Catalyst and method for converting 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) to 1,1,2-trifluoroethane (HFC-143)

Abstract

HFO-1132, particularly HFO-1132E, can be produced from 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113). In the first step, 1,1,2-trifluoroethane (HFC-143) is produced by hydrogenating 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) in the presence of a catalyst for producing 1,1,2-trifluoroethane (HFC-143). This highly exothermic hydrogenation step can be mitigated by diluting the catalyst and / or diluting the 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) starting material. Next, 1,1,2-trifluoroethane (HFC-143) can be dehydrofluorinated in the presence of a catalyst to produce trans-1,2-difluoroethylene (HFO-1132E) and / or cis-1,2-difluoroethylene (HFO-1132Z). Then, cis-1,2-difluoroethylene (HFO-1132Z) can be isomerized to produce trans-1,2-difluoroethylene (HFO-1132E).

Description

[Technical Field]

[0001] (Cross-reference of related applications) This application claims priority to U.S. Patent Application No. 18 / 807,095, filed on August 16, 2024, entitled "Catalysts and methods for conversion of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) to 1,1,2-trifluoroethane (HFC-143)," which claims benefits under Section 119(e) of U.S. Patent Act, as expressed herein by reference, of U.S. Provisional Patent Application No. 63 / 534,000, filed on August 22, 2023, entitled "Catalysts and methods for conversion of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) to 1,1,2-trifluoroethane (HFC-143)," the full disclosures of which are expressly incorporated herein by reference.

[0002] (Field of invention) This disclosure relates to a catalyst and method for producing trans-1,2-difluoroethylene (HFO-1132E) from 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113), and more specifically, to a catalyst and method for converting 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) to a 1,1,2-trifluoroethane (HFC-143) intermediate in a process for producing trans-1,2-difluoroethylene (HFO-1132E). [Background technology]

[0003] 1,2-Difluoroethylene (HFO-1132) has recently been found to be increasingly useful for a variety of applications. HFO-1132 may exist as a mixture of two geometric isomers (the E or trans isomer and the Z or cis isomer), which may be used separately or together in various proportions. Potential end uses of 1,2-difluoroethylene (HFO-1132) include refrigerants used alone or in blends with other components, solvents for organic materials, and chemical intermediates in the synthesis of other halogenated hydrocarbon solvents.

[0004] Improved methods for the production of 1,2-difluoroethylene (HFO-1132), particularly trans-1,2-difluoroethylene (HFO-1132E), are desired. Summary of the Invention

[0005] The production of trans-1,2-difluoroethylene (HFO-1132E) from 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) involves a multi-step catalytic process.

[0006] In the first step, 1,1,2-trifluoroethane (HFC-143) is produced by hydrogenating 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) via reaction with hydrogen in the presence of a catalyst to produce 1,1,2-trifluoroethane (HFC-143). 1,1,2-Trifluoroethane (HFC-143) is then dehydrofluorinated in the presence of a catalyst to produce trans-1,2-difluoroethylene (HFO-1132E) and / or cis-1,2-difluoroethylene (HFO-1132Z). Cis-1,2-difluoroethylene (HFO-1132Z) can then be isomerized to produce trans-1,2-difluoroethylene (HFO-1132E).

[0007] This disclosure provides a catalyst and method for controlling the highly exothermic reaction in the first step described above, namely, the first step of producing 1,1,2-trichloro-1,2,2-trifluoroethane (HFC-143) by hydrogenation of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) by reaction with hydrogen in the presence of a catalyst.

[0008] In the first approach, the catalyst used in the aforementioned reaction may be diluted with a diluent that acts as a heat-absorbing medium to help manage the heat generated during the reaction.

[0009] In the second approach, the 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) reactant may be combined with a certain amount of a diluent starting material, such as a non-reactive gas, and / or a certain amount of a diluent starting material in the form of an organic molecule, such as 1,1,2-trifluoroethane (HFC-143), either before or during the reaction, which may be a separate product from the reaction itself or may be introduced independently of the reaction from an external source.

[0010] Each of the above approaches, when used individually or in combination with each other, can increase the selectivity for the desired product 1,1,2-trifluoroethane (HFC-143) and / or the selectivity for the desired intermediate, and / or decrease the selectivity for undesirable by-products.

[0011] In one embodiment, the present disclosure provides a method for producing 1,1,2-trifluoroethane (HFC-143), comprising hydrogenating 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) with hydrogen in the presence of a catalyst to produce 1,1,2-trifluoroethane (HFC-143), wherein the catalyst comprises a catalyst material comprising a catalyst metal supported on a carrier, with the amount being 0.1 to 1.0% by weight based on the total weight of the catalyst metal and the carrier, and a diluent, wherein the amount of the catalyst material is 5 to 70% by volume based on the total volume of the catalyst material and the diluent.

[0012] In the above method, the carrier may be alpha-alumina.

[0013] In another form, the present disclosure provides a palladium metal catalyst useful for hydrogenating 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) with hydrogen to produce 1,1,2-trifluoroethane (HFC-143), wherein the catalyst comprises a catalyst material comprising 0.1 to 1.0% by weight of palladium metal supported on an alumina (Al2O3) support, based on the total weight of the catalyst metal and the support, and a diluent, wherein the amount of the catalyst material is 5 to 70% by volume, based on the total volume of the catalyst material and the diluent.

[0014] In the catalyst described above, the support may be alpha-alumina.

[0015] In a further form, the present disclosure is a method for producing 1,1,2-trifluoroethane (HFC-143), comprising combining 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) with a starting material diluent to form a reaction mixture, The present invention provides a method comprising reacting 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) in a reaction mixture with hydrogen in the presence of a catalyst to produce a product mixture. [Brief explanation of the drawing]

[0016] [Figure 1] This is a schematic diagram of the apparatus used in Example 1 for the conversion of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) to 1,1,2-trifluoroethane (HFC-143). [Figure 2] This graph shows the overall selectivity of the 0.2% Pd / alpha-Al2O3 catalyst for "HFC-143 + recyclable material" as a function of catalyst concentration and temperature, for the experiment in Example 2. [Figure 3]This graph shows the selectivity percentage for undesirable by-products in the experiment of Example 4 as a function of the phase of the alumina support in the range of 200-210°C. [Figure 4] This graph shows the substrate conversion rates of Pd / Al2O3 catalysts with alpha, theta, and delta alumina supports for the experiment in Example 4. [Figure 5] This graph shows the conversion percentage of the 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) substrate using a 0.2% Pd / alpha-Al2O3 catalyst as a function of contact time at three different temperatures, for the experiment in Example 5. [Figure 6] This graph shows the product selectivity as a function of temperature for the conversion of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) to 1,1,2-trifluoroethane (HFC-143) using a 0.2% Pd / alpha-Al2O3 catalyst in the experiment of Example 5. [Figure 7] This graph shows the product selectivity of HFC-143, HCFC-123a, and HCFC-133b as a function of temperature in the conversion process of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) to 1,1,2-trifluoroethane (HFC-143) using a 0.2% Pd / alpha-Al2O3 catalyst in the experiment of Example 5. [Modes for carrying out the invention]

[0017] I. Definition Where used herein, the singular forms "a," "an," and "the" include the plural form unless the context explicitly indicates otherwise. Furthermore, when a quantity, concentration, or other value or parameter is given as a range, a preferred range, or an enumeration of upper preferred values ​​and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pair of any upper limit or upper preferred value and any lower limit or lower preferred value, regardless of whether the range is disclosed separately. Where numerical ranges are enumerated herein, unless otherwise specified, the range is intended to include its endpoints, as well as all integers and fractions within the range. The scope of this disclosure is not intended to be limited to the specific values ​​enumerated when defining the range.

[0018] Where used herein, the phrase "any range encompassing any two of these values ​​as endpoints" literally means that any range can be selected from any two of the values ​​listed before such phrase, regardless of whether the values ​​are in the lower or higher part of the enumeration. For example, a pair of values ​​could be selected from two lower values, two higher values, or a lower value and a higher value.

[0019] As used herein, refrigerant names including ASHRAE numbers such as "R-143," IUPAC names such as "1,1,2-trifluoroethane," and type number abbreviations such as "HFC-143" may all be used interchangeably to refer to the same refrigerant.

[0020] As used herein, catalyst material refers not only to metal catalysts but also to any catalyst support material used in conjunction with a metal catalyst.

[0021] As used herein, catalyst dilution refers to a method of reducing the concentration of a catalyst in a chemical reaction by combining the catalyst material with a diluent that is inert to the reaction or does not catalyze the reaction.

[0022] II. Overview The present invention generally relates to a method for producing E-1,2-difluoroethylene (HFO-1132E) from 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) according to the following three-step process ("Process 1"), the following three steps: (i) Hydrogenating 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) to produce 1,1,2-trifluoroethane (HFC-143) The present invention relates to a method comprising: (ii) a step of defluorinating 1,1,2-trifluoroethane (HFC-143) to produce a mixture of trans-1,2-difluoroethylene (HFO-1132E) and cis-1,2-difluoroethylene (HFO-1132Z); and (iii) a step of isomerizing cis-1,2-difluoroethylene (HFO-1132Z) to trans-1,2-difluoroethylene (HFO-1132E).

[0023] The following are schematic formulas for the three steps of Process 1.

[0024] Process 1 (i)CFCl2-CF2Cl(CFC-113)+3 H2→CFH2-CF2H(HFC-143)+3 HClΔH f = -59.7 kcal / mol (ii) CFH2 - CF2H → × Trans-CFH = CHF(HFO-1132E) + (1-x)Sys-CFH = CFH(HFO-1132Z) + HF (iii) cis-CFH=CFH(HFO-1132Z) → trans-CFH=CHF(HFO-1132E)

[0025] The reaction heat of process (i) was calculated using the Density Functional Theory (DFT) method. ΔH = -59.7 kcal / mol f This indicates that process (i) is a highly exothermic reaction process.

[0026] It has been found that the first step, which involves the conversion of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) to 1,1,2-trifluoroethane (HFC-143), can be improved by using a method to control the large amount of heat generated in the exothermic reaction. In the first approach, the hydrogenation catalyst may be diluted to control the heat and reaction rate generated by the reaction. In the second approach, the 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) reactant may be diluted with a certain amount of starting material diluent before or during the reaction. The aforementioned dilution methods allow for better control of the heat generated in step (i) and minimize catalyst deactivation and the formation of undesirable by-products. Details of catalyst dilution, starting material dilution, and related conditions are provided in Section III below.

[0027] Further details regarding each of processes (i), (ii), and (iii) are provided below.

[0028] III. Process (i) Step (i) of the process for producing 1,2-difluoroethylene (HFO-1132) includes hydrogenating 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) to produce 1,1,2-trifluoroethane (HFC-143). While catalysts can improve the reaction rate and overall efficiency, the exothermic nature of the hydrogenation reaction itself can introduce several drawbacks. It has been found that the high temperature in the hydrogenation reaction of step (i) can lead to catalyst deactivation and rapid loss of catalytic activity. In addition, the increase in heat and energy in the reaction environment can promote undesirable side reactions. Each of the aforementioned may reduce the selectivity for the desired product, 1,1,2-trifluoroethane (HFC-143).

[0029] To overcome these challenges, this disclosure provides a catalyst and a starting material dilution method for improving product selectivity for the conversion of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) to 1,1,2-trifluoroethane (HFC-143).

[0030] A. Dilution of the catalyst This method can be used to control the reaction rate and prevent excessive catalyst deactivation. By diluting the catalyst, the reaction rate can be carefully adjusted, preventing the formation of undesirable by-products and potentially extending the catalyst's lifetime.

[0031] (i) catalyst Catalysts and diluents play important roles in the reaction. Specifically, in the hydrogenation process, catalyst materials may include catalytic metals such as palladium, platinum, rhodium, ruthenium, iron, cobalt, or nickel.

[0032] The catalyst metal may be supported on a carrier such as activated carbon, porous aluminosilicate (e.g., zeolite), alumina, silica, titania, zirconia, zinc oxide, or aluminum fluoride. The alumina may be alpha-alumina, delta-alumina, theta-alumina, or gamma-alumina. The supported catalyst can be produced by impregnating one of the suitable carriers with a solution of a compound of the desired metal component. The carrier may also be in the form of pellets. After the impregnation step, the solvent is removed using heat or under vacuum to produce a solid mass, which can be further dried, calcined, and reduced to form an activated metal catalyst.

[0033] The catalyst material may contain a catalyst metal supported on a carrier in an amount ranging from as low as about 0.01% by weight, about 0.05% by weight, about 0.1% by weight, about 0.2% by weight, about 0.3% by weight, about 0.4% by weight, or as high as about 0.5% by weight, about 0.6% by weight, about 0.7% by weight, about 0.8% by weight, about 0.9% by weight, about 1% by weight, about 1.5% by weight, about 2% by weight, about 5% by weight, about 10% by weight, about 20% by weight, about 30% by weight, about 40% by weight, about 50% by weight, or any range encompassed by any two of the aforementioned values ​​as endpoints. In the case of supported precious metal catalysts such as Pd and Pt, the amount of metal supported may range from about 0.01% by weight to about 5% by weight, preferably about 0.05% by weight to about 2% by weight, and more preferably about 0.1% by weight to about 1% by weight.

[0034] When a palladium catalyst is used, the loading amount of palladium on a support such as an alpha-alumina support may be about 0.01% by weight to about 5% by weight, preferably about 0.05% by weight to about 2% by weight, and more preferably about 0.1% by weight to about 1% by weight.

[0035] The catalyst used in step (i) may have a suitable BET (Brunauer, Emmet, and Teller) surface area. In some embodiments, the BET surface area of the catalyst is as low as about 1 m 2 / g, about 3 m 2 / g, about 5 m 2 / g, about 10 m 2 / g, about 15 m 2 / g, about 20 m 2 / g 2 , about 30 m 2 / g, about 40 m 2 / g, about 50 m 2 / g, about 100 m 2 / g, about 200 m 2 / g, or as high as about 250 m 2 / g, about 300 m 2 / g, about 400 m 2 / g, about 500 m 2 / g, about 600 m 2 / g, about 700 m 2 / g m 2 , about 800 m 2 / g, about 900 m 2 / g, about 1000 m 2 / g, about 2000 m 2 / g, or within any range encompassed by any of the foregoing values as endpoints. In the case of an alumina-supported metal catalyst, the BET surface area is about 1 m 2 / g to about 500 m 2 / g, preferably about 1 m 2 / g to about 200 m 2 / g, more preferably about 1 m 2 / g to about 100 m 2 / g, and most preferably about 1 m 2 / g to about 20 m 2It may also be / g. BET analysis is a standard method for determining surface area from nitrogen adsorption isotherms. The BET surface area of ​​the catalyst can be measured using the TriStar II Micromeritics instrument. The catalyst sample is degassed before analysis using the FlowPrep 060 instrument.

[0036] When a palladium catalyst is used on an alpha-alumina support, the BET surface area is approximately 1 m². 2 / g~about 500m 2 / g, preferably about 1m 2 / g~about 200m 2 / g, comfortably about 1m 2 / g~about 100m 2 / g, and most preferably about 1m 2 / g~about 20m 2 / g is also acceptable.

[0037] (ii) Catalytic pretreatment The catalyst may be pretreated by various methods to improve its performance and effectiveness in the reaction. For example, the catalyst may be dried at high temperatures ranging from as low as about 200°C, 250°C, 300°C, 350°C, 360°C, 370°C, or as high as about 380°C, 390°C, 400°C, 450°C, 500°C, 600°C, 700°C, or any range encompassed by two of the aforementioned values ​​as endpoints. As part of the catalyst pretreatment, the catalyst may be exposed to an inert gas such as N2. The pretreatment process may be as short as about 1 hour, 2 hours, 3 hours, or as long as about 4 hours, 5 hours, 6 hours, 10 hours, 20 hours, or any range encompassed by two of the aforementioned values ​​as endpoints, such as 2 hours to 4 hours.

[0038] When a palladium catalyst is used on an alpha-alumina support, the catalyst may be dried at a temperature of about 200°C to about 700°C, preferably about 200°C to about 500°C, and most preferably about 200°C to about 300°C.

[0039] When a palladium catalyst is used on an alpha-alumina support, the catalyst may be exposed to an inert gas such as N2 for about 1 to 20 hours, preferably about 1 to 10 hours, and most preferably about 1 to 3 hours.

[0040] (iii) Catalyst composition This disclosure also includes catalyst compositions, such as those used in the diluted catalyst hydrogenation process described herein.

[0041] In one embodiment, the catalyst composition is a palladium metal catalyst useful for hydrogenating 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) with hydrogen to produce 1,1,2-trifluoroethane (HFC-143), wherein the catalyst comprises a catalyst material comprising 0.1 to 1.0% by weight of palladium metal supported on an alumina (Al2O3) support, preferably an alpha-alumina support, based on the total weight of the catalyst metal and the support, and a diluent, wherein the amount of catalyst material is about 5 to about 70 volume percent based on the total volume of the catalyst material and the diluent.

[0042] The diluent material may include an inert substance that is not reactive in the reaction of step (i), such as a metal, metal alloy, metal mesh, glass beads, inert alpha alumina, or carbon black. The metal mesh material may be made from stainless steel or nickel alloy, such as Monel or Inconel. These meshes have a relatively large surface area, provide physical support for the catalyst, and allow the reaction mixture to flow while reducing the concentration of the catalyst.

[0043] The diluent can be combined with the catalyst material by simple solid mixing or by solid mixing techniques such as shaking, which uniformly combine and disperse the catalyst material and the diluent.

[0044] The diluent may be present in an amount such that the amount of catalyst material can be as low as about 5 volume percent, about 10 volume percent, about 15 volume percent, about 20 volume percent, about 25 volume percent, or as high as about 30 volume percent, about 35 volume percent, about 40 volume percent, about 45 volume percent, about 50 volume percent, about 55 volume percent, about 60 volume percent, about 65 volume percent, about 70 volume percent, or any range encompassed by any two of the aforementioned values ​​as endpoints, based on the total volume of catalyst material and diluent material. For example, the amount of catalyst material may be about 5 volume percent to about 70 volume percent, about 10 volume percent to about 50 volume percent, or about 10 volume percent to about 30 volume percent, based on the total volume of catalyst material and diluent material.

[0045] The hydrogenation reaction of step (i) may be carried out in the gas phase or vapor phase in a suitable reactor, for example, a tubular reactor made of a temperature-resistant and / or corrosion-resistant material such as nickel and its alloys, including Hastelloy (e.g., Hastelloy C276), Inconel (e.g., Inconel 600), Incoloy, and Monel, and the vessel may be lined with a fluoropolymer.

[0046] The reactor may first be cleaned and flushed with an inert gas such as nitrogen, and then packed with a catalyst as described below. The catalyst may be pretreated in the reactor, such as by drying in a manner further described below, and then the reactants may be metered and supplied to the reactor to start the reaction.

[0047] The process flow may be downward or upward through the catalyst bed. The product may be flowed through one or more scrubbers to remove by-products from the reaction, such as hydrogen fluoride (HF) and / or hydrogen chloride (HCl), and the reaction product may be collected, for example, by capture in a cooled cylinder.

[0048] B. Dilution of raw materials To reduce the heat of reaction, prevent excessive catalyst deactivation, and / or minimize the formation of undesirable by-products, the 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) starting material may be diluted with starting material diluents, such as inert gases or one or more unreactive organic molecules, each of which does not participate in the basic reaction. When the starting material is diluted, either the undiluted catalyst may be used, or the diluted catalyst may be used as described above.

[0049] Suitable inert gases include nitrogen and argon.

[0050] Examples of non-reactive organic molecules that can be used as raw material diluents include internal raw material diluents, which are organic molecules produced in the reaction of step (i), then optionally separated from other products, and recycled back into the reaction of step (i) by combining with the 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) raw material, or otherwise reintroduced.

[0051] For example, a suitable nonreactive organic molecule is 1,1,2-trifluoroethane (HFC-143), which is the target product of the reaction in step (i) and can be separated from the product mixture of step (i) before being combined with the 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) starting material. Alternatively, the 1,1,2-trifluoroethane (HFC-143) starting material diluent may be introduced independently from a source other than the product of the reaction in step (i).

[0052] Other non-reactive organic molecules that can be used as raw material diluents include external raw material diluents, which are organic molecules that are not produced in the reaction of step (i), but rather are introduced into the reaction of step (i) from an external source by being combined with the 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) raw material.

[0053] Non-reactive organic molecules that can be used as external raw material diluents include fluoromethane (HFC-41), difluoromethane (HFC-32), trifluoromethane (HFC-23), 1,1-difluoroethane (HFC-152a), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,2-pentafluoroethane (HFC-125), 1,1,1,2-tetrafluoropropane (HFC-254eb), 1,1,1,2-tetrafluoropropane (HFC-254eb), Possible examples include 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,2,2-pentafluoropropane (HFC-245cb), 1,1,1,2,3-pentafluoropropane (HFC-245eb), 1,1,1,2,3,3-hexafluoropropane (HFC-236ea), 1,1,1,3,3,3-hexafluoropropane (HFC-236fa), 1,1,2,3,3,3-heptafluoropropane (HFC-227ea), and combinations thereof.

[0054] The molar ratio of the raw material diluent to 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) may be in the range of 0.25 / 1 to 10 / 1, preferably 0.5 / 1 to 8 / 1, and more preferably 1 / 1 to 4 / 1.

[0055] C. Reaction in step (i) Figure 1 provides an embodiment of a reactor apparatus suitable for the reaction of step (i). Referring to the process flow diagram 100 shown therein, the supply of N2 acting as an inert carrier is provided from cylinder 102, and the supply of H2 is provided from cylinder 104. Organic feedstock, which may include 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113), is supplied from cylinder 106. Cylinders 102, 104, and 106 are all connected to a KOH scrubber 108 coupled to a vent 110. The N2, H2, and organic feedstocks are supplied into a reactor 112 surrounded by a box oven 114. The reaction can be monitored by taking a sample from outlet 120 and performing GC analysis.

[0056] As the reaction progresses, the product is supplied to a holding tank 116, which is immersed in a dry ice bath or a dry ice and acetone mixture bath 118. The dry ice bath or dry ice and acetone mixture bath is configured to maintain the temperature of the holding tank 116 at approximately -87°C. The holding tank 116 is coupled to a buffer knockout tank 112 to prevent potential backflow of the KOH solution, and the buffer knockout tank 112 is also coupled to a KOH scrubber 124. The scrubber 124 has a vent 126 that opens to the atmosphere. Target product: Recyclable by-products such as 1,1,2-trifluoroethane (HFC-143), 1-chloro-1,1,2-trifluoroethane (HCFC-133b), and 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a), acids such as HCl and HF, 1,1-difluoroethane (HFC-152a), ethane (HC-170), 1,1,1-trifluoroethane (HFC-143a), 1,1-difluoroethylene (HFO-1132) a) Non-recyclable by-products such as 1-chloro-1,1-difluoroethane (HCFC-142b), 1-chloro-1,2-difluoroethane (HCFC-142a), and chloroethane (HCC-160), as well as the unconverted raw material 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) collected in the holding tank 116, can be subjected to several purification steps, such as acid removal, drying, and distillation, to isolate the HFC-143 product. A portion of the purified HFC-143 can be co-supplied to the reactor in step (I) as a diluent.

[0057] The reaction temperature may be as low as about 100°C, about 150°C, about 200°C, about 210°C, about 220°C, about 230°C, about 240°C, about 250°C, about 260°C, about 270°C, about 280°C, about 290°C, or as high as about 300°C, about 350°C, about 400°C, or any range encompassed by any two of the aforementioned values ​​as endpoints, such as 100°C to about 300°C or preferably about 150°C to about 250°C.

[0058] When a palladium catalyst is used on an alpha-alumina support, the reaction temperature may be about 100°C to about 400°C, preferably about 100°C to about 300°C, and most preferably about 150°C to about 250°C.

[0059] The contact time between the reactants and the catalyst may be as short as about 0.1 seconds, about 1 second, about 5 seconds, about 10 seconds, about 15 seconds, or about 20 seconds, or as long as about 25 seconds, about 30 seconds, about 40 seconds, about 50 seconds, about 60 seconds, about 120 seconds, or any range encompassed by two of the aforementioned values ​​as endpoints. For example, the contact time may preferably be between about 1 second and about 60 seconds.

[0060] When the palladium catalyst is used on an alpha-alumina support, the contact time may be about 1 second to about 60 seconds, preferably about 5 seconds to about 40 seconds, and most preferably about 10 seconds to about 30 seconds.

[0061] The pressure may be as low as about 1 psig, about 3 psig, about 5 psig, about 10 psig, about 15 psig, about 20 psig, about 30 psig, about 35 psig, or about 40 psig, or as high as about 50 psig, about 60 psig, about 70 psig, about 80 psig, about 90 psig, about 100 psig, about 120 psig, about 150 psig, about 200 psig, or about 250 psig, about 300 psig, or any range encompassed by two of the aforementioned values ​​as endpoints. For example, the pressure may preferably be about 10 to about 100 psig.

[0062] When the palladium catalyst is used on an alpha-alumina support, the pressure may be about 1 psig to about 300 psig, preferably about 1 psig to about 200 psig, and most preferably about 10 psig to about 100 psig.

[0063] The molar ratio of hydrogen to CFC-113 reactant may be, for example, as small as about 2:1, about 3:1, about 4:1, about 5:1, about 5.5:1, or as large as about 6:1, about 6.5:1, about 7.5:1, or about 8:1, about 12:1, about 15:1, or about 20:1, or within any range encompassed by two of the aforementioned values ​​as endpoints. The molar ratio of hydrogen to CFC-113 may preferably be 3:1 to 15:1, and more preferably 4:1 to 10:1.

[0064] When a palladium catalyst is used on an alpha-alumina support, the molar ratio of hydrogen to CFC-113 reactant may be about 2:1 to about 20:1, preferably 3:1 to 15:1, and most preferably 4:1 to 10:1.

[0065] As demonstrated by the examples herein, the hydrogenation step can achieve selectivity for 1,1,2-trifluoroethane (HFC-143) products ranging from as low as about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70% to as high as about 75%, about 80%, about 90%, or higher, or any range encompassed by two of the aforementioned values ​​as endpoints.

[0066] When a palladium catalyst is used on an alpha-alumina support, the hydrogenation step can achieve a selectivity for 1,1,2-trifluoroethane (HFC-143) products of about 10% to about 70%, preferably about 10% to about 50%, and most preferably about 20% to about 40%.

[0067] The hydrogenation reaction can also produce several intermediates, including 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a), and trifluoroethylene (HFO-1123). These intermediates are recyclable and can ultimately be converted to 1,1,2-trifluoroethane (HFC-143). As demonstrated by the examples herein, the hydrogenation process can achieve composite selectivity for 1,1,2-trifluoroethane (HFC-143), 1-chloro-1,1,2-trifluoroethane (HCFC-133b), and 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) in any range encompassed by two of the aforementioned values ​​as endpoints: over 30%, over 40%, over 50%, over 60%, over 70%, over 80%, over 90%, over 95%, or any range encompassed by two of the aforementioned values ​​as endpoints.

[0068] When a palladium catalyst is used on an alpha-alumina support, the hydrogenation step can achieve a combined selectivity and / or selectivity of about 30%, about 40%, and most preferably about 50% for each of 1,1,2-trifluoroethane (HFC-143), 1-chloro-1,1,2-trifluoroethane (HCFC-133b), and 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a). The hydrogenation reaction may also produce several by-products as a result of the dehydrofluoridation side reaction, including 1,1-difluoroethane (HFC-152a), ethane (HC-170), 1,1,1-trifluoroethane (HFC-143a), 1,1-difluoroethylene (HFO-1132a), 1-chloro-1,1-difluoroethane (HCFC-142b), 1-chloro-1,2-difluoroethane (HCFC-142a), and chloroethane (HCC-160). These by-products are undesirable because they are difficult to recycle or convert to 1,1,2-trifluoroethane (HFC-143). As demonstrated by the examples herein, the hydrogenation process can achieve composite selectivity for 1,1-difluoroethane (HFC-152a), ethane (HC-170), 1,1,1-trifluoroethane (HFC-143a), 1-chloro-1,2-difluoroethane (HCFC-142a), and chloroethane (HCC-160) in any range encompassed by two of the aforementioned values ​​as endpoints: less than about 30%, less than about 25%, less than about 20%, less than about 15%, less than about 10%, less than about 9%, less than about 8%, less than about 7%, less than about 6%, less than 5%, or any range encompassed by two of the aforementioned values ​​as endpoints.

[0069] When a palladium catalyst is used on an alpha-alumina support, the hydrogenation step can achieve a combined selectivity and / or selectivity of less than about 30%, preferably less than about 25%, and most preferably less than about 20% for each of 1,1-difluoroethane (HFC-152a), ethane (HC-170), 1,1,1-trifluoroethane (HFC-143a), 1-chloro-1,2-difluoroethane (HCFC-142a), and chloroethane (HCC-160).

[0070] As demonstrated by the examples herein, the hydrogenation process can achieve conversion rates of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) to 1,1,2-trifluoroethane (HFC-143) ranging from, for example, as low as about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, or about 75% to as high as about 90%, about 95%, about 97%, about 98%, about 99%, or higher, or any range encompassed by two of the aforementioned values ​​as endpoints.

[0071] When a palladium catalyst is used on an alpha-alumina support, the hydrogenation step may achieve a conversion rate of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) to 1,1,2-trifluoroethane (HFC-143) of more than about 10%, preferably more than about 20%, and most preferably more than about 30%.

[0072] After using the catalyst in the reactor for an extended period, it is also beneficial to periodically regenerate the catalyst. Catalyst regeneration can be achieved by any means known in the art, for example, by passing air or air diluted with nitrogen over the catalyst at a temperature of about 100°C to about 400°C, preferably about 200°C to about 375°C, for about 0.5 hours to about 3 days. Subsequently, in the case of carbon and alumina-supported transition metal catalysts, a hydrogen treatment may be carried out at a temperature of about 100°C to about 400°C, preferably about 200°C to about 350°C.

[0073] When a palladium catalyst is used on an alpha-alumina support, one or more of the following properties may be present: The reaction temperature may be about 100°C to about 400°C, preferably about 100°C to about 300°C, most preferably about 150°C to about 250°C. The contact time may be about 1 second to about 60 seconds, preferably about 5 seconds to about 40 seconds, most preferably about 10 seconds to about 30 seconds. The pressure may be about 1 psig to about 300 psig, preferably about 1 psig to about 200 psig, most preferably about 10 psig to about 100 psig. The molar ratio of hydrogen to CFC-113 reactant may be about 2:1 to about 20:1, preferably 3:1 to 15:1, most preferably 4:1 to 10:1. The hydrogenation step can achieve a selectivity for the 1,1,2-trifluoroethane (HFC-143) product of about 10% to about 70%, preferably about 10% to about 50%, and most preferably about 20% to about 40%. The hydrogenation step can achieve a combined selectivity and / or selectivity for each of 1,1,2-trifluoroethane (HFC-143), 1-chloro-1,1,2-trifluoroethane (HCFC-133b), and 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a) of about 30%, preferably about 40%, and most preferably about 50%. The hydrogenation process can achieve a combined selectivity and / or selectivity for each of 1,1-difluoroethane (HFC-152a), ethane (HC-170), 1,1,1-trifluoroethane (HFC-143a), 1-chloro-1,2-difluoroethane (HCFC-142a), and chloroethane (HCC-160) of less than about 30%, preferably less than about 25%, and most preferably less than about 20%. The hydrogenation process can achieve a conversion rate of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) to 1,1,2-trifluoroethane (HFC-143) of more than about 10%, preferably more than about 20%, and most preferably more than about 30%.

[0074] D. Combinations of catalyst dilution and raw material dilution In the hydrogenation reaction of step (i), the catalyst dilution technique and the raw material dilution technique described in the above and below examples may be combined, that is, they may be used simultaneously or in combination with each other.

[0075] IV. Process (ii) The dehydrofluorination reaction of step (ii) may be carried out in the gas phase or vapor phase in a suitable reactor, for example, a tubular reactor made of a temperature-resistant and / or corrosion-resistant material such as nickel and its alloys, including Hastelloy (e.g., Hastelloy C276), Inconel (e.g., Inconel 600), Incoloy, and Monel, and the vessel may be lined with a fluoropolymer.

[0076] The reactor may first be cleaned and flushed with an inert gas such as nitrogen, and then packed with a catalyst as described below. The catalyst may be pretreated in the reactor, such as by drying in a manner further described below, and then the reactants may be metered and supplied to the reactor to start the reaction.

[0077] The process flow may be downward or upward through the catalyst bed. The reactants may be flowed through a scrubber to remove by-products from the reaction, such as hydrogen fluoride (HF) and / or hydrogen chloride (HCl), and the reaction products may be collected, for example, by capture in a cooled cylinder.

[0078] The catalyst and process conditions play a crucial role in the dehydrofluoridation reaction.

[0079] Suitable catalysts for dehydrofluorination reactions include metal oxides such as chromium oxide, aluminum oxide, iron oxide, and magnesium oxide. Fluorination of the catalyst may be carried out using anhydrous HF under conditions effective for converting a portion of the metal oxide to the corresponding metal fluoride, for example, via the procedure disclosed in U.S. Patent No. 6,780,815 by Cerri et al., the disclosure of which is expressly incorporated herein by reference. Other suitable catalysts for dehydrofluorination reactions include metal fluorides such as chromium fluoride, alumina fluoride, iron fluoride, magnesium fluoride, and various combinations thereof.

[0080] Other metals such as Pd and Ni can also be supported on the fluorinated metal oxide, for example, via a wet impregnation process in which a salt of the metal is exposed to a fluorinated metal oxide support in solution, followed by drying, calcination, and then reduction with hydrogen gas.

[0081] The amount of metal supported on the carrier may be in the range of about 0.01% by weight, about 0.05% by weight, about 0.1% by weight, about 0.2% by weight, about 0.3% by weight, about 0.4% by weight, about 0.5% by weight, or about 1% to about 2% by weight, about 3% by weight, 5% by weight, 10% by weight, or 20% by weight, or 30% by weight, or 40% by weight, or 50% by weight, or any range encompassed by two of the aforementioned values ​​as endpoints. In the case of supported precious metal (Pd, Pt, etc.) catalysts, the amount of metal supported may be in the range of 0.01 to 5% by weight, preferably 0.05 to 2% by weight, and more preferably 0.1 to 1% by weight.

[0082] The catalyst used in step (ii) may have a suitable BET (Brunauer, Emmet, and Teller) surface area. In some embodiments, the BET surface area of ​​the catalyst is as low as 10 m². 2 / g, 20m 2 / g, 30m 2 / g, 40m 2 / g, 50m 2 / g, 60m 2 / g, 70m 2 / g, 80m 2 / g, 90m 2 / g, 100m 2 / g, or at most 110m 2 / g, 120m 2 / g, 130m 2 / g, 140m 2 / g, 150m 2 / g, 175m 2 / g, 200m 2 / g, 225m 2 / g, 250m 2 / g, 300m 2It may be within any range encompassed by either / g or the aforementioned values ​​as endpoints. In the case of metal oxide catalysts, the BET surface area is preferably 100 m². 2 The concentration may exceed / g. In the case of fluorinated metal oxide catalysts, the BET surface area is preferably 20 m². 2 It may be greater than / g. BET analysis is a standard method for determining surface area from nitrogen adsorption isotherms. The BET surface area of ​​the catalyst can be measured using the TriStar II Micromeritics instrument. The catalyst sample is degassed before analysis using the FlowPrep 060 instrument.

[0083] The catalyst may also be pretreated by drying at a high temperature of approximately 200°C, 250°C, 300°C, 350°C, 360°C, 370°C, or 380°C, 390°C, 400°C, 450°C, 500°C, or any range encompassed by two of the aforementioned values ​​as endpoints. As part of the catalyst pretreatment, the catalyst may be exposed to an inert gas such as N2. The pretreatment process may be as short as approximately 1 hour, 2 hours, 3 hours, or as long as approximately 4 hours, 5 hours, 6 hours, 10 hours, 20 hours, or any range encompassed by two of the aforementioned values ​​as endpoints, such as approximately 2 hours to 4 hours.

[0084] The temperature range for the defluoride hydrogenation reaction may be as low as about 150°C, about 200°C, about 250°C, about 300°C, about 350°C, about 400°C, about 450°C, or as high as about 500°C, about 550°C, about 600°C, about 650°C, about 700°C, about 750°C, about 800°C, or any range encompassed by two of the aforementioned values ​​as endpoints. The temperature may preferably be about 250°C to about 450°C, and more preferably about 300°C to about 400°C.

[0085] The pressure may be as low as about 1 psig, about 2 psig, about 3 psig, about 4 psig, or about 5 psig, about 10 psig, about 15 psig, about 20 psig, about 25 psig, about 30 psig, about 35 psig, about 40 psig, about 50 psig, or within any range encompassed by two of the aforementioned values ​​as endpoints. For example, the pressure may be about 1 psig to about 50 psig, preferably about 5 psig to about 30 psig, and more preferably about 10 psig to about 20 psig.

[0086] The contact time between the reactants and the catalyst may be as short as approximately 0.1 seconds, 1 second, 5 seconds, 10 seconds, 15 seconds, or 20 seconds, or as long as approximately 25 seconds, 30 seconds, 40 seconds, 50 seconds, 60 seconds, or 120 seconds, or any approximate range encompassed by two of the aforementioned endpoints. For example, the contact time may be between approximately 1 second and 60 seconds.

[0087] In the dehydrofluoridation reaction of step (ii), the cis / trans molar ratio of 1,2-difluoroethylene in the product mixture may be as low as about 1, about 2, about 3, about 4, about 5, about 6, or as high as about 7, about 8, about 9, about 10, about 11, about 12, about 13, about 14, about 15, or any range encompassed by two of the aforementioned values ​​as endpoints. For example, the cis / trans ratio may be between about 2 and about 15.

[0088] The selectivity for the desired 1,2-difluoroethylene product (sum of 1232E and 1232Z) may be as low as about 80%, about 85%, about 90%, about 91%, about 92%, about 93%, about 94%, about 95%, or as high as about 96%, about 97%, about 98%, about 99%, or any range encompassed by two of the aforementioned values ​​as endpoints. For example, the selectivity may be between about 89% and about 99%.

[0089] The conversion rate of the starting material to 1,2-difluoroethylene may be as low as about 10%, about 20%, about 30%, about 40%, or as high as about 50%, about 60%, about 70%, about 80%, about 90%, about 95%, about 99%, or any range encompassed by two of the aforementioned values ​​as endpoints.

[0090] After using the catalyst in the reactor for an extended period, it is also beneficial to periodically regenerate the catalyst. Catalyst regeneration can be achieved by any means known in the art, for example, by passing air or air diluted with nitrogen over the catalyst at a temperature of about 100°C to about 400°C, preferably about 200°C to about 375°C, for about 0.5 hours to about 3 days. This may be followed by a hydrogen fluoride treatment at a temperature of about 100°C to about 400°C, preferably about 200°C to about 350°C, for fluorinated catalysts, or a hydrogen treatment at a temperature of about 100°C to about 400°C, preferably about 200°C to about 350°C, for supported transition metal catalysts.

[0091] During the reaction, by-products formed in step (i) and / or step (ii), such as HCFC-133b, HCFC-1133, HCFC-123a, and HFO-1123, may be recycled to the reactor input if desired.

[0092] In addition, the process advantageously avoids and / or minimizes the formation of 1,1,1-trifluoroethane (HFC-143a), and the product of step (ii), which includes trans-1,2-difluoroethylene (HFO-1132E), may contain less than 5% by weight, less than 3% by weight, less than 1% by weight, less than 0.5% by weight, or less than 0.1% by weight of 1,1,1-trifluoroethane (HFC-143a), based on the total weight of the product composition.

[0093] V. Process (iii) The 1,2-difluoroethylene (HFO-1132) obtained in step (ii) above may be produced as a mixture containing both isomers of trans-1,2-difluoroethylene (HFO-1132E) and cis-1,2-difluoroethylene (HFO-1132Z).

[0094] In step (iii), the cis-1,2-difluoroethylene (HFO-1132Z) isomer may be converted to the trans-1,2-difluoroethylene (HFO-1132E) isomer by either exposure to heat and / or exposure to a catalyst, resulting in a final product containing, consisting of, or comprising the trans-1,2-difluoroethylene (HFO-1132E) isomer in high purity, such as at least about 95% by weight, at least about 99.0% by weight, at least about 99.9% by weight, at least about 99.99% by weight, or higher.

[0095] The isomerization reaction may be carried out in any suitable reaction vessel or reactor, but preferably it should be made of a corrosion-resistant material such as nickel and its alloys, including Hastelloy (e.g., Hastelloy C276), Inconel (e.g., Inconel 600), Incoloy, and Monel, and the vessel may be lined with a fluoropolymer. These may be a single pipe or multiple tubes filled with the isomerization catalyst.

[0096] The temperature range for the isomerization reaction may be as low as approximately 100°C, 150°C, 200°C, 250°C, 300°C, 350°C, 400°C, or 450°C, or as high as approximately 500°C, 550°C, 600°C, 650°C, 700°C, 750°C, or 800°C, or any range encompassed by two of the aforementioned values ​​as endpoints.

[0097] The reaction may be carried out under atmospheric pressure, overpressure, or vacuum. The vacuum pressure can range from approximately 5 Torr to approximately 760 Torr. The contact time between the reactants and the catalyst may range from approximately 0.5 seconds to approximately 120 seconds, but longer or shorter times can be used.

[0098] VI. Reaction Products The multi-step reactions described in sections I to V above may yield compositions containing trans-1,2-difluoroethylene (HFO-1132E) in relatively high purity.

[0099] In one embodiment, the composition may contain, based on the total weight of the composition, trans-1,2-difluoroethylene (HFO-1132E) present in an amount of at least 95% by weight and 1,1,1-trifluoroethane (HFC-143a) present in an amount of less than 5% by weight.

[0100] In another embodiment, the composition may include trans-1,2-difluoroethylene (HFO-1132E) present in an amount of at least 97% by weight, based on the total weight of the composition, and 1,1,1-trifluoroethane (HFC-143a) present in an amount of less than 3% by weight.

[0101] In another embodiment, the composition may include trans-1,2-difluoroethylene (HFO-1132E) present in an amount of at least 99% by weight, based on the total weight of the composition, and 1,1,1-trifluoroethane (HFC-143a) present in an amount of less than 1% by weight.

[0102] It should be understood that the foregoing description is merely illustrative of the present disclosure. Various alternative and modified forms can be devised by those skilled in the art without departing from the present disclosure. Accordingly, the present disclosure is intended to encompass all such alternative forms, modifications, and variations that fall within the scope of the appended claims. [Examples]

[0103] Example 1 Catalyst dilution research This example demonstrates the beneficial effect of catalyst dilution on improving product selectivity when using Pd / Al2O3 as a catalyst for the conversion of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) to 1,1,2-trifluoroethane (HFC-143). The experimental apparatus used in this example is shown in Figure 1. The apparatus includes a supply system including gas flow control devices for N2 and H2, and a Micromotion mass flow meter connected to a research control valve (RCV) that controls the organic matter flow rate. The reactor consists of a 1-inch SS tube packed with catalyst. A thermocouple is inserted into the center of the catalyst bed to read the operating temperature. The pressure control system consists of an RCV that controls the pressure by receiving feedback from a pressure transducer located after the reactor. For GC analysis, samples were taken after the reactor using a sample bag filled with 50 mL of water to capture HCl and HF. Before GC analysis, the sample bag is heated at 60°C for 1 hour to ensure that all organic contents are in the gas phase. Then, the sample is taken using a syringe and injected into the GC instrument for analysis.

[0104] In the first example, a 0.5% Pd / theta Al2O3 catalyst was diluted with 40 mL of 1 / 8-inch SS mesh packing material and then loaded into the reactor. The catalyst was pretreated with H2 at 200°C for 1 hour. Then, 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) was introduced into the reactor at a flow rate of 10 g / hour while passing 150 mL / min of H2 through the catalyst bed at 200°C. Upon introduction of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113), the catalyst bed temperature rose to 216°C. As shown in Table 1, the conversion rate was 73.33%, and the selectivity for "R-143 + recyclable material" was 83.00%. The selectivity for undesirable by-products was 17.00% in total. More specifically, the selectivity was 6.27% for R-142a, 4.23% for ethane, 2.32% for R-160, 1.00% for R-143a, and 0.42% for R-152a.

[0105] In each of the following tables, the product / intermediate may include further recyclable components such as 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a), and trifluoroethylene (HFO-1123). These components are recyclable and can ultimately be converted to 1,1,2-trifluoroethane (HFC-143). Referring to the process flow shown in Figure 1, these recyclable components may be returned to reactor 112 from collection tank 116 through line 128 for further reactions.

[0106] In each of the following tables, the by-products may include 1,1-difluoroethane (HFC-152a), ethane (HC-170), 1,1,1-trifluoroethane (HFC-143a), 1,1-difluoroethylene (HFO-1132a), 1-chloro-1,1-difluoroethane (HCFC-142b), 1-chloro-1,2-difluoroethane (HCFC-142a), and chloroethane (HCC-160). These by-products are the result of the dehydrofluoridation side reaction and are difficult to recycle or convert to 1,1,2-trifluoroethane (HFC-143).

[0107] [Table 1]

[0108] In Table 1, the H2 flow rate was 10 mL / min, the 113 flow rate was 10 g / hour, and the pressure was 45 psig. When diluted, 10 mL of 0.5% Pd / theta Al2O3 catalyst was diluted with 40 mL of 1 / 8 inch SS mesh packed material.

[0109] Figure 1 is a schematic diagram of the apparatus used in Example 1 for the conversion of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) to 1,1,2-trifluoroethane (HFC-143).

[0110] Comparative Example 1 Research on reactions using undiluted catalysts This example demonstrates the conversion of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) to 1,1,2-trifluoroethane (HFC-143) using undiluted Pd / Al2O3. The reaction and product analysis were performed using the same apparatus and procedures as described in Example 1. 50 mL of 0.5% Pd / theta Al2O3 catalyst was loaded into a tubular reactor and pretreated with H2 at 200°C for 1 hour. Then, 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) was introduced into the reactor at a flow rate of 10 g / hour while passing 150 mL / min of H2 through the catalyst bed at 200°C. Upon introduction of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113), the catalyst bed temperature rose to 225°C. As shown in Table 1, the conversion rate was 98.76%, and the selectivity for "R-143 + recyclable material" was 58.34%. The selectivity for undesirable by-products was 41.66% in total. More specifically, the selectivity was 16.65% for R-142a, 12.74% for ethane, 5.73% for R-160, 1.61% for R-143a, and 0.03% for R-152a. This indicates that the Pd / thetaAl2O3 catalyst is highly active against undesirable hydrogen defluorination by-reactions when used undiluted.

[0111] Example 2 Effect of catalyst dilution amount on selectivity for desired product and / or recyclable material This example demonstrates that the maximum selectivity for 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) to 1,1,2-trifluoroethane (HFC-143) in the conversion process using a Pd / alpha-Al2O3 catalyst is achieved when the catalyst concentration is less than 50%. The catalyst concentration is expressed as the volume % of the catalyst relative to the total volume of the catalyst bed. Generally, the total volume of the catalyst bed was 50 mL. In this example, the inventors considered four different catalyst concentrations by mixing 10, 17, 25, and 35 mL of 0.2% Pd / alpha-Al2O3 catalyst with sufficient 1 / 8-inch SS mesh packing material to a total volume of 50 mL. Reaction and product analysis were performed using the same apparatus and procedures as in Example 1.

[0112] As shown in Figure 2, the total selectivity for 143+ recyclable material is lower at a catalyst concentration of 70% compared to less than 50%, which is more evident when looking at higher temperature data. The percentages in the figure represent the volume percentage of the catalyst after dilution with inert material. The H2 flow rate was 10 mL / min, the 113 flow rate was 10 g / hour, and the pressure was 45 psig. The data points shown are the average of 2 to 6 data points collected every 2 hours.

[0113] Example 3 Conversion rate and selectivity to undesirable products using a Pd / Al2O3 catalyst Example 3 demonstrates that the Pd / Al2O3 catalyst exhibits low selectivity for the undesirable byproduct R-152a in the conversion of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) to 1,1,2-trifluoroethane (HFC-143). The reaction and product analysis were performed using the same apparatus and procedures as described in Example 1. Six different Pd / Al2O3 catalysts from different sources were tested. The BET surface area of ​​the catalysts was measured using a TriStar II Micromeritics instrument. Samples were degassed before analysis using a FlowPrep 060 instrument. The measured surface area of ​​the 0.1% Pd / gammaAl2O3 catalyst was 301.0 m². 2 The value is / g, and the 0.5% Pd / gamma Al2O3 catalyst is 302.8m 2 The value is / g, and the 0.3% Pd / delta Al2O3 catalyst is 124.4m 2 The value is / g, and the 0.3% Pd / theta Al2O3 catalyst is 40.2m 2 The value is / g, and the 0.5% Pd / theta Al2O3 catalyst is 41.1m 2 The value is / g, and the 0.2% Pd / alpha Al2O3 catalyst is 3.9m 2 The values ​​were / g. Table 2 shows the conversion rate and selectivity after 2 hours of conversion of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) to 1,1,2-trifluoroethane (HFC-143) when 10 mL of Pd / Al2O3 catalyst was diluted with 40 mL of 1 / 8 inch SS mesh packed material. The results showed that the selectivity for R-152a was preferably in the range of about 0.1% to about 4% across the entire temperature range studied, from about 150°C to about 220°C.

[0114] [Table 2]

[0115] In Table 2, 10 mL of catalyst was diluted with 40 mL of packing material. The H2 flow rate was 10 mL / min, the 113 flow rate was 10 g / hour, and the pressure was 45 psig.

[0116] Comparative Example 3 Comparison of Pd / C catalysts and Pd / Al2O3 catalysts in terms of selectivity for the desired product. Comparative Example 3 demonstrates that the Pd / C catalyst generally exhibits higher selectivity for the undesirable byproduct R-152a in the conversion of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) to 1,1,2-trifluoroethane (HFC-143) compared with the Pd / Al2O3 catalyst (Example 3). The reaction and product analysis were performed using the same apparatus and procedures as described in Example 1. The inventors investigated three different Pd / C catalysts with different Pd weight loads. Table 3 shows the conversion rate and selectivity of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) to 1,1,2-trifluoroethane (HFC-143) when 10 mL of Pd / C catalyst was diluted with 40 mL of 1 / 8-inch SS mesh packed material. The selectivity for R-152a ranged from 5.51% to 11.55% across the entire temperature range studied (150–250°C), which is higher than the selectivity observed for the Pd / Al2O3 catalyst (Example 3). In addition, the maximum selectivity observed for "143 + recyclable material" in the case of the Pd / C catalyst was 93.37% at approximately 162°C for the 1% Pd / C catalyst. Almost all Pd / Al2O3 catalysts showed higher overall selectivity at similar temperatures.

[0117] [Table 3]

[0118] 10 mL of catalyst was diluted with 40 mL of packing material. The H2 flow rate was 10 mL / min, the 113 flow rate was 10 g / hour, and the pressure was 45 psig.

[0119] Example 4 Catalyst thermal stability study Example 4 demonstrates that the alpha phase of alumina is a preferred phase for the conversion of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) to 1,1,2-trifluoroethane (HFC-143) using Pd / Al2O3 as a catalyst. The reaction and product analysis were carried out using the same apparatus and procedures as described in Example 1. Six different Pd / Al2O3 catalysts from different sources were investigated, and the results of the initial conversion rate / selectivity after 2 hours of operation are shown in Table 2. As shown in Table 2 and Figure 3, the formation of by-products follows the trend alpha < theta < delta < gamma. The stability of the support follows the opposite trend, so less stable supports appear to be more reactive for the hydrogen defluorination reaction.

[0120] Figure 3 shows the selectivity for undesirable by-products as a function of the phase of the alumina support in the range of 200–210°C. The alpha-alumina catalyst, theta-alumina catalyst, and delta-alumina catalyst used were 0.2% Pd / alpha-Al2O3 catalyst, 0.3% Pd / theta-Al2O3 catalyst, and 0.3% Pd / delta-Al2O3 catalyst, respectively. For these experiments, 10 mL of catalyst was diluted with 40 mL of packing material. The H2 flow rate was 150 mL / min, the 113 flow rate was 10 g / hour, and the pressure was 45 psig. By-products included R-152a, R-170, R-143a, R-1132a, R-142b, R-142a, R-160, etc.

[0121] The long-term stability of the catalyst is also affected by the support phase. Catalysts using gamma-Al2O3 as the support deactivated very rapidly. The conversion percentage of the 0.5%Pd / gamma-Al2O3 catalyst changed from 56.91% after 2 hours at 165°C to 41.07% after 8 hours. The conversion percentage of the 0.1%Pd / gamma-Al2O3 catalyst changed from 24.52% after 2 hours at 155°C to 19.97% after 8 hours. At similar temperatures, the 0.2%Pd / alpha-Al2O3 catalyst showed no signs of catalyst deactivation up to 250 hours. See Table 4. As shown in Figure 4, 0.3%Pd / delta-Al2O3 deactivated very rapidly after 6 hours at 206°C, and the 0.3%Pd / theta-Al2O3 catalyst showed an 8% decrease in conversion rate (from 92% to 84%) after 15 hours at 210°C. On the other hand, when a 0.2% Pd / alpha-Al2O3 catalyst was used at 200°C, the conversion rate increased from 95.9% to 97.9% during 22 hours of operation.

[0122] The catalysts used in Figure 4 were 0.2% Pd / alpha Al2O3 catalyst, 0.3% Pd / theta Al2O3 catalyst, and 0.3% Pd / delta Al2O3 catalyst, respectively. The temperatures were 200°C for the 0.2% Pd / alpha Al2O3 catalyst, 210°C for the 0.3% Pd / theta Al2O3 catalyst, and 205°C for the Pd / delta Al2O3 catalyst. For the 0.1% Pd / gamma Al2O3 catalyst, 0.5% Pd / gamma Al2O3 catalyst, 0.3% Pd / theta Al2O3 catalyst, and 0.3% Pd / delta Al2O3 catalyst, 10 mL of catalyst was diluted with 40 mL of packing material. For the Pd / alpha Al2O3 catalyst at 200°C, 25 mL of catalyst was diluted with 25 mL of packing material. The flow rate of H2 was 150 mL / min, the flow rate of 113 was 10 g / hour, and the pressure was 45 psig.

[0123] The stability of the 0.2% Pd / alpha-Al2O3 catalyst was evaluated at 160°C for up to 250 hours. The results are summarized in Table 4 below. As shown in Table 2, the initial substrate conversion rate after 2 hours at 160°C was 46.61%, and the selectivity for "143 + recyclable material" was 94.64%. Table 4 shows the performance of this catalyst up to 250 hours under the same conditions. GC samples were collected every 4 hours, and the results were averaged over 50 hours. The conversion rate and the overall selectivity for "143 + recyclable material" increased slowly over time. The selectivity for the undesirable byproduct R-152a decreased over time, but the selectivity for R-170, R-160, and R-142s increased over time, and the net effect was the decrease in the overall selectivity for the undesirable byproduct.

[0124] [Table 4]

[0125] In Table 4, 10 mL of catalyst was diluted with 40 mL of packing material. The H2 flow rate was 150 mL / min, the 113 flow rate was 10 g / hour, and the pressure was 45 psig.

[0126] Example 5 Study on palladium conversion on alpha-alumina catalysts This example demonstrates the optimization of reaction conditions to improve product selectivity for the conversion of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) to 1,1,2-trifluoroethane (HFC-143) using a 0.2% Pd / alpha-Al2O3 catalyst. The reaction and product analysis were performed using the same apparatus and procedures as described in Example 1. Table 5 shows the experiments performed. At a given temperature, the substrate conversion rate increases with increasing contact time (Figure 5). Contact time has only a small effect on product selectivity compared to temperature. As shown in Figure 6, considering all the experiments presented in Table 5, the selectivity for 143 and 123a increases with temperature, while the selectivity for 133b decreases with temperature. In addition, the selectivity for undesirable by-products increases with temperature. As shown in Figure 7, the net effect is a decrease in the overall selectivity for "143 + recyclable material". An overall selection rate of over 95% for "143+ recyclable materials" was achieved at temperatures below 160°C.

[0127] [Table 5]

[0128] In Table 5, a predetermined volume of catalyst was diluted with sufficient packing material to a total volume of 50 mL. All reactions were carried out at 45 psig.

[0129] Figure 5 shows the conversion percentage of the 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) substrate using a 0.2% Pd / alpha-Al2O3 catalyst as a function of contact time at three different temperatures. The data corresponds to the experiments presented in Table 5.

[0130] Figure 6 shows the product selectivity as a function of temperature for the conversion of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) to 1,1,2-trifluoroethane (HFC-143) using a 0.2% Pd / alpha-Al2O3 catalyst. The data corresponds to the experiments presented in Table 5.

[0131] Figure 7 shows the product selectivity as a function of temperature for 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) to 1,1,2-trifluoroethane (HFC-143) in the conversion process using a 0.2% Pd / alpha-Al2O3 catalyst, specifically for 143, 123a, and 133b. The data correspond to the experiments presented in Table 5.

[0132] Example 6 Dilution of raw materials using inert gas Example 6 demonstrates the beneficial effect of feed dilution with N2 as a diluent in improving product selectivity when Pd / Al2O3 is used as a catalyst for the conversion of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) to 1,1,2-trifluoroethane (HFC-143). The reaction and product analysis were carried out using the same apparatus and procedure as described in Example 1. 50 mL of 0.3% Pd / theta Al2O3 catalyst was loaded into a tubular reactor and pretreated with 150 mL / min of H2 at 150°C for 1 hour. Next, while the desired flow rates of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) and N2 (specified in Table 6) passed through the catalyst bed, the catalyst bed temperature rose to 167-174°C upon introduction of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113), depending on the flow rate. The conversion rate and selectivity values ​​are shown in Table 7. In Table 6 below, "X" represents the mole fraction assuming ideal gas behavior.

[0133] [Table 6]

[0134] [Table 7]

[0135] In Table 7, all experiments were conducted at 45 psig. The reactor bed temperature before the introduction of organic matter was 150°C, and this temperature rose to the specified temperature in the table due to the exothermic reaction.

[0136] Comparative Example 6 Reaction in the absence of raw material dilution Comparative Example 6 demonstrates the conversion of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) to 1,1,2-trifluoroethane (HFC-143) using 0.3% Pd / theta Al2O3 without feed dilution (Experiment No. 1, Tables 6 and 7). The reaction and product analysis were carried out using the same apparatus and procedures as described in Example 1. 50 mL of 0.3% Pd / theta Al2O3 catalyst was loaded into a tubular reactor and pretreated with H2 at 150°C for 1 hour. Then, 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) was introduced into the reactor at a flow rate of 15 g / hour while passing 150 mL / min of H2 through the catalyst bed at 150°C. The supply gas composition was 82% H2 and 18% 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113). Upon introduction of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113), the catalyst bed temperature rose to 171°C, and then slowly rose to 174°C over the following two hours. As shown in Table 7 (Experiment No. 1), the conversion rate was 77.47%, and the selectivity for "R-143 + recyclable material" was 82.14%. The selectivity for undesirable by-products was 17.85% in total. More specifically, the selectivity was 5.46% for R-142a, 5.55% for ethane, 2.46% for R-160, 0.72% for R-143a, and 0.31% for R-152a.

[0137] Example 7 Dilution of raw materials using organic molecules Example 7 demonstrates the beneficial effect of using 1,2,2-trifluoroethane (HFC-143) as a diluent to improve the product selectivity when Pd / Al2O3 is used as a catalyst for the conversion of 1,1,2-trichloro-1,1,2-trifluoroethane (CFC-113) to 1,1,2-trifluoroethane (HFC-143).

[0138] The experiment is carried out in the same manner as described in Example 6, except that the diluent is 1,1,2-trifluoroethane (HFC-143). Similar results are observed in the presence of each of the diluents containing HFC-41, HFC-32, HFC-23, HFC-152a, HFC-134a, HFC-125, HFC-254eb, HFC-254fb, HFC-245fa, HFC-245cb, HFC-245eb, HFC-236ea, HFC-236fa, HFC-227ea, and HFC-143, including lower hotspot temperatures and higher composite selectivity for 1,1,2-trifluoroethane (HFC-143), 1-chloro-1,1,2-trifluoroethane (HCFC-133b), and 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a), compared to the absence of any of these diluents. Lower selectivity was also observed for by-products including 1,1-difluoroethane (HFC-152a), ethane (HC-170), 1,1,1-trifluoroethane (HFC-143a), 1,1-difluoroethylene (HFO-1132a), 1-chloro-1,1-difluoroethane (HCFC-142b), 1-chloro-1,2-difluoroethane (HCFC-142a), and / or chloroethane (HCC-160).

[0139] Example 8 Combination of catalyst dilution and raw material dilution The catalyst dilution processes of Examples 1 to 5 are combined with the raw material dilution processes of Examples 6 and 7. Similar or improved results are also observed, including lower hotspot temperatures, higher composite selectivity for 1,1,2-trifluoroethane (HFC-143), 1-chloro-1,1,2-trifluoroethane (HCFC-133b), and 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a), as well as lower selectivity for by-products including 1,1-difluoroethane (HFC-152a), ethane (HC-170), 1,1,1-trifluoroethane (HFC-143a), 1,1-difluoroethylene (HFO-1132a), 1-chloro-1,1-difluoroethane (HCFC-142b), 1-chloro-1,2-difluoroethane (HCFC-142a), and / or chloroethane (HCC-160).

[0140] manner Embodiment 1 is a method for producing 1,1,2-trifluoroethane (HFC-143), comprising hydrogenating 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) with hydrogen in the presence of a catalyst to produce 1,1,2-trifluoroethane (HFC-143), wherein the catalyst comprises a catalyst material, which is a catalyst metal supported on a carrier, containing 0.1 to 1.0% by weight based on the total weight of the catalyst metal and the carrier, and a diluent, wherein the amount of the catalyst material is 5 to 70% by volume based on the total volume of the catalyst material and the diluent.

[0141] Embodiment 2 is the method according to Embodiment 1, wherein the amount of catalyst material is 10 to 50 volume percent based on the total volume of catalyst material and diluent material.

[0142] Embodiment 3 is the method according to Embodiment 1 or 2, wherein the metal contains palladium.

[0143] Embodiment 4 is the method according to any one of Embodiments 1 to 3, wherein the carrier comprises alumina (Al2O3).

[0144] Embodiment 5 is the method according to any one of Embodiments 1 to 4, wherein the diluent comprises a metal or a metal alloy.

[0145] Embodiment 6 is the method according to any one of Embodiments 1 to 5, wherein the carrier is selected from alpha alumina, gamma alumina, delta alumina, and theta alumina.

[0146] Embodiment 7 is a method according to any one of Embodiments 1 to 6, wherein the carrier comprises alpha alumina.

[0147] Embodiment 8 is the method according to any one of Embodiments 1 to 7, wherein the hydrogenation process is carried out at a temperature of approximately 100°C to approximately 300°C.

[0148] Embodiment 9 is a method according to any one of Embodiments 1 to 8, wherein the hydrogenation process is carried out at a temperature of approximately 150°C to approximately 250°C.

[0149] Embodiment 10 is the method according to any one of Embodiments 1 to 9, wherein the hydrogenation process is carried out at a pressure of about 10 psig to about 100 psig.

[0150] Embodiment 11 is a method according to any one of Embodiments 1 to 10, wherein the hydrogenation step is carried out in a ratio of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) to hydrogen of about 3:1 to about 15:1.

[0151] Embodiment 12 is a method according to any one of Embodiments 1 to 11, wherein the hydrogenation step achieves a selectivity of more than approximately 20% for 1,1,2-trifluoroethane (HFC-143).

[0152] Embodiment 13 is a method according to any one of Embodiments 1 to 12, wherein the hydrogenation step achieves a combined selectivity of over 80% for 1,1,2-trifluoroethane (HFC-143), 1-chloro-1,1,2-trifluoroethane (HCFC-133b), and 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a).

[0153] Embodiment 14 is a method according to any one of Embodiments 1 to 13, wherein the hydrogenation step achieves a combined selectivity of less than approximately 20% for 1,1-difluoroethane (HFC-152a), ethane (HC-170), 1,1,1-trifluoroethane (HFC-143a), 1-chloro-1,2-difluoroethane (HCFC-142a), and chloroethane (HCC-160).

[0154] Embodiment 15 is a method according to any one of Embodiments 1 to 14, wherein the hydrogenation process is carried out with a contact time of approximately 1 second to approximately 60 seconds.

[0155] Embodiment 16 is the method according to any one of Embodiments 1 to 15, further comprising the additional step of defluorinating 1,1,2-trifluoroethane (HFC-143) in the presence of a catalyst to produce trans-1,2-difluoroethylene (HFO-1132E) and / or cis-1,2-difluoroethylene (HFO-1132Z).

[0156] Embodiment 17 is the method of Embodiment 16, further comprising the additional step of isomerizing cis-1,2-difluoroethylene (HFO-1132Z) to produce trans-1,2-difluoroethylene (HFO-1132E).

[0157] Embodiment 18 is a composition produced from the method of Embodiment 16 or 17, comprising, based on the total weight of the composition, trans-1,2-difluoroethylene (HFO-1132E) present in an amount of at least 95% by weight and 1,1,1-trifluoroethane (HFC-143a) present in an amount of less than 5% by weight.

[0158] Embodiment 19 is the composition according to Embodiment 18, comprising, based on the total weight of the composition, trans-1,2-difluoroethylene (HFO-1132E) present in an amount of at least 97% by weight and 1,1,1-trifluoroethane (HFC-143a) present in an amount of less than 3% by weight.

[0159] Embodiment 20 is the composition according to Embodiment 19, comprising, based on the total weight of the composition, trans-1,2-difluoroethylene (HFO-1132E) present in an amount of at least 99% by weight and 1,1,1-trifluoroethane (HFC-143a) present in an amount of less than 1% by weight.

[0160] Embodiment 21 is a palladium metal catalyst useful for hydrogenating 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) with hydrogen to produce 1,1,2-trifluoroethane (HFC-143), wherein the catalyst comprises a catalyst material containing 0.1 to 1.0% by weight of palladium metal supported on an alumina (Al2O3) support, based on the total weight of the catalyst metal and the support, and a diluent, wherein the amount of catalyst material is 5 to 70 volume percent based on the total volume of the catalyst material and the diluent.

[0161] Embodiment 22 is the catalyst according to Embodiment 21, wherein the amount of catalyst material is 10 to 50 volume percent based on the total volume of catalyst material and diluent material.

[0162] Embodiment 23 is the catalyst according to Embodiment 21 or 22, wherein the support is selected from alpha-alumina, delta-alumina, and theta-alumina.

[0163] Embodiment 24 is a catalyst according to any one of Embodiments 21 to 23, wherein the support comprises alpha alumina.

[0164] Embodiment 25 is a catalyst according to any one of Embodiments 21 to 24, wherein the diluent contains a metal or a metal alloy.

[0165] Embodiment 26 is a method for producing 1,1,2-trifluoroethane (HFC-143), comprising: combining 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) with a starting material diluent to form a reaction mixture; and reacting the 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) in the reaction mixture with hydrogen in the presence of a catalyst to produce a product mixture.

[0166] Embodiment 27 is the method of Embodiment 26, wherein the product mixture comprises 1,1,2-trifluoroethane (HFC-143), and the method further comprises the additional steps of separating 1,1,2-trifluoroethane (HFC-143) from the product mixture and transporting 1,1,2-trifluoroethane (HFC-143) to the reactant mixture.

[0167] Embodiment 28 is the method according to Embodiment 27, wherein the reaction mixture comprises 1,1,2-trifluoroethane (HFC-143) to 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) in a molar ratio of about 0.25:1 to about 10:1.

[0168] Embodiment 29 is the method according to Embodiment 28, wherein the reaction mixture comprises 1,1,2-trifluoroethane (HFC-143) to 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) in a molar ratio of about 0.5:1 to about 8:1.

[0169] Embodiment 30 is a method of any of Embodiments 1 to 25, which is used simultaneously with any of Embodiments 26 to 29.

Claims

1. A method for producing 1,1,2-trifluoroethane (HFC-143), The process includes hydrogenating 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) with hydrogen in the presence of a catalyst to produce 1,1,2-trifluoroethane (HFC-143), wherein the catalyst is A catalyst material comprising a catalyst metal supported on a carrier, the catalyst material containing 0.1 to 1.0% by weight based on the total weight of the catalyst metal and the carrier, A method comprising a diluent and a catalyst, wherein the amount of the catalyst is 5 to 70 volume percent based on the total volume of the catalyst and the diluent.

2. The method according to claim 1, wherein the amount of the catalyst material is 10 to 50 volume percent based on the total volume of the catalyst material and the diluent.

3. The method according to claim 1 or 2, wherein the metal includes palladium and the diluent includes a metal or a metal alloy.

4. The method according to any one of claims 1 to 3, wherein the carrier is selected from alpha alumina, delta alumina, and theta alumina.

5. The method according to any one of claims 1 to 4, wherein the hydrogenation step is carried out at a temperature of about 100°C to about 300°C.

6. The method according to any one of claims 1 to 5, wherein the hydrogenation step achieves a combined selectivity of more than approximately 80% for 1,1,2-trifluoroethane (HFC-143), 1-chloro-1,1,2-trifluoroethane (HCFC-133b), and 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a).

7. The method according to any one of claims 1 to 6, wherein the hydrogenation step achieves a combined selectivity of less than about 20% for 1,1-difluoroethane (HFC-152a), ethane (HC-170), 1,1,1-trifluoroethane (HFC-143a), 1-chloro-1,2-difluoroethane (HCFC-142a), and chloroethane (HCC-160).

8. The method according to any one of claims 1 to 7, further comprising the additional step of defluoridating 1,1,2-trifluoroethane (HFC-143) in the presence of a catalyst to produce trans-1,2-difluoroethylene (HFO-1132E) and / or cis-1,2-difluoroethylene (HFO-1132Z).

9. A composition produced by the method according to any one of claims 1 to 8, wherein, based on the total weight of the composition, Trans-1,2-difluoroethylene (HFO-1132E) is present in an amount of at least 95% by weight, A composition comprising 1,1,1-trifluoroethane (HFC-143a) present in an amount of less than 5% by weight.

10. A palladium metal catalyst useful for hydrogenating 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) with hydrogen to produce 1,1,2-trifluoroethane (HFC-143), wherein the catalyst is A catalyst material, alumina (Al ２ O ３ A catalyst material comprising palladium metal supported on a carrier, comprising 0.1 to 1.0% by weight based on the total weight of the catalyst metal and the carrier, A palladium metal catalyst comprising a diluent, wherein the amount of the catalyst material is 5 to 70 volume percent based on the total volume of the catalyst material and the diluent.

11. The catalyst according to claim 10, wherein the amount of the catalyst material is 10 to 50 volume percent based on the total volume of the catalyst material and the diluent.

12. The catalyst according to claim 10 or 11, wherein the carrier is selected from alpha alumina, delta alumina, and theta alumina.

13. The catalyst according to any one of claims 10 to 12, wherein the diluent comprises a metal or a metal alloy.

14. A method for producing 1,1,2-trifluoroethane (HFC-143), The reaction mixture is formed by combining 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) with a raw material diluent. A method comprising reacting the 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) in the reaction mixture with hydrogen in the presence of a catalyst to produce a product mixture.

15. The method according to claim 14, wherein the diluted composition comprises 1,1,2-trifluoroethane (HFC-143) to 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) in a molar ratio of about 0.25:1 to about 10:1.

Images