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    • 专利摘要:
    COMPOSITIONS, METHOD TO PRODUCE COOLING, METHOD TO PRODUCE HEAT, METHOD TO FORM A FOAM AND PROCESS TO PRODUCE AEROSOL PRODUCTS. The present invention relates to compositions comprising 2,3,3,3-tetrafluoropropene which can be useful as heat transfer compositions, aerosol propellants, foaming agents, blow agents, solvents, cleaning agents , carrier fluids, displacement drying agents, buffering abrasion agents, polymerization media, expansion agents for polyolefins and polyurethane, gaseous dielectrics, extinguishing agents, and liquid or gaseous fire suppression agents. In addition, the present description relates to compositions comprising 1, 1,2,3-tetrachloropropene, 2-chloro-3,3,3-trifluoropropene, or 15 2-chloro-1, 1,1,2-tetrafluoropropane, which can be useful in processes to produce 2,3,3,3-tetrafluoropropene.
    公开号:BR112012015260B1
    申请号:R112012015260-2
    申请日:2010-12-22
    公开日:2020-11-10
    发明作者:Mario Joseph Nappa
    申请人:E.I. Du Pont De Nemours And Company；
    IPC主号:
    专利说明:

    FIELD OF THE INVENTION
    [001] The present invention relates to the field of compositions which can be useful as heat transfer compositions, aerosol propellants, foaming agents (blow agents), solvents, cleaning agents, carrier fluids, displacement drying agents, buffering abrasion agents, polymerization media, foaming agents for polyolefins and polyurethane, gaseous dielectrics, extinguishing agents and fire suppression agents in liquid or gaseous form. In particular, the present description relates to compositions that may be useful as heat transfer compositions, such as, for example, 2,3,3,3-tetrafluoropropene (HFO-1234yf, or 1234yf) or compositions comprising 1 , 1,1,2,3-pentafluoropropane (HFC-245eb, or 245eb), which are useful in processes to produce HFO-1234yf. BACKGROUND OF THE INVENTION
    [002] New environmental regulations have led to the need for new compositions for use in refrigeration, air conditioning and heat pump devices. Low potential global warming compounds are of particular interest. BRIEF DESCRIPTION OF THE INVENTION
    [003] Applicants found that when preparing such new compounds with low global warming potential, such as, HFO-1234yf, that certain additional compounds are present in small amounts.
    [004] Therefore, in accordance with 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-260db, HCC-240aa , HCO-1230xa, HCFO-1233xf, HCFO-1233zd, HCFC-244bb, HCFC-244db, HFO-1234ze, HFC-245cb, HFO-1243zf, HCFO-1223za, HCFO-1224zb, HFO-1225zd, HCFC-2425zc, HCFC-2425zd -242dc, HCFO-1232xf, HCFO-1231xf, and HCFO-1233yf. The composition can contain less than about one weight percent of at least one additional compound, based on the total weight of the composition.
    [005] Additionally, in accordance with the present invention, there is provided a composition comprising HCO-1230xa and at least one additional compound selected from the group consisting of propylene, HCO-1260zf, HCC-260da, HCC-260db, HCO -1250xf, HCC-250aa, and HCC-240aa.
    [006] Additionally, in accordance with the present invention, there is provided a composition comprising HCFO-1233xf and at least one additional compound selected from the group consisting of propylene, HCO-1260zf, HCC-260da, HCC-260db, HCO -1250xf, HCC-250aa, HCC-240aa, HCO-1230xa, HFO-1243zf, HCFO-1223za, HCFO-1224zb, HFO-1225zc, HCFO-1225zf, HCFO-1232xf, HCFC-1231xf, HCFC-241db, eFCFC-241db, and 242dc.
    [007] Additionally, in accordance with the present invention, there is provided a composition comprising HCFC-244bb and at least one additional compound selected from the group consisting of 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-1233y. BRIEF DESCRIPTION OF THE DRAWINGS
    [008] Figure 1 shows a reaction sequence useful for the formation of compositions of the present invention. DETAILED DESCRIPTION OF THE INVENTION COMPOSITIONS
    [009] It has been suggested that HFO-1234yf (2,3,3,3-tetrafluoropropene) be used as a refrigerant, heat transfer fluid, aerosol propellant, foaming blowing agent, among other uses. It has also been advantageously revealed that HFO-1234yf has a low global warming potential (GWP), as reported by V.C. Papadimitriou, et al. in Physical Chemistry Chemical Physics, 2007, volume 9, pages 1 to 13. So, HFO-1234yf is a good candidate to replace the higher saturated HFC refrigerants with higher GWP.
    [010] In one embodiment, the present description 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-241d, HCFC-241d HCFO-1232xf, HCFO-1231xf, and HCFO-1233yf.
    [011] The compositions of the present invention can comprise HFO-1234yf and an additional compound, or two additional compounds, or three or more additional compounds.
    [012] In another embodiment, the compositions of the present invention comprise HFO-1234yf and HCFO-1232xf.
    [013] In another embodiment, the compositions of the present invention comprise HFO-1234yf and at least one compound selected from HCFC-243db, HCFO-1233xf, HCFO-1231xf, HCFC-242dc and HCFC-241 db.
    [014] In another embodiment, the compositions of the present invention comprise at least one compound selected from the group consisting of HCFC-243db and HFC-245fa.
    [015] In one embodiment, the total amount of additional compound (s) in the composition comprising HFO-1234yf ranges from more than zero weight percent to less than 1 weight percent, based on the total weight of the composition. In another embodiment, the total amount of additional compound (s) ranges from more than zero weight percent to less than 0.5 weight percent, based on the total weight of the composition.
    [016] In one embodiment, the composition comprising HFO-1234yf and other compounds may additionally comprise a specific signaling compound, such as, for example HFC-245cb. In this embodiment, the HFC-245cb flag can be present at a concentration of from about 1 part per million (ppm) to about 1,000 ppm in the composition. In another embodiment, the HFC-245cb flag may be present at a concentration of from about 1 ppm to about 500 ppm. Alternatively, the HFC-245cb flag can be present at a concentration of from about 10 ppm to about 300 ppm.
    [017] The compositions described in this document that comprise HFO-1234yf are useful as low global warming potential (GWP) heat transfer compositions, aerosol propellants, foaming agents, blow agents, solvents, cleaning agents, carrier fluids, displacement drying agents, buffering abrasion agents, polymerization means, expansion agents for polyolefins and polyurethane, gaseous dielectrics, extinguishing agents, and fire suppression agents in liquid or gaseous form. The described compositions can act as a working fluid used to carry heat from a heat source to a heat sink. Such heat transfer compositions can also be useful as a refrigerant in a cycle in which the fluid undergoes a phase change; that is, from a liquid to a gas and vice versa.
    [018] Examples of heat transfer systems include, but are not limited to, air conditioners, freezers, refrigerators, heat pumps, water coolers, soaked evaporator coolers, direct expansion coolers, cooling chambers, heat pumps heat, mobile refrigerators, mobile air conditioner units and combinations thereof.
    [019] As used in this document, mobile refrigeration appliance, mobile air conditioner or mobile heating appliance refers to any refrigeration appliance, air conditioner, or heating device incorporated in a transport unit for the road, railroad , sea or air. In addition, mobile refrigeration units or air conditioners include such devices that are independent of any mobile carrier and are known as “intermodal” systems. Such intermodal systems include “containers” (combined sea / land transport) as well as “exchange bodies” (combined road / rail transport).
    [020] As used in this document, stationary heat transfer systems are associated systems inside or attached to buildings of any variety. These stationary applications can be stationary conditioner and heat pumps (which includes, but is not limited to, coolers, high temperature heat pumps, residential, commercial or industrial air conditioning systems, and which include window systems, without ducts , with ducts, packaged terminal, coolers, and those outside, but not connected to the building, such as terrace systems). In stationary refrigeration applications, the compositions described may be useful in refrigeration equipment at high temperature, medium temperature, and / or low temperature that include commercial, industrial or residential refrigerators or freezers, ice machines, stand-alone chillers and freezers, food coolers. soaked evaporators, direct expansion chillers, cooling and freezing chambers, vertical chillers and freezers, and combination systems. In some embodiments, the described compositions may be used in supermarket refrigerators and / or freezers.
    [021] The compounds that make up the described compositions are defined in Table 1. TABLE 1

    [022] HCFO-1233xf, HCFC-244bb, and many other compounds as listed in Table 1 are available from specialty chemical producers, which includes SynQuest Laboratories, Inc. (Alachua, FL, USA) or can be manufactured by methods known in the art. For example, HCFO-1233xf, and HCFC-244bb can be prepared by non-catalytic chlorination of HFO-1243zf, as described in International Patent Application Publication No. W02008 / 054782, published on May 8, 2008. In addition, HCFO- 1233xf and HCFC-244bb can be prepared by catalytic fluorination of HCFC-243db as described in International Patent Application Publication No. W02008 / 054781, published on May 8, 2008. The additional compounds present in each composition described will depend on the method of manufacture .
    [023] Alternatively, HCO-1230xa can be produced from 1,2,3-trichloropropane as described in US2007 / 0197842 A1. In addition, the reaction of HCO-1230x with HF in the presence of catalyst in the vapor phase to form HCFO-1233xf is described in US2007 / 0197842.
    [024] Alternatively, HCFO-1233xf can also be produced by the fluorination of 1,1,2,3-tetrachloropropene, (HCO-1230xa) with the additional fluorination forming HCFC-244bb and the subsequent dehydrochlorination forming HFO-1234yf, as described in document No. US2009 / 0240090.
    [025] Some of the compounds listed in Table 1 may exist in more than one isomer, in particular HFO-1234ze, HCFO-1233zd, and HCFO-1224zb. For example, HFO-1234ze can exist as the E-isomer or Z-isomer. As used herein, HFO-1234ze is intended to refer to any of the E-isomers, Z-isomers or any mixture of these isomers. As used herein, HCFO-1233zd is intended to refer to any of the E-isomers, Z-isomers or any mixture of these isomers. As used herein, HFO-1224zb is intended to refer to any of the E-isomers, Z-isomers or any mixture of these isomers.
    [026] Additionally, in accordance with the present invention, there is provided a composition comprising HCO-1230xa and at least one additional compound selected from the group consisting of propylene, HCO-1260zf, HCC-260da, HCC-260db, HCO -1250xf, HCC-250aa, and HCC-240aa.
    [027] In another embodiment, the compositions of the present invention comprise HCO-1230xa and HCC-240aa. And in another embodiment, the compositions of the present invention can comprise HCO-1230xa, HCC-240aa, and at least one compound selected from the group consisting of HCC-250aa and HCC-260da.
    [028] Additionally, in accordance with the present invention, a composition is provided which comprises HCFO-1233xf and at least one additional compound selected from the group consisting of 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, eFCFC-241db, and 242dc.
    [029] In another embodiment, the compositions of the present invention comprise HCO-1230xa and HCFO-1232xf. And in another embodiment, the compositions of the present invention comprise, HCO-1230xa, HCFO-1232xf and HCFO-1231xf.
    [030] Additionally, in accordance with the present invention, there is provided a compound comprising HCFC-244bb and at least one additional compound selected from the group consisting of 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-1233y.
    [031] In another embodiment, the compositions of the present invention comprising HCFC-244bb may additionally comprise at least one compound selected from the group consisting of HCFC-243db and HFC-245fa.
    [032] The series of reactions that can form the compositions of the present invention are shown in Figure 1. The sequence of steps begins with the chlorination of propylene by the reaction with chlorine, CI2, to form allyl chloride or HCO-1260zf (CH2 = CHCH2CI). The next step involves additional chlorination in the presence of CI2 to produce HCC-260db (CH2CICHCICH2CI). The reaction of HCC-260db with aqueous NaOH (or other caustic solution) forms HCO-1250xf (CH2 = CCICH2CI). And the reaction of HCO-1250xf with chlorine, CI2, produces HCC-250aa (CH2CICCI2CH2CI, or 1,2,2,3-tetrachloropropane). Additional chlorination with CI2 will result in HCC-240da (CHCI2CCI2CH2CI). The reaction of HCC-240da with aqueous NaOH (or other caustic solution) will form HCO-1230xa (CCl2 = CCICH2CI).
    [033] In another embodiment, any of the compositions as described above may additionally comprise hydrogen fluoride (HF), due to the presence of HF either as a reagent or as a by-product of the reaction chemistry to produce each composition.
    [034] Compositions that are free from HCI, compositions that are free from HF and compositions that are free from both HCI and HF are noteworthy. Compositions that are acid-free are particularly noteworthy. Acids can be removed by processes known in the art, such as distillation and washing with water or caustic. FLUORATION OF HCQ-1230XA
    [035] 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 Figure 1.
    [036] The fluorochlorination reaction can be carried out in the vapor or liquid phase. For liquid phase embodiments of the invention, the reaction of HCO-1230x with HF can be conducted in a liquid phase reactor that operates in continuous, semi-continuous, batch and semi-batch modes. In batch mode, HCO-1230xa and HF are combined in an autoclave or other suitable container and heated to the desired temperature.
    [037] In one embodiment, this reaction is performed in a semi-blown mode when feeding HCO-1230xa to a liquid phase reactor containing HF. In another embodiment, HF can be fed to a liquid phase reactor that contains a mixture of HCO-1230xa and formation products formed by the reaction of HF and HCO-1230xa. In another embodiment of the liquid phase process, HF and HCO-1230xa can be fed concurrently to the desired stoichiometric ratio to the reactor that contains a mixture of HF and reaction products formed by the reaction of HF and HCO-1230xa.
    [038] Suitable temperatures for the reaction of HF with HCO-1230x in the liquid phase reactor are, in one embodiment, from about 80 ° C to about 180 ° C, and in another embodiment, from about 100 ° C to about 150 ° C. Higher temperatures typically result in a higher conversion of HCO-1230x.
    [039] A suitable molar ratio of HF to total amount of HCO-1230x fed to the liquid phase reactor is, in one embodiment, at least stoichiometric (about 3: 1, HF for HCO-1230xa), and in another embodiment , is about 5: 1 to about 100: 1. The achievements in which the molar ratio of HF to HFO-1243zf is from about 8: 1 to about 50: 1 are noteworthy.
    [040] The reactor pressure in the liquid phase process is not critical and, in batch reactions, it is generally the autogenous pressure of the system at the reaction temperature. The system pressure increases as hydrogen chloride is formed by replacing hydrogen substituents with chlorine, and replacing chlorine substituents with fluorine in the starting materials and intermediate reaction productions. In a continuous process, it is possible to determine the reactor pressure so that the lower boiling products are exhaled from the reactor, optionally through a stuffed column or condenser. In this way, lower boiling intermediates remain in the reactor and the volatile products are removed. Typical reaction pressures range from about 239 kPa (20 psig) to about 6,994 kPa (1,000 psig).
    [041] In some embodiments in which the reaction is conducted using a liquid phase process, catalysts that can be used include carbon, AIF3, BF3, FeCIs-aFa (where a = 0 to 3), FeXs sustained on carbon , SbCIs-aFa, AsFs, MCIs-bFb (where b = 0a5eM = Sb, Nb, Ta, or Mo), and M'Cl4-cFc (where c = 0 to 4, and M '= Sn, Ti, Zr, or Hf). In another embodiment, catalysts for the liquid phase process are MCIs-bFb (where b = 0 to 5 and M = Sb, Nb, or Ta).
    [042] In another embodiment, the reaction of HF with HCO-1230xa is performed in the vapor phase. Typically, a heated reactor is used. Several reactor configurations are possible, including those of vertical and horizontal orientation of the reactor as well as the HCO-1230x reaction sequence with HF. In one embodiment of the invention, the HCO-1230xa can be initially vaporized and fed to the reactor as a gas.
    [043] Suitable temperatures for the steam vessel reaction are about 120 ° C to about 500 ° C. Higher temperatures result in a higher conversion of HCO-1230x and higher degrees of fluorination and halation in the converted compounds.
    [044] Suitable reactor pressures for the vapor phase reactor can be from about 1 to about 30 atmospheres. A pressure of about 15 to about 25 atmospheres can be advantageously employed to facilitate the separation of HCI from other reaction products, and the appropriate reaction time can vary from about 1 to about 120 seconds, preferably from about from 5 to about 60 seconds.
    [045] The molar ratio of HF to the total amount of HCO-1230x for the vapor phase reaction is, in one embodiment, about the stoichiometric ratio of HF to the total amount of HCO-1230x (3: 1 HF to HCO-1230x) at about 50: 1 and, in another embodiment, from about 10: 1 to about 30: 1.
    [046] In one embodiment, a catalyst is used in the reaction zone for the HF vapor phase reaction with (3: 1 HF to HCO-1230x). Clofofluorination catalysts that can be used in the vapor phase reaction include carbon; graphite; alumina; fluoridated alumina; aluminum fluoride; carbon-supported alumina; aluminum fluoride supported on carbon; fluorinated alumina supported on carbon; magnesium fluoride supported on aluminum fluoride; metals (which include elemental metals, metal oxides, metal halides, and / or other metal salts); metals supported on aluminum fluoride; metals supported by fluoridated alumina; metals supported on alumina; and carbon-supported metals; mixtures of metals.
    [047] Metals suitable for use as catalysts (optionally supported on alumina, aluminum fluoride, fluoridated 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 that have an atomic number from 58 to 71 (ie, lanthanide metals). In one embodiment, when used on a support, the total metal content of catalyst will be about 0.1 to about 20 weight percent based on the total weight of the catalyst; in another embodiment, from about 0.1 to about 10 weight percent based on the total weight of the catalyst.
    [048] Chlorofluorination catalysts suitable for vapor phase reactions include catalysts containing chromium, including chromium (III) oxide (C ^ Os); CrcOs with other metals, such as magnesium halides or zinc halides supported on Cr20s; chrome (III) halides supported on carbon; mixtures of chromium and magnesium (which include elemental metals, metal oxides, metal halides, and / or other metal salts) optionally supported in graphite; and mixtures of chromium and other metals (including elemental metals, metal oxides, metal halides, and / or other metal salts) optionally supported in graphite, alumina, or aluminum halides, such as aluminum fluoride .
    [049] Chromium-containing catalysts are well known in the art. They can be prepared either by precipitation methods or by impregnation methods, as is generally described by Satterfield on pages 87 to 112 in Heterogeneous Catalysis in Industrial Practice, 2nd edition (McGraw-Hill, New York, 1991).
    [050] Noteworthy are the chlorofluorination catalysts that comprise at least one component containing chromium selected from the group consisting of crystalline alpha-chromium oxide where from about 0.05 in% atomic to about 6 in% atomic content of the chromium atoms in the alpha-chromium oxide lattice are replaced by trivalent cobalt atoms, and crystalline alpha-chromium oxide where about 0.05% atomic to about 6% atomic chromium atoms in the lattice of alpha-chromium oxide are replaced by trivalent cobalt atoms that have been treated with a fluorination agent. These catalysts, including their preparation, were presented in Patent Application Publication No. US2005 / 0228202.
    [051] In another embodiment, the vapor phase catalyst for reacting HCO-1230x with HF may be a catalyst composition comprising Cr2θ3 prepared by (NH4) 2Cr2O pyrolysis as described in US 5,036,036.
    [052] Optionally, the metal containing catalysts described above can be pretreated with HF. This pretreatment can be carried out, for example, by placing metal-containing catalysts in a suitable container and, after that, passing the HF over the metal-containing catalyst. In one embodiment, such a container can be the reactor used to perform the 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. FLUORATION OF HCFO-1233XF
    [053] In some embodiments, HCFO-1233xf can be used to make HCFC-HCFC-244bb, and / or HFO-1234yf by fluorination. These reactions are shown in Figure 1.
    [054] In one embodiment, the reaction from HCFO-1233xf to HCFC-244bb can be performed in the liquid phase. In another embodiment, the reaction can be carried out in the vapor phase.
    [055] In one embodiment, the reaction from HCFO-1233xf to HCFC-244bb can be performed in batch mode. In another embodiment, the reaction can be carried out continuously.
    [056] In one embodiment, a liquid phase reaction from HCFO-1233xf to HCFC-244bb can be performed in the presence of a catalyst. In one embodiment, the catalyst can be a Lewis acid catalyst. In one embodiment, the catalyst can be a metal-halide catalyst. In another embodiment, the catalyst can 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 the same. In another embodiment, the catalysts can be at least one catalyst selected from antimony pentachloride (SbCIs), antimony trichloride (SbCIs), antimony pentafluoride (SbFs), tin tetrachloride (SnCk), tin tetrachloride (TiCk) , iron trichloride (FeCIs), and combinations thereof. In some embodiments, the reaction can be carried out with any known fluorination catalyst for liquid phase reactions.
    [057] In one embodiment, the reaction from HCFO-1233xf to HCFC-244bb can be performed in the absence of a catalyst.
    [058] In one embodiment, a vapor phase reaction from HCFO-1233xf to HCFC-244bb can be performed 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 combinations thereof. In one embodiment, the chromium-based catalyst is a chromium oxide (for example, Cr2θ3). In one embodiment, the iron-based catalyst can be FeCk on carbon.
    [059] In one embodiment, the vapor phase reaction from HCFO-1233xf to HCFC-244bb is performed in the absence of a catalyst. HCFC-244BB DEHYDROCHLORATION
    [060] In some embodiments, HCFC-244bb dehydrochlorination is used to prepare HFO-1234yf.
    [061] In one embodiment, dehydrochlorination from HCFC-244bb to HFO-1234yf is performed in the vapor phase.
    [062] In one embodiment, the vapor phase dehydrochlorination is performed 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 can be selected from an activated carbon, a nickel-based catalyst, a palladium-based catalyst, or any combination of these catalysts. In one embodiment, the catalyst can be selected from a group consisting of nickel mesh, palladium on carbon, palladium on aluminum oxide, or combinations thereof.
    [063] In one embodiment, catalyzed vapor phase dehydrochlorination is performed 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 1,034,213 kPa.
    [064] In another embodiment, HFO-1234yf is prepared by thermal dehydrochlorination of HCFC-244bb. In one embodiment, this reaction occurs in the absence of a catalyst. In one embodiment, HCFC-244bb is introduced into a reaction vessel in which the temperature is maintained at a temperature high enough to effect the thermal dehydrochlorination of HCFC-244bb. In one embodiment, the temperature is high enough to effect the termaldeshydrochlorination dehydrochlorination of HCFC-244bb for a percentage conversion of at least 50%. In another embodiment, the temperature is high enough to effect the thermal dehydrochlorination of HCFC-244bb for a percentage conversion of at least 65%. In yet another embodiment, the temperature is high enough to effect the thermal dehydrochlorination of HCFC-244bb for a percentage conversion of at least 80%. In yet another embodiment, the temperature is high enough to effect the thermal dehydrochlorination of HCFC-244bb for a percentage conversion of at least 70% for at least 12 hours of continuous operation.
    [065] In one embodiment, HCFC-244bb is introduced into a reaction vessel whose temperature is maintained in the range of about 500 ° C to about 700 ° C. In another embodiment, the temperature of the reaction vessel is maintained in the range of 500 ° C to about 650 ° C. In yet another embodiment, the temperature of the reaction vessel is maintained at a temperature high enough to effect the pyrolysis of HCFC-244bb to HFO-1234yf with a selectivity of 80% or greater. In yet another embodiment, the temperature of the reaction vessel is maintained at a temperature high enough to effect the pyrolysis of HCFC-244bb to HFO-1234yf with a selectivity of 85% or greater.
    [066] In one embodiment, for both a catalyzed and a non-catalytic dehydrochlorination reaction, the reaction zone is a reaction vessel that comprises materials that are resistant to corrosion. In one embodiment, these materials comprise alloys, such as, for example, nickel-based alloys such as Hastelloy®, nickel-chromium alloys commercially available from Special Metals Corp, under the trade name Inconel® (hereinafter “Inconel®” ) nickel-copper alloys commercially available from Special Metals Corp. (New Hartford, New York) under the trade name Monel®, or containers that have fluoropolymer coatings.
    [067] 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.
    [068] In some embodiments, an inert diluent gas is used as a carrier for HCFC-244bb. In one embodiment, the carrier gas is selected from nitrogen, argon, helium or carbon dioxide.
    [069] Without further elaboration, it is believed that an element skilled in the art can, with the use of the description contained in this document, use the present invention to its maximum capacity. The following specific achievements should therefore be interpreted as merely illustrative, and do not limit the rest of the description in any way. UTILITY
    [070] The compositions described in this document that comprise HFO-1234yf are useful as low global warming potential (GWP) heat transfer compositions, aerosol propellants, foaming blowing agents (also known as foaming agents or blow agents) , solvents, cleaning agents, carrier fluids, displacement drying agents, buffer abrasion agents, polymerization media, foaming agents for polyolefins and polyurethane, gaseous dielectrics, extinguishing agents, and liquid or gaseous fire suppression agents . The described compositions can act as a working fluid used to carry heat from a heat source to a heat sink. Such heat transfer compositions can also be useful as a refrigerant in a cycle in which the fluid undergoes a phase change; that is, from a liquid to a gas and vice versa.
    [071] Examples of heat transfer systems include, but are not limited to, air conditioners, freezers, refrigerators, heat pumps, water coolers, soaked evaporator coolers, direct expansion coolers, cooling chambers, cooling pumps heat, mobile refrigerators, mobile air conditioner units and combinations thereof.
    [072] In one embodiment, the composition comprising HFO-1234yf is useful in transfer systems! mobile heat exchangers, which include cooling, air conditioning, or heat pump systems or appliances. In another embodiment, the compositions are useful in stationary heat transfer systems, which include refrigeration, air conditioning, or heat pump systems or devices.
    [073] As used in this document, mobile heat transfer systems refer to any refrigeration, air conditioner, or heating device incorporated in a road, rail, sea, or air transport unit. In addition, mobile refrigeration or air-conditioning units include such devices that are independent of any mobile carrier and are known as “intermodal” systems. Such intermodal systems include “containers” (combined sea / land transport) as well as “exchange bodies” (combined road / rail transport).
    [074] As used in this document, stationary heat transfer systems are systems that are fixed in place during operation. A stationary heat transfer system can be associated inside or attached to buildings of any variety or they can be autonomous devices located outside, such as, for example, a soft drink vending machine. These stationary applications can be stationary air conditioners and heat pumps (which includes, but is not limited to, coolers, high temperature heat pumps, residential, commercial or industrial air conditioning systems, and which include window systems, with ducts, without ducts, with a packaged terminal, coolers, and those outside, but connected to the building, such as a terrace system). In stationary refrigeration applications, the compositions described may be useful in refrigeration equipment at high temperature, medium temperature, and / or low temperature that include commercial, industrial or residential refrigerators or freezers, ice machines, stand-alone chillers and freezers, food coolers. soaked evaporators, direct expansion chillers, cooling and freezing chambers, vertical chillers and freezers, and combination systems. In some embodiments, the described compositions can be used in supermarket refrigerators and / or freezers.
    [075] Therefore, in accordance with the present invention, the compositions as described herein that contain HFO-1234yf can be useful in methods of producing cooling, producing heat, and transferring heat.
    [076] The compositions described in this document may be useful as substitutes with low global warming potential (GWP) for the refrigerants currently used, which include, but are not limited to, R134a (or HFC-134a, 1,1,1, 2-tetrafluoroethane), R22 (or HCFC-22, chlorodifluoromethane), R12 (CFC-12, dichlorodifluoromethane); R407C (ASHRAE designation for a combination of 52 weight percent R134a, 25 weight percent R125 (pentafluoroethane), and 23 weight percent R32 (difluoromethane)); R410A (ASHRAE designation for a combination of 50 weight percent R125 and 50 weight percent R32); and R404A (ASHRAE designation for a combination of 44 percent by weight of R125, 52 percent by weight of R143a (1,1,1-trifluoroethane), and 4.0 percent by weight of R134a), among others.
    [077] In many applications, some achievements of the present combinations comprising HFO-1234yf are useful as refrigerants and provide at least buyable cooling performance (meaning cooling capacity and energy efficiency) to the refrigerant for which a substitute is being wanted.
    [078] In another embodiment, a method is provided to recharge a heat transfer system containing a refrigerant to be replaced and a lubricant, said method comprising removing the refrigerant to be replaced from the heat transfer system at the same time. that a substantial portion of the lubricant is retained in said system and one of the present compositions comprising HFO-1234yfto is introduced into the heat transfer system.
    [079] In another embodiment, a heat exchange system is provided which contains any of the present compositions comprising HFO-1234yf, wherein said system is selected from the group consisting of air conditioners, freezers, refrigerators, heat pumps , water coolers, soaked evaporator coolers, direct expansion coolers, cooling chambers, heat pumps, mobile coolers, mobile air conditioner units, and systems that have combinations thereof. In addition, the composition comprising HFO-1234yf can be useful in secondary full circuit systems in which these compositions serve as the primary refrigerant, then providing cooling for a secondary heat transfer fluid which thereby cools a remote location.
    [080] Steam compression, air conditioning or heat pump cooling systems include an evaporator, a compressor, a condenser, and an expansion device. A steam re-compression cycle uses refrigerant in multiple stages, which produces a cooling effect in one stage and a heating effect in a different stage. The cycle can be described simply as follows. The liquid refrigerant enters an evaporator through an expansion device, and the liquid refrigerant boils in the evaporator, removing heat from the environment at a low temperature to form a gas and produce cooling. Low pressure gas enters a compressor where the gas is compressed to increase its pressure and temperature. The gaseous refrigerant at the highest pressure (compressed) enters the condenser in which the refrigerant condenses and discharges its heat to the environment. The refrigerant returns to the expansion device through which the liquid expands from the highest pressure level in the condenser to the low pressure level in the evaporator, thus repeating the cycle.
    [081] In one embodiment, a heat transfer system is provided that contains any of the present compositions comprising HFO-1234yf. In another embodiment, a refrigeration, air conditioning or heat pump apparatus is described which contains any of the present compositions comprising HFO-1234yf. In another embodiment, a stationary cooling or air conditioning apparatus is described which contains any of the present compositions comprising HFO-1234yf. In yet another embodiment, a mobile refrigeration or air conditioning apparatus is described which contains a composition as described herein.
    [082] In another embodiment, a method for producing cooling is provided which comprises evaporating any of the present compositions comprising HFO-1234yf in the vicinity of a body to be cooled, and subsequently condensing said composition.
    [083] In another embodiment, a method for producing heat is provided which comprises condensing any of the present compositions comprising HFO-1234yf in the vicinity of a body to be forgotten, and subsequently evaporating said compositions.
    [084] In another embodiment, a method of using the present compositions comprising HFO-1234yf as a heat transfer fluid composition is described. The method comprises transporting said composition from a heat source to a heat sink.
    [085] In another embodiment, the present invention relates to foaming blowing agent compositions comprising HFO-1234yf for use in preparing foams. In other embodiments, the invention provides foaming compositions, and preferably thermosetting foam compositions (such as polyurethane, polyisocyanurate, or phenolic), and thermoplastic foam compositions (such as polystyrene, polyethylene, or polypropylene) and methods of preparing foams. In such foam embodiments, one or more of the present compositions comprising HFO-1234yf are included as a foaming blowing agent in foaming compositions, the composition of which preferably includes one or more additional components capable of reacting and / or mixing and foaming under appropriate conditions to foam or a cell structure.
    [086] The present invention further relates to a method for forming a foam comprising: (a) adding to a foaming composition a composition comprising HFO-1234yf of the present invention; and (b) processing the foaming composition under effective conditions to form a foam.
    [087] Another embodiment of the present invention relates to the use of the compositions of the present invention that comprise HFO-1234yf as propellants in spray compositions. In addition, the present invention relates to spray compositions comprising HFO-1234yf. The active ingredient to be sprayed along with inert ingredients, solvents and other materials can also be present in a spray composition. In one embodiment, a spray composition is an aerosol. The present compositions can be used to formulate a variety of industrial aerosols or other spray compositions such as, for example, contact cleaners, dusters, lubricating sprayers, mold release sprayers, insecticides, and the like, and consumer aerosols, such as example personal care products (such as hair sprayers, deodorants, and perfumes), household products (such as waxes, polishes, pot sprayers, room flavorings, and household insecticides), and automotive products (such as, for example, cleaners and polishes), as well as medicinal materials, such as, for example, anti-asthma and anti-halitosis medications. Examples of these include metered dose inhalers (MDIs) for the treatment of asthma and other lung diseases that cause chronic obstruction and for the delivery of medication to accessible mucous membranes or intranasally.
    [088] The present invention further relates to a process for producing aerosol products comprising the step of adding a composition of the present invention comprising HFO-1234yf to a formulation, including active ingredients in an aerosol container, wherein said composition works as a propellant. In addition, the present invention further relates to a process for producing aerosol products comprising the step of adding a composition of the present invention comprising HFO-1234yf to a barrier-type aerosol package (as in a packaging bag type in a can or piston can) in which said composition is kept separate from the other ingredients of the formulation in an aerosol container, and in which said composition functions as a propellant. In addition, the present invention relates further to a process for producing aerosol products comprising the step of adding only one composition of the present invention comprising HFO-1234yf to an aerosol package, in which said composition works as the active ingredient (for example, a duster, or a cooling or freezing spray).
    [089] The compositions described herein that comprise HCO-1230xa, HCFO-1233xf, and HCFC-244bb are useful in methods for preparing HFO-1234yf as described earlier in this document.
    [090] Without further elaboration, it is believed that an element skilled in the art can, using the description contained in this document, use the present invention to its maximum capacity. The following specific achievements should therefore be interpreted as merely illustrative, and do not limit the rest of the description in any way. EXAMPLES GENERAL PROCEDURE FOR PRODUCT ANALYSIS
    [091] The general procedure below is illustrative of the method used for the analysis of fluorination reaction products. A sample of part of the reactor effluent was collected online for the analysis of organic product using a gas chromatograph equipped with a selective mass detector (GC / MS). Gas chromatography used a 6.1 m long x 0.32 cm diameter tube containing perfluorinated polyether sold under the trade name Krytox® by EI du Pont de Nemours and Company (hereinafter “DuPont”) from Wilmington, Delaware in an inert carbon support. The helium flow was 5.0 x 10'7 m ^ / sec (30 ml / min). The gas chromatography conditions were 60 ° C for an initial three-minute containment period followed by a temperature setting at 200 ° C at a rate of 6 ° C / minute. EXAMPLE 1 FLUORATION FROM HCFO-1233XF TO HCFC-244BB
    [092] The contents of a small PTFE bottle containing 20 grams of viscous SbFs were drained into a 400 ml dry Hastelloy® stir tube. The tube was closed and pressurized with nitrogen to test for leaks. The stirring tube was then cooled to less than -40 ° C with dry ice, slowly ventilated, and then evacuated. 75 grams (3.75 moles) of anhydrous HF were condensed into the stir tube followed by 165 grams (1.26 moles) of HCFO-1233xf. The stirring tube was placed on a barricade and the stirring was started.
    [093] The stirring tube was shaken at room temperature (~ 20 to 23 ° C) and the pressure was 246.114 kPa to 273.693 kPa. After 2 hours, the stirring was stopped and 150 ml of water was carefully pumped into the stirring tube. The tube was left overnight and then cooled to 0 to 5 ° C in an ice bath before depressurizing and transferring the contents to a plastic receptacle. The receptacle was kept on ice.
    [094] The contents of the receptacle were poured into a polypropylene separating funnel that contained an amount of ice. The lower organic layer was a light amber color. The organic layer was separated into a glass medium made under the trade name Pyrex® by Corning (Lowell, MA) (hereinafter “Pyrex®”) containing ~ 50 ml of 4 molar phosphate buffer (pH 7) and ice (~ 100 ml). The organic layer was separated again and poured into a bottle of dry Pyrex® medium medium containing a small amount of anhydrous magnesium sulfate. The gross yield was 164.3 grams (about 120 ml, 86%).
    [095] The GC / MS of the raw material showed that it was mainly HCFC-244bb. Other components included 0.16% of 1233xf, and other by-products which totaled 12.2%. EXAMPLE 2 FLUORATION FROM HCFO-1233XF TO HCFC-244BB
    [096] The contents of a small PTFE bottle containing 20 grams of viscous SbFs were drained into a 400 ml dry Hastelloy® stir tube. The tube was closed and pressurized with nitrogen to test for leaks. The stirring tube was then cooled to less than -40 ° C with dry ice, slowly ventilated, and then evacuated. 53 grams (2.65 moles) of anhydrous HF were transferred to a stir tube followed by condensation of 227 grams (1.74 moles) of HCFO-1233xf inside the cooled stir tube. The stirring tube was placed on a barricade and stirring was started.
    [097] The stirring tube was shaken at room temperature (-18 to 21 ° C) and the pressure was 211,641 to 239,220 kPa. After 2 hours the stirring was stopped and 100 ml of water was carefully pumped into the stirring tube. The tube was left overnight and then cooled to 0 to 5 ° C in an ice bath before depressurizing and transferring the contents to a plastic receptacle. The receptacle was kept on ice.
    [098] The contents of the receptacle were poured into a polypropylene separating funnel that contained an amount of ice. The lower organic layer was a light amber color. The organic layer was separated into a glass medium made under the trade name Pyrex® by Corning (Lowell, MA) (hereinafter “Pyrex®”) containing ~ 50 ml of 4 molar phosphate buffer (pH 7) and ice (-100 ml). The organic layer was separated again and poured into a bottle of dry Pyrex® medium containing a small amount of anhydrous magnesium sulphate. The gross yield was 238.8 grams (about 170 ml, 91 %).
    [099] The GC / MS of the raw 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%. EXAMPLE 3
    [0100] Example 3 demonstrates 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.
    [0101] An empty Inconel® tube (1.27 cm (1/2 inch) outside diameter) with a heated zone of about 30.5 cm was heated to a temperature between 500 ° C and 626 ° C, and HFC -244bb was fed at 0.52 ml / hour through a vaporizer adjusted to 40 ° C using N2 sweep of 4.0 x 10'8 m3 (2.4 sccm). The reactor effluent was analyzed using in-line GCMS, and the results are reported in mol percent. TABLE 2
    EXAMPLE 4
    [0102] Example 4 demonstrates 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.
    [0103] An empty Inconel® tube (1.27 cm (1/2 inch) outside diameter) with a heated zone of about 30.5 cm was heated to a temperature of 575 ° C, and HFC-244bb was fed at 0.35 ml / hour through a vaporizer adjusted to 40 ° C using a 6.0 x 10-8 m3 (3.6 sccm) N2 sweep. The reactor was operated continuously for a total of 19 hours, and samples were collected periodically and analyzed to determine the% conversion of HFC-244bb, and selectivity for HFO-1234yf. The reactor effluent was analyzed using in-line GCMS, and the data in Table 6 below is an average of at least two in-line injections at a given condition; percentages are in mol percent. TABLE 3
    EXAMPLE 5
    [0104] Example 5 demonstrates the dehydrochlorination of HCFC-244bb (2-chloro-1,1,1,2-tetrafluoropropane) in the presence of an activated carbon catalyst.
    [0105] An Inconel® tube (1.27 cm (1/2 inch) outside diameter) was filled with 4 cm3 (1.99 g) of carbon based on Calgon acid washed PCB Polynesian coconut shell (mesh 6 to 10). HFC-244bb was fed at 1.04 ml / hour through a vaporizer set at 40 ° C using an N2 scan of 4.0 x 10'8 m3 (2.4 sccm) which gives a total time of contact for about 32 seconds while controlling the reactor temperature at 400 ° C.
    [0106] The data in Table 4 shows the composition of reactor effluent in mol percent for this process performed with an activated carbon catalyst to make HFC-1234yf by eliminating HCI over the period of 7 hours of operation. TABLE 4

    权利要求:
    Claims (8)
    [0001]
    1. COMPOSITION, characterized by comprising HFO-1234yf and at least one additional compound selected from the group consisting of HCFO-1232xf and HCFO-1231xf.
    [0002]
    2. COMPOSITION according to claim 1, characterized in that it comprises HCFO-1232xf.
    [0003]
    3. COMPOSITION according to claim 2, characterized in that it further comprises at least one compound selected from the group consisting of HCFO-1233xf, HCFO-1231xf, HCFC-242dc and HCFC-241db.
    [0004]
    4. COMPOSITION according to claim 1, characterized in that it contains less than 1 weight percent of said additional compound, based on the total weight of the composition.
    [0005]
    5. METHOD FOR PRODUCING COOLING, characterized in that it comprises evaporating a composition, as defined in claim 1, in the vicinity of a body to be cooled, and subsequently condensing said composition.
    [0006]
    6. METHOD FOR PRODUCING HEAT, characterized in that it comprises condensing a composition, as defined in claim 1, in the vicinity of a body to be heated, and subsequently evaporating said compositions.
    [0007]
    7. METHOD FOR FORMING A FOAM, characterized by comprising: (a) adding a composition to a foaming composition, as defined in claim 1; and (b) processing the foaming composition under effective conditions to form a foam.
    [0008]
    8. PROCESS TO PRODUCE AEROSOL PRODUCTS, characterized by comprising the step of adding a composition, as defined in claim 1, to a formulation, including active ingredients in an aerosol container, in which said composition functions as a propellant.
    类似技术:
    公开号 | 公开日 | 专利标题
    US10688329B2|2020-06-23|Compositions comprising 2,3,3,3-tetrafluoropropene, 1,1,2,3-tetra-chloropropene, 2-chloro-3,3,3-trifluoropropene, or 2-chloro-1,1,1,2-tetrafluoropropane
    KR102145804B1|2020-08-19|Compositions comprising 2,3-dichloro-1,1,1-trifluoropropane, 2-chloro-1,1,1-trifluoropropene, 2-chloro-1,1,1,2-tetrafluoropropane or 2,3,3,3-tetrafluoropropene
    AU2016216544B2|2018-03-01|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
    AU2015201437B2|2016-09-08|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
    同族专利:
    公开号 | 公开日
    CA3016991C|2020-10-27|
    AU2010341533A1|2012-06-07|
    US9051500B2|2015-06-09|
    BR122019007817B1|2021-02-23|
    EP3581631A1|2019-12-18|
    US10688329B2|2020-06-23|
    MX2019015438A|2020-02-17|
    SG181873A1|2012-07-30|
    CN102686694B|2015-09-09|
    US20120240477A1|2012-09-27|
    CA3146256A1|2011-07-21|
    MX356473B|2018-05-30|
    JP2013515158A|2013-05-02|
    BR112012015260A2|2017-04-25|
    EP2845891A2|2015-03-11|
    WO2011087825A1|2011-07-21|
    JP2019112648A|2019-07-11|
    US20200282249A1|2020-09-10|
    CA3088186A1|2011-07-21|
    MX351915B|2017-11-03|
    US20150247675A1|2015-09-03|
    SG10201509239XA|2015-12-30|
    CA3091878A1|2011-07-21|
    US20150247674A1|2015-09-03|
    PL2845891T3|2020-04-30|
    ES2762350T3|2020-05-22|
    CA2782592A1|2011-07-21|
    US9308408B2|2016-04-12|
    US20150251033A1|2015-09-10|
    KR20180011354A|2018-01-31|
    KR101983081B1|2019-05-30|
    JP2022028738A|2022-02-16|
    CA3017000A1|2011-07-21|
    JP2020073681A|2020-05-14|
    AU2010341533B2|2015-04-23|
    CA3017000C|2021-04-06|
    JP2018141159A|2018-09-13|
    MX2012007292A|2012-07-04|
    EP2845891A3|2015-09-02|
    CA3016991A1|2011-07-21|
    CN105062427A|2015-11-18|
    HUE047698T2|2020-05-28|
    KR20190058703A|2019-05-29|
    KR20210064415A|2021-06-02|
    MY159904A|2017-02-15|
    US20180214727A1|2018-08-02|
    US20150241095A1|2015-08-27|
    CA2782592C|2019-01-15|
    JP2018031013A|2018-03-01|
    EP2516577A1|2012-10-31|
    MX359549B|2018-10-02|
    CN102686694A|2012-09-19|
    RU2012131170A|2014-01-27|
    MX370726B|2019-12-20|
    SI2845891T1|2020-02-28|
    MX359434B|2018-09-27|
    US9943717B2|2018-04-17|
    EP2845891B1|2019-10-02|
    KR101823169B1|2018-01-29|
    KR20120123355A|2012-11-08|
    JP2021169622A|2021-10-28|
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    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-02-12| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2019-10-08| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2020-07-07| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-11-10| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 22/12/2010, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US28902709P| true| 2009-12-22|2009-12-22|
    US61/289,027|2009-12-22|
    PCT/US2010/061716|WO2011087825A1|2009-12-22|2010-12-22|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|BR122019007817-3A| BR122019007817B1|2009-12-22|2010-12-22|composition, method for producing cooling, method for producing heat, method for forming a foam and process for producing aerosol products|
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