Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/013—Preparation of halogenated hydrocarbons by addition of halogens
  • C07C17/06—Preparation of halogenated hydrocarbons by addition of halogens combined with replacement of hydrogen atoms by halogens
• • 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
  • C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms

Definitions

• the present invention relates to processes for the production of chlorinated alkanes in a nonaqueous media.
• Hydrofluorocarbon (HFC) products are widely utilized in many applications, including refrigeration, air conditioning, foam expansion, and as propellants for aerosol products including medical aerosol devices. Although HFC's have proven to be more climate friendly than the chlorofluorocarbon and hydrochlorofluorocarbon products that they replaced, it has now been discovered that they exhibit an appreciable global warming potential (GWP).
• GWP global warming potential
• HFO hydrofluoro-olefin
• HFO high-strength-olefinoprop-l-ene
• feedstocks of chlorocarbons e.g., highly chlorinated alkanes, e.g., tetra- and pentachloroalkanes.
• the present invention provides efficient processes for the production of highly chlorinated alkanes. More particularly, the processes make use of one or more inorganic iodine salts, or other inorganic precursors to at least one hypervalent iodine species, and/or low levels of elemental iodine desirably as part of a mixed catalyst system further comprising at least one Lewis acid.
• inorganic iodine salts is advantageous as compared to conventional processes, in that inorganic iodine salts are not as corrosive or volatile as elemental iodine when employed at conventional levels, and so, are more readily and conveniently incorporated into large scale manufacturing process.
• the inorganic iodine salts are recoverable and/or reusable, providing significant cost savings to the process. Further cost savings are provided in that low intensity process conditions, e.g., low temperatures, ambient pressure and minimal reactor residence time, are utilized.
• the present invention provides a process for the production of chlorinated alkanes.
• the process comprises catalyzing the chlorination of a feedstream comprising one or more alkanes and/or alkenes in a nonaqueous media with a mixed catalyst system comprising one or more inorganic iodine salts, and/or less than 10,000 ppm elemental iodine and at least one Lewis acid.
• a mixed catalyst system comprising one or more inorganic iodine salts, and/or less than 10,000 ppm elemental iodine and at least one Lewis acid.
• an inorganic iodine salt is used as part of the catalyst system, and in some advantageous embodiments, no iodine is added to the starting alkane and/or alkene.
• the one or more inorganic iodine salts may comprise hypoiodites (IO ), iodites (IO 2 ), iodates (IO 3 ), and/or periodates (IO 4 ), including metaperiodates and orthoperiodates, or combinations of these.
• the concentration of elemental iodine used, if any, may be from 1 ppm to 5000 ppm, or from 5 ppm to 1000 ppm, or from 10 ppm to 100 ppm.
• the source of chlorine atoms may comprise chlorine gas, sulfuryl chloride or a combination of these, and in some embodiments comprises sulfuryl chloride, which may also act as a diluent or solvent as well as a chlorine source.
• the alkane and/or alkene may initially be unchlorinated, or, may already comprise chlorine atoms, and may comprise any number of carbon atoms.
• first”, “second”, and the like, as used herein do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. Also, the terms “a” and “an” do not denote a limitation of quantity, but rather denote the presence of at least one of the referenced item, and the terms “front”, “back”, “bottom”, and/or “top”, unless otherwise noted, are merely used for convenience of description, and are not limited to any one position or spatial orientation.
• inorganic iodine salt is meant to include any inorganic salt, incorporating, or otherwise capable of providing or forming in a reaction mixture, at least one hypervalent iodine species. Typically, such compounds may further be characterized in that they comprise at least metal and iodine elements.
• hypervalent refers to iodine sources having oxidation states of greater than or equal to +1, e.g., +1, +3, +5, +7, etc.
• the present invention provides efficient processes for the production of chlorinated alkanes.
• the present processes catalyze the chlorination of a feedstream comprising one or more alkanes and/or alkenes with one or more inorganic iodine salt and at least one Lewis acid. Further, the processes take place in a nonaqueous media, and as a result, the one or more inorganic iodine salts may be recovered in whole or in part, and/or reused.
• inorganic iodine salts do not present the volatility and corrosion issues that can be presented by elemental iodine when used at conventional levels, as is used in conventional processes for the production of chlorinated alkanes.
• any inorganic iodine salt can be used in the mixed catalyst system, and those of ordinary skill in the art are expected to be familiar with many. Suitable examples include, but are not limited to, hypoiodites (IO ), iodites (IO 2 ), iodates (IO 3 ), and/or periodates (IO 4 ), including mesoperiodates and orthoperiodates, or combinations of these. Specific examples of inorganic iodine salts include, but are not limited to sodium iodate, silver iodate, calcium iodate, potassium iodate, iodic acid, sodium periodate, potassium periodate, barium periodate, and periodic acid, and derivatives or combinations of any number of these.
• elemental iodine may be used, but at levels much lower than previously thought to be effective. That is, it has now been discovered that amounts of iodine much lower than conventionally utilized, e.g., 0.01 wt%, provide improvements in yield and selectivity while yet not presenting the corrosion and volatility issues that may arise when these conventional levels are utilized. More specifically, amounts of elemental iodine of from 1 ppm to 5000 ppm, or from 5 ppm to 1000 ppm, or from 10 ppm to 100 ppm, have now surprisingly been discovered to provide selectivities to the desired chloropropanes of greater than 60%, in some cases greater than 70%, and in some cases greater than 80%.
• the mixed catalyst system used in the process also desirably comprises at least one Lewis acid.
• Any Lewis acid that at least marginally enhances the process can be utilized, and examples of these include, but are not limited to ferric chloride, antimony pentafluoride, boron trichloride, aluminum trichloride, and stannic chloride. Combinations of two or more of these may also be used, if desired.
• anhydrous aluminum chloride may desirably be utilized as the at least one Lewis acid.
• Suitable amounts of the Lewis acid will range from 0.01% to 20% by weight each with respect to the dichlorinated alkane, or from 0.1% to 10%, or from 1% to 5 wt%, inclusive of all subranges therebetween.
• concentrations e.g., as much as 5, or 10, or 15 or even 20 times lower will not only be effective, but be effective over the entire course of plant operability.
• the chlorine atoms are desirably supplied by chlorine gas, sulfuryl chloride, or both.
• Sulfuryl chloride SO 2 CI 2
• SO 2 CI 2 can also act as a solvent for the mixed catalyst systems and/or reactions, thereby assisting in the provision of an acceptable reaction rate and/or yield.
• sulfuryl chloride may desirably be used as the chlorinating agent.
• a solvent may be used in the present processes.
• any solvent will be inert to the desired chemistry, allow for adequate mass transfer during the chemical reaction, and create a homogenous phase to insure uniform reactivity throughout the reactor.
• Chlorocarbon solvents are especially well suited for the present processes due to their ease in handling and relative resistance to the desired chemistry, and many of these are known to those of ordinary skill in the art.
• chlorocarbon solvents include, but are not limited to carbon tetrachloride, methylene chloride, chloroform, 1,2,3- trichloropropane, 1, 1,2,3-tetrachloropropane, and 1, 1,2,2,3, 3-hexachloropropane.
• the chlorocarbon solvent may comprise methylene chloride or 1,2,3- trichloropropane.
• the reaction conditions under which the process is carried out are advantageously low intensity. That is, low temperatures, e.g., of less than 100°C, or less than 90°C, or less than 80°C or less than 70°C, or less than 60°C, may be utilized and the desired selectivities to the desired chlorinated alkanes yet be realized. In some embodiments, temperatures of from 40°C to 90°C, or from 50°C to 80°C, or from 55°C to 75°C may be utilized. Similarly, ambient pressure is suitable for carrying out the process, or pressures within 250, or 200, or 150, or 100, or 50, or 40, or 30, or 20, or even lOpsi, of ambient are suitable.
• Reactor occupancy may also be minimized with the desired selectivities yet seen - for example, reactor occupancy times of less than 20 hours, or less than 15 hours, or less than 10 hours, or less than 9, 8, 7, 6, or even 5 hours, are possible.
• the reactor may be any suitable liquid phase reactor, such as a batch or continuous stirred tank autoclave reactor with an internal cooling coil.
• a shell and multitube exchanger followed by vapor liquid disengagement tank or vessel can also be used.
• the present process can make use of one or more alkanes or alkenes to produce the desired chlorinated alkanes.
• Alkanes or alkenes having any number of carbon atoms and that are desirably chlorinated in a nonaqueous media may benefit from application of the present process.
• alkanes or alkenes comprising from 2-10 carbon atoms, or from 2-8 carbon atoms, or from 2-6 carbon atoms, or from 2-5 carbon atoms, or from 2-4 carbon atoms, are particularly suitable.
• the alkane or alkene may comprise a propane or propene.
• the alkane and or alkene may be unchlorinated, or may comprise chlorine atoms prior to application of the process. That is, the alkane and/or alkene may comprise any number of chlorine atoms, including zero. To some degree, the number of chlorine atoms in the alkane or alkene will be limited by the number of carbon atoms, as well as the chlorinated alkane desirably produced. In some embodiments, the alkane and/or alkene may comprise from 0-4 chlorine atoms, or may comprise 1-3 chlorine atoms.
• the alkane and/or alkene may be a mono-, di-, or trichlorinated propane, such as 1- or 2- chloropropane, 1,2-dichlorinated propane, and/or 1, 1,2-trichlorinated propane.
• the chlorinated alkane produced by the process will depend upon the alkane and/or alkene used as a starting material, and so, in some embodiments, and due to the commercial significance of trichlorinated alkanes having three to six carbon atoms, the use of one or more propanes, propenes, butanes, butenes, pentanes, pentenes, hexanes and hexanes as starting materials may be preferred.
• a dichloropropane e.g., 1,2-dichloropropane
• sulfuryl chloride in the presence of sodium iodate at a temperature of from 55°C to 75°C, ambient pressure and a reactor occupancy of less than five hours to produce a pentachloropropane, e.g., 1, 1,2,2, 3-pentachloropropane at regioselectivities of greater than 10: 1, or greater than 20: 1 or greater than 30: 1, or even greater than 40: 1, over other pentachloropropane products.
• 1, 1,2,2, 3-pentachloropropane at regioselectivities of greater than 10: 1, or greater than 20: 1 or greater than 30: 1, or even greater than 40: 1, over other pentachloropropane products.
• Example 1 Chlorination of 1,2-dichloropropane to 1, 1, 2,2,3 -pentachloropropane using sodium periodate as inorganic iodine salt, aluminum chloride as Lewis acid and sulfuryl chloride as chlorinating agent.
• GC and NMR analysis of the final product mixture shows a yield of 4.7g of 1, 1,2,2, 3-pentachloropropane, 0.7g of tetrachloropropane isomers, 0.4g of 1, 1,2- trichloropropane, 0.3g of hexachloropropane isomers, and 0.2g of 1,2,3-trichloropropane.
• Example 2 Chlorination of 1,2-dichloropropane to 1, 1, 2,2,3 -pentachloropropane using recovered sodium periodate as inorganic iodine salt, aluminum chloride as Lewis acid and sulfuryl chloride as chlorinating agent.
• reaction mixture and methylene chloride wash are combined, slowly poured into an ice water bath, and allowed to stir until quenched.
• the organic and aqueous phases are separated and the aqueous phase is extracted with an equal volume of methylene chloride.
• the combined organic fractions are dried over magnesium sulfate, the excess solvent is removed by rotary evaporator, and the final product is isolated as a colored oil.
• GC and NMR analysis of the final product mixture shows a yield of 3. lg of 1, 1,2,2, 3-pentachloropropane, 0.5g of hexachloropropane isomers, O. lg of 1,2,3- trichloropropane, and O. lg of tetrachloropropane isomers.
• Example 3 Chlorination of 1,2-dichloropropane to 1, 1, 2,2,3 -pentachloropropane using sodium iodate as inorganic iodine salt, aluminum chloride as Lewis acid and sulfuryl chloride as chlorinating agent.
• GC and NMR analysis of the final product mixture shows a yield of 5.4g of 1, 1,2,2, 3 -pentachloropropane, 0.6g of tetrachloropropane isomers, 0.4g of hexachloropropane isomers, 0.3g of 1, 1,2-trichloropropane and 0.2g of 1,2,3-trichloropropane.
• Example 4 Chlorination of 1,2-dichloropropane to 1, 1, 2,2,3 -pentachloropropane using sodium iodate as inorganic iodine salt, aluminum chloride as Lewis acid and sulfuryl chloride as chlorinating agent.
• reaction mixture is slowly poured into an ice water bath and allowed to stir until quenched.
• the organic and aqueous phases are separated and the aqueous phase is extracted with an equal volume of methylene chloride.
• the sodium iodate is recovered in the aqueous wash as indicated by ion chromatography analysis.
• the combined organic fractions are dried over magnesium sulfate, the excess solvent is removed by rotary evaporator, and the final product is isolated as a colored oil.
• GC and NMR analysis of the final product mixture shows a yield of 2.3g of 1, 1,2,2, 3-pentachloropropane, 1.4g of 1,1,2-trichloropropane, 0.9g of tetrachloropropane isomers, 0.8g of 1,2,3-trichloropropane, and 0.2g of hexachloropropane isomers.
• Example 5 Chlorination of 1,1,2-trichloropropane to 1, 1, 2,2,3 -pentachloropropane using low levels of elemental iodine, aluminum chloride as Lewis acid, chlorine as chlorinating agent, and methylene chloride as chlorocarbon solvent.
• a product stream is prepared by feeding chlorine gas at 30 seem through a starting mixture of 22.6wt% 1 ,2-dichloropropane, 1.3wt% aluminum chloride, and 76.1wt% methylene chloride at 130psig and 70°C until GC analysis indicates that the starting dichloropropane has undergone 68% conversion to give 1, 1,2-trichloropropane as the major intermediate species.
• This stream is charged with 35ppm elemental iodine dissolved in 15mL of methylene chloride based on initial dichloropropane within the reaction mixture.
• Example 6 Chlorination of 1 , 1 ,2-trichloropropane to 1, 1, 2,2,3 -pentachloropropane using conventional levels of iodine, aluminum chloride as Lewis acid, chlorine as chlorinating agent, and methylene chloride as inert chlorocarbon solvent.
• a product stream is prepared by feeding chlorine gas at 30 seem through a starting mixture of 22.6wt% 1 ,2-dichloropropane, 1.3wt% aluminum chloride, and 76.1wt% methylene chloride at 130psig and 70°C until GC analysis indicates that the starting dichloropropane has undergone 69.7wt% conversion to give 1, 1,2-trichloropropane as the major intermediate species.
• This stream is charged with 0.57wt% elemental iodine dissolved in 15mL of methylene chloride based on initial dichloropropane within the reaction mixture.
• Example 7 Chlorination of 1 , 1 ,2-trichloropropane to 1, 1, 2,2,3 -pentachloropropane in the absence of elemental iodine using aluminum chloride as Lewis acid, chlorine as chlorinating agent, and methylene chloride as inert chlorocarbon solvent.
• a product stream is prepared by feeding chlorine gas at 30 seem through a starting mixture of 22.6wt% 1 ,2-dichloropropane, 1.3wt% aluminum chloride, and 76.1wt% methylene chloride at 130psig and 70°C until GC analysis indicates that the starting dichloropropane has undergone 71.5wt% conversion to give 1, 1,2-trichloropropane as the major intermediate species.
• This stream is charged with 15mL of methylene chloride.

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• 2012
  • 2012-11-30 EP EP12799450.7A patent/EP2785671B1/en not_active Not-in-force
  • 2012-11-30 WO PCT/US2012/067268 patent/WO2013082410A1/en not_active Ceased
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