WO2019195258A1 - Improved process for preparing chloroalkanes and/or chlorofluoroalkanes - Google Patents

Abstract

The present invention provides processes for the production of chloroalkanes, chlorofluoroalkanes, or combinations thereof from one or more alkenes, chlorinated alkenes, fluorinated alkenes, or combinations thereof.

Description

IMPROVED PROCESS FOR PREPARING CHLOROALKANES AND/OR

CHLOROFLUOROALKANES

FIELD OF THE INVENTION

[0001 ] The present disclosure generally relates to processes for preparing chloroalkanes and/or chlorofluoroalkanes.

BACKGROUND OF THE INVENTION

[0002] Chloroalkanes and chlorofluoroalkanes are useful as products and intermediates for agricultural products, pharmaceuticals, blowing agents, solvents, gums, and refrigerants. Generally, these processes can be moderately efficient, can be time consuming, can generate large volumes of waste, can require multiple

purifications, and lack reproducibility.

[0003] The chlorination of alkenes is widely known. Generally, a chlorinating agent is reacted with an alkene, either in liquid or gas phase. Yet, these processes have drawbacks with respect to yield, efficiency, kinetics, and increased by-product formation. These processes often are limited to low conversion in order to prevent high by-product formation.

[0004] One highly sought group of chlorinated alkanes or chlorofluoroalkanes are pentachloropropanes, especially 1 ,1 ,1 ,2,3-pentachloropropane (240DB). These pentachloropropanes are useful in agricultural products and intermediates for the next generation refrigerants. Processes to produce pentachloropropanes can be either in gas phase or liquid phase and are sometimes conducted in the presence of a Lewis acid (catalyst). Some useful catalysts reported are FeCI₂, FeCI₃, AICI₃, and SbCI_5. Catalysts are generally used if the starting material is a chloroalkane that must be dehydrochlorinated, prior to chlorination. These processes can be run to completion where the trichloropropenes are consumed in the process (high percent conversion) or they can be run at lower conversion to reduce by-product formation. After the reaction is completed, the desired pentachloropropane is produced with significant amounts of heavy by-products. When these processes are used to produce 240DB, they are somewhat efficient, they lack consistent yields, and they require extensive purification strategies to remove heavy by-products.

[0005] Developing a simplified process for the production of chloroalkanes or chlorofluoroalkanes from a chloroalkene, a fluoroalkene, or a chlorofluoroalkene, where the process utilizes a low cost catalyst and exhibits a selectivity of at least 95% for the desired chlorinated alkane be desirable. Processes that also reduce the number of purifications or simplify the purification of the desired chlorinated alkane are more desirable. Such processes that also reduce manufacturing costs, and reduce the amount of waste produced would be particularly desirable. Especially preferred is when such processes are used to make 1 ,1 ,1 ,2,3-pentachloropropane (240DB) from one or more trichloropropenes,

SUMMARY OF THE INVENTION

[0006] In one aspect, provided herein are processes for preparing chlorinated alkanes, chlorofluoroalkanes, or combinations thereof, via the reaction of one or more alkenes, chloroalkenes, fluoroalkenes, chlorofluoroalkenes, or combinations thereof, a chlorinating agent, and a catalyst. The process comprises forming a reaction mixture in a reactor by contacting one or more chloroalkenes, fluoroalkenes, chlorofluoroalkenes or combinations thereof, a chlorinating agent, and a catalyst, and forming the

chloroalkane, chlorofluoroalkane, or combinations thereof, wherein the catalyst comprises at least one of a metal, a metal alloy, or combinations thereof. Separation of the chloroalkanes, chlorofluoroalkanes, or combinations thereof would be simplified, producing the chloroalkanes, chlorofluoroalkanes, or combinations thereof in high purity and high yield.

[0007] In another aspect, provided are processes for preparing chloroalkanes, chlorofluoroalkanes, or combinations thereof from the reaction of one or more chlorinated alkenes, fluorinated alkenes, chlorofluoroalkenes, or combinations thereof comprising between 2 to 6 carbon atoms, a chlorinating agent, and a catalyst in a reactor, and forming chloroalkanes, chlorofluoroalkanes, or combinations thereof, wherein the catalyst comprises at least one metal, a metal alloy, or combinations thereof. Separating the chloroalkanes, chlorofluoroalkanes, or combinations thereof comprising between 2 to 6 carbon atoms from the remainder of the contents of the reactor would produce the chloroalkanes, chlorofluoroalkanes, or combinations thereof comprising between 2 and 6 carbon atoms in high purity and yield.

[0008] In a further aspect, provided herein are processes for preparing 1 ,1 ,1 ,2,3- pentachloropropane. The process comprises contacting 1 ,1 ,3-trichloropropene, 3,3,3- trichloropropene, or combinations thereof with a chlorinating agent, and a catalyst comprising at least one of iron, an iron alloy, carbon steel, or combinations thereof and producing 1 ,1 ,1 ,2,3-pentachloropropane, wherein the chlorinating agent comprises sulfuryl chloride, chlorine gas, or combinations thereof. 1 ,1 ,1 ,2,3-Pentachloropropane would be easily separated from the reaction mixture, which would afford the 1 ,1 ,1 ,2,3- pentachloropropane in high yield and purity.

[0009] Other features and iterations of the invention are described in more detail below.

BRIEF DESCRIPTION OF THE FIGURES

[0010] The present patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee.

[0011 ] FIG. 1 presents percent conversion of mixtures of 1 ,1 ,3-trichloropropene and 3,3,3-trichloropropene versus reaction time. Separate experiments were conducted using either dried trichloropropenes or wet trichloropropenes. Control experiments and three different catalyst experiments; stainless steel, Monel, and carbon steel were run.

[0012] FIG. 2 presents percent conversion of 1 ,1 ,3-trichloropropene versus reaction time. Separate experiments were conducted using either dried

trichloropropenes or wet trichloropropenes. Control experiments were run and two different catalysts, i.e. , iron metal and ferric chloride were tested.

[0013] FIG. 3 presents the purity of 240DB made by chlorinating 1 ,1 ,3- trichloropropene with the removal of light impurities, i.e., only the impurities heavier than 240DB remain. The data is reported in mole% versus the % conversion of 1 ,1 ,3- trichloropropene.

[0014] FIG. 4 presents data on the overall conversion of a blend of 1 ,1 ,3- trichloropropene and 3,3,3-trichloropropene to 240DB. The data is reported in percent conversion versus time at 35°C.

[0015] FIG. 5 presents the purity of 240DB made by chlorinating a mixture of 113e and 333e, after removal of light impurities. The data is reported in product purity (in mole%) versus % conversion at 35°C.

DETAILED DESCRIPTION OF THE INVENTION

[0016] Disclosed herein are processes for the production of chloroalkanes, chlorofluoroalkanes, or combinations thereof. In general, the process comprises a reaction between one or more alkene, chloroalkenes, a fluoroalkenes,

chlorofluoroalkenes, or combinations thereof, a chlorinating agent, and a catalyst in a reactor under conditions detailed below.

[0017] In all embodiments, the catalyst, as detailed below, comprises a metal, a metal alloy, or combinations thereof, without the use of a promoter, an initiator (such as free radical initiators), or a ligand. Examples of free radical initiators include Non- limiting examples of suitable organic or inorganic free radical initiators may include azobisisobutyronitrile, 1 ,T-azobis(cyclohexanecarbonitrile), 2,2’-azobis(2- methylpropionitrile, di-tert-butylperoxide, tert-butyl peracetate, tert-butyl peroxide, methyl ethyl ketone peroxide, acetone peroxide, cyclohexane peroxide, 2,4- pentanedione peroxide, or combinations thereof. Examples of ligands include trialkylphosphites, trialkylphosphates and combinations thereof, or other ligands commonly used in telomerization reactions. A specific example of a trialkylphosphate is tributylphosphate (TBP). In addition, the process is conducted to a selectivity of at least 95% for the chloroalkanes, chlorofluoroalkanes, or combinations thereof and at least a 50% conversion of the one or more chloroalkenes, fluoroalkenes, chlorofluoroalkenes, or combinations thereof. By using this methodology, after removal of the unreacted one or more chlorinated alkenes, fluorinated alkenes, chlorofluoroalkenes, or combinations thereof and light by-products, the chloroalkanes, chlorofluoroalkanes, or combinations thereof is highly pure and an additional purification of the chloroalkanes,

chlorofluoroalkanes, or combinations thereof is not required.

[0018] These processes have been shown to be highly cost effective, have a reduced unit manufacturing cost, have a reduction in waste, and higher through put as compared to other existing processes.

(I) Processes for Producing Chloroalkanes, Chlorofluoroalkanes, or

Combinations Thereof.

[0019] One aspect of the present disclosure encompasses processes for the preparation of chloroalkanes, chlorofluoroalkanes, or combinations thereof. The processes comprise forming a reaction mixture in a reactor comprising one or more alkene, chloroalkenes, fluoroalkenes, chlorofluoroalkenes, or combinations thereof, a chlorinating agent, and a catalyst. Once this reaction mixture is formed, the chlorinated alkane, chlorofluoroalkane, or combinations thereof is formed. The processes are conducted to a selectivity of at least 95% and at least a 50% conversion. Surprisingly, after separation of one or more chloroalkene, fluoroalkene, chlorofluoroalkene, or combinations thereof, and the light by-products, the chloroalkane, chlorofluoroalkane, or combinations thereof are produced in high yield and high purity with lower amounts of heavy by-products, when compared to other processes.

(a) reaction mixture

[0020] The processes commence by preparing a reaction mixture in a reactor comprising one or more alkenes, chloroalkenes, fluoroalkenes, chlorofluoroalkenes, or a combination thereof, at least one chlorinating agent, and at least one metal catalyst.

(i) alkene, chloroalkene, fluoroalkene, chlorofluoroalkene, or combinations thereof

[0021 ] A wide variety of alkenes, chlorinated alkenes, fluorinated alkenes, chlorofluoroalkenes, or combinations thereof may be used as a starting material in the process. The starting material may be a single compounds or a mixture of one or more chlorinated alkenes, fluorinated alkenes, or chlorofluoroalkenes. As appreciated by the skilled artisan, the starting material may be introduced in the reaction as a liquid or a gas. Under conditions of the process as detailed below, the starting material (or a component thereof) may undergo a phase transition where the gas is condensed to a liquid.

[0022] Generally, the starting alkene, chloroalkene, fluoroalkene, and

chlorofluoroalkene comprises between 2 to 6 carbon atoms and may be linear, branched or cyclic. Additionally, the starting material may be wet or dry. In various embodiments, the starting material has a water content below 1000 ppm, i.e. indicating the alkene is essentially dry. In various embodiments, the starting material has a water content above l OOOppm, i.e. indicating the alkene is wet. In other embodiments, the starting material has a water content above the solubility limit and an aqueous phase exists. Examples of alkenes include ethylene, propylene, butylenes, pentenes, and hexenes. A preferred alkene is ethylene. Examples of noncyclic chlorinated alkenes, fluorinated alkenes, and chlorofluoroalkenes include vinyl chloride, allyl chloride, vinylidene chloride, 2-chloropropene, 3-chloropropene, 1 ,3-dichloropropene, 2,3- dichloropropene, 3,3-dichloropropene, 1 ,2,3-trichloropropene, 1 ,1 ,3-trichloropropene, 3,3,3-trichloropropene, 1 ,1 ,2,3-tetrachloropropene, 2-chloro-1 -butene, 3-chloro-1 - butene, 2-chloro-2-butene, 1 ,4-dichloro-2-butene, 3, 4-dichloro-1 -butene, 1 ,3-dichloro-2- butene, 2,3,4-trichloro-1 -butene, 1 ,2,3,4-tetrachloro-2-butene, 1 ,1 ,2,4-tetrachloro-l - butene, 2, 3-dichloro-1 ,3-butadiene, 1 -chloro-3-methyl-2-butene, 3-chloro-3-methyl- butene, 5-chloro-1 -pentene, 4-chloro-1 -pentene, 3-chloro-1 -pentene, 3-chloro-2- pentene, 1 ,2-dichloro-1 -pentene, 1 ,1 ,5-trichloro-1 -pentene, 6-chloro-1 -hexene, 1 ,2- dichloro-1 -hexene, and combinations thereof. Examples of cyclic chlorinated and/or fluorinated alkenes include 1 -chlorocyclopentene, 2-chlorocyclopentene, 3- chlorocyclopentene, 1 ,2-dichlorocyclopentene, 4,4-dichlorocyclopentene, 3,4- dichlorocyclopentene, 1 -chloro-1 ,3-cyclopentadiene, 2- chloro-1 ,3-cyclopentadiene, 5- chloro-1 ,3-cyclopentadiene, 1 ,2-dichloro-1 ,3-cyclopentadiene, 1 ,3-dichloro-1 ,3- cyclopentadiene, 1 ,4- dichloro-1 ,3-cyclopentadiene, 5,5 dichloro-1 ,3-cyclopentadiene, 1.2.3-trich loro-1 ,3-cyclopentadiene, 1 ,2,3,4-tetrachloro-1 ,3-cyclopentadiene, 1 -chloro-

1.3-cyclohexadiene, 3-chloro-1 ,4-cyclohexyldiene, chlorofluoroethylene, 1 ,2- dichlorofluoroethylene, 1 -chloro-2-fluoropropene, 3-chloro2-fluoropropene, 1 ,1 -dichloro- 2-fluoropropene, 1 -chloro-3,3,3-trifluoropropene, 1 -chloro-1 -fluorobutene, 2-chloro-

3.3.3-trifluoropropene, 1 -chloro-1 -fluoropentene, 1 -fluoro-5-chlorocyclopentene, vinyl fluoride, vinylidene fluoride (1 ,2-difluoroethylene), trifluoroethylene, tetrafluoroethylene,

2-fluoropropene, 3-fluoropropene, 1 ,1 -difluoropropene, 1 ,3-difluoropropene, 3,3,3- trifluoropropene, 1 ,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, 2-fluorobutene,

3-fluorobutene, 4 fluorobutene, 1 ,1 -difluorobutene, 2,3-difluorobutene, 2,2,3- trifluorobutene, 1 ,1 ,1 ,4,4,4-hexafluorobutene, 4-fluoropentene, 5-fluoropentene, 1 ,1 - difluoropentene, 2,2-difluoropentene, 1 ,5-difluoropentene, 1 ,1 ,1 -trifluoropentene, 1 - fluorocyclopentene, 1 -fluorocyclohexene, 3-fluorocyclohexene, 4-fluorocyclohexene, 2- fluorohexene, 3 fluorohexene, 1 ,1 -difluorohexene, 1 ,1 -difluoro-2-hexene, and

combinations thereof. In an embodiment, the one or more chlorinated alkenes, chlorofluoroalkenes, or combinations thereof are trichloroalkenes. In a preferred embodiment, the starting material is at least one chlorinated alkene. More preferably, in one embodiment, the starting material is a mixture of two chlorinated alkenes. Still more preferably, at least one the one or more chlorinated alkenes includes 1 ,1 ,3- trichloropropene, 3,3,3-trichloropropene, or combinations thereof. In one embodiment, the liquid chlorinated alkene contains greater than 1 ppm water.

(ii) chlorinating agent

[0023] A large number of chlorinating agents may be used in the process. Non- limiting examples of chlorinating agents include chlorine gas, sulfuryl chloride, thionyl chloride, oxalyl chloride, phosphorus (III) chloride, phosphorus (V) chloride, phosphorus (V) oxychloride, and combinations thereof. In a preferred embodiment, the chlorinating agent is sulfuryl chloride, chlorine gas, or a combination thereof. More preferably, the chlorinating agent is chlorine gas.

[0024] While substoichiometric amounts of chlorinating agents may be used, generally, the chlorinating agent is used in excess. The molar ratio of the chlorinating agent to the chloroalkene, chlorofluoroalkene, or combinations thereof may range from 1.0:1.0 to about 1000:1. In various embodiments, the molar ratio of the molar ratio of the chlorinating agent to the chloroalkene, chlorofluoroalkene, or combinations thereof may range from 1 : 1 to about 1000: 1 , from 2: 1 to about 750: 1 , from 3: 1 to about 100: 1 , or from 4:1 to about 50:1. The chlorinating agent is essentially dry, i.e. , it has a water content of the below 1000 ppm. Lower water concentrations are preferred, but not required.

(iii) catalyst

[0025] A catalyst is used in the chlorination reaction. As used herein, the term “catalyst” refers to an elemental metal, a metal containing alloy, or combinations thereof. As appreciated by the skilled artisan, the oxidation state of suitable metals are in the (0) oxidation state. The catalyst, as described herein, does not utilize a ligand or a promoter. Non-limiting examples of metals which may be utilized as a catalyst include iron, copper, aluminum, titanium, nickel, manganese, cobalt, chromium, tin, antimony, zinc, gold, zirconium, silicon, molybdenum, niobium, tungsten, vanadium, or

combinations thereof. Non-limiting examples of metal containing alloys that may be used in the process may be an alloy of aluminum, an alloy of chromium, an alloy of cobalt, an alloy of copper, an alloy of iron, an alloy of titanium, an alloy of nickel, an alloy of manganese, an alloy of tin, an alloy of antimony, an alloy of zinc, an alloy of gold, an alloy of zirconium, an alloy of silicon, an alloy of molybdenum, an alloy of niobium, an alloy of tungsten, an alloy of vanadium, or combinations thereof. Non- limiting common names for these alloys include 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. In a further embodiment, the catalyst is selected from a group consisting of cast iron, pig iron, Damascus steel, wrought iron, anthracite iron, wootz steel, carbon steel, crucible steel, blister steel, and combinations thereof. In a preferred embodiment, the catalyst is iron, an iron alloy, carbon steel, or combinations thereof.

[0026] In various embodiments, the configuration of the catalyst may be of various dimensions, shapes, thicknesses, and weights. Non-limiting examples of configurations of the catalyst may be a foil, a screen, a rod, a wire, a ball, a ball bearing, a tube, a ferrule, a nut, a bolt, a nail, a coil, a plate, a sheet, a pipe or combinations thereof. In another embodiment, the catalyst may be suspended within the reaction mixture or affixed to the reactor below the surface of the reaction mixture so the catalyst contacts the reaction mixture. In other embodiments, the catalyst may be part of a fixed bed or a tray.

[0027] In various embodiments, the catalyst is in the form of a structured or unstructured packing. Non-limiting examples of structured packing may be Flexipac ®, Flexipac HC ®, Intalox ®, Sulzer ®, wire gauze structured packing, or combinations thereof. These structured packing may in various sizes, configurations, and corrugation sizes. Non-limiting examples of corrugation sizes may be extruded, perforated and waffled, perforated and grooved, perforated, smooth, and combinations thereof. Non- limiting examples of unstructured packing may be Flexiring ®, Fly-Pak ®, IMTP ®, Intalox ®, Ultra ®, or combinations thereof. These unstructured packing may be in various sizes and configurations.

[0028] In other embodiments, the catalyst may be a part in the reactor assembly. Non-limiting assembly parts of a reactor may be a reactor wall, a stirrer blade, an impeller blade, a stirrer shaft, a draft tube insert, a stirrer, a static mixer, a baffle, or combinations thereof. The catalysts described, used, and claimed herein do not cover the metals used to make the reactor. Such metals are believed to not catalyze the chlorination reaction and if they do catalyze the reaction, they have insufficient surface area to be commercially viable. [0029] As appreciated by the skilled artisan, the catalyst, once in the process, may undergo and oxidation and/or reduction to produce an activated catalytic species in various oxidation states. The oxidation state of these active iron catalytic species may vary, and include iron having oxidation states of (I), (II), and/or (III). In one aspect, the active iron catalyst may in the Fe(l) oxidation state. In another aspect, the active iron catalyst may be Fe(ll). In still another aspect, the active iron catalyst may be in the Fe(lll) oxidation state. In an additional aspect, the active iron catalyst may comprise a mixture of Fe(l) and Fe(ll). In still another aspect, the active iron catalyst may comprise a mixture of Fe(l) and Fe(lll) oxidation states. In yet another aspect, the active iron catalyst may be in the Fe(ll) and Fe(lll) oxidation states. In another aspect, the active iron catalyst may in the Fe(l), Fe(ll) and Fe(lll) oxidation states. In still another embodiment, an electrochemical cell may be utilized to adjust the ratio of Fe(l), Fe(ll), and Fe(lll) in the process.

[0030] In general, the weight ratio of the catalyst to the starting material is from about 0.0001 : 1 to about 1000: 1 . In various embodiments, the weight ratio of the catalyst to the starting material is from 0.0001 : 1 to about 1000:1 , from 0.0001 : 1 to about 500:1 , from about 0.001 : 1 to about 250:1 , from about 0.01 :1 to about 100: 1 , from about 0.1 :1 to about 50: 1 , or from about 1 : 1 to about 10:1 .

[0031 ] In general, the surface area per unit reactor volume of the catalyst may range 1 to about 10,000 cm²/(kg/hr) of reactants. In various embodiments, the surface area of the catalyst may range 1 to about 10,000 cm²/(kg/hr), from 10 to about 5,000 cm²/(kg/hr), from 100 to about 3,000 cm²/(kg/hr), or from 500 to about 2,000 cm²/(kg/hr) of reactants.

(b) reaction conditions

[0032] As appreciated by the skilled artisan, the above processes may be run in a batch mode, semi-batch mode, or a continuous mode, with continuous mode preferred. Additionally, the skilled artisan appreciates the processes are conducted in a reactor which would not participate in the process such as a hastelloy or a glass reactor. [0033] In a continuous mode, a stirred tank reactor may be used, or a series of stirred tank reactors to approach the performance of an ideal plug flow reactors may be utilized to improve the overall efficiency of the process. In another embodiment, the process in continuous modes may be stirred in various methods to improve the mixing of the components as appreciated by the skilled artisan.

[0034] There are many methods to adequately stir the process. In various embodiments, jet mixing utilizing at least one nozzle may be used. In other

embodiments, jet mixing utilizing at least one eductor may be utilized. In still other embodiments, jet mixing utilizing at least one nozzle and at least one eductor may be utilized.

[0035] Jet mixing utilizing at least one nozzle, as appreciated by the skilled artisan, withdraws a portion of the reactor liquid effluent (the liquid phase of the reaction mixture) and recycling the reactor liquid effluent into the reactor by feeding the recycle stream and other fresh liquid feed through at least one nozzle, thereby creating turbulence in the liquid phase. The at least one nozzle may be positioned below the surface of the liquid phase, thereby creating turbulence in the liquid phase and providing increased mixing. The at least one nozzle may be positioned at the surface of the reaction mixture or above the surface of the reaction mixture directed into the reaction mixture, thereby providing increased turbulence of the reaction mixture and mixing the gaseous and liquid components of the reaction mixture.

[0036] Jet mixing utilizing at least one eductor, as appreciated by the skilled artisan, withdraws at least a portion of the reactor liquid effluent and pumps the reactor liquid effluent back into the reactor through at least one gas educting nozzle. The eductor nozzle provides suction in the eductor which pulls gas from the headspace of the reactor, mixes the gas with the circulated reactor liquid effluent, and returns the resulting mixture of liquid and gas back into the liquid phase of the reactor. When the flow from the eductor nozzle is directed towards the liquid phase of the reaction mixture, increased turbulence of the reaction mixture results. If desired, the jet mixing may be accomplished by feeding at least a portion of a recycle stream through an eductor. [0037] Jet mixing may also utilize at least one nozzle and at least one eductor. In this configuration, as described above, increased turbulence in the reaction mixture but also increased gas absorption of the gas into the liquid phase may be realized.

[0038] As appreciated by the skilled artisan, at least one of the above described methods or a combination of these may be utilized in the process. In a preferred embodiment, jet mixing using at least one eductor nozzle wherein the flow from the eductor nozzle is directed towards the liquid phase of the reaction mixture is utilized.

[0039] In general, the process for the preparation of chlorinated alkanes will be conducted to maintain the temperature from about -30°C to about 90°C utilizing either an internal or external heat device or a cooling device. In various embodiments, the temperature of the reaction may be maintained from about -30°C to about 90°C, from - 10°C to about 70°C, from 0°C to 60°C, from 10°C to about 50°C, from 15°C to 50°C or from about 25°C to about 40°C.

[0040] Generally, the process may be conducted at a pressure of -14 psig to about 200 psig so the reaction may proceed and maintain the kinetics of the process. In various embodiments, the pressure of the process may be from about -14 psig to about 200 psig, from 0 to 120 psig, from about -7 psig to about 100 psig, from about 0 psig to about 75 psig, or from 10 psig to about 40 psig.

[0041 ] Generally, the reaction is allowed to proceed for a sufficient period of time until the conversion to the desired chlorinated alkane is greater than 70%. In other embodiments, the reaction is allowed to proceed for a sufficient period of time until the conversion to the desired chlorinated alkane is greater than 95%, 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 may range from about 5 minutes to about 16 hours. In some embodiments, the duration of the reaction may range from about 5 minutes to about 16 hours, from about 30 minutes to about 12 hours, from about 1 hour to about 5 hours, or from about 2 hours to about 3 hours. (c) output from the process

[0042] The process, as outlined above, produces chloroalkanes,

chlorofluoroalkanes, or combinations thereof. In general, the process produces the chloroalkanes, chlorofluoroalkanes, or combinations thereof in at least 95% selectivity.

In various embodiments, the chloroalkanes, chlorofluoroalkanes, or combinations thereof are produced in a selectivity of at least 95%, in at least 96%, in at least 97%, in at least 98%, in at least 99%, or in at least 99.5%.

[0043] In general, the process converts one or more chloroalkene, fluoroalkene, chlorofluoroalkene, or combinations thereof to the product chloroalkanes,

chlorofluoroalkanes, or combinations thereof in a conversion of at least 50%. The skilled artisan understands the percent conversion (% conversion) is determined by the percentage of the one or more chlorinated alkene, fluorinated alkene,

chlorofluoroalkene, or combinations thereof converted to the produces chloroalkanes, chlorofluoroalkanes, or combinations thereof. In various embodiments, the %

conversion of the process is at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 99%, or even 100%.

[0044] In general, the process produces the product chloroalkanes,

chlorofluoroalkanes, or combinations thereof in at least 50 weight percent (wt%) in the reaction mixture of the reactor. In various embodiments, the chloroalkanes,

chlorofluoroalkanes, or combinations thereof are produced in at least 50 wt%, in at least 60 wt%, in at least 70 wt%, in at least 80 wt%, in at least 90 wt%, in at least 95 wt%, or in at least 99 wt% in the reaction mixture of the reactor.

[0045] Generally, the process produces chloroalkanes, chlorofluoroalkanes, or combinations thereof with little or no heavy by-products. These heavy by-products are produced in less than 5 weight % in the entire product distribution. In various

embodiments, these heavy by-products may be less than 5 weight %, less than 1 weight %, less than 0.5 weight %, or less than 0.1 weight %.

[0046] In an embodiment, the process produces chloroalkanes,

chlorofluoroalkanes, or a combination thereof which is a pentachloropropane. In preferred embodiments, the chloroalkanes, chlorofluoroalkanes, or a combination thereof is 1 ,1 ,1 ,2,3,-pentachloropropane (240DB).

[0047] In an embodiment, the process produces a product that comprises a chloroalkane that is ethylene dichloride, which can be prepared from an alkene that is ethylene.

(II) Separation of the Chloroalkane, Chlorofluoroalkane, or Combinations Thereof and Recycle Streams

[0048] The first step in the separation of the chloroalkanes, chlorofluoroalkanes, or a combination thereof comprises removal of the catalyst and/or deactivated catalyst from the reaction mixture and thereby producing a reactor liquid effluent. In various embodiments, the catalyst may be removed from the reaction mixture by decantation, filtration, extraction, or combinations thereof. Other methods known to the skilled artisan may be utilized in this capacity.

[0049] The next step in the process comprises separating purified chloroalkanes, chlorofluoroalkanes, or a combination thereof from the reactor liquid effluent which comprises starting material and at least one chlorinating agent, by using a separator. Since the selectivity of the process, as described herein is at least 95% and the % conversion is at least 50%, removal of the unreacted starting material and chlorinating agent(s) produces a chlorinated alkane with high purity. Since the purity of the chloroalkanes, chlorofluoroalkanes, or a combination thereof is high, no additional purifications are required. But if desired, additional purification steps may be used.

[0050] In various embodiments, the separator may be a distillation column or a multistage distillation column which comprises at least one theoretical plate. Non- limiting examples of distillations may be a simple distillation or a vacuum distillation. Additionally, the 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 divided 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 where the product effluent streams comprise chlorinated alkene, the chlorinated alkane, chlorinating agent, heavy by-products, or combinations thereof. A portion of various product effluent streams produced by the process may be recycled back into the reactor to provide increased kinetics, increased efficiencies, reduced overall cost of the process, increased selectivity of the desired chloroalkane, chlorofluoroalkane, or combinations thereof, and increased yield of the desired chloroalkane, chlorofluoroalkane, or combinations thereof.

[0051 ] As appreciated by the skilled artisan, separating the purified chlorinated alkane, chlorofluoroalkane, or combinations thereof from the reactor liquid effluent would produce at least two product effluent streams. In various embodiments, separating the purified chlorinated alkane, chlorofluoroalkane, or combinations thereof from the reactor liquid effluent may produce three, four, or more product effluent streams depending on the separation device utilized. As an example, the separation of the purified chlorinated alkane, chlorofluoroalkane, or combinations thereof from the reactor liquid effluent using two product effluent streams is described below.

[0052] The process utilizing one separator commences by transferring at least a portion of the reactor liquid effluent into the separator. In this operation, a portion of the reactor liquid effluent may be separated into two distinct product effluent streams, product effluent stream (a) and (b). Product effluent stream (a) comprises the starting material, which is separated from product effluent stream (b) which comprises the product, i.e., the chloroalkane, chlorofluoroalkane, or a combination thereof.

[0053] In another embodiment, a portion of product effluent stream (a) may be further transferred into additional separators to achieve the desired purity of the starting material.

[0054] In various embodiments, at least a portion of product effluent stream (a) is recycled back into the reactor in a recycle stream. This product effluent stream may also be fed into another process to produce other products. These steps may be performed in order to improve the efficiency, reduce the cost, reduce contaminants, and increase through-put of the process. [0055] In another embodiment, at least a portion of product effluent stream (a) may be mixed with fresh material feeds comprising starting material, the chlorinating agent, the catalyst, or combinations thereof, before being recycled back into the reactor, in batch mode or continuous mode. In various embodiments, the product effluent stream and fresh material feed streams may be introduced into the reactor separately or mixed together before entering the process. Or the fresh material feed comprising fresh alkene(s), chlorinated alkenes, fluorinated alkenes, chlorofluoroalkenes, or

combinations thereof, the chlorinating agent; and/or the catalyst is mixed with the recycle stream before being recycled back to the reactor. The introduction of these fresh material feed streams into the reactor or mixing the product effluent streams with fresh feeds increases the efficiency of the process, reduces the overall cost, maintains the kinetics, increase the through-put, and reduces the by-products produced by the process. The amount of the product effluent stream recycled to the reactor or fresh material feeds added to the reactor may be the same or different. One way to measure the amount of product effluent stream and/or fresh material 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 material feeds being added to the reactor has a fresh material feed mass flow. Mass flows may be measured using methods known in the art.

[0056] Generally, the mass ratio of the product effluent stream mass flow being recycled to the fresh material 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) comprising the chloroalkane,

chlorofluoroalkane, or combinations thereof produced in the process may have a yield of at least about 20%. In various embodiments, the product effluent stream (b) comprising the chloroalkane, chlorofluoroalkane, or combinations thereof produced in the process may have a yield of at least about 30%, 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%. [0058] Product effluent stream (b) may have a weight% of at least 95 wt%. In various embodiments, the weight percentage of the chloroalkane, chlorofluoroalkane, or combinations thereof may have a weight percentage of at least 95wt%, of at least 96 wt%, of at least 97 wt%, of at least 98 wt%, of at least 99 wt%, or at least 99.5 wt%.

(Ill) Preferred Embodiments: 1, 1, 1,2,3-Pentachloropropane

(a) process for the preparation of 1,1,1,2,3-pentachloropropane

[0059] Another aspect of the present disclosure encompasses processes for the preparation of 1 , 1 , 1 ,2,3-tetrachloropropane (240DB). The process commences by contacting 1 ,1 ,3-trichloropropene, 3,3,3-trichloropropene, or combinations thereof, at least one chlorinating agent, and at least one metal catalyst under the reaction conditions described above. The chlorinating agent is described above in Section (l)(a)(ii) and the catalyst is described in Section (l)(a)(iii). In a preferred embodiment, the chlorinating agent is sulfuryl chloride, chlorine gas, or combinations thereof and the catalyst is iron, an alloy of iron, carbon steel, or combinations thereof.

[0060] In another embodiment, the chlorinating agent comprises chlorine gas and the catalyst comprises iron. In a more preferred aspect, the one or more chlorinated alkenes comprise liquid 1 ,1 ,3-trichloropropene, 3,3,3-trichloropropene, or combinations thereof.

(b) reaction conditions

[0061 ] The reaction conditions are described above in Section (l)(b).

(c) output from the process to prepare 1 ,1 ,1 ,2,3-pentachloropropane

[0062] In a preferred embodiment, the process produces 1 ,1 ,1 ,2,3- pentachloropropane. As appreciated by the skilled artisan, the process is conducted to minimize the formation of byproducts and maximize the formation of 1 ,1 ,1 ,2,3- pentachloropropane by maximizing the selectivity of 1 ,1 ,1 ,2,3-pentachloropropane.

After removal of the unreacted trichloropropenes, and the chlorinating agents, the 1 ,1 ,1 ,2,3-pentachloropropane may be used directly without further purification or the

1 ,1 ,1 ,2,3-pentachloropropane may be further purified to achieve the desired purity.

[0063] In general, the process produces the 1 ,1 ,1 ,2,3-pentachloropropane in at least 20 weight percent (wt%) in the reaction mixture of the reactor. In various embodiments, the 1 ,1 ,1 ,2,3-pentachloropropane is produced in at least 20 wt%, in at least 50 wt%, in at least 70 wt%, in at least 80 wt%, in at least 90 wt%, in at least 95 wt%, in at least 99 wt% or in at least 99.9 wt% in the reaction mixture of the reactor.

[0064] Generally, the process produces 1 ,1 ,1 ,2,3-pentachloropropane with little or no heavy by-products. These heavy by-products are produced in less than 1 weight % in the entire product distribution. In various embodiments, these heavy impurities or heavy by-products may be less than 1 weight %, less than 0.5 weight %, less than 0.25 weight %, or less than 0.1 weight %.

(d) separation of 1 ,1 ,1 ,2,3-pentachloropropane and recycle streams

[0065] The separation of the 1 ,1 ,1 ,2,3-pentachloropropane and recycle streams is described in Section (II).

[0066] 1 ,1 ,1 ,2,3-Pentachloropropane produced in the process may have a yield of at least about 20%. In various embodiments, the 1 ,1 ,1 ,2,3-pentachloropropane produced in the process may have a yield of at least about 20%, at least about 50%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, or at least about 99%.

[0067] 1 ,1 ,1 ,2,3-Pentachloropropane produced in the above process may have a weight% of at least 95 wt%. In various embodiments, the weight percentage of the

1 ,1 ,1 ,2,3-pentachloropropane may have a weight percentage of at least 95wt%, of at least 96 wt%, of at least 97 wt%, of at least 98 wt%, of at least 99 wt%, or at least 99.5 wt%.

(e) process for the preparation of ethylene dichloride

[0068] Another aspect of the present disclosure encompasses processes for the preparation of ethylene dichloride. The process commences by contacting ethylene, at least one chlorinating agent, and at least one metal catalyst under the reaction conditions described above. The chlorinating agent is described above in Section (l)(a)(ii) and the catalyst is described in Section (l)(a)(iii). In a preferred embodiment, the chlorinating agent is sulfuryl chloride, chlorine gas, or combinations thereof and the catalyst is iron, an alloy of iron, carbon steel, or combinations thereof.

[0069] In another embodiment, the chlorinating agent comprises chlorine gas and the catalyst comprises iron.

(f) reaction conditions

[0070] The reaction conditions are described above in Section (l)(b).

(g) output from the process to prepare ethylene dichloride

[0071 ] In a preferred embodiment, the process produces ethylene dichloride. As appreciated by the skilled artisan, the process is conducted to minimize the formation of byproducts and maximize the formation of ethylene dichloride. After removal of the unreacted ethylene, and the chlorinating agents, the ethylene dichloride may be used directly without further purification or it may be further purified to achieve the desired purity.

[0072] In general, the process produces the ethylene dichloride in at least 20 weight percent (wt%) in the reaction mixture of the reactor. In various embodiments, it is produced in at least 20 wt%, in at least 50 wt%, in at least 70 wt%, in at least 80 wt%, in at least 90 wt%, in at least 95 wt%, in at least 99 wt% or in at least 99.9 wt% in the reaction mixture of the reactor.

[0073] Generally, the process produces ethylene dichloride with little or no heavy by-products. These heavy by-products are produced in less than 1 weight % in the entire product distribution. In various embodiments, these heavy impurities or heavy by- products may be less than 1 weight %, less than 0.5 weight %, less than 0.25 weight %, or less than 0.1 weight %. (h) separation of ethylene dichloride and recycle streams

[0074] The separation of the ethylene dichloride and recycle streams is described in Section (II).

[0075] The ethylene dichloride produced in the process may have a yield of at least about 20%. In various embodiments, it is produced in 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%.

[0076] The ethylene dichloride produced in the above process may have a weight% of at least 95 wt%. In various embodiments, the weight percentage of the ethylene dichloride may have a weight percentage of at least 95wt%, of at least 96 wt%, of at least 97 wt%, of at least 98 wt%, of at least 99 wt%, or at least 99.5 wt%.

(IV) Further Reaction of the Chloroalkanes, Chlorofluoroalkanes, or Combinations

Thereof

[0077] In one aspect, disclosed herein are processes for the conversion of the chloroalkane, chlorofluoroalkane, or combinations thereof, such as 1 , 1 , 1 ,2,3- pentachloropropane or ethylene dichloride, to one or more hydrofluoroolefins and/or fluorinated products. These processes comprise contacting the chloroalkane, chlorofluoroalkane, or combinations thereof with a fluorinating agent in the presence of a fluorination catalyst, in a single reaction or two or more reactions. These processes can be conducted in either gas phase or liquid phase with the gas phase being preferred at temperatures ranging from 50°C to 400°C.

[0078] Generally, a wide variety of fluorinating agents can be used. Non-limiting examples of fluorinating agents include HF, F₂, CIF, AIF₃, KF, NaF, SbF₃, SbF₅, SF₄, or combinations thereof. The skilled artisan can readily determine the appropriate fluorination agent and catalyst. Examples of hydrofluoroolefins that may be produced utilizing these processes include, but are not limited to 2,3,3,3-tetrafluoroprop-1 -ene (FIFO-1234yf), 1 ,3,3,3-tetrafluoroprop-1 -ene (FIFO-1234ze), 3,3,3-trifluoroprop-1 -ene (FIFO-1243zf), and 1 -chloro-3,3,3-trifluoroprop-1 -ene (HFCO-1233zd). DEFINITIONS

[0079] 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.

[0080] The term“113e” refers to 1 ,1 ,3-trichloropropene.

[0081 ] The term“333e” refers to 3,3,3-trichloropropene.

[0082] 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

[0083] The following examples illustrate various embodiments of the invention.

Example 1: Preparation of 1,1, 1,2, 3-Pentachloropropane (No catalyst, wet

Trichloropropenes)

[0084] Into a round bottom flask equipped with a reflux condenser was introduced 20 mL a mixture of 1 ,1 ,3-trichloropropene and 3,3,3-trichloropropene (113e and 333e) (wet). The reactor was stirred using magnetic stirring. The flask was purged with nitrogen and then warmed to 80°C by an oil bath. Chlorine gas was added continuously introduced subsurface at rate of 0.06-0.1 g/ minute to the reactor using a 1/16” PTFE tube. Samples were removed from the reaction at specific times and each sample was evaluated by gas chromatography.

Example 2: Preparation of 1,1, 1,2, 3-Pentachloropropane (No catalyst, dry

Trichloropropenes)

[0085] Into a round bottom flask equipped with a reflux condenser was introduced 20 mL a mixture of 113e and 333e which was dried over molecular sieves. The reactor was stirred using magnetic stirring. The flask was purged with nitrogen and then warmed to 80°C by an oil bath. Chlorine gas was added continuously introduced subsurface at rate of 0.06-0.1 g/ minute to the reactor using a 1/16” PTFE tube.

Samples were removed from the reaction at specific times and each sample was evaluated by gas chromatography.

Example 3: Preparation of 1,1,1,2,3-Pentachloropropane (316L SS ferrules, wet Trichloropropenes)

[0086] Into a round bottom flask equipped with a reflux condenser was introduced 20 ml_ a mixture of 113e and 333e (wet) and four, ½” 316L stainless steel ferrules. The reactor was stirred using magnetic stirring. The flask was purged with nitrogen and then warmed to 80°C by an oil bath. Chlorine gas was added continuously introduced subsurface at rate of 0.06-0.1 g/ minute to the reactor using a 1/16” PTFE tube.

Samples were removed from the reaction at specific times and each sample was evaluated by gas chromatography. The stainless steel ferrules were removed, washed, and dried. The stainless steel ferrules showed no weight change.

Example 4: Preparation of 1,1,1,2,3-Pentachloropropane (316L SS ferrules, dry Trichloropropenes)

[0087] Into a round bottom flask equipped with a reflux condenser was introduced 4, ½” 316L stainless steel ferrels and 20 ml_ a mixture of 113e and 333e which was dried over molecular sieves. The reactor was stirred using magnetic stirring. The flask was purged with nitrogen and then warmed to 80°C by an oil bath. Chlorine gas was added continuously introduced subsurface at rate of 0.06-0.1 g/ minute to the reactor using a 1/16” PTFE tube. Samples were removed from the reaction at specific times and each sample was evaluated by gas chromatography. The stainless steel ferrules were removed, washed, and dried. The stainless steel ferrules showed no weight change. Example 5: Preparation of 1,1,1,2,3-Pentachloropropane (Monel ferrules, wet Trichloropropenes)

[0088] Into a round bottom flask equipped with a reflux condenser was introduced 20 ml_ a mixture of 113e and 333e (wet) and 4, ½” Monel ferrules. The reactor was stirred using magnetic stirring. The flask was purged with nitrogen and then warmed to 80°C by an oil bath. Chlorine gas was added continuously introduced subsurface at rate of 0.06-0.1 g/ minute to the reactor using a 1/16” PTFE tube. Samples were removed from the reaction at specific times and each sample was evaluated by gas

chromatography. The Monel ferrules were removed, washed, and dried. The Monel ferrules showed an increase in weight by 0.13 weight %.

Example 6: Preparation of 1,1,1,2,3-Pentachloropropane (Monel ferrules, dry Trichloropropenes)

[0089] Into a round bottom flask equipped with a reflux condenser was introduced four, ½” Monel ferrules and 20 ml_ of a mixture of 113e and 333e which was dried over molecular sieves. The reactor was stirred using magnetic stirring. The flask was purged with nitrogen and then warmed to 80°C by an oil bath. Chlorine gas was added continuously introduced subsurface at rate of 0.06-0.1 g/ minute to the reactor using a 1/16” PTFE tube. Samples were removed from the reaction at specific times and each sample was evaluated by gas chromatography. The Monel ferrules were removed, washed, and dried. The Monel ferrules showed an increase in weight by 0.28 weight %.

Example 7: Preparation of 1,1,1,2,3-Pentachloropropane (Carbon Steel, wet Trichloropropenes)

[0090] Into a round bottom flask equipped with a reflux condenser was introduced 20 ml_ a mixture of 113e and 333e (wet) and pieces of carbon steel to provide a surface area equivalent to the ferrules. The reactor was stirred using magnetic stirring. The flask was purged with nitrogen and then warmed to 80°C by an oil bath. Chlorine gas was added continuously introduced subsurface at rate of 0.06-0.1 g/ minute to the reactor using a 1/16” PTFE tube. Samples were removed from the reaction at specific times and each sample was evaluated by gas chromatography. The carbon steel pieces were removed, washed, and dried. The carbon steel pieces showed a decrease in weight by 0.08 weight %.

Example 8: Preparation of 1,1,1,2,3-Pentachloropropane (Carbon Steel, dry

Trichloropropenes)

[0091 ] Into a round bottom flask equipped with a reflux condenser was introduced pieces of carbon steel and 20 ml_ of a mixture of 113e and 333e which was dried over molecular sieves. The reactor was stirred using magnetic stirring. The flask was purged with nitrogen and then warmed to 80°C by an oil bath. Chlorine gas was added continuously introduced subsurface at rate of 0.06-0.1 g/ minute to the reactor using a 1/16” PTFE tube. Samples were removed from the reaction at specific times and each sample was evaluated by gas chromatography. The carbon steel pieces were removed, washed, and dried. The carbon steel pieces showed a decrease in weight by 4.39 weight %.

[0092] Figure 1 shows the percent conversion of 113e/333e to 240DB for each of the above examples. As Figure 1 indicates, the conversion of 113e/333e is faster in carbon steel as compared to stainless steel or a glass reactor. Monel ferrules showed similar conversion when wet trichloropropene was used.

Examples 9-17: Preparation of 1 ,1 ,1 ,2,3-Pentachloropropane

[0093] To an autoclave equipped with stirring and temperature control was added 10 ml of purified 1 ,1 ,3-trichloropropene. The vessel was closed and purged with nitrogen two times and then with chlorine two times by padding to about 50 psig and then de-padding to 0 psig. Chlorine gas then was fed continuously to maintain a specified pressure. Temperature rose about 15°C beyond the specified set point for about 10 minutes due to heat of chlorine absorption and reaction, and then was brought under control. In Runs 8, 9, 10 and 21 , no special drying procedures were conducted and the liquid contained about 100 ppm water. In Run 17, about 1 ml water was added such that an aqueous phase existed. In Runs 19, 20, 23 and 24, the liquid was dried with molecular sieve to about 7 ppm water and was introduced without air contact. In Run 21 , about 0.003 g FeCI₃ was added. In Runs 20, 23 and 24, a coil of pure iron wire 1.2 mm diameter X 30.5 cm length was added in the bottom of the autoclave. All runs were continued until conversion was near complete. Samples were taken and analyzed by gas chromatography.

[0094] Figure 2 shows the progress of conversion during each run. Generally, conversion was faster with higher temperature and pressure, and under wet conditions with FeCI₃ or iron wire present. Figure 3 shows the resulting product purity versus conversion. This number is the mole percent 240DB if everything lighter than 240DB were distilled out of the product. Addition of iron wire or FeCI₃ improved product purity at high conversion. Lower temperature also yielded a small improvement.

Examples 18-26 Preparation of 1,1,1,2,3-Pentachloropropane

[0095] To an autoclave equipped with stirring and temperature control was added 10 ml of purified blend of 1 ,1 ,3- and 333-trichloropropene. The vessel was closed and purged with nitrogen two times and then with chlorine two times by padding to about 50 psig and then de-padding to 0 psig. Chlorine gas was then fed continuously to maintain a specified pressure. Temperature rose about 15°C beyond the specified set point for about 10 minutes due to heat of chlorine absorption and reaction, and then was brought under control at 35°C. In Runs 30, 32, 35-37 and 42 no special drying procedures were conducted and the liquid contained about 100 ppm water. In Runs 27, 28 and 31 , the liquid was dried with molecular sieve to about 7 ppm water and was introduced without air contact. In Runs 27, 28, 32 and 37, a coil of pure iron wire 1.2 mm diameter X 30.5 cm length was added in the bottom of the autoclave. In Runs 35, 42 and 36, additional wire was added to provide 2, 3 and 4 times the iron surface area, respectively. In Run 36, steel wire of smaller diameter was used. All runs were continued until conversion was near complete. Samples were taken and analyzed by gas chromatography. [0096] Figure 4 shows the progress of conversion during each run. Generally, conversion was faster with higher pressure, and under wet conditions with more iron wire present, except for Run 42 with 3 times the original amount of iron, which started off more slowly for unknown reasons. In Run 37, the pressure was lower and a water phase was present. Figure 5 shows the resulting product purity versus conversion. This number is the mole percent 240DB if everything lighter than 240DB were distilled out of the product. Comparing Runs 31 and 32 without iron wire, wetness had a negative impact on purity. Addition of iron wire under dry conditions in Runs 27 and 28 improved product purity slightly as compared to Run 31. Addition of iron wire under wet conditions in Run 32 improved product purity significantly as compared to Runs 27 and 28. Very wet conditions (water phase) in Run 37 improved even further. Addition of higher amounts of iron in Runs 35, 36 and 42 under wet conditions improved purity compared to the baseline amount of iron in Run 32.

[0097] In the figures, which as described above, were run at small or lab scale, one or more of the following abbreviations appear: 20# is 20psig; Fe3X means three times the surface area of“Fe” by itself; 35 C means 35 degrees centigrade; dry means about 7 ppm water; wet means about 100 ppm water; while very wet (v. wet) means a water phase existed.

Claims

CLAIMS What is claimed is:

1. A process for producing a chloroalkane, chlorofluoroalkane, or

combinations thereof, the process comprising:

a) preparing a reaction mixture in a reactor comprising one or more alkenes, chlorinated alkenes, fluorinated alkenes, chlorofluoroalkenes, or combinations thereof, a chlorinating agent; and a catalyst comprising at least one of a metal, a metal alloy, or combinations thereof; b) producing a product effluent stream comprising chloroalkane and/or a chlorofluoroalkane, and heavy by-products.

2. The process of claim 1 , wherein the process is stirred.

3. The process of claim 2, wherein stirring the reaction mixture comprises conventional stirring, jet mixing, mixing though at least one eductor, or combinations thereof.

4. The process of claim 1 , wherein at least one chlorinated alkene comprises 2 carbon atoms to 6 carbon atoms.

5. The process of claim 4, wherein at least one chlorinated alkene comprises a trichloropropene.

6. The process of claim 5, wherein the trichloropropene comprisesl ,1 ,3- trichloropropene, 3,3,3-trichloropropene, or combinations thereof.

7. The process of claim 1 , wherein the chlorinated alkane comprises two additional chlorine atoms as compared to the chlorinated alkene.

8. The process of claim 7, wherein the chlorinated alkane is a

pentachloropropane.

9. The process of claim 8, wherein the pentachloropropane is 1 ,1 ,1 ,2,3- pentachloropropane (240DB).

10. The process of any one of the claims 1 -9, wherein the chlorinating agent comprises chlorine, sulfuryl chloride, oxalyl chloride, thionyl chloride, phosphorus (III) chloride, phosphorus (V) chloride, phosphorus (V) oxychloride, or

combinations thereof.

11. The process of claim 9, wherein the chlorinating agent is chlorine, sulfuryl chloride or combinations thereof.

12. The process of any one of the claims 1 -11 , wherein the catalyst comprises iron, aluminum, titanium, nickel, manganese, cobalt, chromium, tin, antimony, zinc, gold, zirconium, silicon, molybdenum, niobium, tungsten, vanadium, or combinations thereof.

13. The process of any one of the claims 1 -12, wherein catalyst comprises an alloy of aluminum, an alloy of chromium, an alloy of cobalt, an alloy of iron, an alloy of titanium, an alloy of nickel, an alloy of manganese, an alloy of tin, an alloy of antimony, an alloy of zinc, an alloy of zirconium, an alloy of gold, an alloy of silicon, an alloy of molybdenum, an alloy of niobium, an alloy of tungsten, an alloy of vanadium, or combinations thereof.

14. The process of any one of the claims 1 -13, wherein the catalyst is iron metal, an iron alloy, carbon steel, or combinations thereof.

15. The process of claim 14, wherein the catalyst is selected from a group consisting of cast iron, pig iron, Damascus steel, wrought iron, anthracite iron, wootz steel, carbon steel, crucible steel, blister steel, and combinations thereof.

16. The process of claims 13-15, wherein the metal alloy is in the form of a structured or unstructured packing.

17. The process of any one of the claims 1 -16, wherein the temperature of the process is from about -30°C to 90°C.

18. The process of any one of the claims 1 -17, wherein the pressure of the process is from about -14.0 psig to about 200 psig.

19. The process of any one of the claims 1 -18, wherein the process may be batch or continuous.

20. The process of any one of the claims 1 -19, wherein the selectivity of the process is at least 50%.

21. The process of any one of the claims 1 -20, wherein the conversion of the process is at least 50%.

22. A process according to claim 1 for producing 1 ,1 ,1 ,2,3- pentachloropropane, the process comprising:

a) preparing a reaction mixture comprising 1 ,1 ,3-trichloropropene, 3,3,3- trichloropropene, or combinations thereof, chlorine, and a catalyst comprising at least one of iron metal, iron alloy, and carbon steel;

b) producing 1 ,1 ,1 ,2,3-pentachloropropane.

23. A process according to claim 22, wherein the catalyst is carbon steel.

24. A process according to any one of claims 22 or 23, wherein the reaction temperature is 0°C to 60°C.

25. A process according to anyone of claims 22-24, wherein the reaction temperature is 15°C to 50°C.

26. A process according to anyone of claims 22-25, wherein the reaction pressure is 0 to 120 psig.

27. A process according to any one of claims 1 -26, wherein the one or more liquid alkenes, and/or chlorinated alkenes are dried.

28. A process according to any one of claims 1 -27, wherein the one or more liquid chlorinated alkenes contains greater than 1 ppm water.

29. A process according to any one of claims 1 -28, wherein the reaction is continuous.

30. The process according to any one of the claims 22 or 23, wherein the catalyst is in the form of a structured or unstructured packing.

31. The process according to any one of the claims 1 -30, wherein the catalyst comprises an iron metal or iron alloy.

32. The process according to any one of the claims 1 -31 , wherein at least a portion of the product effluent stream is recycled back to the reactor in a recycle stream, wherein the recycle stream comprise the chlorinated alkenes, fluorinated alkenes, chlorofluoroalkenes, or combinations thereof, the chlorinating agent; and/or the catalyst, or combinations thereof.

33. The process of claim 32, wherein fresh material feed comprising fresh alkenes, chlorinated alkenes, fluorinated alkenes, chlorofluoroalkenes, or combinations thereof, the chlorinating agent; and/or the catalyst is mixed with the recycle stream before being recycled back to the reactor.

34. The process of any one of claims 3-33, wherein the jet mixing is at least partly accomplished by withdrawing at least a portion of the reactor liquid effluent and recycling the reactor liquid effluent back into the reactor by feeding the recycle stream and other fresh liquid feed through at least one gas educting nozzle.

35. The process according to any one of the claims 1 -34, wherein the chloroalkanes, chlorofluoroalkanes, or combinations thereof are converted to one or more fluorinated products.

36. The process of any one of claims 1 -4, 10-21 , and 27-34 wherein the alkene is ethylene.

37. The process of claim 36 wherein the chloroalkane product is ethylene dichloride.