A composition comprising 1,1,1-trifluoro-2,3-dichloropropane

Abstract

To provide a composition comprising 1,1,1-trifluoro-2,3-dichloropropane.SOLUTION: The present invention relates to a composition comprising 1,1,1-trifluoro-2,3-dichloropropane, optional 3,3,3-trifluoropropene, and a catalyst, where the catalyst comprises at least one metal halide, where the metal is a metal from Group 13, 14 or 15 of the periodic table or a transition metal or combination thereof.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] Over the past few decades, many manufacturing industries have been working to find alternatives to ozone-depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs). These CFCs and HCFCs have been widely used. Their uses include aerosol propellants, refrigerants, cleaning agents; blowing agents for thermoplastic and thermosetting foams; heat transfer media, gaseous dielectric materials; digestion and fire extinguishing agents; power cycle working fluids, polymerization media, particulate removal fluids, dispersion media fluids, buffing abrasive agents, and substitution desiccants. In the search for alternatives to these widely used compounds, many manufacturing industries have focused on the use of hydrofluorocarbons (HFCs).

[0003] Although the HFCs do not contribute to stratospheric ozone depletion, they are a concern because they contribute to the "greenhouse effect". That is, HFCs contribute to global warming. As a result of contributing to global warming, HFCs are the subject of detailed investigations and their widespread use will also be restricted in the future. Therefore, there is a need for chemical compounds with low ozone depletion potential (ODP) and low global warming potential (GWP).

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

[0005] (1) In a gas phase reactor filled 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 filled 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 a 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, which is the product of the process of the present application.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] There have been various methods for manufacturing HCFC-243db. For example, the chlorination of 3,3,3-trifluoro-1-propene (HFO-1243zf) is carried out using ultraviolet light, or at high temperature, or in a catalyst-free liquid phase. However, there are many problems associated with these methods. The approach using ultraviolet light has poor selectivity and is difficult to scale up to a commercial process. Also, the reaction in a catalyst-free liquid phase is very slow and needs to be carried out at high temperature. Even under these conditions, tar is formed.

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

Means for Solving the Problems

[0009] The process of the present application relates to a process for preparing 1,1,1-trifluoro-2,3-dichloropropane, which process comprises contacting chlorine with 3,3,3-trifluoropropene in the presence of a catalyst to form 1,1,1-trifluoro-2,3-dichloropropane, wherein the catalyst comprises at least one metal halide, and the metal is an element of Group 13, 14 or 15 of the periodic table, or a transition metal, or a combination thereof. This reaction can be carried out either in the gas phase or in the liquid phase.

Effects of the Invention

[0010] By means of the said process, 1,1,1-trifluoro-2,3-dichloropropane is produced with excellent yield and high selectivity.

Brief Description of the Drawings

[0011] The following figures further illustrate the present invention in a non-limiting manner.

Figure 1

Figure 2

Mode for Carrying Out the Invention

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

[0013] Also, the use of "a", "an" is employed to describe the element(s) and component(s) described herein. This is merely for convenience and to give a general scope to the scope of the invention. This description should be construed to mean one or at least one, and includes the plural as well as the singular unless it is apparent that it means something else.

[0014] When expressing a numerical range, in another embodiment, it includes from the one specific numerical value and / or to the other specific numerical value. Similarly, when a numerical value is expressed approximately by the use of the antecedent "about", the specific numerical value is understood to form another embodiment. All ranges are inclusive and combinable. Further, references to numerical values shown in the range include any and all numerical values within the range.

[0015] Unless otherwise defined, all scientific and technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It is possible to use methods and materials similar or equivalent to those described herein in the practice and testing of embodiments of the present invention. However, appropriate 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 particular part is cited. In case of conflict, this specification, including definitions, will control. Further, the materials, methods, and examples are illustrative only and not intended to be limiting.

[0016] Although many forms and embodiments are described herein, they are merely illustrative and not restrictive. Those skilled in the art who read this specification will understand that other forms and embodiments are possible without departing from the scope of the present invention. The features and advantages of any one or more of the embodiments will be apparent from the following detailed description and the claims.

[0017] As described above, the process of the present application relates to a process for chlorinating 3,3,3-trifluoropropene in the presence of a catalyst to form 1,1,1-trifluoro-2,3-dichloropropane, wherein the catalyst contains at least one metal halide, and the metal is a metal belonging to 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] As used herein, the term "metal" means a metal of 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 of 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 antimony is a metalloid as defined herein and is a metal according to the definition herein.

[0020] The term "transition metal" means the elements of Groups 3, 4, 5, 6, 7, 8, 9, 10, 11 and 12 including lanthanides. 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] Since the catalyst used in the chlorination reaction described herein is in the form of a metal halide, the metal used here has a positive oxidation number of +1, +2, +3, +4 or +5 depending on the nature of the metal that forms a salt with the halide.

[0022] The term "activated carbon" includes any carbon having a relatively large surface area, such as from about 50 to about 3000 m 2 or from about 100 to about 2000 m 2 such as (e.g., from about 200 to about 1500 m 2 or from about 300 to about 1000 m 2 ). Activated carbon can be obtained from any carbonaceous material, such as coal (e.g., charcoal), nut shells (e.g., coconut), and wood. Activated carbon in any form, such as powdered, granular, and pelletized, may be used. 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 one or more compounds 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, potassium hydroxide, etc.

[0024] Furthermore, 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. Further 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 form, the activated carbon is immersed for at least 1 hour, such as 1 to 36 hours, or 1 to 10 hours. Optionally, the activated carbon may be stirred during immersion. Optionally, the activated carbon is rinsed with deionized water after washing to increase the pH to 5 - 8. In some embodiments, the activated carbon is washed with at least one acid and at least one base to reduce the calcined ash and remove silicates.

[0025] The metal in the metal halide used as a catalyst is a metal of Groups 13 and 14 of the periodic table, a transition metal, and antimony which is a metalloid. Examples of the metal 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 antimony is a metalloid as defined herein. However, as defined herein, metalloids are included in the definition of metals. Examples of the metal halide include nickel halide, chromium halide, iron halide, scandium halide, yttrium halide, lanthanum halide, titanium halide, zirconium halide, hafnium halide, vanadium halide, molybdenum halide, tungsten halide, manganese halide, rhenium halide, ruthenium halide, osmium halide, cobalt halide, palladium halide, copper halide, zinc halide, antimony halide, tantalum halide, aluminum halide, tin halide, and lead halide. 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 a chloride. In yet another embodiment, the halide is a chloride. In another embodiment, the metal halide is nickel chloride, iron chloride, chromium chloride, or a combination thereof.

[0026] The metal halide which is the catalyst for the chlorination process of the present application may or may not be supported on activated carbon. The activated carbon may be an unwashed product, or an acid-washed or base-washed product.

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

[0028] 3,3,3-Trifluoropropene is commercially available. Alternatively, it can be prepared using techniques known in the art. For example, reference can be made to Patent Document 1, the content of which is incorporated by reference.

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

[0030] When carried out in the gas phase, the process is carried out at an effective temperature and pressure. In one embodiment, the reaction is carried out at a temperature in the range of about 80 to about 200 °C. In another embodiment, the reaction is carried out at a temperature in the range of 80 to about 160 °C. In yet another embodiment, the chlorination reaction is carried out at a temperature in the range of about 80 to about 130 °C, and in another embodiment, at a temperature in the range of about 80 to about 120 °C. The process can be carried out at a pressure in the range of about 10 psig (170.3 kPa) to about 100 psig (790.8 kPa). In another embodiment, the pressure range is in the range of about 1 atm (101.3 kPa) to about 50 psig (446.1 kPa), and in another embodiment, the pressure range is in the range of about 20 psig (239.2 kPa) to about 50 psig (446.1 kPa). Thus, in one embodiment, the process is carried out in the gas phase at a temperature in the range of about 80 to about 200 °C and at a pressure in the range of about 10 psig (170.3 kPa) to about 100 psig (790.8 kPa), in another embodiment, in the range of about 1 atm (101.3 kPa) to about 50 psig (446.1 kPa), and in another embodiment, in the range of about 10 psig (170.3 kPa) to about 50 psig (446.1 kPa), for example, in the range of about 20 psig (239.2 kPa) to about 50 psig (446.1 kPa). In another embodiment, the chlorination reaction is carried out at a temperature in the range of about 80 to about 160 °C and at a pressure in the range of about 10 psig (170.3 kPa) to about 100 psig (790.8 kPa), in another embodiment, in the range of about 1 atm (101.3 kPa) to about 50 psig (446.1 kPa), and in another embodiment, in the range of about 20 psig (239.2 kPa) to about 50 psig (446.1 kPa). In a further embodiment, the chlorination reaction is carried out at a temperature in the range of about 80 to 130 °C and at a pressure in the range of about 10 psig (170.3 kPa) to about 100 psig (790.8 kPa), in another embodiment, in the range of about 1 atm (101.3 kPa) to about 50 psig (446.1 kPa), and in another embodiment, in the range of 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 an effective amount for the chlorination reaction to occur. The molar amount of 3,3,3-trifluoropropene is present in excess of the molar amount of chlorine gas in one embodiment. 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 of the chlorination reaction, i.e., the time for the reaction to occur, can range from about 0.1 second to about 120 seconds, and in another embodiment, from about 5 seconds to about 1 minute. However, longer or shorter times can also be used. The contact time used herein is calculated by the following formula: Contact time (seconds) = 1 / ((Total gas flow (SCCM) / 60 / Catalyst volume)) x (14.7 + P (PSIG)) / 14.7 x (298 / (273 + T (°C)) where SCCM is standard cubic centimeters per minute, P is pressure, PSIG is the gauge pressure in pounds per square inch of the operating pressure, not the absolute pressure. T (°C) is the temperature in degrees Celsius, and the catalyst volume is in cubic centimeters.

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

[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 number of moles of the reactant consumed (molar ratio of 3,3,3-trifluoropropene) by the number of moles of the reactant fed to the reactor (molar ratio of 3,3,3-trifluoropropene) and multiplying by 100. The selectivity to the resulting 1,1,1-trifluoro-2,3-dichloropropane is preferably 60% or more, more preferably 80% or more. The selectivity is calculated by dividing the number of moles of the product formed (1,1,1-trifluoro-2,3-dichloropropane) by the number of moles of the reactant consumed.

[0035] The process of the present application in the gas phase gives a 243db selectivity higher than that of the activated carbon itself at high temperatures such as 100 - 160°C, and in another embodiment, about 120 - about 200°C. Therefore, in these temperature ranges, the chlorination reaction can be carried out at pressures in the range of vacuum to about 100 psig (790.8 kPa), in another embodiment about 1 atm (101.3 kPa) to about 50 psig (446.1 kPa), and in another embodiment about 10 psig (170.3 kPa) to about 50 psig (446.1 kPa). The process of the present application can operate the process at a higher back pressure exceeding the dew point of 243db.

[0036] This chlorination reaction can be carried out in any reactor suitable for gas-phase chlorination reactions. In one embodiment, the reactor is composed of materials durable against the corrosive effects of chlorine and the catalyst, such as Hastalloy, Inconel, Monel, and fluoropolymer-lined materials. The vessel is a fixed catalyst bed or a fluidized bed. If necessary, an inert gas such as nitrogen or argon may be used inside the reactor during operation.

[0037] In one embodiment, as described above, the catalyst during the gas-phase reaction is supported on activated carbon, and the activated carbon may be an unwashed product, or an acid-washed or base-washed product.

[0038] In another embodiment, the chlorination reaction is carried out in the liquid phase. The process of the present application 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. This apparatus described herein is, in one embodiment, made of one or more materials resistant to corrosion, such as stainless steel, particularly austenitic stainless steel; high nickel alloys such as Monel (trademark) nickel-copper alloy, Hastelloy (trademark) nickel-based alloy, and Inconel (trademark) nickel-chromium alloy; and copper-coated steel. The process of the present application can be carried out batchwise or continuously.

[0039] To complete the reaction, intense vibration, agitation and / or stirring may be required. The degree of agitation depends on the desired reaction rate, which in turn depends on the shape of the reactor, the residence time, the structure of the agitator and baffles, 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 linear perfluoroalkyl compounds (where n is an integer from 3 to 6, including both ends of the range); or perhalogenated compounds such as hexachloroacetone and 1,1,1-trifluoro-2,3-dichloropropane are included.

[0041] The amount of the solvent used in the reaction in the chlorination step is not particularly limited as long as 3,3,3-trifluoropropene can be dissolved thereby. In one embodiment, the amount of the solvent present is in the range of about 1 to about 1000% by mass, based on the raw material components (the total amount of 3,3,3-trifluoropropene and chlorine), and in another embodiment, in the range of about 50 to about 100% by mass. The catalyst used herein may be a heterogeneous system or may be partially dissolved in the 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 an effective amount of chlorine gas and 3,3,3-trifluoropropene to form 1,1,1-trifluoro-2,3-dichloropropane. Similar to the case of the gas-phase 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 amount of 3,3,3-trifluoropropene relative to chlorine is in the range of about 1:0.02 to about 1:1, in another embodiment, about 1:0.1 to 1:0.9, and in another embodiment, in the range of about 1:0.1 to about 1:0.95.

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

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

[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 in the range of about 0.1 to 10 wt% of the reactants (i.e., the total amount of chlorine and 3,3,3-trifluoropropene), in another embodiment, in the range of about 0.5 to about 6 wt%, and in another embodiment, in the range of about 1 to about 4 wt%.

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

[0047] The chlorination reaction in both the liquid phase and the gas phase is preferably carried out so as to achieve a conversion rate of about 50% or more, preferably 90% or more. As described above, the reaction is carried out in one embodiment when the molar amount of 3,3,3-trifluoropropene is equal to or exceeds that of chlorine. The conversion rate is calculated by dividing the number of moles of the consumed reactant (molar ratio of 3,3,3-trifluoropropene) by the number of moles of the reactant supplied 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 number of moles of the formed product (1,1,1-trifluoro-2,3-dichloropropane) by the number of moles of the consumed reactant.

[0048] Regardless of whether the reaction is carried out in the gas phase or in the liquid phase, 1,1,1-trifluoro-2,3-dichloropropane is isolated, that is, separated and collected. The product containing 1,1,1-trifluoro-2,3-dichloropropane is taken out of the reactor by techniques known in the art such as siphoning. In the case of the gas phase, the product is allowed to flow out of the reactor and liquefied. The product containing 1,1,1-trifluoro-2,3-dichloropropane is purified by techniques known in the art such as distillation. The process of the present application can be commercially utilized and can be easily scaled up for commercial production regardless of whether it is carried out in the gas phase or in the liquid phase. Furthermore, the rate of the chlorination reaction using the process described herein is faster than the process previously used to chlorinate 3,3,3-trifluoropropene to 1,1,1-trifluoro-2,3-dichloropropane (HCFC243db), providing a higher conversion rate 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 the following.

[0050] a. Conversion of 243db to 1,1,1-trifluoro-3-chloropropene CF3CHClCH2Cl -> CF3CCl=CH2+ CF3CH=CHCl + HCl 243db 1233xf 1233zd b. Conversion of 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, although it does not exist in the gas phase, in the liquid-phase chlorination reaction, there is a risk of oligomerization and the formation of black tar.

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

[0052] Furthermore, the formation of the product can be confirmed by installing an analytical device such as gas chromatography on the reactor and performing continuous measurement.

[0053] In one embodiment, in both gas-phase and liquid-phase reactions, anhydrous HCl, such as HCl gas, is cofed with 3,3,3-trifluoropropene. The added HCl suppresses side reactions and helps to effect high heat formation as a diluent. In one embodiment, the HCl is present in an amount in the range of about 0.5% to about 20 mol%, in another embodiment in the range of about 1 to about 10 mol%, and in another embodiment in the range of about 1.5 to about 5 mol% relative to the amount of 1243zf present.

[0054] Those skilled in the art can, without further effort, utilize the present invention to its fullest extent using the descriptions herein. Accordingly, the following specific embodiments are to be construed as merely illustrative and not limiting the remainder of the disclosure in any way.

[0055] In the following non-limiting examples, the present invention is further illustrated.

Examples

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

[0057]

Table 1

[0058] (Example 2) Chlorination of 1243zf at 25 psig (273.7 kPa) using 5% CrCl3-supported - acid-washed activated carbon: 2 ml of a 5% CrCl3 / C catalyst with a mesh size of 12 - 20 was placed into a 1 / 2-inch Monel reactor. Under 100 sccm of N2, the catalyst was dried at 200 °C for 1 hour, and then, at 25 psig (273.7 kPa), 1243zf and chlorine were supplied from the top of the reactor. The flow from the reactor 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 atmospheric pressure using 15% CrCl3-supported acid-washed activated carbon: 5 ml of a 15% CrCl3 / C catalyst with a mesh size of 12 - 20 was placed into a 1 / 2-inch Monel reactor. Under 100 sccm of N2, the catalyst was dried at 200 °C for 1 hour, and then, at atmospheric pressure, 1243zf and chlorine were supplied from the top of the reactor. The flow from the reactor was analyzed by GC and GC-MS. The test results are shown in Table 3. The catalyst showed high activity and selectivity.

[0061] [Table 3]

[0062] (Example 4) Chlorination of 1243zf at 25 psig (273.7 kPa) using 15% CrCl3-supported acid-washed activated carbon: 5 mL of a 15% CrCl3 / C catalyst with a mesh size of 12 - 20 was charged into a 1 / 2-inch Monel reactor. Under 100 sccm of N2, the catalyst was dried at 200 °C for 1 hour, and then 1243zf and chlorine were supplied from the top of the reactor at 25 psig (273.7 kPa). The flow from the reactor was analyzed by GC and GC-MS. The test results are shown in Table 4. The catalyst showed high activity and selectivity.

[0063] [Table 4]

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

[0065] [Table 5]

[0066] (Example 6) Chlorination of 1243zf at atmospheric pressure using 5% FeCl3-supported - acid-washed activated carbon: 2 mL of a 5% FeCl3 / C catalyst with a mesh size of 12 - 20 was charged into a 1 / 2-inch Monel reactor. Under 100 sccm of N2, the catalyst was dried at 200 °C for 1 hour, and then 1243zf and chlorine were supplied from the top of the reactor at atmospheric pressure. The flow from the reactor was analyzed by GC and GC-MS. The test results are shown in Table 6. The catalyst showed high activity and selectivity.

[0067]

Table 6

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

[0069]

Table 7

[0070] (Example 8) Chlorination of 1243zf at atmospheric pressure using 12.6% FeCl3-supported and acid-washed activated carbon: 2 ml of a 12.6% FeCl3 / C catalyst with a mesh size of 12 - 20 was charged into a 1 / 2-inch Monel reactor. Under 100 sccm of N2, the catalyst was dried at 200 °C for 1 hour, and then, at atmospheric pressure, 1243zf and chlorine were supplied from the top of the reactor. The flow from the reactor was analyzed by GC and GC-MS. The test results are shown in Table 8. The catalyst showed high activity and selectivity.

[0071]

Table 8

[0072] (Example 9) Chlorination of 1243zf at atmospheric pressure using 30% FeCl3-supported pickled activated carbon: 5 ml of a 30% FeCl3 / C catalyst with a mesh size of 12 - 20 was placed into a 1 / 2-inch Monel reactor. Under 100 sccm of N2, the catalyst was dried at 200 °C for 1 hour, and then 1243zf and chlorine were supplied from the top of the reactor at atmospheric pressure. The flow from the reactor was analyzed by GC and GC-MS. The test results are shown in Table 9. The catalyst shows high activity and selectivity.

[0073] [Table 9]

[0074] (Comparative Example 1) Chlorination of 1243zf at atmospheric pressure using pickled activated carbon: 5 ml of a carbon catalyst with a mesh size of 12 - 20 was placed into a 1 / 2-inch Monel reactor. Under 100 sccm of N2, the catalyst was dried at 200 °C for 1 hour, and then 1243zf and chlorine were supplied from the top of the reactor at atmospheric pressure. The flow from the reactor was analyzed by GC and GC-MS. The test results are shown in Table 10. The catalyst shows high activity but lower selectivity.

[0075] [Table 10]

[0076] Figure 1 compares the 243db selectivity at atmospheric pressure in the temperature range of 60 °C to 180 °C 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). As clearly shown, when activated carbon is the catalyst, the selectivity of 243db begins to decrease at about 100 °C and decreases rapidly at about 120 °C, whereas when a metal halide supported on activated carbon is used, high selectivity is maintained even at temperatures above 160 °C. (Example 10) Chlorination of 1243zf using FeCl3 as the catalyst in a liquid-phase reactor: 3 g of FeCl3 was charged into a 200 ml Hastelloy shaker tube. The reactor was evacuated and purged twice with N2 and then cooled to -40 °C. At -40 °C, the reactor was evacuated again and 80 g (0.84 mol) of 1243zf and 56 g (0.76 mol) of Cl2 were added to the reactor. While stirring, the reactor was heated to 40 °C and stirred at 40 °C for 1.5 hours. As the reaction proceeded, the pressure decreased continuously. At the end of the reaction, the pressure in the reactor decreased 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 Na2SO3 solution. The organic layer was then separated from the liquid phase and 122.82 g of the product was recovered. The product was analyzed by GC-MS. The data reported in Table 11 below are shown by the area percentages obtained from GC-MS. Analysis of the liquid phase of the product showed that the selectivity of 243db was ~99.8%.

[0077]

Table 11

[0078] (Example 11) Chlorination of 1243zf at 50 °C using FeCl3 as a catalyst in the liquid phase in an autoclave reactor: A 1-liter Hastelloy autoclave was charged with 12.4 g of anhydrous FeCl3. The reactor was evacuated and purged twice with N2 and then cooled to -40 °C. At -40 °C, the reactor was evacuated again and 337 g (3.51 mol) of 1243zf was added. Then 1243zf was heated to 50 °C with stirring. Thereafter, 242 g (3.41 mol) of Cl2 was fed at 50 °C over 50 minutes. After all of the Cl2 had been added, the reaction mixture was stirred at 50 °C for an additional hour. As the reaction proceeded, the pressure decreased continuously. By the end of the reaction, the pressure in the reactor had dropped from 150 psig (1136 kPa) to 11 psig (177.2 kPa). The pressure graph for this reaction is plotted in Figure 2 (lower plot). The reaction using the FeCl3 catalyst is clearly much faster, as the pressure drop is faster than the reactions of Comparative Examples 2 and 3 without a catalyst. 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 shown as area percentages obtained from GC-MS. Analysis of the liquid phase of the product showed that the selectivity for 243db was ~99.8%. The selectivity for 243db using the FeCl3 catalyst was also higher than the selectivities of Comparative Examples 2 and 3 without a catalyst.

[0079]

Table 12

[0080] (Comparative Example 2) Chlorination of 1243zf at 80 °C without a catalyst in the liquid phase in an autoclave reactor: A 1-liter Hastelloy autoclave was used. The reactor was evacuated, purged twice with N2, and then cooled to -40°C. At -40°C, the reactor was evacuated again and 338 g (3.52 moles) of 1243zf was added. Then, 1243zf was heated to 80°C with stirring. Thereafter, 242 g (3.41 moles) of Cl2 was fed at 80°C over 119 minutes. After all of the Cl2 was added, the reaction mixture was stirred at 80°C for an additional 3.5 hours. As the reaction proceeded, the pressure continuously decreased. By the end of the reaction, the pressure in the reactor had decreased from 320 psig (2308 kPa) to 40 psig (377.1 kPa). The pressure graph for this reaction is plotted in Figure 2. The reaction without a catalyst at 80°C (Comparative Example 2, middle plot) was clearly much slower, as the pressure drop was slower than the reaction at 50°C using FeCl3 in Example 11 (lower plot). 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 the product was recovered and analyzed using GC-MS. The data reported in Table 13 below is shown by the area percentages obtained from GC-MS. Analysis of the liquid phase of the product showed that the selectivity for 243db was ~94.2%. The 243db selectivity without a catalyst was lower than that of Example 11 using an FeCl3 catalyst.

[0081]

Table 13

[0082] (Comparative Example 3) Chlorination of 1243zf at 100°C without a catalyst in the liquid phase in an autoclave reactor: A 1-liter Hastelloy autoclave was used. The reactor was evacuated, purged twice with N2, and then cooled to -40°C. At -40°C, the reactor was evacuated again and 339 g (3.53 moles) of 1243zf was added. Then, 1243zf was heated to 100°C with stirring. Thereafter, 212 g (2.98 moles) of Cl2 was fed at 100°C over 84 minutes. After all of the Cl2 was added, the reaction mixture was stirred at 100°C for an additional 2 hours. As the reaction proceeded, the pressure continuously decreased. By the end of the reaction, the pressure in the reactor decreased from 450 psig (3204 kPa) to 264 psig (1992 kPa). The pressure graph of this reaction is plotted in Figure 2 (upper plot). Based on the pressure drop, the reaction at 100°C without a catalyst is faster than the reaction at 80°C without a catalyst in Comparative Example 2, but is of the same rate as the reaction at 50°C using the FeCl3 catalyst in Example 11. 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. 439 g of the product was recovered and analyzed using GC-MS. Black tar was also seen in the reactor. The data reported in Table 14 below are shown by the area percentages obtained from GC-MS. Analysis of the liquid phase of the product showed that the selectivity for 243db was ~91.8%. The selectivity for 243db without a catalyst is lower than the selectivity in Example 11 using the FeCl3 catalyst.

[0083]

Table 14

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

[0085] Note that not all of the operations described in the general description and examples above are required, that some specific operations may not be necessary, and that one or more additional operations may be performed in addition to the operations described. Further, the order of the list of operations is not necessarily the order of execution.

[0086] In this specification, unless otherwise indicated, % is by weight.

[0087] In the above description of the specification, the concept of the present application has been described with respect to specific embodiments. However, those skilled in the art can understand that various modifications and changes can be made without departing from the scope of the invention defined in the claims described below. Therefore, the specification of the present application should be regarded as being in an exemplary sense rather than a restrictive sense, and all such modifications are intended to be included within the scope of the present invention.

[0088] In connection with specific embodiments, advantages and other benefits, and solutions to problems have been described so far. However, such advantages, benefits, solutions to problems; and any characteristics that give rise to or clarify any advantages, benefits, solutions should not be construed as decisive, essential, or inherent characteristics of any or all of the claims.

[0089] For clarity, some features are described herein in the context of separate embodiments, but it should be understood that they may be provided in combination within a single embodiment. Conversely, various features are described in a single embodiment for brevity, but may be provided separately or in any sub-combination.

Claims

1. A composition comprising 1,1,1-trifluoro-2,3-dichloropropane, 3,3,3-trifluoropropene, chlorine gas, a catalyst, 1,1,1-trifluoro-3-chloropropene and a solvent, wherein the catalyst comprises at least one metal chloride, the metal is nickel, chromium, iron, or a combination thereof, the at least one metal chloride is supported on activated carbon, and the molar ratio of 3,3,3-trifluoropropene to chlorine gas is in the range of 1:0.02 to 1:

1.

2. The composition according to claim 1, wherein the metal chloride is nickel chloride, iron chloride, or chromium chloride.

3. The composition according to claim 1, wherein the molar ratio of 3,3,3-trifluoropropene to chlorine is in the range of 1:0.1 to 1:0.

8.

4. The composition according to claim 3, wherein the molar ratio of 3,3,3-trifluoropropene to chlorine is in the range of 1:0.1 to 1:0.

5.

5. The solvent is selected from the group consisting of carbon tetrachloride, 1,1,2-trichloro-1,2,2-trifluoroethane, C 3 (CF 2 ) n CF 3 -represented C 5-8 linear perfluoroalkyl compound (wherein n is an integer from 3 to 6), and hexachloroacetone, the composition according to claim 1.

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