WO2008157043A1 - Processes for producing higher hydrocarbons from methane - Google Patents

Processes for producing higher hydrocarbons from methane

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Publication number
WO2008157043A1
WO2008157043A1 PCT/US2008/065833 US2008065833W WO2008157043A1 WO 2008157043 A1 WO2008157043 A1 WO 2008157043A1 US 2008065833 W US2008065833 W US 2008065833W WO 2008157043 A1 WO2008157043 A1 WO 2008157043A1
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WO
Grant status
Application
Patent type
Prior art keywords
methane
halide
metal
gaseous
hydrocarbons
Prior art date
Application number
PCT/US2008/065833
Other languages
French (fr)
Other versions
WO2008157043A8 (en )
Inventor
George W. Cook, Jr.
Joe D. Sauer
Allen M. Beard
Joseph E. Coury
Mario A. Garcia
Original Assignee
Albemarle Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date

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Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/76Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G50/00Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06Halogens; Compounds thereof
    • C07C2527/125Compounds comprising a halogen and scandium, yttrium, aluminium, gallium, indium or thallium
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06Halogens; Compounds thereof
    • C07C2527/125Compounds comprising a halogen and scandium, yttrium, aluminium, gallium, indium or thallium
    • C07C2527/126Aluminium chloride

Abstract

Processes are provided for producing higher hydrocarbons wherein at least gaseous methane and a meta! halide are combined at a temperature hot enough to gasify a portion of the meta! halide.

Description

PROCESSES FOR PRODUCING HIGHER HYDROCARBONS FROM METHANE

BACKGROUND

[0001] Methane is a major constituent of natural gas and also of biogas. World reserves of natural gas are constantly being increased, e.g., due to new discoveries, etc. However, a significant portion of the world reserves of natural gas is in remote locations, where gas pipelines frequently cannot be economically justified. Natural gas is often co-produced with oil in remote offsite locations where reinjection of the gas is not feasible. Much of the natural gas produced along with oil at remote locations, as well as methane produced in petroleum refining and petrochemical processes, is flared. Since methane is classified as a greenhouse gas, future flaring of natural gas and methane may be prohibited or restricted. Thus, significant amounts of natural gas and methane are available to be utilized.

[0002] Different technologies have been described for utilizing these sources of natural gas and methane. For example, technologies are available for converting natural gas to liquids, which are more easily transported than gas. Various technologies are described for converting methane to higher hydrocarbons and aromatics.

[0003] In regard to converting natural gas to liquid fuels, the Fischer Tropsch (FT) reaction involves the synthesis of liquid hydrocarbons or their oxygenated derivatives from the mixture of carbon monoxide and hydrogen, which can be obtained, e.g., by the partial combustion of methane or by the gasification of coal. This synthesis is carried out with metallic catalysts such as iron, cobait, or nickel at high temperature and pressure. The overall efficiency of the FT reaction and subsequent water gas shift chemistry is estimated at about 15% to 30%, when allowing for the energy required to make the conversion. While FT does provide a route for the liquefication of coal stocks, it is not adequate in its present level of understanding and production for commercial conversion of methane-rich stocks to liquid fuels. FT requires a heavily discounted natural gas source to be economical. Additionally, a FT plant is expensive and bulky, and therefore not suitable for use in many remote locations, such as on an offshore oil rig where natural gas comprising methane is routinely flared. [0004] It is possible to hydrogenate carbon monoxide to generate methanol. Methanol, by strict definition of the "gas to liquid" descriptor, would seem to fulfil! the target desire of liquefication of normally gaseous, toxic feedstocks. However, in many regards, the oxygen containing molecules have already relinquished a significant percentage of their chemical energy by the formation of the C-O bond present. A true "methane to liquid hydrocarbon" process would afford end products that would not suffer these losses.

[0005] Yet another approach for methane utilization involves the halogenation of the hydrocarbon molecule to halomethane and subsequent reactions of that intermediate in the production of a variety of materials. Again, the efficiency and overall cost performance of such routes would be commercially prohibitive. Such a halogenation process would also suffer from decrease of stored chemical energy during the C-X bond formation. Additionally, the halogen species has to be satisfactorily accounted for (Le,, either recycled, or captured in some innocuous, safe form) within the end-use of the product from this overall route.

[0006] Gas to liquid processes that can convert methane into liquid fuels have been a significant challenge to the petrochemical industry at large. Of note are the works of Karl Ziegler and Giulio Natta regarding aluminum catalysts for ethylene chain growth, culminating in the 1963 Nobel Prize for Chemistry; the work of George Olah in carbocation technology, for which Mr. Olah received the 1994 Nobel Prize for Chemistry; and the work of Peter Wasserscheid regarding transition metal catalysis in ionic liquid media.

[0007] In spite of technologies that are currently described and available, a need exists for commercially feasible means for converting methane to useful hydrocarbons.

THE INVENTION

[0008] This invention meets the above-described needs by providing processes for producing C-2 and higher hydrocarbons, comprising combining at least gaseous methane and a metal halide within a temperature range in which at least some of the metal halide is gaseous. In processes of this invention, the gaseous methane and the metal halide can combine to form a second stream and the second stream can be at at least a temperature high enough to initiate polymerization of the methane. This invention also provides processes for producing C2 and higher hydrocarbons, comprising combining at least gaseous methane, a metal halide, and a halogen within a temperature range in which at least some of the metal haiide is gaseous. This invention also provides processes for producing C2 and higher hydrocarbons, comprising combining at least gaseous methane, a metal halide, and a hydrogen halide within a temperature range in which at least some of the metal halide is gaseous. [0009] We have discovered that usable higher hydrocarbons can be produced directly from methane by processes that comprise combining at least gaseous methane and a metal halide suitable for catalyzing polymerization of the methane. Even in view of extensive research that has been conducted in the areas of catalysis and in looking for commercially suitable utilization of methane, processes such as we disclose herein are not commercially available. Processes of this invention are particularly advantageous in that produced higher hydrocarbons are useful, e.g., as gasoline, diesel fuel, chemical feedstock, heating oils, lubricating oils, and the like. An added benefit of processes of this invention is that usable H2 is produced, as is described in greater detail below. A component suitable for absorbing hydrogen can be used in processes of this invention for recovery of the usable H2. Alternatively, H2 can be recovered by techniques familiar to those skilled in the art, such as by pressure swing absorption, distillation, and the like. The availability of usable H2 is advantageous in that it can be used as a dean- burning fuei with reduced CO2 emissions as compared to traditional fuels. [0010] Also provided by this invention are processes comprising combining at least gaseous methane and a metal halide at at least a temperature at which at least some of the metal halide is gaseous, yielding C2 and higher hydrocarbons; such processes wherein the metal halide comprises aluminum bromide, aluminum chloride, aluminum fluoride, titanium bromide, or aluminum iodide; such processes wherein the metal halide comprises aluminum bromide and the temperature is about 1000C; such processes wherein at least some of the gaseous methane and some of the gaseous metal halide (e.g., aluminum bromide) combine to form a second stream and the second stream is at at least a reaction temperature high enough to initiate polymerization of the methane (e.g., about 25O0C) ; such processes further comprising combining an additional component with the at least gaseous methane and metal halide, wherein the additional component comprises methyl iodide, titanium bromide, a branched hydrocarbon, ethane, hydrogen, an alkyl halide, an olefin, or a metal haiide comprising Li, Na, K, Mg, Ca, Sc, Y, Zr, Cu, Hf, V, Nb, Ta, Fe, Ru, Co, Ni, Pb, B, Ga, Ge, Sn, or Sb and bromine, chlorine, fluorine, or iodine; such processes further comprising combining a hydrogen halide with the at least gaseous methane and metal halide; such processes further comprising combining a hydrogen halide and an additional component with the at least gaseous methane and metal halide, wherein the additional component comprises methyl iodide, titanium bromide, a branched hydrocarbon, ethane, hydrogen, an alkyl halide, an olefin, or a metal halide comprising Li, Na, K, Mg, Ca, Sc, Y, Zr, Cu, Hf, V, Nb, Ta, Fe, Ru, Co, Ni, Pb, B, Ga, Ge, Sn, or Sb and bromine, fluorine, chlorine, or iodine.

[0011] Also provided are processes for producing C2 and higher hydrocarbons, comprising: (a) heating a metal halide to a temperature at least high enough to gasify at least some of the metal halide, and (b) combining at least gaseous methane and the heated metal halide, yielding C2 and higher hydrocarbons; such processes wherein at least the gaseous methane and the heated metal halide combine to form a second stream and the second stream is at at least a reaction temperature high enough to initiate polymerization of the methane; such processes wherein the metal halide comprises aluminum bromide and the reaction temperature is about 2500C; such processes wherein (b) is replaced with: (b) combining at least gaseous methane, the heated metal halide, and a component suitable for absorbing hydrogen; such processes wherein the component suitable for absorbing hydrogen comprises Raney nickel, platinum, paladium, tantalum, niobium, yttrium, platinum on carbon, paladium on carbon, platinum on activated carbon, or paladium on activated carbon. [0012] Also provided are processes for producing C2 and higher hydrocarbons, comprising passing at least gaseous methane through a container containing at least a metal halide at at least a temperature at which at least some of the metal halide is gaseous, and yielding C2 and higher hydrocarbons.

[0013] Also provided are processes for producing C2 and higher hydrocarbons, comprising (a) heating a metal halide to a temperature at least high enough to gasify at least some of the metal halide, and (b) passing at least gaseous methane through a container containing at least the heated metal halide, yielding C2 and higher hydrocarbons.

[0014] Also provided are processes comprising combining at least gaseous methane, a metal halide, a hydrogen halide, and an additional component at at least a temperature at which at feast some of the metal halide is gaseous, yielding C2 and higher hydrocarbons, wherein the additional component comprises methyl iodide, titanium bromide, a branched hydrocarbon, ethane, hydrogen, an alkyl halide, an olefin, or a metal halide comprising Li, Na, K, Mg, Ca, Sc, Y, Zr, Cu, Hf, V, Nb, Ta, Fe, Ru, Co,

Ni, Pb, B, Ga, Ge, Sn, or Sb and bromine, fluorine, chlorine, or iodine. [0015] Also provided are processes comprising combining at least gaseous methane and a Lewis acid at at least a temperature at which at least some of the Lewis acid is gaseous, yielding C2 and higher hydrocarbons. Suitable Lewis acids include, without limitation, metal hafides such as aluminum bromide. As is familiar to those skilled in the art, a Lewis acid is defined as a compound capable of accepting an electron pair. [0016] Also provided are processes comprising combining at least gaseous methane, a Lewis acid, and a Bronsted acid, e.g., HBr, at at least a temperature at which at least some of the Lewis acid is gaseous, yielding C2 and higher hydrocarbons. As is familiar to those skilled in the art, a Bronsted acid is defined as a compound capable of donating a proton.

[0017] These and other aspects of the invention are described herein and by reference to the Figures, in which:

Figure 1 iilustrat.es a batch process according to this invention; and Figure 2 illustrates a batch process according to this invention; and Figure 3 illustrates a batch process according to this invention; and Figure 4 illustrates a continuous process according to this invention; and Figure 5 illustrates a continuous process according to this invention. [0018] C2 and higher hydrocarbons produced according to processes of this invention can include without limitation C2 to C30 hydrocarbons, particularly C2 to C12 hydrocarbons or C4 to C8 hydrocarbons. The C2 and higher hydrocarbons produced according to this invention can include normal and iso alkanes (CnH2n+2), cyclic alkanes (CnH2n), alkenes (CnH2n), alkynes (CnH2n-2), aromatics, and the like. [0019] The gaseous methane can be provided by a natural gas stream co-produced with oil or otherwise produced, or a natural gas stream from any other suitable source. For example, the gas stream can be produced from coal beds (e.g., anthracite or bituminous); biogas produced by the anaerobic decay of non-fossil organic materia! from swamps, marshes, landfills, and the like; biogas produced from sewage sludge and manure by way of anaerobic digesters; biogas produced by enteric fermentation particularly in cattle and termites; and from other gas sources. H2 can be added with the gas stream.

[0020] The gas stream can comprise at least about 50 vol% methane, or at least about 75 vol% methane. Other components can be present in the gas stream, for example, ethane, butane, propane, carbon dioxide, nitrogen, helium, hydrogen sulfide, water, odorants, mercury, organosulfur compounds, etc. Such components can be removed as needed from the gas stream prior to, during, or after processing according to this invention using techniques familiar to those skilled in the art. The gas stream can consist essentially of methane, e.g., can be zero grade, or essentially pure, methane.

[0021] This invention also provides processes for producing C-2 and higher hydrocarbons, comprising combining at least a hydrocarbon feed source and a metal halide within a temperature range in which at least some of the metal halide is gaseous. Suitable hydrocarbon feed sources include, without limitation, paraffin waxes, high density polyethylene, plastic grocery bags, C-ie straight chain paraffins, isopentane, cyclohexane, heptane, acetylene, ethylene, etc.

[0022] Other components can be present in the hydrocarbon feed source, for example, oxygen, nitrogen, helium, hydrogen sulfide, water, odorants, mercury, organosulfur compounds, etc. Such components can be removed as needed from the hydrocarbon feed source prior to, during, or after processing according to this invention using techniques familiar to those skilled in the art.

[0023] The metal halide or other Lewis acid can be suitable for catalyzing polymerization of methane and can comprise aluminum bromide (e.g., AIBr3 or aluminum chloride, aluminum fluoride, aluminum iodide, titanium bromide, and the like, including mixtures thereof. For example, titanium bromide in the form of TiBr2, TiBr4, and the like can be used. Without limiting this invention, metal halides comprising a metal such as Li, Na, K, Mg, Ca, Sc, Y, Zr, Cu, Hf, V, Nb, Ta, Fe, Ru, Co, Ni, Pb, B, Ga, Ge, Sn, or Sb and a halogen such as bromine, chlorine, iodine, or fluorine may also be used in processes of this invention. The metal halide can have a purity of 100% or less than 100%. For example, the metal halide can be of a commercial grade, can have a purity of at least about 95%, or at least about 98%, or at least about 99%, or at least about 99.9%. Impurities can be present on the surface of the metal haϊide(s); and such impurities can participate in reactions that occur during processes of this invention. [0024] The metal halide can be heated such that it is at a temperature, or is within a temperature range, that is at least high enough to gasify at least some of the metal halide. When the metal halide comprises aluminum bromide, the temperature can be at least about 1000C, and can be from about 1000C to about 4000C, or about 2500C to about 35O0C. [0025] When a hydrogen halide is used in processes of this invention, any suitable hydrogen halide can be used, for example hydrogen bromide. When a hydrogen halide, such as hydrogen bromide for example, is used, it can have a purity of about 100% or less than about 100%. For example, the hydrogen halide can be of a commercial grade, can have a purity of at least about 95%, or at least about 98%, or at least about 99%, or at least about 99.9%. Additionally, the hydrogen halide can have a purity of at least about 50% or at least about 90% and can comprise various impurities such as H2O, CO, CO2, O2, HCi, HF, Br2, Cl2, fluorine, or iodine, to name a few. The same is true when another hydrogen halide is used, such as hydrogen fluoride, or hydrogen chloride, or hydrogen iodide.

[0026] The component suitable for absorbing hydrogen can comprise Raney nickel, platinum, paladium, tantalum, niobium, yttrium, platinum on carbon, paladium on carbon, platinum on activated carbon, paladium on activated carbon, etc. Raney nickel can be comprised of aluminum-nickel alloy. Given the teachings of this disclosure, one skilled in the art can select an suitable component for absorbing hydrogen. [0027] Processes according to this invention for producing C2 and higher hydrocarbons can comprise combining at least gaseous methane, a metal halide, and an additional component. Without limiting this invention, the additional component (sometimes referred to herein as a promoter) can comprise a halogen such as bromine, chlorine, fluorine, or iodine; methyl iodide; titanium bromide; metal halides comprising a metal such as Li, Na, K1 Mg1 Ca, Sc, Y, Zr, Cu, Hf, V, Nb, Ta, Fe, Ru1 Co, Ni, Pb, B, Ga, Ge, Sn, or Sb and a halogen such as bromine, chlorine, fluorine, or iodine; branched hydrocarbons such as isopentane, neopentane, and the like; ethane; hydrogen; alkyl halides such as methyl bromide, ethyl bromide, and the like; and/or olefins such as propene, butene, and the like. One or more additional components can be combined. Such additional components can be generated in situ. For example, combined methane and bromine can generate methyl bromide in situ; combined hydrogen bromide and ethylene can generate ethylene bromide in situ, etc.. [0028] Referring, for example, to Figure 1 , in processes of this invention, the metal halide 114 can catalyze polymerization of methane in gaseous methane stream 118 to C2 and higher hydrocarbons. Gaseous methane stream 118 can comprise ethane, butane, olefins, etc., in addition to the methane. The meta! halide 114 can be in a container 112. The container 112 can be heated by any suitable means, e.g., by a heated sand bed 116, so that the metal halide 114 is heated, e.g., at least to its melting temperature. The gaseous methane stream 118 can be injected into (or otherwise put into) the container 112 such that the metal halide 114 catalyzes polymerization of the methane. For example, the residence time of methane in the gaseous methane stream 118 within the container 112 and other conditions, such as temperature, can be adequate to initiate polymerization of the methane. For example, residence time can be up to about one minute. Longer residence times can be used. For example, residence time of methane in the gaseous methane stream 118 within the container 112 can be longer than about one minute, for example from about one minute to about five minutes, or up to about two minutes. A substantia! portion of the polymerization can occur in vapor phase 119. Simultaneously with the polymerization in vapor phase 119, some of the polymerized higher hydrocarbons can be cracked, e.g., by thermal cracking, acid cracking, etc.. At appropriately high temperatures, olefins are formed and hydrogen given off can assist in the cracking process. For example, the temperature can be above about 35O0C, or can be from about 35O0C to about 10000C, or from about 350°C to about 4000C. At lower temperatures, cracking can be achieved without the assistance of olefins by addition of hydrogen. For example, at a temperature of up to about 3500C, or at about 1100C, cracking can be assisted by addition of hydrogen under pressure. Thermal reforming of hydrocarbons, isomerization of hydrocarbons, and other reactions can also occur in vapor phase 119 and/or elsewhere in container 112. Skeletel or bond isomerization can occur. The metal halide can catalyze polymerization of the methane by action as a Lewis acid. Although not illustrated in Figure 1 , hydrogen given off during the polymerization of the methane can be recovered for sale or use, e.g., by being absorbed by a component suitable for absorbing hydrogen, which component may be in the container 112 with the metal halide 114 or may be in a separate container through which the gaseous methane stream 118 (or a resulting product/product stream (not shown in Figure 1)) is subsequently passed. Produced C-2 and higher hydrocarbons can be recovered from container 112 by means known to those skilled in the art (not illustrated in Figure 1). Given the teachings of this disclosure, those skilled in the art can determine appropriate temperatures, pressures, and other process parameters as desired to achieve desired results using processes of this invention.

[0029] Referring, for example, to Figure 2, in processes of this invention, metal halide 214 can catalyze polymerization of methane in gaseous methane stream 218 to C-2 and higher hydrocarbons. The metal halide 214 can be in a container 212. Also, component 215 (e.g., packing) can be put into container 212, e.g., for the purpose of increasing surface area within container 212 and/or for supporting the metal halide 214. One benefit of component 215 is that additional surface area is provided for surface activated polymerization reactions. Gas/vapor phase polymerization reactions can also occur. Suitable packing materials will be well known to those skilled in the art, given the teachings of this disclosure, and can include, for example, glass beads, aluminum oxides, and zeolites. The container 212 can be heated by any suitable means, e.g., by a heated sand bed 216, so that the metal halide 214 is heated, e.g., to at least its melting temperature. The gaseous methane stream 218 can be injected into (or otherwise put into) the container 212 such that the metal halide 214 catalyzes polymerization of the methane. For example, the residence time of methane in the gaseous methane stream 218 within the container 212 and other conditions, such as temperature, can be adequate to initiate polymerization of the methane. A substantial portion of the polymerization can occur on the surface of component 215 and/or in vapor phase 219. Simultaneously with the polymerization on the surface of component 215 and/or in vapor phase 219, some of the polymerized higher hydrocarbons can be cracked by, e.g., therma! cracking, acid cracking, or the like. Thermal reforming of hydrocarbons, isomerization of hydrocarbons, and other reactions can also occur in vapor phase 219 and/or elsewhere in container 212. Although not illustrated in Figure 2, hydrogen given off during the polymerization of the methane can be recovered for sale or use, e.g., by being absorbed by a component suitable for absorbing hydrogen, which component may be in the container with the metal halide or may be in a separate container through which the gaseous methane stream is subsequently passed. Produced C-2 and higher hydrocarbons can be recovered from container 212 by means known to those skilled in the art (not illustrated in Figure 2),

[0030] The vapor phase (e.g., 119 in Figure 1 or 219 in Figure 2) can comprise ionic species in that the pressure and temperature conditions allow a substantial portion of the metal halide to remain available as a salt in the vapor phase. A vapor phase containing such ionic species can be conducive to reactions such as alkylation, isomerization, and the like. At least some of such monomolecular ionic species can form a cloud and can, and do, migrate to available surfaces and maintain activity. [0031] Byproducts of processes according to this invention can include red oil or red oil like substances. Red oil is a clathrate of at least olefinic hydrocarbon(s), aluminum halide(s), and, in some cases, Bronsted acid(s) and/or other Lewis acid(s). [0032] A benefit of processes of this invention is that components having a catalytic effect on the polymerization reactions taking place, e.g., aluminum bromide and hydrogen bromide, for example, either do not require regeneration, e.g., when conditions are maintained to minimize tar formation during processes of this invention, or can be regenerated in situ with hydrogen pressure at the appropriate temperature.

Examples

[0033] The following examples are illustrative of the principles of this invention. It is understood that this invention is not limited to any one specific embodiment exemplified herein, whether in the examples or the remainder of this patent application. [0034] At an offshore oil production site, natural gas comprising at least about 50 vo!% methane is being co-produced with oil. Given the remote location of the production site and limited available space on the offshore platform, the natural gas is being flared. None of the valuable energy potential of the methane is being utilized. [003S] To improve the situation, a process according to the present invention is used to produce higher hydrocarbons from the methane. The higher hydrocarbons as well as the hydrogen produced during the process are utilized as fuel at the platform, thus providing a substantia! economic benefit to the site.

[0036] Referring to Figure 3, natural gas stream 318 comprises on average from about 70 vol% to about 85 vol% methane, and also includes other components such as ethane, butane, propane, carbon dioxide, nitrogen, helium, and hydrogen sulfide. Instead of being flared, at least a portion of natural gas stream 318 is passed through container 312. Device 313 in container 312 is supported by inert material 310. Device 313 is made from glass, an inert material. Inert material 310 is glass beads; and in addition to supporting device 313, inert material 310 fills at least some of the otherwise empty space in container 312. In general, inert materials 310 used in this invention can include glass and other suitable inert materials. A slurry 317 of about 3 grams to about 5 grams of aluminum bromide 314 and about 0.5 grams to about 2 grams platinum-on-activated-charcoal 315 is in device 313. The temperature inside container 312 is maintained between about 25O0C and 4000C by heated sand bed 316. Residence time of methane (in natural gas stream 318) within container 312 is from about 1 minute to about 30 minutes. The conditions in container 312 are adequate to catalyze polymerization of methane to C2 and higher hydrocarbons. A substantial portion of the polymerization occurs in vapor phase 319. Simultaneously with the polymerization in vapor phase 319, some of the polymerized higher hydrocarbons are thermally cracked. During the polymerization, produced hydrogen is absorbed by platinum-on-activated-charcoal 315, or another suitable hydrogen absorber. Outlet gas stream 320, exiting container 312 and comprising produced C2 and higher hydrocarbons and any unreacted methane, is input to device 330. Within device 330, recycle stream 334 comprising any unreacted methane is separated from product stream 332 comprising liquefied C2 and higher hydrocarbons. Recycle stream 334 comprising methane is input into container 312 along with natural gas stream 318. Product stream 332 comprising liquefied C2 and higher hydrocarbons is removed from device 330 and is put into storage containers (not illustrated in Figure 3) for use as fuel and for chemical feedstock needed at the offshore production site, or is used directly without being stored. Intermittently, platinum-on-activated-charcoal 315 is removed from device 313 in container 312 and replaced with fresh platinum-on-activated- charcoal 315. Hydrogen is recovered as removed platinum-on-activated-charcoal 315 is regenerated for reuse within container 312, using means known to those skilled in the art. The replacement and regeneration of platinum-on-activated-charcoal 315, and recovery of hydrogen therefrom, are not illustrated in Figure 3. Recovered hydrogen is stored for use as fuel, or used directly without being stored.

|0037] Figure 4 illustrates a process according to this invention. In Figure 4, devices 410, 420, and 430 can each be separate devices; devices 410 and 420, or devices 420 and 430, can both be portions or zones of a single device; or all of devices 410, 420, and 430 can each be a portion or zone of a single device. As shown in [ I ] of Figure 4, at least a portion of natural gas stream 318 is passed into device 410. Aluminum bromide 414 and packing 415 are in device 410. The temperature inside device 410 is maintained between about 2500C and 4000C by means known to those skilled in the art, and the pressure inside device 410 is at about atmospheric. As shown in [ Il ] of Figure 4, at least a portion of the contents of device 410 flow into device 420. Additionally, methane stream 417, at pipeline pressure or higher, e.g., at a pressure of about just above ambient to about 2000 psi is added to the contents of device 410 as it exits device 410. The temperature within device 420 is lower than that within device 410, e.g., between about ambient and about 25O0C. The conditions in device 420 are adequate to catalyze polymerization of methane to C2 and higher hydrocarbons. As shown in [ !H ] of Figure 4, at least a portion of the contents of device 420 flow into device 430. C2 and higher hydrocarbons are removed from device 430, e.g., via product stream 435. The C2 and higher hydrocarbons are removed from device 430, e.g., by changing the temperature and/or pressure conditions in device 430. As illustrated by [ SII ] of Figure 4, the process illustrated in Figure 4 is a continuous process once started (as shown in [ I ] and [ II ]). Although not shown, aluminum bromide 414 and packing 415 in devices 410, 420, and/or 430 are replenished as needed.

[0038] Referring to Figure 5, which illustrates continuous process system 599 according to this invention, gaseous feedstock in container 500 comprises gaseous methane, HBr, ethane and hydrogen. The gaseous feedstock is fed via conduit 510 to conduit 520. Pressure regulator 530 is used to regulate the pressure within container 500. Flow valve 540 is used to control flow through rotometer 545. Container 550 contains aluminum bromide 560. Aluminum bromide 580 is heated to about 1000C by heat provided by a heating source, e.g., a heating mantle (not shown in Figure 5) with heat from the heating source being transferred through a heat transfer material 555, e.g., sand. Nitrogen from a nitrogen source (not shown in Figure 5) is fed through conduit 570 (via flow valve 572 and rotometer 574) through the aluminum bromide in container 550. Pressure indicator 565 indicates the pressure within container 550. Gaseous nitrogen and aluminum bromide exit container 550 via conduit 580. Both the gaseous feedstock from conduit 510 and the gaseous nitrogen and aluminum bromide from conduit 580 flow into conduit 520 in container 521. Each of conduits 580 and 520 is insulated, e.g., with heating tape. The contents of conduit 520 are fed to stainless capillary coil 590, which is heated to a temperature of about 3250C by heat provided by a heating source, e.g., a heating mantle (not shown in Figure 5) with heat from the heating source being transferred through sand bed 592 in container 591. Stainless capillary coil 590 is about 100 yards long. Product comprising C2 and higher hydrocarbons exits container 591 (coil 590) via conduit 600. Device 610 is an all-in-one condenser, separator, collector, and sight glass). Flow valve 611 is used to control flow of product comprising C-2 and higher hydrocarbons to storage and/or end use facilities (not shown in Figure 5). Flow valve 620 in conduit 625 controls flow of gaseous fluid through rotometer 640 that is used to regulate flow through continuous process system 599. Gaseous fluid in conduit 625 is vented via vent 623; samples of gaseous fluid in conduit 625 can be taken through valve 645.

[0039] Given the teachings of this disclosure, those skilled in the art can determine appropriate temperatures, pressures, and other process parameters as desired to achieve desired results using processes of this invention. [004Oj It is to be understood that the reactants and components referred to by chemical name or formula anywhere in the specification or claims hereof, whether referred to in the singular or plural, are identified as they exist prior to being combined with or coming into contact with another substance referred to by chemical name or chemical type (e.g., another reactant, a solvent, or etc.). It matters not what chemical changes, transformations and/or reactions, if any, take place in the resulting mixture or solution or reaction medium as such changes, transformations and/or reactions are the naturai result of bringing the specified reactants and/or components together under the conditions called for pursuant to this disclosure. Thus the reactants and components are identified as ingredients to be brought together in connection with performing a desired chemical reaction or in forming a mixture to be used in conducting a desired reaction. Accordingly, even though the claims hereinafter may refer to substances, components and/or ingredients in the present tense ("comprises", "is", etc.), the reference is to the substance, component or ingredient as it existed at the time just before it was first contacted, combined, blended or mixed with one or more other substances, components and/or ingredients in accordance with the present disclosure. Whatever transformations, if any, which occur in situ as a reaction is conducted is what the claim is intended to cover. Thus the fact that a substance, component or ingredient may have lost its original identity through a chemical reaction or transformation during the course of contacting, combining, blending or mixing operations, if conducted in accordance with this disclosure and with the application of common sense and the ordinary skill of a chemist, is thus wholly immaterial for an accurate understanding and appreciation of the true meaning and substance of this disclosure and the claims thereof. As will be familiar to those skilled in the art, the terms "combined", "combining", and the like as used herein mean that the components that are "combined" or that one is "combining" are put into a container with each other. Likewise a "combination" of components means the components having been put together in a container.

[0041] While the present invention has been described in terms of one or more preferred embodiments, it is to be understood that other modifications may be made without departing from the scope of the invention, which is set forth in the claims below.

Claims

CLAIMSWhat is claimed is:
1. A process comprising combining at least gaseous methane and a metal halide at at least a temperature at which at least some of the metal halide is gaseous, yielding C2 and higher hydrocarbons.
2. The process of claim 1 wherein the metal halide comprises aluminum bromide, aluminum chloride, aluminum fluoride, titanium bromide, or aluminum iodide.
3. The process of claim 1 wherein the metal halide comprises aluminum bromide and the temperature is about 1000C.
4. The process of claim 1 wherein at least some of the gaseous methane and some of the gaseous metal halide combine to form a second stream and the second stream is at at least a reaction temperature high enough to initiate polymerization of the methane.
5. The process of claim 4 wherein the metal halide comprises aluminum bromide and the reaction temperature is about 2500C.
6. The process of claim 1 further comprising combining an additional component with the at least gaseous methane and metal halide, wherein the additional component comprises methyl iodide, titanium bromide, a branched hydrocarbon, ethane, hydrogen, an alkyl halide, an olefin, or a metal halide comprising Li, Na, K, Mg, Ca, Sc, Y, Zr, Cu, Hf, V, Nb, Ta, Fe, Ru, Co, Ni, Pb, B, Ga, Ge, Sn, or Sb and bromine, fluorine, chlorine, or iodine.
7. The process of claim 1 further comprising combining a halogen with the at least gaseous methane and metal halide.
8. The process of claim 1 further comprising combining a hydrogen halide with the at Seas! gaseous methane and metal halide.
9. The process of claim 1 further comprising combining at least a hydrogen halide and an additional component with the at least gaseous methane and metal halide, wherein the additional component comprises methyl iodide, titanium bromide, a branched hydrocarbon, ethane, hydrogen, an alkyl halide, an olefin, or a metal halide comprising Li, Na, K, Mg1 Ca1 Scs Y, Zr, Cu, Hf, V, Nb, Ta, Fe, Ru, Co, Ni, Pb, B, Ga, Ge, Sn, or Sb and bromine, fluorine, chlorine, or iodine.
10. A process for producing C2 and higher hydrocarbons, comprising:
(a) heating a metal halide to a temperature at least high enough to gasify at least some of the metal halide, and
(b) combining at least gaseous methane and the heated metal halide, yielding C2 and higher hydrocarbons.
11. The process of claim 10 wherein at least the gaseous methane and the heated metal halide combine to form a second stream and the second stream is at at least a reaction temperature high enough to initiate polymerization of the methane.
12. The process of claim 11 wherein the metal halide comprises aluminum bromide and the reaction temperature is about 2500C.
13. The process of claim 10 wherein (b) is replaced with:
(b) combining at least gaseous methane, the heated metal halide, and a component suitable for absorbing hydrogen.
14. The process of claim 13 wherein the component suitable for absorbing hydrogen comprises Raney nickel, platinum, paladium, tantalum, niobium, yttrium, platinum on carbon, paladium on carbon, platinum on activated carbon, or paladium on activated carbon.
15. A process for producing C2 and higher hydrocarbons, comprising passing at least gaseous methane through a container containing at least a metal halide at at least a temperature at which at least some of the metal halide is gaseous, and yielding C2 and higher hydrocarbons.
16. A process for producing C2 and higher hydrocarbons, comprising
(a) heating a metal halide to a temperature at least high enough to gasify at least some of the metal halide, and
(b) passing at least gaseous methane through a container containing at least the heated metal halide, yielding C2 and higher hydrocarbons.
17. A process comprising combining at least gaseous methane, a metal halide, a hydrogen halide, and an additional component at at least a temperature at which at least some of the metal halide is gaseous, yielding C2 and higher hydrocarbons, wherein the additional component comprises methyl iodide, titanium bromide, a branched hydrocarbon, ethane, hydrogen, an alkyl halide, an olefin, or a metal halide comprising Li, Na, K, Mg, Ca, Sc, Y, Zr, Cu, Hf, V, Nb, Ta, Fe, Ru, Co, Ni, Pb, B, Ga, Ge, Sn, or Sb and bromine, fluorine, chlorine, or iodine.
18. A process comprising combining at least gaseous methane and a Lewis acid at at least a temperature at which at least some of the Lewis acid is gaseous, yielding C2 and higher hydrocarbons.
19. A process comprising combining at least gaseous methane, a Lewis acid, and a Bronsted acid at at least a temperature at which at least some of the Lewis acid is gaseous, yielding C2 and higher hydrocarbons.
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US7880041B2 (en) 2004-04-16 2011-02-01 Marathon Gtf Technology, Ltd. Process for converting gaseous alkanes to liquid hydrocarbons
US8008535B2 (en) 2004-04-16 2011-08-30 Marathon Gtf Technology, Ltd. Process for converting gaseous alkanes to olefins and liquid hydrocarbons
US8173851B2 (en) 2004-04-16 2012-05-08 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons
US9206093B2 (en) 2004-04-16 2015-12-08 Gtc Technology Us, Llc Process for converting gaseous alkanes to liquid hydrocarbons
US8232441B2 (en) 2004-04-16 2012-07-31 Marathon Gtf Technology, Ltd. Process for converting gaseous alkanes to liquid hydrocarbons
US7674941B2 (en) 2004-04-16 2010-03-09 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons
US8921625B2 (en) 2007-02-05 2014-12-30 Reaction35, LLC Continuous process for converting natural gas to liquid hydrocarbons
US8282810B2 (en) 2008-06-13 2012-10-09 Marathon Gtf Technology, Ltd. Bromine-based method and system for converting gaseous alkanes to liquid hydrocarbons using electrolysis for bromine recovery
US9133078B2 (en) 2010-03-02 2015-09-15 Gtc Technology Us, Llc Processes and systems for the staged synthesis of alkyl bromides
US8198495B2 (en) 2010-03-02 2012-06-12 Marathon Gtf Technology, Ltd. Processes and systems for the staged synthesis of alkyl bromides
US8367884B2 (en) 2010-03-02 2013-02-05 Marathon Gtf Technology, Ltd. Processes and systems for the staged synthesis of alkyl bromides
US8815050B2 (en) 2011-03-22 2014-08-26 Marathon Gtf Technology, Ltd. Processes and systems for drying liquid bromine
US8436220B2 (en) 2011-06-10 2013-05-07 Marathon Gtf Technology, Ltd. Processes and systems for demethanization of brominated hydrocarbons
US8829256B2 (en) 2011-06-30 2014-09-09 Gtc Technology Us, Llc Processes and systems for fractionation of brominated hydrocarbons in the conversion of natural gas to liquid hydrocarbons
US8802908B2 (en) 2011-10-21 2014-08-12 Marathon Gtf Technology, Ltd. Processes and systems for separate, parallel methane and higher alkanes' bromination
US9193641B2 (en) 2011-12-16 2015-11-24 Gtc Technology Us, Llc Processes and systems for conversion of alkyl bromides to higher molecular weight hydrocarbons in circulating catalyst reactor-regenerator systems
EP2841535A4 (en) * 2012-04-23 2015-12-09 Shell Int Research A process for the aromatization of a methane-containing gas stream

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