Process for treating heavy by-product streams from chlorinated propane production - Patent Application 20070122997

Abstract

A process for treating a heavy by-product stream from an initial chlorinated propane-forming reaction to increase the final yield of chlorinated propenes and remove a metal catalyst. In particular, the process disclosed herein provides a primary stream in which the chlorinated propane is converted to chlorinated propenes in a catalytic dehydrochlorination reaction, while also treating a separate by-product stream with caustic to precipitate metals from the metal catalyst and convert any remaining chlorinated propane to chlorinated propenes in order to increase the final yield of chlorinated propenes.

Description

[Technical Field]

[0001] cross reference This application is an international application based on U.S. Provisional Patent Application No. 63 / 119,434, filed November 30, 2020, which is incorporated herein by reference in its entirety.

[0002] Technical Field The present disclosure relates generally to processes for treating chloroalkane streams, and in particular to the treatment of by-product streams, and for the formation of chloroalkenes and chloroalkenes. [Background technology]

[0003] Chloroalkenes are useful intermediates for many products, including agricultural products, refrigerants, pharmaceuticals, cleaning solvents, blowing agents, rubber, silicones, and refrigerants. To form such chloroalkenes, an initial reaction is generally carried out to form intermediate products comprising chlorinated alkanes. These chloroalkanes are then subjected to subsequent reactions to produce the chloroalkenes.

[0004] The crude intermediate product from the initial reaction may contain components other than chloroalkanes, including catalyst, heavy chlorinated by-products, and other compounds. Separation processes may be performed on the crude intermediate product to obtain a purified intermediate product prior to subsequent reaction to form chloroalkenes. Various residue streams may result from these separations, which may be recycled, further processed, or disposed of.

[0005] Implementations of the present technology will now be described, by way of example only, and with reference to the accompanying drawings, in which: [Brief explanation of the drawings]

[0006] [Figure 1] FIG. 1 is a schematic diagram of one exemplary embodiment of a process for caustic treatment of heavy by-product streams. [Figure 2]FIG. 1 is a schematic diagram of one exemplary embodiment of a process for caustic treatment of heavy by-product streams. DETAILED DESCRIPTION OF THE INVENTION

[0007] Detailed Description Various embodiments of the present disclosure are discussed in detail below. While the concepts of the present disclosure are susceptible to various modifications and alternative forms, specific embodiments thereof have been shown by way of example in the drawings and are herein described in detail. It should be understood, however, that there is no intention to limit the concepts of the present disclosure to the particular forms disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives consistent with the present disclosure and the appended claims.

[0008] In the figures, some structural or methodological features may be shown in a particular arrangement and / or order. However, it should be understood that such a particular arrangement and / or order may not be required. Rather, in some embodiments, such features may be arranged in a different manner and / or order than that shown in the illustrative figures. Additionally, the inclusion of a structural or methodological feature in a particular figure is not intended to imply that such feature is required in all embodiments, and in some embodiments may not be included or may be combined with other features.

[0009] (I) Introduction Fluorocarbons are highly valuable compounds employed in numerous products, most of which are used as refrigerants. In the chemical pathway to the formation of fluorocarbons, numerous intermediate compounds are also prepared. These intermediate compounds are not only valuable in themselves, but the processes for their preparation are also valuable in order to reduce the overall cost of preparing fluorocarbons. To reduce costs, more efficient and effective processes for their formation are needed. Such intermediate compounds include various chlorinated alkanes and chlorinated alkenes.

[0010] Disclosed herein is a process for treating a heavy by-product stream from an initial chlorinated propane-forming reaction to increase the final yield of chlorinated propenes and remove metal catalysts. In particular, the process disclosed herein provides a primary or main stream in which the chlorinated propane is converted to chlorinated propenes in a catalytic dehydrochlorination reaction, while also treating a separate by-product stream with caustic to convert any remaining chlorinated propane to chlorinated propenes in order to increase the final chlorinated propene yield.

[0011] The initial reaction is carried out via telomerization to form chlorinated propane. This reaction produces a crude chlorinated propane product having the desired chlorinated propane intermediate and various heavy by-products and residual reaction components. This crude chlorinated propane product is subjected to a separation process to produce a light fraction having purified chlorinated propane and a heavy fraction having heavy by-products and residual reaction components. The chlorinated propane in the light fraction can be further purified to remove components lighter than chlorinated propane. The purified chlorinated propane is then converted to chlorinated propenes using a Lewis catalyst in a dehydrochlorination reaction. The heavy fraction typically contains chlorinated propane and by-products heavier than chlorinated propane, as well as other residual components from the initial reaction, including metal catalysts, promoters, complexes of the catalyst and promoter, or other reaction products.

[0012] Conventionally, this heavy by-product stream may be considered a waste stream and may be fed to an incinerator for disposal or at least partially recycled to return catalyst components to the initial reaction. Problems associated with the heavy by-product stream include: (1) the uncomplexed promoter in the stream is catalytically active when recycled to the initial chlorinated alkane production step (e.g., a telomerization step), whereas the metal catalyst-promoter complex is relatively inactive; (2) the metal content of the heavy by-product stream makes it difficult to dispose of via incineration due to regulatory requirements; and (3) the heavy by-product stream still contains significant amounts (30-70%) of useful chlorinated propane intermediate products, which represent yield losses and increase the volume of the incineration stream, thereby increasing incineration costs.

[0013] However, as disclosed herein, this heavy by-product stream can instead be treated to achieve many positive results, including at least (1) removal of any metal catalyst from the stream and (2) conversion of residual chlorinated propane to chlorinated propenes. Treatment can include contacting the heavy fraction with a caustic, such as an aqueous base. This results in a precipitation reaction within the aqueous base, which causes metals to precipitate from the metal catalyst, and a dehydrochlorination reaction, which converts the chlorinated propane to chlorinated propenes. Contacting the aqueous base with the heavy fraction also forms two phases: an aqueous phase and an organic phase. The metals precipitate in the aqueous phase, and the organic phase contains the chloropropane and / or chloropropene product and the heavy by-products. The aqueous phase can be separated from the organic phase and further treated to remove the precipitated metals. The organic phase can also be subjected to additional separation to remove the chloropropene product and / or recycled to the crude chloropropane product separation, with the chlorinated propane product being distilled overhead along with the chlorinated propane intermediate product.

[0014] Benefits of the present disclosure include that the lower boiling chlorinated propene products can be more easily recovered by distillation or other separation operations from the treated heavy by-product stream and combined with the chlorinated propene products from the catalytic dehydrochlorination of chloropropane with a Lewis acid catalyst. Advantages include increasing the overall yield of desirable chloropropene products and reducing the volume of the by-product stream that must be incinerated, thereby reducing incineration costs.

[0015] Another improvement resulting from the present disclosure is that because the chlorinated propane product remaining in the heavy by-product stream is recovered as chlorinated propene by caustic dehydrochlorination, the requirement for crude chlorinated propane product separation, such as vacuum distillation, can be relaxed, allowing more chlorinated propane product to remain in the heavy by-product stream. Reducing the vacuum requirement for distillation reduces capital and operating costs, and reducing the temperature of the distillation reduces promoter thermal decomposition, thereby improving the effectiveness of promoter recycle and preventing plugging problems in the chlorinated propane production reaction system (e.g., telomerization) caused by promoter decomposition products.

[0016] Another improvement resulting from the present disclosure is that the uncomplexed promoter contained in the treated heavy by-product stream is more active in the initial telomerization reactor. A portion of the treated heavy by-product stream can be recycled directly to the initial reactor, or it can be recycled to the crude chloropropane product separation and then recycled to the initial reactor along with a portion of the untreated heavy by-product stream. In the latter case, the recycled promoter includes both complexed and uncomplexed promoter. In such an embodiment, a greater amount of uncomplexed promoter is recycled to the initial reactor than if only the untreated heavy by-product stream were recycled.

[0017] The specific chlorinated propane formed in the initial reaction may be 1,1,1,3-tetrachloropropane and / or 1,1,1,3,3-pentachloropropane. The chlorinated propene formed from the dehydrochlorination reaction depends on which chlorinated propane is being converted. Generally, chloride is removed and double bonds are added during the reaction. For example, 1,1,1,3-tetrachloropropane may be converted to one or more of 1,1,3-trichloropropene or 3,3,3-trichloropropene, and 1,1,1,3,3-pentachloropropane may be converted to one or more of 1,1,3,3-tetrachloropropene and 1,3,3,3-tetrachloropropene.

[0018] (II) Chlorinated propane formation reaction As disclosed herein, the process may begin with a chlorinated propane production reaction, which may be a telomerization reaction. Any method may be employed to produce one or more desired chlorinated propanes. To form the desired chlorinated propanes, a reaction mixture may be formed containing chlorinated methane, an alkene or chlorinated alkene, a metal catalyst, and a promoter. These components react together to form the desired chlorinated propane product, as well as a crude chlorinated propane product containing other heavy by-product chlorinated alkanes, the metal catalyst, the promoter, and a complex of the catalyst and promoter. The reaction mixture may be stirred and heated to induce the reaction.

[0019] In some methods, the formation of chlorinated propane can be considered a telomerization reaction. The telomerization reaction can be considered a form of polymerization and can involve a free radical mechanism. Telomerization involves the reaction of a telogen with a taxogen to produce telomeres. According to the present disclosure, chlorinated methane can be considered the telogen, and the alkene and / or chlorinated alkene can be considered the taxogen, with telomerization producing one or more of the aforementioned chlorinated alkanes having one more carbon than the alkene and / or chlorinated alkene.

[0020] (a) Chlorinated propane The desired chlorinated propane formed from the reaction can be any chlorinated propane. Although the basic hydrocarbon has three carbons, any number of chlorines can be attached to the propyl backbone, including one, two, three, four, five, six, or more chlorine atoms. The specific number of chlorine atoms can be four or five. The chlorines can be located on the first, second, or third carbon within the propane hydrocarbon chain. There can be one, two, or three chlorides on the first carbon, one or two on the second carbon, and / or one, two, or three on the third carbon, or a mixture of the foregoing. In some examples, there can be two or three chlorides on the first carbon and one or two chlorides on the third carbon.

[0021] The at least one chlorinated propane may be selected from one or more of monochloropropane, dichloropropane, trichloropropane, tetrachloropropane, pentachloropropane, hexachloropropane, and combinations thereof. Non-limiting examples of trichloropropane, tetrachloropropane, pentachloropropane, and hexachloropropane include 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, Examples of the chlorochloropropane include 1,3-tetrachloropropane, 1,1,2,3-tetrachloropropane, 1,1,3,3-tetrachloropropane, 1,1,1,2,3-pentachloropropane, 1,1,2,3,3-pentachloropropane, 1,1,2,2,3-pentachloropropane, 1,1,1,3,3-pentachloropropane, 1,1,1,3,3-pentachloropropane, 1,1,1,3,3,3-hexachloropropane, 1,1,2,2,3,3-hexachloropropane, and combinations thereof.

[0022] Specific chlorinated propanes include 1,1,1,3-tetrachloropropane (250fb) and / or 1,1,1,3,3-pentachloropropane (240fa).

[0023] (b) Chlorinated methane The reaction involves a first compound capable of initiating a free radical reaction, including a decomposable compound that releases one or two radicals, such as a halogen radical, particularly a chloride. This first compound can include any chlorinated methane, such as methane with one, two, three, or four chlorides. Examples of chlorinated methanes include one or more of methyl chloride (monochloromethane), dichloromethane, chloroform (trichloromethane), or carbon tetrachloride. A specific example is carbon tetrachloride.

[0024] The first compound can contain a halogen in addition to chloride, such as fluoride, bromide, or iodide, including, for example, dichloromonofluoromethane, trichlorofluoromethane, difluorochloromethane, trifluorochloromethane, bromochloromethane, dibromochloromethane, tribromochloromethane, chloroiodomethane, chlorodiiodomethane, chlorotriiodomethane, bromochlorofluoromethane, bromochlorodifluoromethane, chlorodibromofluoromethane, bromochlorofluoroiodomethane, bromochlorodiiodomethane, and combinations thereof.

[0025] The chlorinated methane may be in a liquid phase and may serve as a solvent for the reaction. The metal catalyst, promoter, and optional phase transfer catalyst may be part of the liquid phase, e.g., may be dissolved or mixed in the liquid phase as well.

[0026] (c) Alkene or haloalkene The first compound reacts with the second compound, which is an alkene (also called an olefin) or a haloalkene (also called a halogenated alkene). The halogen of the haloalkene can include one or more of chloride, fluoride, iodide, or bromide, or a combination thereof. In particular, the haloalkene is a chloroalkene. The haloalkene can include one or more chlorides, and can include one or more other halogens in addition to one or more chlorides.

[0027] The alkene or haloalkene can have 1 to 6 carbon atoms, for example, 1, 2, 3, 4, 5, or 6 carbon atoms, and can be linear, branched, or cyclic. Non-limiting examples of alkenes include ethene, propene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, 3-pentene, 2-methyl-2-butene, 2-methyl-1-butene, and 3-methyl-1-butene. Non-limiting examples of haloalkenes include chloroethene (also known as vinyl chloride), vinyl bromide, vinyl fluoride, allyl chloride, allyl fluoride, 1-chloro-2-butene, 1-fluoro-2-butene, 3-chloro-1-butene, 3-fluoro-1-butene, 3-chloro-1-pentene, 3-fluoro-1-pentene, and combinations thereof. In a particular example, the alkene is ethene and the haloalkene is chloroethene (monochlorethene).

[0028] The reaction for the formation of one or more chlorinated propanes comprises reacting chloromethane with ethylene or vinyl chloride in the presence of a catalyst and a promoter. The reaction may optionally include a phase transfer catalyst.

[0029] Generally, the chlorinated methane may be used in excess. Generally, the molar ratio of the chlorinated methane to the second compound, which may be an alkene and / or haloalkene, may range from about 0.1:1 to about 100:1, or from about 0.5:1 to about 75:1, or from about 0.9:1 to about 20:1, or from about 1:1 to about 10:1, or from about 1.2:1 to about 5:1, or any combination of the foregoing.

[0030] The alkene or haloalkene may be in the gas phase and introduced into the reaction in the gas phase. The alkene or haloalkene may be mixed with a liquid phase having chlorinated methane to carry out the reaction as further described below. Various methods of mixing the gaseous alkene or haloalkene with the chlorinated liquid reaction mixture can be employed, including jet mixing, eductive, packed or trayed absorption columns, or spray absorbers.

[0031] (d) Catalyst The chlorinated propane production reaction can be carried out in the presence of a metal catalyst. The term metal catalyst herein refers to elemental metal, metal salt, metal alloy, or other form or compound containing metal, or a combination thereof. The metal can be a transition metal or a transition metal salt. As used herein, the term "transition metal catalyst" refers to elemental transition metal, transition metal salt, transition metal-containing alloy, or a combination thereof. Non-limiting examples of transition metals in the at least one catalyst can include iron and copper. A specific example of a useful catalyst includes iron chloride (FeCl2 or FeCl3). As will be understood by those skilled in the art, the oxidation state of suitable metals can vary, for example, (0), (I), (II), and (III). Non-limiting examples of suitable transition metals can be copper(0), copper(I), copper(II), iron(0), iron(II), and iron(III).

[0032] In one embodiment, at least one catalyst may be in the form of a salt. These may include salts having an organic compound as a counterion to the metal. Non-limiting examples of suitable metal salts may include acetates, acetylacetonates, alkoxides, butyrates, carbonyls, dioxides, halides, hexanoates, hydrides, mesylates, octanates, nitrates, nitrosyl halides, nitrosyl nitrates, sulfates, sulfides, sulfonates, phosphates, and combinations thereof. Non-limiting examples of suitable metal salts may include copper chloride, copper bromide, copper iodide, iron chloride, iron bromide, iron iodide, iron bromide, copper oxide, and iron oxide.

[0033] Non-limiting examples of alloys can be gliding metal, bronze, magnesium bronze, tin bronze, aluminum bronze, phosphor bronze, red brass, brass, cast iron, pig iron, steel, tool steel, and wootz steel.

[0034] The molar ratio of soluble metal salt or metal complex catalyst to chlorinated methane can range from about 0 to about 0.1:1, or from about 0.0001:1 to about 0.05:1, or from about 0.0025:1 to about 0.01:1, or from about 0.005:1 to about 0.008:1, or from about 0.001:1 to about 0.007:1, or any combination thereof.

[0035] In some embodiments, at least one metal component of the catalyst is solid, and the ratio of the surface area of ​​the solid metal catalyst to the halogenated methane containing at least one chlorine atom is at least 0.1 cm 2 In another embodiment, the ratio of the surface area of ​​the catalyst to the halogenated methane containing at least one chlorine atom can be at least 1.0 cm 2 / (g / hr).

[0036] The solid metal catalyst may be in the form of a foil, sheet, screen, wool, wire, ball, plate, pipe, rod, bar, or powder. In various embodiments, at least one catalyst may be immobilized on the surface of a support. Non-limiting examples of suitable supports may be alumina, silica, silica gel, diatomaceous earth, carbon, and clay.

[0037] The solid metal catalyst, when present, can be part of a fixed catalyst bed. The solid metal catalyst can be part of a cartridge. Additionally, the solid metal catalyst can be part of structured or unstructured packing, with the metal being part of the packing or unstructured packing. Using a fixed bed, cartridge, structured packing, or unstructured packing, the catalyst can be contained and easily replaced.

[0038] (e) Accelerators In various embodiments, a promoter may be employed in the first chlorinated propane production reaction. The promoter may be a phosphorus-containing compound. As will be understood by those skilled in the art, the phosphorus-containing compound may form a complex with a metal catalyst, particularly a transition metal catalyst, to form a transition metal-phosphorus-containing compound complex that is soluble in the reaction medium. Non-limiting examples of the phosphorus-containing compound may include alkyl phosphates or alkyl phosphites, such as trialkyl phosphate, trialkyl phosphite, or a combination thereof. Suitable non-limiting examples of trialkyl phosphates and trialkyl phosphites may include triethyl phosphate, tripropyl phosphate, triisopropyl phosphate, tributyl phosphate ("TBP"), trimethyl phosphite, triethyl phosphite, tripropyl phosphite, triisopropyl phosphite, tributyl phosphite, and tri-tertbutyl phosphite. The phosphorus-containing compound is a trialkyl phosphate, i.e., tributyl phosphate.

[0039] (f) Reaction conditions The chlorinated propane production reaction may be carried out in batch mode or continuous mode, or may be carried out in continuous mode. In continuous mode, a stirred tank reactor may be used, or a series of stirred tank reactors may be utilized to approach the performance of an ideal plug flow reactor, improving the overall efficiency of the process. As will be understood by those skilled in the art, a process in continuous mode may be stirred in various ways to improve the mixing of the gas-liquid-solid system.

[0040] Generally, processes for preparing halogenated alkanes are conducted using internal or external heat exchangers to maintain a temperature of about 80°C to about 140°C. The reactor temperature may be maintained in part by boiling or evaporating a portion of the reactants and products. The temperature of the reaction may be maintained at about 80°C to about 140°C, 85°C to about 130°C, 90°C to about 120°C, or about 95°C to about 115°C.

[0041] The process may be carried out at a pressure of about atmospheric pressure (about 14.7 psi) to about 200 psi, which allows for suitable amounts of gas and liquid to proceed and maintain the reaction rate of the process. The preferred pressure of the process may depend on the reactants being fed. In embodiments where the taxogen is ethylene, the process pressure may be about atmospheric pressure (about 14.7 psi) to about 200 psi, about 50 psi to about 150 psi, or about 90 psi to about 130 psi. In embodiments where the taxogen is chloroethylene (vinyl chloride), the process pressure may be about atmospheric to about 100 psi, atmospheric to about 70 psi, or atmospheric to about 50 psi.

[0042] The reaction is allowed to proceed for a sufficient period of time to reach completion, as determined by any method known to those skilled in the art, such as chromatography (e.g., GC - gas chromatography). The duration of the reaction, or residence time in a continuous reactor, may be less than 10 hours, or alternatively less than 7 hours, or alternatively less than 5 hours, or alternatively less than 3 hours, and may be at the lower end of a sufficient time to allow the reaction to reach completion or near completion, such as 5 minutes, or 30 minutes, or 1 hour, and may range from about 5 minutes to about 16 hours, or 5 minutes to about 12 hours, or from about 10 minutes to about 10 hours, or from about 30 minutes to about 7 hours, or from about 1 hour to about 5 hours.

[0043] As mentioned, the chlorinated methane may be in the liquid phase along with the chlorinated alkane product, metal catalyst, promoter, and optional phase transfer catalyst. The alkene and / or chlorinated alkene may be in the gas phase and / or introduced into the reaction in the gas phase. The gas and liquid phases may be contacted or mixed to induce the reaction, with greater mixing facilitating a more efficient reaction. For example, the reaction mixture may be mixed or stirred to increase gas absorption into the liquid phase. Non-limiting methods for sufficiently stirring the liquid phase contents of the reactor include jet stirring, eductors, impellers, baffles in the reactor, nozzles, spray nozzles, or combinations thereof. Jet stirring may employ eductors and / or nozzles. In some examples, the liquid phase is pumped into the gas phase through a spray nozzle, resulting in gas absorption into the liquid spray. Alternatively or additionally, the nozzle may be positioned at the surface of the liquid phase or directed through the gas phase into the liquid phase, thereby providing increased turbulence of the reaction mixture, but also increased absorption through the gas phase into the liquid phase.

[0044] The reaction mixture of the first and second compounds is essentially dry, i.e., it has a water content of less than 1000 ppm. Lower water concentrations are desirable, but not required.

[0045] (III) Separation of crude chlorinated propane stream After producing crude chlorinated propane, the outlet stream can be subjected to separation in a separation unit. The separation process step separates one or more desired chlorinated propanes from one or more heavy by-products and other reaction components. In the separation process, the desired chlorinated propane and low-boiling compounds can be separated into a first stream, and the heavy by-products and high-boiling reaction components, such as catalysts and promoters, can be separated into a second stream. The first stream can be a light fraction or top stream, and the second stream can be a heavy fraction or bottom stream. Thus, they can be separated according to boiling point or based on other properties. Alternatively, components boiling lower than the desired chlorinated propane can be first separated from the crude chlorinated product, and then the desired chlorinated propane can be separated into a light fraction from a heavy fraction.

[0046] While some separation process steps may separate most or nearly all of the chlorinated propane in the crude product stream into a top fraction, in reality, some desirable chlorinated propane is ultimately separated into a heavy fraction stream. This may be due to natural inefficiencies, the complexity and cost of the chemical and separation processes, and the adjustment of the separation unit. Whatever the cause, not all of the desirable chlorinated propane is separated into the top stream, with at least a portion being separated into a bottom stream. As disclosed herein, these chlorinated propanes can be converted to chlorinated propenes by treatment with an aqueous base. Thus, most of the desirable chlorinated propane from the crude chlorinated propane product is separated into a light fraction and converted to chlorinated propenes via reaction with a Lewis acid catalyst, while the remaining chlorinated propane in the heavy fraction is converted to chlorinated propenes via aqueous base.

[0047] Thus, the light fraction may have at least half of the chlorinated propanes from the crude product stream, or alternatively, at least more than half of the chlorinated propanes from the crude product stream.

[0048] In some embodiments, a majority of the chlorinated propane from the crude product stream is separated into a light fraction. For example, separator conditions can be set so that most of the chlorinated propane is separated into a light fraction. Thus, the amount of chlorinated propane from the crude product stream that is separated into a light fraction can range from about 50% to about 99%. Such ranges can include at least 70%, alternatively at least 90%, alternatively at least 95%, alternatively at least 99%, but less than 100%, of the chlorinated propane in the crude product mixture, with the remaining chlorinated propane being separated into a heavy fraction.

[0049] Because the heavy fraction is processed and the chlorinated propane should be converted to chlorinated propene rather than disposed of, the separator can be adjusted to less severe conditions to allow a greater amount of chlorinated propane to be separated into the heavy fraction. This can save costs because the separator does not need to recover as much of the chlorinated propane in the light fraction. Thus, a smaller percentage of the chlorinated propane from the crude stream can be separated into a light fraction, such as from about 50% to about 90%, or from 50% to 70%, such that the light fraction can have at least 50%, alternatively more than 50%, alternatively at least 55%, alternatively at least 60%, alternatively at least 70%, alternatively at least 75%, alternatively at least 80%, or alternatively at least 85% of the chlorinated propane from the crude product stream.

[0050] The light fraction itself may consist mostly of more than 50% by weight, alternatively at least 60% by weight, alternatively at least 75% by weight, alternatively at least 90% by weight, alternatively at least 95% by weight, alternatively at least 99% by weight, etc., of chlorinated propane products.

[0051] Thus, the light fraction may contain residues of components other than the desired chlorinated propane, such as residual chlorinated methane from the first reaction, alkenes and / or chlorinated alkenes from the first reaction, heavy by-products, and other chlorinated alkanes or alkenes other than the desired chlorinated propane. The residual chlorinated methane, alkenes, and / or chlorinated alkenes from the first reaction may constitute less than 50 wt%, alternatively less than 30 wt%, alternatively less than 10 wt%, or alternatively less than 5 wt% of the light fraction. The heavy by-products may constitute less than 5 wt%, alternatively less than 3 wt%, alternatively less than 2 wt%, alternatively less than 1 wt%, or alternatively less than 0.5 wt% of the light fraction. These components other than the desired chlorinated propane can be further removed, and the chlorinated propane light fraction can be further purified to increase the concentration of the desired chlorinated propane. Any components removed from the light fraction can be recycled to the first reaction or disposed of.

[0052] The separation unit can be a flash column or a multi-stage distillation column. Generally, it is preferred to operate the separation unit at the lowest possible temperature that results in vaporization of the light fraction; therefore, the unit is preferably run under vacuum. Lower temperatures result in less catalyst and / or promoter decomposition. The unit can operate at temperatures from about 70°C to about 130°C, or from about 90°C to about 120°C, or from about 95°C to about 115°C. The pressure within the unit can be from 5 torr to about 50 psi, from about 30 torr to atmospheric pressure, or from about 50 torr to about 200 torr. Operating at higher vacuums increases capital and operating costs. Therefore, to maintain low temperatures at moderate vacuum, it is desirable to leave a portion of the chlorinated propane product in the bottom heavy fraction, up to about 30% to about 70% by weight of the bottom fraction.

[0053] The heavy by-products separated into the heavy fraction are other chlorinated alkanes or alkenes in the crude product stream that are undesirable or that are not converted to the desired chlorinated propenes and may be disposed of otherwise. The heavy by-products are those having a higher boiling point than the desired chlorinated propanes. The one or more chlorinated propanes separated into the light fraction are those previously mentioned, and include, in particular, 1,1,1,3-tetrachloropropane (250FB) and / or 1,1,1,3,3-pentachloropropane (240fa). Thus, the heavy by-products are those having a higher boiling point than the desired chlorinated propanes in the crude chlorinated propane stream. Thus, when 1,1,1,3-tetrachloropropane is the chlorinated propane, the heavy by-products include those having a higher boiling point, more chlorine, and / or more carbon. These include, for example, tetrachlorpentane (1,1,1,5- and / or 1,3,3,5-) and / or small amounts of pentachloropropane. When 1,1,1,3,3-pentachloropropane (240fa) is the chlorinated propane, heavy by-products can include, for example, hexachloropentane and small amounts of hexachloropropane.

[0054] The heavy fraction itself may comprise at least 30-70% by weight, alternatively 35-50% by weight, or alternatively at least 25% by weight, alternatively at least 30% by weight, alternatively at least 35% by weight, alternatively at least 40% by weight, alternatively at least 50% by weight, etc., of the desired chlorinated propanes.

[0055] Other reaction components in the heavy fraction may include reactants, products, or reagents from the first chlorinated propane production reaction, including the metal catalyst, the promoter, the complex of the metal catalyst and the promoter, and, if present, the phase transfer catalyst. The heavy fraction also contains any remaining chloropropane that was not separated into the light fraction.

[0056] The separation may be carried out by a separation unit, which may separate components based on boiling point. The separation unit may include a distillation column or a flash unit and may be carried out under vacuum or an atmosphere. Various distillation columns may be used in this capacity. The distillation column may be a single- or multi-stage distillation column and / or a divided-wall column. The distillation column may include a side draw and / or a bottom stage, and combinations thereof. The separation unit may be composed of one, two, or more sub-separation units. The separation unit may include a reboiler. In some embodiments, a side draw column or distillation column providing an outlet stream from an intermediate stage, or a divided-wall column (a divided-wall column (DWC) is a single-shell, fully thermally coupled distillation column capable of separating a mixture of three or more components into high-purity products) may be used as the separator. A portion of the various product streams produced by the process can be recycled back to the reactor to provide increased reaction rates, increased efficiency, reduced overall process costs, increased selectivity to the desired halogenated alkane, and increased yield of the desired halogenated alkane.

[0057] (IV) Catalytic dehydrochlorination of light fraction streams to chlorinated propenes The top stream from the separation unit, particularly the light fraction or further purified light fraction, can be subjected to a dehydrochlorination reaction using a catalyst. The catalyst can be a Lewis acid catalyst, and the reaction can be carried out in a reactor vessel. The Lewis acid catalyst can be dissolved in a solvent prior to being added to the reactor. The Lewis acid catalyst can be a homogeneous or heterogeneous catalyst. In various embodiments, the Lewis acid catalyst comprises gallium, iron, aluminum, or a combination thereof. Non-limiting examples of these Lewis acid catalysts can be gallium metal, a gallium salt, a gallium alloy, iron metal, an iron salt, an iron alloy, aluminum, an aluminum salt, an aluminum alloy, or a combination thereof. Iron can be in any of its oxidation states, including Fe(I), Fe(II), and Fe(III), and gallium can have any of its oxidation states, including Ga(I), Ga(II), and Ga(III).

[0058] For gallium, iron, and / or aluminum salts, suitable anions include organic or halide anions, including acetate, acetylacetonates, alkoxides, butyrate, carbonyl, dioxide, hexonate, hydride, mesylate, octanoate, nitrate, nitrosyl halides, nitrosyl nitrates, sulfate, sulfide, sulfonate, phosphate, chloride, fluoride, iodide, bromide, and combinations thereof. A particular example ion is chloride.

[0059] Specific exemplary catalysts include iron chloride (FeCl), gallium chloride (GaCl), and / or aluminum chloride (AlCl). Non-limiting examples of the form or configuration of the Lewis acid catalyst can be a dissolved species in a liquid phase, a species deposited on a solid support, packing, unstructured packing, foil, sheet, screen, wool, wire, ball, plate, pipe, rod, bar, salt, or powder.

[0060] The weight percent (wt%) of the Lewis acid catalyst in the reaction mixture can range from about 0.0001 wt% to about 2.0 wt%. The reaction can be anhydrous, with less than 100 ppm water. The reaction temperature can be 50-200°C, or 100-175°C, or 120-165°C. The reaction pressure can be 20 torr to 200 psig, 30 torr to atmospheric pressure, or 50 torr to 200 torr. The reaction can be operated as a reactive distillation, with products such as HCl and / or chlorinated propenes being removed from the reactor as an overhead stream as the reaction proceeds. The extent of removal is dictated by the operating temperature and pressure.

[0061] Conversion of chlorinated propane to chlorinated propenes may be at least 85%, or at least 90%, or at least 95%, or at least 98%. Selectivity to chloropropenes may be at least 85%, or at least 90%, or at least 95%, or at least 98%.

[0062] The same types of reactors and mixing methods employed in the first chlorinated propane production reaction can be applied to the catalytic dehydrochlorination reaction. Thus, the reaction can be carried out in any reactor, including reactors made of carbon steel or inert materials such as Hastelloy, tantalum, or glass-lined reactors. Jet agitation, eductors, nozzles, impellers, and / or baffles can be employed to agitate or mix the contents to induce efficient and complete reaction. The reactor can also be a reactive distillation reactor, in which the chlorinated propene product, the HCl by-product, or both are continuously vaporized and distilled overhead from the liquid reaction mixture.

[0063] The chlorinated propene products formed depend on which chlorinated propanes were formed in the first chlorinated propane formation reaction.

[0064] (V) Bottom Stream Caustic Dehydrochlorination and Precipitation (a) Treatment of the heavy fraction with caustic The bottom stream from the separation unit, particularly the heavy fraction, may be treated with caustic, such as aqueous base, for simultaneous precipitation and dehydrochlorination reactions. The heavy fraction may be diluted with chlorinated methane or other suitable solvent, particularly carbon tetrachloride, and pretreated with caustic. The caustic treatment results in (1) the precipitation of metals from the metal catalyst as metal hydroxides, and (2) the conversion of chlorinated propanes in the heavy fraction to one or more chlorinated propenes. Addition of aqueous base to the heavy fraction forms an aqueous phase and an organic phase. Metals from the metal catalyst precipitate in the aqueous phase, while chlorinated propenes are formed in the organic phase. The aqueous and organic phases may then be separated to reuse the catalyst or promoter and produce chlorinated propenes in separate streams.

[0065] The treatment of the heavy fraction stream may involve the use of an aqueous base. The base may be an inorganic base, such as an alkali metal or alkaline earth metal hydroxide. The inorganic base may be an alkali metal or alkaline earth metal hydroxide. Non-limiting examples of these alkali metal or alkaline earth metal bases may include LiOH, NaOH, KOH, Ba(OH), Ca(OH), NaCO, KCO, NaHCO, KHCO, or combinations thereof. In particular, the alkali or alkaline earth metal base may include NaOH, KOH, or combinations thereof, particularly NaOH. During the dehydrochlorination reaction, the base may react with one or more chlorines or other halogens of the compounds in the heavy fraction, thereby forming an alkali metal or alkaline earth metal chloride salt. A particular salt that may be formed as a result of the dehydrochlorination reaction described herein is sodium chloride.

[0066] The concentration of the inorganic base in water can range from 5% to about 50% by weight. In various embodiments, the concentration of the dehydrochlorination reagent can range from 5% to about 50% by weight, 7% to about 40% by weight, 9% to about 30% by weight, or 10% to about 20% by weight. In certain embodiments, the concentration of the inorganic base can range from 5% to about 12% by weight.

[0067] Generally, the molar ratio of base to chlorinated propane can range from 0.1:1.0 to about 2.0:1.0. In various embodiments, the molar ratio of base to chlorinated alkane can range from 0.1:1.0 to about 2.0:1.0, or from 1.0:1.0 to about 1.75:1.0, or from 1.05:1.0 to about 1.3:1.0. If other components in the feed to the dehydrochlorination reactor are dehydrochlorinated, such as heavy by-products from the first reaction, these ranges can also apply to the molar ratio of base to the total of components that can be dehydrochlorinated.

[0068] Conversion of chlorinated propane to chlorinated propenes may be at least 85%, or at least 90%, or at least 95%, or at least 98%. Selectivity to chloropropenes may be at least 85%, or at least 90%, or at least 95%, or at least 98%.

[0069] The process temperature may vary depending on the concentration of the compounds involved, the type of base selected, and the concentration of the base. Generally, the process temperature may be from about 20°C to about 120°C, alternatively from about 45°C to about 95°C, or from about 55°C to about 85°C.

[0070] Generally, the pressure can range from about 0 psig to about 1000 psig, from about 0 psig to about 500 psig, or from about 0 psig to about 200 psig, or from about 0 psig to about 40 psig. The process can be carried out under an inert atmosphere such as nitrogen, argon, or helium.

[0071] The precipitation and dehydrochlorination process can be carried out in batch or continuous mode. The process can be agitated by the methods disclosed herein to improve mixing of the two-phase system. The same types of reactors and mixing methods employed in the first chlorinated propane production reaction can be applied to the catalytic dehydrochlorination reaction. Thus, the reaction can be carried out in any reactor, including reactors made of carbon steel or inert materials such as Hastelloy, tantalum, or glass-lined reactors. Jet agitation, eductors, nozzles, impellers, and / or baffles can be employed to agitate or mix the contents to induce efficient and complete reaction. Jet mixing can include feeding a fresh liquid feed, a product waste stream, a recycle stream, or a combination thereof, to at least one nozzle. In this jet-agitated reactor system, liquid materials, including internal recycle, fresh feed, or both, are introduced vertically, tangentially, or radially into the reactor by external pumps.

[0072] The reaction may be allowed to proceed for a sufficient time until the reaction is complete.

[0073] In some instances, the caustic dehydrochlorination may utilize a phase transfer catalyst. Non-limiting examples of phase transfer catalysts may be quaternary ammonium salts, phosphonium salts, and pyridinium salts. In some embodiments, the phase transfer catalyst may be a quaternary ammonium salt. Non-limiting examples of suitable salts are chloride, bromide, iodide, or acetate salts. Non-limiting examples of quaternary ammonium salts include trioctylmethylammonium chloride (Aliquat® 336), trioctylmethylammonium bromide, dioctyldimethylammonium chloride, dioctyldimethylammonium bromide, Arquad 2HT-75, benzyldimethyldecylammonium chloride, benzyldimethyldecylammonium bromide, benzyldimethyldecylammonium iodide, benzyldimethyltetradecylammonium chloride, dimethyldioctadecylammonium chloride, dodecyltrimethylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium acetate, tetrahexylammonium chloride, tetraoctylammonium chloride, tridodecylmethylammonium chloride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, or combinations thereof. In some embodiments, more than one phase transfer catalyst is used. In a preferred embodiment, the phase transfer catalyst is trioctylmethylammonium chloride (Aliquat® 336).

[0074] Chlorinated methanes, especially carbon tetrachloride, can be added to the heavy fraction prior to caustic dehydrochlorination. This can aid in phase separation as well as removing chlorinated propene products from the organic phase.

[0075] The amount of phase transfer catalyst can range from about 0.1 wt. % to about 5.0 wt. %, alternatively from about 0.3 wt. % to about 1 wt. %, or from 0.4 wt. % to about 0.7 wt. %, based on the total weight of the components. The amount of phase transfer catalyst added to achieve these concentrations depends on the amount, if any, already present in the heavy fraction from the first reaction.

[0076] (b) Reaction products The precipitation reaction and the dehydrochlorination reaction from contact with an aqueous base result in the formation of a crude chlorinated propene product, which constitutes the organic phase of the reaction product. The crude chlorinated propene product includes chlorinated propene and other by-products and reaction components. The dehydrochlorination reaction product depends on which chlorinated alkane was provided to the reaction. Generally, the dehydrochlorination reaction results in the loss of chloride and the formation of double bonds in the compound being dehydrochlorinated. In some embodiments, the dehydrochlorination of tetrachloropropane results in trichloropropene, the dehydrochlorination of pentachloropropane results in tetrachloropropene, and the dehydrochlorination of hexachloropropane results in pentachloropropene.

[0077] Exemplary chlorinated propene products include 1,1,3-trichloropropene, 3,3,3-trichloropropene, 1,2,3-trichloropropene, 1,1,3,3-tetrachloropropene, 1,3,3,3-tetrachloropropene, and mixtures thereof. In particular, 1,1,1,3-tetrachloropropane (250fb) is dehydrochlorinated to one or more of 1,1,3-trichloropropene or 3,3,3-trichloropropene. 1,1,1,3,3-pentachloropropane (240fa) is dehydrochlorinated to one or more of 1,1,3,3-tetrachloropropene and 1,3,3,3-tetrachloropropene.

[0078] In addition to the desired chlorinated propene, the crude chlorinated propene product contains other by-products, including other chlorinated alkanes and alkenes, which may contain heavier components having higher boiling points than the desired chlorinated propene. Additionally, there may be residual components from the first chlorinated alkane-producing reaction, such as promoters and / or phase transfer catalysts.

[0079] In addition to dehydrochlorinating the chlorinated propane, treatment with an aqueous base also produces precipitated reaction products. In particular, metals from the metal catalyst employed in the first chlorinated propane production reaction precipitate in the aqueous phase. The metals from the catalyst react with the base to form metal hydroxides. Thus, precipitation products include metal hydroxides from the metal catalyst, and thus the products formed depend on the metal employed in the metal catalyst. Non-limiting examples of precipitation products include iron hydroxide and / or copper hydroxide, or other alloys or metals used as the metal catalyst in the first chlorinated propane production reaction. The reaction with the base also forms salt by-products, which may be, for example, alkali metal or alkaline earth metal halides, such as sodium chloride.

[0080] (VI) Separation of caustic reaction products The aqueous base treatment forms a stream having an aqueous phase and an organic phase. The aqueous phase contains metal chlorides and metals precipitated from the organic phase, or crude chlorinated propane, chlorinated propene, and heavy by-products, as well as the promoter and phase transfer catalyst from the first reaction, if used. The aqueous and organic phases may be separated from each other. They may then be treated or disposed of separately. The aqueous phase may be treated to remove metal hydroxides from the aqueous phase. For example, solid metal hydroxides may be removed by conventional solid techniques such as settling, filtration, or centrifugation. This removal of metal hydroxides may occur within the reactor, after removal from the reactor, and / or after separation of the aqueous phase from the organic phase.

[0081] The metal hydroxide precipitate can be used to produce a catalyst or can be otherwise disposed of. Alternatively, the metal hydroxide can be left in the aqueous phase and the mixture can be disposed of by sending it to a wastewater treatment facility.

[0082] (VII) Separation of crude chlorinated propene reaction products Removal of metals from the organic phase facilitates further processing, recycling, and / or incineration of the crude chlorinated propene reaction product components. This outlet stream from the caustic reaction can be fed to a second separation unit. The second separation unit separates the crude chlorinated propene stream into a light fraction having purified chlorinated propenes and a heavy fraction. The lower heavy fraction contains heavy by-products including chlorinated alkanes and alkenes. These heavy by-products have boiling points higher than the desired chlorinated propenes in the light fraction. The heavy fraction also contains reaction components from the first chlorinated alkane-producing reaction, such as the promoter and any phase transfer catalyst fed to the first reaction or the caustic reaction. The light fraction has a higher concentration of desirable chlorinated propenes than the crude chlorinated propene reaction product and may comprise at least 95% chlorinated propenes, alternatively at least 96% chlorinated propenes, alternatively at least 97% chlorinated propenes, alternatively at least 98% chlorinated propenes, alternatively at least 99% chlorinated propenes, alternatively at least 99.9% chlorinated propenes, alternatively at least 99.99% chlorinated propenes.

[0083] The heavy fraction can be disposed of, such as by being provided to an incinerator, or can be recycled to the first chlorinated alkane production reaction and / or the first crude chlorinated alkane separator. The light fraction can contain water dissolved in the organic phase from the caustic dehydrochlorination reaction. The light fraction can be dried to remove the water. The light fraction can be provided to or combined with the chloropropene reaction product from the catalytic dehydrochlorination. If provided to the first crude chlorinated alkane separator, the chlorinated propenes therein are separated into a light fraction from that separator, along with the chlorinated propane sent to the catalytic dehydrochlorination reaction.

[0084] This separation can be carried out employing a separation unit similar to those previously described herein. This separation unit can separate components based on boiling point. In particular, the separation unit can include a distillation column or a flash unit and can be carried out under vacuum or atmospheric pressure. Exemplary distillation columns include single or multi-stage distillation columns and / or divided wall columns. The separation unit can include a distillation column or a flash unit and can be carried out under vacuum or atmospheric pressure.

[0085] (VIII) Separation of crude chlorinated propene products from catalytic dehydrochlorination reactions. Returning again to the catalytic dehydrochlorination, as mentioned, the reaction produces a chlorinated propene product, which can be provided to a separation unit. Prior to being provided to the separation unit, the chlorinated propene product may be combined with a light fraction separated from the chlorinated propene obtained from the caustic dehydrochlorination reaction.

[0086] The separator further refines the chlorinated propenes to produce a light fraction having purified chlorinated propenes and a heavy fraction including heavy by-products, the heavy by-products having a higher boiling point than the chlorinated propenes in the light fraction.

[0087] Example Process FIG. 1 illustrates an exemplary process 100 for producing additional chloropropenes by treating a by-product stream. As shown, an initial feed 105 containing chlorinated methane, in this case carbon tetrachloride (“Tet”), an alkene or haloalkane, in this case ethene (olefin), and a promoter, in this case TBP, is fed to a reactor 110 along with a metal catalyst, in this case iron metal and / or iron chloride (FeCl and / or FeCl). The reactor 110 may also contain iron metal. Ethene is introduced in the gas phase, and the ethene, TBP, and Tet are in the liquid phase. The gas and liquid may be mixed in the reactor 110 using jet agitation. The components react in the reactor 110 in a first chlorinated alkane production reaction. As a result of the reaction, a crude chlorinated propane product 115 having one or more desired chlorinated propanes is formed. These desirable chlorinated propanes can be, for example, 1,1,1,3-tetrachloropropane (250fb), or 1,1,1,3,3-pentachloropropane (240fa) if vinyl chloride is fed to reactor 110 instead of ethylene. Both 1,1,1,3-tetrachloropropane and 1,1,1,3,3-pentachloropropane may be produced together, or one or the other may be made. The crude chlorinated propane product 115 includes other reaction components such as TBP, Tet, iron chloride, complexes of iron chloride with TBP, and heavy by-products.

[0088] These heavy by-products in crude chlorinated propane product 115 include chlorinated alkanes and / or alkenes having one or more carbons or one or more chlorides other than the desired 1,1,1,3-tetrachloropropane and 1,1,1,3,3-pentachloropropane. These heavy by-products may have a higher boiling point than one or more of the desired chlorinated propanes and may include tetrachloropentanes, such as 1,1,1,5-pentachloropropane and / or 1,3,3,5-pentachloropropane, pentachloropropane, hexachloropentane, hexachloropentane, or combinations thereof.

[0089] The crude chlorinated propane product 115 is then provided to a separation unit 120, which can be a vacuum distillation column. The crude chlorinated propane product 115 is separated into a light fraction 125 and a heavy fraction 130. At least half of the chlorinated propane from the crude chlorinated propane product 115 is separated into the light fraction 125. The light fraction 125 is a purified stream containing a higher concentration of the desired chlorinated propane. Because the concentration of chlorinated propane in the light fraction 125 can be as low as about 50% due to conversion in the first reaction, the light fraction 125 can be further purified to remove any remaining reaction components or heavy by-products (not shown). The light fraction 125 or the further purified light fraction is fed to a catalytic dehydrochlorination reactor 130 having a Lewis acid dehydrochlorination catalyst. The light fraction 125 is then subjected to a dehydrochlorination reaction to convert the chlorinated propane into a crude chlorinated propene stream 195. The crude chlorinated propene stream 195 contains desirable chlorinated propenes such as 1,1,3-trichloropropene, 3,3,3-trichloropropene, 1,1,3,3-tetrachloropropene, 1,3,3,3-tetrachloropropene, and mixtures thereof. The crude chlorinated propene stream 195 also contains heavy by-products having higher boiling points than the desirable chlorinated propenes.

[0090] Heavy fraction 135 includes heavy by-products from crude chlorinated propane product 115. These include chlorinated alkanes and alkenes with higher boiling points than the desired chlorinated propane. Additionally, heavy fraction 135 also includes residuals from the reaction in reactor 110, including TBP, iron chloride, and complexes of TBP and iron chloride. Heavy fraction 135 also includes any remaining chlorinated propane that was not separated into light fraction 125, which may be 30-70 wt.% of the mixture. Because the stream is treated to produce chlorinated propenes rather than simply disposed of, the requirements of separation unit 120 may be relaxed, allowing a greater amount of chlorinated propane to be passed to heavy fraction 135. A portion of heavy fraction 135 may be recycled in recycle stream 150 back to reactor 110.

[0091] The heavy fraction 135 is provided to a caustic reactor 145. An aqueous base feed 150, in this case NaOH, is fed to the caustic reactor 145. Although not shown, a phase transfer catalyst may also be employed. Within this reactor, a precipitation reaction occurs in which iron from the iron chloride precipitates as iron hydroxide in the aqueous phase. Additional by-product NaCl is also produced as a result of the dehydrochlorination reaction. The iron hydroxide can be removed via outlet stream 155 by settling, filtration, or centrifugation. Removal of iron from the heavy fraction 135 improves the catalytic activity of the organic stream if a portion is recycled to reactor 110, and also facilitates its disposal.

[0092] A crude chlorinated propene stream 160 exits caustic reactor 145. This stream contains chlorinated propenes produced by the reaction in caustic reactor 145 and heavy by-products. The stream also contains TBP and an optional phase transfer catalyst, if any, and is provided to reactor 110 or caustic reactor 145. Exit stream 160 is fed to separation unit 165, which may be a distillation column. The chlorinated propenes are separated into a light fraction 170, which may be recycled to separation unit 120 and / or provided to crude chlorinated propene stream 195 exiting catalytic reactor 130. This crude chlorinated propene stream 195 may be provided to separation unit 196, where the desired chlorinated propenes are separated into a light fraction 197 and heavy by-products, such as those compounds having a higher boiling point than the chlorinated propenes in light fraction 197, are separated into a heavy fraction 198.

[0093] A heavy fraction 180 is withdrawn from separation unit 165. Heavy fraction 180 includes heavy by-products having a boiling point higher than that of the chlorinated propenes. All or a portion of this heavy fraction 180 may be recycled to reactor 110 or separation unit 120, or all or a portion of this heavy fraction 180 may be disposed of.

[0094] By treating the heavy fraction 120 with aqueous base in caustic reactor 150, iron is removed from this stream and the chlorinated propanes are converted to more useful chlorinated propenes. The removal of iron allows for the creation of a more useful stream for recycling, and the conversion to chlorinated propenes creates a useful product rather than an unused stream that would otherwise be disposed of.

[0095] Thus, the primary conversion of chlorinated propane to chlorinated propene can be carried out using a catalytic reaction, but the heavy by-product stream can be made more valuable by treating it with caustic to remove metals from the catalyst and produce a more useful chlorinated propene end product rather than a waste product.

[0096] FIG. 2 illustrates an exemplary process 200 for producing additional chloropropenes by treating a by-product stream. Process 200 in FIG. 2 is similar to the process in FIG. 1 but has fewer recycle steps. As shown, an initial feed 205 containing chlorinated methane, Tet, an alkene or haloalkene, TBP, and iron chloride (FeCl) is fed to reactor 210. Reactor 210 may also contain iron metal. Ethene is introduced in the gas phase, and ethene, TBP, and Tet are in the liquid phase. The gas and liquid may be mixed in reactor 210 using jet agitation. The components react in reactor 210 in a first chlorinated alkane production reaction.

[0097] As a result of the reaction, a crude chlorinated propane product 215 having one or more desired chlorinated alkanes is formed. The crude chlorinated propane product 215 includes other reaction components such as TBP, Tet, iron chloride, and a complex of iron chloride and TBP.

[0098] The crude chlorinated propane product 215 is then provided to a separation unit 220. Separation unit 220 can be a vacuum flash or distillation column. The crude chlorinated propane product 215 is separated into a light fraction 225 and a heavy fraction 230. At least half of the chlorinated propane from the crude chlorinated propane product 215 is separated into the light fraction 225.

[0099] Light fraction 225 is a purified stream containing a higher concentration of the desired chlorinated propane. Because the concentration of chlorinated propane in light fraction 125 can be as low as about 50% due to conversion in the first reaction, light fraction 225 can be further purified to remove any remaining reaction components or heavy by-products (not shown). Light fraction 225 or a further purified light fraction is fed to catalytic dehydrochlorination reactor 230 having a dehydrochlorination Lewis acid catalyst. Light fraction 225 is then subjected to a dehydrochlorination reaction, and the chlorinated propane is converted into crude chlorinated propene stream 240. Crude chlorinated propene stream 240 also contains heavy by-products having a higher boiling point than the desired chlorinated propene. This crude chlorinated propene stream 240 may be provided to separation unit 270 where the desired chlorinated propenes are separated into a light fraction 275 and heavy by-products, such as those compounds in light fraction 275 that have a higher boiling point than the chlorinated propenes, are separated into a heavy stream 280.

[0100] Heavy fraction 235 includes heavy by-products from crude chlorinated propane product 215. These include chlorinated alkanes with higher boiling points than the desired chlorinated propane. Additionally, heavy fraction 235 includes residuals from the reaction in reactor 210, including TBP, iron chloride, and complexes of TBP and iron chloride. Heavy fraction 235 also includes any remaining desired chloropropane that was not separated into light fraction 225, which may be 30-70% of the mixture. A portion of heavy fraction 235 may be recycled in recycle stream 232 back to reactor 210.

[0101] Heavy fraction 235 is provided to caustic reactor 245. An aqueous base feed 250, in this case NaOH, is fed to caustic reactor 245. Although not shown, a phase transfer catalyst may also be employed. Within this reactor, a precipitation reaction occurs in which iron from the iron chloride precipitates as iron hydroxide in the aqueous phase. Additional by-product NaCl is also produced as a result of the dehydrochlorination reaction. The iron hydroxide can be removed via outlet stream 255 by settling, filtration, or centrifugation. Removal of iron from heavy fraction 235 improves the catalytic activity of the organic stream if a portion is recycled to reactor 210, and also facilitates its disposal.

[0102] Crude chlorinated propene stream 260 exits caustic reactor 245. This stream contains chlorinated propenes and heavy by-products produced by the reaction in caustic reactor 245. The stream also contains TBP and any phase transfer catalyst, if any, provided in reactor 210 or caustic reactor 245. A portion of outlet stream 260 may be recycled to separation unit 220, while the remainder may be disposed of via outlet line 265. Alternatively (not shown), some or all of stream 260 may be combined with stream 240. In this embodiment, heavy stream 280 from separator 270 contains the combined heavy components from both reactors 245 and 230. Heavy stream 280 may then be partially recycled to separator 220 or reactor 210, with the remainder sent to disposal.

[0103] As used herein, the terms chlorinated propane and / or chlorinated propene, and chloropropane and / or chloropropene, encompass mono-, di-, tri-, and penta-forms of the compounds, encompassing all isomers of the compounds and all positions of the chloride along the hydrocarbon chain that constitutes the propane or propene base chain. For example, the term trichloropropene encompasses all isomers of trichloropropene, including cis and trans, such as 1,1,3-trichloropropene, 2,3,3-trichloropropene, cis-1,2,3-trichloropropene, and trans-1,2,3-trichloropropene. Similarly, the term trichloropropane encompasses all isomers of trichloropropane, including 1,2,3-trichloropropane. The term tetrachloropropene encompasses all isomers of tetrachloropropene, including 1,1,2,3-tetrachloropropene and 2,3,3,3-tetrachloropropene. The term tetrachloropropane includes all isomers of tetrachloropropane, including 1,1,2,3-tetrachloropropane and 1,2,2,3-tetrachloropropane. The term pentachloropropane includes all isomers of pentachloropropane, including 1,1,1,2,3-pentachloropropane, 1,1,2,2,3-pentachloropropane, and 1,1,2,3,3-pentachloropropane. [Example]

[0104] The following examples of specific embodiments are provided to facilitate understanding of the present disclosure, but should not be read as limiting the scope of the disclosure in any way.

[0105] Example 1 Caustic treatment of heavy fractions from 250fb production The telomerization reaction was carried out using carbon tetrachloride and ethylene, iron metal, FeCl3, and tributyl phosphate ("TBP") as promoters. The crude chlorinated propane product from the telomerization was distilled to remove the desired 1,1,1,3-tetrachloropropane (250fb) product and most of the lighter components. The remaining heavy fraction, with heavy by-products, weighed 15.65 g. GC analysis of the heavies showed 2.4 wt% 1-chlorobutane, 54.2 wt% 250fb, 1.6 wt% pentachloropropane isomers, 30.5 wt% tetrachloropentane isomers, and 8.6 wt% TBP (organic basis). Iron analysis by extraction into aqueous HCl, reduction of Fe(III) to Fe(II), and analysis of the HCl by the colorimetric phenanthroline complexation method showed 1.6 wt% Fe. The high TBP content was likely due to breakdown at the GC inlet.

[0106] This crude product stream heavies was mixed with 21.8 g of 19.4% aqueous caustic, 10 g of water, and 0.1 g of Aliquate 336® phase transfer catalyst. After stirring at 62-68°C for 3.7 hours, the mixture was centrifuged to recover 9.9 g of an organic phase, 60 g of a clear aqueous phase (some additional water was added), and 3.5 g of a precipitated iron hydroxide sludge.

[0107] The organic phase was clear, dark brown, and free-flowing. GC analysis of the organic phase showed 0.2 wt% chlorobutanes, 12.6 wt% 3,3,3-trichloropropene, 18.7 wt% 1,1,3-trichloropropene, 4.9 wt% 250 fb, 2.4 wt% pentachloropropane isomers, 32.0 wt% tetrachloropentane isomers, and 17.6 wt% TBP. Most of the unidentified components were compounds boiling at temperatures higher than 250 fb (longer retention times in the GC). The increase in TBP was greater than expected and likely resulted from an underreporting of the TBP content in the starting heavies material, caused by TBP destruction at high temperature and in the GC inlet with high iron content.

[0108] The treated heavy by-product was distilled to remove most of the trichloropropene product, producing 6.6 g of a final organic stream containing 4.2 wt. % 1,1,3-trichloropropene, 1.3 wt. % 250 fb, 46.0 wt. % tetrachloropentane isomers, and 27.2 wt. % TBP. All of the unidentified components (21.3 wt. %) boiled above 250 fb, and about one-third (7.7 wt. %) boiled above the two major tetrachloropentane isomers. The final treated and distilled heavy by-product material was clear, dark brown, and free-flowing.

[0109] The precipitated iron, which had the form of sludge from the caustic treatment, was dissolved in HCl and centrifuged, and 0.5 g of additional organic phase was recovered. The HCl was analyzed and contained 0.3 g of Fe. The clear aqueous phase from the caustic treatment was 2.2% NaOH and contained no detectable organics by GC analysis. The aqueous phase was acidified to precipitate a white solid that was not readily soluble in water or methanol. The solid was washed with methanol, dried, and weighed 0.04 g. Energy dispersive X-ray (EDX) analysis of the solid revealed it to contain 59.4 mol% carbon, 2.1 mol% nitrogen, 10.9 mol% phosphorus, 1.4 mol% chlorine, and 3.1 mol% iron. The C / P ratio suggested that the solid was primarily dibutyl phosphate and monobutyl phosphate.

[0110] Example 2 : Pure 240fa caustic treatment A telomerization reaction was carried out to produce 26 g of 1,1,1,3,3-pentachloropropane (240 fa) (99.2 mol%). This was mixed with 27.4 g of 19.4 wt% aqueous NaOH. The mixture was stirred and heated to an average temperature of 66°C for 1.5 hours. GC analysis indicated that only 1.3 wt% of the 1,1,1,3,3-pentachloropropane had been dehydrochlorinated to tetrachloropropene. To the organic phase, 0.117 g of Aliquat 336 was added as a phase transfer catalyst. The mixture was stirred and heated to an average temperature of 65°C for an additional 3 hours. The organic phase was separated, analyzed by GC, and found to contain 42.5 mole % 1,1,3,3-tetrachloropropene (1230ZA), 18.3 mole % of another tetrachloropropene isomer (presumed to be 1,3,3,3-tetrachloropropene), and 38.1 mole % 240fa. This demonstrates that heavies from 1,1,1,3,3-pentachloropropane production can be treated with caustic to obtain results similar to those in Example 1 with 1,1,1,3-tetrachloropropane starting material. The inventions described in the claims of the original application are as follows: [1] A process for producing chlorinated propenes, comprising: contacting together in a first reaction a chlorinated methane, a metal-containing catalyst, a promoter, and an alkene or a chlorinated alkene to form a crude chloropropane product comprising chloropropane and heavy by-products; a crude chloropropane product separation, separating the crude chloropropane product into a light fraction and a heavy fraction, wherein the light fraction comprises at least half of the chloropropane from the crude chloropropane and the heavy fraction comprises the remaining chloropropane, the heavy by-products, the metal-containing catalyst, the promoter, and any complexes formed between the promoter and the metal-containing catalyst; contacting at least a portion of the heavy fraction with an aqueous base in a second reaction, thereby forming an aqueous phase comprising metals precipitated from the metal-containing catalyst and an organic phase comprising a crude chloropropene product comprising chloropropenes formed via a dehydrochlorination reaction; separating the aqueous phase from the organic phase; The process includes: [2] The process of [1], further comprising contacting the light fraction with a Lewis acid catalyst in a separate dehydrochlorination reaction, thereby forming chloropropenes. [3] The process of [2], wherein the light fraction is further purified to remove one or more components other than the chloropropane prior to the separate dehydrochlorination reaction. [4] The process of [1], wherein a solvent is added to the heavy fraction prior to the second reaction. [5] The process of [1], wherein at least a portion of the heavy fraction and / or the organic phase is recycled to the first reaction or the crude chloropropane product separation. [6] The process of [1], further comprising separating the organic phase into a dehydrochlorinated light fraction comprising the chloropropene and a dehydrochlorinated heavy fraction comprising the promoter, the heavy by-products, and compounds having a boiling point higher than that of the chloropropene. [7] The process of [6], further comprising one or more of: recycling at least a portion of the dehydrochlorinated heavy fraction to the first reaction; recycling at least a portion of the dehydrochlorinated heavy fraction to the crude chloropropane product separation; incinerating at least a portion of the dehydrochlorinated heavy fraction; or combinations thereof. [8] The process of [1], further comprising recycling the dehydrochlorinated light fraction to the crude chloropropane product separation. [9] The process of [1], wherein the precipitated metal is in the form of a metal hydroxide.

[10] The process of [1], further comprising removing the precipitated metal from the aqueous phase.

[11] The process of

[10] , wherein after removal from the aqueous and organic phases, the precipitated metal is washed with a solvent or dissolved in an aqueous acid.

[12] The process of [1], wherein the chloropropane is selected from the group consisting of 1,1,1,3-tetrachloropropane, 1,1,1,3,3-pentachloropropane, and mixtures thereof.

[13] The process of [1], wherein the chloropropene is selected from the group consisting of 1,1,3-trichloropropene, 3,3,3-trichloropropene, 1,2,3-trichloropropene, 1,1,3,3-tetrachloropropene, 1,3,3,3-tetrachloropropene, and mixtures thereof.

[14] The process of [1], wherein the chloropropane comprises 1,1,1,3-tetrachloropropane.

[15] The crude chloropropane comprises a heavy by-product, the heavy by-product having a higher boiling point than 1,1,1,3-tetrachloropropane; 2. The process of claim 1, wherein the crude chloropropane product separation comprises separating the heavy by-products into the heavy fraction.

[16] The process of

[15] , wherein the chloropropene comprises trichloropropene.

[17] The process of

[16] , wherein the chloropropene is selected from the group consisting of 1,1,3-trichloropropene, 3,3,3-trichloropropene, 1,2,3-trichloropropene, and mixtures thereof.

[18] The process of

[17] , wherein the crude chloropropenes comprise a dehydrochlorination heavy by-product, the dehydrochlorination heavy by-product comprising compounds having a higher boiling point than 1,1,3-trichloropropene, 3,3,3-trichloropropene, 1,2,3-trichloropropene, and mixtures thereof.

[19] The process of [1], wherein the chloropropane comprises 1,1,1,3,3-pentachloropropane.

[20] The crude chloropropane comprises a heavy by-product, the heavy by-product having a higher boiling point than 1,1,1,3,3-pentachloropropane;

[19] The process of

[19] , wherein the crude chloropropane product separation comprises separating the heavy by-products into the heavy fraction.

[21] The process of

[20] , wherein the chloropropene comprises tetrachloropropene.

[22] The process of

[21] , wherein the chloropropene is selected from the group consisting of 1,1,3,3-tetrachloropropene, 1,3,3,3-tetrachloropropene, and mixtures thereof.

[23] The process of

[22] , wherein the crude chloropropene comprises a dehydrochlorination heavy by-product, the dehydrochlorination heavy by-product comprising compounds having a boiling point higher than 1,1,3,3-tetrachloropropene, 1,3,3,3-tetrachloropropene, and mixtures thereof.

[24] The process of [1], wherein the chlorinated methane is carbon tetrachloride.

[25] The process of [1], wherein the metal catalyst is a transition metal catalyst.

[26] The metal catalyst is iron metal, FeCl 3 or a combination of the two.

[27] The process of [1], wherein the accelerator comprises a phosphate.

[28] The process of [1], wherein the accelerator is selected from a trialkyl phosphate or a trialkyl phosphite.

[29] The process of [1], wherein a phase transfer catalyst is present in the second reaction.

[30] The process of [1], wherein the phase transfer catalyst is selected from tetraalkylammonium compounds, tetraalkylphosphonium compounds, pyridinium salts, trioctylmethylammonium chloride (Aliquat 336), dioctyldimethylammonium chloride, Arquad 2HT-75, benzyldimethyldecylammonium chloride, benzyldimethyltetradecylammonium chloride, dimethyldioctadecylammonium chloride, dodecyltrimethylammonium chloride, methyltrioctylammonium chloride, tetrabutylammonium chloride, tetrahexylammonium chloride, tetraoctylammonium chloride, tridodecylmethylammonium chloride, tetramethylphosphonium chloride, tetraphenylphosphonium bromide, trihexyltetradecylphosphonium chloride, and combinations thereof.

[31] The process according to any one of [1] to

[30] , wherein the dehydrochlorination reaction in the second reaction is carried out at a temperature of 45°C to 100°C and a pressure of 0 Pa (0 psig) to 1380 kPa (200 psig).

[32] The process of [1], wherein the aqueous base is NaOH.

[33] The process of [1], wherein the NaOH present in the aqueous base contacting the heavy fraction is present in an amount of 1 to 20 wt.%.

[34] The process of [1], wherein the aqueous base contacting the heavy fraction comprises an alkali metal or alkaline earth metal chloride salt selected from the group consisting of lithium chloride, sodium chloride, potassium chloride, barium chloride, calcium chloride, or a combination thereof.

[35] The process of [1], wherein the molar ratio of the aqueous base to the chlorinated methane is 0.1 to 2.0.

[36] The process of [1], wherein the process is a batch or continuous process.

[37] The process of [1], wherein any one of the reaction steps is carried out in a jet-stirred reactor or a series of jet-stirred reactors.

[38] The process of [1], wherein the process further comprises contacting the chloropropene with a chlorinating agent.

[39] A process for treating a chloropropane stream, comprising: reacting together in a first reaction a telogen, a metal-containing catalyst, a promoter, and a taxogen to form a crude chloropropane product comprising chloropropane and heavy by-products; splitting the crude chloropropane product into a light stream and a heavy stream, wherein the light stream comprises a majority of the chloropropane and the heavy stream comprises the remaining chloropropane, the heavy by-products, the metal-containing catalyst, the promoter, and any complexes formed from the promoter and the metal-containing catalyst; contacting the heavy stream with an aqueous base to cause precipitation of metals from the metal-containing catalyst into an aqueous phase and formation of a crude chloropropene product comprising chloropropenes from a dehydrochlorination reaction; separating the aqueous phase from the organic phase; The process includes:

[40] A system comprising: a first reactor for reacting a mixture of chlorinated methane, a metal-containing catalyst, a promoter, and an alkene chloride or vinyl chloride to form a crude chloropropane product comprising chloropropane; a separator in which the crude chloropropane product is separated into a light fraction and a heavy fraction, the light fraction comprising at least half of the chloropropane from the crude chloropropane, and the heavy fraction comprising the remaining chloropropane, the metal-containing catalyst, the promoter, and any complexes formed between the promoter and the metal-containing catalyst; a second reactor in which the heavy fraction is contacted with an aqueous base, thereby forming an aqueous phase comprising metal compounds precipitated from the metal-containing catalyst and an organic phase comprising a crude chloropropene product comprising chloropropenes, wherein the crude chloropropene product is formed via a dehydrochlorination reaction; and A system comprising:

[41] The process of

[40] , further comprising a second separator in which the aqueous phase is separated from the organic phase.

Claims

1. 1. A process for producing chlorinated propenes, comprising: contacting together in a first reaction a chlorinated methane, a metal-containing catalyst, a promoter, and an alkene or a chlorinated alkene to form a crude chloropropane product comprising chloropropane and heavy by-products; a crude chloropropane product separation, separating the crude chloropropane product into a light fraction and a heavy fraction, wherein the light fraction comprises at least half of the chloropropane from the crude chloropropane and the heavy fraction comprises the remaining chloropropane, the heavy by-products, the metal-containing catalyst, the promoter, and any complexes formed between the promoter and the metal-containing catalyst; contacting at least a portion of the heavy fraction with an aqueous base in a second reaction, thereby forming an aqueous phase comprising metals precipitated from the metal-containing catalyst and an organic phase comprising a crude chloropropene product comprising chloropropenes formed via a dehydrochlorination reaction; separating the aqueous phase from the organic phase; contacting at least a portion of said light fraction with a Lewis acid catalyst in a separate catalytic dehydrochlorination reaction, thereby forming chloropropenes; The process includes:

2. 2. The process of claim 1, wherein the light fraction is further purified to remove one or more components other than the chloropropane prior to the separate catalytic dehydrochlorination reaction.

3. 3. The process of claim 1 or 2, wherein a solvent is added to the heavy fraction prior to the second reaction.

4. 4. The process of claim 1, wherein at least a portion of the heavy fraction and / or the organic phase is recycled to the first reaction or the crude chloropropane product separation.

5. separating the organic phase into a dehydrochlorinated light fraction comprising the chloropropene and a dehydrochlorinated heavy fraction comprising the promoter, the heavy by-products, and compounds having a boiling point higher than the chloropropene; optionally, further comprising one or more of: recycling at least a portion of the dehydrochlorinated heavy fraction to the first reaction; recycling at least a portion of the dehydrochlorinated heavy fraction to the crude chloropropane product separation; incinerating at least a portion of the dehydrochlorinated heavy fraction; or combinations thereof; Optionally, further comprising recycling at least a portion of the dehydrochlorinated lights fraction to the crude chloropropane product separation, combining at least a portion of the dehydrochlorinated lights fraction with the chloropropene reaction product from the catalytic dehydrochlorination reaction, or a combination thereof. The process according to any one of claims 1 to 4.

6. The process of any one of claims 1 to 5, wherein the precipitated metal is in the form of a metal hydroxide.

7. further comprising removing the precipitated metals from the aqueous and organic phases; Optionally, after removal from the aqueous and organic phases, the precipitated metal is washed with a solvent or dissolved in an aqueous acid. The process according to any one of claims 1 to 6.

8. 8. The process of any one of claims 1 to 7, wherein the chloropropane is selected from the group of 1,1,1,3-tetrachloropropane, 1,1,1,3,3-pentachloropropane, and mixtures thereof, and the chloropropene is selected from the group of 1,1,3-trichloropropene, 3,3,3-trichloropropene, 1,2,3-trichloropropene, 1,1,3,3-tetrachloropropene, 1,3,3,3-tetrachloropropene, and mixtures thereof.

9. 9. The process of any one of claims 1 to 8, wherein the chlorinated methane is carbon tetrachloride.

10. The metal-containing catalyst is iron metal, FeCl ３ , gallium metal, GaCl ３ 10. The process of claim 1, wherein the transition metal catalyst comprises:

11. 11. The process of any one of claims 1 to 10, wherein the promoter comprises a phosphate or phosphite, and the promoter phosphate or phosphite at least partially complexes with the metal-containing catalyst.

12. The process of any one of claims 1 to 11, wherein the accelerator is selected from trialkyl phosphates or trialkyl phosphites.

13. a phase transfer catalyst is present in the second reaction; Optionally, the phase transfer catalyst is selected from tetraalkylammonium compounds, tetraalkylphosphonium compounds, pyridinium salts, trioctylmethylammonium chloride (Aliquat 336), dioctyldimethylammonium chloride, Arquad 2HT-75, benzyldimethyldecylammonium chloride, benzyldimethyltetradecylammonium chloride, dimethyldioctadecylammonium chloride, dodecyltrimethylammonium chloride, methyltrioctylammonium chloride, tetrabutylammonium chloride, tetrahexylammonium chloride, tetraoctylammonium chloride, tridodecylmethylammonium chloride, tetramethylphosphonium chloride, tetraphenylphosphonium bromide, trihexyltetradecylphosphonium chloride, and combinations thereof; The process according to any one of claims 1 to 12.

14. 14. The process of any one of claims 1 to 13, wherein the dehydrochlorination reaction in the second reaction is carried out at a temperature of from 45°C to 100°C and a pressure of from 0 psig to 1380 kPa (200 psig).

15. - the aqueous base is NaOH; and the NaOH present in the aqueous base contacting the heavy fraction is present in an amount of 1 to 20% by weight; The process according to any one of claims 1 to 14.

16. 16. The process of any one of claims 1 to 15, wherein the molar ratio of the aqueous base to the chloropropane is from 0.1 to 2.

0.

17. 17. The process of any one of claims 1 to 16, wherein the process is a batch or continuous process and / or at least one reaction step is carried out in a jet-stirred reactor or a series of jet-stirred reactors.

18. 1. A process for treating a chloropropane stream comprising: reacting together in a first reaction a telogen, a metal-containing catalyst, a promoter, and a taxogen to form a crude chloropropane product comprising chloropropane and heavy by-products; splitting the crude chloropropane product into a light stream and a heavy stream, wherein the light stream comprises a majority of the chloropropane and the heavy stream comprises the remaining chloropropane, the heavy by-products, the metal-containing catalyst, the promoter, and any complexes formed from the promoter and the metal-containing catalyst; contacting the heavy stream with an aqueous base to cause precipitation of metals from the metal-containing catalyst into an aqueous phase and formation of a crude chloropropene product comprising chloropropenes from a dehydrochlorination reaction; separating the aqueous phase from the organic phase; contacting the light fraction with a Lewis acid catalyst in a separate dehydrochlorination reaction, thereby forming chloropropenes; The process includes:

19. 1. A system comprising: a first reactor for reacting a mixture of chlorinated methane, a metal-containing catalyst, a promoter, and an alkene chloride or vinyl chloride to form a crude chloropropane product comprising chloropropane; a separator in which the crude chloropropane product is separated into a light fraction and a heavy fraction, the light fraction comprising at least half of the chloropropane from the crude chloropropane, and the heavy fraction comprising the remaining chloropropane, the metal-containing catalyst, the promoter, and any complexes formed between the promoter and the metal-containing catalyst; a second reactor in which the heavy fraction is contacted with an aqueous base, thereby forming an aqueous phase comprising metal compounds precipitated from the metal-containing catalyst and an organic phase comprising a crude chloropropene product comprising chloropropenes, the chloropropenes being formed via a dehydrochlorination reaction; a third reactor in which the light fraction is contacted with a Lewis acid catalyst in a separate dehydrochlorination reaction, thereby forming chloropropenes; A system comprising:

20. 20. The system of claim 19, further comprising a second separator in which the aqueous phase is separated from the organic phase.

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