WO2020041731A1 - Gallium catalyzed dehydrochlorination of a chlorinated alkane - Google Patents

Abstract

The present invention provides processes for the preparation of a chlorinated alkene from a chloroalkane starting material, at least one Lewis acid catalyst comprising at least one of gallium metal, a salt of gallium, a gallium alloy, or combinations thereof, and optionally a solvent.

Description

GALLIUM CATALYZED DEHYDROCHLORINATION OF A CHLORINATED ALKANE

FIELD OF THE INVENTION

[0001 ] The present disclosure generally relates to process for

dehydrochlorination of a chloroalkane starting material to form a chlorinated alkene, using a Lewis acid catalyst comprising at least one of gallium metal, a salt of gallium, a gallium alloy, or combinations thereof.

BACKGROUND OF THE INVENTION

[0002] Chlorinated alkenes are useful intermediates for many products including agricultural products, pharmaceuticals, cleaning solvents, gums, silicones, and refrigerants. One method for producing a chlorinated alkene comprises contacting the chlorinated alkane with an aqueous base in a dehydrochlorination process. Generally, these processes are efficient, yet they require a co-solvent such as an alcohol to provide miscibility of the organic and aqueous phases. Processes that do not utilize a co-solvent have been developed, but they are inefficient and require additional separation steps, which reduce the yield of the chlorinated alkene and generally require disposal of large quantities of waste.

[0003] An improvement to the base dehydrochlorination process described above utilizes a small amount of a phase transfer catalyst. The phase transfer catalyst enables transfer of active species between the organic and aqueous phases and enhances the kinetics of the process. Due to the cost of the phase transfer catalyst, the overall cost for producing a chlorinated alkene on a production scale by adding a phase transfer catalyst is increased. At the completion of the process, the phase transfer catalyst is normally purged to waste.

[0004] Another method for preparing chloroalkenes involves using a catalyst, such as a Lewis acid catalyst to dehydrochlorinate a chlorinated alkane. Common dehydrochlorination catalysts include Lewis acids, such as FeC or AICI3, which are not complexed with a ligand. The ligand can reduce the reaction rate and yield of the dehydrochlorination reaction. US 8,877,991 discloses a process for the preparation of 1 ,1 ,3-trichloropropene from 1 ,1 ,1 ,3-tetrachloropropane utilizing 0.08 wt% FeCI₃ and up to 0.4 wt% water at 120°C. This patent further discloses that added water improves the selectivity of the process yet reduces the conversion to about 30%. In an alternate process, US 8,889,927 discloses a process for the preparation of 1 ,1 ,3-trichloropropene from 1 ,1 ,1 ,3-tetrachloropropane utilizing 0.08 wt% FeCI₃ and 0.5 wt%

tetrachloropentane at 50-140°C where the weight % (wt%) of the trichloropropene isomers range from 40 to 70 wt% with high selectivity. Another method utilizes reactive distillation. US 9,624,149 discloses a process for preparing a variety of chlorinated alkenes from chlorinated alkanes by maintaining the chlorinated alkene to chlorinated alkane ratio less than 50:50 in the reaction zone. These processes have been shown to be useful providing the chlorinated alkenes in good yields. Yet, additional purification protocols are necessary to remove the catalyst from the chlorinated alkene which can inhibit subsequent processes.

[0005] It would be desirable to develop a process for preparing a chlorinated alkene with increased reaction kinetics, low unit manufacturing cost, high purity, and one that enables efficient recycle strategies.

SUMMARY OF THE INVENTION

[0006] In one aspect, disclosed herein are processes for preparing chlorinated alkenes. In general, the process comprises forming a liquid phase reaction mixture comprising contacting at least one chloroalkane starting material, at least one Lewis acid catalyst comprising at least one of gallium metal, a salt of gallium, a gallium alloy, or combinations thereof, and optionally a solvent in a reactor under conditions detailed below. In all embodiments, the liquid phase reaction mixture is devoid of a halogenating agent such as chlorine, bromine, fluorine, or combinations thereof. A product mixture is generated comprising anhydrous HCI and at least one chlorinated alkene product having one or more fewer chlorines than the at least one chloroalkane starting material.

[0007] In another aspect, disclosed herein are processes for preparing 1 ,1 ,3- trichloropropene, 3,3,3-trichloropropene, or combinations thereof. The process comprises forming a liquid phase reaction mixture comprising contacting 1 ,1 , 1 ,3- tetrachloropropane, at least one Lewis acid catalyst comprising at least one of gallium metal, a salt of gallium, a gallium alloy, or combinations thereof, and optionally a solvent in a reactor under conditions detailed below. A product mixture is generated comprising anhydrous HCI and 1 ,1 ,3-trichloropropene, 3,3,3-trichloropropene, or combinations thereof.

[0008] In an additional aspect, disclosed herein are processes for preparing 1 ,1 ,3-trichloropropene, 3,3,3-trichloropropene, 1 ,2,3-trichloropropene, 2,3- dichloropropene, 1 -chloropropene, 2-chloropropene, or combinations thereof. The process comprises forming a liquid phase reaction mixture comprising contacting 1 ,2- dichloropropane, 1 ,2,3-trichloropropane, 1 ,1 ,2-trichloropropane, 1 , 1 ,1 ,3- tetrachloropropane, 1 ,2,2,3-tetrachloropropane, 1 ,1 ,2,3-tetrachloropropane, or combinations thereof, at least one Lewis acid catalyst comprising at least one of gallium metal, a salt of gallium, a gallium alloy, or combinations thereof, and optionally a solvent in a reactor under conditions detailed below. A product mixture is generated comprising anhydrous HCI and 1 ,1 ,3-trichloropropene, 3,3,3-trichloropropene, 1 ,2,3- trichloropropene, 2,3-dichloropropene, 1 -chloropropene, 2-chloropropene or

combinations thereof.

[0009] In another aspect, disclosed herein are processes for preparing 1 ,1 ,1 ,3- tetrachloropropene; 1 ,1 ,3,3-tetrachloropropene; 1 ,1 ,2,3-tetrachloropropene; 2, 3,3,3- tetrachloropropane or combinations thereof. The process comprises forming a liquid phase reaction mixture comprising contacting 1 ,1 ,1 ,3,3-pentachloropropane; 1 ,1 ,1 ,2,3- pentachloropropane or combinations thereof, at least one Lewis acid catalyst

comprising at least one of gallium metal, a salt of gallium, a gallium alloy, or

combinations thereof, and optionally a solvent in a reactor under conditions detailed below. A product mixture is generated comprising anhydrous HCI and 1 , 1 ,1 ,3- tetrachloropropene; 1 ,1 ,3,3-tetrachloropropene; 1 ,1 ,2,3-tetrachloropropene; 2, 3,3,3- tetrachloropropane or combinations thereof.

[0010] In another aspect, disclosed herein are processes for preparing 1 ,1 ,3,3- tetrachloropropene, 1 ,3,3,3-tetrachloropropene, or combinations thereof. The process comprises forming a liquid phase reaction mixture comprising contacting 1 ,1 , 1 ,3, 3- pentachloropropane, at least one Lewis acid catalyst comprising at least one of gallium metal, a salt of gallium, a gallium alloy, or combinations thereof, and optionally a solvent in a reactor under conditions detailed below. A product mixture is generated comprising anhydrous HCI and 1 ,1 ,3,3-tetrachloropropene, 1 ,3,3,3-tetrachloropropene, or combinations thereof.

[0011 ] Other features and iterations of the invention are described in more detail below.

DETAILED DESCRIPTION OF THE INVENTION

[0012] In one aspect, the processes for preparing chlorinated alkenes comprise contacting a chloroalkane starting material, at least one Lewis acid catalyst comprising at least one of gallium metal, a salt of gallium, a gallium alloy, or combinations thereof, and optionally a solvent, in a reactor. A product mixture is generated comprising anhydrous HCI and a chlorinated alkene product having one or more fewer chlorines than the chloroalkane starting material.

(I) Processes to Prepare Chlorinated Alkenes

[0013] The process commences by preparing a liquid phase reaction mixture in a reactor comprising contacting a chloroalkane starting material, at least one Lewis acid catalyst comprising at least one of gallium metal, a salt of gallium, a gallium alloy, or combinations thereof, and optionally a solvent in a reactor. In all embodiments, the liquid phase reaction mixture contains less than 0.5 wt % halogenating agent.

Preferably, the reaction mixture contains less than 0.1 wt % halogenating agent. Even more preferably, the reaction mixture contains less than 0.01 wt % halogenating agent. Most preferably, the reaction mixture is devoid of a halogenating agent. Examples of halogenating agents include fluorine, chlorine, bromine, iodine, or combinations thereof. After forming the liquid reaction mixture, a product mixture is formed comprising anhydrous HCI, and a chlorinated alkene having one or more fewer chlorines than the chloroalkane starting material. (a), chlorinated alkane starting material

[0014] The at least one chloroalkane starting material useful in this process may be a dichloropropane, trichloropropane, a tetrachloropropane, a pentachloropropane, a hexachloropropane, or combinations thereof. In one embodiment, the at least one chloroalkane starting material is a chlorinated propane. Non-limiting examples of chlorinated propanes 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; 1 ,1 ,1 ,2-tetrachloropropane; 1 , 1 ,2,2- tetrachloropropane; 1 ,1 ,1 ,3-tetrachloropropane; 1 ,1 ,2,3-tetrachloropropane; 1 , 1 ,3,3- tetrachloropropane; 1 ,2,2,3-tetrachloropropane; 1 ,1 ,1 ,2,3-pentachloropropane;

1.1.1.2.2-pentachloropropane, 1 , 1 ,2,3,3-pentachloropropane; 1 , 1 ,2,2,3- pentachloropropane; 1 ,1 ,1 ,3,3-pentachloropropane; 1 ,1 ,1 ,3,3,3-hexachloropropane;

1 ,1 ,2,2,2,3-hexachloropropane; or combinations thereof.

[0015] One method for preparing these chloroalkane starting materials is through a telomerization process. In this process, carbon tetrachloride (Tet), an alkene or chlorinated alkene, a catalyst system comprising metallic iron, ferric chloride, and/or ferrous chloride, and a trialkylphosphate and/or a trialkylphosphite are contacted to produce the chlorinated alkanes. As an illustrative example, using ethylene as the alkene in the above described telomerization process yields tetrachloropropanes, such as 1 ,1 ,1 ,3-tetrachloropropane (HCC-250fb). Utilizing vinyl chloride as the chlorinated alkene, pentachloropropanes, such as 1 ,1 ,1 ,3,3-pentachloropropane (HCC-240fa) would result. The skilled artisan readily knows other methods for preparing

chloroalkane starting materials. In a preferred embodiment, the chloroalkane starting material comprises 1 ,1 ,1 ,3-tetrachloropropane (HCC-250fb). In another preferred embodiment, the chloroalkane starting material comprises 1 ,1 ,1 ,2,3- pentachloropropane (HCC-240db). In still another preferred embodiment, the chloroalkane starting material comprises 1 ,1 ,1 ,3,3-pentachloropropane (HCC-240fa).

In yet another preferred embodiment, the chloroalkane starting material comprises 1 ,2- dichloropropane, 1 ,2,3-trichloropropane, 1 ,1 ,2-trichloropropane, 1 ,1 , 1 ,3- tetrachloropropane, 1 ,2,2,3-tetrachloropropane, or combinations thereof. The at least one chloroalkane starting material may be prepared using methods known in the art.

For example, 1 ,1 ,1 ,2,3-pentachloropropane may be produced by the chlorinating 1 ,1 ,1 ,3-tetrachloropropane using at least one Lewis acid catalyst. In one embodiment, the catalyst comprises GaCI_3.

[0016] 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. In an embodiment, the chloroalkane starting material is devoid of a halogenating agent such as chlorine, bromine, fluorine, or combinations thereof. To be clear, the concentration of any halogenating agents in the reaction mixture should be minimized. One common method of purifying the chlorinated alkane is distillation. Non-limiting examples of distillations may be a simple distillation, flash distillation, fractional distillation, steam distillation, vacuum distillation or

combinations thereof.

[0017] Generally, the chloroalkane starting material useful in the process may have a purity greater than 10 wt%. In various embodiments, the purity of the

chlorinated alkane 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%. It is generally known in the art that the use of purer starting materials is desirable, because fewer byproducts are formed.

(b). the at least one Lewis acid catalyst comprising gallium metal, a gallium alloy, a gallium salt, or combinations thereof.

[0018] A variety of Lewis acid catalyst comprising at least one of gallium metal, a salt of gallium, a gallium alloy, or combinations thereof may be used in the

dehydrochlorination process. In various embodiments, the at least one gallium based Lewis acid catalyst comprises gallium metal, a gallium alloy, a gallium salt, 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. [0019] In some embodiments, the at least one Lewis acid catalyst may be gallium metal. As appreciated by the skilled artisan, 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.

[0020] In some embodiments, the at least one Lewis acid catalyst useful in the process may be a gallium alloy. Non-limiting examples of gallium containing alloys useful in the process may be Al Ga, galfenol, galinstan, or combinations thereof.

[0021 ] In other embodiments, the catalytic species may be a salt of gallium. As appreciated by the skilled artisan, salts of gallium can exist in a number of oxidation states. Non-limiting oxidation states of gallium salts useful in the dehydrochlorination process may be Ga(l), Ga (II), Ga (III), or combinations thereof. As appreciated by the skilled artisan, a wide variety of anions may be part of a metal salt. Non-limiting examples of suitable anions in the 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. In a preferred embodiment, the anion in the metal salt comprises a chloride. In an embodiment, the gallium salt may be gallium dichloride (gallium (I, III) chloride/digallium tetrachloride), GaCI₂

(GaGaCL), gallium (II) chloride (Ga₂CI₄), gallium (III) chloride (GaC ), or combinations thereof.

[0022] As appreciated by the skilled artisan, Lewis acid catalyst comprising at least one of gallium metal, a salt of gallium, a gallium alloy, 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). In an

embodiment, the active gallium catalyst may be 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 (I) 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 be in the Ga (I), Ga (II) and Ga (III) oxidation states. In one preferred embodiment, the catalyst comprises gallium metal, GaCh or combinations thereof.

[0023] In one embodiment, the at least one Lewis acid catalyst comprising at least one of 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 process by increasing the kinetics of the process, improving the percent conversion, and increasing the selectivity of the process. A large variety of additional Lewis acid catalysts may be used with the at least one of gallium metal, a salt of gallium, a gallium alloy, or combinations thereof in the process. In some embodiments, the additional Lewis acid catalyst may be a transition metal. As used herein, the term“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 catalytic species may be selected from the group consisting of aluminum, 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. In a preferred embodiment, the catalytic species may comprise a solid transition metal selected from the group consisting of iron, copper, and combinations thereof.

[0024] 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, ultimet, 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.

[0025] In various embodiments, the additional Lewis acid catalyst may comprise a transition metal salt. Non-limiting examples of suitable transition metal salts may include a salt of aluminum, 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. Examples of suitable transition metal salts may include, iron (II) chloride, iron (III) chloride, aluminum (III) chloride, antimony (III) chloride, antimony (V) chloride, or combinations thereof.

[0026] Generally, at least one Lewis acid catalyst comprising at least one of 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, gallium chloride (GaCI₃), or combinations thereof may be a solution, 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, or a powder. In other embodiments, the at least one Lewis acid catalyst comprising at least one of gallium metal, a salt of gallium, a gallium alloy, or combinations thereof may be immobilized on the surface of a support. Non-limiting examples of suitable supports may be alumina, silica, silica gel, diatomaceous earth, carbon, molecular sieves, and clay.

[0027] In still another embodiment, the at least one Lewis acid catalyst comprising at least one of 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. In still another embodiment, the at least one Lewis acid catalyst may be part of at least one cartridge. In still another embodiment, the at least one Lewis acid catalyst 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. Using a fixed catalyst bed, a cartridge, structured packing, or unstructured packing, the at least one Lewis acid catalyst may be contained and easily replaced when consumed. Non-limiting examples of structured and unstructured packing may be any metallic form for random packing, or

combinations thereof.

[0028] In one embodiment, the at least one Lewis acid catalyst comprising at least one of gallium metal, a salt of gallium, a gallium alloy, or combinations thereof is dissolved in a solvent prior to adding to the reactor.

[0029] Generally, for homogeneous (dissolved) catalysts that are not immobilized on a support, the concentration of the at least one Lewis acid catalyst comprising at least one of gallium metal, a salt of gallium, a gallium alloy, or combinations thereof in the reactor is less than about 2,000 ppm. In various embodiments, the concentration of the gallium metal, gallium alloy, gallium salts, or combinations thereof in the reactor is less than about 2,000 ppm, less than about 1 ,000 ppm, less than about 750 ppm, or less than about 500 ppm or less than about 100 ppm or less than about 50 ppm.

[0030] Generally, for solid catalysts or catalysts immobilized on a support, the porosity of the at least one Lewis acid catalyst comprising at least one of gallium metal, a salt of gallium, a gallium alloy, or combinations thereof is less than 0.95. In various embodiments, the porosity of the catalyst is less than 0.95, less than 0.8, less than 0.5, less than 0.3, or less than 0.1. Further, the porosity range from 0.1 to about 0.95, from 0.3 to about 0.8, or from 0.4 to about 0.6. [0031 ] The catalyst may be added continuously or piecemeal. The goal is to maintain the productivity of the reactor. The catalyst addition may be as a pure substance or in the form of a mixture with the chlorinated organic reactant and/or with any suitable solvent, including but not limited to methanol or carbon tetrachloride.

(c). optional solvent.

[0032] In various embodiments, the reaction mixture may optionally comprise a solvent. Non-limiting examples of solvents may be CCI₄, C2CI₄ (tetrachloroethylene), the chloroalkane starting material having one or more chlorines than the chloroalkene product, or a combination of two or more of these. In one embodiment, a solvent comprising CCI₄ is preferred.

(d). reaction conditions

[0033] There are many methods to stir the contents of reactor comprising liquid phase from the reaction vessel, and to provide mixing with at least one Lewis acid catalyst. These methods would provide increased interaction between the liquid phase and the at least one Lewis acid catalyst. Non-limiting methods to adequately stir the liquid phase contents of the reactor may be jet stirring, impellers, baffles in the reactor, pumps or combinations thereof.

[0034] The importance of mixing when using solid catalysts or catalysts immobilized on a solid support is to maximize solid-liquid mass-transfer by maximizing contact between the liquid phase and the at least Lewis acid catalyst comprising at least one of gallium metal, a salt of gallium, a gallium alloy, or combinations thereof.

Therefore, the type of mixing depends on the form of the at least one Lewis acid catalyst comprising at least one of gallium metal, a salt of gallium, a gallium alloy, or combinations thereof. For example, when the at least Lewis acid catalyst comprising at least one of gallium metal, a salt of gallium, a gallium alloy, or combinations thereof is in powder form, an impeller with or without baffles aids in suspending, mixing, and fluidizing of the at least one Lewis acid catalyst comprising at least one of gallium metal, a salt of gallium, a gallium alloy, or combinations thereof to maximize contact area and provide fresh liquid contact with the powder.

[0035] In another embodiment, when the at least one Lewis acid catalyst comprising at least one of gallium metal, a salt of gallium, a gallium alloy, or

combinations thereof is in the form of a fixed bed, then the liquid phase is fed directly into the fixed bed from one end of the fixed bed and exit of the other end. The fixed bed may be contained within a cylindrical or tubular container. Generally, the L/D

(length/diameter) of the cylindrical or tubular container may be greater than 1. In various embodiments, 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. The fixed bed reactor temperature may also be independently varied from the absorber temperature by heat exchanging the reactor recycle stream. The fixed bed temperature may also be controlled by including internal heat exchanger such as the use of multitube exchanger. As appreciated by the skilled artisan, at least one of the aforementioned methods or a combination of these may be utilized in the process.

[0036] In general, the process for the preparation of chlorinated alkenes will be conducted to maintain the temperature from about 20°C to about 220°C using an internal or external heat exchanger. In various embodiments, the temperature of the process may be maintained from about 25°C to about 200°C, from 30°C to about 180°C, from 40°C to about 160°C, from 50°C to about 150°C, or from about 65°C to about 150°C or from about 65°C to about 140°C. In a preferred embodiment, the temperature is about 50°C to about 150°C. In another preferred embodiment, the temperature is less than 150°C.

[0037] Generally, the process may be conducted at a pressure of about 0.001 psia to about 1000 psi or about 0.01 psia to about 200 psi. In various embodiments, the pressure of the process may be from about 0.01 psi to about 40 psi or about 14.7 psi to about 40 psi. In another embodiment, the pressure is 0.1 psi to about atmospheric pressure (~14.7 psi). If reactive distillation is used to effect the reaction, it is understood that typically, lower pressures are used, since lower pressures allow for the more facile removal of any anhydrous HCI and/or lights and/or chlorinated alkene products that are generated. Selecting the pressure to use for reactive distillation is known in the art. In other embodiments, the pressure is from about 10 psi to about 50 psi or about 14.7 psi to about 40 psi.

[0038] In general, anhydrous HCI is produced as a by-product from the process. In various embodiments, the anhydrous HCI, under the reaction conditions described above, may be separated from the product mixture, either directly from the reactor as a vapor, or by distilling the liquid product mixture leaving the reactor. Similarly, the at least one chlorinated alkene product may be separated from the product mixture, either directly from the reactor as a vapor, or by distilling the liquid product mixture leaving the reactor. These various embodiments include reactive distillation, i.e. , where the chemical reactor is also the distillation apparatus. Removing the anhydrous HCI will increase the kinetics of the process.

[0039] Generally, the reaction is allowed to proceed for a sufficient period of time until the reaction is complete, as determined by any method known to one skilled in the art, such as chromatography (e.g., GC-gas chromatography). The duration of the reaction is less than 24 hours or less than 20 hours or less than 16 hour or less than 14 hours. In some embodiments, the duration of the reaction is from about 1 hour to about 12 hours or from about 1 hour to about 7 hours.

[0040] The processes described herein may be run in a batch mode or a continuous mode where continuous mode is preferred. In another embodiment, the process in continuous modes may be stirred in various methods as appreciated by the skilled artisan.

[0041 ] The chlorinated alkane fed to the above described process may be converted to the chlorinated alkene isomers in at least 10 wt% conversion. In various embodiments, the conversion of chlorinated alkane to the chlorinated alkene isomers 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%. In other embodiments, the total conversion is less than 80 %, less than 70 %, less than 60 %, or less than 40 %. While it is desirable to increase the conversion of the starting material to the alkene product, it is known in the art that as the starting material is consumed, side reactions and degradation reactions increase. This is particularly true of consecutive reactions, wherein the chlorinated alkene product may undergo reactions to byproducts. The skilled person understands this and can adjust the reaction conditions such as conversion or concentration of reactants and products in a manner to afford the desired purity of the alkene product.

[0042] In one embodiment, the reaction mixture is anhydrous. Preferably, the reaction mixture is anhydrous.

(e). Chloroalkene products

[0043] A wide variety of chloroalkene products can be produced using the starting materials and methods described herein. A non-exhaustive list of products that may be prepared includes 1 ,1 ,3-trichloropropene; 3,3,3-trichloropropene; 1 ,2,3- trichloropropene; 2,3-dichloropropene; 1 -chloropropene, 2-chloropropene, 3- chloropropene, 1 ,1 ,1 ,3-tetrachloropropene; 1 ,1 ,3,3-tetrachloropropene; 2, 3,3,3- tetrachloropropene; 1 ,1 ,2,3-tetrachloropropene; or combinations of two or more thereof.

[0044] In one embodiment, the chlorinated alkene product comprises 2, 3,3,3- tetrachloropropene, 1 ,1 ,3,3-tetrachloropropene, 1 ,1 ,2,3-tetrachloropropene, or combinations thereof and the chloroalkane starting material comprises 1 ,1 ,1 ,2,2- pentachloropropane, 1 , 1 ,2,2,3-pentachloropane, 1 ,1 ,1 ,2,3-pentachloropropane,

I ,1 ,1 ,3,3-pentachloropropane, or combinations thereof.

II. Separation and Recycle Streams.

[0045] The next step in the process comprises separating purified chlorinated alkene product from the liquid reaction mixture comprising the chlorinated alkene product, the at least one Lewis acid catalyst comprising at least one of gallium metal, a salt of gallium, a gallium alloy, or combinations thereof, an optional solvent, lighter by- products (such as anhydrous HCI), heavier by-products, and unreacted chloroalkane starting material, as effluent streams. Depending on the purity of the chloroalkane starting material used in the process, further components in the liquid phase reaction mixture may be a trialkylphosphate, a trialkylphosphite, and iron hydroxide or iron chloride from the telomerization process. In one embodiment, the product mixture is removed from the reactor as vapor and/or a liquid and is then distilled. The chlorinated alkene product is then isolated. The heavies are continuously or intermittently purged from the reactor or from a distillation bottom stream. In one embodiment, 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. Examples of chelating agents include amines, nitrites, amides, thiols, alcohols, phosphates (such as alkyiphosphates) and phosphites (such as alkylphosphites). Examples of specific chelating agents that may he used include, stear lamines, lauryiamines, cyclohexylamines, octyiamines, 2-ethy!hex lamine, 2- octylamine, tert-octylamine, diaminododecane (Ciahhg a), hexamethylenediamine, ethylenediamine, tetramethylenediamine, acetonitrile, pentanenitrile, benzonitrile, tolunitriles, H-ethyiacetamide, acetanilide, acetc-p-toluidide,

hexamethiyenephosphoramide dimercaprol, tributylphosphate, triethylphosphate trimethylphosphate, and triphenylphosphate.

[0046] The separation process commences by transferring at least a portion of the liquid phase reaction mixture from the reactor into a separator or multiple

separators. In various embodiments, the at least one of the first separator and the second separator may be a distillation column or a multistage distillation column.

Additionally, the 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. In one embodiment, a side draw column or a distillation column which provides 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, increased yield of the desired halogenated alkene, and increased mixing.

[0047] As appreciated by the skilled artisan, each effluent stream, as described below, is enriched in the particular component of the liquid phase reaction mixture.

Further separations may be required to produce highly pure compounds.

[0048] In another embodiment, the process may be conducted in a reactive distillation column. In this configuration, the chemical reactor and a distillation step are combined in a single operating step, thus allowing for simultaneous addition of reactants into the process, formation of various product streams, and distillation of the various product streams.

[0049] In embodiments where the chlorinated alkene product is not separated from the liquid reaction mixture by reactive distillation, a portion of the liquid reaction mixture may be transferred to a separator. In an embodiment, 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.

[0050] Separating the purified chlorinated alkene product from the liquid reaction mixture would produce at least two product effluent streams. In various embodiments, separating the purified chlorinated alkene product may produce three product effluent streams, four product effluent streams, or more product streams depending on the separation device utilized. As an example, the separation of the chlorinated alkene product from the contents of the reactor using three product streams is described below.

[0051 ] The liquid reaction mixture may be distilled to produce three product streams, product effluent streams (a), (b), and (c). Product effluent stream (a) comprises the optional solvent, light by-products, and anhydrous hydrogen chloride which under the process conditions described above is removed an overhead vapor stream during the separation. Product effluent stream (a) may be produced directly from the reactor by reactive distillation, as described above, or it may be produced by sending the reactor product stream to a separate separation device. Product effluent stream (b) comprises the chlorinated alkene product which may be removed as a side stream from a reactive distillation system or from a distillation step that is separate from the reactor. Product (c) comprises unreacted chloroalkane starting material, heavy by- products, and the at least one Lewis acid catalyst comprising gallium metal, a gallium alloy, a gallium salt, or combinations thereof which comprise the bottom stream.

[0052] Generally, product effluent stream (a) comprising the optional solvent, anhydrous hydrogen chloride, 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, light by- products and product effluent stream (e), obtained as the bottom stream, comprising the optional solvent. The overhead product effluent stream (d) may be further purified since anhydrous hydrogen chloride is a valuable commercial material.

[0053] Product effluent stream (c) may be further purified producing two additional product effluent streams (f) and (g) wherein product effluent stream (f) comprises the unreacted chloroalkane and product effluent stream (g) comprises heavy by-products and the at least one Lewis acid catalyst comprising at least one of gallium metal, a salt of gallium, a gallium alloy, or combinations thereof.

[0054] In order to improve the efficiency of the process, various product effluent streams may be externally recycled back into the process. In various embodiments, at least a portion of the product effluent stream (c) comprising unreacted chloroalkane, heavy by-products, and the at least one Lewis acid catalyst comprising gallium metal, a gallium alloy, a gallium salt, or combinations thereof, (e) comprising the optional solvent, product stream (f) comprising unreacted chloroalkane, and product steam (g)

comprising heavy by-products and the at least one Lewis acid catalyst comprising gallium metal, a gallium alloy, a gallium salt, or combinations thereof may be recycled back into the dehydrochlorination process, as described above.

[0055] In another embodiment, at least a portion of product effluent stream (c), product effluent stream (e) and/or product effluent stream (f) 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. In various embodiments, the product effluent streams and fresh liquid feeds may be introduced into the reactor separately or mixed together before entering the process.

To be clear, fresh feed streams may contain all or less than all of the following: the chloroalkane starting material, additional catalyst, 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.

[0056] Generally, the mass 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.

[0057] Product effluent stream (b) from the separator comprising the chlorinated alkene product produced in the dehydrohalogenation process may have a yield of at least about 10%. In various embodiments, product effluent stream (b) comprising chlorinated alkene 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%.

(III). Preferred Embodiments: Process for Preparing of 1,1,3-Trichloropropene, 3,3,3-Trichloropropene, or Combinations Thereof

[0058] Another aspect of the present disclosure encompasses process for preparing 1 ,1 ,3-trichloropropene; 3,3,3-trichloropropene, or combinations thereof. 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 gallium alloy, a gallium salt, or combinations thereof, 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) and the optional solvent is described above in Section (l)(c). In a preferred embodiment, the at least one Lewis acid catalyst comprises gallium metal, a gallium alloy, a gallium salt, or combinations thereof and the optional solvent comprises carbon tetrachloride and/or 1 , 1 , 1 ,3- tetrachloropropane. The reaction conditions are described above in Section (l)(d). The process for separating the 1 ,1 ,3-trichloropropene; 3,3,3-trichloropropene, or

combinations thereof from the reactor contents is described above in Section (II).

Specific recycle streams useful in improving the efficiency of the process are described above in Section (II).

(IV). Preferred Embodiments: Process for Preparing of 1,1,3-Trichloropropene, 3,3,3-Trichloropropene, 1 ,2,3-Trichioropropene, 2,3-Dichloropropene, or

Combinations Thereof

[0059] Another aspect of the present disclosure encompasses process for preparing 1 ,1 ,3-trichloropropene, 3,3,3-trichloropropene, 1 ,2,3-trichloropropene, 2,3- dichloropropene, or combinations thereof. The process commences by preparing a liquid phase reaction mixture comprising 1 ,2,3-trichloropropane, 1 , 1 ,1 ,3- tetrachloropropane, 1 ,2,2,3-tetrachloropropane, or combinations thereof; at least one Lewis acid catalyst comprising gallium metal, a gallium alloy, a gallium salt, or combinations thereof, 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) and the optional solvent is described above in Section (l)(c). In a preferred embodiment, the at least one Lewis acid catalyst comprises gallium metal, a gallium alloy, a gallium salt, or combinations thereof and the optional solvent comprises carbon tetrachloride, 1 ,2,3-trichloropropane, 1 , 1 ,1 ,3- tetrachloropropane, 1 ,2,2,3-tetrachloropropane, and/or combinations thereof. The reaction conditions are described above in Section (l)(d). The process for separating the 1 ,1 ,3-trichloropropene, 3,3,3-trichloropropene, 1 ,2,3-trichloropropene, 2,3- dichloropropene, or combinations thereof, or combinations thereof from the reactor contents is described above in Section (II). Specific recycle streams useful in improving the efficiency of the process are described above in Section (II).

(V). Preferred Embodiments: Process for Preparing of 2,3,3,3-Tetrachioropropene,

1.1.3.3-Tetrachloropropene, 1 ,1 ,2,3-Tetrachloropropene, or Combinations Thereof

[0060] Another aspect of the present disclosure encompasses process for preparing 2,3,3,3-tetrachloropropene, 1 ,1 ,3,3-tetrachloropropene, 1 ,1 , 2, 3- tetrachloroproene, or combinations thereof. The process commences by preparing a liquid phase reaction mixture comprising 1 ,1 ,1 ,2,3-pentachloropropane, 1 ,1 ,1 ,3,3- pentachloropropane, or combinations thereof; at least one Lewis acid catalyst comprising gallium metal, a gallium alloy, a gallium salt, or combinations thereof, 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) and the optional solvent is described above in Section (l)(c). In a preferred

embodiment, the at least one Lewis acid catalyst comprises gallium metal, a gallium alloy, a gallium salt, or combinations thereof and the optional solvent comprises carbon tetrachloride, 1 ,1 ,1 ,2,3-pentachloropropane, 1 ,1 ,1 ,3,3-pentachloropropane, and/or combinations thereof. The reaction conditions are described above in Section (l)(d).

The process for separating the 2,3,3,3-tetrachloropropene, 1 , 1 ,3,3-tetrachloropropene,

1.1.1.2.3-pentachloropropane, 1 ,1 ,1 ,3,3-pentachloropropane, or combinations thereof, from the reactor contents is described above in Section (II). Specific recycle streams useful in improving the efficiency of the process are described above in Section (II).

(V). Preferred Embodiments: Process for Preparing of 1 ,1 ,3,3-Tetrachioropropene,

1.3.3.3-Tetrachloropropene, or Combinations Thereof

[0061 ] Another aspect of the present disclosure encompasses process for preparing 1 ,1 ,3,3-tetrachloropropene, 1 ,3,3,3-tetrachloropropene, or combinations thereof. 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 gallium alloy, a gallium salt, or combinations thereof, 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) and the optional solvent is described above in Section (l)(c). In a preferred embodiment, the at least one Lewis acid catalyst comprises gallium metal, a gallium alloy, a gallium salt, or combinations thereof and the optional solvent comprises carbon tetrachloride and/or 1 ,1 ,1 ,3,3-pentachloropropane. The reaction conditions are described above in Section (l)(d). The process for separating the 1 , 1 ,3,3-tetrachloropropene, 1 ,3,3,3- tetrachloropropene, or combinations thereof from the reactor contents is described above in Section (II). Specific recycle streams useful in improving the efficiency of the process are described above in Section (II).

DEFINITIONS

[0062] When introducing elements of the embodiments described herein, the articles "a", "an", "the" and "said" are intended to mean that there are one or more of the elements. The terms "comprising", "including" and "having" are intended to be inclusive and mean that there may be additional elements other than the listed elements.

[0063] Having described the invention in detail, it will be apparent that

modifications and variations are possible without departing from the scope of the invention defined in the appended claims.

EXAMPLES

[0064] The following examples illustrate various embodiments of the invention.

Example 1: Preparation of 1,1,3-trichloropropene

[0065] In a 250 ml_ three necked flask equipped with a dry ice condenser, magnetic stir bar and a sparge tube was charged with 50 g (274.72 mmol) of 1 ,1 ,1 ,3- tetrachloropropane (250fb, Synquest Laboratories, cat. no. 1100-5-33, lot# 00009664). The vent line from the condenser was connected to a scrubber containing 20% sodium hydroxide solution. Nitrogen was sparged through the solution in the flask for 3 minutes. Gallium trichloride (Alfa Aesar, ultra dry, 99.999% metals basis, cat. no. 43879, lot# T31 D002) was then added. The reaction mixture was stirred and heated to the desired temperature. The product composition was measured as a function of reaction time. Table 1 shows that using l OOOppm Gallium trichloride about 90% conversion can be obtained in 5 hour residence time but with about 69% selectivity to 1 ,1 ,3- trichloropropene (113e) at 100°C. At 50ppm GaCI₃ concentration and a reaction temperature of 115°C about 99% and 97% selectivity can be achieved at 44 and 62% conversion respectively as shown in Run #2. As a comparison, FeCI₃ shows lower conversion as shown in Run #3 at similar condition and run time. In Run #4, AICI₃ shows little activity at similar conditions. Run #5 shows that Ga(0) can also be used with similar activity as GaCI_3. Note: the catalyst was prepared, an inert atmosphere was not used, and the 250fb was not dried.

Example 2: Preparation of 1,1,2,3-tetrachloropene

[0066] The overall procedure and equipment from Example 1 were used in Example 2, except the catalyst was prepared in a nitrogen atmosphere and the 240db was dried over molecular sieves. 1 ,1 ,1 ,2,3-pentachloropropane (PCP, 240db) was treated with 500 ppm GaCI₃ at 70°C. The dehydrochlorinated product, 1 ,1 ,2,3- tetrachloropropene (1230xa) was formed. As shown in the table below, after 86 minutes about 35% of the PCP is converted to 1230XA and HCI with high selectivity. Reported concentrations are fractional. At conversions above 35%, heavies (mostly dimer) were formed.

Dimer

Time (Min) Concentration Concentration Concentration

The data in the above tables suggest that the use of reactive distillation would be effective to remove the 1 ,1 ,3-tetrachloropropene and 1230xa products and maintain the product concentrations below about 54 and 40%, respectively. It is known to those skilled in the art that accumulation of high product concentration can lead to an increase in consecutive reactions.

Example 3: Preparation of 1,1,3,3-tetrachloropropene from 1,1, 1,3, 3- pentachloropropane by Reactive Distillation with GaCI₃ Catalyst

[0067] Pure (99.93 weight %) 1 ,1 ,1 ,3,3-pentachloropropane (240fa) was dried using molecular sieve. To 2549 g of dried 240fa was added 0.38 ml of 13.3 weight % GaCh dissolved in carbon tetrachloride to produce a solution with 20 ppm GaCI3. A 500 ml flask equipped with a heater, jacketed packed distillation column and overhead condenser at 15°C was charged with 455 g of the solution, and heated to 154°C. As the reaction began at 80 m after starting heat, 150 ml/h of the 240fa solution with 20 ppm GaCh was started to the flask to maintain level as product was removed overhead. The system was run for 458 m with a total feed of 1989 g. During this time, the pressure was 14.7 psia and the sump temperature was maintained at 161 °C, the distillation top at 157°C and the condenser exit at 139°C. Samples of the condensed overhead product were 98.7 +/- 0.2 weight % 1 ,1 ,3,3-tetrachloropropene. The main by-product in the overhead was 1 ,3,3,3-tetrachloropropane at 1.25 % average. Samples of the sump were 21 % 240fa and 78 % 1 ,1 ,3,3-tetrachloropropene at 120 m after starting, and 38 % and 61 %, respectively, at 458 m. The sum of by-products in the sump heavier than 240fa ranged from 0.14 to 0.28 %. At the end, a total of 813 g of condensed overhead product was collected, and 392 g of sump material had been purged. The level remaining in the sump flask was about 350 g. By mass balance, some product was lost with the HCI vent, and could have been recovered with a colder condenser. This example demonstrates the effectiveness of GaCI₃ catalyst for dehydrochlorination in a reactive distillation system.

Example 4: Preparation of 1,1,3-trichloropropene from 1,1,1,3,-tetrachloropropane (250fb) using heterogeneous catalyst

[0068] A 23.8 ml Monel reactor tube (0.43 inch ID and 10 inches long) was charged with 13.0 g catalyst. The catalyst was 20% GaCI₃ (Aldrich) on activated carbon (Norit). The catalyst was prepared by insipient wetness technique using a GaCI₃ 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 75°C. Feed of 1 ,1 ,1 ,3-tetrachloropropane (Synquest Laboratories) was introduced to the bottom end of the reactor at 0.36 ml/m using a piston pump. The reactor was maintained essentially at atmospheric pressure, with effluent flowing through an open tube outside of the oven and into a bottle at room temperature. The condensed reaction product exiting the reactor was sampled and was analyzed by GC. The conversion of 1 ,1 ,1 ,3-tetrachloropropane was 12.5%. The selectivity of 1 ,1 ,3-trichloropropene was 85%. Byproducts were predominantly heavier compounds than 1 ,1 ,1 ,3-tetrachloropropane.

Claims

CLAIMS What is claimed is:

1. Methods of preparing chlorinated alkenes, the methods comprising:

a. forming a reaction mixture comprising at least one chloroalkane starting material, at least one Lewis acid catalyst comprising at least one of gallium metal, a salt of gallium, a gallium alloy, or combinations thereof, and optionally a solvent, in a reactor; and

b. generating a product mixture comprising anhydrous HCI and at least one chlorinated alkene product having one or more fewer chlorines than the at least one chloroalkane starting material.

2. Methods according to claim 1 , wherein the reaction mixture does not contain a halogenating agent, such as fluorine, chlorine, and/or bromine.

3. Methods according to any one of claims 1 -2, wherein the reaction mixture optionally further comprises a solvent.

4. Methods according to claim 3, wherein the solvent comprises at least one of CCI₄, C2CI₄, or chloroalkane.

5. Methods according to any one of claims 1 -4, wherein the at least one

chloroalkane starting material comprises a chlorinated propane.

6. Methods according to claim 5, wherein the chlorinated propane comprises at least two chlorine atoms.

7. Methods according to any one of claims 5-6, wherein the chlorinated propane comprises at least one of 1 ,1 ,1 ,3-tetrachloropropane; 1 ,1 ,1 ,2,3-pentachloropropane;

1 ,1 ,1 ,3,3-pentachloropropane; 1 ,1 ,1 ,2,2-pentachloropropane; 1 , 1 ,2,2,3- pentachloropropane; 1 ,2,3-trichloropropane; 1 ,1 ,2-trichloropropane; 1 , 2,2,3- tetrachloropropane; 1 ,1 ,2,3-tetrachloropropane; or 1 ,2-dichloropropane.

8. Methods according to any one of claims 1 -7, wherein the reaction is conducted in the liquid phase.

9. Methods according to any one of claims 1 -8, wherein at least part of the at least one Lewis acid catalyst is in homogeneous or heterogeneous form.

10. The methods according to any one of claims 1 -9, wherein at least part of the at least one Lewis acid catalyst is a heterogeneous catalyst and is deposited on a substrate comprising alumina, silica, silica gel, diatomaceous earth, carbon, molecular sieves, and clay or combinations thereof.

11. The methods according to claim 10, wherein the Lewis acid catalyst deposited on a substrate is contained in a catalyst bed.

12. The methods according to claim 11 , wherein the reaction mixture contacts the catalyst bed by, for example, flowing through it.

13. The methods according to any one of the claims 1 -12, wherein the at least one Lewis acid catalyst further comprises Fe metal, FeCI₂, FeCI₃, AICI₃, SbCI₃, SbCI₅, bismuth or combinations of two or more thereof.

14. The methods according to any one of claims 1 -13, wherein the Lewis acid comprises GaCI_3.

15. Methods according to any one of claim 1 -14, wherein the process temperature is about 20°C to about 220°C and preferably about 25 °C to about 200 °C, about 30°C to about 180 °C, or about 40 °C to about 160 °C, or about 65 °C to about 150 °C.

16. The methods according to any one of the claims 1 -15, wherein the reaction mixture has a process pressure that is from about 0.001 psia to about 1000 psig or preferably from about 0.01 psia to about 200 psig.

17. Methods according to any one of claim 1 -16, wherein the reaction time is less than 24 hours, or less than 20 hours or less than 16 hours or less 14 hours.

18. Methods according to any one of claims 1 -17, wherein the chloroalkene product comprises at least one of 1 ,1 ,3-trichloropropene; 3,3,3-trichloropropene; 1 ,2,3- trichloropropene; 2,3-dichloropropene; 1 ,1 ,1 ,3-tetrachloropropene; 1 , 1 ,3,3- tetrachloropropene; 2,3,3,3-tetrachloropropene; 1 ,1 ,2,3-tetrachloropropene; 1 - chloropropene; 2-chloropropene; 3-chloropropene.

19. Methods according to any one of claims 1 -18, wherein anhydrous HCI is separated from the product mixture, either directly from the reactor as a vapor, or by distilling the liquid product mixture leaving the reactor.

20. Methods according to any one of claims 1 -19, wherein the product mixture is removed from the reactor as vapor and/or as liquid and distilled, and the chlorinated alkene product is isolated.

21. Methods according to any one of claims 1 -20, wherein unreacted chloroalkane starting material, at least one Lewis acid catalyst, and/or any solvent is recycled to the reactor.

22. Methods according to any one of claims 1 -21 , wherein at least 10 % of the chloroalkane starting material is converted to a chlorinated alkene product.

23. Methods according to any one of claims 1 -22, wherein the concentration of the at least one Lewis acid catalyst in homogeneous form in the reactor is less than about 2,000 ppm or less than about 1 ,000 ppm or less than about 750 ppm or less than about 500 ppm or less than about 100 ppm or less than about 50 ppm.

24. Methods according to any one of claims 1 -23, wherein the chlorinated alkene product is continuously removed from the reactor, either directly from the reactor as a vapor, or by distilling the liquid product mixture leaving the reactor.

25. Methods according to any one of claims 1 -24, wherein the selectivity of the reaction is at least 60% and/or the conversion is less than 80%

26. Methods according to any one of the claims 1 -25, wherein the chlorinated alkene product comprises at least one of 1 ,1 ,3-trichloropropene or 3,3,3-trichloropropene, and the chloroalkane starting material comprises 1 ,1 ,1 ,3-tetrachloropropane.

27. Methods according to any one of the claims 1 -26, wherein the chlorinated alkene product comprises 1 ,1 ,3-trichloropropene, 3,3,3-trichloropropene, 1 ,2,3- trichloropropene, 2,3-dichloropropene, or combinations thereof and the chloroalkane starting material comprises 1 ,2,3-trichloropropane, 1 ,1 ,1 ,3-tetrachloropropane, 1 , 2,2,3- tetrachloropropane, or combinations thereof.

28. Methods according to any one of the claims 1 -27, wherein the chlorinated alkene product comprises 2,3,3,3-tetrachloropropene, 1 ,1 ,3,3-tetrachloropropene, 1 , 1 ,2,3- tetrachloropropene, or combinations thereof and the chloroalkane starting material comprises 1 ,1 ,1 ,2,2-pentachloropropane, 1 ,1 ,2,2,3-pentachloropane, 1 ,1 ,1 ,2,3- pentachloropropane, 1 ,1 ,1 ,3,3-pentachloropropane.

29. Methods according to any one of the claims 1 -28, wherein the catalyst is added continuously or in any frequency to maintain the productivity of the reactor.

30. Methods according to any one of claims 1 -29, wherein the reaction mixture is anhydrous.

31. The methods of any one of the claims 1 -30, wherein the chloroalkane starting material is 1 ,1 ,1 ,2,3-pentachloropropane and it is produced by the chlorination of

1 ,1 ,1 ,3-tetrachloropropane.

32. The methods of claim 31 , wherein at least one Lewis acid comprising GaCh catalyzes the chlorination of 1 ,1 ,1 ,3-tetrachloropropane.

33. The methods of any one of the claims 1 -30, wherein the at least one Lewis acid catalyst comprising at least one of gallium metal, a salt of gallium, a gallium alloy, or combinations thereof is dissolved in a solvent prior to adding to the reactor.

34. The method of any one of the claims 1 -33, wherein the heavies contain active or deactivated catalyst and the heavies are continuously or intermittently purged from the reactor.

35. The method of any of claims 1 -34, wherein 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.

36. The method of claim 35, wherein the catalyst is removed by adding water, activated carbon, or via ion exchange.

37. The method of claims 35 or 36, wherein the catalyst is deactivated by adding a chelating agent to the product mixture.

38. The method of claim 37 wherein the chelating agent contains N, S, and/or P.

39. The method of claim 38, wherein the chelating agent comprises at least one of stearyiamines, lauryiamines, cydohexyiamines, octyiamines, 2-ethylhexyiamine, 2- octylamine. tert-octylamine, diaminododecane

hexamethy!enediamine, ethylenediamine, tetramethylenediamine, acetonitrile, pentanenstrile. benzonitriie, tolunitriies, N-ethylacetamide, acetanilide, aceto-p-toluidide,

hexamethlyenephosphoramide dimercaprol, tributylphosphate, triethylphosphate trimethylphosphate, or triphenylphosphate.