Composition including 1,1,1-trifluoro-2,3-dichloropropane

Abstract

To provide a composition including 1,1,1-trifluoro-2,3-dichloropropane.SOLUTION: A composition includes 1,1,1-trifluoro-2,3-dichloropropane, 3,3,3-trifluoropropene, a chlorine gas, a catalyst, and 1,1,1-trifluoro-3-chloropropylene. The catalyst includes at least one metal chloride. The metal is nickel, iron, chromium, or a combination of them. The at least one metal chloride is supported on activated carbon. The molar ratio of 3,3,3-trifluoropropene to the chlorine gas ranges from 1: 0.02 to 1: 1.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a process for the production of 2,3-dichloro-1,1,1-trifluoropropane (HCFC-243db) by chlorination of 3,3,3-trifluoro-1-propene (HFO-1243zf). [Background technology]

[0002] For the past several decades, many manufacturing industries have been working to find alternatives to ozone-depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs). These compounds have a wide range of uses, including as aerosol propellants, refrigerants, and cleaning agents; blowing agents for thermoplastic and thermoset foams; heat transfer media, gaseous dielectric materials; fire extinguishing and suppression agents; power cycle working fluids, polymerization media, particulate removal fluids, carrier fluids, buffing abrasive agents, and displacement desiccants. In their search for alternatives to these versatile compounds, many manufacturing industries have turned their attention to the use of hydrofluorocarbons (HFCs).

[0003] Although HFCs do not contribute to the depletion of stratospheric ozone, they are of concern because they contribute to the "greenhouse effect." That is, HFCs contribute to global warming. As a result of their contribution to global warming, HFCs have come under scrutiny and their widespread use may also be restricted in the future. Therefore, there is a need for chemical compounds that combine low ozone depletion potential (ODP) and low global warming potential (GWP).

[0004] One such useful compound with a low GWP is 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf). This compound is useful as a refrigerant and blowing agent. This compound can be produced in many ways, one of which is via the following process:

[0005] (1) In a gas-phase reactor packed with a solid catalyst (CX2=CCl-CH2X or CX3-CCl=CH2 or CX3-CHCl-CH2X) + HF -> 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) + HCl (2) in a liquid-phase reactor packed with a liquid hydrofluorination catalyst 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) + HF -> 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) (3) In the gas phase reactor 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) 2,3,3,3-Tetrafluoropropene (HFO-1234yf) Thus, 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) is an intermediate in the process for producing 2,3,3,3-tetrafluoropropene (HFO-1234yf). HCFC-1233xf is obtained by dehydrochlorination of HCFC-243db, the product of the present process. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] US Patent Application Publication No. 2011 / 0118513 Summary of the Invention [Problem to be solved by the invention]

[0007] There have been various methods for producing HCFC-243db, including the chlorination of 3,3,3-trifluoro-1-propene (HFO-1243zf) using ultraviolet light, at high temperatures, or in the liquid phase without a catalyst. However, there are many problems associated with these methods. The ultraviolet light approach is less selective and difficult to scale up to a commercial process. Also, the liquid phase reaction without a catalyst is very slow and requires high temperatures. However, even under these conditions, tar is still formed.

[0008] Therefore, there is a need in the art for a new process for producing HCFC-243db that does not suffer from the drawbacks of the prior art. The present invention overcomes these problems. [Means for solving the problem]

[0009] The present process relates to a process for preparing 1,1,1-trifluoro-2,3-dichloropropane, the process comprising contacting 3,3,3-trifluoropropene with chlorine in the presence of a catalyst to form 1,1,1-trifluoro-2,3-dichloropropane, the catalyst comprising at least one metal halide, the metal being an element of Group 13, 14, or 15 of the Periodic Table, or a transition metal, or a combination thereof. The reaction can be carried out in either the gas phase or the liquid phase. [Effects of the Invention]

[0010] The process produces 1,1,1-trifluoro-2,3-dichloropropane in excellent yield and with high selectivity. [Brief explanation of the drawings]

[0011] The following figures further explain the present invention in a non-limiting manner. [Figure 1]Figure 1 graphically compares the 243db selectivity for the chlorination of 1243zf using the following catalysts: activated carbon (Comparative Example 1), 15% CrCl / C (Example 1), 5% FeCl / C (Example 3), and 5% CrCl / C (Example 6). [Figure 2] In Figure 2, the results of the present process are compared with a reaction conducted at elevated temperature and without a catalyst using graphs of pressure as a function of time. The lower plot graphically depicts the change in pressure as a function of time for the product formed according to the procedure of Example 11. The middle plot graphically depicts the change in pressure as a function of time for the product formed according to the procedure of Comparative Example 2. The upper plot graphically depicts the change in pressure as a function of time for the product formed according to the procedure of Comparative Example 3. DETAILED DESCRIPTION OF THE INVENTION

[0012] As used herein, the words "comprises," "comprising," "includes," "including," "has," "having," or any other variation thereof, are intended to encompass a non-exclusive inclusion. For example, a process, method, article, or apparatus that includes listed elements is not necessarily limited to only those elements and may include other elements not expressly listed or that are inherent to such process, method, article, or apparatus. Further, unless expressly stated, "or" is an inclusive or, not an exclusive or. For example, a condition A or B can be satisfied by any one of the following: A is true (or present) and B is false (or absent); A is false (or absent) and B is true (or present); or both A and B are true (or present).

[0013] Additionally, the use of "a" and "an" is employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be interpreted as one, or at least one, and the singular also includes the plural unless it is clear that something else is meant.

[0014] When a range of values ​​is expressed, another embodiment includes from the one particular value and / or to the other particular value. Similarly, when values ​​are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value forms another embodiment. All ranges are inclusive and binding. Furthermore, reference to values ​​stated in ranges includes each and every value within that range.

[0015] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Methods and materials similar or equivalent to those described herein can be used in the practice and testing of embodiments of this invention. However, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety, unless a specific portion is cited. In case of conflict, the present specification, including definitions, will control. Furthermore, the materials, methods, and examples are illustrative only and not intended to be limiting.

[0016] While many aspects and embodiments are described herein, they are intended to be illustrative and not limiting. After reading this specification, one skilled in the art will recognize that other aspects and embodiments are possible without departing from the scope of the invention. The features and benefits of any one or more of the embodiments will be apparent from the following detailed description and claims.

[0017] As noted above, the present process relates to the chlorination of 3,3,3-trifluoropropene to form 1,1,1-trifluoro-2,3-dichloropropane in the presence of a catalyst, the catalyst comprising at least one metal halide, the metal being a metal from Group 13, 14, or 15 of the Periodic Table, or a transition metal.

[0018] As used herein, the term "halide" means fluoride, chloride, bromide and iodide.

[0019] The term metal, as used herein, refers to a metal in the periodic table. Non-metals, halogens, noble gases, and actinides are excluded. However, as used herein, the term metal includes metalloids. Examples of metals include metals in Groups 13 and 14 of the periodic table. The term also includes transition metals as defined herein. Examples of metals include nickel, chromium, iron, scandium, yttrium, lanthanum, titanium, zirconium, hafnium, vanadium, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, cobalt, palladium, copper, zinc, tantalum, antimony, aluminum, tin, and lead. It should be noted that, as defined herein, antimony is a metalloid and, by the definition herein, a metal.

[0020] The term "transition metal" refers to the elements, including the lanthanides, of Groups 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12. Examples of transition metals include nickel, chromium, iron, scandium, yttrium, lanthanum, titanium, zirconium, hafnium, vanadium, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, cobalt, palladium, copper, zinc, and tantalum.

[0021] The catalysts used in the chlorination reactions described herein are in the form of metal halides, and therefore the metals used therein have a positive oxidation number of +1, +2, +3, +4, or +5, depending on which metal forms a salt with the halide.

[0022] The term "activated carbon" refers to a carbon dioxide concentration of approximately 50 to 3000 m 2 Or about 100 to about 2000 m 2 (for example, about 200 to about 1500 m) 2 Or about 300 to about 1000 m 2 ), including any carbon with a relatively large surface area. Activated carbon can be obtained from any carbonaceous material, such as coal (e.g., charcoal), nut shells (e.g., coconut), and wood. Any form of activated carbon may be used, such as powder, granules, and pellets. Activated carbon modified (e.g., impregnated) with Cr, Mn, Au, Fe, Sn, Ta, Ti, Sb, Al, Co, Ni, Mo, Ru, Rh, Pd, and / or Pt and / or compounds of one or more of these metals (e.g., halides) may also be used.

[0023] In some embodiments, the activated carbon is washed with at least one basic solution to remove silicates. For example, the activated carbon is washed with an alkali metal hydroxide, an alkaline earth metal hydroxide, or ammonium hydroxide. Examples of basic solutions that have been used to wash activated carbon include sodium hydroxide, ammonium hydroxide, and potassium hydroxide.

[0024] Further, other suitable forms of activated carbon include, but are not limited to, acid-washed activated carbon powder produced by steam activation of lignite. In some embodiments, organic and / or inorganic nitrogen-containing acids, such as nitric acid, are used. Additional acids that can be used include, but are not limited to, sulfuric acid, hydrochloric acid, phosphoric acid, and combinations thereof. The acid preferably has an aqueous solution concentration of 2 to 12 mol / L. According to one embodiment, the activated carbon is soaked for at least 1 hour, e.g., 1 to 36 hours, or 1 to 10 hours. Optionally, the activated carbon may be agitated during soaking. Optionally, the activated carbon is rinsed with deionized water after washing to increase the pH to 5 to 8. In some embodiments, the activated carbon is washed with at least one acid and at least one base to reduce calcined ash and remove silicates.

[0025] The metal in the metal halide used as the catalyst is antimony, which is a metal, transition metal, and metalloid of Groups 13 and 14 of the periodic table. Examples of metals include nickel, chromium, iron, scandium, yttrium, lanthanum, titanium, zirconium, hafnium, vanadium, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, cobalt, palladium, copper, zinc, tantalum, aluminum, tin, and lead. It should be noted that, as defined herein, antimony is a metalloid. However, as defined herein, metalloids are included in the definition of metal. Examples of metal halides include nickel halides, chromium halides, iron halides, scandium halides, yttrium halides, lanthanum halides, titanium halides, zirconium halides, hafnium halides, vanadium halides, molybdenum halides, tungsten halides, manganese halides, rhenium halides, ruthenium halides, osmium halides, cobalt halides, palladium halides, copper halides, zinc halides, antimony halides, tantalum halides, aluminum halides, tin halides, and lead halides. In one embodiment, the metal halide is nickel halide, iron halide, chromium halide, or a combination thereof, and is used as a catalyst with or without being supported on activated carbon. In another embodiment, the metal halide is a bromide or chloride. In yet another embodiment, the halide is a chloride. In another embodiment, the metal halide is nickel chloride, iron chloride, or chromium chloride, or a combination thereof.

[0026] The metal halide catalyst of the present chlorination process may be unsupported or supported on activated carbon, which may be unwashed, acid-washed, or base-washed.

[0027] In the chlorination reaction, chlorine is present in a gaseous state. Chlorine gas may be used or chlorine gas may be generated in situ from the reaction of gaseous hydrogen chloride with oxygen. In one embodiment, the chlorination reaction is carried out in the absence of water. If water is present, it is present at less than 1 wt % in one embodiment, and less than 0.5 wt % in another embodiment.

[0028] 3,3,3-trifluoropropene is commercially available. Alternatively, it can be prepared using techniques known in the art. For example, see Patent Document 1, the contents of which are incorporated by reference.

[0029] As described below, the chlorination reaction can be carried out in either the gas phase or the liquid phase.

[0030] When carried out in the vapor phase, the process is carried out at an effective temperature and pressure. In one embodiment, the reaction is carried out at a temperature ranging from about 80 to about 200°C. In another embodiment, the reaction is carried out at a temperature ranging from 80 to about 160°C. In yet another embodiment, the chlorination reaction is carried out at a temperature ranging from about 80 to about 130°C, and in another embodiment, from about 80 to about 120°C. The process can be carried out at a pressure ranging from about 10 psig (170.3 kPa) to about 100 psig (790.8 kPa). In another embodiment, the pressure ranges from about 1 atmosphere (101.3 kPa) to about 50 psig (446.1 kPa), and in another embodiment, the pressure ranges from about 20 psig (239.2 kPa) to about 50 psig (446.1 kPa). Thus, in one embodiment, the process is conducted in the vapor phase at a temperature ranging from about 80 to about 200°C, and at a pressure ranging from about 10 psig (170.3 kPa) to about 100 psig (790.8 kPa), in another embodiment from about 1 atmosphere (101.3 kPa) to about 50 psig (446.1 kPa), and in another embodiment from about 10 psig (170.3 kPa) to about 50 psig (446.1 kPa), for example, from about 20 psig (239.2 kPa) to about 50 psig (446.1 kPa). In another embodiment, the chlorination reaction is conducted at a temperature ranging from about 80°C to about 160°C, and at a pressure ranging from about 10 psig (170.3 kPa) to about 100 psig (790.8 kPa), in another embodiment from about 1 atmosphere (101.3 kPa) to about 50 psig (446.1 kPa), and in another embodiment from about 20 psig (239.2 kPa) to about 50 psig (446.1 kPa). In further embodiments, the chlorination reaction is carried out at a temperature ranging from about 80 to 130° C. and at a pressure ranging from about 10 psig (170.3 kPa) to about 100 psig (790.8 kPa), in another embodiment from about 1 atmosphere (101.3 kPa) to about 50 psig (446.1 kPa), and in another embodiment from about 20 psig (239.2 kPa) to about 50 psig (446.1 kPa).

[0031] The 3,3,3-trifluoropropene and chlorine gas are present in amounts effective to cause a chlorination reaction. In one embodiment, the molar amount of 3,3,3-trifluoropropene is present in excess of the molar amount of chlorine gas. In one embodiment, the molar ratio of 3,3,3-trifluoropropene to chlorine gas ranges from about 1:0.02 to about 1:1. In another embodiment, the molar ratio of 3,3,3-trifluoropropene to chlorine gas ranges from about 1:0.1 to about 1:0.8. In yet another embodiment, the molar ratio of 3,3,3-trifluoropropene to chlorine gas ranges from about 1:0.1 to about 1:0.5.

[0032] The contact time for the chlorination reaction, i.e., the time allowed for the reaction to occur, can range from about 0.1 seconds to about 120 seconds, and in other embodiments, from about 5 seconds to about 1 minute. However, longer and shorter times can also be used. As used herein, contact time is determined by the following formula: Contact time (seconds) = 1 / ((total gas flow (SCCM) / 60 / catalyst volume))x(14.7+P(PSIG)) / 14.7x(298 / (273+T(℃)) where SCCM is standard cubic centimeters per minute, P is pressure, PSIG is gauge pressure, which is the working pressure in pounds per square inch, not absolute pressure, T (°C) is temperature in degrees Celsius, and catalyst volume is in cubic centimeters.

[0033] The metal halide catalyst is present in a catalytically effective amount in the vapor phase in the chlorination reaction. In one embodiment, the catalyst is supported on activated carbon, which is unwashed or acid- or base-washed. In one embodiment, the metal halide is supported on activated carbon and is present in an amount ranging from about 2 to about 30% by weight of the activated carbon, in another embodiment from about 3 to about 25% by weight, and in another embodiment from about 5 to about 20% by weight.

[0034] In one embodiment, the chlorination reaction is carried out to achieve a conversion rate of about 50% or more, preferably about 90% or more. The conversion rate is calculated by dividing the moles of reactants consumed (the mole ratio of 3,3,3-trifluoropropene) by the moles of reactants fed to the reactor (the mole ratio of 3,3,3-trifluoropropene) and multiplying by 100. The selectivity to 1,1,1-trifluoro-2,3-dichloropropane obtained is preferably 60% or more, more preferably 80% or more. The selectivity is calculated by dividing the moles of the product (1,1,1-trifluoro-2,3-dichloropropane) formed by the moles of the reactants consumed.

[0035] The present process in the vapor phase provides higher 243 db selectivity than activated carbon itself at elevated temperatures, such as 100-160°C, and in another embodiment, from about 120°C to about 200°C. Thus, within these temperature ranges, the chlorination reaction can be carried out at pressures ranging from vacuum to about 100 psig (790.8 kPa), in another embodiment from about 1 atmosphere (101.3 kPa) to about 50 psig (446.1 kPa), and in another embodiment from about 10 psig (170.3 kPa) to about 50 psig (446.1 kPa). The present process allows for operation at higher backpressures above the 243 db dew point.

[0036] The chlorination reaction can be carried out in any reactor suitable for gas-phase chlorination reactions. In one embodiment, the reactor is constructed of materials that are resistant to the corrosive effects of chlorine and the catalyst, such as Hastalloy, Inconel, Monel, and fluoropolymer lining materials. The vessel can be a fixed catalyst bed or a fluidized bed. Optionally, an inert gas, such as nitrogen or argon, can be used in the reactor during operation.

[0037] In one embodiment, as noted above, the catalyst in the gas phase reaction is supported on activated carbon, which may be unwashed, acid washed, or base washed.

[0038] In another embodiment, the chlorination reaction is carried out in the liquid phase. The present process in the liquid phase can be carried out in any suitable apparatus, such as a static mixer, a tubular reactor, or a stirred vapor-liquid disengagement vessel. The apparatus described herein, in one embodiment, is made from one or more materials resistant to corrosion, such as stainless steel, particularly austenitic stainless steel; high-nickel alloys such as Monel™ nickel-copper alloy, Hastelloy™ nickel-based alloy, and Inconel™ nickel-chromium alloy; and copper-coated steel. The present process can be carried out batchwise or continuously.

[0039] Vigorous shaking, stirring, and / or agitation may be required to complete the reaction. The degree of agitation depends on the desired reaction rate, which in turn depends on the reactor configuration, residence time, agitator and baffle configuration, and the solubility of 3,3,3-trifluoropropene in the solvent. Therefore, the chlorination reaction in the liquid phase is carried out with stirring.

[0040] In the liquid phase, the chlorination reaction can be carried out with or without an inert solvent. The inert solvent is a solvent in which the 3,3,3-trifluoropropene is soluble and can be easily separated from the 3,3,3-trifluoropropene and the 1,1,1-trifluoro-2,3-dichloropropane. The term "inert" means that the solvent does not react with chlorine, 3,3,3-trifluoropropene, or 1,1,1-trifluoro-2,3-dichloropropane under the reaction conditions. Suitable solvents include, for example, carbon tetrachloride, 1,1,2-trichloro-1,2,2-trifluoroethane, CF3 (CF2) n C represented by CF3 5-8 These include straight chain perfluoroalkyl compounds (where n is an integer from 3 to 6, inclusive); or perhalogenated compounds such as hexachloroacetone and 1,1,1-trifluoro-2,3-dichloropropane.

[0041] The amount of solvent used in the reaction in the chlorination step is not particularly limited, as long as 3,3,3-trifluoropropene can be dissolved therein. In one embodiment, the amount of solvent present ranges from about 1 to about 1000% by mass, and in another embodiment, from about 50 to about 100% by mass, based on the raw material components (total amount of 3,3,3-trifluoropropene and chlorine). The catalyst used herein may be heterogeneous or partially dissolved in a liquid phase containing 3,3,3-trifluoro-1-propene / 2,3-dichloro-1,1,1-trifluoropropane (1243zf / 243db). In another embodiment, the catalyst is a homogeneous catalyst.

[0042] The reaction is carried out using effective amounts of chlorine gas and 3,3,3-trifluoropropene to form 1,1,1-trifluoro-2,3-dichloropropane. As in the gas-phase reaction, the molar amount of 3,3,3-trifluoropropene is, in one embodiment, present in excess of the molar amount of chlorine gas. In one embodiment, the molar amount of 3,3,3-trifluoropropene to chlorine ranges from about 1:0.02 to about 1:1, in another embodiment from about 1:0.1 to 1:0.9, and in another embodiment from about 1:0.1 to about 1:0.95.

[0043] The chlorination reaction is carried out at an effective temperature, which in one embodiment ranges from about 20 to about 200°C, while in another embodiment ranges from about 30 to about 110°C, and in another embodiment ranges from about 35 to about 90°C.

[0044] The reactor pressure in a liquid phase process is not critical and in a batch reaction is usually the autogenous pressure of the system at the reaction temperature.

[0045] In the liquid phase, the metal halide catalyst is present in a catalytically effective amount. In one embodiment, the catalyst is unsupported. In one embodiment, the catalyst is present in an amount ranging from about 0.1 to 10 weight percent of the reactants (i.e., the total amount of chlorine and 3,3,3-trifluoropropene), in another embodiment, from about 0.5 to about 6 weight percent, and in another embodiment, from about 1 to about 4 weight percent.

[0046] The reaction time for the chlorination reaction in the liquid phase may vary over a wide range, but will typically be in the range of from about 0.01 to about 100 hours, for example, from about 0.5 to about 50 hours.

[0047] The chlorination reaction in both the liquid phase and the gas phase is preferably carried out to achieve a conversion of about 50% or more, preferably 90% or more. As mentioned above, in one embodiment, the reaction is carried out when the molar amount of 3,3,3-trifluoropropene is equal to or exceeds that of chlorine. The conversion is calculated by dividing the moles of reactants consumed (molar ratio of 3,3,3-trifluoropropene) by the moles of reactants fed to the reactor (molar ratio of 3,3,3-trifluoropropene) and multiplying by 100. The selectivity of 1,1,1-trifluoro-2,3-dichloropropane achieved is preferably about 60% or more, more preferably about 80% or more. The selectivity is calculated by dividing the moles of the product (1,1,1-trifluoro-2,3-dichloropropane) formed by the moles of reactants consumed.

[0048] Whether the reaction is carried out in the gas phase or the liquid phase, 1,1,1-trifluoro-2,3-dichloropropane is isolated, i.e., separated and collected. The 1,1,1-trifluoro-2,3-dichloropropane-containing product is removed from the reactor by techniques known in the art, such as siphoning. In the gas phase, the product is allowed to flow from the reactor and liquefied. The 1,1,1-trifluoro-2,3-dichloropropane-containing product is purified by techniques known in the art, such as distillation. Whether carried out in the gas phase or the liquid phase, the present process is commercially viable and easily scaled up for commercial production. Furthermore, the chlorination reaction rate using the process described herein is faster than processes previously used to chlorinate 3,3,3-trifluoropropene to 1,1,1-trifluoro-2,3-dichloropropane (HCFC243db), providing higher conversion and selectivity.

[0049] In both the gas-phase and liquid-phase chlorination reactions, there are several side reactions that compete with the formation of the 2,3-dichloro-1,1,1-trifluoropropane product (HCFC243db). These side reactions include:

[0050] Conversion of a.243db to 1,1,1-trifluoro-3-chloropropylene CF3CHClCH2Cl -> CF3CCl=CH2+ CF3CH=CHCl + HCl 243db 1233xf 1233zd b. Converting 1233xf to 233ab CF3CCl=CH2+ Cl2-> CF3CCl2CH2Cl 1233xf 233ab c. Conversion of 1233zd to 233da CF3CH=CClH + Cl2-> CF3CHCl-CHCl2 1233zd 233da d. Formation of 1223xd CF3CCl2CH2Cl + CF3CHClCHCl2-> CF3CCl=CHCl + HCl 233ab 233da 1223xd e. Formation of 223aa from 1223xd CF3CCl=CHCl + Cl2-> CF3CCl2CHCl2 1223xd 223aa f. Conversion of 223aa to 1213xa CF3CCl2CHCl2-> CF3CCl=CCl2+ HCl 223aa 1213xa g. Conversion of 1213xa to 213ab CF3CCl=CCl2+ Cl2-> CF3CCl2CCl3 1213xa 213ab h. Conversion of 243db to 244db and 242dc CF3CHClCH2Cl -> CF3CHClCH2F + CF2ClCHClCH2Cl 243db 244db 242dc Furthermore, oligomerization and black tar formation are possible in liquid phase chlorination reactions, which are not present in the gas phase.

[0051] However, despite all these side reactions, the selectivity and conversion using the present process are surprisingly high.

[0052] Additionally, product formation can be confirmed by continuous measurements using analytical equipment such as gas chromatography installed on the reactor.

[0053] In one embodiment, anhydrous HCl, such as HCl gas, is co-fed with 3,3,3-trifluoropropene in both the vapor and liquid phase reactions. The added HCl suppresses side reactions and serves as a diluent to manage high heat formation. In one embodiment, the HCl is present in an amount ranging from about 0.5% to about 20 mol %, in another embodiment from about 1 to about 10 mol %, and in another embodiment from about 1.5 to about 5 mol %, based on the amount of 1243zf present.

[0054] Without further ado, it is believed that one skilled in the art can, using the description herein, utilize the present invention to its fullest extent. The following specific embodiments are, therefore, to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.

[0055] The present invention is further illustrated in the following non-limiting examples. [Example]

[0056] Example 1 Chlorination of 1243zf at ambient pressure using 5% CrCl3-loaded acid-washed activated carbon: Two milliliters of 12-20 mesh 5% CrCl3 / C catalyst was loaded into a 1 / 2-inch Monel reactor. The catalyst was dried at 200°C under 100 sccm N2 for 1 hour, and then 1243zf and chlorine were fed into the top of the reactor at atmospheric pressure. The reactor stream was analyzed by GC and GC-MS. The test results are shown in Table 1. The catalyst exhibited high activity and selectivity.

[0057] [Table 1]

[0058] Example 2 Chlorination of 1243zf using 5% CrCl3 on acid-washed activated carbon at 25 psig (273.7 kPa): Two milliliters of 12-20 mesh 5% CrCl / C catalyst was loaded into a 1 / 2-inch Monel reactor. The catalyst was dried at 200°C under 100 sccm N for 1 hour, and then 1243zf and chlorine were fed into the top of the reactor at 25 psig (273.7 kPa). The reactor stream was analyzed by GC and GC-MS. The test results are shown in Table 2. The catalyst showed high activity and selectivity at 25 psig (273.7 kPa).

[0059] [Table 2]

[0060] Example 3 Chlorination of 1243zf at ambient pressure using 15% CrCl3-loaded acid-washed activated carbon: Five milliliters of 12-20 mesh 15% CrCl / C catalyst was loaded into a ½-inch Monel reactor. The catalyst was dried at 200°C under 100 sccm N for 1 hour, and then 1243zf and chlorine were fed into the top of the reactor at atmospheric pressure. The reactor stream was analyzed by GC and GC-MS. The test results are shown in Table 3. The catalyst exhibited high activity and selectivity.

[0061] [Table 3]

[0062] Example 4 Chlorination of 1243zf using 15% CrCl3 on acid-washed activated carbon at 25 psig (273.7 kPa): Five milliliters of 12-20 mesh 15% CrCl / C catalyst was loaded into a 1 / 2-inch Monel reactor. The catalyst was dried at 200°C under 100 sccm N for 1 hour, and then 1243zf and chlorine were fed into the top of the reactor at 25 psig (273.7 kPa). The reactor stream was analyzed by GC and GC-MS. The test results are shown in Table 4. The catalyst exhibited high activity and selectivity.

[0063] [Table 4]

[0064] Example 5 Chlorination of 1243zf with 15% CrCl3 on acid-washed activated carbon at 40 psig (377.1 kPa): 2 ml of 12-20 mesh 15% CrCl3 / C catalyst was loaded into a 1 / 2-inch Monel reactor. The catalyst was dried at 200°C for 1 hour under 100 sccm N2, and then 1243zf and chlorine were fed into the top of the reactor at 40 psig (377.1 kPa). The reactor stream was analyzed by GC and GC-MS. The test results are shown in Table 5. The catalyst exhibits high activity and selectivity.

[0065] [Table 5]

[0066] Example 6 Chlorination of 1243zf at ambient pressure using 5% FeCl3-loaded acid-washed activated carbon: Two milliliters of 12-20 mesh 5% FeCl3 / C catalyst was loaded into a 1 / 2-inch Monel reactor. The catalyst was dried at 200°C under 100 sccm N2 for 1 hour, and then 1243zf and chlorine were fed into the top of the reactor at atmospheric pressure. The reactor stream was analyzed by GC and GC-MS. The test results are shown in Table 6. The catalyst exhibits high activity and selectivity.

[0067] [Table 6]

[0068] Example 7 Chlorination of 1243zf at 25 psig (273.7 kPa) using 5% FeCl3-loaded acid-washed activated carbon: Two milliliters of 12-20 mesh 5% FeCl3 / C catalyst was loaded into a 1 / 2-inch Monel reactor. The catalyst was dried at 200°C under 100 sccm N2 for 1 hour, and then 1243zf and chlorine were fed into the top of the reactor at 25 psig (273.7 kPa). The reactor stream was analyzed by GC and GC-MS. The test results are shown in Table 7. The catalyst exhibited high activity and selectivity.

[0069] [Table 7]

[0070] Example 8 Chlorination of 1243zf at ambient pressure using 12.6% FeCl3-loaded acid-washed activated carbon: Two milliliters of 12.6% FeCl3 / C catalyst with 12-20 mesh was loaded into a 1 / 2-inch Monel reactor. The catalyst was dried at 200°C under 100 sccm of N2 for 1 hour, and then 1243zf and chlorine were fed into the top of the reactor at atmospheric pressure. The reactor stream was analyzed by GC and GC-MS. The test results are shown in Table 8. The catalyst exhibits high activity and selectivity.

[0071] [Table 8]

[0072] Example 9 Chlorination of 1243zf at ambient pressure using 30% FeCl3-loaded acid-washed activated carbon: Five milliliters of 12-20 mesh 30% FeCl3 / C catalyst was loaded into a 1 / 2-inch Monel reactor. The catalyst was dried at 200°C under 100 sccm N2 for 1 hour, and then 1243zf and chlorine were fed into the top of the reactor at atmospheric pressure. The reactor stream was analyzed by GC and GC-MS. The test results are shown in Table 9. The catalyst exhibits high activity and selectivity.

[0073] [Table 9]

[0074] (Comparative Example 1) Chlorination of 1243zf at ambient pressure using acid-washed activated carbon: Five milliliters of 12-20 mesh carbon catalyst was loaded into a ½ inch Monel reactor. The catalyst was dried at 200°C under 100 sccm of N2 for 1 hour, and then 1243zf and chlorine were fed into the top of the reactor at atmospheric pressure. The reactor stream was analyzed by GC and GC-MS. The test results are shown in Table 10. The catalyst exhibits high activity but lower selectivity.

[0075] [Table 10]

[0076] Figure 1 compares the 243db selectivity for the chlorination of 3,3,3-trifluoropropene in a gas phase reaction using activated carbon as the catalyst (Comparative Example 1), 15% CrCl3 / C as the catalyst (Example 1), 15% CrCl3 / C as the catalyst (Example 3), and 5% FeCl3 / C as the catalyst (Example 6) at temperatures ranging from 60°C to 180°C and ambient pressure. As clearly shown, when activated carbon is the catalyst, the 243db selectivity begins to decrease at about 100°C and drops sharply at about 120°C, whereas when metal halides supported on activated carbon are used, high selectivity is maintained even at temperatures above 160°C. Example 10 Chlorination of 1243zf using FeCl3 as catalyst in a liquid phase reactor: A 200 ml Hastelloy shaker tube was charged with 3 g of FeCl. The reactor was evacuated, purged twice with N, and then cooled to -40°C. At -40°C, the reactor was again evacuated, and 80 g (0.84 mol) of 1243zf and 56 g (0.76 mol) of Cl were added to the reactor. With stirring, the reactor was heated to 40°C and stirred at 40°C for 1.5 hours. The pressure was continuously reduced as the reaction proceeded. At the end of the reaction, the reactor pressure dropped from 112 psig (873.5 kPa) to 7 psig (149.6 kPa). The reactor was cooled back to room temperature, and the liquid contents were transferred to a glass bottle containing 50 ml of 15% aqueous NaSO. The organic layer was then separated from the liquid phase, and 122.82 g of product was recovered. The product was analyzed by GC-MS. The data reported in Table 11 below are presented in area percent from GC-MS. Analysis of the liquid phase of the product indicated a selectivity of ∼99.8% at 243 db.

[0077] [Table 11]

[0078] Example 11 Chlorination of 1243zf in liquid phase in an autoclave reactor using FeCl as catalyst at 50 °C: A 1-liter Hastelloy autoclave was charged with 12.4 g of anhydrous FeCl3. The reactor was evacuated and purged twice with N2, then cooled to -40°C. At -40°C, the reactor was again evacuated and 337 g (3.51 mol) of 1243zF was added. The 1243zF was then heated to 50°C with stirring. 242 g (3.41 mol) of Cl2 was then fed in 50 minutes at 50°C. After all the Cl2 had been added, the reaction was stirred for an additional hour at 50°C. The pressure continuously decreased as the reaction proceeded. By the end of the reaction, the reactor pressure had decreased from 150 psig (1136 kPa) to 11 psig (177.2 kPa). A pressure graph of this reaction is plotted in Figure 2 (lower plot). The reaction using the FeCl catalyst is clearly much faster than the reactions in Comparative Examples 2 and 3 without a catalyst, as evidenced by the faster pressure drop. The reactor was cooled back to room temperature, and the liquid contents were transferred to a glass bottle. 568 g of product was recovered and analyzed using GC-MS. The data reported in Table 12 below are presented in area percent from GC-MS. Analysis of the liquid product phase indicated a 243db selectivity of ∼99.8%. The 243db selectivity using the FeCl catalyst is also higher than the selectivity of Comparative Examples 2 and 3 without a catalyst.

[0079] [Table 12]

[0080] (Comparative Example 2) Chlorination of 1243zf at 80°C without catalyst in the liquid phase in an autoclave reactor: A 1-liter Hastelloy autoclave was used. The reactor was evacuated and purged twice with N2, then cooled to -40°C. At -40°C, the reactor was again evacuated and 338 g (3.52 mol) of 1243zf was added. The 1243zf was then heated to 80°C with stirring. 242 g (3.41 mol) of Cl2 was then fed at 80°C in 119 minutes. After all the Cl2 was added, the reaction was stirred for an additional 3.5 hours at 80°C. The pressure continuously decreased as the reaction proceeded. By the end of the reaction, the reactor pressure had decreased from 320 psig (2308 kPa) to 40 psig (377.1 kPa). A pressure graph for this reaction is plotted in Figure 2. The reaction at 80°C without a catalyst (Comparative Example 2, middle plot) is clearly much slower than the reaction at 50°C with FeCl3 in Example 11 (lower plot), as evidenced by the slower pressure drop. After the reactor was cooled back to room temperature, the liquid contents were transferred to a glass bottle containing 100 ml of 10% aqueous Na2SO3. 568 g of product was recovered and analyzed using GC-MS. The data reported in Table 13 below are presented in terms of area percent obtained from GC-MS. Analysis of the liquid product phase indicated a 243db selectivity of ∼94.2%. The 243db selectivity without a catalyst is lower than that of Example 11, which used the FeCl3 catalyst.

[0081] [Table 13]

[0082] (Comparative Example 3) Chlorination of 1243zf at 100°C without catalyst in the liquid phase in an autoclave reactor: A 1-liter Hastelloy autoclave was used. The reactor was evacuated and purged twice with N2, then cooled to -40°C. At -40°C, the reactor was again evacuated and 339 g (3.53 mol) of 1243zf was added. The 1243zf was then heated to 100°C with stirring. 212 g (2.98 mol) of Cl2 was then fed in 84 minutes at 100°C. After all the Cl2 was added, the reaction was stirred for an additional 2 hours at 100°C. The pressure continuously decreased as the reaction proceeded. By the end of the reaction, the reactor pressure had decreased from 450 psig (3204 kPa) to 264 psig (1992 kPa). A pressure graph of this reaction is plotted in Figure 2 (top plot). Based on pressure drop, the uncatalyzed reaction at 100°C was faster than the uncatalyzed reaction at 80°C in Comparative Example 2, but similar in rate to the reaction at 50°C with the FeCl catalyst in Example 11. After the reactor cooled to room temperature, the liquid contents were transferred to a glass bottle containing 100 ml of 10% aqueous NaSO. 439 g of product was recovered and analyzed using GC-MS. Black tar was also observed in the reactor. The data reported in Table 14 below are presented in terms of area percent obtained from GC-MS. Analysis of the liquid product phase indicated a 243db selectivity of ∼91.8%. The uncatalyzed 243db selectivity is lower than that of Example 11 using the FeCl catalyst.

[0083] [Table 14]

[0084] Comparative Example 4 Chlorination of 1243zf in the liquid phase in an autoclave reactor using activated carbon as catalyst at 60°C: To a 400 mL Hastelloy shaker tube was added 3 g of activated carbon, 80 g (0.84 mol) of 1243zf, and 54 g (0.76 mol) of chlorine in the liquid phase. The mixture was stirred at 40°C for 20 minutes. The reactor pressure remained at ~160 psig (~1204 kPa), indicating no sign of reaction. The reactor was then heated to 60°C and held at 60°C for 90 minutes. The reaction pressure only decreased slightly from 236 psig (1728 kPa) to 200 psig (1480 kPa), indicating a very slow reaction. This result indicates that activated carbon does not catalyze the chlorination of 1243zf in the liquid phase.

[0085] It should be noted that not all of the steps described in the general description or examples above are required, some specific steps may not be required, and one or more additional steps may be performed in addition to the steps described above. Furthermore, the order in which the steps are listed is not necessarily the order in which they should be performed.

[0086] In this specification, percentages are by weight unless otherwise indicated.

[0087] The foregoing specification has described the concepts of the present application with reference to specific embodiments. However, those skilled in the art will recognize that various modifications and variations can be made without departing from the scope of the invention, as defined in the following claims. Accordingly, the specification is to be regarded in an illustrative rather than a restrictive sense, and all such modifications are intended to be included within the scope of the present invention.

[0088] Although benefits, advantages, and solutions to problems have been described above with reference to specific embodiments, the benefits, advantages, and solutions to problems; and any features that cause or make apparent any benefit, advantage, or solution; should not be construed as critical, required, or essential features of any or all claims.

[0089] It should be understood that some features, which are, for clarity, described herein in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features, which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any subcombination.

Claims

1. 1. A composition comprising 1,1,1-trifluoro-2,3-dichloropropane, 3,3,3-trifluoropropene, chlorine gas, 1,1,1-trifluoro-3-chloropropylene, anhydrous HCl, and a catalyst, wherein the catalyst comprises at least one metal chloride.

2. 10. The composition of claim 1, wherein the pre-noble metal is selected from nickel, iron, and chromium, or a combination thereof, and the at least one metal chloride is supported on activated carbon.

3. 2. The composition of claim 1, wherein the molar ratio of 3,3,3-trifluoropropene to chlorine gas is within the range of 1:0.02 to 1:

1.

4. 2. The composition of claim 1, wherein HCl is present in an amount of 0.5 mole % to 20 mole % relative to the amount of 3,3,3-trifluoropropene present.

5. 2. The composition of claim 1, wherein HCl is present in an amount of 1 mol % to 10 mol % relative to the amount of 3,3,3-trifluoropropene present.

6. 2. The composition of claim 1, wherein HCl is present in an amount of 1.5 mol % to 5 mol % relative to the amount of 3,3,3-trifluoropropene present.

7. 3. The composition of claim 2, wherein the activated carbon is acid-washed or base-washed.

8. 2. The composition of claim 1, wherein the molar ratio of 3,3,3-trifluoropropene to chlorine gas is within the range of 1:0.1 to 1:0.

8.

9. 2. The composition of claim 1, wherein the molar ratio of 3,3,3-trifluoropropene to chlorine gas is within the range of 1:0.1 to 1:0.

5.

10. The chlorine is HCl and O 2 2. The composition of claim 1, obtained by the reaction of:

11. A solvent is further present, said solvent being carbon tetrachloride, 1,1,2-trichloro-1,2,2-trifluoroethane, CF 3 (CF 2 ) n CF 3 C represented by 5-8 2. The composition of claim 1, wherein the compound is selected from the group consisting of linear perfluoroalkyl compounds, where n is an integer from 3 to 6, and hexachloroacetone.

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