Compositions including olefin and hydrofluoroalkane

Information

  • Patent Grant
  • 12006274
  • Patent Number
    12,006,274
  • Date Filed
    Thursday, November 3, 2022
    2 years ago
  • Date Issued
    Tuesday, June 11, 2024
    6 months ago
Abstract
A method hydrofluorinates an olefin of the formula: RCX=CYZ to produce a hydrofluoroalkane of formula RCXFCHYZ or RCXHCFYZ, where X, Y, and Z are independently the same or different and are selected from the group consisting of H, F, Cl, Br, and C1-C6 alkyl which is partially or fully substituted with chloro or fluoro or bromo; and R is a C1-C6 alkyl which is unsubstituted or substituted with chloro or fluoro or bromo. The method includes reacting the olefin with HF in the vapor phase, in the presence of SbF5, at a temperature ranging from about −30° C. to about 65° C. and compositions formed by the process.
Description
BACKGROUND OF THE INVENTION

This disclosure relates to novel methods for preparing fluorinated organic compounds, and more particularly to methods of producing fluorinated hydrocarbons.


Hydrofluorocarbons (HFCs), in particular hydrofluoroalkenes or fluoroolefins, such as tetrafluoropropenes (including 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf or 1234yf)) have been disclosed to be effective refrigerants, fire extinguishants, heat transfer media, propellants, foaming agents, blowing agents, gaseous dielectrics, sterilant carriers, polymerization media, particulate removal fluids, carrier fluids, buffing abrasive agents, displacement drying agents and power cycle working fluids. Unlike chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs), both of which potentially damage the Earth's ozone layer, HFCs do not contain chlorine and, thus, pose no threat to the ozone layer.


In addition to ozone depleting concerns, global warming is another environmental concern in many of these applications. Thus, there is a need for compositions that meet both low ozone depletion standards as well as having low global warming potentials. Certain fluoroolefins are believed to meet both goals. Thus, there is a need for manufacturing processes that provide halogenated hydrocarbons and fluoroolefins that contain no chlorine that also have a low global warming potential.


One such HFO is 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf or 1234yf). The preparation of HFO-1234yf starting from CQ2=CCl—CH2Q or CQ3-CCl=CH2 or CQ3-CHCl—CH2Q may include three reaction steps, as follows:

    • (i) (CQ2=CCl—CH2Q or CQ3-CCl=CH2 or CQ3-CHCl—CH2Q)+HF-2-chloro-3,3,3-trifluoropropene (HCFO-1233xf or 1233xf)+HCl in a vapor phase reactor charged with a solid catalyst;
    • (ii) 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf)+HF-2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb or 244bb) in a liquid phase reactor charged with a liquid hydrofluorination catalyst; and
    • (iii) 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb)-2,3,3,3-tetrafluoropropene (HFO-1234yf) in a vapor phase reactor;
    • wherein Q is independently selected from F, Cl, Br, and I, provided that at least one Q is not fluorine.


The hydrofluorination of 1233xf to 244bb is usually conducted in the presence of fluorinated SbCl5 at temperatures above 70° C.; otherwise the catalyst will freeze. Under these conditions, the 1233xf is not completely converted to 244bb because of equilibrium limitations, especially at higher temperatures. As a result, significant amounts of 1233xf are present in the product formed. Since the boiling points of 1233xf and 244bb are only about 2° C. apart, separation of these two species is difficult and expensive.


Moreover, the presence of 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) in the reaction starting materials, such as HCFC-244bb feedstock, can lead to dramatically reduced conversion of HCFC-244bb to HFO-1234yf. In addition, the 2-chloro-3,3,3-trifluoropropene copresence in the starting material, when subjected to dehydrochlorination, can lead to the formation of trifluoropropyne and oligomers, which can produce tar. This result is disadvantageous from the standpoint of a reduced yield of the desired product. Therefore, there is a need for a better catalytic reaction to achieve a higher conversion of 1233xf to 244bb to avoid and/or minimize the need for purification.


The present invention fulfills that need.


SUMMARY OF THE INVENTION

The disclosure relates to a method for hydrofluorination of an olefin of the formula: RCX=CYZ to produce hydrofluoroalkanes of formula RCXFCHYZ and RCHXCFYZ, wherein X, Y and Z are independently the same or different and are selected from the group consisting of H, F, Cl, Br, and C1-C6 alkyl which is partly or fully substituted with chloro or fluoro or bromo, and R is a C1-C6 alkyl which is partially or fully substituted with chloro or fluoro or bromo, comprising reacting the fluoroolefin with HF in the liquid-phase, in the presence of SbF5, at a temperature ranging from about −30° C. to about 65° C.







DETAILED DESCRIPTION OF THE INVENTION

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


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


Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described below. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.


The term “olefin”, as used herein refers to a compound containing a carbon-carbon double bond. It is defined herein relative to the formula RCX=CYZ.


The terms “hydrofluoroalkene” or “fluoroolefin”, as used herein, denotes a compound containing hydrogen, carbon, fluorine, and at least one carbon-carbon double bond and optionally chlorine.


“HFO”, as used herein, indicates a compound containing hydrogen, carbon, fluorine, and at least one carbon-carbon double, and no chlorine. “HCFO”, as used herein, indicates a compound containing hydrogen, carbon, chlorine, fluorine, and at least one carbon-carbon double. “HCO”, as used herein, indicates a compound containing hydrogen, carbon, chlorine, and at least one carbon-carbon double bond, and no fluorine.


The term “hydrofluorination” is understood to mean the addition reaction of hydrogen fluoride to a carbon-carbon double bond.


The term “hydrofluoroalkane”, as used herein, refers to an alkane having two or more carbon atoms containing hydrogen, fluorine, and optionally chlorine, whereby a fluorine atom and a hydrogen atom are substituted on two adjacent carbon atoms. As used herein, the hydrofluoroalkane can be the product from the hydrofluorination of the fluoroolefin.


The HF used herein is an anhydrous liquid hydrogen fluoride which is commercially available or it may be a gas that is bubbled into the reactor. Anhydrous HF is sold by, for example, Solvay S. A, The Chemours Company FC, LLC and Honeywell International, Inc.


As used herein, the term “conversion” with respect to a reactant, which typically is a limiting agent, refers to the number of moles reacted in the reaction process divided by the number of moles of that reactant initially present in the process multiplied by 100.


As used herein, percent conversion is defined as 100%, less the weight percent of starting material in the effluent from the reaction vessel.


As used herein, the term “selectivity” with respect to an organic reaction product refers to the ratio of the moles of that reaction product to the total of the moles of the organic reaction products multiplied by 100.


As used herein, “percent selectivity” is defined as the weight of a desired product formed, as a fraction of the total amount of the products formed in the reaction, and excluding the starting material.


Some fluoroolefins of this disclosure, e.g., CF3CH═CHCl (HCFO-1233zd or 1233zd), exist as different configurational isomers or stereoisomers. When the specific isomer is not designated, the present disclosure is intended to include all single configurational isomers, single stereoisomers, or any combination thereof. For instance, HCFO-1233zd is meant to represent the E-isomer, Z-isomer, or any combination or mixture of both isomers in any ratio.


Described is a method for producing hydrofluoroalkanes of formula RCXFCHYZ, wherein X, Y and Z may independently be the same or different and are selected from H, F, Cl and an alkyl group having 1 to 6 carbon atoms, which alkyl group is partially or fully substituted with fluorine or chlorine; and R is an alkyl group having 1 to 6 carbon atoms, which alkyl group is partially or fully substituted with fluorine or chlorine comprising reacting a fluoroolefin of the formula RCX=CYZ with HF in the liquid-phase, in the presence of a catalytic effective amount of SbF5.


The terms “alkyl group is partially or fully substituted with chlorine” and “chlorinated alkyl” are synonymous and it is meant that the alkyl group must be at least monosubstituted with Cl. Similarly, the terms “alkyl group is partially or fully substituted with fluorine” and “fluorinated alkyl” are synonymous and it is meant that the alkyl group must be at least monosubstituted with F. However, in both cases, the alkyl group may have one or more fluoro substituents thereon or one or more chloro substituents thereon or a combination of one or more chloro or fluoro groups thereon. Some of the carbon atoms may be substituted with one or more chloro or fluoro atoms. In an embodiment, the alkyl group is substituted with one or more fluoro atoms. In an embodiment, the alkyl group is fully substituted with chloro or fluoro or combination of both chloro and fluoro.


In another embodiment, the alkyl group is perchlorinated, while in another embodiment, the alkyl group is perfluorinated.


The alkyl group may be branched or linear. In an embodiment, the alkyl group is linear. In an embodiment, the alkyl group contains 1-4 carbon atoms, and in another embodiment, it contains 1 or 2 or 3 carbon atoms and in still another embodiment 1 or 2 carbon atoms. In another embodiment, it contains only 1 carbon atom. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.


As defined herein, the carbon atoms which are part of the carbon-carbon double bond are substituted with R, X, Y, and Z. R is defined, among other things, as being partially or fully substituted with chloro or fluoro and X, Y, or Z may be, among other things, partially or fully substituted with chloro or fluoro. In one embodiment, X, Y, Z are independently partially or fully substituted with chloro or fluoro, and in another embodiment, two of X, Y, and Z are partially or fully substituted with chloro or fluoro, and in another embodiment, one of X, Y, and Z is partially or fully substituted with chloro or fluoro, in still another embodiment, three of X, Y and Z are partially or fully substituted with chloro or fluoro, and in another embodiment, none of X, Y, Z are partially or fully substituted with chloro or fluoro. With respect to X, Y, and Z, when defined as partially or fully substituted with chloro or fluoro, and with respect to R, in an embodiment, at least one carbon atom alpha or beta to the carbon atom bearing the double bond (if alkyl group contains 2 or more carbon atoms) is substituted with chloro or fluoro.


In one embodiment, X, Y, and Z are independently H or fluoro or chloro. In another embodiment, R is perchlorinated or perfluorinated. In some embodiments of this invention, R is —CF3 or —CF2CF3. In another embodiment, X, Y, and Z are independently H or fluoro or chloro and R is perfluorinated or perchlorinated. In still further embodiment, X, Y, Z are independently H or fluoro or chloro and R is perfluorinated, for example, —CF3 or —CF2CF3.


The process according to the invention can be carried out in any reactor made of a material that is resistant to reactants employed, especially to hydrogen fluoride. As used herein, the term “reactor” refers to any vessel in which the reaction may be performed in either a batchwise mode, or in a continuous mode. Suitable reactors include tank reactor vessels with and without agitators, or tubular reactors.


In one embodiment, the reactor is comprised of materials which are resistant to corrosion including stainless steel, Hastelloy, Inconel, Monel, gold or gold-lined or quartz. In another embodiment, the reactor is TFE or PFA-lined.


The olefin described herein has the formula RCX=CYZ, where R, X, Y, Z are as defined hereinabove. Examples include RCC1=CH2, RCH═CHCI, RCCI=CHC1, RCH═CCl2 and RCH═CH2, and the like. In one embodiment, R is trifluoromethyl and in another embodiment, R is pentafluoroethyl. Representative olefins include 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 1-chloro-3,3,3-trifluooropropene (HCFO-1233zd), chlorotetrafluoropropenes (HCFO-1224 or 1224), 2,3,3,3-tetrafluoropropene (1234yf), dichlorotetrafluoropropenes (HCFO-1214 or 1214), 1,3,3,3-tetrafluoropropene (1234ze), 3,3,3-trifluoropropene (HFO-1243zf or 1234zf), and the like.


The hydrofluoroalkanes described herein are the addition products of HF to the fluoroolefins, as defined hereinabove. As defined herein, they have the formula RCXFCHYZ or RCXHCFYZ, wherein R, X, Y, Z are as defined hereinabove. As described hereinabove, in one embodiment, R is trifluoromethyl and in another embodiment, R is pentafluoroethyl.


Representative hydrofluoropropanes include 1,1,1,2-tetrafluoro-2-chloropropane, 1,1,1,3-tetrafluoro-3-chloropropane, 1,1,1,3,3-pentafluoro-3-chloropropane, 1,1,1,2,2-pentafluoro-3-chloropropane, 1,1,1,2,2-pentafluoropropane, 1,1,1,3,3-pentafluoropropane and the like.


The present process adds HF across the double bond of the fluoroolefin to produce a hydrofluoroalkane. The F atom may add to an internal or terminal carbon atom and the hydrogen atom may add to a terminal or internal carbon atom. Thus, for example, in accordance with the present disclosure, when the fluoroolefin is RCCl=CH2, the product is RCFClCH3. In another embodiment, when the fluoroolefin is RCH═CHCl, the product is RCH2CHFCl. In another embodiment, when the fluoroolefin is RCH═CCl2, the hydrofluoropropane is RCH2CFCl2. In yet another embodiment, when the fluoroolefin is RCH═CH2, the hydrofluoropropanes formed are RCHFCH3 and RCH2CH2F. With respect to the aforementioned examples, in an embodiment, R can be CF3 or C2F6.


In one embodiment, the fluoroolefin is 2-chloro-3,3,3-trifluoropropene and the hydrofluoroalkane is 2-chloro-1,1,1,2-tetrafluoropropane. In another embodiment, the fluoroolefin is 3,3,3-trifluoropropene and the hydrofluoroalkane is 1,1,1,2-tetrafluoropropane and 1,1,1,3-tetrafluoropropane. In another embodiment, the fluoroolefin is (Z)- or (E)-1-chloro-3,3,3-tetrafluoropropene and the hydrofluoroalkane is 3-chloro-1,1,1,3-tetrafluoropropane. In another embodiment, the fluoroolefin is cis- or trans-1,2-dichloro-3,3,3-trifluoropropene and the hydrofluoroalkane is 1,1,1,2-tetrafluoro-2,3-dichloropropane and 1,1,1,3-tetrafluoro-2,3-dichloropropane. In another embodiment, the fluoroolefin is 2,3,3,3-tetrafluoropropene, and the hydrofluoroalkane is 1,1,1,2,2-pentafluoropropane. In yet another embodiment, the fluoroolefin is 1,3,3,3-tetrafluoropropene and the hydrofluoroalkane is 1,1,1,3,3-pentafluoropropane.


Without wishing to be bound, it is believed that with respect to HF addition to a carbon-carbon double bond, the fluorine atom adds to the carbon atom of the double bond which has the most halogens attached thereto. Otherwise, without wishing to be bound, the HF is added to the carbon atom of the double bond in accordance with Markovnikov's rule, i.e., the hydrogen of HF will add to the carbon atom that will form the more stable carbonium ion. Thus, for example, if one of the carbon atoms of the carbon-carbon double bond has more hydrogen atoms substituted thereon than the other carbon atom of the carbon-carbon double bond, the hydrogen atom of HF will add to the carbon atom having the most hydrogen atoms substituted thereon.


The above process is conducted in the liquid phase. The fluoroolefin as well as the hydrogen fluoride are liquids at reaction conditions. Since water is used to quench the reaction, the amount of water present is minimized. For example, the hydrogen fluoride used is anhydrous.


The hydrogen fluoride can be bubbled in as a gas or added as a liquid into the liquid fluoroolefin or it may be present in an anhydrous solvent, such as pyridine. Thus, for example, in an embodiment, although not necessary, the fluoroolefin is dried with a desiccant before being mixed with HF or the catalyst. By “desiccant,” it is meant any material which will absorb water without dissolving in or otherwise contaminating the fluoroolefin being dried, e.g., calcium sulfate or molecular sieves, and the like. In another embodiment, the reaction can be conducted in an inert atmosphere, such as under nitrogen, helium, argon and the like. However, in an embodiment, the reaction can be conducted in air and in another embodiment, the reaction is conducted without drying the fluoroolefin.


In an embodiment, when anhydrous liquid HF is used or HF is fed as a gas, the reaction is conducted without any solvent in addition to the solvent in which the anhydrous HF is dissolved.


If the HF is fed as a gas, such as, being bubbled in as a gas, the reaction may be conducted without any solvent present.


In one embodiment, the hydrofluorination reaction is conducted at a temperature ranging from about −30° C. to about 65° C. In another embodiment, the hydrofluorination reaction is conducted at a temperature ranging from about −10° C. to about 40° C. In another embodiment, the hydrofluorination reaction is conducted at a temperature ranging from about 0° C. to about 30° C.


In still another embodiment, the hydrofluorination reaction is conducted at a temperature ranging from about 0° C. to about 25° C. In another embodiment, the hydrofluorination reaction is conducted at a temperature ranging from about 5° C. to about 25° C. In still another embodiment, the hydrofluorination reaction is conducted at a temperature ranging from about 5° C. to about 20° C. Moreover, the hydrofluorination reaction can be conducted at any temperature in-between the ranges disclosed hereinabove, and these temperatures are contemplated within the scope of the present invention. Thus, the hydrofluorination described hereinabove is conducted in a reaction vessel at about −30° C., about −29° C., about −28° C., about −27° C., about −26° C., about −25° C., about −24° C., about −23° C., about −22° C., about −21° C., about −20° C., about −19° C., about −18° C., about −17° C., about −16° C., about −15° C., about −14° C., about −13° C., about −12° C., about −11° C., about −10° C., about −9° C., about −8° C., about −7° C., about −6° C., about −5° C., about −4° C., about −3° C., about −2° C., about −1° C., about 0° C., about 1° C., about 2° C., about 3° C., about 4° C., about 5° C., about 6° C., about 7° C., about 8° C., about 9° C., about 10° C., about 11° C., about 12° C., about 13° C., about 14° C., about 15° C., about 16° C., about 17° C., about 18° C., about 19° C., about 20° C., about 21° C., about 22° C., about 23° C., about 24° C., about 25° C., about 26° C., about 27° C., about 28° C., about 29° C., about 30° C., about 31° C., about 32° C., about 33° C., about 34° C., about 35° C., about 36° C., about 37° C., about 38° C., about 39° C., about 40° C., about 41° C., about 42° C., about 43° C., about 44° C., about 45° C., about 46° C., about 47° C., about 48° C., about 49° C., about 50° C., about 51° C., about 52° C., about 53° C., about 54° C., about 55° C., about 56° C., about 57° C., about 58° C., about 59° C., about 60° C., about 61° C., about 62° C., about 63° C., about 64° C., or about 65° C.


In an embodiment, the reaction mixture is stirred using techniques known in the art. For example, the reaction mixture is spun using a stirring bar. Alternatively, the reactor in which the reaction takes place is equipped with an impeller or other stirring device which stirs the reaction mixture.


In another embodiment, mixing may be provided by alternatives to stirring devices. Such methods are known in the industry and include using the mixing provided by gas bubbles from gas added to the vessel or generated within the vessel by vaporization of liquid. Mixing can also be provided by withdrawing the liquid from the vessel to a pump and pumping the liquid back into the vessel. A static mixer or other device intended to mix the contents can be present in the circulation path of the liquid to provide additional mixing power input.


In one embodiment, the mole ratio of HF to fluoroolefin ranges from about 0.5 to about 20.


In another embodiment, the mole ratio of HF to fluoroolefin is from about 1 to about 10. In another embodiment, the mole ratio of HF to fluoroolefin is from about 1 to about 5.


The SbF5 is present in catalytic effective amounts. In one embodiment, the SbF5 catalyst is present from about 1% to about 50% by weight of the mixture. In another embodiment, the SbF5 catalyst is present from about 2% to about 30% by weight. In another embodiment, the SbF5 catalyst is present from about 3% to about 15% by weight.


As described hereinabove, hydrofluoroalkanes are prepared by catalytic fluorination of the fluoroolefin. In one embodiment, the catalytic fluorination of the fluoroolefin results in a percent conversion to the hydrofluoroalkane of at least 90 mole %. In another embodiment, the catalytic fluorination of the fluoroolefin results in a percent conversion to the hydrofluoroalkane of at least 95%. In another embodiment, the catalytic fluorination of the fluoroolefin results in a percent conversion to the hydrofluoroalkane of at least 98%. In still another embodiment, the catalytic fluorination of the fluoroolefin results in a percent conversion to the hydrofluoroalkane of at least 99%.


An aspect of the invention is to replace step (ii) of the reaction for making 1234yf described in the introduction with the present process.


One of the advantages of the present disclosure is that the catalytic reaction for hydrofluorination, as described herein, takes place at lower temperatures, much lower than other catalysts for the other hydrofluorination reactions of fluoroolefin, such as SbCl5 or fluorinated SbCl5. Unlike these other catalysts, SbF5 is a liquid at these lower temperatures that are used in the present process. Therefore, less energy is required to conduct these hydrofluorination reactions.


In addition, in the present process, the catalyst has substantial activity at the lower temperature.


Thus, the catalytic process proceeds at a low temperature, thereby making it more efficient.


In addition, another advantage is that the ratio of the desired hydrofluoroalkane produced relative to the starting olefin is about 90:1 or greater, and in another embodiment, is about 100:1 or greater and in another embodiment is about 110:1 or greater. Thus, for another reason, this reaction is quite efficient.


Moreover, in view of the efficiency, if an olefin and the resulting hydrofluoroalkane from the hydrofluorination reaction, such as 1233xf and 244bb, were mixed together and reacted under the conditions of the present invention with SbF5, additional hydrofluoroalkane product would be formed. For example, in one embodiment, if the feed material ratio of olefin, such as 1233xf, to hydrofluoroalkane, such a 244bb, is greater than about 1 mole %, the present process will significantly convert the unreacted olefin to hydrofluoroalkane, thereby increasing the amount of the hydrofluoroalkane in the mixture. The present disclosure thus provides a method of maximizing the yield of the desired hydrofluoroalkane relative to the olefin. Thus, in the above example, wherein the olefin is 1233xf and the hydrofluoroalkane is 244bb, if 1233xf is present in greater than about 1 mole %, the resulting product would have significantly more 244bb present than prior to the reaction.


Thus, in one embodiment, this advantage of the present disclosure can be used to improve the yield of HFO-1234yf being produced. As described hereinabove, the preparation of HFO-1234yf may include at least three reaction steps, as follows:

(i) (CQ2=CCl-CH2Q or CQ3-CCl=CH2 or CQ3-CHCl-CH2Q)+HF-2-chloro-3,3,3-

trifluoropropene (HCFO-1233×f)+HCl in a vapor phase reactor charged with a solid catalyst;

(ii)2-chloro-3,3,3-trifluoropropene(HCFO-1233×f)+HF→2-chloro-1,1,1,2

-tetrafluoropropane (HCFC-244bb) in a liquid phase reactor charged with a liquid hydrofluorination catalyst; and

    • (iii) 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb)-2,3,3,3-tetrafluoropropene (HFO-1234yf) in a vapor phase reactor.


The general reactions of steps (i), (ii) and (iii) are well known in the art. For example, they are described in U.S. Pat. No. 8,846,990, the contents of which are incorporated by reference.


In the first step, a starting composition, which comprises 1,1,2,3-tetrachloropropene (HCO-1230xa or 1230xa), reacts with anhydrous HF in a first reactor (fluorination reactor) to produce a mixture of at least HCFO-1233×f (2-chloro-3,3,3-trifluoropropene) and HCl. The reaction is carried out in a reactor in the gaseous phase at a temperature of about 200° C. to about 400° C. and a pressure of about 0 to about 200 psig. The effluent stream exiting in the vapor phase reactor may optionally comprise additional components, such as un-reacted HF, un-reacted starting composition, heavy intermediates, HFC-245cb, or the like.


This reaction may be conducted in any reactor suitable for a vapor phase fluorination reaction. The reactor may be constructed from materials which are resistant to the corrosive effects of hydrogen fluoride such as Hastelloy, Inconel, Monel, and the like. In the case of a vapor phase process, the reactor is filled with a vapor phase fluorination catalyst. Any fluorination catalysts known in the art may be used in this process. Suitable catalysts include, but are not limited to, metal oxides, hydroxides, halides, oxyhalides, inorganic salts thereof and their mixtures, any of which may be optionally halogenated, wherein the metal includes, but is not limited to, chromium, aluminum, cobalt, manganese, nickel, iron, and combinations of two or more thereof.


Combinations of catalysts suitable for the present invention nonexclusively include Cr2O3, FeCl3/C, Cr2O3/Al2O3, Cr2O3/AlF3, Cr2O3/carbon, CoCl2/Cr2O3/Al2O3, NiCl2/Cr2O3/Al2O3, CoCl2/AlF3, NiCl2/AlF3 and mixtures thereof. Chromium oxide/aluminum oxide catalysts are described in U.S. Pat. No. 5,155,082, the contents of which are incorporated herein by reference. Chromium (III) oxides such as crystalline chromium oxide or amorphous chromium oxide are preferred with amorphous chromium oxide being most preferred. Chromium oxide (Cr203) is a commercially available material which may be purchased in a variety of particle sizes. Fluorination catalysts having a purity of at least 98% are preferred. The fluorination catalyst is present in an excess but in at least an amount sufficient to drive the reaction.


This first step of the reaction is not necessarily limited to a vapor phase reaction and may also be performed using a liquid phase reaction or a combination of liquid and vapor phases, such as that disclosed in U.S. Published Patent Application No. 2007/0197842, the contents of which are incorporated herein by reference. It is also contemplated that the reaction can be carried out batch wise or in a continuous manner, or a combination of these.


For embodiments in which the reaction comprises a liquid phase reaction, the reaction can be catalytic or non-catalytic. Lewis acid catalysts, such as metal-halide catalysts, including antimony halides, tin halides, thallium halides, iron halides, and combinations of two or more of these, may be employed. In certain embodiments, metal chlorides and metal fluorides are employed, including, but not limited to, SbCl5, SbCl3, SbF5, SnCl4, TiCl4, FeCl3, and combinations of two or more of these. It is noted that SbF5 is a liquid at low temperature.


In the second step of the process for forming 2,3,3,3-tetrafluoropropene, HCFO-1233×f is converted to HCFC-244bb. In one embodiment, this step can be performed in the liquid phase in a liquid phase reactor, which may be TFE or PFA-lined. Such a process can be performed in a temperature range of about 70° C. to about 120° C. and at a pressure ranging from about 50 to about 120 psig. Any liquid phase fluorination catalyst may be used that is effective at these temperatures.


A non-exhaustive list includes Lewis acids, transition metal halides, transition metal oxides, Group IVb metal halides, Group Vb metal halides, or combinations thereof. Non-exclusive examples of liquid phase fluorination catalysts are antimony halide, tin halide, tantalum halide, titanium halide, niobium halide, molybdenum halide, iron halide, fluorinated chrome halide, fluorinated chrome oxide or combinations thereof. Specific non-exclusive examples of liquid phase fluorination catalysts are SbCl5, SbCl3, SbF5, SnCl4, TaCl5, TiCl4, NbCls, MoCl1, FeCl3, fluorinated species of SbCl5, fluorinated species of SbCl3, fluorinated species of SnCl4, fluorinated species of TaCl5, fluorinated species of TiCl4, fluorinated species of NbCl5, fluorinated species of MoCl6, fluorinated species of FeCl3, or combinations thereof.


These catalysts can be readily regenerated by any means known in the art if they become deactivated. One suitable method of regenerating the catalyst involves flowing a stream of chlorine through the catalyst. For example, from about 0.002 to about 0.2 lb per hour of chlorine can be added to the liquid phase reaction for every pound of liquid phase fluorination catalyst. This may be done, for example, for from about 1 to about 2 hours or continuously at a temperature of from about 65° C. to about 100° C.


This second step of the reaction is not necessarily limited to a liquid phase reaction and may also be performed using a vapor phase reaction or a combination of liquid and vapor phases, such as that disclosed in U.S. Published Patent Application No. 2007/0197842, the contents of which are incorporated herein by reference. To this end, the HCFO-1233×f containing feed stream is preheated to a temperature of from about 50° C. to about 400° C., and is contacted with a catalyst and fluorinating agent. Catalysts may include standard vapor phase agents used for such a reaction and fluorinating agents may include those generally known in the art, such as, but not limited to, hydrogen fluoride.


In the process described in the art, such as that described in U.S. Published Patent Application No. 2007/0197842, the product from the second step is then transferred to a third reactor wherein the 244bb is dehydrohalogenated. The catalysts in the dehydrochlorination reaction may be or comprise metal halide, halogenated metal oxide, neutral (or zero oxidation state) metal or metal alloy, or activated carbon in bulk or supported form. Metal halide or metal oxide catalysts may include, but are not limited to, mono-, bi-, and tri-valent metal halides, oxides and their mixtures/combinations, and more preferably mono-, and bi-valent metal halides and their mixtures/combinations. Component metals of metal halides, oxides and their mixtures/combinations include, but are not limited to, Cr3+, Fe3+, Mg2+, Ca2+, Ni2+, Zn2+, Pd2+, Li+, Na+, K+, and Cs+. Component halides include, but are not limited to, F, Cl, Br, and I. Examples of useful mono- or bi-valent metal halide include, but are not limited to, LiF, NaF, KF, CsF, MgF2, CaF2, LiCi, NaCl, KCl, and CsCl. Halogenation treatments can include any of those known in the prior art, particularly those that employ HF, F2, HCl, Cl2, HBr, Br2, HI, and I2 as the halogenation source.


When the catalyst is or comprises a neutral, i.e., zero valent metal, then metals and metal alloys and their mixtures are used. Useful metals include, but are not limited to, Pd, Pt, Rh, Fe, Co, Ni, Cu, Mo, Cr, Mn, and combinations of the foregoing as alloys or mixtures. The catalyst may be supported or unsupported. Useful examples of metal alloys include, but are not limited to, SS 316, Monel 400, Inconel 825, Inconel 600, and Inconel 625. Such catalysts may be provided as discrete supported or unsupported elements and/or as part of the reactor and/or the reactor walls.


Preferred, but non-limiting, catalysts include activated carbon, stainless steel (e.g., SS 316), austenitic nickel-based alloys (e.g., Inconel 625), nickel, fluorinated 10% CsCl/MgO, and 10% CsCl/MgF2. A suitable reaction temperature is about 300° C. to about 550° C. and a suitable reaction pressure may be between about 0 psig to about 150 psig. The reactor effluent may be fed to a caustic scrubber or to a distillation column to remove the byproduct of HCl to produce an acid-free organic product which, optionally, may undergo further purification using one or any combination of purification techniques that are known in the art.


The dehydrohalogenation reaction is carried out in the vapor phase. It may be carried out at a temperature range of from about 200° C. to about 800° C., from about 300° C. to about 600° C., or from about 400° C. to about 500° C. Suitable reactor pressures range from about 0 psig to about 200 psig, from about 10 psig to about 100 psig, or from about 20 to about 70 psig.


A method of increasing the yield and conversion of 1233×f to 1234yf and to make the process more efficient is to react the product of step (ii), which contains a mixture of 1233×f and 244bb, with SbF5 in accordance with the process of the present invention prior to the dehydrochlorination step. This increases the amount of 244bb present (decreasing the amount of 1233×f present) and the resulting product can then be subjected to step (iii) above. By conducting this additional hydrofluorination reaction, more 244bb is produced, and as a result, significantly more 1234yf is produced. The 244bb thus produced is then transferred to another reactor wherein it undergoes dehydrohalogenation, in accordance with step (iii).


Alternatively, as described above, instead of conducting step (ii) of the process, the 1233×f produced in step (i) is hydrofluorinated with HF in the presence of SbF5, in accordance with the present invention, as described herein. The 244bb product thus formed is then dehydrochlorinated to form 1234yf, in accordance with step (iii) described hereinabove.


The following non-limiting examples further illustrate the invention.


Examples
Example 1-1233×f Hydrofluorination by HF with SbF5 Catalyst at 30 C

13.8 g of HF and 5 g of SbF5 were loaded into a 210 mL shaker tube reactor. The reactor was then evacuated and chilled to −15° C. 30 g of 1233×f was added into the reactor. The reactor was then heated to 30° C. with agitation. Once the temperature reached 30° C., water was added to the reactor to quench the catalyst. The organic layer was vapor transferred into a stainless steel cylinder and analyzed by GC-MS. Table 1 below shows the results of the GC-MS analysis.













TABLE 1









mol ratio




mol %
1233xf/244bb









143a
 0.005%




245cb
 0.032%




245fa
 0.059%




Unknown
 0.001%




244bb
99.420%
0.48%



1233xf
 0.474%




243ab
 0.009%










Example 2-1233×f Hydrofluorination by HF with SbF5 Catalyst at 10 C

13.8 g of HF and 5 g of SbF5 were loaded into a 210 mL shaker tube reactor. The reactor was then evacuated and chilled to −15° C. 30 g of 1233×f was added into the reactor. The reactor was then heated to 10° C. with agitation. Once the temperature reached 10° C., water was added to the reactor to quench the catalyst. The organic layer was vapor transferred into a stainless steel cylinder and analyzed by GC-MS. Table 2 below shows the results of the GC-MS analysis.













TABLE 2









mol ratio



Compounds
mol %
1233xf/244bb









245cb
 0.017%




245fa
0.0200%




244bb
98.236%




1233xf
 0.794%
0.81%



1233xf dimer
 0.934%










Examdle 3-m233×fHydrofluorination by HF with SbF5 Catalyst at 30/4

10.0Og ofHBF and 5 g of SbFS were loaded into a 210 mL shaker tube reactor. The reactor was then evacuated and chilled to −40 C. 308 g of 1233×f was added into the reactor. The reactor was then heated to 30° C. with agitation and stirred for an hour. The reactor was chilled to −30° C. quickly and 75 mL of water was added to the reactor to quench the catalyst. The organic layer was vapor transferred into a stainless steel cylinder and analyzed by GC-MS. Table 3 below shows the results of the GC-MS analysis.













TABLE 3









mol ratio



Compound
mol %
1233xf/244bb









245cb
14.412%




245fa
 0.096%




244bb
84.147%




1233xf
 0.768%
0.91%



243ab
 0.576%










Comparative Example 1-1233×f-244bb Equilibrium by HF with Fluorination SbCl5 Catalyst at 80° C.

18.0 g of HF and 14.0 g of SbCl5 were loaded into a 210 mL shaker tube reactor and heated at 100° C. for 2 hours with agitation. The reactor was then evacuated and chilled to 0° C. to vent off HCl. 20 g of 244bb (99.7 mol %) was added into the reactor. The reactor was then heated to 80° C. for an hour and then quickly chilled to 30° C. Water was added to the reactor to quench the catalyst. The organic layer was vapor transferred into a stainless steel cylinder and analyzed by GC-MS. Table 4 below shows the results of the GC-MS analysis. The 1233×f/244bb ratio increased to 1.95 mol % from 0.3 mol %. This indicates the existence of equilibrium between 1233×f and 244bb which prevents the full conversion of 1233×f to 244bb.













TABLE 4









mol ratio




mol %
1233xf/244bb









245cb
 0.089%




244bb
92.907%




1233xf
 1.815%
1.95%



243ab
 4.905%




Others
 0.284%










Many aspects and embodiments have been described and are merely exemplary and not limiting. After reading the specification, skilled artisans appreciate that other aspects and embodiments are possible without departing from the scope of the invention.


Other features and benefits of any one or more of the embodiments will be apparent from the hereinabove detailed description and the claims.

Claims
  • 1. A composition comprising: a mixture comprising HF, SbF5, olefin, and a hydrofluoroalkane;wherein the olefin and the hydrofluoroalkane are selected from:a) the olefin is (Z)-1-chloro-3,3,3-trifluoropropene or (E)-1-chloro-3,3,3-trifluoropropene and the hydrofluoroalkane is 3-chloro-1,1,13-tetrafluoropropane;b) the olefin is 1-chloro-2,3,3,3-tetrafluoropropene and the hydrofluoroalkane is 1,1,1,2,2-pentafluoro-3-chloropropane and 1,1,1,2,3-pentafluoro-3-chloropropane;c) the olefin is 2,3,3,3-tetrafluoropropene and the hydrofluoroalkane is 1,1,1,2,2-pentafluoropropane; andd) the olefin is 1,3,3,3-tetrafluoropropene and the hydrofluoroalkane is 1,1,1,3,3-pentafluoropropane; andwherein the SbF5 is present in an amount in the range of about 2% to about 30%, by weight of the mixture.
  • 2. The composition of claim 1, wherein the SbF5 is present in an amount in the range of about 3% to about 15%, by weight of the mixture.
  • 3. The composition of claim 2, wherein the SbF5 is present in an amount in the range of about 10% to about 11%, by weight of the mixture.
  • 4. The composition of claim 3, wherein the composition is a liquid.
  • 5. The composition of claim 1, wherein the mole ratio of HF to the olefin is in the range of from 1 to 10.
  • 6. The composition of claim 5, wherein the mole ratio of HF to the olefin is in the range of from 1 to 5.
  • 7. The composition of claim 1, wherein the olefin is (Z)-1-chloro-33,3-trifluoropropene or (E)-1-chloro-3,3,3-trifluoropropene and the hydrofluoroalkane is 3-chloro-1,1,1,3-tetrafluoropropane.
  • 8. The composition of claim 1, wherein the olefin is 1-chloro-2,3,3,3-tetrafluoropropene and the hydrofluoroalkane is 1,1,1,2,2-pentafluoro-3-chloropropane and 1,1,1,2,3-pentafluoro-3-chloropropane.
  • 9. The composition of claim 1, wherein the olefin is 2,3,3,3-tetrafluoropropene and the hydrofluoroalkane is 1,1,1,2,2-pentafluoropropane.
  • 10. The composition of claim 1, wherein the olefin is 1,3,3,3-tetrafluoropropene and the hydrofluoroalkane is 1,1,1,3,3-pentafluoropropane.
  • 11. The composition of claim 7, wherein the olefin is (Z)-1-chloro-3,3,3-trifluoropropene.
  • 12. The composition of claim 7, wherein the olefin is (E)-1-chloro-3,3,3-trifluoropropene.
  • 13. The composition of claim 7, wherein the SbF5 is present in an amount in the range of about 3% to about 15%, by weight of the mixture.
  • 14. The composition of claim 13, wherein the SbF5 is present in an amount in the range of about 10% to about 11%, by weight of the mixture.
  • 15. The composition of claim 8, wherein the SbF5 is present in an amount in the range of about 3% to about 15%, by weight of the mixture.
  • 16. The composition of claim 15, wherein the SbF5 is present in an amount in the range of about 10% to about 11%, by weight of the mixture.
  • 17. The composition of claim 9, wherein the SbF5 is present in an amount in the range of about 3% to about 15%, by weight of the mixture.
  • 18. The composition of claim 17, wherein the SbF5 is present in an amount in the range of about 10% to about 11%, by weight of the mixture.
  • 19. The composition of claim 10, wherein the SbF5 is present in an amount in the range of about 3% to about 15%, by weight of the mixture.
  • 20. The composition of claim 19, wherein the SbF5 is present in an amount in the range of about 10% to about 11%, by weight of the mixture.
CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of co-pending U.S. application Ser. No. 17/656,340 filed Mar. 24, 2022, which is a divisional of co-pending U.S. application Ser. No. 17/220,427 filed Apr. 1, 2021, which is a divisional of U.S. application Ser. No. 16/423,352 filed May 28, 2019, now U.S. Pat. No. 11,008,267, which is a continuation of U.S. application Ser. No. 15/575,526 filed Nov. 20, 2017, now U.S. Pat. No. 10,301,236, which is a 371 National Stage Application of PCT/US2016/033450 filed May 20, 2016, which claims the benefit of and priority to U.S. Provisional Application No. 62/164,631 filed May 21, 2015, all of which are hereby incorporated by reference in their entirety.

US Referenced Citations (178)
Number Name Date Kind
5155082 Tung et al. Oct 1992 A
5446217 Van Der Puy Aug 1995 A
5689019 Aoyama et al. Nov 1997 A
7795480 Merkel et al. Sep 2010 B2
7803283 Pham et al. Sep 2010 B2
7829748 Tung Nov 2010 B1
8034251 Merkel et al. Oct 2011 B2
8058486 Merkel et al. Nov 2011 B2
8067649 Kopkalli et al. Nov 2011 B2
8070975 Pham et al. Dec 2011 B2
8071825 Johnson et al. Dec 2011 B2
8076521 Elsheikh et al. Dec 2011 B2
8114308 Merkel et al. Feb 2012 B2
8119845 Merkel et al. Feb 2012 B2
8168837 Merkel et al. May 2012 B2
8203022 Nappa Jun 2012 B2
8252964 Devic et al. Aug 2012 B2
8252965 Merkel et al. Aug 2012 B2
8314159 Chen et al. Nov 2012 B2
8344191 Nose et al. Jan 2013 B2
8367878 Merkel et al. Feb 2013 B2
8426658 Pham et al. Apr 2013 B2
8445735 Nappa May 2013 B2
8454853 Van Horn et al. Jun 2013 B2
8455704 Johnson et al. Jun 2013 B2
8481793 Merkel et al. Jul 2013 B2
8519201 Merkel et al. Aug 2013 B2
8546624 Pham et al. Oct 2013 B2
8563789 Elsheikh et al. Oct 2013 B2
8618338 Elsheikh et al. Dec 2013 B2
8618340 Kopkalli et al. Dec 2013 B2
8648123 Van Horn et al. Feb 2014 B2
8664455 Merkel et al. Mar 2014 B2
8680345 Merkel et al. Mar 2014 B2
8697922 Nappa Apr 2014 B2
8716538 Merkel et al. May 2014 B2
8741828 Hulse et al. Jun 2014 B2
8754271 Mukhopadhyay et al. Jun 2014 B2
8772364 Van Horn et al. Jul 2014 B2
8772554 Nose et al. Jul 2014 B2
8796493 Merkel et al. Aug 2014 B2
8835698 Johnson et al. Sep 2014 B2
8845921 Merkel et al. Sep 2014 B2
8846990 Wang et al. Sep 2014 B2
8859829 Kopkalli et al. Oct 2014 B2
20070197842 Mukhopadhyay et al. Aug 2007 A1
20080157022 Singh et al. Jul 2008 A1
20090030244 Merkel et al. Jan 2009 A1
20090030247 Johnson et al. Jan 2009 A1
20090149680 Wang Jun 2009 A1
20090182179 Merkel et al. Jul 2009 A1
20090211988 Pham et al. Aug 2009 A1
20090224207 Pham et al. Sep 2009 A1
20090227822 Pham et al. Sep 2009 A1
20090240090 Merkel et al. Sep 2009 A1
20090242832 Pham et al. Oct 2009 A1
20090256110 Merkel et al. Oct 2009 A1
20090287026 Kopkalli et al. Nov 2009 A1
20090287027 Merkel et al. Nov 2009 A1
20100036179 Merkel et al. Feb 2010 A1
20100048961 Merkel et al. Feb 2010 A1
20100056657 Chen et al. Mar 2010 A1
20100076100 Chen Mar 2010 A1
20100087557 Chen et al. Apr 2010 A1
20100105788 Chen et al. Apr 2010 A1
20100105789 Van Horn et al. Apr 2010 A1
20100105967 Nappa Apr 2010 A1
20100112328 Van Horn et al. May 2010 A1
20100113629 Van Horn et al. May 2010 A1
20100154419 Kontomaris Jun 2010 A1
20100185030 Elsheikh et al. Jul 2010 A1
20100187088 Merkel et al. Jul 2010 A1
20100331583 Johnson et al. Dec 2010 A1
20110001080 Van Horn et al. Jan 2011 A1
20110004035 Merkel et al. Jan 2011 A1
20110012052 Van Horn et al. Jan 2011 A1
20110031436 Mahler Feb 2011 A1
20110088418 Kontomaris et al. Apr 2011 A1
20110105807 Kopkalli et al. May 2011 A1
20110105809 Devic et al. May 2011 A1
20110178344 Nose et al. Jul 2011 A1
20110197602 Abbas et al. Aug 2011 A1
20110201851 Nose et al. Aug 2011 A1
20110207974 Kopkalli et al. Aug 2011 A9
20110207975 Merkel et al. Aug 2011 A9
20110210289 Merkel et al. Sep 2011 A9
20110219811 Kontomaris Sep 2011 A1
20110226004 Kontomaris Sep 2011 A1
20110240902 Merkel et al. Oct 2011 A1
20110245548 Merkel et al. Oct 2011 A1
20110270000 Bektesevic et al. Nov 2011 A1
20120037843 Pham et al. Feb 2012 A1
20120043492 Williams et al. Feb 2012 A1
20120053371 Johnson et al. Mar 2012 A1
20120059202 Elsheik et al. Mar 2012 A1
20120065437 Merkel et al. Mar 2012 A1
20120078020 Elsheik et al. Mar 2012 A1
20120101177 Van Horn et al. Apr 2012 A1
20120108688 Van Horn et al. May 2012 A1
20120136182 Merkel et al. May 2012 A1
20120178977 Merkel et al. Jul 2012 A1
20120187330 Singh et al. Jul 2012 A1
20120190901 Merkel et al. Jul 2012 A1
20120202904 Chen et al. Aug 2012 A1
20120215035 Nappa Aug 2012 A1
20120215036 Sun et al. Aug 2012 A1
20120215037 Sun et al. Aug 2012 A1
20120215038 Sun et al. Aug 2012 A1
20120215039 Hulse et al. Aug 2012 A1
20120216551 Minor et al. Aug 2012 A1
20120222448 Chaki et al. Sep 2012 A1
20120225961 Van Horn et al. Sep 2012 A1
20120232316 Nappa Sep 2012 A1
20120232317 Nappa Sep 2012 A1
20120240477 Nappa Sep 2012 A1
20120272668 Van Horn et al. Nov 2012 A1
20120292556 Van Horn Nov 2012 A1
20120296128 Merkel et al. Nov 2012 A1
20120304682 Kontomaris Dec 2012 A1
20120304686 Kontomaris Dec 2012 A1
20130035410 Chen et al. Feb 2013 A1
20130035526 Elsheik et al. Feb 2013 A1
20130041048 Chen et al. Feb 2013 A1
20130085308 Merkel et al. Apr 2013 A1
20130096218 Rached et al. Apr 2013 A1
20130099154 Boussand et al. Apr 2013 A1
20130105296 Chaki et al. May 2013 A1
20130119300 Van Horn et al. May 2013 A1
20130158305 Takahashi Jun 2013 A1
20130197282 Merkel et al. Aug 2013 A1
20130217928 Takahashi et al. Aug 2013 A1
20130246288 Van Horn et al. Sep 2013 A1
20130253235 Johnson et al. Sep 2013 A1
20130281557 Van Horn et al. Oct 2013 A1
20130338408 Merkel et al. Dec 2013 A1
20140005288 Chen et al. Jan 2014 A1
20140012047 Merkel et al. Jan 2014 A1
20140012048 Sun et al. Jan 2014 A9
20140012051 Pigamo et al. Jan 2014 A1
20140012052 Pham et al. Jan 2014 A1
20140018582 Sun et al. Jan 2014 A1
20140031442 Van Horn et al. Jan 2014 A1
20140039228 Pigamo et al. Feb 2014 A1
20140051776 Chen et al. Feb 2014 A1
20140070129 Kennoy et al. Mar 2014 A1
20140100393 Johnson et al. Apr 2014 A9
20140103248 Van Horn et al. Apr 2014 A1
20140121424 Nose et al. May 2014 A1
20140147343 Merkel et al. May 2014 A1
20140194656 Chaki et al. Jul 2014 A1
20140213677 Jimenez et al. Jul 2014 A1
20140213678 Van Horn et al. Jul 2014 A1
20140235903 Wang et al. Aug 2014 A1
20140235904 Bektesevic et al. Aug 2014 A1
20140249336 Komatsu et al. Sep 2014 A1
20140256995 Wang et al. Sep 2014 A1
20140256996 Wang et al. Sep 2014 A1
20140275646 Wang et al. Sep 2014 A1
20140275648 Chiu Sep 2014 A1
20140275649 Wang et al. Sep 2014 A1
20140275650 Kopkalli et al. Sep 2014 A1
20140275651 Wang et al. Sep 2014 A1
20140275652 Wang et al. Sep 2014 A1
20140275653 Pigamo et al. Sep 2014 A1
20140275655 Wang et al. Sep 2014 A1
20140296360 Chen et al. Oct 2014 A1
20140296585 Deur-Bert et al. Oct 2014 A1
20140303409 Wang et al. Oct 2014 A1
20140303412 Karube et al. Oct 2014 A1
20140303413 Merkel et al. Oct 2014 A1
20140309462 Nappa et al. Oct 2014 A1
20140309463 Bektesvic et al. Oct 2014 A1
20150241095 Nappa Aug 2015 A1
20150247674 Nappa Sep 2015 A1
20150247675 Nappa Sep 2015 A1
20150251033 Nappa Sep 2015 A1
20180208528 Giddis et al. Jul 2018 A1
20180214727 Nappa Aug 2018 A1
Foreign Referenced Citations (154)
Number Date Country
2010341533 Jun 2012 AU
112012015260 Apr 2017 BR
2782592 Jul 2011 CA
3016991 Jul 2011 CA
3017000 Jul 2011 CA
102686694 Sep 2012 CN
104140354 Nov 2014 CN
104140355 Nov 2014 CN
105062427 Nov 2015 CN
2 096 096 Sep 2009 EP
2 098 499 Sep 2009 EP
2 103 587 Sep 2009 EP
2 107 048 Oct 2009 EP
2 108 638 Oct 2009 EP
2 119 692 Nov 2009 EP
2 151 425 Feb 2010 EP
2 157 073 Feb 2010 EP
2 258 789 Dec 2010 EP
2 287 271 Feb 2011 EP
2 412 753 Feb 2012 EP
2 516 577 Oct 2012 EP
2 583 959 Apr 2013 EP
2 615 079 Jul 2013 EP
2 634 165 Sep 2013 EP
2 634 166 Sep 2013 EP
2 634 231 Sep 2013 EP
2 634 232 Sep 2013 EP
2 690 129 Jan 2014 EP
2 756 883 Jul 2014 EP
2 845 891 Mar 2015 EP
H0824362 Jan 1996 JP
H08193039 Jul 1996 JP
H10251172 Sep 1998 JP
2009167187 Jul 2009 JP
2010043080 Feb 2010 JP
2010215622 Sep 2010 JP
2013515158 May 2013 JP
2018031013 Mar 2018 JP
2018141159 Sep 2019 JP
20120123355 Nov 2012 KR
20180011354 Jan 2018 KR
351915 Nov 2017 MX
356473 May 2018 MX
159904 Feb 2017 MY
2012131170 Jan 2014 RU
181873 Jan 2014 SG
10201509239X Dec 2015 SG
2006069362 Jun 2006 WO
2008121776 Oct 2008 WO
2008121778 Oct 2008 WO
2008121779 Oct 2008 WO
2008121783 Oct 2008 WO
2008121785 Oct 2008 WO
2008121787 Oct 2008 WO
2008121790 Oct 2008 WO
2009003084 Dec 2008 WO
2009015317 Jan 2009 WO
2009018561 Feb 2009 WO
2009114397 Sep 2009 WO
2009137658 Nov 2009 WO
2009140563 Nov 2009 WO
2009148191 Dec 2009 WO
2009151669 Dec 2009 WO
2010001025 Jan 2010 WO
2010013795 Feb 2010 WO
2010013796 Feb 2010 WO
2010062527 Jun 2010 WO
2010062888 Jun 2010 WO
2010080467 Jul 2010 WO
2011031598 Mar 2011 WO
2011038081 Mar 2011 WO
2011050017 Apr 2011 WO
2011056441 May 2011 WO
2011056824 May 2011 WO
2011059078 May 2011 WO
2011082003 Jul 2011 WO
2011087825 Jul 2011 WO
2011091404 Jul 2011 WO
2011126620 Oct 2011 WO
2011126634 Oct 2011 WO
2011126679 Oct 2011 WO
2011130108 Oct 2011 WO
2011137033 Nov 2011 WO
2011139646 Nov 2011 WO
2012006206 Jan 2012 WO
2012009114 Jan 2012 WO
2012011609 Jan 2012 WO
2012024252 Feb 2012 WO
2012033088 Mar 2012 WO
2012057367 May 2012 WO
2012067980 May 2012 WO
2012087667 Jun 2012 WO
201209447 Jul 2012 WO
2012098421 Jul 2012 WO
2012098422 Jul 2012 WO
2012115930 Aug 2012 WO
2012115934 Aug 2012 WO
2012115938 Aug 2012 WO
2012115957 Aug 2012 WO
2012121876 Sep 2012 WO
2012141822 Oct 2012 WO
2012158870 Nov 2012 WO
2012173273 Dec 2012 WO
2013007906 Jan 2013 WO
2013015068 Jan 2013 WO
2013037286 Mar 2013 WO
20130139260 Mar 2013 WO
2013045791 Apr 2013 WO
2013049105 Apr 2013 WO
2013049742 Apr 2013 WO
2013049743 Apr 2013 WO
2013049744 Apr 2013 WO
2013053555 Apr 2013 WO
2013055722 Apr 2013 WO
2013055726 Apr 2013 WO
2013055894 Apr 2013 WO
2013065617 May 2013 WO
2013067350 May 2013 WO
2013067356 May 2013 WO
2013071024 May 2013 WO
2013074324 May 2013 WO
2013088195 Jun 2013 WO
2013093272 Jun 2013 WO
2013106305 Jul 2013 WO
2013111911 Aug 2013 WO
2013114015 Aug 2013 WO
2013116416 Aug 2013 WO
2013119919 Aug 2013 WO
2013130385 Sep 2013 WO
2013138123 Sep 2013 WO
2013174844 Nov 2013 WO
2013182816 Dec 2013 WO
2013182818 Dec 2013 WO
2013184865 Dec 2013 WO
2014010750 Jan 2014 WO
2014015315 Jan 2014 WO
2014022610 Feb 2014 WO
2014025065 Feb 2014 WO
2014028574 Feb 2014 WO
2014047230 Mar 2014 WO
2014102479 Jul 2014 WO
2014147310 Sep 2014 WO
2014147311 Sep 2014 WO
2014147312 Sep 2014 WO
2014147313 Sep 2014 WO
2014147314 Sep 2014 WO
2014150889 Sep 2014 WO
2014151270 Sep 2014 WO
2014151441 Sep 2014 WO
2014151448 Sep 2014 WO
2014152325 Sep 2014 WO
2014159809 Oct 2014 WO
2014159818 Oct 2014 WO
2014164611 Oct 2014 WO
Non-Patent Literature Citations (5)
Entry
Cn104140354a, machine translation, pp. 1-5, Dec. 12, 2014 (Year: 2014).
English Translation of JP Office Action, JP Application No. 2017-560782, dated Mar. 9, 2020.
European Examination Report for EP Application No. 16797362.7, dated May 27, 2020, 3 pages.
International Search Report dated Aug. 22, 2016 issued in PCT/US2016/033450.
Teinz et al., “Catalytic formulation of 2,3,3,3-tetrafluoropropene from 2-chloro-3,3,3-trifluoropropene at fluorinated chromia: A study of reaction pathways”, Applied Catalysis B: Environmental, vol. 165, pp. 200-208 (2015).
Related Publications (1)
Number Date Country
20230075222 A1 Mar 2023 US
Provisional Applications (1)
Number Date Country
62164631 May 2015 US
Divisions (2)
Number Date Country
Parent 17220427 Apr 2021 US
Child 17656340 US
Parent 16423352 May 2019 US
Child 17220427 US
Continuations (2)
Number Date Country
Parent 17656340 Mar 2022 US
Child 18052391 US
Parent 15575526 US
Child 16423352 US