor phase in the presence of a fluorination catalyst.

15. The method of claim 14, wherein the fluorination catalyst comprises at least one chromium-containing component selected from the group consisting of: crystalline alpha-chromium oxide, wherein from about 0.05 atomic% to about 6 atomic% of the chromium atoms in the alpha-chromium oxide lattice are substituted with trivalent cobalt atoms; and crystalline alpha-chromium oxide treated with a fluorinating agent, wherein from about 0.05 atomic% to about 6 atomic% of the chromium atoms in the alpha-chromium oxide lattice are replaced with trivalent cobalt atoms.

16. A process for preparing at least one product compound selected from the group consisting of CF₃CH₂CHF₂、CF₃CHF and CF₃CH ═ CHCl, the method comprising:

reacting at least one starting material with HF in a reaction zone, optionally in the presence of a fluorination catalyst, said starting material being selected from the group consisting of: from the formula CX₃CHClCH₂Halopropanes represented by X, represented by the formula CX₃CCl＝CH₂Halopropenes of the formula CX₂＝CClCH₂Halopropenes represented by X, wherein each X is independently selected from the group consisting of F and Cl, thereby forming a halogenated propylene comprising HF, HCl, CF₃CH₂CHF₂、CF₃CHF and CF₃A product mixture of CH ═ CHCl, wherein the molar ratio of HF to the total amount of starting materials fed to the reaction zone is at least stoichiometric; and

recovering the at least one product compound from the product mixture.

17. The process of claim 16, wherein CF₃CHF is recovered.

18. The process of claim 17 wherein CF is excluded from the product mixture₃CH₂CHF₂Dehydrofluorination to produce additional CF₃CH＝CHF。

19. The process of claim 16 wherein CF is excluded from the product mixture₃Fluorination of CH ═ CHCl to CF₃CH₂CHF₂And CF₃CH is at least one of CHF.

20. The process of claim 16, wherein CF₃CH₂CHF₂And recovering.

21. The process of claim 16, wherein the product mixture further comprises CF₃CF＝CH₂(ii) a And wherein CF in the product mixture₃CF＝CH₂To obtainAnd (6) recovering.

22. The process of claim 16, wherein the product mixture further comprises CF₃CF₂CH₃(ii) a And wherein CF₃CF₂CH₃And CF₃The mixture of CH ═ CHF is recovered and further reacted in the liquid phase with HF under fluorination conditions in the presence of a fluorination catalyst to produce a catalyst comprising CF₃CH₂CHF₂And CF₃CF₂CH₃A mixture of (a).

23. The process of claim 16, wherein the product mixture further comprises CF₃CF₂CH₃(ii) a And wherein CF₃CF₂CH₃And CF₃The mixture of CH ═ CHF is recovered and further reacted under dehydrofluorination conditions in the presence of a dehydrofluorination catalyst to produce a catalyst comprising CF₃CHF and CF₃CF＝CH₂A mixture of (a).

24. The process of claim 16, wherein CF in the product mixture₃CH₂CHF₂、CF₃CHF and CF₃CH ═ CHCl with CF in the product mixture₃CF₂CH₃、CF₃CF＝CH₂And CF₃CCl＝CH₂If present, together in the liquid phase under fluorination conditions in the presence of a fluorination catalyst to form a composition comprising CF₃CH₂CHF₂And CF₃CF₂CH₃A mixture of (a).

25. The method of claim 24, wherein CF is excluded from the mixture₃CH₂CHF₂And CF₃CF₂CH₃Dehydrofluorination to CF₃CHF and CF₃CF＝CH₂Both of them; and wherein CF₃CHF and CF₃CF＝CH₂Are all recovered.

26. The process of claim 16, wherein the product mixture further comprises CF₃CCl＝CH₂(ii) a And wherein CF in the product mixture₃CCl＝CH₂、CF₃CH₂CHF₂And CF₃CH ═ CHCl is further reacted in the liquid phase with HF under fluorination conditions in the presence of a fluorination catalyst to produce a catalyst comprising CF₃CH₂CHF₂And CF₃CF₂CH₃A mixture of (a).

27. The process of claim 16 wherein the starting materials are reacted in the vapor phase in the presence of a fluorination catalyst.

28. The method of claim 27, wherein the fluorination catalyst comprises at least one chromium-containing component selected from the group consisting of: crystalline alpha-chromium oxide, wherein from about 0.05 atomic% to about 6 atomic% of the chromium atoms in the alpha-chromium oxide lattice are substituted with trivalent cobalt atoms; and crystalline alpha-chromium oxide treated with a fluorinating agent, wherein from about 0.05 atomic% to about 6 atomic% of the chromium atoms in the alpha-chromium oxide lattice are replaced with trivalent cobalt atoms.

29. A process for preparing at least one product compound selected from the group consisting of CF₃CF₂CH₃And CF₃CF＝CH₂The method comprising: reacting at least one starting material with HF in a reaction zone, optionally in the presence of a fluorination catalyst, said starting material being selected from the group consisting of: from the formula CX₃CHClCH₂Halopropanes represented by X, represented by the formula CX₃CCl＝CH₂Halopropenes of the formula CX₂＝CClCH₂Halopropenes represented by X, wherein each X is independently selected from the group consisting of F and Cl, thereby forming a halogenated propylene comprising HF, HCl, CF₃CF₂CH₃And CF₃CF＝CH₂Wherein the molar ratio of HF to the total amount of starting materials fed to the reaction zone is at least stoichiometric; and

recovering the at least one product compound from the product mixture.

30. The process of claim 29, wherein said feedstock comprises CF₃CCl＝CH₂。

31. A composition, comprising:

(a)CF₃CCl＝CH₂and are and

(b) HF; wherein said HF is present in an effective amount to react with said CF₃CCl＝CH₂An azeotropic combination is formed.

32. A composition, comprising:

(a)CF₃CF₂CH₃and are and

(b) HF; wherein said HF is present in an effective amount to react with said CF₃CF₂CH₃An azeotropic combination is formed.