WO2020014211A1

WO2020014211A1 - Eductor nozzle to improve gas hold up in gas-liquid reactor

Info

Publication number: WO2020014211A1
Application number: PCT/US2019/040980
Authority: WO
Inventors: Max Tirtowidjojo; Marc Sell; John D. Myers; Michael Schluter
Original assignee: Blue Cube Ip Llc
Priority date: 2018-07-09
Filing date: 2019-07-09
Publication date: 2020-01-16

Abstract

The present invention provides an improved reactor design for increasing the mass transfer of a gas in a liquid by a liquid driven eductor nozzle. The reactor or gas/liquid absorber comprises at least one eductor nozzle, at least one annular chamber, at least one draft tube on the central axis of the reactor. Using this design, improved processes for preparing halogenated alkanes are described. The processes comprise contacting a halogenated alkane comprising at least one chlorine atom, a liquid alkene, a liquid chlorinated alkene, or combinations thereof with a gas comprising an alkene, a chlorinated alkene, or chlorine gas in the presence of at least one solid metallic catalyst in the above reactor design.

Description

EDUCTOR NOZZLE TO IMPROVE GAS HOLD UP IN GAS-LIQUID REACTOR

FIELD OF THE INVENTION

[0001 ] The present disclosure generally relates to reactor designs that improve the mass transfer of gas absorption and gas hold up in gas-liquid processes and processes which utilize such reactors to prepare halogenated alkanes.

BACKGROUND OF THE INVENTION

[0002] Halogenated alkanes are useful intermediates for many products including agricultural products, pharmaceuticals, cleaning solvents, blowing agents, solvents, gums, silicones, and refrigerants. The processes to prepare halogenated alkanes can be time consuming, moderately efficient, and lack reproducibility.

[0003] One widely known method for preparing halogenated alkanes is through a telomerization process. This process comprises contacting a halogenated methane comprising at least one chlorine atom and an alkene or halogenated alkene in the presence of a catalyst. Even though these telomerization processes are useful, these processes have variable yields, low reproducibility, large amounts of waste, and high unit manufacturing costs.

[0004] One subset of highly sought halogenated alkanes are

chloropropanes especially 1 ,1 ,1 ,3-tetrachloropropane, 1 ,1 ,1 ,3,3-pentachloropropane, and 1 ,1 ,1 ,3,3,3-hexachloropropane which are useful intermediates for many products, including refrigerants and agricultural products. A general process for their preparation consists of reacting an alkene or a halogenated alkene, carbon tetrachloride, a trialkylphosphate, and an iron catalyst in a telomerization process. US 4,650,914 teaches such a process where the process is conducted in batch mode, using a non- powder form of an iron and mechanical stirring. All materials are introduced into an autoclave wherein the ethylene is added to pressurize the autoclave. US 2004/0225166 teaches a similar process using a single reactor in a continuous process. Ethylene is fed into the reactor comprising carbon tetrachloride, tributylphosphate, and iron powder. The reactor is pressurized from 40 to 200 psi to maintain a concentration of ethylene. In US 8,907,147, a similar process is described as is US 2004/0225166 wherein the ethylene is added continuously. In each of these references, gaseous ethylene is added to the reactor and must be absorbed into the liquid phase of the reaction, which allows the telomerization process to proceed. Since ethylene is only partially soluble in carbon tetrachloride, the alkene or halogenated alkene is used in excess to maintain the concentration of the ethylene in the liquid phase. Similarly, iron (Fe(0)) utilized as a solid in these processes must undergo an oxidation and/or reduction to form the active, soluble catalytic species necessary to initiate the telomerization process.

[0005] Another subset of highly sought halogenated alkane are

chloropropanes especially 1 ,1 ,1 ,2,3-pentachloropropane and ethylene dichloride.

Generally, these chloropropanes can be prepared through many synthetic methods but a preferred method consists of chlorinating an alkene or chloroalkene. Since chlorine gas is only partially soluble in organic solvents, a large excess of chlorine gas is normally used to ensure complete chlorination of the alkene or chloroalkene.

[0006] These processes depend on the mass transfer of the ethylene or chlorine gas into the liquid phase of the reaction. Also, the processes also depend on the iron forming an active catalyst which would be soluble in the liquid phase. With competing mass transfer processes occurring in the same process, one skilled in the art would find it difficult to optimize the kinetics or improve the kinetics of the process. With optimization of the mass transfer, the kinetics of the process can be therefore optimized resulting in a lower overall cost of the process.

[0007] Thus, conventional processes can be moderately efficient yet lack reproducibility, utilize expensive manufacturing equipment, have large waste factors, and/or provide the chlorinated propane at a higher unit manufacturing cost.

[0008] Developing a reactor design which facilitates the absorption of a gas into a liquid would be desirable. The process conducted in this reactor would exhibit high mass transfer, increased kinetics, high reproducibility, reduced amounts of waste, and reduced manufacturing costs. SUMMARY OF THE INVENTION

[0009] In one aspect, disclosed herein are reactors for controlling gas-hold up and increasing the mass transfer of a gas in a liquid using a liquid driven eductor nozzle. The reactor or gas/liquid absorber comprises a) at least one eductor nozzle; b) at least one annular chamber with inlets and outlets; c) at least one draft tube with a top and bottom opening; d) an impinging plate located at the bottom of the draft tube and above the bottom of the reactor; e) one or more gas or liquid inlets; f) at least one liquid outlet; g) as least one optional gas outlet; h) at least one external recycle loop; i) at least one external pump; and j) at least one external heat exchanger, wherein the at least one eductor nozzle is centered in the inlet of the at least one draft tube and is located at the top of the draft tube; and wherein the at least one eductor nozzle, at least one chamber, and the at least one draft tube are oriented on a central axis of the reactor or gas/liquid absorber.

[0010] In another aspect, disclosed herein are processes for preparing halogenated alkanes by feeding a liquid phase comprising a liquid halogenated alkane comprising at least one chlorine atom; a liquid alkene, a liquid halogenated alkene, or combinations thereof, through at least one eductor nozzle that is contained in a reactor or gas/liquid absorber that contains a liquid phase (which may be the same or different from the liquid phase added being added to the reactor or gas/liquid absorber). The height of the liquid phase in the reactor or gas/liquid absorber is above the top of the at least one draft tube but below the top of the annular chamber, where the outlet of the at least one eductor nozzle is immersed in the liquid phase. Gas comprising an alkene, a chlorinated alkene, or chlorine is fed through one or more inlets into the reactor. The gas is at least partially drawn through the at least one annular chamber by the liquid moving through the at least one eductor nozzle and through the at least one draft tube. This produces an increased concentration of the gas in the liquid phase, which improves mass transfer and reaction kinetics. In one embodiment, when starting the reactor or gas/liquid absorber for the first time, the liquid phase contains at least one of liquid alkene, halogenated alkene, or halogenated alkane. [0011 ] In an additional aspect, disclosed herein are processes for preparing 1 ,1 ,1 ,3-tetrachloropropane (250FB). The process comprises feeding a liquid phase comprising carbon tetrachloride through at least one eductor nozzle that is contained in a reactor or gas/liquid absorber that contains a liquid phase (which may be the same or different from the liquid phase added being added to the reactor or gas/liquid absorber). The height of the liquid phase in the reactor or gas/liquid absorber is above the top of the at least one draft tube but below the top of the annular chamber, and the outlet of the at least one eductor nozzle is immersed in the liquid phase. Upon feeding a gas comprising ethylene into the reactor through one or more inlets, the ethylene is at least partially drawn through the at least one annular chamber by the liquid moving through the at least one eductor nozzle and through the at least one draft tube. This produces an increased concentration of gas in the liquid phase.

[0012] In another aspect, disclosed herein are processes for preparing

1.1.1.3.3-pentachloropropane (240FA). The process comprises feeding a liquid phase comprising carbon tetrachloride through at least one eductor nozzle that is contained in a reactor or gas/liquid absorber that contains a liquid phase (which may be the same or different from the liquid phase added being added to the reactor or gas/liquid absorber). The height of the liquid phase in the reactor or gas/liquid absorber is above the top of the at least one draft tube but below the top of the annular chamber, and the outlet of the at least one eductor nozzle is immersed in the liquid phase. Upon feeding a gas comprising vinyl chloride into the reactor or gas/liquid absorber through one or more inlets, the vinyl chloride is at least partially drawn through the at least one chamber by the liquid moving through the at least one eductor nozzle and through the at least one draft tube. This produces an increased concentration of gas in the liquid phase and 240FA is produced.

[0013] In another aspect, disclosed herein are processes for preparing

1.1.1.2.3-pentachloropropane (240DB). The process comprises feeding a liquid phase comprising 1 ,1 ,3-trichloropropene, 3,3,3-trichloropropene, or combinations thereof through at least one eductor nozzle that is contained in a reactor or gas/liquid absorber that contains a liquid phase (which may be the same or different from the liquid phase added being added to the reactor or gas/liquid absorber). The height of the liquid phase in the reactor or gas liquid absorber is above the top of the at least one draft tube but below the top of the annular chamber, and the outlet of the at least one eductor nozzle is immersed in the liquid phase. Upon feeding a gas comprising chlorine into the reactor or gas/liquid absorber through one or more inlets, the chlorine is at least partially drawn through the at least one annular chamber by the liquid moving through the at least one eductor nozzle and through the at least one draft tube. This produces an increased concentration of chlorine in the liquid phase and 240DB is produced.

[0014] In another aspect, disclosed herein are processes for preparing ethylene dichloride (1 ,2-dichloroethane). The process comprises feeding a liquid phase comprising ethylene, dichloroethane or combinations thereof, through at least one eductor nozzle that is contained in a reactor or gas/liquid absorber that contains a liquid phase (which may be the same or different from the liquid phase added being added to the reactor or gas/liquid absorber). The height of the liquid phase in the reactor or gas liquid absorber is above the top of the at least one draft tube but below the top of the annular chamber, and the outlet of the at least one eductor nozzle is immersed in the liquid phase. Upon feeding a gas comprising chlorine, ethylene or combinations thereof into the reactor or gas/liquid absorber through one or more inlets, the chlorine, ethylene or combinations thereof is at least partially drawn through the at least one annular chamber by the liquid moving through the at least one eductor nozzle and through the at least one draft tube. This produces an increased concentration of chlorine, ethylene or combinations thereof, in the liquid phase and ethylene dichloride is produced.

[0015] In another aspect, disclosed herein are processes for preparing 1 ,1 ,1 ,3,3,3-hexachloropropane. The process comprises feeding a liquid phase comprising carbon tetrachloride through at least one eductor nozzle that is contained in a reactor or gas/liquid absorber that contains a liquid phase (which may be the same or different from the liquid phase added being added to the reactor or gas/liquid absorber). The height of the liquid phase in the reactor or gas/liquid absorber is above the top of the at least one draft tube but below the top of the annular chamber, and the outlet of the at least one eductor nozzle is immersed in the liquid phase. Upon feeding a gas comprising vinylidene chloride into the reactor or gas/liquid absorber through one or more inlets, the vinylidene chloride is at least partially drawn through the at least one annular chamber by the liquid moving through the at least one eductor nozzle and through the at least one draft tube. This produces an increased concentration of vinylidene chloride in the liquid phase and 1 ,1 ,1 ,3,3,3-Hexachloropropane is produced.

[0016] Other features and iterations of the invention are described in more detail below.

BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 A is a representation of the reactor design which increases the concentration of a gas in a liquid reaction mixture, through the use of an long eductor nozzle with a annular chamber.

[0018] Figure 1 B is a table showing specific measurements in one embodiment of the reactor design. The values provided in the table represent the specific measurement/ the diameter of the reactor.

[0019] Figure 2 is a graphical representation of the comparison using a longer gas eductor nozzle (B) with an annular chamber versus a shorter gas eductor nozzle (A) with a short annular chamber for gas holdup in dependency of liquid flow rate.

[0020] Figure 3 is a graph of the mass transfer performance of the eductor nozzle with draft tube compared to a 1 ½” ID commercial eductor nozzle, without a draft tube.

DETAILED DESCRIPTION OF THE INVENTION

[0021 ] One aspect of the present disclosure encompasses a reactor or gas/liquid absorber for improving the mass transfer of gas absorption in a liquid by a liquid driven eductor nozzle. The reactor or gas/liquid absorber, as described herein, improves the mass transfer of gas absorption using a combination of at least one eductor nozzle, at least one annular chamber, at least one draft tube, and an impinging plate. With the improvement of the mass balance within the reactor or gas/liquid absorber, the kinetics of the process are increased.

(I) Device for Improving Mass Transfer of Gas Absorption by a Liquid

[0022] One aspect of the present disclosure encompasses a reactor or gas/liquid absorber for improving the mass transfer of gas absorption in a liquid phase by a liquid driven eductor nozzle. In practice, a liquid is fed into at least one eductor nozzle, while gas is fed into the top of the reactor and/or into the side of the reactor in the space outside of the draft tube. The gas that accumulates in the head space of the reactor will then be drawn into the annular chamber of the eductor and will thoroughly mix with the liquid moving through the eductor and/or the liquid phase in the reactor. As previously described, the eductor nozzle outlet is located below the level of the liquid phase of the reactor and at the top opening of the draft tube. This thorough mixing of the gas and liquid improves the kinetics of the reaction.

[0023] As shown in Figure 1 A, the reactor or gas/liquid absorber comprises at least one eductor nozzle (101), at least one annular chamber (102), and at least one draft tube (103). These parts are essentially oriented on the central axis of the reactor or gas/liquid absorber. The at least one eductor nozzle (101 ) is centered in the at least one annular chamber (102). The at least one annular chamber (102) is located within the at least one draft tube (103) and the at least one eductor nozzle outlet is located at the inlet opening of the at least one draft tube (103). The at least one draft tube (103) extends most of the length of the reactor or gas/liquid absorber (100). An impinging plate (104) is located at the outlet of the at least one draft tube (103) and above the liquid outlet at the bottom of the reactor or gas/liquid absorber (100). A number of gas and liquid inlets and outlets (105, 106, and 107) are also part of the reactor or gas/liquid absorber, and they provide fresh liquid feed and gas feed to the reactor or gas/liquid absorber (100), or they allow gas and/or liquid to leave the reactor or gas/liquid absorber (100). In various embodiments, the at least one liquid outlet (106) comprises at least one external recycle loop (108) which is connected to inlet (105), other inlets (not shown) and/or the eductor (101 ). The at least one external recycle loop (108) allows for the recycling of the reaction mixture back to the process. This at least one external recycle loop (108) further comprises at least one external pump (109) and optionally, at least one external heat exchanger (110). These parts not only provide circulation of liquid but also provide temperature control for the reactor. Fresh feeds may be added to the reactor via at least one external recycle loop (108) and/or the products may be removed via at least one external recycle loop (108).

[0024] Importantly, the liquid level in the reactor should not be higher than the portion of the gas nozzle that is within the reactor. For example, the liquid level shown in Figure 1A is the highest level the liquid should be. It is undesirable to have liquid pass over the top edge of the gas nozzle and into annular space (102), as this will needlessly necessitate expending energy to move liquid through the eductor (101). To be clear, it is greatly preferred to maintain the liquid level in the reactor (100) below the top edge of the gas nozzle, i.e. , the liquid level in Figure 1 A should be lower than is shown.

[0025] The at least one eductor nozzle (101), as described above consists of an inlet and an outlet. Generally, the outlet of the at least one eductor nozzle’s inner diameter (ID) to the inlet of the at least one eductor nozzle’s ID ranges from 0.3 to 0.75. In various embodiments, the ratio of the diameter of the outlet of the at least one eductor nozzle’s inner diameter to the inlet of the at least one eductor nozzle’s ID ranges from 0.3 to 0.75, from 0.4 to 0.7, from 0.45 to 0.65, or from 0.5 to 0.6.

[0026] As noted above, the outlet of the at least one eductor nozzle (101) is located within and centered within the annular chamber (102). The position of the at least one eductor nozzle is important because it allows for increased absorption of gas within the liquid, by drawing gas through the at least one annular chamber (102) using the liquid driven in the at least one eductor nozzle (101). Generally, the ratio of the x- sectional flow area of the at least one eductor nozzle outlet to the diameter of the inlet of the at least one chamber may range from about 0.5 to 0.9. In various embodiments, the ratio of the x-sectional flow area of the at least one eductor nozzle (101 ) outlet to the diameter of the inlet of the at least one annular chamber may range from about 0.25 to 0.9, from about 0.4 to 0.8, or from about 0.5 to 0.6. [0027] The outlet of the at least one eductor nozzle (101 ) is situated at the inlet of the at least one draft tube (103). The position of the at least one annular chamber (102) is located below the inlet of the opening of the at least one draft tube (103). Generally, at least 5% of the length of the at least one annular chamber (102) is located within the inlet of the at least one draft tube (103) as compared to the total length of the at least one annular chamber (102). In various embodiments, the length of the at least one chamber located within the inlet of the at least one draft tube (103) as compared to the total length of the at least one annular chamber (102) is at least 5%. In various embodiments, the length of the at least one chamber located within the inlet of the at least one draft tube (103) as compared to the total length of the at least one annular chamber (102) is at least 5%, at least 6%, at least 7%, at least 8%, at least 9%, at least 10%, or more.

[0028] The at least one draft tube (103) is centered on the central axis of the reactor or gas/liquid absorber (100). In general, the diameter of the at least one draft tube (103) to the diameter of the reactor or gas/liquid absorber (100) may be from about 0.2 to 0.5 when one draft tube (103) is used. In various embodiments, the diameter of the at least one draft tube (103) to the diameter of the reactor or gas/liquid absorber (100) may be from about 0.2 to 0.5, from about 0.25 to about 0.45, from about 0.3 to 0.4, or from 0.32 to about 0.37 when one draft tube (103) is used.

[0029] Generally, the ratio of the length of the at least one draft tube (103) to the total length of the reactor or gas/liquid absorber (100) may range from 0.6 to 0.8. In various embodiments, the ratio of the length of the at least one draft tube (103) to the total length of the reactor or gas/liquid absorber (100) may range from 0.6 to 0.8, from about 0.62 to about 0.78, from about 0.65 to about 0.75, or from about 0.68 to about 0.72.

[0030] As previously indicated, the outlet of the at least one eductor nozzle (101 ) is located within the at least one annular chamber (102). The outlet of the at least one eductor nozzle (101 ) is positioned near the top of the at least one draft tube (103) and above the outlet of the annular chamber. Generally, the ratio of the diameter of the outlet of the at least one eductor nozzle (101 ) to the diameter of the at least one draft tube (103) ranges from about 0.05 to 0.2. In various embodiments, the ratio of the diameter of the outlet of the at least one eductor nozzle (101 ) to the diameter of the at least one draft tube (103) ranges from about 0.05 to 0.2, from about 0.07 to 0.18, from about 0.1 to 0.15, or from about 0.11 to 0.14.

[0031 ] The impinging plate (104) is located just below the outlet of the draft tube (103) and is centered on the outlet of the at least one draft tube (103). The position and size of the impinging plate (104) is not important. Once gas bubbles are formed from the at least one eductor nozzle (101) and at least one annular chamber (102), the bubbles are recycled to the top of the reactor or gas/liquid absorber by flowing down the at least one draft tube (103) and are diverted by the impinging plate (104) where they rise through the liquid to the top of the reactor outside the at least one draft tube (103). Typically, the impinging plate (104) is made of the same material as the reactor or gas/liquid absorber (100). As for the shape of the impinging plate (104), the skilled person will be able to determine an appropriate shape to use. In an embodiment, the impinging plate (104) is circular.

[0032] In general, the ratio of the diameter to the impinging plate (104) to the diameter of the reactor or gas/liquid absorber (100) may range from about 0.45 to about 0.90. In various embodiments, the ratio of the diameter to the impinging plate (104) to the diameter of the reactor gas/liquid absorber (100) may range from about 0.45 to about 0.90, from about 0.50 to about 0.80, from about 0.55 to about 0.76, or from 0.60 to about 0.70.

[0033] The impinging plate (104) is located below the outlet of the at least one draft tube (103) and above the bottom of the reactor or gas/liquid absorber (100). Generally, the ratio of the distance of the impinging plate (104) to the bottom of the reactor or gas/liquid absorber (100) to the total length of the reactor or gas/liquid absorber (100) may range from 0.01 to about 0.05. In various embodiments, the ratio of the distance of the impinging plate (104) to the bottom of the reactor or gas/liquid absorber (100) to the total length of the reactor or gas/liquid absorber (100) may range from 0.01 to about 0.05, from 0.015 to about 0.035, from about 0.018 to about 0.032, or from about 0.022 to about 0.028. [0034] In all embodiments, the reactor or gas/liquid absorber further comprises at least one external recirculation loop (108). The at least one external recirculation loop (108) connects liquid outlet (106) to inlet (105), other inlets (not shown in Figure 3A) and/or the eductor (101 ). Recycled liquid from the reactor or gas/liquid absorber is recirculated through an at least one in-line external pump (109) to at least one liquid inlet (105). Additionally, at least one external heat exchanger (110) may be located on the at least one external recirculation loop (108), on the reactor or gas/liquid absorber, or a combination thereof. These heat exchangers would provide the reactor or gas/liquid absorber contents with a set process temperature.

[0035] As appreciated by the skilled artisan, the reactor or gas liquid absorber may be produced from various metals which are chemically resistant to the processes conducted within the reactor or gas/liquid absorber. Generally, reactor or gas/liquid absorber is capable of maintaining a pressure of 14.5 psig to about 200 psig.

(II) Processes using Device for Improving Mass Transfer of Gas Absorption by a Liquid

[0036] Another aspect of the disclosure provides processes which utilize the reactor or gas/liquid absorber, as described above, for improving mass transfer of gas absorption in a liquid by a liquid eductor nozzle. The processes, as defined herein, utilize a liquid phase comprising a halogenated alkane comprising at least one chlorine atom, a liquid alkene, a liquid chlorinated alkene, or combinations thereof, at least one solid metallic catalyst, and a gas comprising an alkene, a chlorinated alkene, or chlorine gas.

(a) reaction mixture

[0037] The process commences by forming a liquid reaction mixture in the reactor or gas/liquid absorber comprising a halogenated alkane comprising at least one chlorine atom, a liquid alkene, a liquid chlorinated alkene, or combinations thereof and optionally, at least one catalyst. In various embodiments, the reaction mixture may further comprise a solvent. (i) halogenated methane comprising at least one chlorine atom.

[0038] A wide variety of halogenated methanes comprising at least one chlorine atom may be used as the liquid in this process. Non-limiting examples of halogenated methanes comprising at least one chlorine atom include methyl chloride, methylene chloride, chloroform, carbon tetrachloride, chlorofluoromethane,

dichloromonofluoromethane, trichlorofluoromethane, difluorochloromethane,

trifluorochloromethane, bromochloromethane, dibromochloromethane,

tribromochloromethane, chloroiodomethane, chlorodiiodomethane,

chlorotriiodomethane, bromochlorofluoromethane, bromochlorodifluoromethane, chlorodibromofluoromethane, bromochlorofluoroiodomethane,

bromochlorodiiodomethane, and combinations thereof. In an embodiment, the halogenated methane comprising at least one chlorine atom is methylene chloride, chloroform, or carbon tetrachloride.

[0039] In general, the halogenated methane comprising at least one chlorine atom may be used in excess. Generally, the molar ratio of the halogenated methane comprising at least one chlorine atom to an alkene, a halogenated alkene, or chlorine gas may range from 0.1 :1 to about 100:1. In various embodiments, the molar ratio of the halogenated methane comprising at least one chlorine atom to an alkene, a halogenated alkene, or chlorine gas may range from 0.1 :1 to about 100:1 , from 0.5:1 to about 75:1 , from 1 :1 to about 10:1 , or from 1.2:1 to about 5:1. In various embodiments, the molar ratio of the halogenated methane comprising at least one chlorine atom to an alkene, a halogenated alkene, chlorine gas may range from 1.2:1 to about 2:1. The halogenated methane comprising at least one chlorine atom and an alkene, a halogenated alkene, or chlorine gas are essentially dry, i.e. , it has a water content of the below 1000 ppm. Lower water concentrations are preferred, but not required.

(ii) a liquid alkene, a liquid halogenated alkene, or combinations thereof

[0040] A wide variety of alkenes, halogenated alkenes, or combinations thereof may be used in the process. As appreciated by the skilled artisan, the alkene, halogenated alkene, or combinations thereof may be introduced in the reaction as a liquid or a gas. Under conditions of the process as detailed below, the alkene, halogenated alkene, or combinations thereof may be liquid and then may undergo a phase transition from a liquid to a gas. Utilizing the pressure of the process, once the process commences, the gas may undergo a phase transition back to a liquid.

[0041 ] Generally, the at least one alkene, halogenated alkene, or combinations thereof comprise between 2 and 5 carbon atoms. Non-limiting examples of alkenes may be ethylene, propylene, 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 halogenated alkenes may be 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 one embodiment, the alkene comprises ethylene, propylene, 1 -butene, 2- butene, isobutylene, or combinations thereof. In one preferred embodiment, the alkene comprises ethylene. In another embodiment, the halogenated alkene is selected from a group consisting of a monochloroethene, a dichloroethene, a trichloroethene, a tetrachloroethene, monochloropropene, a dichloropropene, a trichloropropene, a tetrachloropropene, or combinations thereof. Non-limiting examples may be vinyl chloride, vinylidene chloride, trichloroethylene, perchloroethylene, 1 ,2,3- trichloropropene, 1 ,1 ,3-trichloropropene, 3,3,3-trichloropropene, or combinations thereof. In one embodiment, the halogenated alkene comprises 1 ,1 ,3-trichloropropene, 3,3,3-trichloropropene, or combinations thereof. In another embodiment, the

halogenated alkene comprises vinyl chloride or vinylidene chloride.

(iii) ligand

[0042] In various embodiments, a ligand may be used in the process. The ligand, as the skilled artisan appreciates, may form a complex with the catalyst, with the resulting complex being soluble in the reaction media.

[0043] In one embodiment, the ligand comprises a phosphorus containing compound. Examples of phosphorus containing compounds may include

trialkylphosphates, trialkylphosphites, or combinations thereof. Suitable non-limiting examples of trialkylphosphates and trialkylphosphite may include trimethylphosphate, triethylphosphate, tripropylphosphate, triisopropylphosphate, tributylphosphate, trimethylphosphite, triethylphosphite, tripropylphosphite, triisopropylphosphite, tributylphosphite, and tri-tertbutylphosphite. In one preferred embodiment, the phosphorus containing compound comprises a trialkylphosphate, namely

tributylphosphate.

(iv). optional, at least one solid metallic catalyst

[0044] A wide variety of at least one metallic solid catalyst as a source of the catalytic species may be used in the process. In some embodiments, the catalytic species of the at least one metallic solid catalyst may comprise a transition metal. As used herein, the term“transition metal” refers to a transition metal element, a transition metal containing alloy, a transition metal containing compound, or combinations thereof. Non limiting examples of transition metals in the at least catalytic species may be selected from the group consisting of aluminum, bismuth, chromium, cobalt, copper, gallium, gold, indium, iron, lead, magnesium, manganese, mercury, nickel, platinum, palladium, rhodium, samarium, scandium, silver, titanium, tin, zinc, zirconium, and combinations thereof. In a preferred embodiment, the catalytic species may comprise a solid transition metal selected from the group consisting of iron.

[0045] Non-limiting examples of metal containing alloys useful in the process may be an alloy of aluminum, an alloy of bismuth, an alloy of chromium, an alloy of cobalt, an alloy of copper, an alloy of gallium, an alloy of gold, an alloy of indium, an alloy of iron, an alloy of lead, an alloy of magnesium, an alloy of manganese, an alloy of mercury, an alloy of nickel, an alloy of platinum, an alloy of palladium, an alloy of rhodium, an alloy of samarium, an alloy of scandium, an alloy of silver, an alloy of titanium, an alloy of tin, an alloy of zinc, an alloy of zirconium, and combinations thereof. Non-limiting common names for these alloys may be Al-Li, Alnico, Birmabright, duraluminum, hiduminum, hydroalium, magnalium, Y alloy, nichrome, stellite, ultimet, vitallium, various alloys of brass various alloys of brass, bronze, Constantin, Corinthian bronze, cunife, cupronickel, cymbal metals, electrum, haptizon, manganin, nickel silver, Nordic gold, tumbaga, crown gold, colored gold, electrum, rhodite, rose gold, tumbaga, white gold, cast iron, pig iron, Damascus steel, wrought iron, anthracite iron, wootz steel, carbon steel, crucible steel, blister steel, alnico, alumel, brightray, chromel, cupronickel, ferronickel, German silver, Inconel, monel metal, nichrome, nickel-carbon. Nicrosil, nitinol, permalloy, supermalloy, 6al-4v, beta C, gum metal, titanium gold, Babbitt, britannium, pewter, solder, terne, white metal, sterling silver, zamak, zircaloy, or combinations thereof. In one embodiment, the at least one metallic solid catalyst comprises a metal, a metal powder, an alloy of a metal, or combinations thereof. In a preferred embodiment, at least one metallic solid catalyst as a source of the catalytic species may be iron metal, an iron containing compound, an alloy of iron, or

combinations thereof, and may be in various forms.

[0046] Generally, at least one solid metallic catalyst as a source of the catalytic species may be in various forms or configuration. Non-limiting examples of the forms or configuration of at least one metallic solid catalyst may be a packing, an unstructured packing, a foil, a sheet, a screen, a wool, a wire, a ball, a plate, a pipe, a rod, a bar, or a powder. Non-limiting examples of suitable supports may be alumina, silica, silica gel, diatomaceous earth, carbon and clay. Further examples may be iron on carbon, iron on diatomaceous earth, and iron on clay.

[0047] As appreciated by the skilled artisan, the catalyst, once in the process, may undergo oxidation and/or reduction to produce an activated catalytic species in various oxidation states. The oxidation state of these active iron catalytic species may vary, and may be for examples (0), (I), (II), and (III). In one aspect, the active iron catalyst may in the Fe(0) or 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 one aspect, the active iron catalyst may in the Fe(l), 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.

[0048] In still another embodiment, the at least one metallic solid as a source of the catalytic species in a continuous reactor or continuous gas/liquid absorber may be part of at least one fixed catalyst bed. In still another embodiment, the at least one metallic solid in a continuous reactor or continuous gas/liquid absorber may be part of at least one cartridge. In still another embodiment, the at least one metallic solid may be part of a structured or un-structured packing where the at least one catalyst is a part of the packing or un-structured packing. Using a fixed catalyst bed, a cartridge, structured packing, or unstructured packing, the catalytic species may be contained and easily replaced when consumed. Non-limiting examples of structured and unstructured packing may be any metallic form for random packing, or combinations thereof. In an embodiment, the packing comprises Raschig™ rings, pall rings, saddles, cylinders, spheres, mesh, Koch Sulzer™ packing, bars, nails, random shapes, or combinations thereof.

[0049] Generally, the porosity of the at least one metallic solid is less than 0.95. In various embodiments, the porosity of the at least one catalytic species is less than 0.95, less than 0.8, less than 0.5, less than 0.3, or less than 0.1 . Further, the porosity of may range from 0.1 to about 0.95, from 0.3 to about 0.8, or from 0.4 to about 0.6.

[0050] The ratio of the surface area of the catalyst to the halogenated methane comprising at least one chlorine atom is at least 0.1 cm²/(g/hr). In various embodiments, the ratio of the surface area of the catalyst to the halogenated methane comprising at least one chlorine atom is at least 0.1 cm²/(g/hr), at least 0.5 cm²/(g/hr), at least 1.0 cm²/(g/hr), at least 1.5 cm²/(g/hr), or at least 2.0 cm²/(g/hr).

[0051 ] In general, the molar ratio of the dissolved elemental metal to the ligand may range from 1 : 1 to about 1 : 1000. In various embodiments, the molar ratio of the dissolved elemental metal to the ligand may range from 1 : 1 to about 1 :1000, from 1 : 1 to about 1 :500, from 1 : 1 to about 1 : 100, or from 1 : 1 to about 1 : 10. In one preferred embodiment, the molar ratio of the dissolved elemental metal to the ligand may range from 1 :1.5 to about 1 :3

(b) gas introduction

[0052] In order to initiate the process for the preparation of halogenated alkanes, the liquid reaction mixture, as defined above, is introduced into the reactor or gas/liquid absorber (100) and the reactor or gas/liquid absorber is filled to the top inlet of the at least one annular chamber (102). The gas, as defined herein, may be introduced through gas inlet (105) or other inlets, and fills the headspace of the reactor or gas/liquid absorber (100) at a specified pressure. The headspace is defined as the space above the liquid level of the reactor or gas/liquid absorber. Actuation of at least one external pump (109) provides liquid reaction mixture, being drawn from at least one liquid outlet (106), and introduced through inlet (105) and/or other inlets (not shown in Figure 3A) and through the least one eductor nozzle (101). With actuation of the at least one eductor nozzle (101 ), gas is drawn through the at least one chamber contacting the liquid reaction mixture and forming gas bubbles in the liquid reaction mixture. These gas bubbles travel down the at least one draft tube (103), contacting the impinging plate (104), and are diverted into the reactor or gas/liquid absorber (100) outside the at least one draft tube thereby increasing the concentration of the gas in the liquid reaction mixture.

[0053] A wide variety of gases may be used in the process. The gas may be an alkene, halogenated alkene, or chlorine gas. As appreciated by the skilled artisan, the alkene, halogenated alkene, or chlorine gas may be introduced in the reaction as a liquid or a gas wherein the alkene, halogenated alkene, or chlorine gas may be at least partially soluble in the liquid reaction mixture. In various embodiments, the alkene, halogenated alkene, chlorine gas may be introduced above the surface or below the surface of the liquid reaction mixture. Under conditions of the process as detailed below, the alkene, halogenated alkene, chlorine gas may be liquid and then may undergo a phase transition from a liquid to a gas. As appreciated by the skill artisan, the alkene, a halogenated alkene, and/or chlorine gas may be introduced into the reactor to maintain the pressure with the reactor.

[0054] Generally, the alkene, halogenated alkene, or combinations thereof comprise between 2 and 5 carbon atoms. Non-limiting examples of alkenes may be ethylene, propylene, 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 halogenated alkenes may be 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, vinylidene chloride, vinylidene bromide, and combinations thereof. In one embodiment, the alkene comprises ethylene, propylene,

1 -butene, 2-butene, isobutylene, or combinations thereof. In an embodiment, the gas comprises ethylene. In another embodiment, the gas comprises vinyl chloride, vinylidene chloride, or combinations thereof. In still another embodiment, the gas may be chlorine gas.

(c) reaction conditions

[0055] As appreciated by the skilled artisan, using at least one eductor nozzle provides adequate stirring for the process. This stirring method would provide increased interaction between the liquid reaction mixture and the gas. Therefore, the kinetics of the process is increased.

[0056] In another embodiment, when the at least one solid metallic catalyst is in the form of a fixed bed, then the liquid phase is fed directly into the fixed bed from one end of the fixed bed and exit of the other end. The fixed bed may be contained within a cylindrical or tubular container. Generally, the L/D (length/diameter) of the cylindrical or tubular container may be greater than 1. In various embodiments, the L/D (length/diameter) of the cylindrical or tubular container may be greater than 1 , greater than 2, greater than 4, greater than 6, or greater than 8. The residence time and velocity of the fluid in the fixed bed may be varied by recycling a portion of the fixed bed reactor effluent back to the inlet. The fixed bed reactor temperature may also be independently varied from the reactor temperature by heat exchanging the reactor recycle stream. The fixed bed temperature may also be controlled by including internal heat exchanger such as the use of multi-tube exchanger.

[0057] In general, the process for the preparation of halogenated alkanes will be conducted to maintain the temperature from about ambient temperature (~20°C) to about 250°C using an internal or external heat exchanger. In various embodiments, the temperature of the reaction may be maintained from about 20°C to about 250°C, from 40°C to about 200°C, from 80°C to about 160°C, or from about 100°C to about 120°C.

[0058] Generally, the process may be conducted at a pressure of about atmospheric pressure (~14.7 psi) to about 200 psi so the amount of the gases and liquid are in suitable quantities so the reaction may proceed and maintain the kinetics of the process. In various embodiments, the pressure of the process may be from about atmospheric pressure (~14.7 psi) to about 200 psi, from about 20 psi to about 180 psi, from about 40 psi to about 160 psi, from about 80 psi to about 140 psi, or from 100 psi to about 120 psi. In one embodiment, the pressure within the gas/ liquid absorber and the reaction vessel are the same. In another embodiment, the pressure within the gas/ liquid absorber and the reaction vessel are different.

[0059] Generally, the reaction is allowed to proceed for a sufficient period of time until the reaction is complete, as determined by any method known to one skilled in the art, such as chromatography (e.g., GC-gas chromatography). The duration of the reaction 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 1 hour to about 12 hours, from about 2 hours to about 10 hours, from about 4 hours to about 8 hours, or from about 5 hours to about 7 hours. The reaction may be run as a batch process or continuously.

(d) output from process

[0060] The process, as outlined above, produces the halogenated alkane(s), light by-products and heavy by-products. In general, the process produces the halogenated alkanes in at least 50 weight percent (wt%) in the liquid phase of the reactor. In various embodiments, the halogenated alkane is 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 liquid phase of the reactor.

[0061 ] In general, the halogenated methane comprising at least one chlorine atom is converted into the halogenated alkane in at least 50%. In various embodiments, the % conversion of the halogenated methane comprising at least one chlorine atom into the halogenated alkane is at least 50%, in at least 60%, in at least 70%, in at least 80%, in at least 90%, or at least 95%.

[0062] Generally, the process produces halogenated alkanes, light by- products, and 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 4 weight %, less than 3 weight %, less than 2 weight %, or less than 1 weight %.

[0063] Generally, the halogenated alkane is a chlorinated alkane comprising between 3 and 4 carbons and between 2 and 8 chlorine atoms. Non-limiting examples of chlorinated propanes which may be prepared by this process may be 1 ,1 ,1 ,3-tetrachloropropane (250FB); 1 ,1 ,1 ,3,3-pentachloropropane (240FA); 1 ,1 ,1 ,2,3- pentachloropropane (240DB), ethylene dichloride, 1 ,1 ,1 ,3,3,3-hexachloropropane (111333); or combinations thereof.

(e) separation of the halogenated alkane and recycle streams

[0064] The next step in the process comprises separating purified halogenated alkane from the liquid reaction mixture effluent stream, which comprises halogenated alkane, a liquid comprising a halogenated methane comprising at least one chlorine atom, a liquid alkene, a liquid halogenated alkene, or combinations thereof, the at least one ligand, at least one metallic catalytic species, heavy by-products, and light by-products. The separation commences by transferring at least a portion of the liquid reaction mixture effluent stream through at least one separator and alternatively a second separator in order to isolate the halogenated alkane in the desired yield and/or purity. In various embodiments, at least one of the first separator and the second separator may be a distillation column or a multistage distillation column. Additionally, the at least one of the first separator and the second separator may further comprise a reboiler, a bottom stage, or a combination thereof. Various distillation columns may be used in this capacity. In one embodiment, a side draw column or a distillation column which provides an outlet stream from an intermediate stage or a dividing wall column (dividing wall column (DWC) is a single shell, fully thermally coupled distillation column capable of separating mixtures of three or more components into high purity products, i.e. , product effluent streams) may be used as a separator. Product effluent streams are purer than the reaction mixture effluent stream, because they are generated by treating the reaction mixture effluent stream and removing at least some undesired components. A portion of various product effluent streams or a portion of the reaction mixture effluent streams produced by the process are optionally recycled back into the reactor to provide increased kinetics, increased efficiencies, reduced overall cost of the process, increased selectivity of the desired halogenated alkane, and increased yield of the desired halogenated alkane. In one embodiment, at least a portion of the reaction mixture effluent stream is treated to remove light by-products, heavy by-products, or combinations thereof from the halogenated alkane. If desired, at least a portion of the heavy by-products is recycled to the reaction vessel, or both at least a portion of both the light by-products and heavy by-products are recycled.

[0065] Separating the purified halogenated alkane from the reaction mixture effluent stream from the reactor would produce at least two effluent streams. In various embodiments, separating the purified chlorinated alkane may produce three, four, five, or more product effluent streams depending on the separation device utilized. As an example, the separation of the chlorinated alkane from the reaction mixture effluent stream into three product effluent streams is described below.

[0066] The process utilizing one separator commences by transferring a portion of the reaction mixture effluent from the reaction vessel into a separator. In this operation, at least a portion of the reaction mixture effluent stream is separated into two product streams, which may be further distilled or purified, as needed. In one embodiment, at least a portion of the reaction mixture effluent stream is separated into three distinct product effluent streams, product effluent stream (a), (b), and (c). Product effluent stream (a), as an overhead stream, comprises light by-products, hydrogen chloride, an alkene, halogenated alkene, or combinations thereof, and the halogenated methane comprising at least one chlorine atom; product effluent stream (b) comprising the halogenated alkane; and product effluent stream (c), as a bottom stream, comprising heavy by-products, the at least one ligand, and the at least one catalytic species.

[0067] In another embodiment, product effluent stream (a) may be transferred into a second separator producing two distinct product effluent streams (d) and (e). Product effluent stream (d) comprising hydrogen chloride may be captured or recycled to another process since hydrogen chloride is a valuable commercial material. A portion of product effluent stream (e) comprising which comprises halogenated alkane, a liquid comprising a halogenated methane comprising at least one chlorine atom, a liquid alkene, a liquid halogenated alkene, or combinations thereof, the at least one ligand, at least one active catalytic species, heavy by-products, and light by- products may be recycled or used in another process.

[0068] In yet another embodiment, product effluent stream (b) comprising the halogenated alkane may be transferred into an additional separation device to achieve the desired purity of the halogenated alkane.

[0069] In still another embodiment, at least a portion of product effluent stream (c) comprising heavy by-products, the at least one ligand, and the at least one active catalytic species may be recycled to the reaction vessel or used in another process.

[0070] In various embodiments, at least a portion of product effluent streams (c) and/or (e) may be recycled back into the reaction vessel or mixed with fresh feed before being recycled back into the reaction vessel. These streams may also be fed into another process to produce other products. These steps may be performed in any order to improve the efficiency, reduce the cost, reduce contaminants, and increase through-put of the process. [0071 ] In another embodiment, at least a portion of product effluent streams (c) and/or (e) may be mixed with fresh material feeds before being recycled back into the reactor in continuous mode, where the fresh material feeds comprise a liquid comprising a halogenated methane comprising at least one chlorine atom, a liquid alkene, a liquid halogenated alkene, or combinations thereof, the at least one ligand may be recycled or used in another process., or combinations thereof. The fresh material feed may be reaction vessel. In various embodiments, the recycle product effluent streams and fresh material feed streams may be introduced into the reactor separately or mixed together before entering the process. The introduction of these fresh material feeds or mixing the recycle 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.

Optionally, a portion of the fresh material feed may be added directly into the reaction vessel. Additionally, this fresh material feed may be premixed with the liquid phase or a product effluent stream before being added to the reactor. Also, the fresh material feed may be directly added into the reactor. The amounts of the recycle product effluent streams or fresh material feed streams added to the reactor may be the same or different. One way to measure the amount of the recycle product effluent streams or fresh material feed streams being added to the reactor is to identify the mass flow of each of these streams. The product effluent streams being recycled to the reactor and/or the absorber have a recycle product effluent mass flow, while the fresh material feed streams being added to the reactor has a fresh material feed mass flow. Mass flows may be measured using methods known in the art.

[0072] Generally, the mass ratio of the product effluent stream mass flow being recycled to the fresh material feed mass flow is adjusted to maintain the conversion of the process and/or maintain the kinetics of the process.

[0073] In yet another embodiment, the active catalytic species may be separated from the product stream by means of extraction. This extraction, using water or another polar solvent, may remove deactivated catalyst. The extraction may separate the active catalytic species which may be introduced back into the reaction vessel or other downstream processes. Using the extraction processes defined above may provide added efficiency to the process in respect to overall cost.

[0074] Product effluent streams (b) comprising the halogenated alkane produced in the process may have a yield of at least about 20%. In various

embodiments, the product effluent stream (b) comprising halogenated alkane 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%.

[0075] The halogenated alkane contained in product effluent stream (b) from the process may have a weight percent at least about 50%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, at least about 99%, at least about 99.5%, or at least about 99.9%.

(Ill) Processes for Preparing 1 ,1 ,1 ,3-Tetrachloropropane (250FB)

[0076] One aspect of the present disclosure encompasses processes for the preparation of 1 ,1 ,1 ,3-tetrachloropropane. The process commences by preparing a liquid phase comprising carbon tetrachloride, at least one solid metallic catalyst, and at least one ligand in a reactor. Ethylene is introduced into one or more gas inlets (105) wherein the gas is in the headspace. Once the at least one external pump (109) is activated, the liquid phase is fed through the at least one eductor nozzle (101) creating a vacuum in the at least one annular chamber (102) drawing ethylene through the at least one annular chamber (102) contacting the carbon tetrachloride and creating bubbles of ethylene gas in the at least one draft tube (103) causing the process to commence. At the desire percentage of completion (percent conversion), the product,

1 ,1 ,1 ,3-tetrachloropropane (250FB) is recovered through as an outlet stream through the at least one liquid outlet (106). The at least one solid metallic catalyst utilized in the reaction is described in Section (ll)(a)(lv). The at least one ligand is described in Section (ll)(a)(iii). The reaction conditions for preparing the 1 ,1 ,1 ,3-tetrachloropropane is described above in Section (ll)(c), while the separation of 1 ,1 ,1 ,3-tetrachloropropane and the recycle streams is described above in Section (ll)(e).

(IV) Processes for Preparing 1 ,1 ,1 ,3,3-Pentachloropropane (240FA)

[0077] One aspect of the present disclosure encompasses processes for the preparation of 1 ,1 ,1 ,3,3-pentachloropropane. The process commences by preparing a liquid phase comprising carbon tetrachloride, at least one solid metallic catalyst, and at least one ligand in a reactor or gas/liquid absorber. Vinyl chloride is introduced into one or more inlets (105) wherein the gas is in the headspace. Once the at least one external pump (109) is activated, the liquid phase is fed through the at least one eductor nozzle (101 ) creating a vacuum in the at least one annular chamber (102) drawing vinyl chloride gas through the at least one annular chamber (102) contacting the liquid phase and creating bubbles of vinyl chloride gas in the liquid phase in the at least one draft tube (103), causing the process to commence. At the desire percentage of completion (percent conversion), the product, 1 ,1 ,1 ,3,3-tetrachloropropane (240FA) is recovered through as an outlet stream through the at least one liquid outlet (106). The at least one solid metallic catalyst utilized in the reaction is described in Section

(ll)(a)(lv). The at least one ligand is described in Section (ll)(a)(iii). The reaction conditions for preparing the 1 ,1 ,1 ,3,3-pentachloropropane is described above in Section (ll)(c), while the separation of 1 ,1 ,1 ,3,3-pentachloropropane and the recycle streams is described above in Section (ll)(e).

(IV) Processes for Preparing 1 ,1 ,1 ,2,3-Pentachloropropane (240DB)

[0078] One aspect of the present disclosure encompasses processes for the preparation of 1 ,1 ,1 ,2,3-pentachloropropane. The process commences by preparing a liquid phase comprising 1 ,1 ,3-trichloropropene (113), 3,3,3-trichloropropene (333), or combinations thereof, in a reactor or gas/liquid absorber. Chlorine gas is introduced into one or more gas inlets (105) wherein the gas is in the headspace. Once the at least one external pump (109) is activated, the liquid phase is fed through the at least one eductor nozzle (101 ) creating a vacuum in the at least one annular chamber (102) drawing chlorine gas through the at least one annular chamber (102) contacting the liquid phase and creating bubbles of chlorine gas in the liquid phase in the at least one draft tube (103) causing the process to commence. At the desire percentage of completion (percent conversion), the product, 1 ,1 ,1 ,2,3-tetrachloropropane (240DB), is recovered through as an outlet stream through the at least one liquid outlet (106). The reaction conditions for preparing the 1 ,1 ,1 ,2,3-tetrachloropropane (240DB) is described above in Section (ll)(c), while the separation of 1 ,1 ,1 ,2,3-pentachloropropane and the recycle streams is described above in Section (ll)(e).

(V) Processes for Preparing Ethylene Dichloride (EDC)

[0079] One aspect of the present disclosure encompasses processes for the preparation of ethylene dichloride. The process commences by preparing a liquid phase comprising ethylene in a reactor or gas/liquid absorber. Chlorine gas is introduced into one or more gas inlets (105) wherein the gas is in the headspace. Once the at least one external pump (109) is activated, the liquid phase is fed through the at least one eductor nozzle (101 ) creating a vacuum in the at least one chamber (102) drawing chlorine gas through the at least one chamber (102) contacting the liquid phase comprising ethylene and creating bubbles of chlorine gas in the liquid phase in the at least one draft tube (103) causing the process to commence. At the desire percentage of completion, the product, ethylene dichloride, is recovered through as an outlet stream through the at least one liquid outlet (106). The reaction conditions for preparing the ethylene dichloride is described above in Section (ll)(c), while the separation of ethylene dichloride and the recycle streams is described above in Section (ll)(e).

(VI) Processes for Preparing 1, 1, 1,3,3,3-Hexachloropropane

[0080] One aspect of the present disclosure encompasses processes for the preparation of 1 ,1 ,1 ,3,3,3-hexachloropropane. The process commences by preparing a liquid phase comprising carbon tetrachloride, at least one solid metallic catalyst, and at least one ligand in a reactor or gas/liquid absorber. Vinylidene chloride is introduced into one or more gas inlets (105) wherein the gas is in the headspace. Once the at least one external pump (109) is activated, the liquid phase is fed through the at least one eductor nozzle (101 ) creating a vacuum in the at least one chamber (102) drawing vinylidene chloride through the at least one chamber (102) contacting the carbon tetrachloride and creating bubbles of vinylidene chloride in the liquid phase in the at least one draft tube (103) causing the process to commence. At the desire percentage of completion, the product, 1 ,1 ,1 ,3,3,3-hexachloropropane, is recovered through as an outlet stream through the at least one liquid outlet (106). The at least one solid metallic catalyst utilized in the reaction is described in Section (ll)(a)(lv). The at least one ligand is described in Section (ll)(a)(iii). The reaction conditions for preparing the 1 ,1 ,1 ,3,3,3-hexachloropropane is described above in Section (ll)(c), while the separation of 1 ,1 ,1 ,3,3,3-hexachloropropane and the recycle streams is described above in Section (ll)(e).

DEFINITIONS

[0081 ] 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.

[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 other compounds using eductor nozzle?

[0084] Figure 1 A shows the schematic of a 29cm ID reactor with an eductor nozzle and a draft tube and an impinging plate below the draft tube. The eductor nozzle consists of two tubular section where the liquid mixture enter the shorter inner tube. As the liquid exit the inner tube into the outer tube (mark in red) the liquid jet educts the gas through the annular section of the nozzle. The design requires a smaller diameter at the outlets of the tube nozzles to provide mixing of the gas and liquid and hence large gas/liquid interface. The entrance to the draft tube is placed at the same height as the inner eductor nozzle exit. The outer eductor nozzle tube is placed below the draft tube entrance to enhance the eduction of reactor gas/liquid mixture into the draft tube. The impinging plate is placed below the exit of the draft tube so that the gas bubbles formed by the eduction are forced to the top of the reactor. This provides time for the adsorption of the gas and therefore mass transfer of the gas into the liquid to minimize mass transfer effects on the desired reaction rate. In addition, the impinging plate diameter to reactor diameter is designed in such a way that only liquid can enter the reactor exit below the impinging plate. The detail geometry is provided in Figure 3.

[0085] In Figure 1 B, all the configurations remain the same as that in Figure 1 A except that the outer chamber of the eductor nozzle is purposely made longer than in 1A. The longer outer nozzle allows the liquid/gas mixture to rise and hence increase the gas hold up and hence increases the gas/liquid interface area. This is illustrated in Figure 2 where the gas hold up using the longer gas eductor nozzle (Figure 1 B) can be adjusted up to 7X larger than that of the short gas eductor nozzle (Figure 1A) depending on the height of liquid level filled the reactor (before the recirculation rate is started) and the jet flow rate.

Example 2: Absorption of 0₂ in water

[0086] Figure 2 shows the comparison of the gas holdup for eductor nozzles of different length. This data shows the longer eductor nozzle with a length of 190mm affords superior gas holdup, when compared to a shorter eductor nozzle with a length of 40mm. When the eductor nozzles suck gas, the gas holdup within the reactor increases until the upper end of the eductor nozzle is reached. At this point the eductor nozzle is sucking a liquid/gas mixture instead of pure gas, and therefore, the gas holdup does not increase further. For the eductor nozzle with a shaft length of 40mm, this happens at a gas holdup of 1 %. With an eductor nozzle having a shaft length of

190mm, the eductor nozzle sucks gas until the gas holdup reaches a maximum, which depends on the static pressure of the liquid/gas column. The higher the volume flow rate, the higher the gas hold up. The gas holdup can be adjusted in advance by using a specific fill level. The higher the fill level, the higher the static pressure of the gas/liquid- mixture and the lower the gas holdup at a certain liquid flow rate. With this configuration, a maximum gas holdup of 7% was achieved.

[0087] Figure 3 shows the mass transfer performance of the eductor nozzle with draft tube compared with a 1 ½” ID commercial eductor nozzle (Schutte & Koerting Single-Nozzle Water Jet Exhauster p. 484). This data shows the eductor nozzle with draft tube affords superior mass transfer performance, when compared to the commercial nozzle at the same pressure drop. The design of the eductor nozzle has been optimized for a low pressure drop with high gas sucking performance. With increasing liquid flow rate, the mass transfer coefficient increases. Higher mass transfer coefficients are achievable with higher volume flow rates.

Claims

CLAIMS What is claimed is:

1. A reactor or gas/liquid absorber (100) comprising:

a. at least one eductor nozzle (101 );

b. at least one annular chamber (102) with inlets and outlets

c. at least one draft tube (103) with a top and bottom opening;

d. an impinging plate (104) located at the bottom of the at least one draft tube and above the bottom of the reactor or gas/liquid absorber;

e. one or more gas and/or liquid inlets (105);

f. at least one liquid outlet(106);

g. at least one optional gas outlet (107);

h. at least one external recycle loop (108)

i. at least one external pump (109); and

j. optionally, at least one external heat exchanger (110);

wherein the outlet of the at least one eductor nozzle (101 ) is centered in the inlet of the at least one draft tube (103) and located near the level of the top of the draft tube and below the inlet of the annular chamber; and

wherein the at least one eductor nozzle (101), at least one annular chamber (102), and the at least one draft tube (103), are oriented on a central axis of the at least one draft tube (103).

2. The reactor or gas/liquid absorber of claim 1 , wherein the ratio of eductor nozzle (101 ) inner diameter outlet (ID) to the eductor nozzle (101) inner diameter inlet (ID) ranges from 0.3 to 0.75.

3. The reactor or gas/liquid absorber of either claim 1 or claim 2, wherein the ratio of the x-sectional flow area of the outlet of the at least one eductor nozzle (101 ) to the inlet of the at least one annular chamber (102) ranges from about 0.25 to about 0.9.

4. The reactor or gas/liquid absorber of any one of the claims 1 -3, wherein at least 5% of the length of the outlet of the at least one annular chamber (102) is located below the inlet of the at least one draft tube (103) as compared to the total length of the at least one annular chamber (102).

5. The reactor or gas/liquid absorber of any one of the claims 1 -4, wherein the ratio of the diameter of the at least one draft tube (103) to the diameter of the reactor or gas/liquid absorber (100) ranges from 0.2 to 0.5 when one draft tube (103) is used.

6. The reactor or gas/liquid absorber of any one of the claims 1 -5, wherein outlet of the at least one eductor nozzle (101 ) is positioned at the top of the at least one draft tube (103) and the ratio of the diameter of the outlet of the at least one eductor nozzle (101 ) to the diameter of the at least one draft tube (103) ranges from 5% to 20%.

7. The reactor or gas/liquid absorber of any one of the claims 1 -6, wherein the ratio of the diameter of the impinging plate (104) to the diameter of the reactor or gas/liquid absorber (100) ranges from 0.45 to 0.90.

8. The reactor or gas/liquid absorber of any one of the claims 1 -7, wherein the ratio of the length of the at least one draft tube (103) to the length of the reactor or gas/liquid absorber (100) ranges from 0.6 to 0.8.

9. The reactor or gas/liquid absorber of any one of the claims 1 -8, wherein the ratio of the distance of the impinging plate (104) to the bottom of the reactor or gas/liquid absorber to the total length of the reactor or gas/liquid absorber (100) ranges from about 1 % to about 5%.

10. The reactor or gas/liquid absorber of any one of the claims 1 -9, further

comprising at least one external pump (109) that is in-line with the at least one external recycle loop (108).

11. The reactor or gas/liquid absorber of any one of the claims 1 -10, further comprising at least one external heat exchanger located (110) on the at least one external recycle loop, on the reactor or gas/liquid absorber, or combinations thereof.

12. The reactor or gas/liquid absorber of any one of the claims 1 -11 , wherein the reactor or gas/liquid absorber is capable of maintaining a pressure of 0 psig to 200 psig.

13. A continuous process for the preparation of halogenated alkanes, the process comprises: feeding a liquid phase into the at least one eductor nozzle (101 ) wherein the liquid phase level in the reactor or gas/liquid absorber is at or below the level of the inlet of the at least one annular chamber (102) and the outlet of the at least one eductor nozzle (101 ) is immersed in the liquid phase and feeding a gas into the one or more gas inlets (105) wherein the gas is above the level of the liquid and is drawn through the at least one annular chamber (102); and recovering the halogenated alkane as an outlet stream through the at least one liquid outlet (106).

14. The process of claim 13, wherein the liquid phase comprises a halogenated alkane comprising at least one chlorine atom, a liquid alkene, a liquid chlorinated alkene, or combinations thereof.

15. The process of claim 14, wherein the liquid phase further comprises a solvent.

16. The process of either claim 14 or 15, wherein the halogenated alkane comprising at least one chlorine atom is selected from a group consisting of methylene chloride, chloroform, carbon tetrachloride, or combinations thereof.

17. The process of either claim 14 or 15, wherein the liquid alkene is selected from a group consisting of ethylene, propylene, 1 -butene, 2-butene, isobutylene, or

combinations thereof.

18. The process of either claim 14 or 15, wherein the liquid chlorinated alkene is selected from a group consisting of a dichloroethylene, a trichloroethylene, a

monochloropropene, a dichloropropene, a trichloropropene, a tetrachloropropene, or combinations thereof.

19. The process of claim 13, wherein the gas comprises an alkene, a chlorinated alkene, or chlorine gas.

20. The process of claim 19, wherein the alkene is selected from a group consisting of ethylene, propylene, 1 -butene, 2-butene, isobutylene, or combinations thereof.

21. The process of either claims 19 or 20, wherein the alkene comprises ethylene.

22. The process of claim 19, wherein the chlorinated alkene is selected allyl chloride, vinyl chloride, vinylidene chloride, or combinations thereof.

23. The process of claim 13, wherein the process further comprises at least one catalyst.

24. The process of any one of the claims 13-23, wherein the at least one catalyst comprises iron metal, iron containing compound, iron containing alloy, or combinations thereof.

25. The process of any one of the claims 15-26, wherein at least one catalyst comprises Fe(0), Fe(ll), Fe(lll), or combinations thereof.

26. The process of either of claims 23 or 24, wherein the at least one catalyst further comprises at least one ligand.

27. The process of claim 26, wherein the ligand comprises a trialkylphosphate, trialkylphosphite, or combinations thereof and wherein the ligand is complexed to Fe(ll), Fe(lll), or combinations thereof.

28. The process of any one of the claims 13-27, wherein the trialkylphosphate comprises trimethylphosphate, triethylphosphate, tripropylphosphate,

triisopropylphosphate, tributylphosphate, or combinations thereof.

29. The process of any one of the claims 13-28, wherein the trialkylphosphite comprises trimethylphosphite, triethylphosphite, tripropylphosphite,

triisopropylphosphite, tributylphosphite, tri-tertbutylphosphite, or combinations thereof.

30. The process of any one of the claims 13-29, wherein the chlorinated alkane comprises a dichloropropene, trichloropropane, a tetrachloropropane, a

pentachloropropane, or combinations thereof.

31. The process of any one of the claims 13-30, wherein fresh material feeds comprising at least one alkene, halogenated alkene, or combinations thereof; a halogenated methane comprising at least one chlorine atom, and at least one ligand is added to the reactor.

32. The process of claim 31 , wherein the material being recycled to the reactor has a recycle product effluent mass flow, and the fresh material feeds have a fresh material feed mass flow, wherein the mass ratio of the recycle product effluent mass flow to the fresh material feed mass flow is adjusted to maintain the conversion of the process and/or to maintain the kinetics of the process.

33. The process of any one of the claims 13-32, wherein the chlorinated alkane comprises 1 ,1 ,1 ,3-tetrachloropropane (250FB), 1 ,1 ,1 ,3,3-pentachloropropane (240FA),

1 ,1 ,1 ,2,3-pentachloropropane (240DB), 1 ,2-dichloroethane, 1 ,1 ,1 ,3,3,3- hexachloropropane (111333), or combinations thereof.

34. The process of any one of the claims 13-33, wherein the process is conducted at a temperature from ambient temperature (~20°C) to about 250°C.

35. The process of any one of the claims 13-34, wherein the process is conducted at a pressure from atmospheric pressure (~14,7 psia) to about 200 psig.

36. The process of any one of the claims 13-35, wherein the selectivity of the process is at least 50%.

37. The process of any one of the claims 13-36, wherein the conversion of the process is at least 50%.

38. A continuous process for the preparation of 1 , 1 , 1 ,3-tetrachloropropane, the process comprises:

feeding a liquid phase comprising carbon tetrachloride into the at least one eductor nozzle (101 ) wherein the liquid phase level in the reactor is at or below the top level of the at least one annular chamber (102) and the outlet of the at least one eductor nozzle (101 ) is immersed in the liquid phase and feeding a gas comprising ethylene into the one or more gas inlets (105) wherein the gas is above the level of the liquid and is drawn through the at least one annular chamber (102) contacting the liquid phase comprising carbon tetrachloride; and

recovering 1 ,1 ,1 ,3-tetrachloropropane as an outlet stream through the at least one liquid outlet (106).

39. A continuous process for the preparation of 1 , 1 , 1 ,3,3-pentachloropropane, the process comprises:

feeding a liquid phase comprising carbon tetrachloride into the at least one eductor nozzle (101 ) wherein the liquid phase level in the reactor or gas/liquid absorber is at or below the top level of the at least one annular chamber (102) and the outlet of the at least one eductor nozzle (101 ) is immersed in the liquid phase and feeding vinyl chloride into the one or more gas inlets (105) wherein the gas is above the level of the liquid and is drawn through the at least one annular chamber (102); and

recovering 1 ,1 ,1 ,3,3-pentachloropropane as an outlet stream through the at least one liquid outlet (106).

40. A continuous process for the preparation of 1 , 1 , 1 ,2,3-pentachloropropane, the process comprises:

feeding a liquid phase comprising 1 ,1 ,3-trichloropropene (113e), 3,3,3- trichloropropene (333e), or combinations thereof into the at least one eductor nozzle (101 ) wherein the liquid phase level in the reactor or gas/liquid absorber is at or below the top level of the at least one annular chamber (102) and the outlet of the at least one eductor nozzle (101 ) is immersed in the liquid phase and feeding a gas comprising chlorine gas into the one or more gas inlets (105) wherein the gas is above the level of the liquid and is drawn through the at least one annular chamber (102) contacting the liquid phase; and

recovering 1 ,1 ,1 ,2,3-pentachloropropane as an outlet stream through the at least one liquid outlet (106).

41. A continuous process for the preparation of ethylene dichloride (1 ,2- dichloroethane, or EDC), the process comprises:

feeding a liquid phase comprising ethylene, EDC or combinations thereof into the at least one eductor nozzle (101 ) wherein the liquid phase level in the reactor or gas/liquid absorber is at or near the top level of the at least one annular chamber (102) and the outlet of the at least one eductor nozzle (101) is immersed in the liquid phase and feeding a gas comprising chlorine gas into the one or more gas inlets (105) wherein the gas is above the level of the liquid and is drawn through the at least one annular chamber (102) contacting the liquid phase; and

recovering ethylene dichloride (EDC) as an outlet stream through the at least one liquid outlet (106).

42. A continuous process for the preparation of 1 , 1 , 1 ,3,3,3-hexachloroproane, the process comprises: feeding a liquid phase comprising carbon tetrachloride into the at least one eductor nozzle (101 ) wherein the liquid phase level in the reactor or gas/liquid absorber is at the level of the at least one annular chamber (102) and the outlet of the at least one eductor nozzle (101 ) is immersed in the liquid phase and feeding vinylidne chloride into the one or more gas inlets (105) wherein the gas is above the level of the liquid phase and is drawn through the at least one annular chamber (102) contacting the liquid phase; and

recovering 1 ,1 ,1 ,3,3,3-hexachloropropane as an outlet stream through the at least one liquid outlet (106).