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• • 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
  • C07C17/093—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
  • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
  • C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
  • C07C17/275—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of hydrocarbons and halogenated hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
  • C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
  • C07C17/278—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C19/00—Acyclic saturated compounds containing halogen atoms
  • C07C19/01—Acyclic saturated compounds containing halogen atoms containing chlorine
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C19/00—Acyclic saturated compounds containing halogen atoms
  • C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
  • C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
  • C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine

Definitions

• the invention pertains to a process for the manufacture of haloalkanes, or more particularly to a process for the manufacture of 1,1,1, 3,3-pentachloropropane (HCC-240fa) and/or 1,1,1 ,3-tetrachloropropane (HCC-250fb).
• haloalkanes such as 1,1,1, 3,3- pentachloropropane (HCC-240fa)
• HCC-240fa 1,1,1, 3,3- pentachloropropane
• a halogenated compound such as carbon tetrachloride
• an olefinic compound such as vinyl chloride monomer (VCM)
• VCM vinyl chloride monomer
• the halogenated product then is recovered by separating it from the reactants, catalyst and by-products using conventional techniques such as distillation.
• CataL, 51-60 (1992) discloses a batch process for the preparation of HCC-240fa from carbon tetrachloride and vinyl chloride using as a catalyst, cuprous salts, cuprous chloride and CUf(CH 3 -CN) 4 ]ClO 4 , complexed with a co-catalyst, namely, n-butylamine.
• a co-catalyst namely, n-butylamine.
• the catalyst and co-catalyst are removed by a water wash which destroys the catalyst. Since the catalyst is destroyed, it cannot be recycled. Reusing catalyst, however, is important to a commercially- viable, continuous process.
• HCC-240fa is a commercial raw material for the manufacture of HFC-245fa, and a need exists to develop alternative technologies to manufacture this material.
• the present invention addresses these needs, among others.
• the present invention relates to new catalyst and co-catalyst systems, and to a new concept of dissolving a catalyst and co-catalyst in one of the reactants, e.g. CCl 4 , to form a homogeneous mixture. Subsequently, this mixture is fed to a reaction zone along with another reactant , e.g. VCM, preferably in a solid-free reaction.
• another reactant e.g. VCM
• Fig. 1 is a flow chart illustrating a process of the invention for producing HCC- 240fa.
• the invention provides a process for preparing a haloalkane comprising: (a) mixing a catalyst, co-catalyst and a haloalkane starting material under conditions suitable to produce a homogeneous mixture; (b) reacting the homogeneous mixture with a haloalkene starting material, an alkene starting material or both a haloalkene starting material and an alkene starting material under conditions suitable to produce a haloalkane product stream; and (c) recovering a haloalkane product from said product stream.
• the invention also provides a process for preparing a haloalkane, comprising the steps of:
• step (b) reacting the homogeneous mixture with a haloalkene starting material, an alkene starting material or both a haloalkene starting material and an alkene starting material under conditions suitable to produce a haloalkane product stream; (c) flash-distilling the haloalkane product stream of step (b) to separate a haloalkane product, unreacted haloalkane starting material and unreacted haloalkene starting material from a mixture of said catalyst and co-catalyst; and (d) recycling the catalyst and co-catalyst mixture to step (a).
• the invention further provides a process for preparing 1,1,1,3,3- pentafluoropropane and/or a combination of 1,1,1,3-tetrachloropropane and 3,3,3- trifluoro- 1 -propene comprising :
• the present invention provides a highly selective process for the production of halogenated alkanes in good yield in which process unreacted materials may be recycled. More specifically, the invention provides a process for producing 1,1,1,3,3-pentachloropropane (HCC-240fa) and/or 1,1,1,3-tetrachloropropane (HCC-250fb). HCC-240fa may be used as a raw material for the production of 1,1,1,3,3-pentafluoropropane ("HFC-245fa”), 1,1,1,3-tetrafluoropropane and 3 ,3 ,3 -trifluoro- 1 -propene .
• HFC-245fa 1,1,1,3-tetrafluoropropane
• 3 ,3 ,3 -trifluoro- 1 -propene 1,1,1,3,3-pentafluoropropane
• the process may be conducted with or without a solvent, wherein a catalyst and co-catalyst are dissolved in a haloalkane reactant to form a homogenous mixture, followed by feeding the mixture to a reaction zone along with a haloalkene reactant.
• the reaction is most preferably a solid- free reaction. This may be accomplished simply due to the nature of the reactants and/or catalysts or by removal of solids such as by filtration or by decantation.
• the reactor effluent is distilled, preferably flash-distilled, to separate a haloalkane reaction product (e.g. HCC-240fa or HCC-250fb), any unreacted haloalkane starting material (e.g.
• any unreacted haloalkene or alkene starting material e.g. VCM or ethylene
• the catalyst/co-catalyst mixture is then preferably recycled back to a catalyst preparation tank as a mixture.
• the process may be carried out in either a batch or a continuous system.
• the production system may also be closed to provide substantially complete recycling of any unreacted haloalkane starting material and haloalkene starting material or alkene starting material.
• a catalyst and a co- catalyst are mixed with a haloalkane starting material under conditions suitable to produce a mixture.
• the catalysts useful in the present invention include metal ions and neutral metallic species. Suitable catalysts include cuprous salts, organometallic cuprous compounds, iron wire, iron shavings, iron powder, and iron chlorides. Exemplary cuprous salts and organometallic cuprous compounds include, without limitation, cuprous chloride (CuCl), cuprous bromide, cuprous cyanide, cuprous sulfate, and cuprous phenyl.
• the iron powder useful in this invention is preferably a fine powder of pure metallic iron, preferably with a particle size smaller than 325 mesh. Preferably, cuprous chloride or iron powder is used as the catalyst.
• Co-catalysts useful in the present invention are organic ligands capable of forming a complex with the catalyst used and capable of bringing the catalyst into solution.
• Suitable ligands include organic amines, such as, without limitation, tert- butylamine, n-butylamine, sec-butylamine, 2-propylamine, benzylamine, tri-n- butylamine, pyridine and combinations thereof.
• the preferred organic amine is tert-butylamine.
• the co-catalyst may be a nitrile including, without limitation, acetonitrile, propionitrile, n-butyronitrile, benzonitrile, phenylacetonitrile and combinations thereof.
• the preferred nitrile is acetonitrile.
• the co-catalyst may be an amide including, without limitation, hexamethylphosphoramide (HMPA), dimethylformamide and combinations thereof. Hexamethylphosphoramide is the most preferred amide. Also suitable are combinations of amines, nitriles, amides, phosphate and phosphates.
• the co-catalysts are chelating agents and may also serve as solvents. A solvent may help dissolve the solid catalyst. When a solvent is used, it preferably serves as the co-catalyst. Useful solvents non-exclusively include nitrile compounds.
• the catalysts, co-catalysts and solvents useful in the present invention are commercially available.
• the catalysts and co-catalysts useful in the present invention form a catalyst-co- catalyst system.
• the catalyst is CuCl and the co-catalyst is acetonitrile (CH3CN), tert-butylamine (VBu-NH 2 ), n- butylamine (n-Bu-NH 2 ), sec-butylamine (sec-Bu-NH 2 ), benzyl-amine (benzyl- NH 2 ), ethanol-amine, pyridine or tri-n-butylamine (n-Bu 3 N).
• the catalyst is iron powder, or iron wire, and/or ferric chloride and the co-catalyst is HMPA, tributylphosphite ((BuO) 3 P), trichloroethylphosphite ((ClCH 2 CH 2 O) 3 P), triphenylphosphite ((PhO) 3 P), tributylphosphate, or triphenylphosphate.
• the catalyst-co- catalyst system is cuprous chloride/tert-butylamine, cuprous chloride/acetonitrile, iron powder/hexamethylphosphoramide or iron powder/tributylphosphate. Most preferably, cuprous chloride/tert-butylamine or iron powder/tributylphosphate is used.
• haloalkanes include, without limitation, carbon tetrachloride (CCl 4 ), 1,1,1-trichloroethane, dichlorofluoromethane, 1,1,1- trichlorotrifluoroethane, 1 , 1 ,2-trichlorotrifluoroethane, tetrachloroethane, pentachloroethane, and hexachloroethane.
• CCl 4 carbon tetrachloride
• 1,1,1-trichloroethane dichlorofluoromethane
• 1,1,1- trichlorotrifluoroethane 1 , 1 ,2-trichlorotrifluoroethane
• tetrachloroethane tetrachloroethane
• pentachloroethane and hexachloroethane.
• hexachloroethane Such useful haloalkane starting materials are commercially available.
• haloalkenes and alkenes include, without limitation, ethylene, propylene, butylene, vinyl chloride, 1,1-dichloroethene, trichloroethene, tetrachloroethene, chlorofluoroethene, 1 ,2-dichloroethene, 1,1- dichloro-difluoroethene, 1-chloro-l-propene, 2-chloro-l-propene, 1-chloro-l- butene and 2-chloro-l-butene.
• Such useful haloalkene and alkene starting materials are also commercially available.
• haloalkane and haloalkene/alkene used, as well as the catalyst, co- catalyst, and reaction conditions used will depend on the desired product.
• the preferred haloalkane feed material is carbon tetrachloride, available from Occidental Chemical Corp. of Dallas, TX and the preferred haloalkene is vinyl chloride, available from PPG Industries, Pittsburgh, Pa.
• the preferred haloalkene feed material is 2-chloro-l-propene.
• the catalyst and co-catalyst are used in amounts sufficient to catalyze the reaction of the haloalkane starting material and haloalkene starting material.
• the amount used is a mole ratio of catalyst to co-catalyst from about 0.01 :1 to about 500:1, preferably from about 1 :1 to about 100:1.
• the mole ratio of copper to t- butylamine is about 0.05 : 1 to about 20: 1 , preferably about 0.02: 1 to 1.0: 1 , and more preferably about 0.1 :1 to about 0.7:1.
• the mole ratio of iron powder to tributylphosphate may be about 0.05:1 to about 500.0:1, preferably about 1.0:1 to about 100.0:1, and more preferably about 1.5:1 to about 10:1.
• the preferred concentration of the catalyst in the reaction mixture is from about 0.001 to about 20 weight percent, preferably from about 0.01 to about 10 weight percent, and more preferably from about 0.1 to about 5 weight percent.
• the mole ratio of haloalkane to haloalkene is from about 0.02:1 to about 50:1.
• the ratio is from about 0.1 :1 to about 4.0:1 and more preferably from about 1 : 1 to about 3:1 haloalkane to haloalkene or alkene.
• the catalyst, co-catalyst and a haloalkane starting material are mixed to produce a mixture.
• the catalyst may be added to a mixing tank (catalyst preparation tank) containing the haloalkane starting material and/or co-catalyst.
• the co-catalyst may be added to a mixing tank containing the catalyst and haloalkane.
• the catalyst and co-catalyst are mixed first in the mixing tank followed by adding the haloalkane to form said mixture.
• the temperature of the mixing tank may be higher than or lower than the temperature of the reactor, but preferably is maintained at the same temperature as that of the reactor.
• the catalyst/co-catalyst/haloalkane mixture is filtered by using a filtration device internal or external to the mixing tank to form a homogenous mixture.
• the resulting homogeneous mixture is fed along with the haloalkene or alkene into a reactor at the desired reaction temperature, thereby reacting the mixture with the haloalkene or alkene starting material under conditions suitable to produce a haloalkane product stream.
• the process may be conducted with or without a solvent.
• Useful solvents include CH 3 CN (which is also a co-catalyst) and other nitriles. In the absence of a solvent, it is preferred to use a large excess of the haloalkane reactant, such as CCl 4 for the formation of HCC-240fa.
• the reactor is heated to a temperature of from about 40 0 C to about 180 0 C, preferably from about 85°C to about 150 0 C, with agitation and under the vapor pressure of the reagents.
• the reaction is preferably carried out until a conversion or haloalkene or alkene higher than 95% is achieved, generally for a residence time of from about 0.01 hours to about 24 hours, preferably from about 1 hour to about 12 hours.
• the haloalkane product stream is flash-distilled to remove a "top" stream including unreacted haloalkane (e.g. CCl 4 ) and haloalkene or alkene (e.g.
• VCM or ethylene feed materials and the haloalkane reaction product e.g. HCC-240fa or HCC-250fb
• the distillation may be performed in one or more distillation columns, which are well known in the art.
• the flash- distillation is conducted in two steps: first, flash-distillation is conducted at a temperature less than the reaction temperature under a pressure, preferably under vacuum, to remove the haloalkane reaction product, followed by another vacuum flash-distillation at a lower pressure to remove any unreacted haloalkane and/or haloalkene or alkene.
• the "bottoms" stream is fed back to the mixing tank and recycled back to the reactor.
• the distilled, unreacted haloalkane and haloalkene or alkene may be recycled back to the reactor.
• the purification step includes the addition of an amount of a metal chelating compound sufficient to improve the haloalkane product yield. Preferably, 5 weight percent of tributyl phosphate is used.
• the above process is conducted to prepare 1,1,1,3,3-pentafluoropropane (HFC-245fa), wherein (a) the catalyst, co- catalyst and a haloalkane starting material are combined under conditions suitable to produce a homogeneous mixture; (b) the mixture is reacted with a haloalkene starting material under conditions suitable to produce a 1,1,1,3,3- pentachloropropane product stream; (c) the 1,1,1,3,3-pentachloropropane is then recovered from said product stream; and (d) said 1,1,1,3,3-pentachloropropane is then reacted with hydrogen fluoride under conditions sufficient to yield 1,1,1,3,3- pentafluoropropane.
• HFC-245fa 1,1,1,3,3-pentafluoropropane
• the haloalkane starting material preferably comprises carbon tetrachloride
• the haloalkene starting material preferably comprises vinyl chloride
• the catalyst/co-catalyst system preferably comprises either cuprous chloride/tert-butylamine or iron powder/tributylphosphate.
• the above process is conducted to prepare a combination of 1,1,1, 3-tetrafluoropropane and 3,3,3-trifluoro-l- propene, wherein (a) the catalyst, co-catalyst and a haloalkane starting material are combined under conditions suitable to produce a homogeneous mixture; (b) the mixture is reacted with an alkene starting material under conditions suitable to produce a 1,1,1,3-tetrachloropropane product stream; (c) the 1,1,1,3- tetrachloropropane is then recovered from said product stream; and (d) said 1,1,1 ,3-tetrachloropropane is then reacted with hydrogen fluoride under conditions sufficient to yield a combination of 1,1,1, 3-tetrafluoropropane and 3,3,3-trifluoro-l-propene.
• the haloalkane starting material preferably comprises carbon tetrachloride
• the alkene starting material preferably comprises ethylene
• the catalyst/co-catalyst system preferably comprises either cuprous chloride/tert-butylamine or iron powder/tributylphosphate.
• a plurality of reactions including one or more haloalkene starting materials and one or more alkene starting materials may also be conducted together in the same reaction vessel to form a plurality of reaction products.
• a homogenous mixture of a catalyst, co-catalyst and a haloalkane starting material may be reacted with both a haloalkene starting material (e.g.
• VCM VCM
• alkene starting material e.g. ethylene
• alkene starting material e.g. ethylene
• haloalkane products e.g. 1,1,1,3,3- pentachloropropane produced from a haloalkene starting material and/or 1,1,1,3- tetrachloropropane, produced from an alkene starting material
• EXAMPLE 2 In a Monel autoclave heated to 95°C, 2.5 g cuprous chloride (0.025 mol) and 5.2 g t-butylamine (0.07 mole) are mixed with 634 g (4.1 moles) of carbon tetrachloride to form a mixture. No solvent is used. Solid CuCl remains in the solution and is removed from the mixture by decantation. Thereafter, 119 g (1.9 moles) of vinyl chloride monomer is added to react with the carbon tetrachloride mixture. The reaction time is 10 hours and the initial pressure is about 220 psig. HCC-240 is produced with 93 mol. % selectivity and VCM conversion is 66 mol. %. HCC-470 (CCI 3 CH 2 CHCICH 2 CHCI 2 ) and HCC-240db (CC1 3 CHC1CH 2 C1) are formed as byproducts.
• a catalyst preparation tank as shown in Fig. 1, about 10 kg of iron powder and 1.3 kg of CCl 4 are added.
• the tank is equipped with an agitator and is heated to 100 0 C after adding the 10 kg of iron powder and 1.3 kg Of CCl 4 .
• 9.2 kg/hr of CCl 4 , 0.24 kg/hr of tributylphosphate, and 0.29 kg/hr of ferric chloride are added and mixed in the tank.
• the mixed solution is passed through a filtration screen at the outlet of the tank and fed to a reactor that is controlled at 100 0 C.
• a separate feed line is used to feed 3.8 kg/hr vinyl chloride directly into the reactor.
• the pressure of the reactor is maintained at about 7 kg/cm 2 .
• the crude product leaving the reactor is fed to a flash-distillation column.
• the flash- distillation column is run under a slight vacuum.
• the overhead of the flash column is fed to a fractionation column (see CCl 4 Column in Fig. 1) where un- reacted CCl 4 and vinyl chloride are distilled and fed back to the reactor.
• the bottom of the flash column that contains catalyst and co-catalyst are recycled back to the mixing tank (i.e. Catalyst Preparation Tank in Fig. 1).
• the bottom of the CCI 4 Column is fed to another fractionation column (i.e. the HCC-240 Product Column).
• HCC-240 Purified HCC-240 is isolated as distillate from the overhead stream of the HCC-240 Product Column. Heavy by-products are removed out of the system from the bottom of the Product Column and the heavy purge in the catalyst recycle line. The yields of CCl 4 and VCM are greater than 90%, respectively.
• HCC-470 CCI 3 CH 2 CHCICH 2 CHCI 2
• HCC-240db CCI 3 CHCICH 2 CI

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