WO2017030758A1

WO2017030758A1 - A method of converting an alkane to an alkyl alcohol

Info

Publication number: WO2017030758A1
Application number: PCT/US2016/044173
Authority: WO
Inventors: Aghaddin Kh. MAMEDOV; Xiankuan X. ZHANG
Original assignee: SABIC Global Technologies BV
Current assignee: SABIC Global Technologies BV
Priority date: 2015-08-20
Filing date: 2016-07-27
Publication date: 2017-02-23
Anticipated expiration: 2018-02-20

Abstract

In an embodiment, a method for converting an alkane to an alkyl alcohol comprises, co-currently flowing the alkane, a halogen source, and a catalyst, through a halogenation reactor to form a halogenated stream and a spent catalyst stream; directing the halogenated stream and a water stream to a second hydroxylation reactor end of a hydroxylation reactor; directing the spent catalyst stream to a first hydroxylation reactor end of the hydroxylation reactor, and counter-currently flowing the halogenated stream and the spent catalyst stream through the hydroxylation reactor to form a regenerated catalyst stream comprising the catalyst and a product stream comprising the alkyl alcohol and a hydrogen halide; and directing the regenerated catalyst stream comprising the catalyst back into the halogenation reactor.

Description

A METHOD OF CONVERTING AN ALKANE TO AN ALKYL ALCOHOL

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional Patent Application Serial No. 62/207,437 filed August 20, 2015. The related application is incorporated herein in its entirety by reference.

TECHNICAL FIELD

[0001] This disclosure is related to a method of converting an alkane to an alkyl alcohol.

BACKGROUND

[0002] Significant attention has been given to the production of alkyl alcohols, such as ethyl alcohol, or "ethanol," for use as a fuel additive with gasoline and as an alternative fuel, as ethanol burns cleaner than fossil fuels. Furthermore, ethanol can be used as a commodity feedstock, where it can be, for example, dehydrated to ethylene, which can then be converted to a variety of products, both polymeric and small molecule-based. Ethanol has been produced from petrochemical feed stocks, such as oil; natural gas; coal; feed stock intermediates, such as syngas; or from plant materials, such as corn or sugar cane.

Conventional methods for producing ethanol from petrochemical feed stocks, as well as from cellulose materials, include the acid-catalyzed hydration of ethylene, methanol homologation, direct alcohol synthesis, and Fischer-Tropsch synthesis. Instability in petrochemical feed stock prices contributes to fluctuations in the cost of conventionally produced ethanol, making the need for alternative sources of ethanol production greater when feed stock prices rise. Plant materials can be converted to ethanol by fermentation. However, fermentation is typically used for consumer production of ethanol, which is suitable for fuels or human consumption. In addition, fermentation of plant materials competes with food sources and places restraints on the amount of ethanol that can be produced for industrial use.

[0003] An improved method of producing an alkyl alcohol, such as ethanol, is desired.

BRIEF SUMMARY

[0004] Disclosed herein is a method of converting an alkane to an alkyl alcohol. [0005] In an embodiment, a method for converting an alkane to an alkyl alcohol comprises co-currently flowing the alkane, a halogen source, a catalyst, and optionally an oxidizing agent through a halogenation reactor to form a halogenated stream and a spent catalyst stream; wherein the alkane comprises methane, a halogen containing methane, ethane, a halogen containing ethane, or a combination comprising at least one of the foregoing; wherein the catalyst comprises copper chloride and one or both of potassium chloride and lanthanum chloride, wherein the halogenated stream comprises a halogenated alkane; wherein if the halogen containing methane and/or the halogen containing ethane is present in the alkane, then the halogenated alkane comprises at least one more halogen atom than the respective halogen containing methane and/or the halogen containing ethane;

directing the halogenated stream and a water stream to a second hydroxylation reactor end of a hydroxylation reactor; directing the spent catalyst stream to a first hydroxylation reactor end of the hydroxylation reactor, and counter-currently flowing the halogenated stream and the spent catalyst stream through the hydroxylation reactor to form a regenerated catalyst stream comprising the catalyst and a product stream comprising the alkyl alcohol and a hydrogen halide; wherein the alkyl alcohol comprises methanol, ethanol, ethylene glycol, or a combination comprising at least one of the foregoing; and directing the regenerated catalyst stream comprising the catalyst back into the halogenation reactor.

[0006] In another embodiment, a method for converting an alkane to an alkyl alcohol comprises co-currently flowing the alkane, a halogen source comprising a chlorine source, a catalyst, and optionally an oxidizing agent through a halogenation reactor to form a halogenated stream and a spent catalyst stream; wherein the alkane comprises methane, ethane, or a combination comprising at least one of the foregoing; wherein the catalyst comprises copper chloride, potassium chloride, and optionally lanthanum chloride, wherein the halogenated stream comprises chlorome thane, chloroethane, or a combination comprising at least one of the foregoing; wherein the halogenation reactor has a length that is equal to a bottom portion and a top portion, wherein the bottom portion length is at least 80% of the length, wherein an inner diameter of the bottom portion is 1.3 to 6.S cm and an inner diameter at all locations in the top portion is 5 to 13 cm; directing the halogenated stream and a water stream to a hydroxylation reactor, directing the spent catalyst stream to a first hydroxylation reactor end of the hydroxylation reactor, and counter-currently flowing the halogenated stream and the spent catalyst stream through the hydroxylation reactor to form a regenerated catalyst stream comprising the catalyst and a product stream comprising the alkyl alcohol and a hydrogen chloride; wherein the alkyl alcohol comprises methanol, ethanol, ethylene glycol, or a combination comprising at least one of the foregoing; and directing the regenerated catalyst stream comprising the catalyst back into the halogenation reactor.

[0007] In another embodiment, a method for converting an alkane to an alkyl alcohol comprises co-currently flowing the alkane, a halogen source comprising hydrogen chloride, a catalyst, and an oxidizing agent through a halogenation reactor to form a halogenated stream and a spent catalyst stream; wherein the alkane comprises ethane; wherein based on the total weight of the catalyst, the catalyst comprises 20 to SO wt% copper chloride, 5 to 40 wt% potassium chloride, 20 to 50 wt% lanthanum chloride; wherein the halogenated stream comprises chloroethane, dichloroethane, or a combination comprising at least one of the foregoing; directing the halogenated stream and a water stream to a second hydroxylation reactor end of a hydroxylation reactor, directing the spent catalyst stream to a first hydroxylation reactor end of the hydroxylation reactor, and counter-currently flowing the halogenated stream and the spent catalyst stream through the hydroxylation reactor to form a regenerated catalyst stream comprising the catalyst and a product stream comprising the alkyl alcohol and hydrogen chloride; wherein the alkyl alcohol comprises ethanol, ethylene glycol, or a combination comprising at least one of the foregoing; and directing the regenerated catalyst stream comprising the catalyst back into the halogenation reactor.

[0008] In a further embodiment, a system for producing an alkyl alcohol, comprises a halogenation reactor comprising a first halogenation reactor end and a second halogenation reactor end; and a hydroxylation reactor comprising a first hydroxylation reactor end and a second hydroxylation reactor end; wherein an alkane stream is in fluid communication with the second halogenation reactor end; wherein a halogenation stream is in fluid

communication with the first halogenation reactor end and the second hydroxylation reactor end; wherein a spent catalyst stream is in fluid communication with the first halogenation reactor end and the first hydroxylation reactor end; wherein a regenerated catalyst stream is in fluid communication with the second hydroxylation reactor end and the second halogenation reactor end; wherein a water stream is in fluid communication with the second hydroxylation reactor end; and wherein a product stream is in fluid communication with the first hydroxylation reactor end.

[0009] The above described and other features are exemplified by the following figure and detailed description. BRIEF DESCRIPTION OF THE DRAWING

[0010] Refer now to the figure, which is an exemplary embodiment.

[0011] FIG. 1 is an illustration of an embodiment of the method of converting the alkane to the alkyl alcohol.

DETAILED DESCRIPTION

[0012] Ethanol is produced commercially by the direct hydration of ethene in the liquid or vapor phase over a catalyst. The presence of an amount of ethane in the ethene feed stream makes recycling of any unconverted ethene difficult as it results in a buildup of ethane in the system. Another method for producing ethanol is directly from an alkane. This process is difficult because the oxidation reaction tends to run to completion, resulting in over-oxidation and the production of carbon dioxide. The inventors hereof, surprisingly discovered a method of converting an alkane, such as methane and/or ethane, to an alkyl alcohol, such as methanol and/or ethanol, through a chlorinated intermediate. Specifically, the method comprises co-currently flowing the alkane, a halogen source, and a catalyst through a halogenation reactor to form a halogenated stream and a spent catalyst stream; counter-currently flowing the halogenated stream and the spent catalyst stream through a hydroxylation reactor to form a regenerated catalyst stream comprising the catalyst and a product stream comprising the alkyl alcohol and a hydrogen halide. Here, the alkane is halogenated in the halogenation reactor to form a halogenated alkane and the halogenated alkane is then converted into an alkyl alcohol in the hydroxylation reactor. For example, if the alkane stream comprises ethane and the halogen source comprises chlorine, then one or more of reactions (l)-(3) can occur in the halogenation reactor and one or more of reactions

(4)-(6) can occur in the hydroxylation reactor.

[0013] FIG. 1 illustrates an embodiment of the method of converting the alkane to the alkyl alcohol. Specifically, alkane stream 20 and regenerated catalyst stream 28 can be added to second halogenation reactor end 6 of halogenation reactor 2. Alkane stream 20 can comprise an alkane and a halogen source or the halogen source can be added to second halogenation reactor end 6 as a separate stream. Regenerated catalyst stream 28 comprises a catalyst. The catalyst, the alkane, and the halogen source flow co-currently in halogenation reactor 2 from second halogenation reactor end 6 to first halogenation reactor end 4.

Halogenation reactor 2 can have bottom portion m and top portion n with an increasing diameter. The length of bottom portion m and the length of top portion n can equal the total length, L of halogenation reactor 2. The increasing diameter of the top portion can reduce the velocity of a spent catalyst at the top of halogenation reactor 2 allowing it to be separated as spent catalyst stream 24. Spent catalyst stream 24 can be in fluid communication with a first hydroxylation reactor end 14 of hydroxylation reactor 12. Halogenated stream 22 comprising a halogenated alkane can exit first halogenation reactor end 4 and can be in fluid

communication with second hydroxylation reactor end 16. Halogenated stream 22 can enter a second halogenation reactor for further halogenation prior to entering hydroxylation reactor 12. At least a portion of halogenated stream 22 can be recycled back into halogenation reactor 2 for further halogenation. For example, 5 to 50 volume percent (vol%), or 10 to 30 vol% of halogenated stream 22 can be recycled based on the total volume of the halogenated stream. Halogenated stream 22 can be separated to form a recycle portion, for example, in a distillation column and then added to halogenation reactor 2.

[0014] Water stream 26 can also enter second hydroxylation reactor end 16. The spent catalyst and the halogenated alkane can flow counter-currently through hydroxylation reactor 12 to form an alky] alcohol and the catalyst as a regenerated catalyst. The alkyl alcohol can exit hydroxylation reactor 12 from first hydroxylation reactor end 14 in product stream 30 and the catalyst can exit hydroxylation reactor 12 from second hydroxylation reactor end 16 in regenerated catalyst stream 28 that is in fluid communication with halogenation reactor 2. Fresh catalyst can also be added to halogenation reactor 2.

[0015] The alkyl alcohol in product stream 30 can be purified, for example, in a distillation column. An unre acted alkane can be separated from product stream 30 and recycled into second halogenation reactor end 6. An unreacted halogenated alkane can be separated from product stream 30 and recycled into one or both of halogenation reactor 2 via second halogenation reactor end 6 and hydroxylation reactor 12 via second hydroxylation reactor end 16. The halogen halide in the product stream 30 can be separated and recycled into second halogenation end 6. [0016] The halogenation reactor can be a fluidized bed reactor. The halogenation reactor can operate at a temperature of 350 to 550 degrees Celsius (°C), specifically, 350 to 500°C, more specifically, 400 to 450°C. The halogenation reactor can operate at a pressure of 100 to 2,500 kilopascal (kPa) (1 to 25 atmospheres (arm)). The halogenation reactor can operate at a gas space velocity (GHSV) of 600 to 5,000 inverse hours (1/h), specifically, 1,000 to 5,000 1/h. A contact time between the reactants and the catalyst in the halogenation reactor can be 0.5 to 5 seconds, specifically, 1 to 3 seconds.

[0017] The halogenation reactor can comprise a top portion and a bottom portion. A diameter (e.g. an inner diameter) of the bottom portion can be 1.3 to 6.5 centimeters (cm), specifically, 2.5 to 6.5 cm. The diameter (e.g. the inner diameter) of the top portion can be 5 to 13 cm, specifically, greater than 6.5 to 12.7 cm. The diameter (e.g. the inner diameter) in the top portion can increase with distance towards the first halogenation reactor end. The diameter (e.g. the inner diameter) in the top portion can be greater than the diameter in the bottom portion.

[0018] The hydroxylation reactor can be a fluidized bed reactor. The hydroxylation reactor can operate at a temperature of 350 to 550°C, specifically, 350 to 500°C, more specifically, 400 to 450°C. The hydroxylation reactor can operate at a pressure of 100 to 2,500 kPa (1 to 25 arm). The hydroxylation reactor can operate at a gas space velocity (GHSV) of 500 to 5,000 1/h, or 1,800 to 5,000 1/h. A contact time between the reactants and the catalyst in the hydroxylation reactor can be 2 to 10 seconds, specifically, 5 to 6 seconds.

[0019] The halogenation reactor and the hydroxylation reactor can be two separate reactors or they can be two reaction sections located in a single reactor, for example, as a riser unit with two reaction sections.

[0020] The alkane stream comprises an alkane and/or a halogen containing alkane, for example, a CM alkane such as methane, ethane, propane, butane, or a combination comprising at least one of the foregoing. The alkane can comprise methane, ethane, or a combination comprising at least one of the foregoing.

[0021] The alkane can comprise a halogen containing alkane. The halogen containing alkane can comprise a halogenated alkane that was halogenated in the halogenation reactor and/or an unreacted halogenated alkane separated from the product stream of the

hydroxylation reactor. The halogen containing alkane can comprise chloromethane, dichloromethane, chloroform, bromomethane, dibromoethane, chloroethane, dichloroethane (such as 1,1 -dichloroethane and 1,2-dichloroethane), vinyl chloride, bromoethane, dibromoethane, or a combination comprising at least one of the foregoing. The halogen containing alkane can comprise an iodoalkane. It is noted that the alkane is halogenated in the halogenation reactor such that if the alkane comprises a halogen containing alkane, then the halogenated alkane has at least one more halogen than the halogen containing alkane. For example, if the alkane stream comprises ethane, then the halogenated alkane can comprise chloroethane and if the alkane stream comprises chloroethane, then the halogenated alkane can comprise dichloroethane. Specifically, the alkane can comprise a chlorine containing alkane and the halogenated stream 22 can comprise a further chlorinated alkane comprising at least one more halogen atom then the chlorine containing alkane.

[0022] The alkane stream can comprise 10 to 90 vol% of the alkane based on the total volume of the alkane stream.

[0023] The alkane can be obtained from shale gas. Shale gas is natural gas that is trapped in shale formations. Shale gas can comprise methane (for example, in an amount of 80 to 99 vol% based on the total volume of the shale gas), ethane (for example, in an amount of 1 to 20 vol% or 10 to 18 vol% based on the total volume of the shale gas), propane, butane, or a combination comprising at least one of the foregoing. The shale gas can be added directly to the halogenation reactor, or the method can comprise first separating at least one of methane and ethane from the shale gas to form a separated shale stream and adding the separated shale stream to the halogenation reactor.

[0024] The alkane stream can further comprise a halogen source or the halogen source can be added to the halogenation reactor as a separate stream. The halogen source can comprise a chlorine source, a bromine source, an iodine source, or a combination comprising at least one of the foregoing. The halogen source can comprise hydrogen chloride, hydrogen bromide, hydrogen iodide, chlorine, bromine, iodine, or a combination comprising at least one of the foregoing. The halogen source can comprise hydrogen chloride. A molar ratio of the alkane to the halogen source can be 1:0.1 to 1:10, specifically, 1:0.5 to 1:3, more specifically, 1:1 to 1:3.

[0025] The alkane stream can further comprise an oxidizing agent or an oxidizing agent can be added to the halogenation reactor as a separate stream. The oxidizing agent can comprise oxygen. For example, the oxygen can be pure oxygen or can be present as a mixture with nitrogen, such as, in air or oxygen enriched air. A molar ratio of the alkane to the oxidizing agent can be 1:0.1 to 1:10, or 1:0.5 to 1 :2. A molar ratio of the alkane to the oxidizing agent can be 2:1 to 20:1, or 4:1 to 15:1, or 5:1 to 10:1. A molar ratio of the oxidizing agent to the halogen source can be greater than or equal to 1:2. The halogenation reactor can be free of an oxidizing agent, for example, 0 vol% of an oxidizing agent can be added to the halogenation reactor.

[0026] The alkane stream can further comprise a diluent or a diluent can be added to the halogenation reactor as a separate stream. The diluent can help to reduce the heat in the reactor, which can result in a reduction in the amount of undesired by-products. The diluent can comprise nitrogen, argon, helium, carbon monoxide, carbon dioxide, or a combination comprising at least one of the foregoing. The diluent can be present in an amount of 10 to 70 mole percent (mol%), specifically, 20 to 70 mol% based on the total moles of the alkane, the halogen source, the diluent, and the oxidizing agent.

[0027] The alkane is halogenated in the halogenation reactor to form a halogenated alkane. The halogenated alkane can comprise chloromethane, dichloromethane, chloroform, carbon tetrachloride, bromomethane, dibromoethane, chloroethane, dichloroethane (such as 1,1-dichloroethane and 1 ^-dichloroethane), vinyl chloride, bromoethane, dibromoethane, or a combination comprising at least one of the foregoing. The halogenated alkane can comprise an iodoalkane. The halogenation stream can further comprise carbon monoxide, carbon dioxide, or a combination comprising at least one of the foregoing.

[0028] The halogenated alkane can be directed to the hydroxylation reactor to form a product stream comprising an alky] alcohol and a halogen source. The alkyl alcohol can comprise methanol, ethanol, ethylene glycol, propanol, butanol, or a combination comprising at least one of the foregoing. The alkyl alcohol can comprise methanol, ethanol, ethylene glycol, or a combination comprising at least one of the foregoing. The halogen source can comprise hydrogen chloride, hydrogen bromide, hydrogen iodide, chlorine, bromine, iodine or a combination comprising at least one of the foregoing. The halogen source from the hydroxylation reactor can be separated from the product stream and can be recycled to the halogenation reactor.

[0029] A catalyst is added to the halogenation reactor to facilitate the halogenation of the alkane. The catalyst can comprise a metal, M, comprising copper (Cu), potassium (K), lanthanum (La), cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, holmium, terbium, europium, thulium, lutetium, or a combination comprising at least one of the foregoing. The catalyst can comprise a metal halide, for example, a metal chloride, a metal bromide, a metal iodide, or a combination comprising at least one of the foregoing. Specifically, the catalyst can comprise copper chloride, potassium chloride, lanthanum chloride, or a combination comprising at least one of the foregoing. The catalyst can comprise a compound of the formula MX₃, MOX, or a combination comprising at least one of the foregoing, wherein M is the metal as described above, and X is chloride, bromide, iodide, or a combination comprising at least one of the foregoing. The catalyst can further comprise boron, phosphorous, sulfur, germanium, zirconium, hafnium, or a combination comprising at least one of the foregoing.

[0030] The catalyst can comprise copper chloride and one or both of potassium chloride and lanthanum chloride. The catalyst can comprise copper chloride, potassium chloride, and optionally lanthanum chloride. The catalyst can comprise

or a combination comprising at least one of the foregoing. A molar ratio of lanthanum to copper can be less than or equal to 1 :1, or less than 1:1.

[0031] The catalyst can comprise 5 to 95 weight percent (wt%), specifically, 20 to 50 wt%, specifically, 10 to 25 wt% copper chloride based on the total weight of the catalyst minus any support. The catalyst can comprise 5 to 80 wt%, specifically, 5 to 50 wt%, more specifically, 5 to 25 wt% potassium chloride based on the total weight of the catalyst minus any support. The catalyst can comprise 20 to 50 wt%, specifically, 10 to 25 wt% lanthanum chloride based on the total weight of the catalyst minus any support. The catalyst can comprise 10 to 25 wt% manganese chloride based on the total weight of the catalyst minus any support. The catalyst can comprise 20 to 50 wt%, specifically, 10 to 25 wt% copper chloride; 5 to 40 wt%, specifically, 5 to 25 wt% potassium chloride; 20 to 50 wt%, specifically, 10 to 25 wt% lanthanum chloride; and 10 to 25 wl% manganese chloride based on the total weight of the catalyst minus any support.

[0032] The catalyst can be a supported catalyst, where the support can comprise alumina, silica, silica-alumina, porous aluminosilicate (zeolite), silica-magnesia, bauxite, magnesia, silicon carbide, titanium oxide, zirconium oxide, zirconium silicate, or a combination comprising at least one of the foregoing. The support can be present in an amount of 1 to 90 wt%, specifically, 1 to 50 wt%, based on the total weight of the catalyst and support.

[0033] The catalyst can be a porous catalyst. For example, the catalyst can have a surface area of 3 to 200 meters squared per gram (m²/g), specifically, 30 to 200 m²/g as determined by the BET (Brunauer-Emmet-Teller) method of measuring surface area, described by S. Brunauer, P. H. Emmett, and E. Teller, Journal of the American Chemical Society, 60, 309 (1938).

[0034] The catalyst can have a lifetime of up to 15 days, for example, the catalyst can be used for 5 to 10 days before the catalyst is replaced with a fresh catalyst.

[0035] The following examples are provided to illustrate articles with enhanced thermal capability. The examples are merely illustrative and are not intended to limit devices made in accordance with the disclosure to the materials, conditions, or process parameters set forth therein.

EXAMPLES

Prophetic Example

[0036] Ethane and hydrogen chloride is added to a halogenation reactor at a molar ratio of 1:2. A catalyst comprising on a silica support is co-

currently flowed through the halogenation reactor at a temperature of 450°C, at atmospheric pressure and a gas hourly space velocity of 1,200 1/h. The halogenation reaction results in halogenated hydrocarbons and a spent catalyst. The conversion of ethane to chlorinated ethane is expected to be greater than or equal to 50 vol% or about 55 vol% and the selectivity is expected to be greater than or equal to 60 vol% or about 65 vol%.

[0037] The chlorinated ethane and water from the halogenation reactor are flowed counter-current to the spent catalyst in a hydroxylation reactor set at a temperature of 450°C, at atmospheric pressure and a gas hourly space velocity of 2,000 1/h. The ratio of the water to the chlorinated ethane is 4: 1. The reaction results in ethanol that is purified as product and regenerated catalyst that is added back into the halogenation reactor. The conversion of chlorinated ethane to ethanol is expected to be greater than or equal to 20 vol% or about 25 vol% and the selectivity is expected to be greater than or equal to 55 vol% or about 60 vol%.

[0038] The method of converting an alkane to an alkyl alcohol is further described in the below embodiments.

[0039] Embodiment 1: A method for converting an alkane to an alkyl alcohol comprising: co-currently flowing the alkane, a halogen source, a catalyst, and optionally an oxidizing agent through a halogenation reactor to form a halogenated stream and a spent catalyst stream; wherein the alkane comprises methane, a halogen containing methane, ethane, a halogen containing ethane, or a combination comprising at least one of the foregoing; wherein the catalyst comprises copper chloride and one or both of potassium chloride and lanthanum chloride, wherein the halogenated stream comprises a halogenated alkane; wherein if the halogen containing methane and/or the halogen containing ethane is present in the alkane, then the halogenated alkane comprises at least one more halogen atom than the respective halogen containing methane and/or the halogen containing ethane;

[0040] Embodiment 2: The method of Embodiment 1, wherein the halogen source comprises a chlorine source, a bromine source, an iodine source, or a combination comprising at least one of the foregoing.

[0041] Embodiment 3: The method of any one of the preceding embodiments, further comprising separating the hydrogen halide from the product stream to form a separated hydrogen halide; and wherein the halogen source comprises the separated hydrogen halide.

[0042] Embodiment 4: A method for converting an alkane to an alkyl alcohol comprising: co-currently flowing the alkane, a halogen source comprising a chlorine source, a catalyst, and optionally an oxidizing agent through a halogenation reactor to form a halogenated stream and a spent catalyst stream; wherein the alkane comprises methane, ethane, or a combination comprising at least one of the foregoing; wherein the catalyst comprises copper chloride, potassium chloride, and optionally lanthanum chloride, wherein the halogenated stream comprises chlorome thane, chloroethane, or a combination comprising at least one of the foregoing; wherein the halogenation reactor has a length that is equal to a bottom portion and a top portion, wherein the bottom portion length is at least 80% of the length, wherein an inner diameter of the bottom portion is 1.3 to 6.S cm and an inner diameter at all locations in the top portion is 5 to 13 cm; directing the halogenated stream and a water stream to a hydroxylation reactor, directing the spent catalyst stream to a first hydroxylation reactor end of the hydroxylation reactor, and counter-currently flowing the halogenated stream and the spent catalyst stream through the hydroxylation reactor to form a regenerated catalyst stream comprising the catalyst and a product stream comprising the alkyl alcohol and a hydrogen chloride; wherein the alkyl alcohol comprises methanol, ethanol, ethylene glycol, or a combination comprising at least one of the foregoing; and directing the regenerated catalyst stream comprising the catalyst back into the halogenation reactor.

[0043] Embodiment S: A method for converting an alkane to an alkyl alcohol comprising: co-currently flowing the alkane, a halogen source comprising hydrogen chloride, a catalyst, and an oxidizing agent through a halogenation reactor to form a halogenated stream and a spent catalyst stream; wherein the alkane comprises ethane;

wherein based on the total weight of the catalyst, the catalyst comprises 20 to SO wt% copper chloride, 5 to 40 wt% potassium chloride, 20 to SO wt% lanthanum chloride; wherein the halogenated stream comprises chloroethane, dichloroethane, or a combination comprising at least one of the foregoing; directing the halogenated stream and a water stream to a second hydroxylation reactor end of a hydroxylation reactor, directing the spent catalyst stream to a first hydroxylation reactor end of the hydroxylation reactor, and counter-currently flowing the halogenated stream and the spent catalyst stream through the hydroxylation reactor to form a regenerated catalyst stream comprising the catalyst and a product stream comprising the alkyl alcohol and hydrogen chloride; wherein the alkyl alcohol comprises ethanol, ethylene glycol, or a combination comprising at least one of the foregoing; and directing the regenerated catalyst stream comprising the catalyst back into the halogenation reactor.

[0044] Embodiment 6: The method of any one of the preceding embodiments, wherein the alkane comprises a chlorine containing alkane and wherein the halogenated stream comprises a further chlorinated alkane comprising at least one more halogen atom than the chlorine containing alkane.

[0045] Embodiment 7: The method of any one of the preceding embodiments, wherein a mole ratio of the alkane to the halogen source is 1:0.1 to 1:10.

[0046] Embodiment 8: The method of any one of the preceding embodiments, wherein a mole ratio of the alkane to oxidizing agent is 1:0.1 to 1:10.

[0047] Embodiment 9: The method of any one of Embodiments 1-4 and 6-8, wherein the catalyst comprises 10 to 25 wt% copper chloride, S to 25 wt% potassium chloride, 10 to 25 wt% lanthanum chloride, and 10 to 25 wt% manganese chloride, all based on the total weight of the catalyst minus any support.

[0048] Embodiment 10: The method of any one of the preceding embodiments, wherein the catalyst comprises CuCl₂-KCl-LaCl₃, CuCl₂-KCl, and CuCl₂-KCl-MnCl₂, CuCl₂- KCl-Mn-Cl₂-LaCl₃, or a combination comprising at least one of the foregoing. [0049] Embodiment 11: The method of any one of the preceding embodiments, wherein the catalyst comprises a support.

[0050] Embodiment 12: The method of any one of the preceding embodiments, wherein the halogenated stream comprises chloroethane, 1,1-dichloroethane, 1,2- dichloroethane, cis 1 ,2- vinyl chloride, or a combination comprising at least one of the foregoing.

[0051] Embodiment 13: The method of any one of the preceding embodiments, further comprising separating the alkyl alcohol from the product stream.

[0052] Embodiment 14: The method of any one of the preceding embodiments, further comprising separating an unreacted alkane from the product stream and recycling the unreacted alkane to the halogenation reactor.

[0053] Embodiment 15: The method of any one of the preceding embodiments, further comprising separating the hydrogen halide from the product stream and recycling the hydrogen halide to the halogenation reactor.

[0054] Embodiment 16: The method of any one of the preceding embodiments, wherein the halogenation reactor has one or more of a temperature of 350 to 550°C; a pressure of 100 to 2,500 kPa (1 to 25 atm); a gas space velocity of 600 to 5,000 1/h; and a contact time between the reactants and the catalyst of 0.5 to 5 seconds, specifically, 1 to 3 seconds.

[0055] Embodiment 17: The method of any one of the preceding embodiments, wherein the hydroxylation reactor has one or more of a temperature of 350 to 550°C; a pressure of 100 to 2,500 kPa (1 to 25 atm); a gas space velocity of 600 to 5,000 1/h; and a contact time between the reactants and the catalyst of 0.5 to 5 seconds, specifically, 1 to 3 seconds.

[0056] Embodiment 18: The method of any one of the preceding embodiments, wherein the alkane stream comprises 10 to 90 vol% of the alkane based on the total volume of the alkane stream.

[0057] T Embodiment 19: The method of any one of the preceding embodiments, wherein the alkane is obtained from a shale gas, for example, a purified shale gas.

[0058] Embodiment 20: The method of any one of the preceding embodiments, wherein the alkane stream comprises a diluent. [0059] Embodiment 21 : The method of Embodiment 20, wherein the diluent comprises nitrogen, argon, helium, carbon monoxide, carbon dioxide, or a combination comprising at least one of the foregoing.

[0060] Embodiment 22: The method of any of one of Embodiments 20-21, wherein the diluent is present in an amount of 10 to 70 mol%, specifically, 20 to 70 mol% based on the total moles of the alkane, the halogen source, the diluent, and the oxidizing agent.

[0061] Embodiment 23: The method of any one of the preceding embodiments, wherein the oxidizing agent comprises oxygen.

[0062] Embodiment 24: A system for the producing alkyl alcohol of any one of the preceding embodiments, comprising: the halogenation reactor comprising a first halogenation reactor end and a second halogenation reactor end; and the hydroxylation reactor comprising the first hydroxylation reactor end and the second hydroxylation reactor end; wherein an alkane stream comprising the alkane and optionally the halogen source is in fluid communication with the second halogenation reactor end; wherein the halogenation stream is in fluid communication with the first halogenation reactor end and the second hydroxylation reactor end; wherein the spent catalyst stream is in fluid communication with the first halogenation reactor end and the first hydroxylation reactor end; wherein the regenerated catalyst stream is in fluid communication with the second hydroxylation reactor end and the second halogenation reactor end; wherein the water stream is in fluid communication with the second hydroxylation reactor end; and wherein the product stream is in fluid communication with the first hydroxylation reactor end.

[0063] Embodiment 25: The system of Embodiment 24, wherein the halogenation reactor comprises a top portion having a top diameter and a bottom portion having a bottom diameter; wherein the top diameter is larger than the bottom diameter.

[0064] In general, the invention can alternately comprise, consist of, or consist essentially of, any appropriate components herein disclosed. The invention can additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any components, materials, ingredients, adjuvants or species used in the prior art compositions or that are otherwise not necessary to the achievement of the function and/or objectives of the present invention.

[0065] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other (e.g., ranges of "up to 25 wt%, or, more specifically, 5 to 20 wt%", is inclusive of the endpoints and all intermediate values of the ranges of "5 to 25 wt%," etc.). "Combination" is inclusive of blends, mixtures, alloys, reaction products, and the like. Furthermore, the terms "first," "second," and the like, herein do not denote any order, quantity, or importance, but rather are used to denote one element from another. The terms "a" and "an" and "the" herein do not denote a limitation of quantity, and are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. "Or" means "and/or." The suffix "(s)" as used herein is intended to include both the singular and the plural of the term that it modifies, thereby including one or more of that term (e.g., the film(s) includes one or more films). Reference throughout the specification to "one embodiment," "another embodiment," "an embodiment," and so forth, means that a particular element (e.g., feature, structure, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments.

"Optional" or "optionally" means that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where the event occurs and instances where it does not. Unless defined otherwise, technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art to which this invention belongs. Unless otherwise stated, test standards are the most recent as of the filing date of the application.

[0066] All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if a term in the present application contradicts or conflicts with a term in the incorporated reference, the term from the present application takes precedence over the conflicting term from the incorporated reference.

[0067] In addition, it is to be understood that the described elements can be combined in any suitable manner in the various embodiments.

[0068] While particular embodiments have been described, alternatives,

modifications, variations, improvements, and substantial equivalents that are or can be presently unforeseen can arise to applicants or others skilled in the art. Accordingly, the appended claims as filed and as they can be amended are intended to embrace all such alternatives, modifications variations, improvements, and substantial equivalents.

Claims

1. A method for converting an alkane to an alkyl alcohol comprising:

co-currently flowing the alkane, a halogen source, a catalyst, and optionally an oxidizing agent through a halogenation reactor to form a halogenated stream and a spent catalyst stream; wherein the alkane comprises methane, a halogen containing methane, ethane, a halogen containing ethane, or a combination comprising at least one of the foregoing; wherein the catalyst comprises copper chloride and one or both of potassium chloride and lanthanum chloride, wherein the halogenated stream comprises a halogenated alkane; wherein if the halogen containing methane and/or the halogen containing ethane is present in the alkane, then the halogenated alkane comprises at least one more halogen atom than the respective halogen containing methane and/or the halogen containing ethane;

directing the halogenated stream and a water stream to a second hydroxylation reactor end of a hydroxylation reactor, directing the spent catalyst stream to a first hydroxylation reactor end of the hydroxylation reactor, and counter-currently flowing the halogenated stream and the spent catalyst stream through the hydroxylation reactor to form a regenerated catalyst stream comprising the catalyst and a product stream comprising the alkyl alcohol and a hydrogen halide; wherein the alkyl alcohol comprises methanol, ethanol, ethylene glycol, or a combination comprising at least one of the foregoing; and

directing the regenerated catalyst stream comprising the catalyst back into the halogenation reactor.

2. The method of Claim 1 , wherein the halogen source comprises a chlorine source, a bromine source, an iodine source, or a combination comprising at least one of the foregoing.

3. The method of any one of the preceding claims, wherein the halogenation reactor has a length that is equal to a bottom portion and a top portion, wherein the bottom portion length is at least 80% of the length, wherein an inner diameter of the bottom portion is 1.3 to 6.S cm and an inner diameter at all locations in the top portion is 5 to 13 cm.

4. A method for converting an alkane to an alkyl alcohol comprising:

co-currently flowing the alkane, a halogen source comprising hydrogen chloride, a catalyst, and an oxidizing agent through a halogenation reactor to form a halogenated stream and a spent catalyst stream; wherein the alkane comprises ethane; wherein based on the total weight of the catalyst, the catalyst comprises 20 to 50 wt% copper chloride, 5 to 40 wt% potassium chloride, 20 to 50 wt% lanthanum chloride; wherein the halogenated stream comprises chloroethane, dichloroethane, or a combination comprising at least one of the foregoing;

directing the halogenated stream and a water stream to a second hydroxylation reactor end of a hydroxylation reactor, directing the spent catalyst stream to a first hydroxylation reactor end of the hydroxylation reactor, and counter-currently flowing the halogenated stream and the spent catalyst stream through the hydroxylation reactor to form a regenerated catalyst stream comprising the catalyst and a product stream comprising the alkyl alcohol and hydrogen chloride; wherein the alkyl alcohol comprises ethanol, ethylene glycol, or a combination comprising at least one of the foregoing; and

5. The method of any one of the preceding claims, wherein the alkane comprises a chlorine containing alkane and wherein the halogenated stream comprises a further chlorinated alkane comprising at least one more halogen atom than the chlorine containing alkane.

6. The method of any one of the preceding claims, wherein a mole ratio of the alkane to the halogen source is 1:0.1 to 1:10 and/or a mole ratio of the alkane to oxidizing agent is 1:0.1 to 1:10.

7. The method of any one of Claims 1-3 and 5-6, wherein the catalyst comprises 10 to 25 wt% copper chloride, 5 to 25 wt% potassium chloride, 10 to 25 wt% lanthanum chloride, and 10 to 25 wt% manganese chloride, all based on the total weight of the catalyst minus any support.

8. The method of any one of the preceding claims, wherein the catalyst comprises

or a combination comprising at least one of the foregoing.

9. The method of any one of the preceding claims, wherein the catalyst comprises a support.

10. The method of any one of the preceding claims, wherein the halogenated stream comprises chloroethane, 1,1 -dichloroethane, 1,2-dichloroethane, cis 1,2- vinyl chloride, or a combination comprising at least one of the foregoing.

11. The method of any one of the preceding claims, further comprising separating the alkyl alcohol from the product stream.

12. The method of any one of the preceding claims, further comprising separating an unreacted alkane from the product stream and recycling the unreacted alkane to the halogenation reactor and/or separating the hydrogen halide from the product stream and recycling the hydrogen halide to the halogenation reactor.

13. The method of any one of the preceding claims, wherein one or both of the halogenation reactor and the hydroxylation reactor has one or more of a temperature of 350 to 550°C; a pressure of 100 to 2,500 kPa; a gas space velocity of 600 to 5,000 1/h; and a contact time between the reactants and the catalyst of 0.5 to 5 seconds, specifically, 1 to 3 seconds.

14. The method of any one of the preceding claims, wherein the alkane stream comprises 10 to 90 vol% of the alkane based on the total volume of the alkane stream.

15. The method of any one of the preceding claims, wherein the alkane is obtained from a shale gas, preferably, a purified shale gas.

16. The method of any one of the preceding claims, wherein the alkane stream comprises a diluent, wherein the diluent comprises nitrogen, argon, helium, carbon monoxide, carbon dioxide, or a combination comprising at least one of the foregoing.

17. The method of any of Claim 16, wherein the diluent is present in an amount of 10 to 70 mol%, preferably, 20 to 70 mol% based on the total moles of the alkane, the halogen source, the diluent, and the oxidizing agent.

18. The method of any one of the preceding claims, wherein the oxidizing agent comprises oxygen.

19. A system for producing the alkyl alcohol on any one of the preceding claims, comprising:

the halogenation reactor comprising a first halogenation reactor end and a second halogenation reactor end; and

the hydroxylation reactor comprising the first hydroxylation reactor end and the second hydroxylation reactor end;

wherein an alkane stream comprising the alkane and optionally the halogen source is in fluid communication with the second halogenation reactor end;

wherein the halogenation stream is in fluid communication with the first halogenation reactor end and the second hydroxylation reactor end;

wherein the spent catalyst stream is in fluid communication with the first halogenation reactor end and the first hydroxylation reactor end; wherein the regenerated catalyst stream is in fluid communication with the second hydroxylation reactor end and the second halogenation reactor end;

wherein the water stream is in fluid communication with the second hydroxylation reactor end; and

wherein the product stream is in fluid communication with the first hydroxylation reactor end.

20. The system of Claim 19, wherein the halogenation reactor comprises a top portion having a top diameter and a bottom portion having a bottom diameter; wherein the top diameter is larger than the bottom diameter.