Compositions comprising 2,3,3,3-tetrafluoropropene, 1,1,2,3-tetrachloropropene, 2-chloro-3,3,3-trifluoropropene, or 2-chloro-1,1,1,2-tetrafluoropropane

Abstract

The present invention relates to a composition comprising 2,3,3,3-tetrafluoropropene that may be useful as a heat transfer composition, an aerosol propellant, a foaming agent, a blowing agent, a solvent, a cleaning agent, a carrier fluid, a displacement drying agent, a buffing abrasion agent, a polymerization medium, an expansion agent for polyolefins and polyurethanes, a gas dielectric, an extinguishing agent, and a fire suppression agent in liquid or gaseous form. Additionally, the present invention relates to a composition comprising 1,1,2,3-tetrachloropropene, 2-chloro-3,3,3-trifluoropropene, or 2-chloro-1,1,1,2-tetrafluoropropane that may be useful in a process for producing 2,3,3,3-tetrafluoropropene.

Description

Technology Field

[0001] The present invention relates to the field of compositions that may be useful as heat transfer compositions, aerosol propellants, foaming agents (blowing agents), solvents, cleaning agents, carrier fluids, displacement drying agents, buffing abrasion agents, polymerization media, foaming agents for polyolefins and polyurethanes, gas dielectrics, extinguishing agents, and fire suppression agents in liquid or gaseous form. In particular, the present invention relates to compositions that may be useful as heat transfer compositions, for example, compositions comprising 2,3,3,3-tetrafluoropropene (HFO-1234yf, or 1234yf), or 1,1,1,2,3-pentafluoropropane (HFC-245eb, or 245eb) which is useful in the HFO-1234yf production process. Background Technology

[0002] New environmental regulations have necessitated new compositions for use in refrigeration, air conditioning, and heat pump systems. Compounds with a low global warming potential are of particular interest. Prior art literature

[0003] International Patent Publication WO2008 / 054782 International Patent Publication WO2008 / 054781 US Patent Application Publication No. 2007 / 0197842 A1 US Patent Application Publication No. 2009 / 0240090 US Patent Application Publication No. 2005 / 0228202 US Patent No. 5,036,036

[0004] (Non-patent Literature 1) Literature [VC Papadimitriou, et al. in Physical Chemistry Chemical Physics, 2007, volume 9, pages 1-13] (Non-patent Literature 2) Literature [Heterogeneous Catalysis in Industrial Practice, 2nd edition (McGraw-Hill, New York, 1991)] The problem to be solved

[0005] The inventors discovered that a certain additional compound is present in small amounts during the production of the above-mentioned new compound with a low global warming potential, for example, HFO-1234yf. means of solving the problem

[0006] Therefore, according to the present invention, a composition is provided comprising HFO-1234yf and at least one additional compound selected from the group consisting of HCO-1250xf, HCC-260da, HCC-240aa, HCO-1230xa, HCFO-1233xf, HCFO-1233zd, HCFC-244bb, HCFC-244db, HFO-1234ze, HFC-245cb, HFO-1243zf, HCFO-1223za, HCFO-1224zb, HFO-1225zc, HCFC-241db, HCFC-242dc, HCFO-1232xf, HCFO-1231xf, and HCFO-1233yf. The composition may contain at least one additional compound in an amount of less than about 1 weight percent based on the total weight of the composition.

[0007] In addition, according to the present invention, a composition is provided comprising at least one additional compound selected from the group consisting of HCO-1230xa and propylene, HCO-1260zf, HCC-260da, HCC-260db, HCO-1250xf, HCC-250aa and HCC-240aa.

[0008] In addition, according to the present invention, a composition is provided comprising at least one additional compound selected from the group consisting of HCFO-1233xf and propylene, HCO-1260zf, HCC-260da, HCC-260db, HCO-1250xf, HCC-250aa, HCC-240aa, HCO-1230xa, HFO-1243zf, HCFO-1223za, HCFO-1224zb, HFO-1225zc, HCFO-1233yf, HCFO-1232xf, HCFC-1231xf, HCFC-241db, and HCFC-242dc.

[0009] In addition, according to the present invention, a composition is provided comprising at least one additional compound selected from the group consisting of HCFC-244bb and propylene, HCO-1250xf, HCC-260da, HCC-260db, HCC-240aa, HCO-1230xa, HCFO-1233xf, HFO-1243zf, HCFO-1223az, HCFO-1224zb, HFO-1225zc, HCFC-241db, HCFC-242dc, HCFO-1232xf, HCFO-1231xf, and HCFC-1233yf. Effects of the invention

[0010] The compositions disclosed herein, including HFO-1234yf, are useful as heat transfer compositions with a low Global Warming Potential (GWP), aerosol propellants, foaming agents, blowing agents, solvents, cleaning agents, carrier fluids, displacement desiccants, buffing abrasives, polymerization media, expansion agents for polyolefins and polyurethanes, gas dielectrics, fire extinguishers, and fire suppressants in liquid or gaseous form. The disclosed compositions can serve as working fluids used to transport heat from a heat source to a heat sink. Such heat transfer compositions may also be useful as refrigerants in cycles where the fluid undergoes a phase change, i.e., from liquid to gas and back to the original state, or vice versa. Brief explanation of the drawing

[0011] FIG. 1 illustrates a reaction sequence useful for forming the composition of the present invention. Specific details for implementing the invention

[0012] composition

[0013] HFO-1234yf (2,3,3,3-tetrafluoropropene) has been proposed for use, particularly as a refrigerant, heat transfer fluid, aerosol propellant, and foam expansion agent. Additionally, advantageously, HFO-1234yf has been found to have a low Global Warming Potential (GWP), as reported in the literature [VC Papadimitriou, et al. in Physical Chemistry Chemical Physics, 2007, volume 9, pages 1-13]. Therefore, HFO-1234yf is an excellent candidate to replace saturated HFC refrigerants with higher GWPs.

[0014] In one embodiment, the present invention provides a composition comprising HFO-1234yf and at least one additional compound selected from the group consisting of HCO-1250xf, HCC-260da, HCC-260db, HCC-240aa, HCO-1230xa, HCFO-1233xf, HCFO-1233zd, HCFC-244bb, HCFC-244db, HFO-1234ze, HFC-245cb, HFO-1243zf, HCFO-1223za, HCFO-1224zb, HFO-1225zc, HCFC-241db, HCFC-242dc, HCFO-1232xf, HCFO-1231xf, and HCFO-1233yf.

[0015] The composition of the present invention may include HFO-1234yf and one additional compound, or two additional compounds, or three or more additional compounds.

[0016] In another embodiment, the composition of the present invention comprises HFO-1234yf and HCFO-1232xf.

[0017] In another embodiment, the composition of the present invention comprises HFO-1234yf and at least one compound selected from HCFC-243db, HCFO-1233xf, HCFO-1231xf, HCFC-242dc and HCFC-241db.

[0018] In another embodiment, the composition of the present invention comprises at least one compound selected from the group consisting of HCFC-243db and HFC-245fa.

[0019] In one embodiment, the total amount of additional compound(s) in the composition containing HFO-1234yf is in the range of greater than 0 weight% to less than 1 weight% based on the species weight of the composition. In another embodiment, the total amount of additional compound(s) is in the range of greater than 0 weight% to less than 0.5 weight% based on the species weight of the composition.

[0020] In one embodiment, a composition comprising HFO-1234yf and other compounds may further comprise a specific tracer compound, e.g., HFC-245cb. In this embodiment, the HFC-245cb tracer may be present in the composition at a concentration of about 1 ppm (part per million) to about 1000 ppm. In another embodiment, the HFC-245cb tracer may be present at a concentration of about 1 ppm to about 500 ppm. Alternatively, the HFC-245cb tracer may be present at a concentration of about 10 ppm to about 300 ppm.

[0021] The compositions disclosed herein, including HFO-1234yf, are useful as heat transfer compositions with a low Global Warming Potential (GWP), aerosol propellants, foaming agents, blowing agents, solvents, cleaning agents, carrier fluids, displacement desiccants, buffing abrasives, polymerization media, expansion agents for polyolefins and polyurethanes, gas dielectrics, fire extinguishers, and fire suppressants in liquid or gaseous form. The disclosed compositions can serve as working fluids used to transport heat from a heat source to a heat sink. Such heat transfer compositions may also be useful as refrigerants in cycles where the fluid undergoes a phase change, i.e., from liquid to gas and back to the original state, or vice versa.

[0022] Examples of heat transfer systems include, but are not limited to, air conditioners, chillers, refrigerators, heat pumps, water chillers, flooded evaporator chillers, direct expansion chillers, walk-in coolers, heat pumps, portable refrigerators, portable air conditioning units, and combinations thereof.

[0023] As used herein, a mobile refrigeration unit, mobile air conditioning unit, or mobile heating unit refers to any refrigeration, air conditioning, or heating unit included in a transport unit for road, rail, sea, or air transport. Additionally, a mobile refrigeration or air conditioning unit includes a unit that is independent of any transport carrier and is known as an "intermodal" system. Such an intermodal system includes a "swap body" (for road / rail transport) together with a "container" (for sea / land transport).

[0024] As used herein, a stationary heat transfer system is a system connected to or attached thereto within any various building. Such stationary applications may be stationary air conditioning and heat pumps (including, but not limited to, chillers, high-temperature heat pumps, residential, commercial, or industrial air conditioning systems, and including external but connected to a building such as windows, ductless, ducted, packaged terminals, chillers, and rooftop systems). In stationary refrigeration applications, the disclosed composition may be useful for high, medium, and / or low-temperature refrigeration installations, including commercial, industrial, or residential refrigerators and freezers, ice makers, self-contained coolers and freezers, flooded evaporative chillers, direct expansion chillers, walk-in and reach-in coolers and freezers, and combination systems. In some embodiments, the disclosed composition may be used in supermarket refrigerator and / or freezer systems.

[0025] The compounds constituting the disclosed composition are defined in Table 1.

[0026] [Table 1]

[0027]

[0028] HCFO-1233xf, HCFC-244bb, and many other compounds listed in Table 1 are available from specialty chemical manufacturers, including SynQuest Laboratories, Inc. (Alachua, Florida, USA) or can be produced by methods known in the art. For example, HCFO-1233xf and HCFC-244bb can be produced by the non-catalytic chlorination of HFO-1243zf as described in International Patent Publication WO2008 / 054782, published on May 8, 2008. Additionally, HCFO-1233xf and HCFC-244bb can be produced by the catalytic fluorination of HCFC-243db as described in International Patent Publication WO2008 / 054781, published on May 8, 2008. The additional compounds present in each of the disclosed compositions will depend on the method of preparation.

[0029] Alternatively, HCO-1230xa can be produced from 1,2,3-trichloropropane as described in U.S. Patent Application Publication No. 2007 / 0197842 A1. Additionally, U.S. Patent Application Publication No. 2007 / 0197842 discloses reacting HCO-1230xa with HF in the vapor phase in the presence of a catalyst to form HCFO-1233xf. Alternatively, HCFO-1233xf can also be produced by fluorination of 1,1,2,3-tetrachloropropene (HCO-1230xa) as described in U.S. Patent Application Publication No. 2009 / 0240090, where further fluorination forms HCFC-244bb and subsequent dehydrochlorination forms HFO-1234yf.

[0030] The specified compounds listed in Table 1, in particular HFO-1234ze, HCFO-1233zd, and HCFO-1224zb, may exist as more than one isomer. For example, HFO-1234ze may exist as an E-isomer or a Z-isomer. As used herein, HFO-1234ze is intended to mean any one of the E-isomer, the Z-isomer, or any mixture of these isomers. As used herein, HCFO-1233zd is intended to mean any one of the E-isomer, the Z-isomer, or any mixture of these isomers. As used herein, HFO-1224zb is intended to mean any one of the E-isomer, the Z-isomer, or any mixture of these isomers.

[0031] In addition, according to the present invention, a composition is provided comprising at least one additional compound selected from the group consisting of HCO-1230xa and propylene, HCO-1260zf, HCC-260da, HCC-260db, HCO-1250xf, HCC-250aa and HCC-240aa.

[0032] In another embodiment, the composition of the present invention comprises HCO-1230xa and HCC-240aa. And in another embodiment, the composition of the present invention may comprise at least one compound selected from the group consisting of HCO-1230xa, HCC-240aa, and HCC-250aa and HCC-260da.

[0033] In addition, according to the present invention, a composition is provided comprising at least one additional compound selected from the group consisting of HCFO-1233xf and propylene, HCO-1260zf, HCC-260da, HCC-260db, HCO-1250xf, HCC-250aa, HCC-240aa, HCO-1230xa, HFO-1243zf, HCFO-1223za, HCFO-1224zb, HFO-1225zc, HCFO-1233yf, HCFO-1232xf, HCFC-1231xf, HCFC-241db, and HCFC-242dc.

[0034] In another embodiment, the composition of the present invention comprises HCO-1230xa and HCFO-1232xf. And in another embodiment, the composition of the present invention comprises HCO-1230xa, HCFO-1232xf and HCFO-1231xf.

[0035] In addition, according to the present invention, a composition is provided comprising at least one additional compound selected from the group consisting of HCFC-244bb and propylene, HCO-1250xf, HCC-260da, HCC-260db, HCC-240aa, HCO-1230xa, HCFO-1233xf, HFO-1243zf, HCFO-1223az, HCFO-1224zb, HFO-1225zc, HCFC-241db, HCFC-242dc, HCFO-1232xf, HCFO-1231xf, and HCFC-1233yf.

[0036] In another embodiment, the composition of the present invention comprising HCFC-244bb may further comprise at least one compound selected from the group consisting of HCFC-243db and HFC-245fa.

[0037] A series of reactions capable of forming the composition of the present invention is shown in FIG. 1. The sequence of steps begins with the chlorination of propylene by reaction with chlorine, Cl2, to form allyl chloride or HCO-1260zf (CH2=CHCH2Cl). The next step involves further chlorination in the presence of Cl2 to produce HCC-260db (CH2ClCHClCH2Cl). The reaction of HCC-260db with aqueous NaOH (or other caustic solution) forms HCO-1250xf (CH2=CClCH2Cl). Then, the reaction of HCO-1250xf with chlorine, Cl2, produces HCC-250aa (CH2ClCCl2CH2Cl or 1,2,2,3-tetrachloropropane). Further chlorination with Cl2 will produce HCC-240da (CHCl2CCl2CH2Cl). The reaction of HCC-240da with aqueous NaOH (or other caustic solution) will form HCO-1230xa (CCl2=CClCH2Cl).

[0038] In other embodiments, any of the above-described compositions may additionally contain HF due to the presence of hydrogen fluoride (HF) as either a reactant or a byproduct of the reaction chemistry for producing each composition.

[0039] Compositions free of HCl, compositions free of HF, and compositions free of both HCl and HF are noteworthy. Compositions free of acid are particularly noteworthy. Acid can be removed by processes known in the art, such as distillation and water washing or caustic washing.

[0040] Fluoridation of HCO-1230xa

[0041] HCO-1230xa can be fluorinated by reaction with hydrogen fluoride (HF) in the presence of a catalyst to produce HCFO-1233xf. This reaction is shown in Fig. 1.

[0042] "Fluorochlorination reactions can be carried out in a liquid phase or a vapor phase. In the case of the liquid phase embodiment of the present invention, the reaction of HCO-1230xa and HF can be carried out in a liquid phase reactor operating in a batch, semi-batch, semi-continuous, or continuous manner. In the batch method, HCO-1230xa and HF are mixed in an autoclave or other suitable reaction vessel and heated to a desired temperature.

[0043] In one embodiment, the reaction is carried out in a semi-batch manner by supplying HCO-1230xa to a liquid-phase reactor containing HF. In another embodiment, HF may be supplied to a liquid-phase reactor containing a mixture of HCO-1230xa and the reaction product formed by the reaction of HF and HCO-1230xa. In another embodiment of the liquid-phase process, HF and HCO-1230xa may be supplied simultaneously in a desired stoichiometric ratio to a reactor containing a mixture of HF and the reaction product formed by the reaction of HF and HCO-1230xa.

[0044] The temperature suitable for the reaction of HF and HCO-1230xa in a liquid-phase reactor is about 80°C to about 180°C in one embodiment and about 100°C to about 150°C in another embodiment. The higher the temperature, the more HCO-1230xa is typically converted.

[0045] The suitable molar ratio of the total amount of HF to HCO-1230xa supplied to the liquid-phase reactor is greater than the stoichiometric ratio (about 3:1, HF to HCO-1230xa) in one embodiment and is about 5:1 to about 100:1 in another embodiment. An embodiment in which the molar ratio of HF to HFO-1243zf is about 8:1 to about 50:1 is noted.

[0046] In liquid-phase processes, reactor pressure is not critical, and in batch reactions, it is typically the system's natural pressure at the reaction temperature. The system pressure increases as hydrogen chloride is formed by the replacement of hydrogen substituents in the starting materials and intermediate reaction products with chlorine, and by the replacement of chlorine substituents with fluorine. In continuous processes, it is possible to set the reactor pressure by passing reaction products with lower boiling points through an optionally packed column or condenser to exhaust them from the reactor. In this manner, intermediates with higher boiling points remain in the reactor, and volatile products are removed. Typical reactor pressures range from about 239 kPa (20 psig) to about 6,994 kPa (1,000 psig).

[0047] In some embodiments where the reaction is carried out using a liquid-phase process, catalysts that may be used include carbon, AlF3, BF3, and FeCl 3-a F a (where a is 0 to 3), FeX3, SbCl supported on carbon 3-a F a , AsF3, MCl 5-b F b (where b is 0 to 5 and M is Sb, Nb, Ta, or Mo), and M'Cl 4-c F c (Here, c is 0 to 4, and M' is Sn, Ti, Zr, or Hf) is included. In another embodiment, the catalyst for the liquid phase process is MCl 5-b F b (Here, b is 0 to 5, and M is Sb, Nb, or Ta).

[0048] In another embodiment, the reaction between HF and HCO-1230xa is carried out in the vapor phase. Typically, a heated reactor is used. Multiple reactor arrangements are possible, including the horizontal or vertical orientation of the reactor as well as the reaction sequence of HCO-1230xa and HF. In one embodiment of the present invention, HCO-1230xa may be initially vaporized and supplied to the reactor as a gas.

[0049] The temperature suitable for the vapor phase reaction is about 120°C to about 500°C. The higher the temperature, the more HCO-1230xa is converted, and the higher the degree of fluorination and halogenation in the converted compound.

[0050] A reactor pressure suitable for a vapor phase reactor may be about 101.3 to about 3039.8 kPa (1 to about 30 atmospheres). A pressure of about 1519.9 to about 2533.1 kPa (about 15 to about 25 atmospheres) may be advantageously used to facilitate the separation of HCl from other reaction products, and a suitable reaction time may vary from about 1 to about 120 seconds, preferably about 5 to about 60 seconds.

[0051] The molar ratio of the total amount of HF to HCO-1230xa for the vapor phase reaction is approximately stoichiometric ratio (3:1, HF to HCO-1230xa) to about 50:1 in one embodiment, and about 10:1 to about 30:1 in another embodiment.

[0052] In one embodiment, a catalyst is used in the reaction zone for a vapor phase reaction of HF (3:1 HF to HCO-1230xa). Chlorofluorination catalysts that can be used for a vapor phase reaction include carbon; graphite; alumina; fluoridated alumina; aluminum fluoride; alumina supported on carbon; aluminum fluoride supported on carbon; fluoridated alumina supported on carbon; magnesium fluoride supported on aluminum fluoride; metals (including elemental metals, metal oxides, metal halides, and / or other metal salts); metals supported on aluminum fluoride; metals supported on fluoridated alumina; metals supported on alumina; and metals supported on carbon; and mixtures of metals.

[0053] Metals suitable for use as catalysts (optionally supported on alumina, aluminum fluoride, fluorinated 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 of atomic number 58 to 71 (i.e., lanthanide metals). In one embodiment, when used on a support, the total metal content of the catalyst is about 0.1 to about 20 weight% based on the total weight of the catalyst; in another embodiment, it will be about 0.1 to about 10 weight% based on the total weight of the catalyst.

[0054] Chlorofluorination catalysts suitable for vapor-phase reactions include chromium oxide (III) (Cr2O3); Cr2O3 supported on Cr2O3 with other metals such as magnesium halide or zinc halide; chromium halide (III) supported on carbon; a mixture of chromium and magnesium (including elemental metals, metal oxides, metal halides, and / or other metal salts) optionally supported on graphite; and chromium-containing catalysts including a mixture of chromium and other metals (including elemental metals, metal oxides, metal halides, and / or other metal salts) optionally supported on graphite halide, alumina halide, or aluminum halide, e.g., aluminum fluoride.

[0055] Chromium-containing catalysts are well known in the art. These were described by Satterfield in the literature [Heterogeneous Catalysis in Industrial Practice, 2 nd It can be manufactured by either the precipitation method or the impregnation method as generally described on pages 87 to 112 of the edition (McGraw-Hill, New York, 1991).

[0056] A chlorofluorination catalyst comprising at least one chromium-containing component selected from the group consisting of crystalline alpha-chromium oxide in which about 0.05 atomic percent to about 6 atomic percent of chromium atoms in the alpha-chromium oxide lattice are replaced by trivalent cobalt atoms, and crystalline alpha-chromium oxide treated with a fluorinating agent in which about 0.05 atomic percent to about 6 atomic percent of chromium atoms in the alpha-chromium oxide lattice are replaced by trivalent cobalt atoms. These catalysts, including their preparation, are disclosed in U.S. Patent Application Publication No. 2005 / 0228202.

[0057] In another embodiment, the vapor phase catalyst for the reaction of HCO-1230xa and HF may be a catalyst composition comprising Cr2O3 produced by the thermal decomposition of (NH4)2Cr2O7 as described in U.S. Patent No. 5,036,036.

[0058] Optionally, the metal-containing catalyst described above may be pretreated with HF. Such pretreatment can be achieved, for example, by placing the metal-containing catalyst in a suitable vessel and then passing HF over the metal-containing catalyst. In one embodiment, such a vessel may be a reactor used to carry out a chlorofluorination reaction. In one embodiment, the pretreatment time is about 15 to about 300 minutes, and the pretreatment temperature is about 200°C to about 450°C.

[0059] Fluoridation of HCFO-1233xf

[0060] In some embodiments, HCFO-1233xf may be used to produce HCFC-HCFC-244bb and / or HFO-1234yf. Such a reaction is shown in FIG. 1.

[0061] In one embodiment, the reaction of HCFO-1233xf to HCFC-244bb can be carried out in the liquid phase. In another embodiment, the reaction can be carried out in the vapor phase.

[0062] In one embodiment, the reaction of HCFO-1233xf to HCFC-244bb can be carried out in a batch manner. In another embodiment, the reaction can be carried out in a continuous manner.

[0063] In one embodiment, the liquid-phase reaction of HCFO-1233xf to HCFC-244bb may be carried out in the presence of a catalyst. In one embodiment, the catalyst may be a Lewis acid catalyst. In one embodiment, the catalyst may be a metal halide catalyst. In another embodiment, the catalyst may be at least one catalyst selected from the group consisting of antimony halides, tin halides, thallium halides, iron halides, and combinations of two or more of these. In another embodiment, the catalyst may be at least one catalyst selected from antimony chloride (SbCl5), antimony trichloride (SbCl3), antimony pentafluoride (SbF5), tin tetrachloride (SnCl4), titanium tetrachloride (TiCl4), iron trichloride (FeCl3), and combinations thereof. In some embodiments, the reaction may be carried out using any known fluorination catalyst for the liquid-phase reaction.

[0064] In one embodiment, the reaction of HCFO-1233xf to HCFC-244bb can be carried out in the absence of a catalyst.

[0065] In one embodiment, the vapor-phase reaction of HCFO-1233xf to HCFC-244bb may be carried out in the presence of a catalyst. In one embodiment, the reaction is carried out in the presence of a chromium-based catalyst, an iron-based catalyst, or a combination thereof. In one embodiment, the chromium-based catalyst is chromium oxide (e.g., Cr2O3). In one embodiment, the iron-based catalyst may be FeCl3 on carbon.

[0066] In one embodiment, the vapor phase reaction of HCFO-1233xf to HCFC-244bb is carried out in the absence of a catalyst.

[0067] Dehydrochlorination of HCFC-244bb

[0068] In some embodiments, the dehydrochlorination of HCFC-244bb is used to produce HFO-1234yf.

[0069] In one embodiment, the dehydrochlorination of HCFC-244bb to HFO-1234yf is carried out in the vapor phase.

[0070] In one embodiment, vapor-phase dehydrochlorination is carried out in the presence of a catalyst. In one embodiment, the catalyst is selected from carbon and / or metal-based catalysts. In one embodiment, the catalyst may be selected from activated carbon, nickel-based catalysts, palladium-based catalysts, or any combination of these catalysts. In one embodiment, the catalyst may be selected from the group consisting of Ni-mesh, palladium on carbon, palladium on aluminum oxide, or combinations thereof.

[0071] In one embodiment, catalytic vapor-phase dehydrochlorination is carried out at a temperature of about 200 to 600°C. In another embodiment, catalytic vapor-phase dehydrochlorination is carried out at a temperature of about 250 to 500°C. The reaction pressure is about 0 to 1034.2 kPa (0 to 150 psi).

[0072] In another embodiment, HFO-1234yf is produced by the thermal dehydrochlorination of HCFC-244bb. In one embodiment, this reaction takes place in the absence of a catalyst. In one embodiment, HCFC-244bb is introduced into a reaction vessel where the temperature is maintained at a temperature sufficiently high to cause the thermal dehydrochlorination of HCFC-244bb. In one embodiment, the temperature is sufficiently high to cause the thermal dehydrochlorination of HCFC-244bb to a conversion rate of 50% or more. In another embodiment, the temperature is sufficiently high to cause the thermal dehydrochlorination of HCFC-244bb to a conversion rate of 65% or more. In yet another embodiment, the temperature is sufficiently high to cause the thermal dehydrochlorination of HCFC-244bb to a conversion rate of 80% or more. In another embodiment, the temperature is high enough to cause thermal dehydrochlorination of HCFC-244bb to a conversion rate of 70% or more during continuous operation for more than 12 hours.

[0073] In one embodiment, HCFC-244bb is introduced into a reaction vessel in which the temperature is maintained at a range of about 500°C to about 700°C. In another embodiment, the temperature of the reaction vessel is maintained at a range of about 500°C to about 650°C. In yet another embodiment, the temperature of the reaction vessel is maintained at a temperature high enough to cause thermal decomposition of HCFC-244bb into HFO-1234yf with a selectivity of 80% or more. In yet another embodiment, the temperature of the reaction vessel is maintained at a temperature high enough to cause thermal decomposition of HCFC-244bb into HFO-1234yf with a selectivity of 85% or more.

[0074] In one embodiment, for either a catalytic or non-catalytic dehydrochlorination reaction, the reaction zone is a reaction vessel composed of a corrosion-resistant material. In one embodiment, such material comprises an alloy, for example, a nickel-based alloy such as Hastelloy (Trademark), a nickel-chromium alloy available for purchase from Special Metals Corp. under the trade name Inconel (Trademark) (hereinafter "Inconel (Trademark)"), a nickel-copper alloy available for purchase from Special Metals Corp. (New Hartford, New York, USA) under the trade name Monel (Trademark), or a vessel having a fluoropolymer lining.

[0075] In one embodiment, HCFC-244bb is preheated in a vaporizer to a temperature of about 30°C to about 100°C. In another embodiment, HCFC-244bb is preheated in a vaporizer to a temperature of about 30°C to about 80°C.

[0076] In some embodiments, an inert diluent gas is used as a carrier gas for HCFC-244bb. In one embodiment, the selected carrier gas is nitrogen, argon, helium, or carbon dioxide.

[0077] It is believed that those skilled in the art using the description in this specification will be able to make the most of the invention without further elaboration. Accordingly, the following specific embodiments should be interpreted merely as examples and do not limit the remainder of the disclosure in any way.

[0078] usefulness

[0079] The compositions disclosed herein, including HFO-1234yf, are useful as heat transfer compositions with a low Global Warming Potential (GWP), aerosol propellants, foam expanders (also known as foaming agents or blowing agents), solvents, cleaning agents, carrier fluids, displacement desiccants, buffing abrasives, polymerization media, foaming agents for polyolefins and polyurethanes, gas dielectrics, fire extinguishers, and fire suppressants in liquid or gaseous form. The disclosed compositions can serve as working fluids used to transfer heat from a heat source to a heat sink. Such heat transfer compositions may also be useful as refrigerants in cycles where the fluid undergoes a phase change, i.e., from liquid to gas and back, or vice versa.

[0080] Examples of heat transfer systems include, but are not limited to, air conditioners, chillers, refrigerators, heat pumps, water coolers, flooded evaporative coolers, direct expansion coolers, walk-in coolers, heat pumps, portable refrigerators, portable air conditioning units, and combinations thereof.

[0081] In one embodiment, a composition comprising HFO-1234yf is useful for mobile heat transfer systems, including refrigeration, air conditioning, or heat pump systems or devices. In another embodiment, the composition is useful for stationary heat transfer systems, including refrigeration, air conditioning, or heat pump systems or devices.

[0082] As used herein, a mobile heat transfer system refers to any refrigeration, air conditioning, or heating unit included in a transport unit for road, rail, sea, or air transport. Additionally, a mobile refrigeration or air conditioning unit includes a unit known as a “combined” system that is independent of any transport carrier. Such a combined system includes a “swap body” (for road / rail transport) together with a “container” (for sea / land transport).

[0083] As used herein, a stationary heat transfer system is a system that is fixed in place during operation. A stationary heat transfer system may be connected to or attached within any various building, or it may be a standalone unit located outdoors, such as a soft drink vending machine. Such stationary applications may be stationary air conditioning and heat pumps (including, but not limited to, chillers, high-temperature heat pumps, residential, commercial, or industrial air conditioning systems, and including external but connected to a building, such as windows, ductless, ducted, packaged terminals, chillers, and rooftop systems). In stationary refrigeration applications, the disclosed composition may be useful for high, medium, and / or low-temperature refrigeration installations, including commercial, industrial, or residential refrigerators and freezers, ice makers, standalone coolers and freezers, flooded evaporative chillers, direct expansion chillers, walk-in and reach-in coolers and freezers, and combination systems. In some embodiments, the disclosed composition may be used in supermarket refrigerator systems.

[0084] Accordingly, according to the present invention, the composition disclosed herein containing HFO-1234yf may be useful for a cooling generation method, a heat generation method, and a heat transfer method.

[0085] The compositions disclosed herein are, in particular, R134a (or HFC-134a, 1,1,1,2-tetrafluoroethane), R22 (or HCFC-22, chlorodifluoromethane), R12 (CFC-12, dichlorodifluoromethane); R407C (ASHRAE designation for a blend of 52 wt% R134a, 25 wt% R125 (pentafluoroethane), and 23 wt% R32 (difluoromethane); R410A (ASHRAE designation for a blend of 50 wt% R125 and 50 wt% R32); It may be useful as a low global warming potential (GWP) substitute for currently used refrigerants, including but not limited to R404A (ASHRAE designation for a blend of 44 wt% R125, 52 wt% R143a (1,1,1-trifluoroethane), and 4.0 wt% R134a).

[0086] In many applications, some embodiments of the present composition containing HFO-1234yf are useful as a refrigerant and provide cooling performance (meaning cooling capacity and energy efficiency) that is at least comparable to that of a refrigerant to be replaced.

[0087] In another embodiment, a method for recharging a heat transfer system comprising a refrigerant to be replaced and a lubricant is provided, the method comprising the steps of removing the refrigerant to be replaced from the heat transfer system while retaining a substantial portion of the lubricant in the system, and introducing one of the compositions comprising HFO-1234yf into the heat transfer system.

[0088] In another embodiment, a heat exchange system comprising any of the present compositions comprising HFO-1234yf is provided, wherein the system is selected from the group consisting of air conditioners, chillers, refrigerators, heat pumps, water coolers, flooded evaporative coolers, direct expansion coolers, walk-in coolers, heat pumps, portable refrigerators, portable air conditioning units, and systems having combinations thereof. Additionally, compositions comprising HFO-1234yf may be useful in a secondary loop system, wherein the compositions act as a primary refrigerant to provide cooling to a secondary heat transfer fluid, thereby cooling a distant location.

[0089] Vapor-compression refrigeration, air conditioning, or heat pump systems include an evaporator, a compressor, a condenser, and an expansion unit. The vapor-compression cycle reuses refrigerant in multiple stages, producing a cooling effect in one stage and a heating effect in another. This cycle can be simply described as follows: Liquid refrigerant enters the evaporator through the expansion unit; there, the liquid refrigerant boils in the evaporator by absorbing heat from the environment at a low temperature, forming a gas and generating cooling. The low-pressure gas enters the compressor, where it is compressed, raising its pressure and temperature. Subsequently, the high-pressure (compressed) gaseous refrigerant enters the condenser, condenses, and releases its heat into the environment. This refrigerant returns to the expansion unit, where the liquid expands from the high-pressure level in the condenser to the low-pressure level in the evaporator, repeating the cycle.

[0090] In one embodiment, a heat transfer system comprising any of the present compositions comprising HFO-1234yf is provided. In another embodiment, a refrigeration, air conditioning, or heat pump device comprising any of the present compositions comprising HFO-1234yf is disclosed. In another embodiment, a stationary refrigeration or air conditioning device comprising any of the present compositions comprising HFO-1234yf is disclosed. In yet another embodiment, a mobile refrigeration or air conditioning device comprising the composition disclosed herein is disclosed.

[0091] In another embodiment, a method for generating cooling is provided, comprising the step of evaporating any of the present compositions containing HFO-1234yf near an object to be cooled, and then condensing said compositions.

[0092] In another embodiment, a heat generation method is provided comprising the step of condensing any of the compositions containing HFO-1234yf near an object to be heated, and then evaporating the compositions.

[0093] In another embodiment, a method is disclosed for using the present composition containing HFO-1234yf as a heat transfer fluid composition. The present method comprises the step of transporting the composition from a heat source to a heat sink.

[0094] In another embodiment, the present invention relates to a foam expansion agent composition comprising HFO-1234yf for use in the manufacture of foam. In another embodiment, the present invention provides a foaming composition, and preferably a thermosetting foam composition (such as polyurethane, polyisocyanurate, or phenolic material) and a thermoplastic foam composition (such as polystyrene, polyethylene, or polypropylene), and a method for manufacturing foam. In such foam embodiments, one or more of the compositions comprising HFO-1234yf are included as foam expansion agents in the foaming composition, and the composition preferably comprises one or more additional components capable of reacting and / or mixing and foaming under appropriate conditions to form a foam or cell structure.

[0095] The present invention also relates to a foam-forming method, comprising the steps of: (a) adding a composition of the present invention comprising HFO-1234yf to a foaming composition; and (b) treating the foaming composition under conditions effective for forming a foam.

[0096] Another embodiment of the present invention relates to the use of the composition of the present invention comprising HFO-1234yf as a propellant in a sprayable composition. Additionally, the present invention relates to a sprayable composition comprising HFO-1234yf. An active ingredient to be sprayed together with an inert component, a solvent, and other materials may also be present in the sprayable composition. In one embodiment, the sprayable composition is an aerosol. The composition of the present invention may be used to formulate various industrial aerosols or other sprayable compositions, e.g., contact cleaners, dusters, lubricating sprays, release sprays, insecticides, etc., and consumer aerosols, e.g., personal care products (e.g., hairsprays, deodorizers, and perfumes), household products (e.g., waxes, polishes, pan sprays, room fresheners, and household insecticides), and automotive products (e.g., cleaners and polishes), as well as pharmaceutical substances, e.g., anti-asthmatic agents and anti-odor agents. Examples of this include the treatment of asthma and other chronic obstructive pulmonary diseases, and metered dose inhalers (MDIs) for the delivery of medicine to accessible mucous membranes or into the nasal cavity.

[0097] The present invention also relates to a method for manufacturing an aerosol product, comprising the step of adding a composition of the present invention containing HFO-1234yf to a formulation containing an active ingredient within an aerosol container, wherein the composition acts as a propellant. Additionally, the present invention also relates to a method for manufacturing an aerosol product, comprising the step of adding a composition of the present invention containing HFO-1234yf to a barrier-type aerosol package (such as a bag-in-a-can (BIC) or piston can), wherein the composition is kept separated from other formulation ingredients within the aerosol container, and the composition acts as a propellant. Additionally, the present invention also relates to a method for manufacturing an aerosol product, comprising the step of adding only a composition of the present invention containing HFO-1234yf to an aerosol package, wherein the composition acts as an active ingredient (e.g., a duster, or a cooling or freezing spray).

[0098] The composition disclosed in this specification, comprising HCO-1230xa, HCFO-1233xf and HCFC-244bb, is useful for the method of producing HFO-1234yf described in this specification.

[0099] It is believed that those skilled in the art using the description in this specification will be able to make the most of the invention without further elaboration. Accordingly, the following specific embodiments should be interpreted as mere examples and do not limit the remainder of the disclosure in any way.

[0100] Examples

[0101] General procedures for product analysis

[0102] The following general procedure illustrates the method used to analyze the products of a fluorination reaction. A portion of the total reactor effluent was sampled online for the analysis of organic products using a gas chromatograph (GC / MS) equipped with a mass-selective detector. This gas chromatography utilized a 6.1 m (20 ft) long × 0.32 cm (1 / 8 in) diameter tube containing perfluorinated polyether marketed under the trademark Krytox by E. I. du Pont de Nemours and Company (hereinafter "DuPont"), Wilmington, Delaware, USA, on an inert carbon support. The helium flow rate was 30 mL / min (5.0 × 10⁻⁷ m³ / sec). The gas chromatography conditions were 60°C during an initial hold period of 3 minutes, followed by temperature programming up to 200°C at a rate of 6°C / min.

[0103] Example 1

[0104] Fluorination of HCFO-1233xf to HCFC-244bb

[0105] The contents of a small PTFE vial containing 20 g of viscous SbF5 were poured into a dry 400 mL Hastelloy (registered trademark) shaker tube. The tube was closed and pressurized with nitrogen for a leak test. Subsequently, the shaker tube was cooled to below -40°C using dry ice, slowly vented, and then evacuated. 75 g (3.75 mol) of anhydrous HF was condensed into the shaker tube, followed by 165 g (1.26 mol) of HCFO-1233xf. The shaker tube was placed in a barricade and shaking was started.

[0106] The shaker tube was stirred at ambient temperature (about 20 to 23°C), and the pressure was 144.8 to 172.4 kPa (21 to 25 psig). After 2 hours, shaking was stopped, and 150 mL of water was carefully pumped into the shaker tube. The tube was left overnight, then cooled to 0 to 5°C in an ice bath, depressurized, and the contents were transferred to a plastic container. The container was placed on ice.

[0107] The contents of the container were poured into a polypropylene separatory funnel containing a small amount of ice. The lower organic layer was bright amber in appearance. The organic layer was separated and placed into a glass media bottle commercially available under the trade name Pyrex (registered trademark) by Corning (hereinafter referred to as "Pyrex"), containing about 50 mL of 4 molar (pH 7) phosphate buffer and about 100 mL of ice. The organic layer was separated again and poured into a dry Pyrex media bottle containing a small amount of anhydrous magnesium sulfate. The crude yield was 164.3 g (about 120 mL, 86%).

[0108] GC / MS of the crude material indicated that it was mainly HCFC-244bb. Other components included 0.16% 1233xf and other by-products totaling 12.2%.

[0109] Example 2

[0110] Fluorination of HCFO-1233xf to HCFC-244bb

[0111] The contents of a small PTFE vial containing 20 g of viscous SbF5 were poured into a dry 400 mL Hastelloy (registered trademark) shaker tube. The tube was closed and pressurized with nitrogen for a leak test. Subsequently, the shaker tube was cooled to below -40°C using dry ice, slowly vented, and then scoured. 53 g (2.65 mol) of anhydrous HF was transferred to the shaker tube, and then 227 g (1.74 mol) of HCFO-1233xf was condensed into the cooled shaker tube. The shaker tube was placed in a barricade and shaking was started.

[0112] The shaker tube was stirred at ambient temperature (about 18 to 21°C), and the pressure was 110.3 to 137.9 kPa (16 to 20 psig). After 2 hours, shaking was stopped, and 100 mL of water was carefully pumped into the shaker tube. The tube was left overnight, cooled to 0 to 5°C in an ice bath, air-conditioned, and the contents transferred to a plastic container. The container was placed on ice.

[0113] The contents of the container were poured into a polypropylene separatory funnel containing a small amount of ice. The lower organic layer was bright amber in appearance. The organic layer was separated and placed into a Pyrex (registered trademark) media bottle containing about 50 mL of 4 molar (pH 7) phosphate buffer and ice (about 100 mL). The organic layer was separated again and poured into a dry Pyrex (registered trademark) media bottle containing a small amount of anhydrous magnesium sulfate. The crude yield was 238.8 g (about 170 mL, 91%).

[0114] GC / MS of the crude material indicated that it was mainly HCFC-244bb. Other components included 0.11% HFC-245cb, 0.10% HFC-245eb, 0.26% HCFO-1233xf, and other by-products totaling 9.7%.

[0115] Example 3

[0116] Example 3 describes the conversion of HCFC-244bb (2-chloro-1,1,1,2-tetrafluoropropane) to HFO-1234yf (2,3,3,3-tetrafluoropropene) in the absence of a catalyst.

[0117] A hollow Inconel (registered trademark) tube (1.3 cm (1 / 2 inch) OD) with a heating zone of approximately 30.5 cm (12 inches) was heated to a temperature of 500°C to 626°C, and 2.4 sccm (4.0 × 10⁻) of HFC-244bb was added. 8 m 3 It was supplied at a rate of 0.52 mL / hr through a vaporizer set to 40°C using an N2 sweep. The reactor effluent was analyzed using online GCMS, and the results were reported in mol%.

[0118] [Table 2]

[0119]

[0120] Example 4

[0121] Example 4 describes the conversion of HCFC-244bb (2-chloro-1,1,1,2-tetrafluoropropane) to HFO-1234yf (2,3,3,3-tetrafluoropropane) in the absence of a catalyst.

[0122] A hollow Inconel (registered trademark) tube (1.3 cm (1 / 2 inch) OD) with a heating zone of approximately 30.5 cm (12 inches) was heated to 575°C, and 3.6 sccm (6.0 × 10⁻) of HFC-244bb was added. 8 m 3 Using an N2 sweep, it was supplied at 0.35 mL / hr through an evaporator set to 40°C. The reactor was operated continuously for a total of 19 hours, and samples were periodically taken and analyzed to determine the % conversion rate of HFC-244bb and the selectivity for HFO-1234yf. The reactor effluent was analyzed using online GCMS, and the data in Table 6 below are the average of at least two online injections under specified conditions; percentages are mol%.

[0123] [Table 3]

[0124]

[0125] Example 5

[0126] Example 5 describes the dehydrochlorination of HCFC-244bb (2-chloro-1,1,1,2-tetrafluoropropane) in the presence of an activated carbon catalyst.

[0127] An Inconel (registered trademark) tube (1.3 cm (1 / 2 inch) OD) was filled with 4 cc (1.99 g) of acid-washed PCB Polynesian coconut shell carbon (6 to 10 mesh) from Calgon. HFC-244bb was introduced at 400°C while controlling the reactor temperature to provide a total contact time of approximately 32 seconds at 2.4 sccm (4.0 × 10⁻ 8 m 3 It was supplied at a rate of 1.04 mL / hr through a vaporizer set to 40℃ using an N2 sweep of ).

[0128] The data in Table 4 represent the reactor effluent composition in mol% for this process carried out using an activated carbon catalyst to produce HFC-1234yf through HCl removal over a 7-hour operation period.

[0129] [Table 4]

[0130]

Claims

Claim 1 A method for producing HFO-1234yf, comprising: a step of fluorinating HCFO-1233xf to produce a product mixture containing HCFC-244bb; and b. step of dehydrochlorination of HCFC-244bb to produce a second product mixture containing HFO-1234yf. Claim 2 A method of manufacturing according to claim 1, wherein the fluorination step comprises a liquid-phase reaction in the presence or absence of a catalyst. Claim 3 A method of preparation according to paragraph 2, wherein the liquid phase reaction is carried out in the presence of a catalyst, wherein the catalyst is selected from the group consisting of Lewis acid catalysts, metal halide catalysts, and combinations thereof, or from the group consisting of antimony pentachloride, antimony trichloride, antimony pentafluoride, tin tetrachloride, titanium tetrachloride, iron trichloride, and any combination thereof. Claim 4 A manufacturing method according to paragraph 2, wherein the liquid phase reaction is performed in the absence of a catalyst. Claim 5 A method of manufacturing according to claim 1, wherein the fluorination step comprises a vapor phase reaction in the presence or absence of a catalyst. Claim 6 A method of preparation according to claim 5, wherein a vapor phase reaction is carried out in the presence of a catalyst, wherein the catalyst is selected from the group consisting of chromium-based catalysts, iron-based catalysts, and any combination thereof. Claim 7 A manufacturing method according to claim 5, wherein the vapor phase reaction is carried out in the absence of a catalyst. Claim 8 A method of manufacturing according to claim 1, wherein the dehydrochlorination step comprises a vapor phase reaction in the presence or absence of a catalyst. Claim 9 A method of manufacture according to claim 8, wherein a vapor phase reaction is carried out in the presence of a catalyst, wherein the catalyst is selected from the group consisting of carbon-based catalysts, metal-based catalysts, and any combination thereof. Claim 10 A method of manufacturing according to claim 8, wherein the vapor phase reaction is carried out in the absence of a catalyst. Claim 11 A method of manufacturing according to claim 8, wherein the vapor phase reaction is carried out at a temperature of 200 to 600°C or 250 to 500°C, or at a temperature sufficient to achieve a % conversion rate of 50% or more of HCFC-244bb, or at a temperature of 500 to 700°C. Claim 12 A manufacturing method according to claim 1, wherein the selectivity for HFO-1234yf of dehydrochlorination is 80% or higher.

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