Composition 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

Abstract

To provide a new composition used for refrigerating, air-conditioning and heat pump devices, and a compound having a low global warming potential by new environmental regulations.SOLUTION: The present invention is a composition containing HFO-1234yf, HCFO - 1233xf, and HCFO - 244bb, wherein the total amount of HCFO - 1233xf and HCFO - 244bb is less than 2% by weight.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to heat transfer compositions, aerosol propellants, foaming agents, blowing agents, solvents, cleaners, and the like. Carrier fluids, displacement drying agents, buffing compounds, polymerization media, polyolefins and poly As a urethane expanding agent, gaseous dielectric, fire extinguishing agent and fire extinguishing agent in liquid or gaseous form In particular, the present disclosure relates to the field of compositions useful for 2,3,3,3-tetrafluoroethylene. Hydropropene (HFO-1234yf or 1234yf) or 2,3-dichloro-1, 1,1-trifluoropropane (HCFC-243db or 243db), 2-chloro -1,1,1-trifluoropropene (HCFO-1233xf or 1233xf) or or 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) The present invention relates to compositions useful as heat transfer compositions, such as compositions comprising [Background technology]

[0002] New environmental regulations are driving new compositions for use in refrigeration, air conditioning and heat pump equipment. There has been a need for compounds with low global warming potential. Summary of the Invention [Problem to be solved by the invention]

[0003] Applicant has identified specific Additional compounds were found to be present in small amounts. [Means for solving the problem]

[0004] Therefore, according to the present invention, HFO-1234yf, HFO-1234ze, HFO- 1243zf, HCFC-243db, HCFC-244db, HFC-245cb, H FC-245fa, HCFO-1233xf, HCFO-1233zd, HCFC-25 3fb, HCFC-234ab, HCFC-243fa, ethylene, HFC-23, CF C-13, HFC-143a, HFC-152a, HFO-1243zf, HFC-23 6fa, HCO-1130, HCO-1130a, HFO-1336, HCFC-133 a, HCFC-254fb, HCFC-1131, HFC-1141, HCFO-124 2zf, HCFO-1223xd, HCFC-233ab, HCFC-226ba and and at least one additional compound selected from the group consisting of HFC-227ca. The composition comprises less than about 1 weight percent of at least one additional compound. Contains:

[0005] HCFC-243db, HCFO-1233xf and / or HCFC-244db A composition comprising: , 1234yf, and a composition containing a certain amount of HCFC-243db, HCFO-1233x It may contain HCFC-244db and / or HCFC-244db in addition to other compounds.

[0006] Therefore, according to the present invention, HCFC-243db and ethylene, HFC-23, CFC -13, HFC-143a, HFC-152a, HFO-1234yf, HFO-124 3zf, HFC-236fa, HCO-1130, HCO-1130a, HFO-123 4ze, HFO-1336, HCFC-244bb, HCFC-244db, HFC-2 45fa, HFC-245cb, HCFC-133a, HCFC-254fb, HCFC -1131, HCFO-1233xf, HCFO-1233zd, HCFO-1242z f, HCFC-253fb, HCFO-1223xd, HCFC-233ab, HCFC at least one additional compound selected from the group consisting of HFC-226ba and HFC-227ca and a compound of formula (I). The composition is greater than zero weight percent and is about 99 weight percent. May contain anywhere up to 243db of HCFC-243db.

[0007] Further, according to the present invention, HCFO-1233xf, HCFO-1233zd, HC FO-1232xd, HCFO-1223xd, HCFC-253fb, HCFC-23 3ab, HFO-1234yf, HFO-1234ze, ethylene, HFC-23, CF C-13, HFC-143a, HFC-152a, HFO-1243zf, HFC-23 6fa, HCO-1130, HCO-1130a, HFO-1336, HCFC-244 bb, HCFC-244db, HFC-245fa, HFC-245cb, HCFC-1 33a, HCFC-254fb, HCFC-1131, HCFO-1242zf, HCF O-1223xd, HCFC-233ab, HCFC-226ba and HFC-227 and at least one additional compound selected from the group consisting of The composition contains from greater than zero weight percent to about 99 weight percent HCFO. It may contain -1233xf somewhere.

[0008] Furthermore, according to the present invention, HCFC-244bb, HCFO-1233zd, HCF O-1232xd, HCFO-1223xd, HCFC-253fb, HCFC-233 ab, HFO-1234yf, HFO-1234ze, ethylene, HFC-23, CFC -13, HFC-143a, HFC-152a, HFO-1243zf, HFC-236 fa, HCO-1130, HCO-1130a, HFO-1336, HCFC-244d b, HFC-245fa, HFC-245cb, HFC-245eb, HCFC-133 a, HCFC-254fb, HCFC-1131, HCFO-1242zf, HCFO- 1223xd, HCFC-233ab, HCFC-226ba and HFC-227ca and at least one additional compound selected from the group consisting of: The composition may contain from greater than zero weight percent up to about 99 weight percent HCFC-244b It may contain b anywhere. [Brief explanation of the drawings]

[0009] [Figure 1] FIG. 1 is a schematic diagram showing the reaction for producing HFO-1234yf from 243db. DETAILED DESCRIPTION OF THE INVENTION

[0010] HFO-1234yf has several uses, including refrigeration, heat transfer fluids, and aerospace applications. It has been suggested that HFO-1234yf can be used as a sol spray agent and a foaming expansion agent. , VC Papadimitriou et al., Physical Chemistr y Chemical Physics, 2007, Volume 9, Pages 1-13 As such, it is also known to have a low global warming potential (GWP), which is advantageous. Therefore, HFO-1234yf is a good candidate to replace high GWP saturated HFC refrigerants.

[0011] In one embodiment, the present disclosure provides a method for producing a cyclohexane-1234-methyl-2-propanol (HFO-1234yf)-1234ze (HFO-1234ze). , HFO-1243zf, HCFC-243db, HCFC-244db, HFC-24 5cb, HFC-245fa, HCFO-1233xf, HCFO-1233zd, HC FC-253fb, HCFC-234ab, HCFC-243fa, ethylene, HFC- 23, CFC-13, HFC-143a, HFC-152a, HFC-236fa, HC O-1130, HCO-1130a, HFO-1336, HCFC-133a, HCFC -254fb, HCFC-1131, HFO-1141, HCFO-1242zf, HC FO-1223xd, HCFC-233ab, HCFC-226ba, HFC-227c and at least one additional compound selected from the group consisting of:

[0012] In one embodiment, the total amount of additional compounds in the composition comprising HFO-1234yf is , ranging from greater than zero weight percent to less than 1 weight percent.

[0013] In one embodiment, HCFC-243db, HCFO-1233xf, and HCF The impurities present in C-244bb remain intact during the reaction to produce HFO-1234yf. Therefore, it is included in the additional compounds.

[0014] In other embodiments, the present disclosure provides a method for producing a mixture of HCFC-243db and ethylene, HFC- 23, CFC-13, HFC-143a, HFC-152a, HFO-1234yf, H FO-1243zf, HFC-236fa, HCO-1130, HCO-1130a, H FO-1234ze, HFO-1336, HCFC-244bb, HCFC-244db , HFC-245fa, HFC-245cb, HCFC-133a, HCFC-254f b, HCFC-1131, HCFO-1233xf, HCFO-1233zd, HCFO -1242zf, HCFC-253fb, HCFO-1223xd, HCFC-233a b, at least one selected from the group consisting of HCFC-226ba and HFC-227ca and one additional compound.

[0015] In one embodiment, the total amount of additional compounds in the composition comprising HCFC-243bd is In other embodiments, the range is from greater than zero weight percent to about 99 weight percent. wherein the total amount of the additional compounds ranges from about 1 weight percent to about 80 weight percent. In other embodiments, the total amount of additional compounds is from about 1 weight percent to about 5 In other embodiments, the total amount of additional compounds ranges from about 1 to about 0 percent by weight. In other embodiments, the range is from about 30 weight percent to about 30 weight percent. The total amount of the compounds ranges from about 1 weight percent to about 10 weight percent.

[0016] In one embodiment, the specific precursor compound to HCFC-243db is HCF In other embodiments, the additional compound contains an impurity that appears at C-243db. In another embodiment, HCFC-243 is formed by the reaction of these precursor impurities. The reaction conditions that produce db also produce by-products, which are This means that additional compounds can be produced by alternative reaction pathways depending on the specific conditions used.

[0017] In other embodiments, the present disclosure provides a method for producing HCFO-1233xf and HCFO-123 3zd, HCFO-1232xd, HCFO-1223xd, HCFC-253fb, H CFC-233ab, HFO-1234yf, HFO-1234ze, ethylene, HFC -23, CFC-13, HFC-143a, HFC-152a, HFO-1243zf, HFC-236fa, HCO-1130, HCO-1130a, HFO-1336, HC FC-244bb, HCFC-244db, HFC-245fa, HFC-245cb, HCFC-133a, HCFC-254fb, HCFC-1131, HCFO-1242 zf, HCFO-1223xd, HCFC-233ab, HCFC-226ba, HFC and at least one additional compound selected from the group consisting of: provide.

[0018] In one embodiment, the total amount of additional compounds in the composition comprising HCFO-1233xf ranges from greater than zero weight percent to about 99 weight percent. wherein the total amount of the additional compounds ranges from about 1 weight percent to about 80 weight percent. In other embodiments, the total amount of additional compounds ranges from about 1 weight percent to about In other embodiments, the total amount of additional compounds is in the range of about 50 weight percent. In other embodiments, the range is from 1 weight percent to about 30 weight percent. The total amount of compounds ranges from about 1 weight percent to about 10 weight percent.

[0019] In certain embodiments, the specific precursor compound to HCFO-1233xf is HC In another embodiment, the additional compound is , formed by the reaction of these precursor impurities. The reaction conditions that produce 233xf also produce by-products, such as HCFO-1233x This means that additional compounds can be produced by alternative reaction pathways depending on the specific conditions under which f is produced. do.

[0020] In other embodiments, the present disclosure provides a method for producing a HCFC-244bb and a HCFO-1233 zd, HCFO-1232xd, HCFO-1223xd, HCFC-253fb, HC FC-233ab, HFO-1234yf, HFO-1234ze, ethylene, HFC- 23, CFC-13, HFC-143a, HFC-152a, HFO-1243zf, H FC-236fa, HCO-1130, HCO-1130a, HFO-1336, HCF C-244db, HFC-245fa, HFC-245cb, HFC-245eb, HC FC-133a, HCFC-254fb, HCFC-1131, HCFO-1242zf , HCFO-1223xd, HCFC-233ab, HCFC-226ba, HFC-2 and at least one additional compound selected from the group consisting of 27ca. do.

[0021] In one embodiment, the total amount of additional compounds in the composition comprising HCFC-244bb is In other embodiments, the range is from greater than zero weight percent to about 99 weight percent. wherein the total amount of the additional compounds ranges from about 1 weight percent to about 80 weight percent. In other embodiments, the total amount of additional compounds is from about 1 weight percent to about 5 In other embodiments, the total amount of additional compounds ranges from about 1 to about 0 percent by weight. In other embodiments, the range is from about 30 weight percent to about 30 weight percent. The total amount of the compounds ranges from about 1 weight percent to about 10 weight percent.

[0022] In one embodiment, the specific precursor compound to HCFC-244bb is HCF In other embodiments, the additional compound contains an impurity that appears in C-244bb. In another embodiment, HCFC-244 is formed by the reaction of these precursor impurities. The reaction conditions that produce bb also produce by-products that appear in HCFC-243db, which Depending on the specific conditions, additional compounds may be produced by other reaction pathways to form HCFC-244bb. This means that it can be generated.

[0023] The compositions disclosed herein, including HFO-1234yf, have low global warming potential (GW P) Heat transfer compositions, aerosol propellants, foaming agents, blowing agents, solvents, cleaning agents, rear fluids, displacement drying agents, buffing compounds, polymerization media, polyolefin and polyurethane swelling agents Useful as a gasifier, gas dielectric, fire extinguishing agent and fire suppressant in liquid or gaseous form. The disclosed compositions are useful as working fluids used to transfer heat from a heat source to a heat sink. Such heat transfer compositions may also act as a heat source when the fluid undergoes a phase change, i.e., from liquid to gas. and back or vice versa in a similar cycle.

[0024] Heat transfer systems include, but are not limited to, air conditioners, freezers, refrigerators, Heat pump, water cooler, flooded evaporative cooler, direct expansion cooler, walk-in cooler, possible Examples include mobile refrigerators, mobile air conditioning units, and combinations thereof.

[0025] As used herein, a mobile refrigeration unit, mobile air conditioning unit, or mobile heating unit is defined as a unit that is installed on a road, rail, or , refers to any refrigeration, air conditioning or heating equipment incorporated into a marine or air transport unit Also, mobile refrigeration or air conditioning units must have an "in- Page 11 11 Page 11 ... This includes equipment known as "intermodal" systems. The systems are "vessels (combined sea / land transport)" and "swap bodies (combined sea / land transport)". Combined road / rail transport (combined road / rail transport) is one example.

[0026] As used herein, a fixed heat transfer system refers to a system associated with or attached to a variety of buildings. These stationary applications include (but are not limited to) stationary air conditioning and heat pumps. but not limited to: chillers, high temperature heat pumps, residential, commercial or industrial air conditioning systems, windows, Ductless, ducted, packaged terminal, chiller and rooftop systems connected to buildings In stationary refrigerant applications, the disclosed compositions are suitable for commercial, industrial, and or residential refrigerators and freezers, ice makers, built-in coolers and freezers, flooded evaporative cooling Direct expansion coolers, walk-in and reach-in coolers and freezers and combinations In one embodiment, the disclosed compositions are useful in equipment including systems for combining The composition may be used in supermarket refrigeration systems.

[0027] The compounds that make up the disclosed compositions are shown in Table 1.

[0028] [Table 1]

[0029] HCFC-243db, HCFO-1233xf and HCFC-244bb are nQuest Laboratories, Inc. (Alachua, FL, US A.) and other specialty chemical manufacturers, or as described herein. For example, HCFC-243db, HCFO-123 3xf and HCFC-244bb are specified in International Publication No. 2008 / 05 / 08, published on May 8, 2008. HFO-1243zf non-catalyzed as described in brochure 054782 It can be prepared by chlorination. 244bb is a pamphlet of International Publication No. 2008 / 054781 published on May 8, 2008. It can be prepared by catalytic fluorination of 243 dB as described in The additional compounds present in each disclosed composition will vary depending on the method of manufacture.

[0030] In some embodiments, HCFC-243db, HCFO-1233xf, or HCF Certain precursor compounds to C-244bb may be used in combination with additional compounds in the described compositions. In other embodiments, these precursor compounds themselves contain impurities that appear as During the formation of HCFC-43db, it reacts to form additional compounds that appear in the HCFC-243db composition. In other embodiments, HCFC-243db, HCFO-1233xf or The reaction conditions under which HCFC-244bb is produced also produce by-products. Various reaction pathways occur simultaneously, resulting in the formation of HCFC-243db, HCFO-1233xf, or H This means that compounds other than CFC-244bb are produced. The quantity and identification are HCFC-243db, HCFO-1233xf or HCFC-24 Depends on the specific conditions under which 4bb is generated.

[0031] In one embodiment, HFO-1234yf is produced in a single step from HCFC-243db. In other embodiments, the reaction sequence may be carried out in a stepwise manner. In another embodiment, HCFO-1233xf is produced from HCFC-243db. After synthesis, HCFO-1233xf may be directly converted to HFO-1234yf. In yet another embodiment, HCFC-244bb is produced from HCFC-243db. The HCFC-244bb may then be converted to HFO-1234yf.

[0032] Fluorochlorination of HFO-1243zf In one embodiment, HFO-1243zf is used to produce HCl by fluorochlorination. FC-243db, HCFO-1233xf, HCFC-244db and / or HF HFO-1234yf may be prepared from EI DuPont de Nemours and Company. e Nemours and Company(Wilmington,DE,USA) It is more commercially available.

[0033] The fluorochlorination reaction may be carried out in the liquid phase or the gas phase. For example, the reaction of HFO-1243zf with HF and Cl2 can be carried out in batch, semi-batch, and semi-continuous modes. Alternatively, it may be carried out in a liquid phase reactor operated in continuous mode. HFO-1243zf, Cl2, and HF were added to an autoclave or other suitable reaction vessel. The mixture is mixed in a vessel and heated to the desired temperature.

[0034] In one embodiment, the reaction is carried out in a solvent containing Cl2, HF, and HFO-1243zf. or HFO-1243zf and Cl2 are fed to a liquid phase reactor containing HF. or Cl2, a mixture containing HF and HFO-12 and the reaction product formed by first heating 43zf and HF. In another embodiment, HF and Cl are reacted in a semi-batch mode with The mixture containing FO-1243zf was reacted with HF, Cl2 and HFO-1243zf. and a reaction product formed by reacting the reactant with the reactant. In another embodiment of the liquid phase process, HF, Cl2 and HFO-1243zf are A mixture of HF, HF, Cl2 and HFO-1243zf was reacted in the desired stoichiometric ratio. The reaction product formed by mixing the reactants may be simultaneously fed to a reactor containing the reactants.

[0035] A suitable method for reacting HF and Cl2 with HFO-1243zf in a liquid phase reactor is In one embodiment, a suitable temperature is about 80°C to about 180°C, and in another embodiment, About 100°C to about 150°C. At higher temperatures, HFO-1243zf typically The conversion goes too far.

[0036] The preferred molar ratio of HF to the total amount of HFO-1243zf fed to the liquid phase reactor is In embodiments, it is at least stoichiometric, and in other embodiments, it is about 5:1 to It is noteworthy that the molar ratio of HF to HFO-1243zf is about 8:1 to In an embodiment, the ratio of Cl to the total amount of HFO- fed to the liquid-phase reactor is about 50:1. The preferred molar ratio of 1243zf is about 1:1 to about 2:1.

[0037] The reactor pressure in a liquid phase process is not critical, and in a batch reaction, the reaction is the autogenous pressure of the system at temperature. The pressure of the system is affected by factors such as the replacement of hydrogen substituents by chlorine. and substitution of chlorine substituents by fluorine in starting materials and intermediate reaction products to form chloride hydrochlorides. In a continuous process, the lower boiling products of the reaction, e.g. For example, HCl, HFO-1234yf(CF3CF=CH2), E / Z-1234ze(E / Z-CF3CH=CHF) and HFC-245cb (CF3CF2CH3), optionally Set the reactor pressure so that the gas leaves the reactor through a packed column or condenser. In this way, the high boiling intermediates remain in the reactor and the volatile products are Typical reactor pressures range from about 20 psig (239 kPa) to about 1,000 psig (6.994 kPa).

[0038] In certain embodiments where the reaction is carried out using a liquid phase process, catalysts that may be used include calcium carbonate, methyl ... Carbon, AlF3, BF3, FeCl 3-a F a (wherein a = 0 to 3), carbon-supported FeX3 , SbCl 3-a F a , AsF3, MCl 5-b F b (Wherein b=0 to 5 and M=Sb, Nb, Ta or Mo) and M'Cl 4-c F c(wherein c=0 to 4 and M′=Sn, Ti, Z In another embodiment, the liquid phase process catalyst is MCl 5- b F b (wherein b=0 to 5 and M=Sb, Nb or Ta).

[0039] In another embodiment, the reaction of HFO-1243zf with HF and Cl2 is carried out in the liquid phase. Typically, a heated reactor is used. The reactor may be horizontally or vertically oriented, as well as Many reactions, including the reaction sequence of HFO-1243zf with HF and Cl2, In one embodiment of the present invention, HFO-1243zf is first The resulting mixture may be condensed and supplied as a gas to the reactor.

[0040] In another embodiment of the present invention, HFO-1243zf is reacted with HF and, optionally, Cl. The reaction may be carried out in a pre-reactor prior to the reaction in the gas phase reactor. In embodiments, the pre-reactor may be empty. Suitable fillers, for example, are available from Special Metals Corp. (New Hartford, NY). , New York) under the trademark Monel (registered trademark) (hereinafter "Monel Nickel-copper alloys commercially available under the trademark "Haynes International" ional (Kokomo, Indiana) under the trademark Hastelloy® (hereinafter "Hastelloy®") commercially available nickel-based alloys or Other nickel alloy compositions or wool, or HFO-1243zf and HF vapor Fill with other materials inert to HCl and HF that are well miscible.

[0041] In one embodiment, the suitable temperature of the pre-reactor is about 80°C to about 250°C. In other embodiments, the temperature is from about 100°C to about 200°C. , HFO-1243zf is converted to some extent to highly fluorinated compounds. This results in significant conversion of the HFO-1243zf entering the reactor, and the converted compounds are highly Under these conditions, for example, HF, Cl2 and HFO-1243 The mixture of HCFC-243db and HCFC-244db (CF3CH ClCHF) into a mixture containing

[0042] The degree of fluorination is determined by the chlorine substituents in HFO-1243zf and its chlorination products. The number of fluorine substituents that replace the substituents reflects the number of fluorine substituents. For example, HCFC-253fb is HCC -250fb represents a higher degree of fluorination, and HFO-1243zf is HCO-124 Represents a higher degree of fluorination than 0zf.

[0043] The molar ratio of HF to the total amount of HFO-1243zf in the pre-reactor is, in one embodiment, In this case, the ratio of HF to the total amount of HFO-1243zf is about stoichiometric to about 50:1. In another embodiment, the ratio of HF to the total amount of HFO-1243zf in the pre-reactor is The ratio of HF to total HFO-1243zf is from about 2 times the stoichiometric ratio to about 30:1. In another embodiment, the molar ratio of HF to the total amount of HFO-1243zf is Once present in the reactor, no additional amount of HF is added to the gas phase reaction zone.

[0044] In another embodiment, HFO-1243zf is reacted with Cl in a pre-reactor: Optionally, HF may be present to contact the reaction prior to the reaction in the gas phase reactor.

[0045] The preferred temperature of the pre-reactor in this embodiment of the present invention is about 80°C to about 250°C, preferably The temperature is about 100 to about 200°C. Under these conditions, at least At high temperatures, some of the HCFCs are converted to HFO-1243z. f is highly halogenated.

[0046] The degree of halogenation is determined by the halogen content in the halopropane and / or halopropene products. reflects the total number of fluorine and chlorine substituents. For example, HFO-1234yf is It is more highly halogenated (i.e., 4) than HFO-1243zf (i.e., 3). .

[0047] The molar ratio of Cl to the total amount of HFO-1243zf is, in one embodiment, about 0.5 :1 to about 2:1. In other embodiments, the total amount of Cl to HFO-1243zf is about 1.1:1 to about 1:1.

[0048] In one embodiment, HFO-1243zf is vaporized, optionally in the presence of HF, to form HF and Cl2 are fed to a pre-reactor or gas phase reactor.

[0049] The temperature suitable for the gas phase reaction is about 120°C to about 500°C. A temperature of about 350° C. is preferred for the formation of HFO-1234yf and HFC-245cb. ~A temperature of about 450°C is used for HFO-1234ze, HFC-245fa and HCFO-1 At temperatures between about 250°C and about 450°C, HCFO-1233x is formed. At high temperatures, HFO-1243zf is converted to a large extent, and The resulting compound is highly fluorinated.

[0050] Suitable reactor pressures for gas phase reactors will be from about 1 to about 30 atmospheres. The use of pressures of this order may be advantageous in facilitating the separation of HCl from other reaction products. The reaction time can be varied from about 1 to about 120 seconds, preferably from about 5 to about 60 seconds.

[0051] The molar ratio of HF to the total amount of HFO-1243zf for the gas phase reaction is, in one embodiment, In some cases, the stoichiometric ratio of HF to the total amount of HFO-1243zf ranges from about 50:1; In terms of form, the ratio is about 10:1 to about 30:1.

[0052] In one embodiment, the reaction zone of the gas phase reaction of HF and Cl with HFO-1243zf A catalyst is used in the gas phase reaction. Chlorofluorination catalysts that may be used in the gas phase reaction include carbon , graphite, alumina, fluorinated alumina, aluminum fluoride, carbon-supported aluminum Mina, carbon-supported aluminum fluoride, carbon-supported fluorinated alumina, aluminum fluoride magnesium fluoride, metals (elemental metals, metal oxides, metal halides and and / or other metal salts), metal supported on aluminum fluoride, gold supported on fluorinated alumina Examples include metals, alumina-supported metals and carbon-supported metals, and mixtures of metals.

[0053] Catalyst (optionally alumina, aluminum fluoride, fluorinated alumina or carbon supported) Suitable metals for use as the catalyst include chromium, iron, cobalt, nickel, and ruthenium. , rhodium, palladium, osmium, iridium, platinum, manganese, rhenium, scandium Sodium, yttrium, lanthanum, titanium, zirconium, hafnium, copper, silver, gold , zinc and / or metals with atomic numbers between 58 and 71 (i.e., lanthanide metals) In one embodiment, when used on a support, the total metal content of the catalyst is In other embodiments, the amount of the catalyst is about 0.1 to about 20 weight percent, based on the total weight of the catalyst. In this case, the amount is about 0.1 to about 10 weight percent based on the total weight of the catalyst.

[0054] Suitable chlorofluorination catalysts for gas phase reactions include chromium(III) oxide (Cr2O3), Cr2O3 supported on magnesium halide or zinc halide , carbon-supported chromium(III) halides, optionally graphite-supported chromium and chromium Mixtures of magnesium (elemental metal, metal oxides, metal halides and / or other metals) metal salts), and optionally, graphite, alumina or aluminum fluoride, etc. Mixtures of chromium and other metals supported on aluminum halides (elemental metals, metal oxides) , including metal halides and / or other metal salts).

[0055] Chromium-containing catalysts are well known in the art. They are generally classified as Satt Heterogeneous Catalysis in In Industrial Practice, 2nd edition, pp. 87-112 (McGraw-Hil by either the precipitation method described in (Illegible Text, New York, 1991) or the impregnation method. It can be made.

[0056] Importantly, about 0.05 atomic percent to about 6 atomic percent of the alpha-chromium oxide lattice is trivalent. Crystalline alpha-chromium oxide substituted with alpha atoms and treated with a fluorinating agent. Approximately 0.05 atomic percent to approximately 6 atomic percent of the cobalt-chromium oxide lattice is substituted with trivalent cobalt atoms. at least one chromium-containing component selected from the group consisting of crystalline alpha-chromium oxides; These catalysts, including their preparation, are described in U.S. Pat. It is disclosed in Publication No. 2005 / 0228202.

[0057] Optionally, the metal-containing catalysts described above can be pretreated with HF. This pretreatment is carried out by: For example, the metal-containing catalyst may be placed in a suitable container and then HF may be passed through the metal-containing catalyst. In one embodiment, such a vessel can be used to carry out a chlorofluorination reaction. In one embodiment, the pretreatment time is about 15 to about 3 The pretreatment temperature is about 200°C to about 450°C.

[0058] In one embodiment, the product mixture is HFC-245cb, HFC-245fa, H FO-1234yf, HFO-1234ze, HCFO-1233zd and HCFO- Includes 1233xf.

[0059] In one embodiment, halogenated fluoropropanes with a higher degree of halogenation than pentafluoropropane and / or Halopropane by-products that may be formed in the chlorofluorination reaction include: , CF3CCl2CF3(CFC-216aa), CF3CClFCClF2(CFC-21 6ba), CF3CClFCF3 (CFC-217ba), CF3CF2CClF2 (CFC -217ca), CF3CHFCF3(HFC-227ea), CF3CF2CHF2(HF C-227ca), CF3CClFCHF2(HCFC-226ba), CF3CF2CHC lF(HCFC-226ca), CF3CHClCF3(HCFC-226da), CF3 CCl2CHF2(HCFC-225aa), CF3CClFCHClF(HCFC-22 5ba), CF3CF2CHCl2(HCFC-225ca), CF3CCl2CClF2(C FC-215aa), CF3CClFCCl2F(CFC-215bb), CF3CCl2C Cl2F(HCFC-214ab), CF3CCl2CHClF(HCFC-224aa) and CF3CClFCHCl2 (HCFC-224ba).

[0060] In one embodiment, chlorofluorines of higher halogenation than tetrafluoropropene are Halopropene by-products that may be formed in the polymerization reaction include CF3CCl=CHC l(HCFO-1223xd) is an example.

[0061] In one embodiment, the product is a mixture of HCFC-243db, ethylene, HFC-23, CFC-13, HFC-143a, HFC-152a, HFO-1234yf, HFO- 1243zf, HFC-236fa, HCO-1130, HCO-1130a, HFO- 1234ze, HFO-1336, HCFC-244db, HFC-245fa, HFC -245cb, HCFC-133a, HCFC-254fb, HCFC-1131, HC FO-1233xf, HCFO-1233zd, HCFO-1242zf, HCFC-2 53fb, HCFO-1223xd, HCFC-233ab, HCFC-226ba and and at least one additional compound selected from the group consisting of HFC-227ca. .

[0062] 1. The product mixture produced by the process of the present invention comprises: (i) the product compound HFC-24 5cb, HFC-245fa, HFO-1234yf, HFO-1234ze, HCFO -1233zd and HCFO-1233xf, (ii) HF, HCl and Cl2, ( iii) high boiling by-products, such as CF3CHClCH2Cl (HCFC-243db); CF3CHClCH2F (HCFC-244bb) and (iv) chlorinated by-products, e.g. , including C3HCl3F4, C3HCl2F5, C3HClF6, C3Cl3F5 and C3Cl2F6 In some cases, a separation process, such as distillation, may be used to separate the product compounds from such a product mixture. can be recovered.

[0063] Fluorination of HCFC-243db In one embodiment, HCFC-243db is used to replace HCFC-HCFO-123 3xf, HCFC-244db and / or HFO-1234yf by fluorination These reactions are shown in Figure 1. Fluorination reactions can be carried out in either the liquid or gas phase. For liquid phase embodiments of the present invention, the reaction of HCFC-243db with HF can be The process may be carried out in a liquid phase reactor operated in batch, semi-batch, semi-continuous or continuous mode. In batch mode, the starting HCFC-243db and HF are heated in an autoclave or The components are mixed in a refrigerated or other suitable reaction vessel and heated to the desired temperature.

[0064] In one embodiment, the reaction is carried out by dissolving HF in a liquid phase reactor containing HCFC-243db. or HCFC-243db is fed to a liquid phase reactor containing HF. or HF, a mixture containing HF, and HCFC-243db and HF first The reaction was carried out in semi-batch mode by feeding the reaction mixture to the reactor. In another embodiment, HF is mixed with a mixture of HCFC-243db and HF and and a reaction product formed by reacting HCFC-243db. In another embodiment of the liquid phase process, HF and HCFC may be fed to the reactor. -243db is a mixture of HF and HF and HCFC-243d in the desired stoichiometric ratio. and a reaction product formed by reacting b with each other. Good too.

[0065] A suitable temperature for reacting HF with HCFC-243db in a liquid phase reactor is: In one embodiment, the temperature is about 80°C to about 180°C, and in another embodiment, the temperature is about 100°C to about 180°C. Approximately 150°C. Higher temperatures typically result in more conversion of HCFC-243db. It's too much.

[0066] A suitable molar ratio of HF to HCFC-243db fed to the liquid phase reactor is, in one embodiment, In other embodiments, the ratio is at least stoichiometric, and in other embodiments, the ratio is from about 5:1 to about 100. It is noteworthy that the molar ratio of HF to HCFC-243db is from about 8:1 to about 50: This is an embodiment in which

[0067] The reactor pressure in a liquid phase process is not critical, and in a batch reaction, the reaction The system pressure is the internal pressure of the system at the temperature. As hydrogen chloride is formed by the replacement of chlorine substituents by fluorine in the intermediate reaction product In a continuous process, the lower boiling products of the reaction, e.g., HCl, CF3C F=CH2 and E / Z-CF3CH=CHF are optionally passed through a packed column or condenser. The reactor pressure can be set to allow the reactor to be vented. The high boiling intermediates then remain in the reactor and the volatile products are removed. Pressure: Approximately 20 psig (239 kPa) to approximately 1,000 psig (6.994 kPa) is.

[0068] In certain embodiments where the reaction is carried out using a liquid phase process, catalysts that may be used include calcium carbonate, methyl ... Carbon, AlF3, BF3, FeCl 3-a F a (wherein a = 0 to 3), carbon-supported FeX3 , SbCl 3-a F a , AsF3, MCl 5-b F b (Wherein b=0 to 5 and M=Sb, Nb, Ta or Mo) and M'Cl 4-c F c (wherein c=0 to 4 and M′=Sn, Ti, Z In one embodiment, the catalyst for the liquid phase process is MCl 5-b F b (wherein b=0 to 5 and M=Sb, Nb or Ta).

[0069] In one embodiment, the reaction of HF with HCFC-243db is carried out in the liquid phase. Typically, a heated reactor is used. The reactor can be horizontally or vertically oriented, and the starting materials and HF Many reactor configurations are possible, including a sequence of reactions. In this case, the HCFC-243db may be first vaporized and fed to the reactor as a gas.

[0070] In another embodiment of the present invention, HCFC-243db is reacted with HF in a gas phase reactor. The pre-reactor may be empty, but , preferably a suitable filler, such as those available from Special Metals Corp. (N commercially available from New Hartford, New York under the trademark Monel® Nickel-based alloys such as nickel-copper alloys, Hastelloy®, Other nickel alloy compositions or wool, or HCFC-243db and HF vapor is filled with other materials inert to HCl and HF that are well mixed.

[0071] In one embodiment, the suitable temperature of the pre-reactor is about 80°C to about 250°C. In other embodiments, the temperature is from about 100°C to about 200°C. , HCFC-243db is converted to some extent into highly fluorinated compounds. This means that the HCFC-243db entering the reactor is significantly converted, and the converted compounds are highly Under these conditions, for example, a mixture of HF and HCFC-243db are mainly HF, HCl, HCFC-243db, HCFC-244db (CF3CHC HClO-1233xf) into a mixture containing HClO-1233xf.

[0072] The degree of fluorination is determined by the chlorine content in HCFC-243db and their fluorination products. It reflects the number of fluorine substituents that replace the substituent. For example, HFO-1234yf is HC It represents a higher degree of fluorination than FO-1233xf.

[0073] The molar ratio of HF to the total amount of HCFC-243db in the pre-reactor is, in one embodiment, In this case, the ratio of HF to total HCFC-243db is about stoichiometric to about 50:1. In another embodiment, the ratio of HF to the total amount of HCFC-243db in the pre-reactor is The ratio of HF to total HCFC-243db is from about 2 times the stoichiometric ratio to about 30:1. In another embodiment, the molar ratio of the amount of HF to HCFC-243db is When present, no additional amount of HF is added to the gas phase reaction zone.

[0074] In another embodiment, the HCFC-243db and HF are vaporized and introduced into a pre-reactor. , or fed to a gas phase reactor.

[0075] The temperature suitable for the gas phase reaction is about 120°C to about 500°C. Range temperature: HFO-1234yf, HFC-245cb and HCFO-123 A temperature in the range of about 350°C to about 450°C is preferred for the formation of 3xf. e, HFC-245fa and HCFO-1233zd. CFC-243db is converted to a large extent and the resulting compounds are highly fluorinated. Reactor temperatures of 50°C to approximately 275°C promote the formation of HCFO-1233xf as the main product. Preferred.

[0076] Suitable reactor pressures for gas phase reactors will be from about 1 to about 30 atmospheres. The use of pressures of this order may be advantageous in facilitating the separation of HCl from other reaction products. The reaction time can be varied from about 1 to about 120 seconds, preferably from about 5 to about 60 seconds.

[0077] The molar ratio of the amount of HF to HCFC-1243zf for the gas phase reaction is in one embodiment In some embodiments, the ratio of HF to HCFC-243db is from about stoichiometric to about 50:1, and in other embodiments, In this case, the ratio is about 10:1 to about 30:1.

[0078] In one embodiment, in the reaction zone of the gas phase reaction of HF and HCFC-243db Catalysts are used. Fluorination catalysts that may be used in the gas phase reaction include carbon, graphite, Alumina, fluorinated alumina, aluminum fluoride, carbon-supported alumina, carbon-supported Aluminum fluoride, carbon-supported fluorinated alumina, aluminum fluoride-supported fluorinated Magnesium, metals (elemental metals, metal oxides, metal halides and / or other metals) metal salts), aluminum fluoride-supported metals, fluorinated alumina-supported metals, alumina-supported metals Metals and carbon-supported metals, and mixtures of metals are included.

[0079] Catalyst (optionally alumina, aluminum fluoride, fluorinated alumina or carbon supported) Suitable metals for use as the catalyst include chromium, iron, cobalt, nickel, and ruthenium. , rhodium, palladium, osmium, iridium, platinum, manganese, rhenium, scandium Sodium, yttrium, lanthanum, titanium, zirconium, hafnium, copper, silver, gold , zinc and / or metals with atomic numbers between 58 and 71 (i.e., lanthanide metals) In some embodiments, when used on a support, the total metal content of the catalyst is In other embodiments, the amount is about 0.1 to about 20 weight percent based on the total weight of the catalyst. In this case, the amount is about 0.1 to about 10 weight percent based on the total weight of the catalyst.

[0080] In the present invention, a typical fluorination catalyst for the gas phase reaction is chromium(III) oxide ( Cr2O3), Cr2O3-supported magnesium halide, zinc halide, and other metals. Cr2O3, carbon-supported chromium(III) halides, optionally graphite-supported chromium(III) halides Mixtures of chromium and magnesium (elemental metals, metal oxides, metal halides and / or or other metal salts), and optionally graphite, alumina or aluminum fluoride Mixtures of chromium and other metals supported on aluminum halides such as aluminum (elemental metals) , metal oxides, metal halides and / or other metal salts).

[0081] Chromium-containing catalysts are well known in the art. They are generally classified as Satt Heterogeneous Catalysis in In Industrial Practice, 2nd edition, pp. 87-112 (McGraw-Hil by either the precipitation method described in (Illegible Text, New York, 1991) or the impregnation method. It can be made.

[0082] Importantly, about 0.05 atomic percent to about 6 atomic percent of the alpha-chromium oxide lattice is trivalent. Crystalline alpha-chromium oxide substituted with alpha atoms and treated with a fluorinating agent. Approximately 0.05 atomic percent to approximately 6 atomic percent of the cobalt-chromium oxide lattice is substituted with trivalent cobalt atoms. at least one chromium-containing component selected from the group consisting of crystalline alpha-chromium oxides; These catalysts, including their preparation, are described in U.S. Patent Application Publication No. This is disclosed in patent application 2005 / 0228202.

[0083] Optionally, the metal-containing catalysts described above can be pretreated with HF. This pretreatment is carried out by: For example, the metal-containing catalyst may be placed in a suitable container and then HF may be passed through the metal-containing catalyst. In one embodiment, such a vessel can be used to carry out the fluorination reaction in the present invention. Typically, the pretreatment time is about 15 to about 30 minutes. The pretreatment temperature is about 200°C to about 450°C.

[0084] In one embodiment of the present invention, the product mixture is HFC-245cb, HFC-245 fa, HFO-1234yf, HFO-1234ze, HCFO-1233zd and H Includes CFO-1233xf.

[0085] Fluorination of HCFO-1233xf In one embodiment, HCFO-1233xf is used to 4bb and / or HFO-1234yf may be prepared by fluorination. The reaction is shown in Figure 1.

[0086] In one embodiment, the reaction of HCFO-1233xf to HCFC-244bb is carried out in a liquid In other embodiments, the reaction may be carried out in the gas phase.

[0087] In one embodiment, the reaction of HCFO-1233xf to HCFC-244bb is In other embodiments, the reaction may be carried out in a continuous mode.

[0088] In one embodiment, the liquid phase reaction of HCFO-1233xf to HCFC-244bb is In one embodiment, the catalyst may be a Lewis acid catalyst. In one embodiment, the catalyst may be a metal halide catalyst. The catalysts are antimony halides, tin halides, thallium halides, iron halides, At least one selected from the group consisting of fluorides and combinations of two or more thereof In another embodiment, the catalyst may be antimony pentachloride (SbCl5). , antimony trichloride (SbCl3), antimony pentafluoride (SbF5), tin tetrachloride (SnC l4), titanium tetrachloride (TiCl4), iron trichloride (FeCl3) and combinations thereof In some embodiments, the reaction may be carried out in a liquid phase. The reaction may be carried out with any of the known fluorination catalysts for the phase reaction.

[0089] In one embodiment, the reaction of HCFO-1233xf to HCFC-244bb is It may be carried out without a solvent.

[0090] In one embodiment, the vapor phase reaction of HCFO-1233xf to HCFC-244bb is In one embodiment, the reaction is carried out in the presence of a chromium-based catalyst, an iron-based catalyst, or the like. In one embodiment, the reaction may be carried out in the presence of a chromium-based catalyst or a combination thereof. The catalyst is a chromium oxide (e.g., Cr2O3). In one embodiment, the iron-based catalyst is It may be bone-supported FeCl3.

[0091] In one embodiment, the vapor phase reaction of HCFO-1233xf to HCFC-244bb is , carried out without a catalyst.

[0092] Dehydrochlorination of HCFC-244bb In one embodiment, the dehydrochlorination of HCFC-244bb is used to Produce 34yf.

[0093] In one embodiment, dehydrochlorination of HCFC-244bb to HFO-1234yf is carried out in the gas phase.

[0094] In one embodiment, the 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. The catalyst may be activated carbon, a nickel-based catalyst, a palladium-based catalyst, or any of these catalysts. In one embodiment, the catalyst may be selected from any combination of Ni-mesh, Carbide, and Ni-based polymers. Palladium supported on carbon, palladium supported on aluminum oxide, or a combination thereof. The compound may be selected from the group consisting of:

[0095] In one embodiment, HFO-1234yf is used in the thermal dehydrochlorination of HCFC-244bb. In one embodiment, this reaction is carried out without a catalyst. In this state, HCFC-244bb is subjected to thermal dechlorination and hydrogenation of HCFC-244bb. In one embodiment, the temperature is at least It is sufficient to carry out the thermal dechlorination of HCFC-244bb up to a percent conversion of 50%. In other embodiments, the temperature is increased to at least 65% percent conversion. High enough to carry out the thermal dechlorination of CFC-244bb. The temperature is set to at least 80% for thermal dechlorination of HCFC-244bb. In yet another embodiment, the temperature is at least 12 hours. For continuous operation between HCFC-244bb up to a percent conversion of at least 70% is high enough to carry out the thermal dechlorination hydrogenation of

[0096] In one embodiment, HCFC-244bb is heated at a temperature in the range of about 500°C to about 700°C. In another embodiment, the temperature of the reaction vessel is about 500° C. In yet another embodiment, the temperature of the reaction vessel is maintained in the range of H Thermal decomposition of CFC-244bb to HFO-1234yf is achieved with a selectivity of over 80%. In yet another embodiment, the temperature of the reaction vessel is maintained at a temperature high enough to The thermal decomposition of HCFC-244bb to HFO-1234yf must be at least 85% selective. The temperature is maintained high enough to

[0097] In one embodiment, the reaction zone is a reaction vessel constructed of corrosion-resistant materials. In some forms, these materials are alloys, such as Hastelloy®. Nickel-based alloy, Inconel (registered trademark) from Special Metals Corp. Nickel-based alloys commercially available under the trade name Inconel® (hereinafter "Inconel®"). Chrome alloys, or Special Metals Corp. (New Hartford nd, New York under the trade name Monel®. Includes vessels with nickel-copper alloy or fluoropolymer linings.

[0098] In one embodiment, HCFC-244bb is heated to a temperature of about 30°C to about 100°C in air. In another embodiment, HCFC-244bb is preheated in a refrigerant at a temperature of about 30°C to about 80°C. Preheat in a vaporizer to a temperature of

[0099] In one embodiment, the inert diluent gas is a carrier gas for HCFC-244bb. In one embodiment, the carrier gas selected is nitrogen, argon, helium, or sodium or carbon dioxide.

[0100] Without further elaboration, it is believed that one skilled in the art can, using the description herein, utilize the present invention to its fullest extent. It is therefore contemplated that the following specific embodiments may be construed as merely illustrative and not restrictive of the scope of the disclosure. It is not intended to constrain the remainder of the content in any way. [Example]

[0101] Basic steps for product analysis The following general procedure is illustrative of the method used to analyze the products of the fluorination reaction. A portion of the total effluent from the reactor was analyzed by a gas chromatograph equipped with a mass selective detector (GC / M S) was used for online sampling for organic product analysis. For roughy, an inert carbon-supported EI at Wilmington, Delaware .du Pont de Nemours and Company (hereinafter “DuPon perfluorinated polyethers sold under the trade name Krytox® by Use a 20-foot (6.1 m) long x 1 / 8-inch (0.32 cm) diameter pipe containing the The helium flow was 30 mL / min (5.0 × 10 -7 m 3 / sec). Chromatography conditions were 60°C for an initial hold period of 3 minutes, followed by 2 minutes at a rate of 6°C / minute. The temperature was programmed to 00°C.

[0102] Preparation of 98% chromium / 2% cobalt catalyst 784.30 g Cr(NO3)3[9(H2O)] (1.96 mol) and 11.6 A solution of 4 grams Co(NO3)2[6(H2O)] (0.040 mol) was added to 2000 mL of decanter. The solution was prepared in deionized water. The solution was diluted with 950 mL of 7.4 M water until the pH reached approximately 8.5. The slurry was stirred overnight at room temperature and then heated to 110-120°C. The dried catalyst was evaporated to dryness at 400°C for 24 hours in air before use. Grilled.

[0103] Legend 243db is CF3CHClCH2Cl, 244db is CF3CHClCH2F, 245cb is CF3CF2CH3, 245fa is CF3CH2CHF2, 1234yf is CF3CF=CH2, 1233xf is CF3CCl=CH2, 1243zf is CH2=CHCF3, 233ab is CF3CCl2CH2Cl, 1233zd is E- and / or Z-CHCl=CHCF3, 226ba is CF3CClFCHF2, 1234ze is E- and / or Z-CHF=CHCF3, 227ca is CF3CF2CHF2, 1223xd is E- and / or Z-CF3CCl=CHCl, 244bb is CF3CFClCH3, 1141 is CHF=CH2.

[0104] Examples 1 to 6 Chlorofluorination of HFO-1243zf 98% chromium / 2% cobalt catalyst (21.4 grams, 15 ml) prepared as described above L, -12 to +20 mesh (1.68 to 0.84 mm) heated in a fluidized bed sand bath 5 / 8" (1.58cm) diameter Inconel® (Special M etals Corp. (New Hartford, New York) Nickel Alloy The catalyst was pre-fluorinated by treatment with HF as follows: Heat from 45°C to 175°C for approximately 1.5 hours with nitrogen flow (50cc / min). HF was added to the reactor at a flow rate of 50 cc / min for 1.3 hours at a temperature of 175°C. The reactor nitrogen flow was reduced to 20 cc / min and the HF flow was increased to 80 cc / min. The reactor temperature was increased to 400°C over 1 hour. After this period, the HF and nitrogen flows were stopped and the reactor was brought to the desired operating temperature. The flow of HF vapor, HFO-1243zf, and Cl2 into the reactor was started. A portion of the reactor effluent was analyzed by online GC / MS.

[0105] At various operating temperatures and the indicated molar ratios of HF, HFO-1243zf, and Cl2 The results of the chlorofluorination of HFO-1243zf over 98 / 2Cr / Co catalyst are shown in Table 2 Analytical data are given in units of GC area %. The nominal catalyst bed volume was 15 cc, and the contact time was The reaction time (CT) was 15 seconds. Examples 1 and 2 were carried out without a catalyst.

[0106] [Table 2]

[0107] [Table 3]

[0108] Examples 7 to 11 Fluorination of HCFC-243db 98% chromium / 2% cobalt catalyst (21.4 grams, 15 ml) prepared as described above L, -12 to +20 mesh (1.68 to 0.84 mm) heated in a fluidized bed sand bath 5 / 8" (1.58 cm) diameter Inconel® nickel alloy reactor The catalyst was pre-fluorinated by treatment with HF as follows: The catalyst was heated to 45°C. The mixture was heated to 75°C for approximately 1.5 hours with nitrogen flow (50 cc / min). The reactor was loaded at a temperature of 175° C. for 1.3 hours at a flow rate of 50 cc / min. The reactor nitrogen flow was reduced to 20 cc / min and the HF flow was increased to 80 cc / min. The flow was maintained for 0.3 hours. The reactor temperature was gradually increased to 400°C over 1 hour. After this period, the HF and nitrogen flows were stopped and the reactor was allowed to reach the desired operating temperature. The flow of HF vapor and HCFC-243db (CF3CHClCH2Cl) into the reactor A portion of the reactor effluent was analyzed by online GC / MS.

[0109] 98 / 2 at various operating temperatures and the indicated molar ratios of HF and HCFC-243db The results of the fluorination of HCFC-243db over the Cr / Co catalyst are shown in Table 3. The analytical data are , expressed in units of GC area %. The nominal catalyst bed volume is 15 cc and the contact time (CT) is 1 5 seconds. Example 7 was run without a catalyst.

[0110] [Table 4]

[0111] Example 12 Reaction of HFC-243db with HF in the presence of TaF5 In a 210 mL Hastelloy® C tube, add 10.0 grams (0.0599 100 g (0.040 mol) of HCFC-243db and 25.4 g (0.040 mol) of tungsten pentafluoride Next, 40.0 grams (2.0 moles) of hydrogen fluoride was added to the tube. The tube was heated to 150°C and held at 149-150°C for 8 hours with shaking. The tube was emptied and the small organic phase was collected and neutralized. The sample was 91.1% unconverted HCFC-243db, and GC-MS analysis of the conversion products was as follows:

[0112] [Table 5]

[0113] Example 13 Fluorination of HCFO-1233xf to HCFC-244bb The contents of a small PTFE vial containing 20 grams of viscous SbF5 are added to 400 mL of dry H The tube was closed and flushed with nitrogen for leak testing. The shaker tube was cooled to below -40°C with dry ice and slowly released before being vented. 75 grams (3.75 moles) of anhydrous HF, then 165 grams (1.26 moles) of ) of HCFO-1233xf was condensed into a shaking tube. The shaking tube was placed in a barricade and shaken. We started working on this.

[0114] The shaker tube was stirred at ambient temperature (~20-23°C) and the pressure was 21-25 psig. After 2 hours, the shaking was stopped and 150 mL of water was carefully poured into the shaker tube. The tube was left overnight. Allow to stand, then cool in an ice bath to 0-5°C before decompressing the contents and transferring them to a plastic container. The container was kept on ice.

[0115] The contents of the vessel were poured into a polypropylene separatory funnel containing some ice. The appearance of the lower organic layer was: The organic layer was light amber in color. from Corning (Lowell, MA) with buffer and ice (~100 mL). Sold under the trademark Pyrex® (hereinafter "Pyrex®") The organic layer was separated again and added a small amount of anhydrous magnesium sulfate. The crude yield was 164. The volume was 3 grams (approximately 120 mL, 86%).

[0116] GC / MS of the crude material showed it to be mostly HCFC-244bb. Other ingredients are 0.13% 245cb, 0.09% 245eb, 0.16% 1233xf and and other by-products totaling 12.2%.

[0117] Example 14 Fluorination of HCFO-1233xf to HCFC-244bb The contents of a small PTFE vial containing 20 grams of viscous SbF5 were poured into a dry 400-mL The tube was closed and filled with nitrogen for leak testing. The shaker tube was cooled to below -40°C with dry ice and then slowly released. 53 grams (2.65 moles) of anhydrous HF was transferred to the shaker tube, followed by 227 grams. 1.74 moles of HCFO-1233xf was condensed into a cooled shaker tube. The tube was placed in the barricade and shaking commenced.

[0118] The shaker tube was stirred at ambient temperature (approximately 18-21°C) and the pressure was 16-20 psig. After 2 hours, the shaking was stopped and 100 mL of water was carefully poured into the shaker tube. The tube was left overnight. Allow to stand, then cool in an ice bath to 0-5°C before decompressing the contents and transferring them to a plastic container. The container was kept on ice.

[0119] The contents of the vessel were poured into a polypropylene separatory funnel containing some ice. The appearance of the lower organic layer was: The organic layer was light amber in color. The organic layer was washed with approximately 50 mL of 4 molar (pH 7) phosphate buffer. Transfer the mixture to a Pyrex® media bottle containing water and ice (approximately 100 mL). The organic layer was again separated and washed with dry Pyrex (R) containing a small amount of anhydrous magnesium sulfate. The crude yield was 238.8 g (approximately 170 mL, 91%). there were.

[0120] GC / MS of the crude material showed it to be mostly HCFC-244bb. Other components are 0.11% HFC-245cb, 0.10% HFC-245eb, 0.26 %HCFO-1233xf and other by-products totaling 9.7%.

[0121] Example 15 Example 15 is HCFC-244bb (2-chloro-1,1,1,2-tetrafluoroethylene) Catalysis of HFO-1234yf (2,3,3,3-tetrafluoropropene) This shows the conversion without a catalyst.

[0122] Heating zone approximately 12 inches of empty Inconel® pipe (1 / 2 inch OD) The mixture was heated to a temperature of 500°C to 626°C, and HFC-244bb was added at a rate of 0.52 mL / hour. , 2.4 sccm (4.0 × 10) through a vaporizer set at 40 °C. -8 m 3 )'s N2 The reactor effluent was analyzed by online GSMS. The results were expressed as mole fractions. It is recorded as a percentage.

[0123] [Table 6]

[0124] Example 16 Example 16 is HCFC-244bb (2-chloro-1,1,1,2-tetrafluoroethylene) Catalysis of HFO-1234yf (2,3,3,3-tetrafluoropropane) This shows the conversion without a catalyst.

[0125] Heating zone approximately 12 inches of empty Inconel® pipe (1 / 2 inch OD) The mixture was heated to 575°C, and HFC-244bb was added at 0.35 mL / hr under a pressure set at 40°C. 3.6 sccm (6.0 × 10 -8 m 3 ) supplied with an N2 sweep The reactor was operated continuously for a total of 19 hours, with samples taken periodically and analyzed to determine the HFC The % conversion of -244bb and selectivity to HFO-1234yf were determined. The material was analyzed using online GCMS. The data in Table 6 below shows the results under the given conditions. is the average of at least two online injections of do.

[0126] [Table 7]

[0127] Example 17 Example 17 is HCFC-244bb (2-chloro-1,1,1,2-tetrafluoroethylene) This shows the dehydrochlorination of propane in the presence of an activated carbon catalyst.

[0128] Inconel® tubing (1 / 2 inch OD) was filled with 4 cc (1.99 gm) of acid. Polynesian coconut shell PCB made of Calgon (6-10 mesh) washed with water HFC-244bb was pumped at 1.04 mL / hour through a gas atmosphere set at 40°C. Through the condenser, 2.4 sccm (4.0 × 10 -8 m 3 ) N2 sweep was used to supply The actor temperature was controlled at 400°C, and the total contact time was approximately 32 seconds.

[0129] According to the data in Table 7, over a 7-hour operating period, HFC-1 The mole fraction for this process carried out over activated carbon catalyst to produce 234yf was 1 shows the reactor effluent composition in cents. The present invention includes the following embodiments. 1. HFO-1234yf, HFO-1234ze, HFO-1243zf, HCFC -243db, HCFC-244db, HFC-245cb, HFC-245fa, HC FO-1233xf, HCFO-1233zd, HCFC-253fb, HCFC-23 4ab, HCFC-243fa, ethylene, HFC-23, CFC-13, HFC-14 3a, HFC-152a, HFC-236fa, HCO-1130, HCO-1130a , HFO-1336, HCFC-133a, HCFC-254fb, HCFC-1131 , HFO-1141, HCFO-1242zf, HCFO-1223xd, HCFC-2 a small amount selected from the group consisting of HCFC-33ab, HCFC-226ba and HFC-227ca and at least one additional compound. 2. The composition of claim 1 containing less than about 1 weight percent of said at least one additional compound. The composition described. 3. HCFC-243db, ethylene, HFC-23, CFC-13, HFC-143 a, HFC-152a, HFO-1234yf, HFO-1243zf, HFC-236 fa, HCO-1130, HCO-1130a, HFO-1234ze, HFO-133 6, HCFC-244bb, HCFC-244db, HFC-245fa, HFC-24 5cb, HCFC-133a, HCFC-254fb, HCFC-1131, HCFO- 1233xf, HCFO-1233zd, HCFO-1242zf, HCFC-253f b, HCFO-1223xd, HCFC-233ab, HCFC-226ba and HF and at least one additional compound selected from the group consisting of C-227ca. . 4.HCFO-1233xf, HCFO-1233zd, HCFO-1232xd, H CFO-1223xd, HCFC-253fb, HCFC-233ab, HFO-123 4yf, HFO-1234ze, ethylene, HFC-23, CFC-13, HFC-14 3a, HFC-152a, HFO-1243zf, HFC-236fa, HCO-113 0, HCO-1130a, HFO-1336, HCFC-244bb, HCFC-244 db, HFC-245fa, HFC-245cb, HCFC-133a, HCFC-25 4fb, HCFC-1131, HCFO-1242zf, HCFO-1223xd, HC Selected from the group consisting of FC-233ab, HCFC-226ba and HFC-227ca and at least one additional compound. 5.HCFC-244bb, HCFO-1233zd, HCFO-1232xd, HC FO-1223xd, HCFC-253fb, HCFC-233ab, HFO-1234 yf, HFO-1234ze, ethylene, HFC-23, CFC-13, HFC-143 a, HFC-152a, HFO-1243zf, HFC-236fa, HCO-1130 , HCO-1130a, HFO-1336, HCFC-244db, HFC-245fa , HFC-245cb, HFC-245eb, HCFC-133a, HCFC-254f b, HCFC-1131, HCFO-1242zf, HCFO-1223xd, HCFC HCFC-233ab, HCFC-226ba, and HFC-227ca and at least one additional compound.

[0130] [Table 8]

Claims

1. A compound containing HFO-1234yf, HCFO-1233xf, and HCFO-244bb The total amount of HCFO-1233xf and HCFO-244bb is less than 2% by weight. A composition that is

2. 10. Use of the composition of claim 1 as a refrigerant.

3. Air conditioning, freezers, refrigerators, heat pumps, water coolers, flooded evaporative coolers, direct expansion coolers, Centrifugal coolers, walk-in coolers, mobile refrigerators, mobile air conditioning units and the like 10. Use of the composition of claim 1 as a refrigerant in combination with

4. 10. Use of the composition of claim 1 as an aerosol propellant.

5. 10. Use of the composition of claim 1 as a foaming agent.

6. 10. A method of using the composition of claim 1, comprising transferring heat from a heat source to a heat sink. 。

7. 1 as a refrigerant in a cycle containing a composition that undergoes a phase transition from liquid to gas and back. and a method of using the composition.

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