WO2020041667A1 - Déshydrochloration/chloration monotope d'un chloroalcane pour produire un mélange d'alcènes chlorés et d'alcanes chlorés - Google Patents

Déshydrochloration/chloration monotope d'un chloroalcane pour produire un mélange d'alcènes chlorés et d'alcanes chlorés Download PDF

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WO2020041667A1
WO2020041667A1 PCT/US2019/047845 US2019047845W WO2020041667A1 WO 2020041667 A1 WO2020041667 A1 WO 2020041667A1 US 2019047845 W US2019047845 W US 2019047845W WO 2020041667 A1 WO2020041667 A1 WO 2020041667A1
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product
chlorinated
combinations
methods
trichloropropene
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PCT/US2019/047845
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English (en)
Inventor
John D. Myers
Max Tirtowidjojo
Marc Sell
Jr. William J. Kruper
Daniel R. Henton
Pulikkottil Jacob THOMAS
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Blue Cube Ip Llc
Board Of Trustees Of Michigan State University
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Publication of WO2020041667A1 publication Critical patent/WO2020041667A1/fr

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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
    • C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons

Definitions

  • the present disclosure generally relates to the one pot preparation of a mixture of chlorinated alkene products and chlorinated alkane products by
  • Halogenated alkanes are useful intermediates for many products including agricultural products, pharmaceuticals, cleaning solvents, solvents, gums, silicones, and refrigerants.
  • the processes to prepare halogenated alkanes are varied and can be time consuming, moderately efficient, and lack reproducibility.
  • halogenated alkanes are formed by telomerizing a halogenated alkane starting material and an alkene or halogenated alkene to form a longer chained halogenated alkane product.
  • This product is typically purified, and subsequently dehydrohalogenated in one reactor, using a dehydrohalogenation catalyst or caustic, and halogenated in another reactor to form higher halogenated alkanes.
  • this method on an industrial scale has been applied to chlorinated alkanes.
  • Lewis acid catalysts include FeCh, SbCIs, as well as others. Examples have been reported which demonstrate this simultaneous dehydrochlorination/ chlorination of a chlorinated alkane starting material. Additionally, under normal process conditions, these catalysts will also perform further dehydrochlorination/ chlorination on the desired product producing amounts of undesired by-products such as higher chlorinated alkanes and heavy by-products.
  • US 9,139,495 claims the simultaneous dehydrochlorination/ chlorination of 1 , 1 , 1 ,3-tetrachloropropane to form 1 ,1 ,1 ,2,3-pentachloropropane.
  • US 8,115,038 teaches the simultaneous dehydrochlorination/ chlorination of 1 ,1 ,1 ,3-tetrachloropropane to produce 1 ,1 ,1 ,2,3-pentachloropropane using FeCl3. Dehydrochlorination of the 1 , 1 , 1 ,2,3-pentachloropropane to form 1 , 1 ,2,3- tetrachloropropene is also described.
  • Other US patents (US 8,614363 and US
  • 2015/0045591 uses a pentavalent antimony compound, such as SbCI 5. These processes produce significant amounts of higher chlorinated alkanes and by-products, which reduces the yields of the desired products and increases the overall
  • the process comprises forming a reaction mixture comprising contacting at least one chloroalkane starting material, at least one Lewis acid catalyst comprising gallium metal, a salt of gallium, a gallium alloy, or combinations thereof, a chlorinating agent, and optionally a solvent in a reactor under conditions detailed below.
  • a product mixture is generated comprising anhydrous HCI, at least one chlorinated alkene product, and at least one chlorinated alkane product, wherein the concentration of the at least one chlorinated alkene within the reaction mixture is controlled between 1 % and 99% by weight, by manipulating the amount of chlorinating agent supplied, process temperature, process pressure, concentration of reactants or combinations thereof.
  • the process comprises forming a reaction mixture comprising 1 ,1 ,1 ,3-tetrachloropropane, at least one Lewis acid catalyst comprising gallium metal, a salt of gallium, a gallium alloy, or combinations thereof, a chlorinating agent, and optionally a solvent in a reactor under conditions detailed below.
  • a product mixture is generated comprising anhydrous HCI, 1 ,1 ,1 ,2,3- pentachloropropane, and 1 ,1 ,3-trichloropropene, 3,3,3-trichloropropene, or
  • the concentration of the 1 ,1 ,3-trichloropropene, 3,3,3- trichloropropene, or combinations thereof, within the reaction mixture is controlled between 1 % and 99% by weight by manipulating the amount of chlorinating agent supplied, process temperature, process pressure, concentration of reactants or combinations thereof.
  • the reaction mixture is a liquid phase reaction mixture.
  • the process commences by forming a reaction mixture comprising ethylene and carbon tetrachloride (CCI 4 ) to prepare 1 ,1 ,1 ,3-tetrachloropropane using a telomerization process.
  • CCI 4 ethylene and carbon tetrachloride
  • a reaction mixture comprising at least one Lewis acid catalyst comprising gallium metal, a salt of gallium, a gallium alloy, or combinations thereof, a chlorinating agent, and optionally a solvent in a reactor under conditions detailed below.
  • a product mixture is generated comprising anhydrous HCI, 1 ,1 ,1 ,2,3-pentachloropropane, and 1 , 1 ,3- trichloropropene, 3,3,3-trichloropropene, or combinations thereof, wherein the concentration of the 1 ,1 ,3-trichloropropene, 3,3,3-trichloropropene, or combinations thereof within the reaction mixture is controlled between 1 % and 99% by weight by manipulating the amount of chlorinating agent supplied, process temperature, process pressure, concentration of reactants or combinations thereof.
  • the reaction mixture is a liquid phase reaction mixture.
  • the process comprises forming a reaction mixture comprising 1 , 1 , 1 ,3,3- pentachloropropane, at least one Lewis acid catalyst comprising gallium metal, a salt of gallium, a gallium alloy, or combinations thereof, a chlorinating agent, and optionally a solvent in a reactor under conditions detailed below.
  • a product mixture is generated comprising anhydrous HCI, 1 ,1 ,1 ,2,3,3-hexachloropropane and 1 , 1 ,3,3- tetrachloropropene, 1 ,3,3,3-tetrachloropropene, or combinations thereof, wherein the concentration of the 1 ,1 ,3,3-tetrachloropropene, 1 ,3,3,3-tetrachloropropene, or combinations thereof, within the reaction mixture is controlled between 1 % and 99% by weight by manipulating the amount of chlorinating agent supplied, process temperature, process pressure, concentration of reactants or combinations thereof.
  • the reaction mixture is a liquid phase reaction mixture.
  • the process commences by forming a reaction mixture comprising vinyl chloride and carbon tetrachloride (CCI 4 ) to prepare 1 , 1 , 1 ,3,3- pentachloropropane using a telomerization process.
  • CCI 4 carbon tetrachloride
  • 1.1.1.2.3.3-hexachloropropane and 1 ,1 ,3,3-tetrachloropropene, 1 ,3,3,3- tetrachloropropene, or combinations thereof comprises forming a reaction mixture comprising 1 ,1 ,1 ,3,3-pentachloropropane, at least one Lewis acid catalyst comprising gallium metal, a salt of gallium, a gallium alloy, or combinations thereof, a chlorinating agent, and optionally a solvent in a reactor under conditions detailed below.
  • a product mixture is generated comprising anhydrous HCI, 1 ,1 ,1 ,2,3,3-hexachloropropane and
  • the reaction mixture is a liquid phase reaction mixture.
  • the process comprises forming a reaction mixture comprising at least one of
  • a product mixture is generated comprising anhydrous HCI, at least one of 1 ,2,2,3-tetrachloropropane,
  • the reaction mixture is a liquid phase reaction mixture.
  • the process commences by preparing a reaction mixture in a reactor comprising contacting a chloroalkane starting material, at least one Lewis acid catalyst comprising gallium metal, a salt of gallium, a gallium alloy, or combinations thereof, a chlorinating agent, and optionally a solvent, in a reactor.
  • a product mixture is formed comprising anhydrous HCI, a chlorinated alkene product, and a chlorinated alkane product wherein the concentration of the chlorinated alkene within the reaction mixture is controlled between 1 % and 99% by weight by manipulating the amount of chlorinating agent supplied, process temperature, process pressure, or combinations thereof.
  • a surprising and unexpected results is the at least one Lewis acid catalyst comprising gallium metal, a salt of gallium, a gallium alloy, or combinations thereof in the process, as described below, produces the chlorinated alkene product and the chlorinated alkane product in high yield with low levels of over dehydrochlorination of the chlorinated alkane product and low levels of heavy by-products.
  • the reaction mixture is a liquid phase reaction mixture.
  • the chlorinated alkane starting material useful in this process may be a chlorinated propane, such as a dichloropropane, a trichloropropane, a
  • tetrachloropropane a pentachloropropane, a hexachloropropane, or combinations thereof.
  • dichloropropanes trichloropropanes
  • tetrachloropropanes pentachloropropanes, and hexachloropropanes include, but are not limited to 1 ,1 -dichloropropane; 1 ,2-dichloropropane; 1 ,3-dichloropropane; 1 ,1 ,1 - trichloropropane; 1 ,1 ,2-trichloropropane; 1 ,2,2-trichloropropane; 1 ,2,3-trichloropropane;
  • One method for preparing these chloroalkane starting materials is through the telomerization process.
  • carbon tetrachloride (Tet) an alkene or chlorinated alkene
  • a catalyst system comprising metallic iron, ferric chloride, and/or ferrous chloride
  • a trialkylphosphate and/or a trialkylphosphite are contacted to produce the chlorinated alkanes.
  • Tet carbon tetrachloride
  • a catalyst system comprising metallic iron, ferric chloride, and/or ferrous chloride
  • a trialkylphosphate and/or a trialkylphosphite are contacted to produce the chlorinated alkanes.
  • ethylene as the alkene in the above described telomerization process yields tetrachloropropanes, such as 1 ,1 ,1 ,3-tetrachloropropane (250FB).
  • the chloroalkane starting materials comprises 1 ,1 ,1 ,3-tetrachloropropane, also known as 250FB.
  • the chloroalkane starting materials comprises 1 ,1 ,1 ,2,3- pentachloropropane, also known as 240DB.
  • the chloroalkane starting material comprises 1 ,1 ,1 ,3,3-pentachloropropane, also known as 240FA.
  • the chloroalkane starting material comprises 1 ,2,3-trichloropropane, 1 ,1 ,1 ,3-tetrachloropropane, 1 , 2,2,3- tetrachloropropane, 1 ,1 ,2,3-tetrachloropropane, or combinations thereof.
  • the chloroalkane starting material may be crude, unpurified product from the telomerization reaction or from another process, partially purified, or fully purified by means known to the skilled artisan.
  • One common method of purifying the chlorinated alkane is distillation. Non-limiting examples of distillations may be a simple distillation, flash distillation, a fractional distillation, a steam distillation, or a vacuum distillation. Use of a stripping gas, such as carbon tetrachloride or nitrogen may also be employed to reduce the distillation temperature.
  • the chloroalkane starting material useful in the process may have a purity greater than 10 wt%. In various embodiments, the purity of the
  • chloroalkane starting material may have a purity greater than 10wt%, greater than 30 wt%, greater than 50 wt%, greater than 75 wt%, greater than 90 wt%, greater than 95 wt%, or greater than 99 wt%.
  • the at least one Lewis acid catalyst comprising gallium metal, a salt of gallium, a gallium alloy, or combinations thereof.
  • the at least one Lewis acid catalyst comprises gallium metal, a salt of gallium, a gallium alloy, or combinations thereof. As appreciated by the skilled artisan, at least part of the at least one Lewis acid catalyst may be in homogeneous or heterogeneous form.
  • the at least one Lewis acid catalyst is gallium metal.
  • gallium metal once introduced into the process may undergo a phase transition from a solid to a liquid since gallium’s melting point is about 29.7°C.
  • Gallium metal may also undergo chlorination to a gallium chloride salt.
  • Gallium metal and gallium salts may be partially soluble or fully soluble in the reaction medium.
  • the at least one Lewis acid catalyst useful in the process is a gallium alloy.
  • gallium containing alloys useful in the process may be Al Ga, galfenol, galinstan, or combinations thereof.
  • the at least one Lewis acid catalyst is a gallium salt.
  • gallium salts can exist in a number of oxidation states. Non-limiting oxidation states of gallium salts useful in the
  • dehydrochlorination process may be Ga (I), Ga (II), Ga (III), or combinations thereof.
  • anions may be part of a metal salt.
  • suitable anions in these transition metal salts may include acetates, acetyacetonates, alkoxides, butyrates, carbonyls, dioxides, halides, hexonates, hydrides, mesylates, octanoates, nitrates, nitrosyl halides, nitrosyl nitrates, sulfates, sulfides, sulfonates, phosphates, and combinations thereof.
  • the anion in the metal salt comprises a chloride.
  • the metal salt may be gallium dichloride (gallium (I, III) chloride/digallium tetrachloride), GaCI 2 (GaGaCL), gallium (II) chloride (Ga 2 CI 4 ), gallium (III)
  • the gallium metal, a gallium alloy, a gallium salt, or combinations thereof, once in the process, may undergo oxidation and/or reduction to produce an activated catalytic species in various oxidation states.
  • the oxidation state of these active gallium catalytic species may vary, and may be for examples (I), (II), and (III).
  • the active gallium catalyst may in the Ga(l) oxidation state. In another aspect, the active gallium catalyst may be Ga (II). In still another aspect, the active gallium catalyst may be in the Ga (III) oxidation state. In an additional aspect, the active gallium catalyst may comprise a mixture of Ga (I) and Ga (II). In still another aspect, the active gallium catalyst may comprise a mixture of Ga(l) and Ga (III) oxidation states. In yet another aspect, the active gallium catalyst may be in the Ga (II) and Ga (III) oxidation states. In another aspect, the active gallium catalyst may in the Ga (I), Ga (II) and Ga (III) oxidation states.
  • the at least one Lewis acid catalyst comprising gallium metal, a salt of gallium, a gallium alloy, or combinations thereof may further comprise an additional Lewis acid catalyst.
  • the combination of the Lewis acid catalysts would provide a synergistic effect in the dehydrochlorination/chlorination process by increasing the kinetics of the process, improving the percent conversion, increasing the selectivity of the process, or combinations of these effects.
  • a large variety of additional Lewis acid catalysts may be used with gallium metal, a salt of gallium, a gallium alloy, or
  • the additional Lewis acid catalyst may be a transition metal.
  • transition metal refers to a transition metal element, a transition metal containing alloy, a transition metal containing compound, or combinations thereof.
  • Non limiting examples of transition metals in the at least one Lewis acid catalyst may be selected from the group consisting of aluminum, antimony, bismuth, chromium, cobalt, copper, gold, indium, iron, lead, magnesium, manganese, mercury, nickel, platinum, palladium, rhodium, samarium, scandium, silver, titanium, tin, zinc, zirconium, and combinations thereof.
  • the additional Lewis acid catalyst comprises iron.
  • Non-limiting examples of transition metal containing alloys useful in the process may be an alloy of aluminum, an alloy of bismuth, an alloy of chromium, an alloy of cobalt, an alloy of copper, an alloy of gold, an alloy of indium, an alloy of iron, an alloy of lead, an alloy of magnesium, an alloy of manganese, an alloy of mercury, an alloy of nickel, an alloy of platinum, an alloy of palladium, an alloy of rhodium, an alloy of samarium, an alloy of scandium, an alloy of silver, an alloy of titanium, an alloy of tin, an alloy of zinc, an alloy of zirconium, and combinations thereof.
  • Non-limiting common names for these alloys may be Al-Li, Alnico, Birmabright, duraluminum, hiduminum, hydroalium, magnalium, Y alloy, nichrome, stellite,3,t, vitallium, various alloys of brass various alloys of brass, bronze, Constantin, Corinthian bronze, cunife, cupronickel, cymbal metals, electrum, haptizon, manganin, nickel silver, Nordic gold, tumbaga, crown gold, colored gold, electrum, rhodite, rose gold, tumbaga, white gold, cast iron, pig iron, Damascus steel, wrought iron, anthracite iron, wootz steel, carbon steel, crucible steel, blister steel, alnico, alumel, brightray, chromel, cupronickel, ferronickel, German silver, Inconel, monel metal, nichrome, nickel-carbon.
  • Nicrosil nitinol, permalloy, supermalloy, 6al-4v, beta C, gum metal, titanium gold, Babbitt, britannium, pewter, solder, terne, white metal, sterling silver, zamak, zircaloy, or combinations thereof.
  • the additional Lewis acid catalyst may comprise a transition metal salt.
  • suitable transition metal salts may include a salt of aluminum, a salt of antimony a salt of bismuth, a salt of chromium, a salt of cobalt, a salt of copper, a salt of gold, a salt of indium, a salt of iron, a salt of lead, a salt of magnesium, a salt of manganese, a salt of mercury, a salt of nickel, a salt of platinum, a salt of palladium, a salt of rhodium, a salt of samarium, a salt of scandium, a salt of silver, a salt of titanium, a salt of tin, a salt of zinc, a salt of zirconium, and combinations thereof.
  • Non-limiting examples of anion for these suitable transition metal salts may include acetates, acetyacetonates, alkoxides, butyrates, carbonyls, dioxides, halides, hexonates, hydrides, mesylates, octanates, nitrates, nitrosyl halides, nitrosyl nitrates, sulfates, sulfides, sulfonates, phosphates, and combinations thereof.
  • suitable transition metal salts may include, iron (II) chloride, iron (III) chloride, aluminum (III) chloride, antimony (III) chloride, antimony (V) chloride, or combinations thereof.
  • the at least one Lewis acid catalyst comprising gallium metal, a salt of gallium, a gallium alloy, or combinations thereof may be in various forms or configuration.
  • Non-limiting examples of the forms or configuration of the at least one Lewis acid catalyst comprising gallium metal, a salt of gallium, a gallium alloy, or combinations thereof may be dissolved in the liquid reaction medium or may exist as a solid.
  • the at least one Lewis acid catalyst comprising gallium metal, a salt of gallium, a gallium alloy, or combinations thereof is heterogeneous and may be immobilized on the surface of a solid support.
  • Non-limiting examples of suitable supports or substrate that may be alumina, silica, silica gel, diatomaceous earth, molecular sieves, carbon, clay or combinations of two or more thereof.
  • the resulting supported catalyst may be introduced into the reaction medium as a packing, an unstructured packing, a foil, a sheet, a screen, a wool, a wire, a ball, a plate, a pipe, a rod, a bar, a granule or a powder.
  • the at least one Lewis acid catalyst is selected from the at least one Lewis acid catalyst
  • the at least one Lewis acid catalyst comprising gallium metal, a salt of gallium, a gallium alloy, or combinations thereof in a continuous reactor may be part of at least one fixed catalyst bed.
  • the at least one Lewis acid catalyst comprising gallium metal, a salt of gallium, a gallium alloy, or combinations thereof in a continuous reactor may be part of at least one cartridge.
  • the at least one Lewis acid catalyst comprising gallium metal, a salt of gallium, a gallium alloy, or combinations thereof may be part of a structured or un-structured packing where the at least one catalyst is a part of the packing or un-structured packing.
  • the concentration of at least one Lewis acid catalyst comprising gallium metal, a salt of gallium, a gallium alloy, or combinations thereof may be used in stoichiometric or catalytic amounts as compared to the chloroalkane starting material. If it is used as a catalyst, generally, less than 10% by weight is used, relative to the amount of chloroalkane in the reactor. In various embodiments, the concentration of the at least one Lewis acid in the reactor is less than about 1 ,000 ppm, less than about 750 ppm, less than about 500 ppm, less than about 250 ppm or less than about 100 ppm. If the gallium metal, gallium alloy, gallium salts, or combinations thereof is immobilized on the surface of a solid support, the concentration relative to the support may be from 0.1 to about 50 % by weight.
  • chlorinating agents may be chlorine gas, sulfuryl chloride, thionyl chloride, oxalyl chloride, PCI 3 , PCI 5 , POCI 3, and combinations thereof.
  • the chlorinating agents may include chlorine gas, sulfuryl chloride, or combinations thereof.
  • the chlorinating agent is chlorine gas. If chlorine gas is used, it may be used at a pressure that is at least atmospheric pressure or at sub-atmospheric pressures.
  • the chlorine gas may be diluted with a carrier gas, such as nitrogen, a noble gas, or combinations thereof.
  • the pressure of the chlorine gas, and the entire reaction is at least atmospheric pressure.
  • the mole ratio of the chlorinating agent to the chloroalkane starting material supplied to the reaction mixture may range from about 0.01 :1.0 to about 1.20:1.0. In various embodiments, the mole ratio of the chlorinating agent to the chloroalkane starting material may range from about 0.01 :1.0 to about 1.20:1.0, from about 0.1 : 1.0 to about 1.10:1.0, from about 0.2:1.0 to about 1.1 : 1.0. In one embodiment, when a second chlorination reaction is to be performed, the mole ratio of the
  • chlorinating agent to the chloroalkane starting material supplied to the reaction mixture may be substoichiometric, i.e. , it may range from about 0.3:1.0 to about 0.8:1.05, from about 0.4: 1.0 to about 0.7: 1.0, from about 0.45:1.0 to about 0.65:1.0.
  • the product distribution of the chlorinated alkene product and the chlorinated alkane product will be dependent on the number of moles of the chlorinating agent used in the process.
  • the reaction mixture may further comprise a solvent.
  • solvents may be CCI 4 , C2CI 4 (tetrachloroethylene), the chloroalkane starting material, the chlorinated alkene product, the chlorinated alkane product, or combinations thereof.
  • the solvent comprises carbon tetrachloride.
  • the type of mixing depends on the form of the at least one Lewis acid catalyst and whether an additional Lewis acid catalyst is used with gallium metal, a salt of gallium, a gallium alloy, or combinations thereof.
  • an impeller with or without baffles aids in suspending, mixing, and fluidizing of the at least one Lewis acid catalyst comprising gallium metal, a salt of gallium, a gallium alloy, or combinations thereof to maximize contact area and provide fresh liquid contact with the powder.
  • the at least one Lewis acid catalyst comprising gallium metal, a salt of gallium, a gallium alloy, or combinations thereof is in the form of a fixed bed
  • the liquid phase is fed directly into the fixed bed from one end of the fixed bed and exits from the other end.
  • the fixed bed may be contained within a cylindrical or tubular container.
  • the L/D (length/diameter) of the cylindrical or tubular container may be greater than 1.
  • the L/D (length/diameter) of the cylindrical or tubular container may be greater than 1 , greater than 2, greater than 4, greater than 6, or greater than 8.
  • the residence time and velocity of the fluid in the fixed bed may be varied by recycling a portion of the fixed bed reactor effluent back to the inlet. All components of the reaction mixture may be fed to the fixed bed, or a separate absorber may be employed in which gaseous and liquid components are mixed prior to entering the fixed bed. When a separate absorber is used, the fixed bed reactor temperature may also be independently varied from the absorber temperature by heat exchanging the feed or the reactor recycle stream. The fixed bed temperature may also be controlled by including internal heat exchanger such as the use of multitube exchanger.
  • the process for the preparation of chlorinated alkene product and chlorinated alkane product will be conducted to maintain the temperature from about 20°C to about 160°C or about 30°C to about 150°C, using an internal or external heat exchanger.
  • the temperature of the reaction may be maintained from about 60°C to about 120°C.
  • the process may be conducted at a pressure of about atmospheric pressure ( ⁇ 14.7 psi) to about 200 psi so the amount of the gases absorbed into the liquid are in suitable quantities so the reaction may proceed and maintain the kinetics of the process.
  • the pressure of the process may be from about atmospheric pressure ( ⁇ 14.7 psi) to about 200 psi, from about 20 psi to about 150 psi, from about 25 psi to about 100 psi, from about 30 psi to about 80 psi, or from 40 psi to about 60 psi.
  • the pressure is from atmospheric pressure to 35 psi.
  • anhydrous HCI is produced as a by-product from the process.
  • the anhydrous HCI under the reaction conditions described above, may be removed directly from the reactor.
  • the anhydrous HCI removed from the reactor may be chilled to condense at least a portion of the chlorine, organic constituents, or combinations thereof, and these condensed constituents may be returned to the reactor. Removing the anhydrous HCI will increase the kinetics of the process.
  • the concentration of the chlorinated alkene product is controlled from about 1 % to about 99% by weight by manipulating the amount of chlorinating agent, process temperature, process pressure, or combinations thereof. Concentration of chlorinated alkene at the higher end of said range will improve the chlorination kinetics, thereby allowing lower chlorinating agent concentration and mitigating over- chlorination, for instance by free radical chlorination reactions.
  • the concentration of the chlorinated alkene product may range from 1 % to about 99% by weight, from about 5% to about 90% by weight, from about 10% to about 80% by weight, from about 25% to about 75% by weight, from about 30% to about 70% by weight, or from about 40% to about 60% by weight.
  • the above process may be run in a batch mode or a continuous mode where continuous mode is preferred.
  • the process in continuous modes may be stirred in various methods as appreciated by the skilled artisan.
  • the chlorinated alkane starting material fed to the above described process may be converted into the chlorinated alkene product and chlorinated alkane product in at least 50 wt% conversion.
  • the conversion of chlorinated alkane into the chlorinated alkene product and chlorinated alkane product may be at least 50 wt%, at least 60 wt %, at least 70 wt %, at least 80 wt %, at least 95 wt %, and at least 99 wt%
  • the concentration of the chlorinated alkene product may be greater than about 1 wt% as compared to concentration of all the components of the reaction mixture. In various embodiments, the concentration of the chlorinated alkene product may be greater than about 5 wt%, greater than about 10 wt%, greater than 20 wt%, greater than about 40 wt%, greater than about 75 wt%, greater than about 90 wt%, or greater than 99 wt%.
  • the concentration of the chlorinated alkane product as compared to the total contents of the reaction mixture may be greater than about 40 wt%. In various embodiments, the concentration of the chlorinated alkane product as compared to the total contents of the reaction mixture may be greater than about 40 wt%, greater than about 50 wt%, greater than about 60 wt%, greater than about 70 wt%, greater than about 80 wt%, greater than about 90 wt%, greater than about 95 wt%, or even greater than about 99 wt%.
  • the combined percentage selectivity of the chlorinated alkane product and the chlorinated alkane product is at least 70%.
  • the combined selectivity of the chlorinated alkane product and the chlorinated alkene product is at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, or at least 99%.
  • the molar ratio of chlorinated propene products to chlorinated propane products in the reaction mixture is greater than 1.
  • chloroalkene products can be produced using the starting materials and methods described herein.
  • a non-exhaustive list of products that may be prepared comprises 1 ,1 ,3-trichloropropene; 3,3,3-trichloropropene; 1 , 3,3,3- tetrachloropropene; 1 ,1 ,3,3-tetrachloropropene; 1 ,1 ,2,3-tetrachloropropene, 1 ,2,3- trichloropropene; 2,3-dichloropropene; 2-chloropropene; 1 -chloropropene; or combinations of two or more thereof.
  • a wide variety of chloroalkane products can be produced using the starting materials and methods described herein.
  • a non-exhaustive list of products that may be prepared comprises 1 ,1 ,1 ,2,3-pentachloropropane; 1 ,1 ,1 ,2,3,3- hexachloropropane; 1 ,2,3-trichloropropane; 1 ,1 ,2-trichloropropane; 1 , 2,2,3- tetrachloropropane; 1 ,1 ,2,3-tetrachloropropane; 1 ,1 ,2,2,3-pentachloropropane; or combinations of two or more thereof.
  • the next step in the process comprises separating at least some of the components of the product mixture.
  • at least some of the anhydrous HCI is removed from the reactor as the product mixture is formed.
  • the chlorinating agent is separated from the product mixture while the HCI is being removed or after the HCI is removed.
  • at least some of the chlorinated alkene product is separated from the product mixture together with HCI or after HCI is removed and it is recycled to the reactor, purified for use in other reactions or sent to a secondary reactor, where it undergoes one or more further reactions.
  • the purified chlorinated alkene product and purified chlorinated alkane product from the liquid reaction mixture comprising the chlorinated alkene product, the chlorinated alkane product, the at least one Lewis acid comprising gallium metal, a gallium salt, or combinations thereof, the chlorinating agent, any remaining hydrogen chloride that was not removed directly from the reactor, an optional solvent, lighter by-products, heavier by-products (also referred to as heavies), and unreacted chloroalkane starting material are separated into one or more product effluent streams.
  • further components in the liquid phase reaction mixture may be a
  • trialkylphosphate a trialkylphosphite
  • iron salts or iron hydroxide from the
  • the product mixture is removed from the reactor as vapor and/or a liquid and is then distilled.
  • the chlorinated alkane product and/or the chlorinated alkene product is then isolated.
  • the heavies are continuously or intermittently purged from the reactor or from a distillation bottom stream.
  • the product mixture further comprises at least one catalyst, which is dissolved therein, and the catalyst is removed and/or deactivated before the product mixture is purified.
  • the catalyst may be removed by adding water, activated carbon or by using ion exchange.
  • the catalyst may be deactivated using one or more chelating agents, such as those that contain N, S, and/or P.
  • chelating agents examples include amines, nitrites, amides, thiols, alcohols, phosphates (such as alkylphosphates) and phosphites (such as aSkylphosphites).
  • specific chelating agents examples include, stearylamines, iaurylamines. cyclohexylamines, octylamines.
  • the separation process commences by transferring at least a portion of the liquid phase reaction mixture from the reactor into a separator or multiple
  • At least one of the first separator and the second separator may a distillation column or a multistage distillation column. Additionally, at least one of the first separator and the second separator may further comprise a reboiler, a bottom stage, or a combination thereof.
  • Various distillation columns may be used in this capacity.
  • a side draw column or a distillation column which provides an outlet stream from an intermediate stage or a dividing wall column (dividing wall column (DWC) is a single shell, fully thermally coupled distillation column capable of separating mixtures of three or more components into high purity products (product effluent streams)) may be used as a separator.
  • a portion of various product effluent streams after separation or a portion of the anhydrous liquid reaction mixture produced by the process may be optionally recycled back into the reactor to provide increased kinetics, increased efficiencies, reduced overall cost of the process, increased selectivity of the desired halogenated alkane, increased yield of the desired halogenated alkane, and increased mixing.
  • At least a portion of the at least one chlorinated alkene product is separated from the product mixture, either directly from the reactor or from distillation of the product mixture after leaving the reactor and the at least a portion of the at least one chlorinated alkene product that was separated from the product mixture is at least partially purified and recycled to the reactor or sent to a second reactor wherein the at least one chlorinated alkene product is contacted with a chlorinating agent with or without the addition of a catalyst to produce the at least one chlorinated alkane product.
  • At least a portion of the at least one chlorinated alkane product is removed from the product mixture, either directly from the reactor or from distillation of the product mixture after leaving the reactor.
  • At least a portion of at least one of the anhydrous HCI, the at least one chlorinated alkene product or the at least one chlorinated alkane product is continuously removed from the product mixture.
  • Each product effluent stream as described below, is enriched in the particular component of the liquid phase reaction mixture. Further separation may be required of each product effluent streams to produce highly pure compounds.
  • the process may be conducted in a reactive distillation column.
  • the chemical reactor and a distillation are combined in a single operating step, thus, allowing for selective removal of various components from the reaction mixture, simultaneous addition of reactants into the process, addition of various product streams, and distillation of various product effluent streams from the process.
  • a portion of the liquid reaction mixture is then transferred into a separator.
  • the separator may utilize at least one simple distillation, at least one vacuum distillation, at least one fractional distillation, or combinations thereof.
  • the distillations may comprise at least one theoretical plate.
  • separating the purified chlorinated alkene and purified chlorinated alkane product may produce three product effluent streams, four product effluent streams, or more product streams depending on the separation device utilized.
  • the separation of the chlorinated alkene and chlorinated alkane from the contents of the reactor using three product streams is described below.
  • the liquid reaction mixture is distilled, and the lights, comprising HCI and the chlorinating agent (typically chlorine) are removed.
  • the HCI and the chlorinating agent may be further separated, where the chlorinating agent can be recycled to the reactor.
  • HCI can be removed before the chlorinating agent is removed.
  • the chlorinated alkene can also be separated from the liquid reaction mixture.
  • the chlorinated alkene can be recycled and chlorinated, to thereby generate the chlorinated alkane product.
  • the chlorinated alkane product can be isolated.
  • Heavies can be removed from the bottom of one or more distillation columns. The heavies are optionally recycled to the reactor.
  • the lights are removed as one fraction, while the chlorinated alkene and the chlorinated alkane product are removed as a second stream.
  • the lights containing stream can be further distilled to separate the HCI from the chlorinating agent (typically chlorine).
  • the second stream can be further distilled and the chlorinated alkene can be recycled to the reactor, where it is chlorinated.
  • the heavies can be recycled to the reactor or discarded.
  • the liquid reaction mixture may be distilled to produce three product streams, product effluent streams (a), (b), and (c), after at least some of the anhydrous HCI is removed.
  • Product effluent stream (a) typically comprises the optional solvent (but not if the solvent is chlorinated alkane product), light by- products, the chlorinating agent and any remaining anhydrous hydrogen chloride which under the process conditions described above is removed as a gas as an overhead stream during the separation.
  • Product effluent stream (b) comprises the chlorinated alkene product and the chloroalkane starting material which may be removed as a side stream.
  • Product (c) comprises chlorinated alkane product, heavy by-products, and the at least one Lewis acid catalyst comprising gallium metal, a salt of gallium, a gallium alloy, or combinations thereof which comprise the bottom stream.
  • product effluent streams (a) comprising the optional solvent, anhydrous hydrogen chloride, the chlorinating agent, and light by-products may be further purified producing two additional product effluent streams (d) and (e) wherein product effluent stream (d) obtained as an overhead stream comprises anhydrous hydrogen chloride, the chlorinating agent, light by-products and product effluent stream (e), obtained as the bottom stream, comprises the optional solvent.
  • the overhead product effluent stream (d) may be further purified since anhydrous hydrogen chloride and the chlorinating agent are valuable commercial materials.
  • (a) may be separated to provide anhydrous HCI overhead and all the other stuff in the bottom.
  • the bottom stream may be separated to remove light by products overhead and a solvent/chlorine stream that can be recycled.
  • Product effluent stream (b) may be recycled to the reactor and at least a portion may be further purified producing two additional product effluent streams (f) and (g) where product effluent stream (f) comprises the chlorinated alkene product and product effluent stream (g) comprises the chloroalkane starting material.
  • Product effluent stream (c) may be further purified producing two additional product effluent streams (h) and (i) wherein product effluent stream (h) comprises the chlorinated alkane product and product effluent stream (i) comprises heavy by-products and the at least one Lewis acid catalyst comprising gallium metal, a salt of gallium, a gallium alloy, or combinations thereof.
  • various product effluent streams may be externally recycled back into the process.
  • at least a portion of the product effluent stream (b) comprising the chlorinated alkene product and the chloroalkane starting material, product effluent stream (e) comprising the optional solvent, product effluent stream (f) comprising the chlorinated alkene product, product effluent stream (g) comprising unreacted chloroalkane starting material, and product effluent steam (i) comprising heavy by-products and the at least one Lewis acid catalyst comprising gallium metal, a salt of gallium, a gallium alloy, or combinations thereof may be recycled back into the dehydrochlorination/chlorination process, as described above.
  • product effluent stream (b), product effluent stream (e), product effluent stream (f), product effluent stream (g), product effluent stream (i), or combinations thereof may be mixed with fresh liquid feed (comprising non-recycled chloroalkane starting material, and optional solvent) before being recycled back into the reactor in batch mode or continuous mode.
  • fresh liquid feed comprising non-recycled chloroalkane starting material, and optional solvent
  • the product effluent streams and fresh liquid feeds may be introduced into the reactor separately or mixed together before entering the process.
  • fresh feed streams may contain all or less than all of the following: the chloroalkane starting material, the chlorinated alkene product, the chlorinating agent, the catalyst or catalysts, and the optional solvent.
  • the introduction of these fresh liquid feeds into the reactor or mixing the recycle streams with fresh liquid feeds increases the efficiency of the process, reduces the overall cost, maintains the kinetics, maintains the reaction conversion, increase the through-put, and reduces the by-products produced by the process.
  • the amounts of the product effluent streams recycled to the reactor or fresh liquid feeds added to the reactor may be the same or different.
  • One way to measure the amount of product effluent streams and/or fresh liquid feeds being added to the reactor is to identify the mass flow of the materials.
  • the product effluent stream being recycled to the reactor has a product effluent stream mass flow, while the fresh liquid feeds being added to the reactor has a fresh liquid feed mass flow. Mass flows may be measured using methods known in the art.
  • the ratio of the product effluent stream mass flow being recycled to the fresh liquid feed mass flow is adjusted to not only maintain the conversion of the process but also maintain the kinetics of the process.
  • Another aspect of the present disclosure encompasses process for preparing 1 ,1 ,1 ,2,3-pentachloropropane and 1 ,1 ,3-trichloropropene, 3,3,3- trichloropropene, or combinations thereof, from 1 ,1 ,1 ,3-tetrachloropropane.
  • the process commences by preparing a liquid phase reaction mixture comprising 1 ,1 , 1 ,3- tetrachloropropane; at least one Lewis acid catalyst comprising gallium metal, a salt of gallium, a gallium alloy, or combinations thereof, a chlorinating agent, and an optional solvent.
  • the at least one Lewis acid catalyst comprising gallium metal, a salt of gallium, a gallium alloy, or combinations thereof is described above in Section (l)(b), the chlorinating agent is described above in Section (l)(c), and the optional solvent is described above in Section (l)(d).
  • the process is controlled by manipulating the amount of chlorinating agent supplied, the concentration of the 1 ,1 ,1 ,3-tetrachloropropane, process temperature, process pressure, or combinations thereof wherein the
  • concentration of the 1 ,1 ,3-trichloropropene, 3,3,3-trichloropropene, or combinations thereof within the reaction mixture is controlled between 1 % and 99% by weight.
  • the 1 ,1 ,1 ,3-tetrachloropropane fed to the above described process may be converted to 1 ,1 ,1 ,2,3-pentachloropropane and 1 ,1 ,3-trichloropropene, 3,3,3- trichloropropene, or combinations thereof in at least 30 wt% conversion.
  • the conversion of 1 ,1 ,1 ,3-tetrachloropropane to 1 ,1 ,1 ,2,3- pentachloropropane and 1 ,1 ,3-trichloropropene, 3,3,3-trichloropropene, or combinations thereof may be at least 50 wt%, at least 60 wt%, at least 75 wt%, at least 85 wt%, at least 95 wt%, and at least 99 wt%.
  • the concentration of 1 ,1 ,3-trichloropropene, 3,3,3-trichloropropene, or combinations thereof may be greater than about 1 wt% as compared to concentration of all the components of the reaction mixture.
  • the concentration of 1 ,1 ,3-trichloropropene, 3,3,3-trichloropropene, or combinations thereof may be greater than about 1 wt% as compared to concentration of all the components of the reaction mixture.
  • concentration of 1 ,1 ,3-trichloropropene, 3,3,3-trichloropropene, or combinations thereof may be greater than about 5 wt%, greater than about 10 wt%, greater than 20 wt%, greater than about 40 wt%, greater than about 75 wt%, greater than about 90 wt%, or greater than 99 wt%.
  • the concentration of 1 ,1 ,1 ,2,3-pentachloropropane as compared to the total contents of the reaction mixture may be greater than about 40 wt%. In various embodiments, the concentration of 1 ,1 ,1 ,2,3-pentachloropropane as compared to the total contents of the reaction mixture may be greater than about 40 wt%, greater than about 50 wt%, greater than about 60 wt%, greater than about 70 wt%, greater than about 80 wt%, greater than about 90 wt%, greater than about 95 wt%, or even greater than about 99 wt%.
  • the product effluent stream (f) from the separator comprising the 1 ,1 ,3- trichloropropene; 3,3,3-trichloropropene, or combinations thereof produced in the process may have a yield of at least about 10%.
  • product effluent stream (f) comprising 1 ,1 ,3-trichloropropene; 3,3,3-trichloropropene, or combinations thereof produced in the process may have a yield of at least about 20%, at least about 50%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, or at least about 99%.
  • the product effluent stream (h) from the separator comprising 1 ,1 ,1 ,2,3- pentachloropropane produced in the process may have a yield of at least about 10%.
  • product effluent stream (h) comprising 1 ,1 ,1 ,2,3- pentachloropropane produced in the process may have a yield of at least about 20%, at least about 50%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, or at least about 99%.
  • IV Preferred Embodiments: Preparation of 1,1,1,2,3-Pentachioropropane and
  • Another aspect of the present disclosure encompasses process for preparing 1 ,1 ,1 ,2,3-pentachloropropane and 1 ,1 ,3-trichloropropene, 3,3,3- trichloropropene, or combinations thereof from ethylene and carbon tetrachloride.
  • the process commences by preparing a liquid phase reaction mixture comprising ethylene, carbon tetrachloride, at least one Lewis acid catalyst comprising ferric chloride, metallic iron or iron alloy, and a ligand forming 1 ,1 ,1 ,3-tetrachloropropane (250FB) using a telomerization process.
  • the process is controlled by manipulating the amount of chlorinating agent supplied, the concentration of carbon tetrachloride, process temperature, process pressure, or combinations thereof wherein the concentration of the 1 , 1 ,3- trichloropropene, 3,3,3-trichloropropene, or combinations thereof within the reaction mixture is controlled between 1 % and 99% by weight.
  • reaction conditions e.g., the concentration of carbon tetrachloride, process temperature, process pressure, or combinations thereof wherein the concentration of the 1 , 1 ,3- trichloropropene, 3,3,3-trichloropropene, or combinations thereof within the reaction mixture is controlled between 1 % and 99% by weight.
  • the 1 ,1 ,1 ,3-tetrachloropropane fed to the above described process from the telomerization process may be converted to 1 ,1 ,1 ,2,3-pentachloropropane and 1 ,1 ,3-trichloropropene, 3,3,3-trichloropropene, or combinations thereof in at least 50 wt% conversion.
  • the conversion of 1 ,1 ,1 ,3-tetrachloropropane to 1 ,1 ,1 ,2,3-pentachloropropane and 1 ,1 ,3-trichloropropene, 3,3,3-trichloropropene, or combinations thereof may be at least 50 wt%, at least 60 wt%, at least 75 wt%, at least 85 wt%, at least 95 wt%, and at least 99 wt%.
  • the concentration of 1 ,1 ,3-trichloropropene, 3,3,3-trichloropropene, or combinations thereof may be greater than about 5 wt% as compared to concentration of all the components of the reaction mixture. In various embodiments, the concentration of 1 ,1 ,3-trichloropropene, 3,3,3-trichloropropene, or combinations thereof may be greater than about 5 wt%, greater than about 10 wt%, greater than 20 wt%, greater than about 40 wt%, greater than about 75 wt%, greater than about 90 wt%, or greater than 99 wt%.
  • the concentration of 1 ,1 ,1 ,2,3-pentachloropropane as compared to the total contents of the reaction mixture may be greater than about 40 wt%. In various embodiments, the concentration of 1 ,1 ,1 ,2,3-pentachloropropane as compared to the total contents of the reaction mixture may be greater than about 40 wt%, greater than about 50 wt%, greater than about 60 wt%, greater than about 70 wt%, greater than about 80 wt%, greater than about 90 wt%, greater than about 95 wt%, or even greater than about 99 wt%. (d) separation of 1 ,1 ,1 ,2,3-pentachioropropane and 1,1,3-trichloropropene, 3,3,3-trichloropropene, or combinations thereof and recycling product effluent streams.
  • the product effluent stream (f) from the separator comprising the 1 ,1 ,3- trichloropropene; 3,3,3-trichloropropene, or combinations thereof produced in the process may have a yield of at least about 10%.
  • product effluent stream (f) comprising 1 ,1 ,3-trichloropropene; 3,3,3-trichloropropene, or combinations thereof produced in the process may have a yield of at least about 20%, at least about 50%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, or at least about 99%.
  • the product effluent stream (h) from the separator comprising 1 ,1 ,1 ,2,3- pentachloropropane produced in the process may have a yield of at least about 10%.
  • product effluent stream (h) comprising 1 ,1 ,1 ,2,3- pentachloropropane produced in the process may have a yield of at least about 20%, at least about 50%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, or at least about 99%.
  • Another aspect of the present disclosure encompasses process for preparing 1 ,1 ,1 ,2,3,3-hexachloropropane and 1 ,1 ,3,3-tetrachloropropene, 1 ,3,3,3- tetrachloropropene, or combinations thereof, from 1 ,1 ,1 ,3,3-pentachloropropane.
  • the process commences by preparing a liquid phase reaction mixture comprising 1 ,1 ,1 ,3,3- pentachloropropane; at least one Lewis acid catalyst comprising gallium metal, a salt of gallium, a gallium alloy, or combinations thereof, a chlorinating agent, and an optional solvent.
  • the at least one Lewis acid catalyst comprising gallium metal, a gallium alloy, a gallium salt, or combinations thereof is described above in Section (l)(b), the chlorinating agent is described above in Section (l)(c), and the optional solvent is described above in Section (l)(d).
  • the process is controlled by manipulating the amount of chlorinating agent supplied, the concentration of the 1 ,1 ,1 ,3,3-pentachloropropane, process temperature, process pressure, or combinations thereof wherein the
  • concentration of the 1 ,1 ,3,3-tetrachloropropene, 1 ,3,3,3-tetrachloropropene, or combinations thereof within the reaction mixture is controlled between 1 % and 99% by weight.
  • the 1 ,1 ,1 ,3,3-pentachloropropane fed to the above described process may be converted to 1 ,1 ,1 ,2,3,3-hexachloropropane and 1 ,1 ,3,3-tetrachloropropene,
  • the conversion of 1 ,1 ,1 ,3,3-pentachloropropane to 1 ,1 ,1 ,2,3,3- hexachloropropane and 1 ,1 ,3,3-tetrachloropropene, 1 ,3,3,3-tetrachloropropene, or combinations thereof may be at least 50 wt%, at least 60 wt%, at least 75 wt%, at least 85 wt%, at least 95 wt%, and at least 99 wt%.
  • the concentration of 1 ,1 ,3,3-tetrachloropropene, 1 ,3,3,3- tetrachloropropene, or combinations thereof may be greater than about 5 wt% as compared to concentration of all the components of the reaction mixture. In various embodiments, the concentration of 1 ,1 ,3,3-tetrachloropropene, 1 ,3,3,3- tetrachloropropene, or combinations thereof may be greater than about 5 wt%, greater than about 10 wt%, greater than 20 wt%, greater than about 40 wt%, greater than about 75 wt%, greater than about 90 wt%, or greater than 99 wt%.
  • the concentration of 1 ,1 ,1 ,2,3,3-hexachloropropane as compared to the total contents of the reaction mixture may be greater than about 40 wt%. In various embodiments, the concentration of 1 ,1 ,1 ,2,3,3-hexachloropropane as compared to the total contents of the reaction mixture may be greater than about 40 wt%, greater than about 50 wt%, greater than about 60 wt%, greater than about 70 wt%, greater than about 80 wt%, greater than about 90 wt%, greater than about 95 wt%, or even greater than about 99 wt%.
  • the product effluent stream (f) from the separator comprising the 1 ,1 ,3,3- tetrachloropropene, 1 ,3,3,3-tetrachloropropene, or combinations thereof produced in the process may have a yield of at least about 10%.
  • product effluent stream (f) comprising 1 ,1 ,3,3-tetrachloropropene, 1 ,3,3,3-tetrachloropropene, or combinations thereof produced in the process may have a yield of at least about 20%, at least about 50%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, or at least about 99%.
  • the product effluent stream (h) from the separator comprising 1 ,1 ,1 ,2,3,3- hexachloropropane produced in the process may have a yield of at least about 10%.
  • product effluent stream (h) comprising 1 ,1 ,1 ,2,3,3- hexachloropropane produced in the process may have a yield of at least about 20%, at least about 50%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, or at least about 99%.
  • VI VI
  • Preferred Embodiments Preparation of 1,1,1,2,3,3-Hexachioropropane and 1 ,1 ,3,3-Tetrachioropropene, 1 ,3,3,3-Tetrachloropropene, or Combinations Thereof, from Vinyl Chloride and Carbon Tetrachloride.
  • Another aspect of the present disclosure encompasses process for preparing 1 ,1 ,1 ,2,3,3-hexachloropropane and 1 ,1 ,3,3-tetrachloropropene, 1 ,3,3,3- tetrachloropropene, or combinations thereof, from vinyl chloride and carbon
  • the process commences by preparing a liquid phase reaction mixture comprising vinyl chloride, carbon tetrachloride, at least one Lewis acid catalyst comprising ferric chloride, metallic iron or iron alloy, and a ligand forming 1 ,1 ,1 ,3,3- tetrachloropropane (240FA) using a telomerization process.
  • a liquid phase reaction mixture comprising vinyl chloride, carbon tetrachloride, at least one Lewis acid catalyst comprising ferric chloride, metallic iron or iron alloy, and a ligand forming 1 ,1 ,1 ,3,3- tetrachloropropane (240FA) using a telomerization process.
  • At least one Lewis acid catalyst comprising gallium metal, a gallium alloy, a gallium salt, or combinations thereof, a chlorinating agent, and an optional solvent.
  • the at least one Lewis acid catalyst comprising gallium metal, a gallium alloy, a gallium salt, or combinations thereof is described above in Section (l)(b)
  • the chlorinating agent is described above in Section (l)(c)
  • the optional solvent is described above in Section (l)(d).
  • the process is controlled by manipulating the amount of chlorinating agent supplied, the concentration of carbon tetrachloride, process temperature, process pressure, or combinations thereof wherein the concentration of the 1 ,1 ,3,3-tetrachloropropene, 1 ,3,3,3-tetrachloropropene, or combinations thereof within the reaction mixture is controlled between 1 % and 99% by weight.
  • reaction conditions 1 ,1 ,3,3-tetrachloropropene, 1 ,3,3,3-tetrachloropropene, or combinations thereof within the reaction mixture is controlled between 1 % and 99% by weight.
  • the 1 ,1 ,1 ,3,3-tetrachloropropane fed to the above described process from the telomerization process may be converted to 1 ,1 ,1 ,2,3,3-hexachloropropane and
  • 1.3.3.3-tetrachloropropene, or combinations thereof may be at least 50 wt%, at least 60 wt%, at least 75 wt%, at least 85 wt%, at least 95 wt%, and at least 99 wt%.
  • the concentration of 1 ,1 ,3,3-tetrachloropropene, 1 ,3,3,3- tetrachloropropene, or combinations thereof may be greater than about 5 wt% as compared to concentration of all the components of the reaction mixture. In various embodiments, the concentration of 1 ,1 ,3,3-tetrachloropropene, 1 ,3,3,3- tetrachloropropene, or combinations thereof may be greater than about 5 wt%, greater than about 10 wt%, greater than 20 wt%, greater than about 40 wt%, greater than about 75 wt%, greater than about 90 wt%, or greater than 99 wt%.
  • the concentration of 1 ,1 ,1 ,2,3,3-hexachloropropane as compared to the total contents of the reaction mixture may be greater than about 40 wt%. In various embodiments, the concentration of 1 ,1 ,1 ,2,3,3-hexachloropropane as compared to the total contents of the reaction mixture may be greater than about 40 wt%, greater than about 50 wt%, greater than about 60 wt%, greater than about 70 wt%, greater than about 80 wt%, greater than about 90 wt%, greater than about 95 wt%, or even greater than about 99 wt%.
  • the product effluent stream (f) from the separator comprising the 1 , 1 ,3,3- tetrachloropropene, 1 ,3,3,3-tetrachloropropene, or combinations thereof produced in the process may have a yield of at least about 10%.
  • product effluent stream (f) comprising 1 ,1 ,3,3-tetrachloropropene, 1 ,3,3,3-tetrachloropropene, or combinations thereof produced in the process may have a yield of at least about 20%, at least about 50%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, or at least about 99%.
  • the product effluent stream (h) from the separator comprising 1 ,1 ,1 ,2,3,3- hexachloropropane produced in the process may have a yield of at least about 10%.
  • product effluent stream (h) comprising 1 ,1 ,1 ,2,3- pentachloropropane produced in the process may have a yield of at least about 20%, at least about 50%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, or at least about 99%.
  • Another aspect of the present disclosure encompasses process for preparing at least one of 1 ,2,2,3-tetrachloropropane, 1 ,1 ,1 ,2,3-pentachloropropane, or
  • the process commences by preparing a liquid phase reaction mixture comprising the at least one of 1 ,2,3-trichloropropane, 1 ,1 ,1 ,3- tetrachloropropane, or 1 ,2,2,3-tetrachloropropane; at least one Lewis acid catalyst comprising gallium metal, a gallium alloy, a gallium salt, or combinations thereof, a chlorinating agent, and an optional solvent.
  • the at least one Lewis acid catalyst comprising gallium metal, a gallium alloy, a gallium salt, or combinations thereof is described above in Section (l)(b), the chlorinating agent is described above in Section (l)(c), and the optional solvent is described above in Section (l)(d).
  • the process is controlled by manipulating the amount of chlorinating agent supplied, concentration of
  • concentration of the at least one of 1 ,1 ,3-trichloropropene, 3,3,3-trichloropropene, 1 ,2,3- trichloropropene, or 2,3-dichloropropene within the reaction mixture is controlled between 1 % and 99% by weight
  • 1.2.2.3-tetrachloropropane fed to the above described process may be converted to at least one of 1 ,2,2,3-tetrachloropropane, 1 ,1 ,1 ,2,3-pentachloropropane, or 1 , 1 ,2,2,3- pentachloropropane and at least one of 1 ,1 ,3-trichloropropene, 3,3,3-trichloropropene,
  • the conversion of 1 , 1 , 1 ,3,3- pentachloropropane to at least one of 1 ,2,2,3-tetrachloropropane, 1 , 1 , 1 ,2,3- pentachloropropane, or 1 ,1 ,2,2,3-pentachloropropane and at least one of 1 ,1 ,3- trichloropropene, 3,3,3-trichloropropene, 1 ,2,3-trichloropropene, or 2,3-dichloropropene, or combinations thereof may be at least 50 wt%, at least 60 wt%, at least 75 wt%, at least 85 wt%, at least 95 wt%, and at least 99 wt%.
  • the concentration of at least one of 1 , 1 ,3-trichloropropene, 3,3,3- trichloropropene, 1 ,2,3-trichloropropene, or 2,3-dichloropropene may be greater than about 5 wt% as compared to concentration of all the components of the reaction mixture.
  • the concentration of at least one of 1 ,1 ,3- trichloropropene, 3,3,3-trichloropropene, 1 ,2,3-trichloropropene, or 2,3-dichloropropene may be greater than about 5 wt%, greater than about 10 wt%, greater than 20 wt%, greater than about 40 wt%, greater than about 75 wt%, greater than about 90 wt%, or greater than 99 wt%.
  • the concentration of at least one of 1 ,2,2,3-tetrachloropropane, 1 ,1 ,1 ,2,3- pentachloropropane, or 1 ,1 ,2,2,3-pentachloropropane as compared to the total contents of the reaction mixture may be greater than about 40 wt%.
  • the concentration of at least one of 1 ,2,2,3-tetrachloropropane, 1 ,1 ,1 ,2,3- pentachloropropane, or 1 ,1 ,2,2,3-pentachloropropane as compared to the total contents of the reaction mixture may be greater than about 40 wt%, greater than about 50 wt%, greater than about 60 wt%, greater than about 70 wt%, greater than about 80 wt%, greater than about 90 wt%, greater than about 95 wt%, or even greater than about 99 wt%. (d) separation of 1,1,1,2,3,3-hexachioropropane and 1,1, 3, 3- tetrachloropropene, 1 ,3,3,3-tetrachloropropene, or combinations thereof
  • 1.1.3.3-tetrachloropropene, 1 ,3,3,3-tetrachloropropene, or combinations thereof from the reactor contents will utilize several different separation devices (such as those described above), which will allow for the purification of various product mixture components, such as 1 ,1 ,1 ,2,3,3-hexachioropropane and 1 ,1 ,3,3-tetrachloropropene,
  • the yield of the 1 ,1 ,3,3-tetrachloropropene, 1 ,3,3,3-tetrachloropropene, or combinations thereof produced in the process may be at least about 20%, at least about 50%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, or at least about 99%.
  • the yield of the 1 , 1 , 1 ,2,3,3-hexachloropropane produced in the process may be at least about 20%, at least about 50%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, or at least about 99%.
  • Example 1 Preparation of 1,1, 1,2, 3 pentachloropropane from 1, 1,1,3- tetrachloropropane using homogeneous catalyst with low formation of tri or tetrachloropropene
  • the byproducts were found to be higher chlorinated and heavier compounds than 1 ,1 ,1 ,2,3- pentachloropropane.
  • the formation of tri or tetrachloropropene byproducts was below detection limit (about 50ppm or less).
  • Example 2 Preparation of 1,1, 1,2, 3 pentachloropropane from 1, 1,1,3- tetrachloropropane using homogeneous catalyst with low formation of
  • Example 3 Preparation of 1,1, 1,2, 3 pentachloropropane from 1, 1,1,3- tetrachloropropane using homogeneous catalyst with higher formation of trichloropropene
  • Example 4 Preparation of 1,1, 1,2, 3 pentachloropropane from 1, 1,1,3- tetrachloropropane using homogeneous catalyst with low formation of
  • Example 5 Preparation of 1,1, 1,2, 3 pentachloropropane from 1, 1,1,3- tetrachloropropane using heterogeneous catalyst with low formation of trichloropropene
  • a 23.8 ml Monel reactor tube (0.43 inch ID and 10 inches long) was charged with 12.9 g catalyst.
  • the catalyst was 20% GaCI3 (Aldrich) on activated carbon (Norit).
  • the catalyst was prepared by insipient wetness technique using a GaCI solution in water and was dried in an oven at a maximum temperature of 150°C under nitrogen purge.
  • the reactor tube was mounted in an oven at a 45° angle, and the oven temperature was controlled at 85°C.
  • Feed of 1 ,1 ,1 ,3-tetrachloropropane (Synquest Laboratories) was introduced to the bottom end of the reactor at 0.15 ml/m in using a piston pump.
  • Chlorine gas (Aldrich, 99.5% pure) was fed to the bottom end of the reactor at 29.6 seem through a mass flow controller.
  • the reactor was maintained essentially at atmospheric pressure, with effluent flowing through an open tube into a bottle.
  • the reaction mixture exiting the reactor was sampled and was analyzed by GC.
  • the GC conversion of 1 , 1 , 1 ,3-tetrachloropropane was 65%.
  • the selectivity of 1 , 1 , 1 ,2,3 pentachloropropane was 73%, of 1 ,1 ,3-trichloropropane was 11 %, and of 1230xa was 9%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

La présente invention concerne des procédés de préparation d'alcènes chlorés et d'alcanes chlorés par traitement d'un matériau de départ d'alcane chloré, au moins un catalyseur d'acide de Lewis comprenant du métal de gallium, un sel de gallium, un alliage de gallium ou des combinaisons de ceux-ci, un agent de chloration et un éventuel solvant.
PCT/US2019/047845 2018-08-24 2019-08-23 Déshydrochloration/chloration monotope d'un chloroalcane pour produire un mélange d'alcènes chlorés et d'alcanes chlorés WO2020041667A1 (fr)

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WO2012166393A1 (fr) * 2011-05-31 2012-12-06 Dow Global Technologies, Llc Procédé pour la production de propènes chlorés
WO2013022806A1 (fr) * 2011-08-07 2013-02-14 Dow Global Technologies, Llc Procédé de production de propènes chlorés
WO2014100039A1 (fr) * 2012-12-19 2014-06-26 Dow Global Technologies, Llc Procédé de production de propènes chlorés
US20150045591A1 (en) 2013-01-22 2015-02-12 Axiall Ohio, Inc. Processes for Producing Chlorinated Hydrocarbons and Methods for Recovering Polyvalent Antimony Catalysts Therefrom

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CN115536487A (zh) * 2022-10-12 2022-12-30 宁波巨化化工科技有限公司 一种高纯低碳烷烃生产工艺及设备

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