# Patent

## Title
Processes and systems for fractionation of brominated hydrocarbons in the conversion of natural gas to liquid hydrocarbons

## Abstract

Process and systems for converting lower molecular weight alkanes to higher molecular weight hydrocarbons that include fractionation of brominated hydrocarbons, wherein the brominated hydrocarbons are formed by reaction of the lower molecular weight alkanes with bromine.

## Background
BACKGROUND
The present invention relates generally to processes and systems for converting lower molecular weight alkanes to higher molecular weight hydrocarbons and, more particularly, in one or more embodiments, to processes for converting lower molecular weight alkanes that include fractionation of brominated hydrocarbons, wherein the brominated hydrocarbons are framed by reaction of the lower molecular weight alkanes with bromine.
Natural gas, which is primarily composed of methane and other light alkanes, has been discovered in large quantities throughout the world. In the United States, the latest proved natural gas reserves are 6,731 billion standard cubic meter (238 trillion standard cubic feet) in 2010, which makes the United States a top-five country in natural gas abundance. Natural gas is generally a cleaner energy source than crude oil. It is normally heavy sulfur-free and contains none or a minimum amount of heavy metals and non-reacting heavy hydrocarbons. For a given amount of heat energy, burning natural gas produces about half as much carbon dioxide as coal.
However, the transportation, storage and distribution of natural gas in a gaseous form are much less favorable than those of crude oil making it more difficult to be a substitute as the predominant energy source. Converting natural gas to higher molecular weight hydrocarbons, which, due to their higher density and value, are able to be more economically transported, can significantly aid the development of natural gas reserves, particularly the stranded remote natural gas reserves.
One technique for converting natural gas to higher molecular weight hydrocarbons is a bromine-based process. In general, the bromine-based process may include several basic steps, as listed below.

    
    
        (1) Bromination: Reacting bromine with lower molecular weight alkanes to produce alkyl bromides and hydrogen bromide (HBr).
        (2) Alkyl Bromides Conversion: Reacting the alkyl bromides over a suitable catalyst under sufficient conditions to produce HBr, methane (C1), light end hydrocarbons (C2-C4) and heavy end hydrocarbons (C5+).
        (3) HBr Recovery: Recovering HBr produced in both steps (1) and (2) by one of several processes, e.g., absorbing HBr and neutralizing the resulting hydrobromic acid with an aqueous solution of partially oxidized metal bromide salts (as metal oxides/oxy-bromides/bromides) to produce metal bromide salt and water in an aqueous solution; reacting HBr with metal oxide; or absorbing HBr into water using a packed tower or other contacting device.
        (4) Bromine Regeneration: Reacting the bromide recovered in step (3) with oxygen or air to yield bromine and treating it sufficiently for recycle to step (1).
        (5) Product Recovery: Fractionating by distillation and cryogenic distillation (demethanizer) the hydrocarbon mixtures contained in the effluent from step (2) and then separated from HBr in step (3) into methane, light end hydrocarbons, and heavy end hydrocarbons. The methane can be compressed for recycle to step (1). The light end hydrocarbons (C2-C4) may be, for example, salable as a product or cracked to produce light olefins. The heavy end hydrocarbons (C5+) may be used, for example, for further petrochemical or fuel processing.
    
    


In the bromine-based processes, monobrominated alkanes created during bromination may be desirable as the predominant reactant species for the subsequent alkyl bromide conversion. Polybrominated alkanes are known to adversely affect the selectivity profiles of the higher molecular weight hydrocarbons produced during the alkyl bromide conversion and, more importantly, promote the formation of coke which can deposit on the catalyst, block the active sites, and cause rapid catalyst deactivation. The higher selectivity of polybrominated alkanes can also lower the utilization efficiency of bromine, requiring a higher circulating flow of bromine which can correspond to a higher cost in recovering HBr and regenerating recyclable bromine.
To achieve higher selectivity of monobrominated alkanes and reduce the formation of bromination carbon/soot, a large excess of methane or large methane-to-bromine ratio can be used. In the case of the bromination of methane, a methane-to-bromine ratio of about 6:1 can be used to increase the selectivity to mono-bromomethane (CH3Br) to average approximately 88% depending on other reaction conditions. If a lower methane-to-bromine ratio of approximately 2.6:1 is utilized, selectivity of CH3Br may fall to the range of approximately 65-75% depending, for example, on other reaction conditions. If a methane-to-bromine ratio significantly less than 2.5:1 is utilized, unacceptably low selectivity to CH3Br occurs, and, moreover, significant formation of undesirable di-bromomethane (CH2Br2), tri-bromomethane (CHBr3), and carbon soot is observed. However, the large methane-to-bromine ratio can be problematic, in that the large excess methane represents a large recycle stream circulating throughout the entire system. For example, the pressure drop of the process gas between the feed to bromination in step (1) and the recycle methane from product recovery in the step (5) can be large, resulting in a high cost of compression for the recycle gas.
In alkyl bromide conversion, the exothermic coupling reaction may be carried out in a fixed-bed, fluidized-bed or other suitable reactor in the presence of suitable catalysts under sufficient conditions (e.g., 150-600° C., 1-80 bars). The catalyst may have to undergo decoking periodically or continuously to maintain adequate performance. In some instances, a fluidized-bed reactor may be considered to be advantageous for the coupling reaction, particularly for commercial scale of operation, as it should allow for continuous removal of coke and regeneration of the spent catalyst without requiring daily shutdowns and expensive cyclic operation. The fluidized-bed configuration should also facilitate removal of reaction heat and provide a steady selectivity to product composition. However, the fluidized-bed reactor for this particular application may be a very costly item to design and construct as it may have to deal with a high density gas due to the large amount of higher molecular weight bromides contained in the reactor feed (in the forms of HBr and alkyl bromides). Elevated operating pressure, 20-50 bars, may be required to minimize the recompression cost of recycle methane, which, however, will further increase the density of the gases in the synthesis reactor, resulting in a large diameter reactor with heavy wall thickness. In some instances, the catalyst deactivation rate can be lowered by feeding none or the minimum amount of polybromides to the coupling reactor and, thus, the fixed bed configuration may be preferentially selected over fluidized bed.
In product recovery, fresh feed gas may be required to replace the lower molecular weight alkanes converted to products. The fresh feed gas stream containing, for example, primarily methane may necessitate sufficient treating to remove excessive amounts of ethane and higher hydrocarbons prior to being combined with bromine and reacted in a bromination reactor. The feed gas stream may or may not mix with the hydrocarbon mixture exiting HBr recovery prior to receiving such treating. While some ethane and higher hydrocarbons may be tolerated in the bromination reactor, due to the much higher bromination rate of the higher hydrocarbons than that of methane, higher concentrations of the higher hydrocarbon impurities may easily over-brominate and, thus, may result in the rapid formation of carbon-containing coke-like solids, which can cause yield loss and reduced process reliability by fouling and plugging the reactor as well as the downstream units. However, the removal of ethane and higher hydrocarbons from the methane by such means as adsorption or cryogenic distillation can be costly. The cost is higher when both the recycle methane and the fresh feed gas stream require the removal of ethane and higher hydrocarbons. The cost is even higher when high methane-to-bromine ratios are used in the bromination, leading to a large flow rate of recycle methane.
Thus, although progress has been made in the conversion of lower molecular weight alkanes to higher molecular weight hydrocarbons, there remains a need for processes that are more efficient, economic, and safe to operate.
SUMMARY
To achieve the foregoing and other objects, and in accordance with the purposes of the present invention, as embodied and broadly described herein, one embodiment of the present invention is a process that comprises reacting at least gaseous alkanes and a halogen to produce at least a halogenation product stream, wherein the halogenation product stream comprises alkyl halides, hydrogen halide, and unreacted alkanes. The process further may comprise separating the halogenation product stream into at least a gaseous stream and a liquid alkyl halides stream, wherein the gaseous stream comprises hydrogen halide and unreacted alkanes, and wherein the liquid alkyl halides stream comprises alkyl halides. The process further may comprise separating the liquid alkyl halides stream into at least a monohalides stream and a polyhalides stream, wherein the monohalides stream comprises monohalogenated alkanes, and wherein the polyhalides stream comprises polyhalogenated alkanes. The process further may comprise reacting at least a portion of the monohalogenated alkanes from the monohalides stream in the presence of a catalyst to produce at least a synthesis product stream, wherein the synthesis product stream comprises higher molecular weight hydrocarbons and hydrogen halide.
Another embodiment of the present invention is a process that comprises reacting at least gaseous alkanes and bromine in a bromination reactor to produce at least a bromination product stream, wherein the bromination product stream comprise alkyl bromides, hydrogen bromide, and unreacted alkanes. The process further may comprise separating the bromination product stream into at least a gaseous alkane/HBr stream and a liquid alkyl bromides stream, wherein the gaseous alkane/HBr stream comprises hydrogen bromide and unreacted alkanes, and wherein the liquid alkyl bromides stream comprises alkyl bromides. The process further may comprise separating the liquid alkyl bromides stream into at least a monobromides stream and a polybromides stream, wherein the monobromides stream comprises monobrominated alkanes, and wherein the polybromides stream comprises polybrominated alkanes. The process further may comprise reacting at least a portion of the monobrominated alkanes from the monobromides stream in a synthesis reactor to produce at least a synthesis product stream, wherein the synthesis product stream comprises higher molecular weight hydrocarbons and hydrogen bromide. The process further may comprise recovering at least a portion of the hydrogen bromide from the synthesis product stream in a hydrogen bromide separator. The process further may comprise providing a natural gas stream. The process further may comprise separating at least the synthesis product stream and the natural gas stream into at least a light ends product stream, a heavy ends product stream, and a feed gas stream, wherein the light ends product stream comprises light end hydrocarbons having from 2 carbons to 4 carbons, wherein the heavy ends product stream comprises heavy end hydrocarbons having 5 or more carbons, and wherein the feed gas stream comprises methane. The process further may comprise compressing the feed gas stream in a feed compressor. The process further may comprise feeding the feed gas stream into the bromination reactor. The process further may comprise generating a recycle alkane stream by recovering at least a portion of the hydrogen bromide from the gaseous alkane/HBr stream in a second hydrogen bromide separator operating at a higher pressure than the hydrogen bromide separator. The process further may comprise compressing the recycle alkane stream in a recycle compressor. The process further may comprise feeding the recycle alkane stream to the bromination reactor.
Yet another embodiment of the present invention is system that comprises a bromination reactor for reacting at least gaseous alkanes and bromine to produce at least a bromination product stream, wherein the bromination product stream comprises alkyl bromides, hydrogen bromide, and unreacted alkanes. The system further may comprise an alkyl bromides fractionation unit in fluid communication with the bromination reactor for separating the bromination product stream into at least a gaseous alkane/HBr stream and a liquid alkyl bromides stream, wherein the gaseous alkane/HBr stream comprises hydrogen bromide and unreacted alkanes, and wherein the liquid alkyl bromides stream comprises alkyl bromides. The system further may comprise a polybromides fractionation unit in fluid communication with the alkyl bromides fractionation unit for separating the liquid alkyl bromides stream into at least a polybromides stream and a monobromides stream, wherein the polybromides stream comprises polybrominated alkanes, and wherein the monobromides stream comprises monohalogenated bromides. The system further may comprise a synthesis reactor in fluid communication with the polybromides fractionation unit for reacting at least a portion of the monobrominated alkanes from the monobromides stream in the presence of a catalyst to produce a synthesis product stream, wherein the synthesis product stream comprises higher molecular weight hydrocarbons and hydrogen bromide. The system further may comprise a hydrogen bromide separator in fluid communication with the synthesis reactor for recovering at least a portion of the hydrogen bromide from the synthesis product stream. The system further may comprise a second hydrogen bromide separator unit in fluid communication with the alkyl bromides fractionation unit for recovering at least a portion of the hydrogen bromide from the gaseous alkane/HBr stream.



BRIEF DESCRIPTION OF THE DRAWINGS
These drawings illustrate certain aspects of some of the embodiments of the present invention and should not be used to limit or define the invention.
FIG. 1 is a schematic view of a process for the conversion of lower molecular weight alkanes to higher molecular weight hydrocarbons that includes fractionation of brominated hydrocarbons in accordance with embodiments of the present invention.
FIG. 2 is a schematic view of another embodiment of a process of the present invention for the conversion of lower molecular weight alkanes to higher molecular weight hydrocarbons that includes fractionation of brominated hydrocarbons, which also produces light end hydrocarbons as another product.
FIG. 3 is a schematic view of another embodiment of a process of the present invention for the conversion of lower molecular weight alkanes to higher molecular weight hydrocarbons that includes fractionation of brominated hydrocarbons configured to incorporate a shift reactor for reducing the content of polybrominated alkanes fed to the synthesis reactor.
FIG. 4 is a schematic view of another embodiment of a process of the present invention for the conversion of lower molecular weight alkanes to higher molecular weight hydrocarbons that includes fractionation of brominated hydrocarbons with recycle of light end hydrocarbons to produce light end bromides for an additional feed to the synthesis reactor.
FIG. 5 is a schematic view of alkyl bromides and polybromides fractionation units in accordance with one embodiment of the present invention.



DETAILED DESCRIPTION OF SPECIFIC EMBODIMENTS
Embodiments of the present invention are directed to processes for converting lower molecular weight alkanes to higher molecular weight hydrocarbons that include fractionation of brominated hydrocarbons, wherein the brominated hydrocarbons are formed by reaction of the lower molecular weight alkanes with bromine.
There may be many potential advantages to the methods and systems of the present invention, only some of which are alluded to herein. One of the many potential advantages of the embodiments of the systems and methods of the present invention is that separation of the methane from the brominated hydrocarbons should reduce the large recycle stream circulating through the entire process due to the large excess methane that may be used in the bromination step. Accordingly, the bromination step may be performed with a large methane-to-bromine ratio with reasonable recompression cost for recycled methane as embodiments, in accordance with present embodiments. In addition, reduction of the large recycle stream circulating throughout the entire system should also reduce the cost for C2+ alkane separation as the recycle stream should not need to be treated for C2+ alkane removal while still meeting the C2+ alkane specification for feed to the bromination step, in some embodiments. Yet another potential advantage of embodiments of the systems and methods of the present invention is that separation of the methane from the brominated hydrocarbons should reduce the feed rate to the synthesis reactor in the alkyl bromide conversation step. Accordingly, the size of the synthesis reactor can be reduced, which may result in considerable costs savings, especially if a fluidized bed reactor is employed, in accordance with present embodiments. Yet another potential advantage of embodiments of the systems and methods of the present invention is that separation of polybrominated alkanes from the monobrominated alkanes prior to feeding the synthesis reactor should reduce coke formation. Accordingly, the deactivation rate of the catalyst can be slowed, potentially allowing for use of a fixed-bed reactor for commercial-scale production, in certain embodiments.
The term “higher molecular weight hydrocarbons” as used herein refers to hydrocarbons comprising a greater number of carbon atoms than one or more components of the feedstock. For example, natural gas is typically a mixture of light hydrocarbons, predominately methane, with lesser amounts of ethane, propane, and butane, and even smaller amounts of longer chain hydrocarbons such as pentane, hexane, etc. When natural gas is used as a feedstock, higher molecular weight hydrocarbons produced in accordance with embodiments of the present invention may include a hydrocarbon comprising C2 and longer hydrocarbon chains, such as propane, butane, C5+ hydrocarbons, aromatic hydrocarbons, and mixtures thereof. In some embodiments, part or all of the higher molecular weight hydrocarbons may be used directly as a product (e.g., LPG, motor fuel, etc.). In other instances, part or all of the higher molecular weight hydrocarbons may be used as an intermediate product or as a feedstock for further processing. In yet other instances, part or all of the higher molecular weight hydrocarbons may be further processed, for example, to produce gasoline grade fuels, diesel grade fuels, and fuel additives. In some embodiments, part or all of the higher molecular weight hydrocarbons obtained by the processes of the present invention can be used directly as a motor gasoline fuel having a substantial aromatic content, as a fuel blending stock, or as feedstock for further processing such as an aromatic feed to a process producing aromatic polymers, such as polystyrene or related polymers.
The end use of the higher molecular weight hydrocarbons may depend on the particular catalyst employed in the oligomerization portion of the methods discussed below, as well as the operating parameters employed in the process. Other uses will be evident to those skilled in the art with the benefit of this disclosure.
The term “alkyl bromides,” as used herein, refers to mono-, di-, and tri-brominated alkanes, and combinations of these. Polybrominated alkanes include di-brominated alkanes, tri-brominated alkanes and mixtures thereof. These alkyl bromides may then be reacted over suitable catalysts so as to form higher molecular weight hydrocarbons.
Lower molecular weight alkanes may be used as a feedstock for the methods described herein. A suitable source of lower molecular weight alkanes may be natural gas. As used herein, the term “lower molecular weight alkanes” refers to methane, ethane, propane, butane, pentane or mixtures of two or more of these individual alkanes. The lower molecular weight alkanes may be from any suitable source, for example, any source of gas that provides lower molecular weight alkanes, whether naturally occurring or synthetically produced. Examples of sources of lower molecular weight alkanes for use in the processes of the present invention include, but are not limited to, natural gas, coal-bed methane, regasified liquefied natural gas, gas derived from gas hydrates and/or clathrates, gas derived from anaerobic decomposition of organic matter or biomass, gas derived in the processing of tar sands, and synthetically produced natural gas or alkanes. Combinations of these may be suitable as well in some embodiments. In some embodiments, it may be desirable to treat the feed gas to remove undesirable compounds, such as sulfur compounds and carbon dioxide. In any event, it is important to note that small amounts of carbon dioxide, e.g., less than about 2 mole %, can be tolerated in the feed gas to the processes of the present invention.
Suitable sources of bromine that may be used in various embodiments of the present invention include, but are not limited to, elemental bromine, bromine salts, aqueous hydrobromic acid, metal bromide salts, and the like. Combinations may be suitable, but as recognized by those skilled in the art, using multiple sources may present additional complications.
FIG. 1 is a schematic diagram illustrating a bromine-based process for the conversion of lower molecular weight alkanes to higher molecular weight hydrocarbons that includes fractionation of alkyl bromides in accordance with one embodiment of the present invention. As illustrated, embodiments of the process may include a bromination reactor 6 for brominating lower molecular alkanes, an alkyl bromides fractionation unit 12 for separation of unreacted alkanes and HBr from the brominated alkanes, a polybromides fractionation unit 18 for separation of polybrominated alkanes from monobrominated alkanes, and a synthesis reactor 24 for production of higher molecular weight hydrocarbons from the monobrominated alkanes. In the illustrated embodiment, the process further includes an HBr separator 28 for recovery of HBr from the higher molecular weight hydrocarbons, a dehydration and product recovery unit 36, and a bromide oxidation unit 38 for recovery of elemental bromine. The process may also include a second HBr separator 56 for recovery of HBr from the unreacted alkanes, a second dehydrator 64 for dehydration of the unreacted alkanes to form a recycle gas stream 58, and a recycle compressor 66 for compressing the recycle gas stream 58.
In the illustrated embodiment, a gas stream 2 comprising lower molecular weight alkanes (which, in some embodiments, may include a mixture of feed gas stream 52 plus recycled gas stream 58) and a bromine stream 4 may be combined and introduced into a bromination reactor 6. In the illustrated embodiment, the gas stream 2 and the bromine stream 4 are premixed to form a bromination feed gas stream 3 prior to feeding the bromination reactor 6. In an alternative embodiment (not illustrated), the gas stream 2 and bromine stream 4 may be combined in the bromination reactor 6. The gas stream 2 and bromine stream 4 may be allowed to react in the bromination reactor 6 to form a bromination product stream 8 that comprises alkyl bromides, HBr vapor, and unreacted alkanes. The bromination product stream 8 may be withdrawn from the bromination reactor 6.
In the bromination reactor 6, the lower molecular weight alkanes in the gas stream 2 may be reacted exothermically with the bromine in the bromine stream 4, for example, at a temperature in the range of about 250° C. to about 600° C., and at a pressure in the range of about 1 bar to about 50 bars to produce gaseous alkyl bromides and HBr. In an embodiment, the operating pressure of the bromination reactor 6 may range from about 20 bars to about 40 bars, for example, to minimize recompression costs and to maximize the condenser temperature required for the alkyl bromides fractionation step. In some embodiments, the feeds to the bromination reactor 6 may be pre-heated to a temperature of about 250° C. to about 400° C., for example, in an inlet pre-heater zone. It should be understood that the upper limit of the operating temperature range is greater than the upper limit of the reaction initiation temperature range to which the feed mixture may be heated due to the exothermic nature of the bromination reaction. Those of ordinary skill in the art will appreciate that the bromination reaction may be a non-catalytic (thermal) or a catalytic reaction as will be appreciated by those of ordinary skill in the art. Bromination of alkanes is described in more detail in U.S. Pat. No. 7,674,941, the disclosure of which is incorporated herein by reference. In the case of methane, it is believed that the formation of multiple brominated compounds occurs in accordance with the following general overall reaction:

aCH4(g)+bBr2(g)→cCH3Br(g)+dCH2Br2(g)+eCHBr3(g)+fCBr4(g)+xHBr(g)

The methane/bromine molar ratio of the feed introduced to the bromination reactor 6 may be at least about 2.5:1, in some embodiments. In alternative embodiments, a larger excess of methane (e.g., about 3:1 to about 10:1) may be used in order to achieve desirable selectivity of CH3Br and reduce the formation of soot, CH3Br is more rapidly brominated than methane under free radical conditions. The C2+ alkanes entering the bromination reactor 6 are known to more rapidly form polybrominated alkanes and coke/soot, as they are much more easily brominated than methane. Accordingly, in some embodiments, the C2+ alkane content entering the bromination reactor 6 can be controlled by treating the natural gas feed stream 32 or its mixture with the hydrocarbon products formed in the synthesis reactor 24 using any suitable means, such as cryogenic separation. In some embodiment, the C2+ alkane concentration in the total alkanes fed to the bromination reactor 6 is less than about 10 mole % in one embodiment, less than about 1 mole % in another embodiment, less than about 0.2 mole % in another embodiment, and less than about 0.1 mole % in yet another embodiment.
As illustrated, the bromination product stream 8 comprising alkyl bromides, HBr vapor, and unreacted alkanes can be withdrawn from the bromination reactor 6 and fed to an alkyl bromides fractionation unit 12. In the alkyl bromides fractionation unit 12, the bromination product stream 8 may be separated into a liquid alkyl bromides stream 14 and a gaseous alkane/HBr stream 16. The liquid alkyl bromides stream 14 may comprise monobrominated alkanes (e.g., CH3Br and other heavier monobrominated alkanes) and polybrominated alkanes (e.g., CH2Br2 and other heavier polybrominated alkanes), and the gaseous alkane/HBr stream 16 may comprise unreacted alkanes and HBr.
In some embodiments, the liquid alkyl bromides stream 14 may be fed to the polybromides fractionation unit 18. Prior to entering the polybromides fractionation unit 18, the liquid alkyl bromides stream 14 may be pumped to a higher pressure or let down to a lower pressure, as desired for a particular application. In some embodiments, the polybromides bromides fractionation unit 18 may have an operating pressure from about 1 bar to about 20 bars, for example, to minimize reboiler temperature (e.g., <250° C., alternatively, <200° C.) required for the polybromides fractionation while allowing the use of an inexpensive cooling medium (e.g., cooling water or air cooler) for the overhead condenser. In the polybromides fractionation unit 18, the liquid alkyl bromides stream 14 may be separated into a monobromides stream 20 comprising CH3Br and other heavier monobrominated alkanes and a polybromides stream 22 comprising CH2Br2 and other heavier polybrominated alkanes. In the illustrated embodiment, the polybromides stream 22 is returned to the bromination reactor 6 for reproportionating with lower molecular weight alkanes to produce a quantity of monobrominated alkanes in addition to those produced from reaction of the bromine and lower molecular alkanes. While not illustrated by FIG. 1, reproportionation of the polybrominated alkanes in the polybromides stream 22 may occur in a separate reactor from the bromination reactor 6 in accordance with alternative embodiments.
The monobromides stream 20 comprising CH3Br and other heavier monobrominated alkanes may be vaporized and fed to the synthesis reactor 24. In the synthesis reactor 24, the monobrominated alkanes may be reacted over a suitable catalyst under sufficient conditions via a catalytic coupling reaction to produce higher molecular weight hydrocarbons and additional HBr vapor. By separating some or all of the polybrominated alkanes from the feed to the synthesis reactor 24, coke formation in the synthesis reactor 24 may be reduced. By reducing coke formation in the synthesis reactor 24, the deactivation rate of the catalyst may be reduced. Due to this reduction in the deactivation rate, a fixed-bed reactor may be suitable, in some embodiments, even for commercial-scale production. In alternative embodiments, a fluidized-bed reactor may be used. Those of ordinary skill in the art will appreciate, with the benefit of this disclosure, that the particular higher molecular weight hydrocarbons produced will be dependent, for example, upon the catalyst employed, the composition of the alkyl bromides introduced, and the exact operating parameters employed. Catalysts that may be employed in the synthesis reactor 24 include synthetic crystalline alumino-silicate catalysts as will be recognized by those of ordinary skill in the art. Formation of higher molecular weight hydrocarbons from reaction of alkyl bromides is described in more detail in U.S. Pat. No. 7,674,941.
As illustrated, a synthesis product stream 26 comprising the higher molecular weight hydrocarbons may be withdrawn from the synthesis reactor 24 and fed to the HBr separator 28 for recovery of HBr. In some embodiments, the synthesis product stream 26 further may comprise an unintended amount of methane produced in the synthesis reactor 24 and the HBr vapor produced in the synthesis reactor 24. In the HBr separator 28, any of a variety of different suitable techniques may be used for separation of HBr, including, but not limited to, the techniques disclosed in U.S. Pat. No. 7,674,941. Non-limiting examples of techniques for HBr separation include absorption of HBr into an aqueous solution or adsorption of HBr on a metal oxide. In the illustrated embodiment, the synthesis product stream 26 may be contacted with recirculating aqueous solution 30 in the HBr separator 28 to recover HBr from the hydrocarbons by absorbing it into the aqueous solution. The resultant aqueous solution comprising HBr dissolved therein may be removed from the HBr separator 28 via aqueous HBr stream 34.
As illustrated, natural gas feed stream 32 may enter the HBr separator 28 for recovery of hydrocarbons or other purposes. For example, the natural feed gas stream 32 may strip out any residual hydrocarbons in the resultant aqueous solution comprising HBr dissolved therein, depending on the solubility of the hydrocarbons in the aqueous solution at the operating conditions. While not illustrated by FIG. 1, the natural gas feed stream 32 may alternatively be fed directly to the product recovery unit 36 for removal of C2+ hydrocarbons. While the present embodiment describes the use of natural gas feed stream 32, as discussed above, embodiments of the present invention encompass the use of other feedstocks of lower molecular weight alkanes.
The aqueous HBr stream 34 from the HBr separator 28 may then be routed to a bromide oxidation unit 38, in some embodiments, to convert the dissolved HBr to elemental bromine using, for example, air or oxygen and to regenerate the aqueous solution for reuse in the HBr separator 28. The regenerated aqueous solution may then be recirculated to the HBr separator 28 via recirculating aqueous solution 30. The bromine may then be treated sufficiently and sent to the bromination reactor 6 via bromine stream 4. In some embodiments, the bromine that is feed into the bromination reactor 6 may be dry bromine in that the bromine is substantially water-free. Effluent water 40 may also be removed from the bromide oxidation unit 38. Line 42 may be used to supply the oxygen or air fed to the bromide oxidation unit 38. Residual oxygen or spent air may be removed from the oxidation unit via line 44.
Hydrocarbon stream 46 comprising an unintended amount of methane produced in the synthesis reactor 24, higher molecular weight hydrocarbons, and the feed gas may be withdrawn from the HBr separator 28. The hydrocarbon stream 46 may be substantially HBr free, in accordance with embodiments of the present invention, for example, containing less than about 1 mppm HBr and alternatively less than 0.1 mppm HBr. As illustrated, the hydrocarbon stream 46 may be routed to dehydration and product recovery unit 36 wherein water may be removed from the remaining constituents, higher molecular weight hydrocarbons may be recovered as liquid hydrocarbon products, and lower molecular weight hydrocarbons (e.g., methane, ethane, etc.) may be recycled to the bromination reactor 6. Any suitable method of dehydration and product recovery may be used, including, but not limited to, solid-bed desiccant adsorption followed by refrigerated condensation, cryogenic separation, or circulating absorption oil or some other suitable solvent. As illustrated, water may be removed via water stream 48. A liquid hydrocarbon product stream 50 comprising higher molecular weight hydrocarbons may be withdrawn for use as a fuel, a fuel blend, or for further petrochemical or fuel processing, for example.
In the illustrated embodiment, the feed gas stream 52 comprising methane from the dehydration and product recovery unit 36 may be fed to the bromination reactor 6 via the feed compressor 54. As illustrated, the feed gas stream 52 may be combined with recycle gas stream 58 prior to feeding the bromination reactor 6. It should be understood that the feed gas stream 52 may also comprise some C2+ alkanes so long as the C2+ content of the alkanes in gas stream 2 (e.g., feed gas stream 52+recycle gas stream 58) fed to the bromination reactor 6 is less than a predetermined value.
As previously mentioned, the alkyl bromides fractionation unit 12 separates the bromination product stream 8 into a liquid alkyl bromides stream 14 comprising monobrominated alkanes and other heavier alkyl bromides and a gaseous alkane/HBr stream 16 comprising unreacted alkanes and HBr. In the illustrated embodiment, the gaseous alkane/HBr stream 16 may be withdrawn from the alkyl bromides fractionation unit 12 and fed to a second HBr separator 56. By routing the gaseous alkane/HBr stream 16 to the second HBr separator 56, in some embodiments, the unreacted alkanes and HBr separated in the alkyl bromides fractionation unit 12 are not fed to the synthesis reactor 24. Accordingly, in accordance with embodiments, the feed to the synthesis reactor 24 should be reduced, and the size of the synthesis reactor 24 can be reduced, resulting in cost savings.
In the second HBr separator 56, any of a variety of different suitable techniques may be used to produce a recycle gas stream 58 by separation of HBr, including, but not limited to, the techniques disclosed in U.S. Pat. No. 7,674,941. Non-limiting examples of techniques for HBr separation include absorption of HBr into an aqueous solution or adsorption of HBr on a metal oxide. In some embodiments, the HBr can be recovered from the unreacted alkanes by absorbing the HBr into an aqueous solution using, for example, a packed column or other suitable contacting device. In the illustrated embodiment, the gaseous alkane/HBr stream 16 may be contacted with second recirculating aqueous solution 60 in the second HBr separator 56 to recover HBr from the hydrocarbons by absorbing it into the aqueous solution.
The second HBr separator 56 and the HBr separator 28 may use the same or different techniques for the removal of HBr from the hydrocarbon streams (e.g., alkane/HBr stream 16, synthesis product stream 26). In addition, the second HBr separator 56 can operate at a different, and preferably, higher pressure than the HBr separator 28 which recovers HBr from the synthesis product stream 26. For example, the second HBr separator 56 can operate at a pressure that is at least about 3 bars higher than the HBr separator 28. In some embodiments, the second HBr separator 56 may operate at a pressure of about 5 bars to about 50 bars while the HBr separator 28 operates at a pressure of about 2 bars to about 47 bars.
The resultant aqueous solution comprising HBr dissolved therein may be removed from the second HBr separator 56 via second aqueous HBr stream 62, in accordance with embodiments of the present invention. The second aqueous HBr stream 62 may be combined with the aqueous HBr stream 34 from the HBr separator 28 and fed to the bromide oxidation unit 38, described above, to produce elemental bromine and regenerate the aqueous solutions for reuse in the HBr separator 28 and the second HBr separator 56. While FIG. 1 illustrates combination of the aqueous HBr stream 34 and second aqueous HBr stream 62 prior to entering the bromide oxidation unit 38, embodiments (not illustrated) may include separately feeding the aqueous HBr streams 34, 62 to the bromide oxidation unit 38.
As illustrated, the recycle gas stream 58 from the second HBr separator 56 may be fed to the second dehydrator 64 for removal of water and then to a recycle compressor 66 for recompression. After dehydration and recompression, the recycle gas stream 58 may be mixed with the feed gas stream 52 from the dehydration and product recovery unit 36 and routed to the bromination reactor 6 without further cryogenic treatment. Therefore, the process cost to control the presence of C2+ alkanes in the bromination reactor 6 is independent of the molar ratio of methane to bromine. In other words, the use of a large excess of methane should not increase the process cost associated with C2+ alkane control as the unreacted alkanes are not circulated throughout the entire system as disclosed in the process schemes used heretofore. While FIG. 1 illustrates combination of the recycle gas stream 58 and the feed gas stream 52 prior to entering the bromination reactor 6, embodiments (not illustrated) may include separately feeding the recycle gas stream 58 and the feed gas stream 52 to the bromination reactor 6.
In the embodiment illustrated by FIG. 1, the unreacted alkanes separated from the alkyl bromides in the alkyl bromides fractionation unit 12 are only circulating through the bromination reactor 6, the alkyl bromides fractionation unit 12, the second HBr separator 56, and the second dehydrator 64, enduring much less pressure drop by avoiding circulation through the entire system as disclosed in the process schemes used heretofore. As a result, the increase in compression cost for using a large excess of methane or high methane-to-bromine ratio in the bromination reactor 6 can be minimized by incorporation of embodiments of the present invention.
Referring now to FIG. 2, a bromine-based process is illustrated for the conversion of lower molecular weight alkanes to higher molecular weight hydrocarbons that includes fractionation of brominated hydrocarbons in accordance with another embodiment of the present invention. The illustrated embodiment is similar to that illustrated by FIG. 1 except that a light ends product stream 74 comprising C2-C4 hydrocarbons is specified as an additional product from the product recovery unit 70. It should be understood that when the light ends product stream 74 is specified, the feed gas stream 52 routed to the bromination reactor 6 can contain substantially pure methane, in some embodiments, in that the C2+ alkane concentration in the feed gas stream 52 may be less than about 1 mole %, in one embodiment, and less than about 0.1 mole %, in another embodiment.
In the illustrated embodiment, hydrocarbon stream 46 comprising an unintended amount of methane produced in the synthesis reactor 24, higher molecular weight hydrocarbons, and the feed gas may be withdrawn from the HBr separator 28 and routed to a dehydrator 68 for removal of water and then a product recovery unit 70 for recovery of a heavy ends product stream 72 comprising C5+ hydrocarbons, a light ends product stream 74 comprising C2-C4 hydrocarbons, and a feed gas stream 52 comprising methane. Any suitable method of dehydration and product recovery may be used, including, but not limited to, solid-bed desiccant adsorption followed by refrigerated condensation, cryogenic separation, or circulating absorption oil or some other solvent.
The feed gas stream 52 comprising methane from the product recovery unit 70 may be fed to the bromination reactor 6 via the feed compressor 54. It should be understood that the feed gas stream 52 may also comprise some C2+ alkanes so long as the C2+ content of the alkanes (e.g., feed gas stream 52+recycle gas stream 58) fed to the bromination reactor 6 is less than a predetermined value. While FIG. 2 illustrates the feed gas stream 52 and the recycle gas stream 58 as separate streams, it should be understood that embodiments include premixing the feed gas stream 52 and the recycle gas stream 58 prior to feeding the bromination reactor 6.
Referring now to FIG. 3, a bromine-based process is illustrated for the conversion of lower molecular weight alkanes to higher molecular weight hydrocarbons that includes fractionation of brominated hydrocarbons in accordance with another embodiment of the present invention. The illustrated embodiment is similar to that illustrated in FIG. 2 except that the light ends product stream 74 comprising C2-C4 hydrocarbons is recycled to reproportionate polybrominated alkanes in a shift reactor 76, producing a quantity of monobrominated alkanes in addition to those produced in the bromination reactor 6.
As illustrated, the light ends product stream 74 comprising C2-C4 hydrocarbons may be fed to the shift reactor 76 via a light ends recycle compressor 78. The polybromides stream 22 from the polybromides fractionation unit 18 comprising CH2Br2 and other heavier polybrominated alkanes may also be fed to the shift reactor 76. In some embodiments, the feeds may be vaporized prior to their introduction into the shift reactor 76. In the shift reactor 76, at least a portion of the polybrominated alkanes in the polybromides stream 22 can be reproportionated into monobrominated alkanes, thus increasing the content of monobrominated alkanes in the feed to the synthesis reactor 24. This shift reaction occurs by reaction of the C2-C4 hydrocarbons in the light ends product stream 74 with the polybrominated alkanes to form monobrominated alkanes, such as CH3Br, ethyl bromide (C2H5Br), propyl bromide (C3H7Br), and the like. In some embodiments, the shift reaction may proceed thermally without a catalyst.
In another embodiment, the shift reaction may be a catalytic reaction. Example techniques for reproportionation of polybrominated alkanes via a shift reaction are described in more detail in U.S. Pat. No. 7,674,941.
In the illustrated embodiment, a reproportionated alkyl bromides stream 80 comprising monobrominated alkanes, unreacted C2-C4 hydrocarbons, and unconverted polybromides may be withdrawn from the shift reactor 76 and routed back to the polybromides fractionation unit 18. As previously discussed, the polybromides fractionation unit 18 also receives a liquid alkyl bromides stream 14 as a feed from the alkyl bromides fractionation unit 12. In the illustrated embodiment, the polybromides fractionation unit 18 separates the reproportionated alkyl bromides stream 80 and liquid alkyl bromides stream 14 into a monobromides stream 20 and a polybromides stream 22. In one embodiment, the monobromides stream 20 may be fed to the synthesis reactor 24 for reaction over a suitable catalyst to produce higher molecular weight hydrocarbons. As illustrated, the polybromides stream 22 may be fed to the shift reactor 76 for another round of reproportionation.
Referring now to FIG. 4, a bromine-based process is illustrated for the conversion of lower molecular weight alkanes to higher molecular weight hydrocarbons that includes fractionation of brominated hydrocarbons in accordance with another embodiment of the present invention. The illustrated embodiment is similar to that illustrated in FIG. 2 except that the light ends product stream 74 comprising C2-C4 hydrocarbons is recycled to a light ends bromination reactor 82 to produce C2+ bromides, preferably C2+ monobromides, for additional feed to the synthesis reactor 24.
As illustrated, the light ends product stream 74 may be fed to the light ends bromination reactor 82 via light ends recycle compressor 78. In the light ends bromination reactor 82, the light end hydrocarbons may be allowed to react with bromine fed to the reactor 82 via line 84 to form products that comprise C2+ alkyl bromides, HBr vapor, and unreacted light end hydrocarbons.
In some embodiments, the light ends bromination reactor 82 may operate at milder conditions than the bromination reactor 6. For example, the light ends bromination reactor 82 may operate at a temperature in the range of about 200° C. to about 500° C., alternatively about 235° C. to about 450° C., and alternatively about 250° C. to about 425° C. By way of further example, the light ends bromination reactor 82 may operate at a pressure in the range of about 1 bar to about 80 bars, alternatively about 10 bars to about 50 bars, and alternatively about 20 bars to about 40 bars. In one embodiment, the light ends bromination reactor 82 may operate at a temperature in the range of about 250° C. to about 425° C., and at a pressure in the range of about 15 bars to about 35 bars while the bromination reactor 6 may operate at a temperature in the range of about 350° C. to about 500° C. and a pressure of about 25 bars to about 40 bars.
The effluent that contains the C2+ alkyl bromides, HBr vapor, and unreacted light end hydrocarbons may be withdrawn from the light ends bromination reactor 82 and fed to the synthesis reactor 24 via line 86. In the synthesis reactor 24, the C2+ alkyl bromides may react over a suitable catalyst to produce higher molecular weight hydrocarbons. While the effluent in line 86 from the light ends bromination reactor 82 and the monobromides stream 20 from the alkyl bromides fractionation unit 12 comprising CH3Br and other heavier monobrominated alkanes are illustrated as separate feeds to the synthesis reactor 24, it should be understood that present embodiments encompass processes in which these streams are combined prior to the synthesis reactor 24.
Referring now to FIG. 5, fractionation of brominated hydrocarbons via an alkyl bromides fractionation unit 12 and a polybromides fractionation unit 18 is illustrated in accordance with embodiments of the present invention. In the illustrated embodiment, the alkyl bromides fractionation unit 12 separates the bromination product stream 8 into a gaseous alkane/HBr stream 16 and a liquid alkyl bromides stream 14, and the polybromides fractionation unit 18 separates the liquid alkyl bromides stream 14 into a monobromides stream 20 and a polybromides stream 22.
As illustrated, a bromination feed gas stream 3 comprising lower molecular weight alkanes (which, in some embodiments, may include a mixture of feed gas stream 52 plus the recycled gas stream 58, as shown on FIG. 1) and bromine may be heated against the bromination product stream 8 in a bromination feed/product cross heat exchanger 88. The bromination feed gas stream 3 may be heated to a temperature of about 250° C. to about 450° C., in one embodiment, and about 300° C. to about 400° C. in another embodiment. The heated bromination feed gas stream 3 may then be combined with polybromides stream 22 from the polybromides fractionator 18 and fed to the bromination reactor 6. In some embodiments, the heated bromination feed gas stream 3 vaporizes the polybromides stream 22 prior to entering the bromination reactor 6.
In the bromination reactor 6, the lower molecular weight alkanes from the feed gas stream 3 may react with bromine to produce brominated alkanes and HBr vapor. In addition, at least a portion of the polybrominated alkanes in the polybromides stream 22 can be reproportionated into monobrominated alkanes. This reproportionation occurs by reaction of the lower molecular weight alkanes in the feed gas stream 3 with the polybrominated alkanes to form monobrominated alkanes, such as CH3Br, C2H5Br, and the like. In one embodiment, the bromination and reproportionation reactions may result in an adiabatic temperature rise to about 450° C. to about 550° C. while producing a bromination product stream 8 comprising gaseous alkyl bromides and HBr. In some embodiments, the bromination reactor 6 may be operated at a pressure in the range of about 1 bar to about 50 bars. To minimize recompression costs and to maximize condenser temperature in the alkyl bromides fractionator 90, the bromination reactor 6 may be operated, for example, at a pressure of about 20 bars to about 40 bars. A bromination product stream 8 comprising the alkyl bromides (e.g., CH3Br and other brominated alkanes), HBr vapor, and unreacted alkanes may be withdrawn from the bromination reactor 6.
In the illustrated embodiment, the bromination product stream 8 can first be cooled prior to entering the alkyl bromides fractionator 90 for separation of the unreacted methane and HBr from the alkyl bromides. As illustrated, the bromination product stream 8 may be first cooled against the bromination feed gas stream 3 in the bromination feed/product cross heat exchanger 88. While not illustrated, the bromination product stream 8 may be further cooled, in some embodiments, by exchanging heat with one or more other process streams in one or more cross heat exchangers. In one embodiment, the bromination product stream 8 may then be cooled, for example, to a temperature of about 33° C. to about 43° C., by exchanging heat with water stream 92 in water-cooled heat exchanger 94. It should be understood that a cooling medium other than water stream 92 may be used in some embodiments, for example, to obtain a lower temperature (e.g., about −10° C. to about 33° C.) for the bromination product stream 8 exiting the heat exchanger 94. The cooled bromination product stream 8, which partially condenses in the water-cooled heat exchanger 94, may then be sent, in one embodiment, to an inlet separator 96 (e.g., drum) for vapor-liquid phase separation. As illustrated, the bromination product stream 8 may be separated into a gas stream 98 and a liquid stream 100 in the inlet separator 96. The liquid stream 100 may be introduced into a lower section of the alkyl bromides fractionator 90 via pump 102. In some embodiments, the alkyl bromides fractionator 90 may include a liquid distributor or manifold (not shown) to more evenly distribute the liquid stream 100 throughout the internal cross sectional area of the alkyl bromides fractionator 90. The alkyl bromides fractionator 90 may comprise a number of trays or equivalent packing material, identified in FIG. 5 by reference number 104. The gas stream 98 from the inlet separator 96 may be further cooled, for example, to a temperature of about 10° C. to about 30° C., by exchanging heat in feed/overheads cross heat exchanger 106 with the gaseous alkane/HBr stream 16 from the overhead of the alkyl bromides fractionator 90 before being introduced into a higher section of the alkyl bromides fractionator 90.
In accordance with present embodiments, the alkyl bromides fractionator 90 should separate CH3Br and heavier bromides from the effluent gas as a bottoms liquid product. The alkyl bromides fractionator 90 may operate at a pressure of about 1 bar to about 50 bars, alternatively about 20 bars to about 40 bars, and alternatively about 30 bars to about 35 bars. As illustrated, the bottoms liquid product can be withdrawn from at or near the bottom of the alkyl bromides fractionator 90 via liquid alkyl bromides stream 14. Liquid alkyl bromides stream 14 should generally comprise monobrominated alkanes (e.g., CH3Br and other heavier monobrominated alkanes) and polybrominated alkanes (e.g., CH2Br2 and other heavier polybrominated alkanes). In some embodiments, the liquid alkyl bromides stream 14 may comprise less than about 2% by weight of the total HBr introduced into the alkyl bromides fractionator 90, alternatively less than about 1%, and alternatively less than about 0.1%. A second bottoms stream 108 comprising CH3Br and other heavier bromides be withdrawn from at or near the bottom of the alkyl bromides fractionator 90 and vaporized in reboiler 110, for example, by means of steam 112 in a manner that will be evident to those of ordinary skill in the art before being introduced back into the alkyl bromides fractionator 90 at or near the bottom thereof. In some embodiments, the reboiler 110 may operate to heat the second bottoms stream 108 to a temperature of about 100° C. to about 200° C., and about 130° C. to about 170° C., in another embodiment.
An overhead vapor stream 114 may be withdrawn at or near the top of the alkyl bromides fractionator 90 and partially condensed in a reflux condenser 116 against a refrigerant 118 and conveyed to a reflux separator drum 120. The reflux condenser 116 may operate to cool the overhead vapor stream 114 to a temperature of about −40° C. to about 0° C. In some embodiments, the overhead vapor stream 114 is cooled to a temperature warmer than about −40° C. and warmer than −34° C., in another embodiment. The reflux condenser 116 may have an operating pressure, for example, of about 20 bars to about 40 bars. The refrigerant 118 in the reflux condenser 116 may include, for example, propane or other available refrigerants. In the reflux separator drum 120, the overhead vapor stream 114 that was partially condensed in the reflux condenser 116 can be separated into a reflux stream 122 and a gaseous alkane/HBr stream 16. The reflux stream 122 may be conveyed via reflux pump 124 back into the alkyl bromides fractionator 90 at or near the top thereof. As illustrated, the gaseous alkane/HBr stream 16 exiting the reflux separator drum 120 may cross exchange in an overheads cross heat exchanger 126 with the overhead vapor stream 114 entering the reflux condenser 116 and in a feed/overheads cross heat exchanger 106 with the gas stream 98 entering the alkyl bromides fractionator 90, for example, to reduce refrigerant use. The gaseous alkane/HBr stream 16 from the reflux separator drum 120 may comprise, for example, HBr and unreacted alkanes (e.g., primarily methane with some heavier alkanes, such as ethane). In some embodiments, the gaseous alkane/HBr stream 16 comprises less than about 100 mppm alkyl bromides, alternatively less than about 10 mppm alkyl bromides, and alternatively less than about 1 mppm alkyl bromides. In accordance with present embodiments, the gaseous alkane/HBr stream 16 may be routed to other process units (e.g., second HBr separator 56 illustrated on FIG. 1) without entering the synthesis reactor 24.
As illustrated, the liquid alkyl bromides stream 14 from the bottom of the alkyl bromides fractionator 90 may be routed to the polybromides fractionator 128. Prior to entering the polybromides fractionator 128, the liquid alkyl bromides stream 14 may be pumped to a higher pressure or let down to lower pressure, as desired for a particular application. In the illustrated embodiment, the liquid alkyl bromides stream 14 may be let down to a lower pressure across valve 130. The polybromides fractionator 128 may operate, for example, at a pressure of about 1 bar to about 30 bars, and alternatively, about 10 bars to about 20 bars. In some embodiments, the polybromides fractionator 128 may include a liquid distributor or manifold (not shown) to more evenly distribute the liquid alkyl bromides stream 14 throughout the internal cross sectional area of the polybromides fractionator 128. The polybromides fractionator 128 may comprise a number of trays or equivalent packing material, identified in FIG. 5 by reference number 132.
In accordance with present embodiments, the polybromides fractionator 128 should separate the liquid alkyl bromides stream 14 into a monobromides stream 20 comprising CH3Br and other heavier monobrominated alkanes and a polybromides stream 22 comprising CH2Br2 and other heavier polybrominated alkanes. As illustrated, the polybromides stream 22 can be withdrawn from at or near the bottom of the polybromides fractionator 128. In some embodiments, the polybromides stream 22 may comprise more than about 0.1 weight % monobrominated alkanes, alternatively, more than about 1 weight % monobrominated alkanes, and alternatively more than about 10 weight % monobrominated alkanes. It should be understood that the content of monobrominated alkanes in polybromides stream 22 can be controlled, in some embodiments, for bottoms temperature control, avoiding potential overheating of the polybromides fractionator 128 bottoms and subsequent polybromides degradation at high temperatures. As previously mentioned, the polybromides stream 22 may be recycled to the bromination reactor 6 via pump 133, as shown on FIG. 5. A second bottoms stream 134 comprising CH2Br2 and other heavier polybromides can be withdrawn from at or near the bottom of the polybromides fractionator 128 and vaporized in reboiler 136, for example, by means of steam 138 in a manner that will be evident to those of ordinary skill in the art before being introduced back into the polybromides fractionator 128 at or near the bottom thereof. In some embodiments, the reboiler 136 may operate to heat the second bottoms stream 134 to a temperature of about 150° C. to about 250° C., and about 150° C. to about 180° C., in another embodiment. Those of ordinary skill in the art should appreciate, with the benefit of this disclosure, that the temperature of reboiler 136 should be controlled, for example, to minimize the risk of polybromides polymerization and fouling.
The overhead vapor stream 140 may be withdrawn at or near the top of the polybromides fractionator 128 and partially condensed in reflux condenser 142 against a coolant 144 and conveyed to a reflux separator drum 146. The reflux condenser 142 may operate to cool the overhead vapor stream 140 to a temperature warmer than about 37° C., in one embodiment, and warmer than about 43° C. in another embodiment. The coolant 144 in the reflux condenser 142 may include, for example, water, air, or other available cooling medium. In the reflux separator drum 146, the overhead vapor stream 140 that was partially condensed in the reflux condenser 142 can be separated into a reflux stream 148 and a monobromides stream 20. The reflux stream 148 may be conveyed via reflux pump 150 back into the polybromides fractionator 128 at or near the top thereof. The monobromides stream 20 from the reflux separator drum 146 may comprise, for example, CH3Br and other heavier monobrominated alkanes. In some embodiments, the monobromides stream 20 may comprise less than about 1,000 mppm polybrominated alkanes, alternatively less than about 100 mppm polybrominated alkanes, alternatively less than about 10 mppm polybrominated alkanes, and alternatively less than about 1 mppm polybrominated alkanes. In accordance with some embodiments, the monobromides stream 20 may be routed to the synthesis reactor 24 (e.g., shown on FIG. 1) for production of higher molecular weight hydrocarbons. In some embodiments, the monobromides stream 20 may be recovered as a liquid, for example, when desired to operate the synthesis reactor 24 at a higher pressure than the polybromides fractionator 128.
While the preceding description is directed to bromine-based processes for the conversion of lower molecular weight alkanes to higher molecular weight hydrocarbons, it should be understood that chlorine or another suitable halogen may be used in accordance with present embodiments. Additionally, it should be understood that the present invention also encompasses conversion of lower molecular weight alkanes to other higher molecular weight hydrocarbons. For example, a catalyst may be selected in the synthesis reactor 24 (e.g., shown on FIG. 1) for the production of olefins from alkyl bromides in a manner that will be evident to those of ordinary skill in the art.
To facilitate a better understanding of the present invention, the following examples of certain aspects of some embodiments are given. The following examples should not be read or construed in any manner to limit, or define, the entire scope of the invention.
EXAMPLE 1
Simulations were conducted using Aspen Hysys V7.1 to analyze the inclusion of a polybromides fractionation unit in a process for converting natural gas to liquid hydrocarbons via a bromine-based method. 50 MMSCFD of natural gas was fed to a first process for converting natural gas to liquid hydrocarbons via a bromine-based method. The first process was similar to the process illustrated by FIG. 1, but without a polybromides fractionation unit, e.g., instead of feeding the polybromides fractionation unit, the liquid alkyl bromides stream from the alkyl bromides fractionation unit fed the synthesis reactor. A bromination feed gas stream comprising a Cl/Br2 mixture having a Cl/Br2 molar ratio of 2.5 was fed to the bromination reactor at a temperature of 200° C. to 400° C. and 35 barg and left at a temperature of 450° C. to about 500° C. In the bromination reactor, essentially all of the Br2 was consumed, resulting in a bromination product stream comprised of 3,378 kmol/h HBr, 5,950 kmol/h unreacted Cl, and 2,494 kmol/h Cl bromide products. The bromide selectivity profile was: 70 mol % CH3Br, 25 mol % CH2Br2, and 5 mol % other bromides and solid carbonaceous compounds. Distilling the bromination product stream in an alkyl bromides fractionator produced a 9,293 kmol/h alkane/HBr stream as an overhead stream and a 2,528 kmol/h liquid alkyl bromides stream as a bottom stream. The liquid alkyl bromides stream containing 24 mol % CH2Br2 was fed to the synthesis reactor generating higher molecular weight hydrocarbons and HBr. The resultant synthesis product stream was then routed to an HBr separator to recover 3,411 kmol/h HBr into a recirculating aqueous solution. The alkane/HBr stream from the overhead of the alkyl bromides fractionator was routed to a second HBr separator to generate 5,950 kmol/h Cl recyclable to the bromination reactor after dehydration and to recover 3,343 kmol/h HBr into a second recirculating aqueous solution. The first and second recirculating aqueous solutions containing HBr dissolved therein produced from the HBr separators were combined and routed to a bromination oxidation unit to convert the dissolved bromide to 3,378 kmol/h elemental bromine for reuse in the bromination reactor.
50 MMSCFD of natural gas was fed to a second process for converting natural gas to liquid hydrocarbons via a bromine-based method. The second process is illustrated by FIG. 1 and comprises an alkyl bromides fractionation unit to separate out Cl/HBr from Cl bromides and a polybromides fractionation unit to separate out CH2Br2 and heavier polybromides from Cl bromides prior to feeding it to the synthesis reactor. A bromination feed gas stream comprising a Cl/Br2 mixture having a Cl/Br2 molar ratio of 2.5 along with a 1,798 kmol/h recycle polybromides stream was fed to the bromination reactor at a temperature of 200° C. to 400° C. and 35 Barg and left at a temperature of 450° C. to 500° C. In the bromination reactor, essentially all of the Br2 was consumed, resulting in a bromination product stream comprised of 2,564 kmol/h HBr, 3,804 kmol/h unreacted Cl, and 4,292 kmol/h Cl bromide products. The bromide selectivity profile was: 68 mol % CH3Br, 29 mol % CH2Br2, and 3 mol % other bromides and solid carbonaceous compounds. Distilling the bromination product stream in a first fractionator (alkyl bromides fractionator) and then the first column bottom stream (liquid alkyl bromides stream) in a second fractionator (polybromides fractionator), produced a 6,343 kmol/h alkane/HBr stream, a 2,498 kmol/h monobromides stream, and a 1,798 kmol/h polybromides stream. The monobromides stream containing 0.1 mol % CH2Br2 was fed to the synthesis reactor in generating higher molecular weight hydrocarbons and HBr. The resultant synthesis product stream was then routed to an HBr separator to recover 2,500 kmol/h HBr into a recirculating aqueous solution. The alkane/HBr stream from the overhead of the alkyl bromides fractionator was routed to a second HBr separator to generate 3,804 kmol/h Cl recyclable to the bromination reactor after dehydration and to recover a 2,538 kmol/h HBr into a second recirculating aqueous solution. The first and second recirculating aqueous solutions containing HBr dissolved therein produced from the two HBr separators were combined and routed to a bromination oxidation unit to convert the dissolved bromide to a 2,519 kmol/h elemental bromine for reuse in the bromination reactor.
The above results are summarized in Table 1. It shows that using the second process with the polybromides fractionation unit, as illustrated in FIG. 1, the utilization efficiency of Br2 significantly increased, requiring 25.4% less Br2 (reduced from 3,378 to 2,519 kmol/h) to process the same amount of natural gas feed while using the same Cl/Br2 molar ratio in the bromination reactor. The concentration of CH2Br2 in the feed to the synthesis reactor was also significantly reduced from 24 to 0.1 mol %.










TABLE 1







First process
Second process



(without
(with



Polybromides
Polybromides



Fractionation)
Fractionation)



















Natural Gas feed
(MMSCFD)
50
50


capacity


C1/Br2 molar ratio

2.5:1
2.5:1


in bromination reactor


Br2 circulation rate
(kgmol/h)
3,378
2,519


CH2Br2 content in the
(mol %)
24
0.1


feed to coupling reactor









EXAMPLE 2
Additional simulations were conducted using Aspen Hysys V7.1 to further analyze the inclusion of a polybromides fractionation unit in a process for converting natural gas to liquid hydrocarbons via a bromine-based method. 50 MMSCFD of natural gas was fed to a process for converting natural gas to liquid hydrocarbons via a bromine-based method. A bromination feed gas stream comprising a Cl/Br2 mixture having a C1/Br2 molar ratio of 2.5 along with a recycle polybromides stream entered the bromination reactor at a temperature of 200° C. to 400° C. and 35 Barg and left at a temperature of 450° C. to 500° C. Excluding carbonaceous solid compounds, the bromination product stream comprised of 24 mol % HBr, 36 mol % Cl, and 40 mol % Cl bromides fed a first distillation column (alkyl bromides fractionator) at a rate of 10,639 kgmol/h. Referring to FIG. 5, this column fractionated the bromination product stream into a 6,343 kgmol/h alkane/HBr stream as an overhead product at 32 barg containing essentially all of the HBr and Cl and a 4,296 kgmol/h liquid alkyl bromides stream as a bottom product containing CH3Br and heavier bromides. The column specifications included 1% HBr recovery in the bottom and 1 mppm CH3Br in the overheads. The condenser temperature was −4.4° C. requiring a refrigeration duty of 10 MW. The reboiler temperature was 171° C. requiring a steam duty of 27 MW.
The liquid alkyl bromides stream from the bottom of the alkyl bromides fractionator was then let down to 15 barg and fed to a second distillation column (polybromides fractionator). The second column fractionated the feed into an a 2,498 kgmol/h monobromides stream as an overhead product containing essentially pure CH3Br and a 1,798 kmol/h polybromides stream as a bottom product enriched in CH2Br2 and heavier bromides. The column specifications included 0.1 mol % CH2Br2 in the overhead and the reboiler temperature of 171° C. The condenser temperature was 102° C. requiring a cooling duty of 5 MW. The reboiler required a steam duty of 13 MW.
The above results are summarized in Table 2.










TABLE 2







Alkyl Bromides
Polybromides



Fractionator
Fractionator



















Feed rate
(kgmol/h)
10,639
4,296


Overhead rate
(kgmol/h)
6,343
2,498


Bottoms rate
(kgmol/h)
4,296
1,798


Condenser temperature
(° C.)
−4.4
102


Condenser duty
(MW)
10
5


Reboiler temperature
(° C.)
171
171


Reboiler duty
(MW)
27
13









Certain embodiments of the methods of the invention are described herein. Although major aspects of what is to believed to be the primary chemical reactions involved in the methods are discussed in detail as it is believed that they occur, it should be understood that side reactions may take place. One should not assume that the failure to discuss any particular side reaction herein means that that reaction does not occur. Conversely, those that are discussed should not be considered exhaustive or limiting. Additionally, although figures are provided that schematically show certain aspects of the methods of the present invention, these figures should not be viewed as limiting on any particular method of the invention.
Therefore, the present invention is well adapted to attain the ends and advantages mentioned as well as those that are inherent therein. The particular embodiments disclosed above are illustrative only, as the present invention may be modified and practiced in different but equivalent manners apparent to those skilled in the art having the benefit of the teachings herein. Although individual embodiments are discussed, the invention covers all combinations of all those embodiments. Furthermore, no limitations are intended to the details of construction or design herein shown, other than as described in the claims below. It is therefore evident that the particular illustrative embodiments disclosed above may be altered or modified and all such variations are considered within the scope and spirit of the present invention. All numbers and ranges disclosed above may vary by some amount. Whenever a numerical range with a lower limit and an upper limit is disclosed, any number and any included range falling within the range are specifically disclosed.

## Claims

1. A process comprising:
reacting at least gaseous alkanes and a halogen to produce at least a halogenation product stream, wherein the halogenation product stream comprises alkyl halides, hydrogen halide, and unreacted alkanes;
separating the halogenation product stream into at least a gaseous stream and a liquid alkyl halides stream, wherein the gaseous stream comprises hydrogen halide and unreacted alkanes, and wherein the liquid alkyl halides stream comprises alkyl halides;
separating the liquid alkyl halides stream into at least a monohalides stream and a polyhalides stream, wherein the monohalides stream comprises monohalogenated alkanes, and wherein the polyhalides stream comprises polyhalogenated alkanes; and
reacting at least a portion of the monohalogenated alkanes from the monohalides stream in the presence of a catalyst to produce at least a synthesis product stream, wherein the synthesis product stream comprises higher molecular weight hydrocarbons and hydrogen halide.

2. The process of claim 1 wherein the halogen comprises bromine.

3. The process of claim 1 wherein the gaseous alkanes comprise alkanes having 2 or more carbons in an amount of less than about 0.1 mole % to less than about 10 mole %.

4. The process of claim 1 wherein the step of separating the halogenation product stream comprises:
cooling the halogenation product stream;
separating the halogenation product stream into a liquid fractionator feed stream and a gaseous fractionator feed stream; and
feeding the liquid fractionator feed stream and the gaseous fractionator feed stream into a fractionator, wherein the gaseous stream and the liquid alkyl halides stream are withdrawn from the fractionator.

5. The process of claim 4 wherein the fractionator operates at a pressure of about 20 bars to about 40 bars.

6. The process of claim 4 further comprising:
withdrawing a second liquid stream from the fractionator and heating the second liquid stream to a temperature of about 100° C. to about 200° C. in a reboiler; and
withdrawing an overhead vapor stream from the fractionator and cooling the overhead vapor stream to a temperature warmer than about −40° C. in a condenser.

7. The process of claim 6 further comprising cooling the overhead vapor stream against the gaseous stream.

8. The process of claim 4 further comprising:
cooling the gaseous fractionator feed stream against the gaseous stream; and
cooling the halogenation product stream against a halogenation feed stream comprising the gaseous alkanes and the halogen from the step of reacting at least gaseous alkanes and a halogen.

9. The process of claim 1 wherein the liquid alkyl halides stream comprises less than about 2% by weight of the hydrogen halide from the halogenation product stream.

10. The process of claim 1 wherein the unreacted alkanes in the gaseous stream comprises methane and alkanes having 2 or more carbons in an amount of less than about 1% by mole.

11. The process of claim 1 wherein the gaseous stream comprises less than about 10 mppm alkyl halides.

12. The process of claim 1 further comprising reducing the liquid alkyl halides stream to a pressure of about 1 bar to about 30 bars.

13. The process of claim 1 wherein the step of separating the liquid alkyl halides stream into at least a monohalides stream and a polyhalides stream comprises: feeding the liquid alkyl halides stream into a second fractionator, wherein the monohalides stream and the polyhalides stream are withdrawn from the second fractionator.

14. The process of claim 13 further comprising:
withdrawing a liquid stream from the second fractionator and heating the liquid stream to a temperature of about 150° C. to about 250° C. in a reboiler; and
withdrawing an overhead vapor stream from the second fractionator and cooling the overhead vapor stream to a temperature warmer than about 37° C. in a condenser.

15. The process of claim 12 wherein the monohalides stream comprises monohalogenated methane, wherein polyhalogenated alkanes are present in the monohalides stream in an amount less than about 100 mppm.

16. The process of claim 1 further comprising:
recovering at least a portion of the hydrogen halide from the gaseous stream; and
recovering at least a portion of the hydrogen halide from the synthesis product stream, wherein recovery of the hydrogen halide from the synthesis product stream occurs in the same unit as the recovery of the hydrogen halide from the gaseous stream.

17. The process of claim 1 further comprising:
recovering at least a portion of the hydrogen halide from the gaseous stream; and
recovering at least a portion of the hydrogen halide from the synthesis product stream; wherein recovery of the hydrogen halide from the synthesis product stream occurs in a different unit than the recovery of the hydrogen halide from the gaseous stream.

18. The process of claim 1 further comprising reacting the gaseous alkanes with at least a portion of the polyhalogenated alkanes from the polyhalides stream to convert at least a portion of the polyhalogenated alkanes to monohalogenated alkanes.

19. The process of claim 1 further comprising reacting at least a portion of the polyhalogenated alkanes from the polyhalides stream with light end hydrocarbons to convert at least a portion of the alkyl halides from polyhalogenated alkanes to monohalogenated alkanes.

20. The process of claim 1 further comprising separating light end hydrocarbons from at least the higher molecular weight hydrocarbons and a natural gas feed, the light end hydrocarbons having from 2 carbons to 4 carbons.

21. The process of claim 20 further comprise reacting at least a portion of the light-end hydrocarbons with a halogen to form a stream comprising alkyl halides and hydrogen halide; and reacting at least a portion alkyl halides in the presence of the catalyst.

22. The process of claim 1 wherein the catalyst comprises a synthetic crystalline alumino-silicate catalyst.

23. A process comprising
reacting at least gaseous alkanes and bromine in a bromination reactor to produce at least a bromination product stream, wherein the bromination product stream comprise alkyl bromides, hydrogen bromide, and unreacted alkanes;
separating the bromination product stream into at least a gaseous alkane/HBr stream and a liquid alkyl bromides stream, wherein the gaseous alkane/HBr stream comprises hydrogen bromide and unreacted alkanes, and wherein the liquid alkyl bromides stream comprises alkyl bromides;
separating the liquid alkyl bromides stream into at least a monobromides stream and a polybromides stream, wherein the monobromides stream comprises monobrominated alkanes, and wherein the polybromides stream comprises polybrominated alkanes;
reacting at least a portion of the monobrominated alkanes from the monobromides stream in a synthesis reactor to produce at least a synthesis product stream, wherein the synthesis product stream comprises higher molecular weight hydrocarbons and hydrogen bromide;
recovering at least a portion of the hydrogen bromide from the synthesis product stream in a hydrogen bromide separator;
providing a natural gas stream;
separating at least the synthesis product stream and the natural gas stream into at least a light ends product stream, a heavy ends product stream, and a feed gas stream, wherein the light ends product stream comprises light end hydrocarbons having from 2 carbons to 4 carbons, wherein the heavy ends product stream comprises heavy end hydrocarbons having 5 or more carbons, and wherein the feed gas stream comprises methane;
compressing the feed gas stream in a feed compressor;
feeding the feed gas stream into the bromination reactor;
generating a recycle alkane stream by recovering at least a portion of the hydrogen bromide from the gaseous alkane/HBr stream in a second hydrogen bromide separator operating at a higher pressure than the hydrogen bromide separator;
compressing the recycle alkane stream in a recycle compressor; and
feeding the recycle alkane stream to the bromination reactor.

24. The process of claim 23 wherein the step of separating the bromination product stream comprises:
cooling the bromination product stream;
separating the bromination product stream into a liquid fractionator feed stream and a gaseous fractionator feed stream; and
feeding the liquid fractionator feed stream and the gaseous fractionator feed stream into an alkyl bromides fractionator, wherein the gaseous alkane/HBr stream and the liquid alkyl bromides stream are withdrawn from the alkyl bromides fractionator, and wherein the alkyl bromides fractionator operates at a pressure of about 20 bars to about 40 bars.

25. The process of claim 23 wherein the liquid alkyl bromides stream comprises less than about 2% by weight of the hydrogen bromide from the bromination product stream.

26. The process of claim 23 wherein the gaseous alkane/HBr stream comprises less than about 10 mppm alkyl bromides.

27. The process of claim 23 further comprising feeding the polybromides stream to the bromination reactor such that at least a portion of the polybrominated alkanes react with the gaseous alkanes to convert at least a portion of the polybrominated alkanes to monobrominated alkanes.

28. The process of claim 23 further comprising reacting at least a portion of the polybrominated alkanes from the polybromides stream with at least a portion of the light end hydrocarbons from the light-ends product stream to convert at least a portion of the polybrominated alkanes to monobrominated alkanes.

29. The process of claim 23 further comprising:
reacting bromine and at least a portion of the light end hydrocarbons from the light-end hydrocarbon stream to form a brominated stream comprising brominated light end hydrocarbons, hydrogen bromide, and unreacted light end hydrocarbons; and
reacting at least a portion of the brominated light end hydrocarbons in the presence of the catalyst in the synthesis reactor.

30. The process of claim 23 wherein the catalyst comprises a synthetic crystalline alumino-silicate catalyst.