WO1998021171A1 - Liquid phase catalytic fluorination of hydrochlorocarbon and hydrochlorofluorocarbon - Google Patents

Liquid phase catalytic fluorination of hydrochlorocarbon and hydrochlorofluorocarbon Download PDF

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Publication number
WO1998021171A1
WO1998021171A1 PCT/US1997/020448 US9720448W WO9821171A1 WO 1998021171 A1 WO1998021171 A1 WO 1998021171A1 US 9720448 W US9720448 W US 9720448W WO 9821171 A1 WO9821171 A1 WO 9821171A1
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Prior art keywords
halide
formula
pentavalent
mixtures
chc1
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PCT/US1997/020448
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French (fr)
Inventor
Alagappan Thenappan
Hsueh S. Tung
Robert L. Bell
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Alliedsignal Inc.
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Publication date
Application filed by Alliedsignal Inc. filed Critical Alliedsignal Inc.
Priority to CA002271341A priority Critical patent/CA2271341C/en
Priority to AU54324/98A priority patent/AU5432498A/en
Priority to DE69707490T priority patent/DE69707490T2/en
Priority to EP97948216A priority patent/EP0938461B1/en
Priority to JP52271998A priority patent/JP3389251B2/en
Publication of WO1998021171A1 publication Critical patent/WO1998021171A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
    • C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
    • C07C17/087—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated halogenated hydrocarbons
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/906—Comminution of transition metal containing catalyst
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/913—Vapor phase polymerization in absence of transition metal containing catalyst

Definitions

  • the present invention relates to the fluorination of hydrochlorocarbons and hydrochlorofluorocarbons. More particularly, the invention pertains to the catalytic fluorination of hydrochlorocarbons and hydrochlorofluorocarbons in the liquid phase.
  • the process is useful for fluorinating hydrochloropropanes, hydrochlorofluoropropanes, hydrochloropropenes and hydrochlorofluoropropenes and most particularly useful for fluorinating 1,1,1,3,3-pentachloropropane to 1, 1,1,3,3-pentafluoropropane.
  • HFCs Hydrofluorocarbons
  • HCFCs hydrochlorofluorocarbons
  • 1, 1, 1,3,3-pentafluoropropane (HFC -245fa), a hydrofluorocarbon having zero ozone depletion potential, is being considered as a replacement for CFCs such as dichlorodifluoromethane in refrigeration systems and trichlorofluoromethane as a blowing agent.
  • CFCs such as dichlorodifluoromethane in refrigeration systems and trichlorofluoromethane as a blowing agent.
  • HFC-245fa Methods to produce HFC-245fa are also known in the art. See, e.g. WO 95/04022 (reaction of 3-chloro-l, 1,1,3, 3-pentafluoropropane with hydrogen over a reduction catalyst); WO 94/29,251 (hydrogenation of 1,1, 3,3,3 -pentafluoropropene with hydrogen in the gas phase at 40-300 °C using a palladium catalyst; European Patent 611,744 (hydrogenation of di- or trichloropropanes); U.S.
  • Patent Application Serial Number 08/519,857, filed August 25, 1995 reaction of carbon tetrachloride with vinyl chloride to give CC1 3 CH 2 CHC1 2 ( HCC-240fa) followed by fluorination with HF in the presence of a fluorination catalyst including pentavalent antimony, niobium, arsenic and tantalum halides and mixed halides.
  • a fluorination catalyst including pentavalent antimony, niobium, arsenic and tantalum halides and mixed halides.
  • fluorination catalysts include tin salts or organotin compounds along with oxygen-containing compounds, see European Patent Application 187,643 (production of 1, 1-dichloro-l-fluoroethane, HCFC-141b), tin tetrachloride, see U.S.S.R. Patent 341 ,788 (liquid-phase process to produce 1, 1- difluoroethane, HFC- 152a from vinyl chloride), and mixtures of pentavalent and trivalent antimony halides, U.S.
  • patent 4 138,355 (production of CF 3 CH 2 CH 2 C1, HCFC-153fb, from 1,1, 1,3-tetrachloropropane, CC1 3 CH 2 CH 2 C1, HCC-250fb). All of the foregoing patents and application are incorporated herein by reference.
  • HCC-240fa fluorination of HCC-240fa with HF to form HFC-245fa in the presence of tin, titanium, molybdenum or mixture of antimony(V) and antimony(III) halides is not known in the art.
  • the invention provides a fluorinating process which comprises reacting at least one hydrochlorocarbon or hydrochlorofluorocarbon compound with hydrogen fluoride
  • TiCU- x F x wherein x is 0 to 4 and (xii) mixtures of a pentavalent antimony halide of the formula SbCls- p F p wherein p is 0 to 5 with a trivalent antimony halide of the formula SbCb- p F p wherein p is 0 to 3.
  • the process of this invention achieves fluorination of HFCs and HCFCs under less corrosive conditions than prior art processes.
  • DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT The invention concerns the catalytic fluorination of HCCs and HCFCs in the liquid phase with hydrogen fluoride.
  • a liquid phase catalyst as described below is charged into a fluorination reactor prior to heating the reactor.
  • the reactor according to this invention may preferably be any suitable fluorination reaction pressure vessel or autoclave but preferably may be constructed from materials which are resistant to the corrosive effects of HF such as Hastelloy- C, Inconel, Monel and fluoropolymer-lined vessels.
  • Such liquid phase fluorination reactors are well known in the art. Then the HF and the HCC or HCFC compound to be fluorinated and HF are fed to the reactor after the reactor reaches the desired temperature.
  • the reaction is conducted at a temperature of from about 50° C to about 200° C, more preferably from about 90° C to about 140° C. In the preferred embodiment, the reaction is conducted for from about 1 to about 25 hours, more preferably from about 2 to about 8 hours.
  • the pressure of the reaction is not critical and it varies depending on the quantity of hydrogen fluoride used, hydrogen chloride generated and conversion of organics. Convenient operating pressure ranges from about 50 to about 600 psig, and preferably from 50-400 psig. Pressure may be adjusted by continuously removing hydrogen chloride and volatile products from the reactor by distillation.
  • the catalyst is present in an amount, based on the mole percent of HCC or HCFC or mixtures thereof of from about 2% to about 80%, and preferably from about 5% to about 50%, and most preferably from about 10% to about 20%. Fluorination catalysts having a purity of at least 98% are preferred.
  • the required mole ratio of HF to organics is at least equal to the number of chlorine atoms to be replaced in the starting organic material and preferably is relatively in an excess.
  • the mole ratio of HF to HCC or HCFC compound ranges from at least about 1: 1, more preferably from about 1 : 1 to about 15: 1 and most preferably from about 6: 1 to about 15: 1.
  • substantially anhydrous HF is preferred.
  • substantially anhydrous we mean that the HF contains less than about 0.05 weight % water and preferably contains less than about 0.02 weight % water.
  • HF suitable for use in the reaction may be purchased from AlliedSignal Inc. of Morristown, New Jersey.
  • the HCC or HCFC compound useful for the invention includes hydrochloroalkanes and hydrochlorofluoroalkanes having the formula CF x Cl 3 . x CH 2 CHF y Cl 2 .
  • hydrochloropropanes and hydrochlorofluoropropanes are more preferred.
  • the most preferred hydrochloroalkanes and hydrochlorofluoroalkanes non-exclusively include CC1 3 CH 2 CHC1 2 , CFC1 2 CH 2 CHC1 2 , CF 2 C1CH 2 CHC1 2 , CF 3 CH 2 CHC1 2 ,
  • the process of the present invention is most particularly useful for fluorinating 1,1, 1,3,3-pentachloropropane to 1,1,1,3,3-pentafluoropropane.
  • Suitable HCCs and HCFCs also include hydrochloroalkenes and hydrochlorofluoroalkenes having the formula CF X C1 3 .
  • X CH CHY wherein x is 0 to 3 and Y is F or Cl.
  • hydrochloropropenes and hydrochlorofluoropropenes are more preferred.
  • HCCs and HCFCs materials to be fluorinated in the present invention are not commercially available. However, they may be prepared by any one of the known methods reported in the art. See B. Boutevin, et al., Monofunctional Vinyl Chloride Telomers. 1. Synthesis and Characterization of Vinyl Chloride Telomer Standards, 18 Eur. Polym. J. 675 (1982) in 97 Chemical Abstracts 182966c (1982); and Kotora, et al., Selective Additions of Polyhalogenated Compounds to Chloro Substituted Ethenes Catalyzed by a Copper Complex, 44(2) React. Kinet. Catal. Lett. 415 (1991). See also the method disclosed in Examples 1 and 2 of U.S. patent application serial number 08/519,857, filed August 25, 1995. All of
  • Suitable catalysts for use in the present invention include: (i) a pentavalent molybdenum halide of the formula MoCls- z F z wherein z is 0 to 5; (ii) a tetravalent tin halide of the formula SnCU- y F y wherein y is 0 to 4; (iii) a tetravalent titanium halide of the formula TiCU- x F x wherein x is 0 to 4; (iv) mixtures of a pentavalent tantalum halide of the formula TaC -nF ⁇ wherein n is 0 to 5 with a tetravalent tin halide of the formula SnCU- y F y wherein y is 0 to 4; (v) mixtures of a pentavalent tantalum halide of the formula TaC -nF consumer wherein n is 0 to 5 with a tetravalent titanium halide of the formula
  • the molar ratios of the components of the mixtures typically range from about 1 9 to about 9: 1, preferably from about 3:7 to about 7:3 and most preferably about 1 : 1.
  • the preferred catalysts are pentavalent molybdenum halides, a tetravalent tin halides, a tetravalent titanium halides, and mixtures of a pentavalent antimony halides or mixed halides with a trivalent antimony halides or mixed halides.
  • the term "mixed halide" means more than one different halide is present in the compound.
  • the most preferred catalysts are tin tetrahalide and mixtures of
  • the catalyst decreases in catalytic effectiveness, it can be regenerated.
  • One method of regenerating the catalyst is to treat it by flowing a stream of an excess of gaseous chlorine over the catalyst for from about 1 to about 2 hours at a temperature of from about 65°C to about 100 °C.
  • Resulting fluorination products such as HFC-245fa may be recovered from the reaction mixture via any separation and purification method known in the art such as neutralization and distillation.
  • the process may be carried out either in a batch or continuous method.
  • the HCC or HCFC compound to be fluorinated and HF are preferably fed simultaneously to the reactor after the reactor reaches the desired temperature.
  • the temperature and pressure of the fluorination reaction remain the same for both the batch and continuous modes of operation.
  • the residence time for a continuous process varies from about 1 second to about 2 hours, preferably from about 5 seconds to about 1 hour and most preferably from about 10 seconds to about 30 minutes.
  • the catalyst concentration is not critical for a continuous process.
  • a 600 ml Monel autoclave equipped with a magnetic drive was charged with 9.4 g SnCUand cooled to -20° C.
  • the autoclave was then evacuated and charged with 60.5 g anhydrous HF.
  • the contents were cooled to -25° C and 54 g CC1 3 CH 2 CHC1 2 was added thereto.
  • the autoclave was then connected to a packed column/condenser assembly, and the condenser was maintained at -5° C.
  • the column condenser assembly serves to vent off gaseous HC1 and effect a HC1/HF separation.
  • the reaction mixture was heated with stirring to about 135° C over 2 hours and maintained at that temperature for an additional 3 hours.
  • Example 1 The experiment described in Example 1 was repeated except that TiCU was used as the catalyst.
  • TiCU was used as the catalyst.
  • To the apparatus described in Example 1 was charged 6.8 g TiCU, 63.1 g HF and 54 g CC1 3 CH 2 CHC1 2 . This mixture was heated with stirring to about 135° C in 2 hours and maintained at that temperature for an additional 3 hours. Venting the reactor completely to the cold traps gave 17.3 g of product.
  • Example 1 The experiment described in Example 1 was repeated except that MoC was used as the catalyst.
  • EXAMPLE 4 Fluorination of CCUCH CHC with HF/SbC SbC The experiment described in Example 1 was repeated except that an equal molar
  • EXAMPLE 5 Fluorination of CCUCH 2 CHC1 7 with HF/TaCU/SnCU The experiment described in Example 1 was repeated except that an equimolar mixture of TaClj and SnCU was used as the catalyst. To the apparatus described in Example 1 was charged 6.5 g of TaC , 4.7 g SnCU, 64.0 g HF and 54 g CC1 3 CH 2 CHC1 2 . This mixture was heated with stirring to about 126° C in 2 hours and maintained at that temperature for an additional 3 hours. Venting the reactor completely to the cold traps gave 32.6 g of product.
  • EXAMPLE 6 Fluorination of CCUCHgCHC with HF/SnCUat 125° C The experiment described in Example 1 was repeated except that the fluorination was conducted at 125 °C. To the apparatus described in Example 1 was charged 9.4 g SnCU, 65.9 g HF and 54 g CC1 3 CH 2 CHC1 2 . This mixture was heated with stirring to about 125° C in 2 hours and maintained at that temperature for an additional 3 hours. Venting the reactor completely to the cold traps gave 23.8 g of product.
  • CF 3 CH CHC1 (1), and CF 2 C1CH 2 CHC1 2 (1).

Abstract

A process for the catalytic fluorination of hydrochlorocarbons and hydrochlorofluorocarbons in the liquid phase. The process is useful for fluorinating hydrochloropropanes, hydrochlorofluoropropanes, hydrochloropropenes and hydrochlorofluoropropenes and most particularly useful for fluorinating 1,1,1,3,3-pentachloropropane to 1,1,1,3,3-pentafluoropropane. Suitable catalysts include (i) a pentavalent molybdenum halide; (ii) à tetravalent tin halide; (iii) a tetravalent titanium halide; (iv) a mixture of a pentavalent tantalum halide with a tetravalent tin halide; (v) a mixture of a pentavalent tantalum halide with a tetravalent titanium halide; (vi) a mixture of a pentavalent niobium halide with a tetravalent tin halide; (vii) a mixture of a pentavalent niobium halide with a tetravalent titanium halide; (viii) a mixture of a pentavalent antimony halide with a tetravalent tin halide; (ix) a mixture of a pentavalent antimony halide with a tetravalent titanium halide; (x) a mixture of a pentavalent molybdenum halide with a tetravalent tin halide; (xi) a mixture of a pentavalent molybdenum halide with a tetravalent titanium halide and (xii) a mixture of a pentavalent antimony halide with a trivalent antimony halide. Products of this process are useful in a variety of applications including solvents, blowing agents, and refrigerants.

Description

LIQUID PHASE CATALYTIC FLUORLNATION OF HYDROCHLOROCARBON AND HYDROCHLOROFLUOROCARBON
BACKGROUND OF THE INVENTION
Field of the Invention
The present invention relates to the fluorination of hydrochlorocarbons and hydrochlorofluorocarbons. More particularly, the invention pertains to the catalytic fluorination of hydrochlorocarbons and hydrochlorofluorocarbons in the liquid phase. The process is useful for fluorinating hydrochloropropanes, hydrochlorofluoropropanes, hydrochloropropenes and hydrochlorofluoropropenes and most particularly useful for fluorinating 1,1,1,3,3-pentachloropropane to 1, 1,1,3,3-pentafluoropropane.
Description of the Prior Art
In recent years there has been universal concern that completely halogenated chlorofluorocarbons (CFCs) might be detrimental to the Earth's ozone layer. Consequently, there is a worldwide effort to use fluorine-substituted hydrocarbons which contain fewer or no chlorine substituents. Hydrofluorocarbons (HFCs) are of great interest due to their potential to replace ozone depleting CFCs and hydrochlorofluorocarbons (HCFCs) in a variety of applications such as solvents, blowing agents, refrigerants, cleaning agents, aerosol propellants, heat transfer media, dielectrics, fire extinguishing compositions and power cycle working fluids. It is known in the art to produce fluorocarbons such as HFCs by reacting hydrogen fluoride with various hydrochlorocarbon
compounds. In this regard, 1, 1, 1,3,3-pentafluoropropane (HFC -245fa), a hydrofluorocarbon having zero ozone depletion potential, is being considered as a replacement for CFCs such as dichlorodifluoromethane in refrigeration systems and trichlorofluoromethane as a blowing agent. See U.S. Patent No. 2,942,036, Canadian 684,687, EP 381 986A, JP 02,272,086, WO 95/04022, U.S. Patent No. 5,496,866 (foam blowing agent) and European Patent No. 2,942,036 (aerosol propellant).
Methods to produce HFC-245fa are also known in the art. See, e.g. WO 95/04022 (reaction of 3-chloro-l, 1,1,3, 3-pentafluoropropane with hydrogen over a reduction catalyst); WO 94/29,251 (hydrogenation of 1,1, 3,3,3 -pentafluoropropene with hydrogen in the gas phase at 40-300 °C using a palladium catalyst; European Patent 611,744 (hydrogenation of di- or trichloropropanes); U.S. Patent Application Serial Number 08/519,857, filed August 25, 1995 (reaction of carbon tetrachloride with vinyl chloride to give CC13CH2CHC12 ( HCC-240fa) followed by fluorination with HF in the presence of a fluorination catalyst including pentavalent antimony, niobium, arsenic and tantalum halides and mixed halides. However, these methods are not without.their shortcomings. For example, hydrogenation of mono-, di- or tri-chloropentafluoropropanes and unsaturated pentafluoropropene has several disadvantages, namely, multiple steps necessary for the preparation of the feed materials, a higher reaction temperature and poor selectivity to the desired product. Fluorination of HCC-240fa with HF in the presence of a pentavalent antimony halide catalyst shows a high corrosion rate when a metallic reactor is used. See U.S. Patent 4,138,355.
Also known in the art are reactions of unsaturated, halogenated olefins such as tri- and tetrachloroethenes with HF in the presence of tantalum pentafluoride, niobium pentafluoride, molybdenum pentachloride, and titanium tetrachloride. See Feiring, A.E. in Journal of Fluorine Chemistry, 14, 7(1979); U.S. Patent 4,258,225 (tantalum pentafluoride and niobium pentafluoride as liquid phase
catalysts).
Other known fluorination catalysts include tin salts or organotin compounds along with oxygen-containing compounds, see European Patent Application 187,643 (production of 1, 1-dichloro-l-fluoroethane, HCFC-141b), tin tetrachloride, see U.S.S.R. Patent 341 ,788 (liquid-phase process to produce 1, 1- difluoroethane, HFC- 152a from vinyl chloride), and mixtures of pentavalent and trivalent antimony halides, U.S. patent 4, 138,355 (production of CF3CH2CH2C1, HCFC-153fb, from 1,1, 1,3-tetrachloropropane, CC13CH2CH2C1, HCC-250fb). All of the foregoing patents and application are incorporated herein by reference.
It would be advantageous to achieve the catalytic fluorination of HCCs and HCFCs with HF under less corrosive conditions using metal reactors. The use of tetravalent tin or titanium halide or an equal molar mixture of trivalent and pentavalent antimony halides or molybdenum pentahalide as a fluorination catalyst to fluorinate polychlorinated compounds with a -CHFyCl2-y, wherein y = 0 or 1 end group to give polyfluorinated compounds with a -CHF2 teirninal group is not known in the art. In particular, fluorination of HCC-240fa with HF to form HFC-245fa in the presence of tin, titanium, molybdenum or mixture of antimony(V) and antimony(III) halides is not known in the art.
SUMMARY OF THE INVENTION
The invention provides a fluorinating process which comprises reacting at least one hydrochlorocarbon or hydrochlorofluorocarbon compound with hydrogen fluoride
in the liquid phase and in the presence of at least one catalyst selected from the group consisting of (i) a pentavalent molybdenum halide of the formula MoCls-zFz wherein z is 0 to 5; (ii) a tetravalent tin halide of the formula SnCU-yFy wherein y is 0 to 4; (iii) a tetravalent titanium halide of the formula TiCU- Fx wherein x is 0 to 4; (iv) mixtures of a pentavalent tantalum halide of the formula TaCl5-nFn wherein n is 0 to 5 with a tetravalent tin halide of the formula SnCU-yFy wherein y is 0 to 4; (v) mixtures of a pentavalent tantalum halide of the formula TaC -JFn wherein n is 0 to 5 with a tetravalent titanium halide of the formula TiCl4-xFx wherein x is 0 to 4; (vi) mixtures of a pentavalent niobium halide of the formula NbC -mFn, wherein m is 0 to 5 with a tetravalent tin halide of the formula SnCU-yFy wherein y is 0 to 4; (vii) mixtures of a pentavalent niobium halide of the formula NbCl5.,„Fra wherein m is 0 to 5 with a tetravalent titanium halide of the formula TiCU-xFx wherein x is 0 to 4; (viii) mixtures of a pentavalent antimony halide of the formula SbC -pFp wherein p is 0 to 5 with a tetravalent tin halide of the formula SnCU-yFy wherein y is 0 to 4; (ix) mixtures of a pentavalent antimony halide of the formula SbC -pFp wherein p is 0 to 5 with a tetravalent titanium halide of the formula TiCU-xFx wherein x is 0 to 4; (x) mixtures of a pentavalent molybdenum halide of the formula MoCl5-zFz wherein z is 0 to 5 with a tetravalent tin halide of the formula SnCU-yFy wherein y is 0 to 4; (xi) mixtures of a pentavalent molybdenum halide of the formula MoCl5.zFz wherein z is 0 to 5 with a tetravalent titanium halide of the formula
TiCU-xFx wherein x is 0 to 4 and (xii) mixtures of a pentavalent antimony halide of the formula SbCls-pFp wherein p is 0 to 5 with a trivalent antimony halide of the formula SbCb-pFp wherein p is 0 to 3.
The process of this invention achieves fluorination of HFCs and HCFCs under less corrosive conditions than prior art processes. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT The invention concerns the catalytic fluorination of HCCs and HCFCs in the liquid phase with hydrogen fluoride. In the practice of the present invention, a liquid phase catalyst as described below is charged into a fluorination reactor prior to heating the reactor. The reactor according to this invention may preferably be any suitable fluorination reaction pressure vessel or autoclave but preferably may be constructed from materials which are resistant to the corrosive effects of HF such as Hastelloy- C, Inconel, Monel and fluoropolymer-lined vessels. Such liquid phase fluorination reactors are well known in the art. Then the HF and the HCC or HCFC compound to be fluorinated and HF are fed to the reactor after the reactor reaches the desired temperature.
In the preferred embodiment, the reaction is conducted at a temperature of from about 50° C to about 200° C, more preferably from about 90° C to about 140° C. In the preferred embodiment, the reaction is conducted for from about 1 to about 25 hours, more preferably from about 2 to about 8 hours. The pressure of the reaction is not critical and it varies depending on the quantity of hydrogen fluoride used, hydrogen chloride generated and conversion of organics. Convenient operating pressure ranges from about 50 to about 600 psig, and preferably from 50-400 psig. Pressure may be adjusted by continuously removing hydrogen chloride and volatile products from the reactor by distillation. In the preferred embodiment, the catalyst is present in an amount, based on the mole percent of HCC or HCFC or mixtures thereof of from about 2% to about 80%, and preferably from about 5% to about 50%, and most preferably from about 10% to about 20%. Fluorination catalysts having a purity of at least 98% are preferred.
Based on reaction stoichiometry, the required mole ratio of HF to organics (i.e. HFCs and HCFCs) is at least equal to the number of chlorine atoms to be replaced in the starting organic material and preferably is relatively in an excess. In the preferred embodiment, the mole ratio of HF to HCC or HCFC compound ranges from at least about 1: 1, more preferably from about 1 : 1 to about 15: 1 and most preferably from about 6: 1 to about 15: 1.
Any water in the HF will react with and deactivate the catalyst. Therefore substantially anhydrous HF is preferred. By "substantially anhydrous" we mean that the HF contains less than about 0.05 weight % water and preferably contains less than about 0.02 weight % water. However, one of ordinary skill in the art will appreciate that the presence of water in the catalyst can be compensated for by increasing the amount of catalyst used. HF suitable for use in the reaction may be purchased from AlliedSignal Inc. of Morristown, New Jersey. In the preferred embodiment, the HCC or HCFC compound useful for the invention includes hydrochloroalkanes and hydrochlorofluoroalkanes having the formula CFxCl3.xCH2CHFyCl2.y, wherein x is 0 to 3 and y is 0 or 1. Of these hydrochloropropanes and hydrochlorofluoropropanes are more preferred. The most preferred hydrochloroalkanes and hydrochlorofluoroalkanes non-exclusively include CC13CH2CHC12, CFC12CH2CHC12, CF2C1CH2CHC12, CF3CH2CHC12,
CF3CH2CHFC1, CC13CH2CHFC1, CFC12CH2CHFC1 , CF2C1CH2CHFC1 and mixtures thereof. The process of the present invention is most particularly useful for fluorinating 1,1, 1,3,3-pentachloropropane to 1,1,1,3,3-pentafluoropropane.
Suitable HCCs and HCFCs also include hydrochloroalkenes and hydrochlorofluoroalkenes having the formula CFXC13.XCH=CHY wherein x is 0 to 3 and Y is F or Cl. Of these, hydrochloropropenes and hydrochlorofluoropropenes are more preferred. The most preferred hydrochloroalkenes and hydrochlorofluoroalkenes non-exclusively include CC13CH=CHF, CC13CH=CHC1, CFC12CH=CHF, CFC12CH=CHC1, CF2C1CH=CHF, CF2C1CH=CHC1, CF3CH=CHF, CF3CH=CHC1, and mixtures
thereof.
Many of the HCCs and HCFCs materials to be fluorinated in the present invention are not commercially available. However, they may be prepared by any one of the known methods reported in the art. See B. Boutevin, et al., Monofunctional Vinyl Chloride Telomers. 1. Synthesis and Characterization of Vinyl Chloride Telomer Standards, 18 Eur. Polym. J. 675 (1982) in 97 Chemical Abstracts 182966c (1982); and Kotora, et al., Selective Additions of Polyhalogenated Compounds to Chloro Substituted Ethenes Catalyzed by a Copper Complex, 44(2) React. Kinet. Catal. Lett. 415 (1991). See also the method disclosed in Examples 1 and 2 of U.S. patent application serial number 08/519,857, filed August 25, 1995. All of
the above patents, application and disclosures are incorporated herein by reference.
Suitable catalysts for use in the present invention include: (i) a pentavalent molybdenum halide of the formula MoCls-zFz wherein z is 0 to 5; (ii) a tetravalent tin halide of the formula SnCU-yFy wherein y is 0 to 4; (iii) a tetravalent titanium halide of the formula TiCU-xFx wherein x is 0 to 4; (iv) mixtures of a pentavalent tantalum halide of the formula TaC -nFπ wherein n is 0 to 5 with a tetravalent tin halide of the formula SnCU-yFy wherein y is 0 to 4; (v) mixtures of a pentavalent tantalum halide of the formula TaC -nF„ wherein n is 0 to 5 with a tetravalent titanium halide of the formula TiCU-xFx wherein x is 0 to 4; (vi) mixtures of a pentavalent niobium halide of the formula NbCU-mFm wherein m is 0 to 5 with a tetravalent tin halide of the formula SnCU-yFy wherein y is 0 to 4; (vii) mixtures of a pentavalent niobium halide of the formula NbC -mFm wherein m is 0 to 5 with a tetravalent titanium halide of the formula TiCU-xFx wherein x is 0 to 4; (viii) mixtures of a pentavalent antimony halide of the formula SbC -pFp wherein p is 0 to 5 with a tetravalent tin halide of the formula SnCU-yFy wherein y is 0 to 4; (ix) mixtures of a pentavalent antimony halide of the formula SbCl5-pFp wherein p is 0 to 5 with a tetravalent titanium halide of the formula TiCU.xFx wherein x is 0 to 4; (x) mixtures of a pentavalent molybdenum halide of the formula MoCl5-zFz wherein z is 0 to 5 with a tetravalent tin halide of the formula SnCU-yFy wherein y is 0 to 4; (xi) mixtures of a pentavalent molybdenum halide of the formula MoCls.zFz wherein z is 0 to 5 with a tetravalent titanium halide of the formula TiCl4-xFx wherein x is 0 to 4 and (xii) mixtures of a pentavalent antimony halide of the formula SbC -pFp wherein p is 0 to 5 with a trivalent antimony halide of the formula SbCl3.pFp wherein p is 0 to 3.
In the preferred embodiment, for group (iv) through (xii) catalysts above, the molar ratios of the components of the mixtures typically range from about 1 9 to about 9: 1, preferably from about 3:7 to about 7:3 and most preferably about 1 : 1. Of the above, the preferred catalysts are pentavalent molybdenum halides, a tetravalent tin halides, a tetravalent titanium halides, and mixtures of a pentavalent antimony halides or mixed halides with a trivalent antimony halides or mixed halides. The term "mixed halide" means more than one different halide is present in the compound. The most preferred catalysts are tin tetrahalide and mixtures of
TaClj and SnCU.
If in the course of conducting the inventive process the catalyst decreases in catalytic effectiveness, it can be regenerated. One method of regenerating the catalyst is to treat it by flowing a stream of an excess of gaseous chlorine over the catalyst for from about 1 to about 2 hours at a temperature of from about 65°C to about 100 °C.
Resulting fluorination products such as HFC-245fa may be recovered from the reaction mixture via any separation and purification method known in the art such as neutralization and distillation. The process may be carried out either in a batch or continuous method. In a continuous process, the HCC or HCFC compound to be fluorinated and HF are preferably fed simultaneously to the reactor after the reactor reaches the desired temperature. The temperature and pressure of the fluorination reaction remain the same for both the batch and continuous modes of operation. The residence time for a continuous process varies from about 1 second to about 2 hours, preferably from about 5 seconds to about 1 hour and most preferably from about 10 seconds to about 30 minutes. The catalyst concentration is not critical for a continuous process. A sufficient quantity of catalyst must be present to effect the fluorination in the residence times described above. The continuous method requires the removal of fluorination products and hydrogen chloride from the reactor continuously as it is formed. Unreacted HF and under-fluorinated materials such as CFC12CH2CHC12; CF2C1CH2CHC12; CF3CH2CHC12; CF3CH2CHFC1, CC13CH2CHFC1; CFC12CH2CHFC1;
CF2C1CH2CHFC1; CF3CH=CHF, CF3CH=CHC1; CC13CH=CHF; CFC12CH=CHF, CFC12CH=CHC1; CF2C1CH=CHF and CF2C1CH=CHC1 may be recycled back to the same reactor or optionally to a separate reactor.
The following non-limiting examples serve to illustrate the invention.
EXAMPLE 1 : Fluorination of CCUCH2CHC1? with HF/SnC
A 600 ml Monel autoclave equipped with a magnetic drive was charged with 9.4 g SnCUand cooled to -20° C. The autoclave was then evacuated and charged with 60.5 g anhydrous HF. The contents were cooled to -25° C and 54 g CC13CH2CHC12 was added thereto. The autoclave was then connected to a packed column/condenser assembly, and the condenser was maintained at -5° C. The column condenser assembly serves to vent off gaseous HC1 and effect a HC1/HF separation. The reaction mixture was heated with stirring to about 135° C over 2 hours and maintained at that temperature for an additional 3 hours. During this period, the pressure in the autoclave was maintained between 300-400 psig by periodically venting pressure in excess of 400 psig. Venting was done from the top of the condenser to an aqueous KOH scrubber which was connected to two -78° C cold traps. The reactor was then completely vented to the cold traps to give 33.2 g of product. Gas chromatographic analysis of the product showed the presence of the following products with their relative area percentages:
CF3CH2CHF2(57), CF3CH2CHFC1 (9), CF3CH=CHF (3), CF3CH=CHC1 (30) and Ce materials (1). Relative area percentages in these examples closely approximates weight percent.
EXAMPLE 2: Fluorination of CCUCH^CHCl, with HF/TiC
The experiment described in Example 1 was repeated except that TiCU was used as the catalyst. To the apparatus described in Example 1 was charged 6.8 g TiCU, 63.1 g HF and 54 g CC13CH2CHC12. This mixture was heated with stirring to about 135° C in 2 hours and maintained at that temperature for an additional 3 hours. Venting the reactor completely to the cold traps gave 17.3 g of product. Gas chromatographic analysis of the product showed the presence of the following products with their relative area percentages: CF3CH2CHF2 (25), CF3CH2CHFC1 (16), CF3CH=CHF (3), CF3CH=CHC1 (55) and C6 materials (1).
EXAMPLE 3: Fluorination of CCUCH?CHC17 with HF/MoC
The experiment described in Example 1 was repeated except that MoC was used as the catalyst. To the apparatus described in Example 1 was charged 10.0 g M0CI5, 65.3g HF and 54.1 g CC13CH2CHC12. This mixture was heated with stirring to about 135° C in 2 hours and maintained at that temperature for an additional 3 hours. Venting the reactor completely to the cold traps gave 15.0 g of product. Gas chromatographic analysis of the product showed the presence of the following products with their relative area percentages: CF3CH2CHF2 (44), CF3CH2CHFC1 (15), CF3CH=CHF (3), CF3CH=CHC1 (37) and C6 materials (1). EXAMPLE 4: Fluorination of CCUCH CHC with HF/SbC SbC The experiment described in Example 1 was repeated except that an equal molar
mixture of SbC and SbCl was used as the catalyst. To the apparatus described in Example 1 was charged 5.4 g SbCl5, 4.1 g SbCl3, 60.2 g HF and 54 g CC13CH2CHC12. This mixture was heated with stirring to about 135° C in 2 hours and maintained at that temperature for an additional 3 hours. Venting the reactor completely to the cold traps gave 26.8 g of product. Gas chromatographic analysis of the product showed the presence of the following products with their relative area percentages: CF3CH2CHF2 (91), CF3CH2CHFCl (5), CF3CH=CHF (1), CF3CH=CHC1 (2) and C6 materials (1).
EXAMPLE 5: Fluorination of CCUCH2CHC17 with HF/TaCU/SnCU The experiment described in Example 1 was repeated except that an equimolar mixture of TaClj and SnCU was used as the catalyst. To the apparatus described in Example 1 was charged 6.5 g of TaC , 4.7 g SnCU, 64.0 g HF and 54 g CC13CH2CHC12. This mixture was heated with stirring to about 126° C in 2 hours and maintained at that temperature for an additional 3 hours. Venting the reactor completely to the cold traps gave 32.6 g of product. Gas chromatographic analysis of the product showed the presence of the following products with their relative area percentages: CF3CH2CHF2 (91), CF3CH2CHFC1 (1.3), CF3CH=CHF (0.2), CF3CH=CHC1 (7.1) and C6 materials (0.4).
EXAMPLE 6: Fluorination of CCUCHgCHC with HF/SnCUat 125° C The experiment described in Example 1 was repeated except that the fluorination was conducted at 125 °C. To the apparatus described in Example 1 was charged 9.4 g SnCU, 65.9 g HF and 54 g CC13CH2CHC12. This mixture was heated with stirring to about 125° C in 2 hours and maintained at that temperature for an additional 3 hours. Venting the reactor completely to the cold traps gave 23.8 g of product. Gas chromatographic analysis of the product showed the presence of the following products with their relative area percentages: CF3CH2CHF2 (40), CF3CH2CHFC1 (19), CF3CH=CHF (3), CF3CH=CHC1 (37) and C6 materials (1).
EXAMPLE 7: Fluorination of CF,CH=CHF with HF/SnCU at 115° C The experiment described in Example 1 was repeated except that CF3CH=CHF was used as the starting material. To the apparatus described in Example 1 was charged 18.8 g SnCU, 42.4 g HF and 57.4 g CF3CH=CHF. This mixture was heated with stirring to about 1 15° C in 2 hours and maintained at that temperature for an additional 3 hours. Venting the reactor completely to the cold traps gave 52.6 g of product. Gas chromatographic analysis of the product showed the presence of the following products with their relative area percentages: CF3CH2CHF2 (39), CF3CH2CHFC1 (2), CF3CH=CHF (47), and CF3CH=CHC1 (11). EXAMPLE 8: Fluorination of CF H=CHF with HF/SbCU at 93° C The experiment described in Example 1 was repeated except that SbC and CF3CH=CHF were used as the catalyst and the starting material. To the apparatus described in Example 1 was charged 21.6 g SbC , 36.0 g HF and 59.2 g CF3CH=CHF. This mixture was heated with stirring to about 93° C in 2 hours and maintained at that temperature for an additional 3 hours. Venting the reactor completely to the cold traps gave 48.0 g of product. Gas chromatographic analysis of the product showed the presence of the following products with their relative area percentages: CF3CH2CHF2 (90), CF3CH2CHFC1 (4), CF3CH=CHF (1), CF3CH=CHC1 (3) and high boilers (2).
EXAMPLE 9: Fluorination of CF.CH=CHF with HF/TaC at 117° C
The experiment described in Example 1 was repeated except that TaC and
CF3CH=CHF were used as the catalyst and the starting material. To the apparatus described in Example 1 was charged 25.8 g TaC , 36.8 g HF and 57.3 g CF3CH=CHF. This mixture was heated with stirring to about 117° C in 2 hours and maintained at that temperature for an additional 3 hours. Venting the reactor completely to the cold traps gave 48.3 g of product. Gas chromatographic analysis of the product showed the presence of the following products with their relative area percentages: CF3CH2CHF2 (98), CF3CH=CHF (1), and CF3CH=CHC1 (1). EXAMPLE 10: Fluorination of CF^CH=CHC1 with HF/SbC at 95° C The experiment described in Example 1 was repeated except that SbC and CF3CH=CHC1 were used as the catalyst and the starting material. To the apparatus described in Example 1 was charged 22.4 g SbCl5, 45.3 g HF and 75.2 g
CF CH=CHC1. This mixture was heated with stirring to about 95° C in 1 hour and maintained at that temperature for an additional 4 hours. Venting the reactor completely to the cold traps gave 72.9 g of product. Gas chromatographic analysis of the product showed the presence of the following products with their relative area percentages: CF3CH2CHF2 (83), CF3CH2CHFC1 (5), CF3CH=CHF (1), CF3CH=CHC1 (9), CF2C1CH2CHC12 (1) and CC13CH2CHC12 (1).
EXAMPLE 11 : Fluorination of CF.CH=CHC1 with HF/TaCU at 116° C The experiment described in Example 1 was repeated except that TaCls and CF3CH=CHC1 were used as the catalyst and the starting material. To the apparatus described in Example 1 was charged 26.9 g TaC , 47.5 g HF and 76.4 g CF3CH=CHC1. This mixture was heated with stirring to about 116° C in 1 hour and maintained at that temperature for an additional 4 hours. Venting the reactor completely to the cold traps gave 79.5 g of product. Gas chromatographic analysis of the product showed the presence of the following products with their relative area percentages: CF3CH2CHF2 (97), CF3CH2CHFC1 (1), CF3CH=CHF (traces),
CF3CH=CHC1 (1), and CF2C1CH2CHC12 (1).

Claims

What is claimed is:
1. A fluorinating process which comprises reacting at least one hydrochlorocarbon or hydrochlorofluorocarbon compound with hydrogen fluoride in the liquid phase and in the presence of at least one catalyst selected from the group consisting of (i) a pentavalent molybdenum halide of the formula MoCls-zFz wherein z is 0 to 5; (ii) a tetravalent tin halide of the formula SnC-4_yFy wherein y is 0 to 4; (hi) a tetravalent titanium halide of the formula TiC-4-xFx wherein x is 0 to 4; (iv) mixtures of a pentavalent tantalum halide of the formula TaCl5.nFn wherein n is 0 to 5 with a tetravalent tin halide of the formula SnCU-yFy wherein y is 0 to 4; (v) rnixtures of a pentavalent tantalum halide of the formula TaCls.nFn wherein n is 0 to 5 with a tetravalent titanium halide of the formula TiCU-χFx wherein x is 0 to 4; (vi) mixtures of a pentavalent niobium halide of the formula NbCl5_mFm wherein m is 0 to 5 with a tetravalent tin halide of the formula SnC -yFy wherein y is 0 to 4; (vii) mixtures of a pentavalent niobium halide of the formula NbCl5.mFm wherein m is 0 to 5 with a tetravalent titanium halide of the formula TiCU-χFx wherein x is 0 to 4; (viii) mixtures of a pentavalent antimony halide of the formula SbCl5.pFp wherein p is 0 to 5 with a tetravalent tin halide of the formula SnCU.xFx wherein x is 0 to 4; (ix) mixtures of a mixture of a pentavalent antimony halide of the formula SbCl5.pFp wherein p is 0 to 5 with a tetravalent titanium halide of the formula TiCl - Fx wherein x is 0 to 4; (x) mixtures of a pentavalent molybdenum halide of the formula MoCl5.zFz wherein z is 0 to 5 with a tetravalent tin halide of the formula SnCU-yFy wherein y is 0 to 4; (xi) mixtures of a pentavalent molybdenum halide of the formula MoCls.zFz wherein z is 0 to 5 with a tetravalent titanium halide of the formula TiCl4-xFs wherein x is 0 to 4 and (xii) mixtures of a pentavalent antimony halide of the formula SbCls-pFp wherein p is 0 to 5 with a trivalent antimony halide of the formula SbCl3_pFp wherein p is 0 to 3.
2. The process of claim 1 wherein the hydrochlorocarbon or hydrochlorofluorocarbon compound is a hydrochloropropane or hydrochlorofluoropropane.
3. The process of claim 1 wherein the hydrochlorocarbon or hydrochlorofluorocarbon compound has the formula CFxCl3-xCH2CHFyCi2-y, wherein x is 0 to 3 and y is 0 or 1.
4. The process of claim 1 wherein the hydrochlorocarbon or hydrochlorofluorocarbon compound is selected from the group consisting of
CC13CH2CHC12, CFC12CH2CHC12> CF2C1CH2CHC12, CF3CH2CHC12) CF3CH2CHFCI, CCI3CH2CHFCI, CFC12CH2CHFC1 , CF2C1CH2CHFC1 and mixtures thereof.
5. The process of claim 1 wherein the hydrochlorocarbon or hydrochlorofluorocarbon compound is selected from the group consisting of CC13CH=CHF, CC13CH=CHC1, CFC12CH=CHF, CFC12CH=CHC1, CF2C1CH=CHF, CF2C1CH=CHC1, CF3CH=CHF and CF3CH=CHC1.
6. The process of claim 1 wherein the hydrochlorocarbon comprises 1,1,1,3,3- pentachloropropane and the product of the fluorination process comprises 1,1,1,3,3- pentafluoropropane.
7. The process of claim 1 wherein the catalyst is selected from the group consisting of pentavalent molybdenum halides, tetravalent tin halides, tetravalent titanium halides, and mixtures of pentavalent antimony halides or mixed halides with trivalent antimony halides or mixed halides.
8. The process of claim 1 wherein the catalyst comprises a mixture of TaCls and SnCU
9. The process of claim 1 which comprises reacting CCI3CH2CHCI2 with hydrogen fluoride and tin tetrahalide catalyst in the liquid phase, wherein the molar ratio of hydrogen fluoride to CCI3CH2CHCI2 is from 6: 1 to about 15: 1 and the catalyst is present in an amount of from about 10% to about 20% based on the mole percent of CCI3CH2CHCI2 and the reaction is conducted at a temperature of from about 90° C to about 140° C for a period of 2-8 hours to produce 1,1,1,3,3-pentafluoropropane.
10. The process of claim 1 which comprises reacting CCI3CH2CHCI2 with hydrogen fluoride and an equimolar mixture of TaCls and SnCU as catalyst in the liquid phase, wherein the molar ratio of hydrogen fluoride to CCI3CH2CHCI2 is from 6: 1 to about 15:1 and the catalyst is present in an amount of from about 10% to about 20% based on the mole percent of CCI3CH2CHCI2 and the reaction is conducted at a temperature of from about 90° C to about 140° C for a period of 2-8 hours to produce 1,1,1,3,3-pentafluoropropane.
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