A composition comprising 1224yd and 1233xf, and at least one additional compound selected from the group consisting of 1234yf and 1243zf.

Abstract

The object of this invention is to provide a composition useful for the synthesis of 2,3,3,3-tetrafluoropropene (1234yf). [Solution] The present invention relates to a composition comprising at least one additional compound selected from the group consisting of 1224yd, 1233xf, and 1234yf, 1243zf, wherein the amount of 1224yd is in the range of 90% to 99.99%.

Description

Technical Field

[0001] (Related Applications) This application claims the benefit of Application No. 62 / 870653, filed on July 3, 2019. The disclosure of Application No. 62 / 870653 is incorporated herein by reference.

[0002] (Field of the Invention) The present invention relates to a method for synthesizing hydrofluoro-olefins (HFO). More particularly, the present invention relates to compositions and methods for the synthesis of 2,3-dichloro-1,1,1,2-tetrafluoropropane and 2,3,3,3-tetrafluoropropene.

Background Art

[0003] Hydrofluorocarbons (HFCs), such as hydrofluoroolefins, have been disclosed as effective refrigerants, fire extinguishing agents, heat transfer media, propellants, foaming agents, blowing agents, gaseous dielectrics, sterilant carriers, polymerization media, particulate removal fluids, dispersion media, buffing abrasives, replacement desiccants, and power cycle working fluids. Hydrofluoro-olefins have replaced chlorofluorocarbons and hydrochlorofluorocarbons, which have the potential to destroy the Earth's ozone layer. Hydrofluoro-olefins do not contain chlorine and thus do not destroy the Earth's ozone layer. Furthermore, hydrofluoro-olefins have a lower global warming potential compared to hydrofluorocarbons, thereby reducing the CO2 equivalent footprint.

[0004] 2,3,3,3-Tetrafluoropropene (1234yf) is an environmentally friendly hydrofluoro-olefin used as a replacement for various chlorofluorocarbons and hydrochlorofluorocarbons. The conventional production of 2,3,3,3-tetrafluoro-2-propene (1234yf) generally focuses on two synthetic routes.

[0005] The first conventional route involves a step in which a strong Lewis catalyst, such as an antimony catalyst (e.g., Sb+5), converts 2-chloro-3,3,3-trifluoropropene (1233xf) to 2-chloro-1,1,1,2-tetrafluoropropane (244bb), and then converts 244bb to 2,3,3,3-tetrafluoropropene (1234yf). Antimony halide catalysts and their combinations with HF are highly corrosive to process equipment, making process operation difficult. Antimony halide catalysts are also expensive to procure.

[0006] A second conventional route for converting 2-chloro-3,3,3-trifluoropropene (1233xf) to 2,3,3,3-tetrafluoro-2-propene (1234yf) proceeds by catalytic gas-phase hydrofluorication. This process has low yield and low selectivity. Numerous undesirable byproducts are formed, and thorough purification of 2,3,3,3-tetrafluoropropene (1234yf) is required before use. [Overview of the project] [Problems that the invention aims to solve]

[0007] on the other hand, 1-Chloro-2,3,3,3-tetrafluoropropene (1224yd) was also developed as a new low-GWP non-flammable refrigerant. Therefore, the object of the present invention is to provide a composition containing 1224yd as the main component, which improves cooling capacity (CAP_c) and heating capacity (CAP_h) compared to conventional compositions without significantly reducing cooling efficiency (COP_c) and heating efficiency (COP_h). [Means for solving the problem]

[0008] In one embodiment, a composition is disclosed herein comprising 1224yd, 1233xf, and at least one additional compound selected from the group consisting of 1234yf and 1243zf, wherein the amount of 1224yd is in the range of 90 to 99.99% by weight based on the total amount of the composition, and in the composition, the amount of the additional compound is in the range of 5 ppm to 8% by weight based on the total amount of the composition, or the amount of the additional compound is in the range of 20 ppm to 1% by weight based on the total amount of the composition.

[0009] In another embodiment, a composition comprising 1224yd, 1233xf, and 1243zf is disclosed herein, wherein the amount of 1224yd is in the range of 90 to 99.99% by weight based on the total amount of the composition, and the amount of 1243zf is in the range of 20 ppm to 1% by weight based on the total amount of the composition.

[0010] The various modes and embodiments of this disclosure can be used individually or in combination with each other. Other features and advantages of the present invention will become apparent from the following more detailed description, which illustrates the principles of the invention as an example. [Modes for carrying out the invention]

[0011] The above general description and the following "Modes for Carrying Out the Invention" are merely illustrative and descriptive, and do not limit the present invention.

[0012] When used herein, “comprises,” “comprising,” “includes,” “including,” “has,” “having,” or any other variation thereof shall deal with non-exclusive inclusion. For example, a process, method, article, or apparatus that includes a list of elements may include other elements that are not expressly described for or specific to such process, method, article, or apparatus, and are not necessarily limited to these elements. Furthermore, unless the opposite is expressly stated, “or” means exclusive or non-exclusive inclusive. For example, condition A or B is satisfied by any one of the following: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); and both A and B are true (or exist).

[0013] The transitional phrase "consisting of" excludes any unspecified elements, processes, or components. In the context of claims, such phrase excludes the inclusion of materials other than those listed, except for impurities normally associated with the materials. If the phrase "consisting of" appears in a clause of the claim rather than immediately following the preamble, it limits the elements to those specified in that clause only, and does not exclude other elements from the claim as a whole.

[0014] The transitional phrase "consisting essentially of" is used to define compositions and methods that include materials, processes, features, components, or elements in addition to those literally disclosed, provided that these additionally included materials, processes, features, components, or elements substantially influence the fundamental and novel characteristics of the claimed invention, particularly the mode of action for achieving any desired result of any of the processes of the invention. The term "consisting essentially of" has an intermediate meaning between "including" and "consisting of."

[0015] If applicants define an invention or part thereof using non-restrictive terms such as "includes," it should be readily understood that (unless otherwise specified) such descriptions should also be interpreted as including inventions that use the terms "essentially consist of" or "consist of."

[0016] Furthermore, the use of "a" or "an" is used to describe the elements and components described herein. This is done solely for convenience and to give a general sense of the scope of the invention. This description should be interpreted as including one or at least one, and the singular form also includes the plural form unless it is evident that it has a different meaning.

[0017] As used herein, the term "selectivity" means the ratio, expressed as a percentage, of the number of moles of the desired product to the number of moles of the undesired product.

[0018] As used herein, the term "yield" means the amount of product produced, based on the amount of limiting reagent, as a percentage of the theoretical maximum amount of product.

[0019] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art in which the present invention pertains. In the event of any conflict, including definitions, this specification shall prevail. Similar or equivalent methods and materials to those described herein may be used in carrying out or testing embodiments of the present invention, but preferred methods and materials are described below. Furthermore, the materials, methods, and examples are merely illustrative and not intended to limit the scope of the invention.

[0020] A method for producing hydrofluoroolefins (HFOs) from hydrochloroolefins and hydrochlorofluoroolefin reagents and intermediates is provided. In exemplary embodiments, 2,3,3,3-tetrafluoropropene (1234yf) is produced from 2-chloro-3,3,3-trifluoropropene (1233xf) by a multi-step process. In some embodiments, the method is either antimony pentahalide-free or essentially antimony-free. "Essentially antimony-free" means that the reagents, intermediates, and products contain antimony(V)-containing compounds at a concentration of less than 100 ppm.

[0021] This method may be carried out in any reactor suitable for gas-phase or liquid-phase fluorination reactions. The reactor is manufactured from a material resistant to the reactants used. The reactor may be made of a material resistant to the corrosive effects of hydrogen fluoride, such as stainless steel, Hastelloy®, Inconel®, Monel®, gold, or gold wire or quartz. The reaction may be batch, continuous, semi-continuous, or a combination thereof. Suitable reactors include batch reaction vessels and tubular reactors.

[0022] In one embodiment, as shown in scheme (1), 2-chloro-3,3,3-trifluoropropene (1233xf) is added to a reactor and heated to contact chlorine Cl2 in the presence of a catalyst at a temperature and pressure sufficient to carry out chlorination, thereby forming 2,2,3-trichloro-1,1,1-trifluoropropane (233ab). CF3CCl=CH2 + Cl2 → CF3CCl2CH2Cl (FeCl3) 1233xf 233ab (1)

[0023] Suitable catalysts include Lewis acids. In one embodiment, the catalyst is at least one of ferric chloride (FeCl3) or activated carbon. In some embodiments, the reaction mixture is heated to a temperature in the range of -50°C to 175°C. In some embodiments, the reaction is carried out at a reactor pressure of 1 pound per square inch gauge (psig) to 300 pounds per square inch gauge (psig). In another embodiment, the reaction is carried out with stirring. In a further embodiment, the reaction is carried out using any catalyst. When used, the catalyst is present in an amount of less than 2%, more than 0% to about less than 2%, and in some cases about 0.1% to about 1.5% of the total weight of the reaction mixture. The selectivity for 233ab is about 60% to about 99.9%, about 65% to about 99%, and in some cases about 80 to about 95%. The yield of the reaction is about 60% to about 99.9%, about 80% to about 99%, and in some cases about 90 to about 98%. The molar ratio of Cl2 / 1233xf can range from about 2 to about 0.1. In a further embodiment, the reaction is carried out using UV light, at atmospheric pressure, sub-atmospheric pressure, or vacuum, at a temperature of about 0°C to about 150°C.

[0024] 2,2,3-Trichloro-1,1,1-trifluoropropane (233ab) may be recovered from the reaction and added to a second reactor. The 2,2,3-Trichloro-1,1,1-trifluoropropane (233ab) is then heated and brought into contact with hydrogen fluoride (HF) in the gas or liquid phase at a temperature and pressure sufficient to induce fluorination, as shown in scheme (2), to form 2,3-Dichloro-1,1,1,2-tetrafluoropropane (234bb). In some embodiments, the reaction mixture is heated to a temperature of 50°C to 175°C. In some embodiments, the reaction is carried out at a reactor pressure of about 1 psig to about 300 psig. In some embodiments, the reaction in scheme (2) may be carried out without a catalyst. In some embodiments, the reaction in scheme (2) may be carried out in the presence of a solvent. In one embodiment, the catalyst includes a Lewis acid. In one embodiment, the reaction is carried out with stirring. The catalyst may be in the range of 0-20%, greater than 0-approximately 15%, and in some cases approximately 5-10% by weight of the total reactants. The molar ratio of HF / 233ab may be in the range of 0.2-approximately 30, approximately 0.5-approximately 25, and in some cases approximately 1-10. The selectivity for 234bb may be in the range of approximately 50-approximately 99%, approximately 70-95%, and in some cases approximately 75-90%. CF3CCl2CH2Cl+HF→CF3CFCl-CH2Cl 233ab 234bb (2)

[0025] Next, 2,3-dichloro-1,1,1,2-tetrafluoro-propane (234bb) is heated and contacted with hydrogen (H2) in the gas phase in the presence of a catalyst at a temperature and pressure sufficient to effect hydrogenation, as shown in Scheme (3), to form 1,1,1,2-tetrafluoro-2-propene (1234yf). In one embodiment, the reaction temperature ranges from about 180 °C to about 400 °C, about 200 to about 350, and in some cases from about 225 to about 325 °C. The catalyst can include at least one of Cu / C and / or Au / Al2O3. The catalyst contact time can range from about 10 seconds to about 120 seconds, about 25 to about 100 seconds, and in some cases from about 50 to about 75 seconds. The selectivity for 1234yf can range from about 80% to about 99%, about 85 to about 98, and in some cases from about 90 to 95%. CF3CFCl-CH2Cl + H2 → CF3CF=CH2 + HCl 234bb 1234yf (3)

[0026] [[ID=Z]] Suitable catalysts include copper supported on carbon (Cu / C) or gold supported on aluminum oxide (Au / Al2O3). In some embodiments, the reaction mixture is heated to a temperature of -50 °C to 300 °C. In some embodiments, the reaction is carried out at a reactor pressure of about 1 psig to about 300 psig.

[0027] In an alternative embodiment, the synthetic steps of Schemes (1) and (2) above may be combined as a single process step. 2-chloro-3,3,3-trifluoropropene (1233xf) in the gas or liquid phase is charged to a reactor and heated in the gas or liquid phase, in the presence or absence of a catalyst, at a temperature and pressure sufficient to effect conversion to 2,3-dichloro-1,1,1,2-tetrafluoro-propane (234bb), and contacted with chlorine gas (Cl2) and hydrogen fluoride (HF). CF3CCl=CH2 + Cl2 + HF → CF3CClFCH2Cl 1233xf 234bb (4)

[0028] It should be noted that there is an error in the original text where "300 °C" should probably be "300 °C". This has been corrected in the translation.The catalyst and reaction conditions for scheme (4) are the same as those described above for schemes (1) and (2). The resulting 2,3-dichloro-1,1,1,2-tetrafluoropropane (234bb) may be converted to 2,3,3,3-tetrafluoropropene (1234yf) by scheme (3) as described above.

[0029] In further embodiments, 234bb may be converted to 1-chloro-2,3,3,3-tetrafluoropropene by reacting with an aqueous caustic agent in or without a catalyst at a temperature sufficient to convert 234bb to 1224yd, as shown in scheme (5). For example, the reaction can be carried out at temperatures of about 20°C to about 100°C, about 25 to about 80°C, and optionally about 30 to 75°C, with or without a phase transfer catalyst. If used, the phase transfer catalyst may constitute about 0.1% to about 3% by weight, about 0.25% to about 2.5% by weight, and optionally about 0.5% to about 2% by weight of the total reactants. The molar ratio of caustic agent / 234bb is in the range of about 0.1 to about 2, about 0.25 to about 1.75, and optionally about 0.5 to about 1.5. The selectivity for 1224 yards is in the range of 80% to 99%, approximately 85% to 99%, and in some cases, approximately 90% to 99%. CF3CClFCH2Cl+NaOH→CF3CF=CHCl+NaCl+NaOH 234bb 1224yd (5)

[0030] The reaction may be batch, continuous, semi-continuous, or a combination thereof. The aqueous caustic agent may be a strong base such as sodium hydroxide, potassium hydroxide, potassium tert-butoxide, calcium oxide, or at least one of calcium hydroxide. The molar ratio of the base to 234bb may range from about 0.1 to about 2, about 0.5 to about 1.75, and optionally about 0.75 to about 1.5. Desired results were obtained by using a base containing NaOH or KOH. Liquid-phase dehydrochlorination may be carried out in or without a phase-transfer catalyst. In some embodiments, the phase-transfer catalyst may include a quaternary ammonium salt, a phosphonium salt, or a crown ether. The amount of the phase-transfer catalyst may range from about 0.5 to about 3% by weight, about 1 to about 2.5%, and optionally about 1.5 to about 2%. Desired results can be obtained by using a quaternary ammonium.

[0031] In further embodiments, 234bb from reaction scheme (2) or (4) can be used in reaction scheme (5), and in certain embodiments, reaction schemes (2) or (4) and (5) are integrated.

[0032] In another embodiment, 234bb may be converted to 1224yd by gas-phase dehydrochlorination in or out of the presence of a catalyst, as shown in the following scheme (6). CF3CClFCH2Cl→CF3CF=CHCl+HCl 234bb 1224yd (6)

[0033] In temperature ranges of approximately 200°C to 550°C, 250°C to 500°C, and in some cases 300°C to 450°C, the contact time is 10 to 120 seconds, 20 to 100 seconds, and in some cases 25 to 75 seconds, and the selectivity is approximately 90% to 99%, and in some cases approximately 95% to 99%.

[0034] In further embodiments, 234bb from reaction scheme (2) or (4) can be used in reaction scheme (6), and in certain embodiments, reaction schemes (2) or (4) and (6) are integrated.

[0035] In one embodiment, the dehydrochlorination of scheme (6) is a heat-driven process in the presence of a dehydrochlorination catalyst. Suitable catalysts include at least one of activated carbon, alumina, chromium oxide, transition metal oxides, metal halides, and combinations thereof. The desired result can be obtained by using activated carbon and carbon-supported metal halides such as carbon-supported KCl on a carbon catalyst. In a temperature range of 200°C to 550°C, about 250°C to about 500°C, and optionally about 275°C to 450°C, the contact time is about 10 to 120 seconds, about 20 to about 100 seconds, and optionally about 25 to about 75 seconds, and the selectivity is 90% to 99% and about 95 to 99%.

[0036] In one embodiment, the Specified Publication discloses compositions comprising 2,3,3,3-tetrafluoropropene and at least one additional compound selected from the group consisting of 254eb, 263fb, and 234bb. These compositions can be produced by processes described herein or obtained by blending the components of the compositions. The amount of this additional compound may range from greater than 0 to about 1%, about 0 to about 0.5%, and possibly about 0 to about 0.1%, with the remainder consisting of 1234yf.

[0037] In one embodiment, the Specified Publication discloses compositions comprising 2,3,3,3-tetrafluoropropene and at least one additional compound selected from the group consisting of 244bb, 244eb, 1233xf, and 263fb. These compositions can be produced by processes described herein or obtained by blending the components of the compositions. The amount of this additional compound may range from greater than 0 to about 1%, about 0 to about 0.5%, and possibly about 0 to about 0.1%, with the remainder consisting of 1234yf.

[0038] In another embodiment, the Specified Publication discloses compositions comprising 234bb, 234da, and at least one additional compound selected from the group consisting of 1234yf, 1243zf, CF3COF, CHCl3, 234bb(Br), 1224yd, 224bb, 243db, 243db(B), 243ab, C6H3Cl2F7, and CF3CFClCH2OCH2CFClCF3. These compositions can be produced by processes described herein or obtained by blending the components of the compositions. The amount of this additional compound may range from greater than 0 to about 10%, greater than 0 to about 5%, and optionally greater than 0 to about 1%, with the remainder consisting of 234bb and 234da.

[0039] In another embodiment, this specification discloses compositions comprising 1224yd, 1233xf, and at least one additional compound selected from the group consisting of 1234yf, 1243zf, 244bb, 1233xf(Br), 243db, 1223xd, 1-chlorotrifluoropropyne, 3,3,3-trifluoropropyne, 1215yb, 1224xe, 253fb, 1214ya, 123, and 124. The amount of this additional compound may range from more than 0 ppm to 10% by weight, about 5 ppm to about 8%, and in some cases about 20 ppm to about 1%. The amounts of 1224yd and 1233xf may range from 90% to 99.99%, respectively. These compositions can be produced by the processes described herein or obtained by blending the components of the compositions.

[0040] The following examples are provided to illustrate specific aspects and embodiments of the present invention and are not intended to limit the scope of the appended claims. [Examples]

[0041] Example 1: Chlorination of 1233xf to 233ab 30.9 g of anhydrous FeCl was placed in a 400 ml Hastelloy C shaking tube. The autoclave was then degassed. Next, 196 g of 1233xf and 107 g of Cl2 were added to the reactor. The mixture was heated to 85°C and stirred at 85°C for 2.5 hours. After the reactor cooled to room temperature, the product was analyzed by GC-MS-FID using a capillary GC column without packing. The GC analysis of the product is shown in Table 1.

[0042] [Table 1]

[0043] Example 2: Chlorofluorination of 1233xf to 234bb 433 g of HF, 68.25 ml of 1233xf, and 45 g of Cl were added to a 1-liter autoclave. This was heated to 90°C and maintained at 90°C for 220 minutes with stirring. After the reactor was cooled to room temperature, the product was quenched in ice and dichlorobenzene and washed with KOH solution. The product was then analyzed by GC-MS-FID using a capillary GC column without packing. The GC analysis of the product is shown in Table 2. The product concentrations in the table were normalized without dichlorobenzene.

[0044] [Table 2]

[0045] Example 3: Hydrogenation and dechlorination of 234bb to 1234yf Example 3 demonstrates the conversion of 234bb to 1234yf on a 10 wt% Cu / C catalyst. 10 cc of 10 wt% Cu supported on acid-washed carbon catalyst granules was placed in a 1 / 2-inch Hastelloy C reactor. The catalyst was conditioned for 2 hours at approximately 250°C with 50 ccm / min H2. Hydrogenation and dechlorination of 234bb were investigated in the temperature range of approximately 200°C to 300°C, and the products are shown in Table 4. The reaction products were analyzed by GC-MS using a capillary GC column without packing, and the GC-MS area percentages shown in Table 3 were obtained.

[0046] [Table 3]

[0047] Example 4: Hydrogenation and dechlorination of 234bb to 1234yf Example 4 demonstrates the conversion of 234bb to 1234yf on a 5 wt% Ru / C catalyst. 10 cc of 10 wt% Ru supported on acid-washed carbon catalyst granules was placed in a 1 / 2-inch Hastelloy C reactor. The catalyst was conditioned for 2 hours at 250°C with 50 ccm / min H2. Hydrogenation and dechlorination of 234bb were investigated in the temperature range of approximately 100°C to 200°C, and the products are shown in Table 4. The reaction products were analyzed by GC-MS using a capillary GC column without packing, and the GC-MS area percentages shown in Table 4 were obtained.

[0048] [Table 4]

[0049] Example 5: Chlorination of 1234yf to 234bb 180 g of 1234yf was mixed with 112 g of Cl2 and 1 g of anhydrous FeCl3 as a catalyst. The reactor was heated to 80°C with stirring and stirred for 4 hours. The liquid phase of the product was rotated and evaporated to remove FeCl3, and then analyzed by GC-MS-FID using a capillary GC column without packing, as shown in Table 5.

[0050] [Table 5]

[0051] Example 6: Chlorination of 1234yf to 234bb 180 g of 1234yf was mixed with 112 g of Cl2 and 1 g of anhydrous FeCl3 as a catalyst, and heated to 100°C with stirring, then stirred at 100°C for 6 hours. The liquid phase of the product was rotated and evaporated to remove FeCl3, and then analyzed by GC-MS-FID using a capillary GC column without packing, as shown in Table 6.

[0052] [Table 6]

[0053] Example 7: Dehydrochlorination of 234bb to 1224yd 150 g of 234 bb was mixed with 200 g of 32 wt% KOH, heated to 90°C with stirring, and then stirred at 90°C for 6 hours. After the reactor cooled to room temperature, the liquid phase of the product was collected and analyzed by GC-MS-FID using a capillary GC column without packing, as shown in Table 7.

[0054] [Table 7]

[0055] Example 8: Dehydrochlorination of 234bb to 1224yd 150 g of 234bb was mixed with 152 g of 25 wt% NaOH and 1.5 g of TBAB, heated to 40°C with stirring, and then stirred at 40°C for 4 hours. As shown in Table 8, the liquid phase of the product was analyzed by GC-MS-FID using a capillary GC column without packing.

[0056] [Table 8]

[0057] Examples 9-12 below were generated using ThermPy software and demonstrate the performance of a composition of the present invention under mobile conditions including cooling (COP_c and CAP_c) and heating (COP_h and CAP_h). T_Condenser=40.0℃ T_evaporator=0.0℃ Overheating=15.0K Compressor efficiency = 0.7

[0058] Example 9: 98% by weight of R-1224yd and Additional compounds R-1233xf and R-1234yf. Table 9 shows that all blends in this example have a higher volume and a lower COP than R-1224yd. When the amount of the additional compound ranges from pure R-1233xf to pure R-1234yf, the CAP decreases and the COP increases as the R-1233xf content increases from 0% to 2% by weight. When the additional compound is R-1233xf (98% R-1224yd and 2% R-1233xf), the COP is the same as R-1224yd and the CAP is greater.

[0059] [Table 9-1]

[0060] [Table 9-2]

[0061] [Table 9-3]

[0062] [Table 9-4]

[0063] [Table 9-5]

[0064] [Table 9-6]

[0065] [Table 9-7]

[0066] Example 10: 98 wt% of R-1224yd and Additional compounds R-1233xf and R-1243zf Table 10 shows that all blends in this example have a higher volume and a lower COP than undiluted R-1224yd. When the amount of additional compound ranges from pure R-1233xf to pure R-1243zf, the CAP decreases and the COP increases as the R-1233xf content increases from 0% by weight to 2%. When the additional compound is R-1233xf (98% R-1224yd and 2% R-1233xf), the COP is the same as R-1224yd and the CAP is greater.

[0067] [Table 10-1]

[0068] [Table 10-2]

[0069] [Table 10-3]

[0070] [Table 10-4]

[0071] [Table 10-5]

[0072] Example 11: 99% by weight of R-1234yf and additional compound R-263fb. Table 11 shows that as the content of the additional compound increases from 0% by weight, the COP increases and the CAP decreases.

[0073] [Table 11]

[0074] Example 12: 99% by weight of R-1234yf and additional compound R-254eb. Table 12 shows that as the content of the additional compound increases from 0% by weight, the COP increases and the CAP decreases.

[0075] [Table 12]

[0076] While the present invention has been described with reference to one or more embodiments, those skilled in the art will understand that various modifications can be made without departing from the scope of the invention, and that equivalents can be used in place of certain elements. In addition, many modifications can be made without departing from the essential scope of the invention to adapt the teachings of the invention to specific situations or materials. Thus, the present invention is not limited to the specific embodiments disclosed as the best mode intended for carrying out the invention, and the invention is intended to include all embodiments included within the scope of the appended claims. Furthermore, all numerical values ​​specified in the detailed description shall be interpreted as if both exact and approximate values ​​were explicitly specified.

Claims

1. A composition comprising 1224yd, 1233xf, and at least one additional compound selected from the group consisting of 1234yf and 1243zf, wherein the amount of 1224yd is in the range of 90 to 99.99% by weight based on the total amount of the composition.

2. The composition according to claim 1, wherein the amount of the additional compound is in the range of 5 ppm to 8% by weight based on the total amount of the composition.

3. The composition according to claim 1, wherein the amount of the additional compound is in the range of 20 ppm to 1% by weight based on the total amount of the composition.

Images