Process for producing methanol and hydrogen from methane using liquid reactants

Abstract

The present disclosure provides processes for producing methanol and hydrogen from methane. The process of the present disclosure comprises the steps of: a) providing a gaseous feed stream comprising methane; b) reacting the gaseous feed stream with at least one halogen reactant under reaction conditions effective to produce an effluent stream comprising methyl halide, hydrogen halide, optionally polyhaloalkane, and optionally unreacted methane; c) recovering the effluent stream, d) reacting the recovered effluent stream with water and at least one organic base under reaction conditions effective to produce an aqueous solution of hydrogen halide and a methanol stream, the methanol stream comprising methanol (MeOH) and dimethyl ether (DME) and / or optionally unreacted methane, and the at least one organic base comprising at least one organic base. E) decomposing the aqueous solution of hydrogen halide by electrolysis under conditions effective to produce a gaseous hydrogen stream and a stream comprising halogen reactants.

Description

Technical Field

[0001] The present disclosure relates to processes and systems for producing methanol. In particular, the present disclosure relates to processes and systems for producing methanol from a gas stream comprising or consisting of methane, thereby producing hydrogen and dimethyl ether (DME). The present process is particularly notable for utilizing water as a liquid reactant in the process of converting methane to methanol and for using electrolysis to produce hydrogen gas. Background Art

[0002] Methanol is a key starting material for producing basic chemicals such as formaldehyde, acetic acid, hydrocarbons (hydrocarbons), olefins, biodiesel, gasoline and gasoline additives such as methyl tertiary butyl ether. Methanol can also be used as a transportation fuel, a fuel cell hydrogen carrier and for wastewater treatment or power generation. Therefore, it is a superior fuel and a key starting material for important industrial reactions. In recent years, methanol has also been considered as a substitute for chemical energy carriers.

[0003] Conventionally, methanol (CH3OH or MeOH) is produced on an industrial scale from synthesis gas "syngas", which is a combination of varying amounts of H2, CO and CO2, typically obtained from gasified coal or natural gas. The catalytic conversion of hydrogen (H2) and carbon monoxide (CO) from coal-derived syngas to methanol involves the following reactions:

[0004]

[0005]

[0006]

[0007] The catalytic system used for methanol synthesis is typically a mixture of copper, zinc oxide, aluminum oxide, and magnesium oxide.

[0008] All three reactions given above are highly exothermic. In particular, in order to favor the formation of methanol, high pressure and / or high temperature are required to shift the equilibrium towards methanol.

[0009] Even, the production of synthesis gas usually involves the reforming of natural gas, which itself is very energy-consuming, because the reaction with water is endothermic, and is typically carried out at high temperature. A typical example of a cracking process is a nickel-catalyzed reaction of methane and steam at 840 ° C in a ratio of 1: 3. Therefore, the synthesis gas produced will have a composition of 3 moles of H2 to each mole of CO. Alternatively, a partial oxidation reaction of methane with oxygen can be carried out to produce carbon monoxide. It can be combined with steam reforming in the same reaction zone to avoid the necessity of providing additional energy input for the reaction. However, partial oxidation (which is sometimes referred to as autothermal reforming) will require the use of pure oxygen, i.e. such a device will require an air separation unit-a highly capital-intensive and energy-intensive device for producing pure oxygen from air. In view of the above, the entire process of manufacturing methanol from synthesis gas is complex, energy-consuming and capital-intensive.

[0010] Therefore, in view of the above, there is a need in the art to provide improved processes for producing methanol.

[0011] There is a need in the art to provide a process for producing methanol with improved efficiency. There is a particular need in the art for a methanol production process that can operate under milder production process conditions, avoiding operation at high temperatures and / or high pressures (which require large amounts of energy to maintain these temperatures and / or pressures).

[0012] There is also a need in the art for methanol production processes involving lower CO / CO2 emissions.

[0013] There is a further need in the art for a methanol production process that allows the production of methanol via different strategies, in particular not starting from a synthesis gas route.

[0014] Document WO 2008 / 143940 relates to a continuous process for converting hydrocarbon feedstocks into high-value products, which uses molecular halogens to activate the CH bonds in the feedstocks and uses electrolysis to convert the hydrogen halides formed in the process back into molecular halogens. When methanol is formed, the formation of methanol is carried out by hydrolysis. The electrolytic recovery of halogens is carried out from NaBr.

[0015] US 2002 / 0198416 relates to the formation of alcohols and / or ethers from alkanes using bromine and methane. Thanks to the metal oxide catalyst, methanol is formed.

[0016] It is therefore an object of the present disclosure to provide a process for producing methanol and / or a combination of methanol and dimethyl ether which allows at least some of the above requirements to be met. For example, a process for producing methanol, DME and hydrogen from methane with a high selectivity to DME is needed. Summary of the invention

[0017] According to the present disclosure, an improved process for producing methanol and hydrogen, and / or methanol, dimethyl ether, and hydrogen from methane is provided.

[0018] In a first aspect, the present invention provides a process for producing methanol (MeOH) and hydrogen (H2) from methane, comprising the following steps:

[0019] a) providing a gaseous feed stream comprising methane;

[0020] b) reacting the gaseous feed stream with at least one halogen reactant (X2) under reaction conditions effective to produce an effluent stream comprising methyl halide (MeX), hydrogen halide (HX), optionally polyhalogenated alkane, and optionally unreacted methane;

[0021] c) recovering an effluent stream comprising methyl halide (MeX), hydrogen halide (HX), optionally polyhalogenated alkane and optionally unreacted methane;

[0022] d) reacting the effluent stream obtained in step c) with water and at least one catalyst under reaction conditions effective to produce:

[0023] - Aqueous solutions of hydrogen halides (HX (aq) ),and

[0024] - a methanol stream comprising methanol (MeOH) and optionally dimethyl ether (DME) and / or optionally unreacted methane, and,

[0025] e) decomposing the aqueous solution of hydrogen halide (HX2) by electrolysis under conditions effective to produce a stream of gaseous hydrogen (H2) and a stream comprising a halogen reactant (X2); (aq) ).

[0026] More particularly, the present disclosure provides thereto a process for producing methanol (MeOH), dimethyl ether (DME) and hydrogen (H2) from methane, comprising the steps of:

[0027] a) providing a gaseous feed stream comprising methane;

[0028] b) reacting the gaseous feed stream with at least one halogen reactant (X2) under reaction conditions effective to produce an effluent stream comprising methyl halide (MeX), hydrogen halide (HX), optionally polyhalogenated alkane, and optionally unreacted methane;

[0029] c) recovering an effluent stream comprising methyl halide (MeX), hydrogen halide (HX), optionally polyhalogenated alkane and optionally unreacted methane;

[0030] d) reacting the effluent stream obtained in step c) with water and an organic base under reaction conditions effective to produce:

[0031] - Aqueous solutions of hydrogen halides (HX (aq) ),and

[0032] - a methanol stream comprising methanol (MeOH) and dimethyl ether (DME) and optionally unreacted methane, and,

[0033] e) decomposing the aqueous solution of hydrogen halide (HX2) by electrolysis under conditions effective to produce a stream of gaseous hydrogen (H2) and a stream comprising a halogen reactant (X2); (aq) ).

[0034] In some embodiments, the process comprises the step of separating the polyhalogenated alkanes formed in step b) from the effluent stream, preferably before reacting the effluent stream with water and at least one catalyst.

[0035] In some embodiments, the process comprises the following steps:

[0036] a) providing a gaseous feed stream comprising methane;

[0037] b) reacting the gaseous feed stream with at least one halogen reactant (X2) under reaction conditions effective to produce an effluent stream comprising methyl halide (MeX), hydrogen halide (HX), optionally polyhalogenated alkane, and optionally unreacted methane;

[0038] c) separating from the effluent stream obtained in step b) the following:

[0039] c1) a monohalide stream comprising methyl halide (MeX) and hydrogen halide (HX), and optionally unreacted methane; and,

[0040] c2) a polyhalogenated alkane stream,

[0041] d) reacting the monohalide stream separated in step c1) with water and at least one catalyst under reaction conditions effective to produce:

[0042] d1) Aqueous solution of hydrogen halide (HX (aq) ),and

[0043] d2) a methanol stream comprising methanol (MeOH) and optionally dimethyl ether (DME) and / or optionally unreacted methane,

[0044] e) decomposing the aqueous solution of hydrogen halide (HX2) produced in step d1) by electrolysis under conditions effective to produce a stream of gaseous hydrogen (H2) and a stream comprising a halogen reactant (X2); (aq) );and,

[0045] f) optionally, recovering methanol from said methanol (MeOH) stream.

[0046] For example, the process comprises the following steps:

[0047] a) providing a gaseous feed stream comprising methane;

[0048] b) reacting the gaseous feed stream with at least one halogen reactant (X2) under reaction conditions effective to produce an effluent stream comprising methyl halide (MeX), hydrogen halide (HX), optionally polyhalogenated alkane, and optionally unreacted methane;

[0049] c) separating from the effluent stream obtained in step b) the following:

[0050] c1) a monohalide stream comprising methyl halide (MeX) and hydrogen halide (HX), and optionally unreacted methane; and,

[0051] c2) a polyhalogenated alkane stream,

[0052] d) reacting the monohalide stream separated in step c1) with water and an organic base under reaction conditions effective to produce:

[0053] d1) Aqueous solution of hydrogen halide (HX (aq) ),and

[0054] d2) a methanol stream comprising methanol (MeOH) and dimethyl ether (DME) and optionally unreacted methane,

[0055] e) decomposing the aqueous solution of hydrogen halide (HX2) produced in step d1) by electrolysis under conditions effective to produce a stream of gaseous hydrogen (H2) and a stream comprising a halogen reactant (X2); (aq) );and,

[0056] f) optionally, recovering methanol from the methanol (MeOH) stream and / or recovering dimethyl ether (DME) from the methanol (MeOH) stream.

[0057] In some embodiments, the halogen reactant is selected from bromine (Br2), chlorine (Cl2), fluorine (F2), iodine (I2) and astatine (At2). Preferably, the halogen reactant is bromine (Br2).

[0058] In some embodiments, the at least one catalyst is a base, preferably an organic base.

[0059] In some embodiments, the at least one catalyst is a polymer containing N, and preferably a polymer containing at least one of the following: amino, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, pyrazole ring, imidazole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, triazole ring, oxadiazole ring, or any combination thereof. Preferably, the N-containing polymer is a polymer containing at least one pyridine ring.

[0060] In some embodiments, the polyhalogenated alkane comprises a polyhalogenated methane and optionally a polyhalogenated C 2+ Alkane.

[0061] In some embodiments, C 2+ The alkyl monohalide is formed in step b).

[0062] In some embodiments, the process comprises the following steps: 2+ Alkyl monohalides are separated from the effluent stream, and preferably prior to separation of the monohalide stream comprising methyl halide (MeX) and hydrogen halide (HX).

[0063] In some embodiments, the gaseous feed stream comprises at least 75.0 vol% methane, preferably at least 80.0 vol% methane, preferably at least 85.0 vol% methane, preferably at least 90.0 vol% methane, preferably at least 95.0 vol% methane, preferably at least 98.0 vol% methane, preferably at least 99.0 vol% methane, preferably at least 99.9 vol% methane, based on the total volume of the gaseous feed stream.

[0064] In some embodiments, the gaseous feed stream used in step a) of the process is substantially free of sulfur species, for example, it contains less than 1.0 mol%, or less than 0.5 mol%, or less than 0.1 mol%, or less than 0.01 mol%, or less than 0.001 mol%, or less than 0.0001 mol%, or less than 0.00001 mol% of sulfur species.

[0065] In some embodiments, the process further comprises the step of returning the halogen reactant (X2) obtained in step e) to step b) of the process.

[0066] In some embodiments, the methanol stream comprising methanol (MeOH) and optionally dimethyl ether (DME) obtained in step d2) is separated from the aqueous solution of hydrogen halide by distillation, and preferably comprises at least 75.0 mol%, e.g., at least 80.0 mol%, or at least 85.0 mol%, or at least 95.0 mol% of the combination of methanol and optionally dimethyl ether, based on the total amount of the methanol stream.

[0067] In some embodiments, the gaseous hydrogen (H2) stream produced in step e) comprises at least 90.0 mol%, such as at least 95.0 mol%, or at least 99.0 mol%, or at least 99.5 mol%, or at least 99.9 mol% hydrogen.

[0068] In a second aspect, the present disclosure provides a system for producing methanol (MeOH) and hydrogen (H2) from methane, comprising:

[0069] - a halogenation reactor configured to react a gaseous feed stream comprising methane with at least one halogen reactant (X2) into an effluent stream comprising methyl halide (MeX) and hydrogen halide (HX) and optionally unreacted methane,

[0070] - Optionally, a polyhalogenated alkane removal unit configured to receive an effluent stream from the halogenation reactor and configured to separate from the effluent stream (i) a polyhalogenated alkane stream comprising polyhalogenated alkanes; and, (ii) a monohalide stream comprising methyl halide (MeX) and hydrogen halide (HX), and optionally unreacted methane; and,

[0071] a hydrolysis reactor fluidly connected to the halogenation reactor and configured to receive an effluent stream from the halogenation reactor; or, fluidly connected to the polyhalogenated alkane removal unit and configured to receive a monohalide stream from the polyhalogenated alkane removal unit; and, wherein the hydrolysis reactor is configured to produce (i) an aqueous solution of hydrogen halide (HX) in an amount effective to produce (aq) (ii) reacting the effluent stream or the monohalide stream with water and at least one catalyst under reaction conditions comprising (i) methanol (MeOH) and optionally dimethyl ether (DME) and / or optionally unreacted methane; and

[0072] an electrolysis unit comprising at least one electrolysis cell and a power source for supplying electric current to the electrolysis cell, the electrolysis unit being fluidically connected to the hydrolysis reactor and configured to receive an aqueous solution of hydrogen halide (HX (aq) ) and the aqueous solution of the hydrogen halide (HX (aq) ) is decomposed into a gaseous hydrogen (H2) stream and a stream comprising a halogen reactant (X2);

[0073] - a feed stream supply system for supplying a gaseous feed stream comprising methane to the halogenation reactor;

[0074] - a halogen supply system for supplying a halogen reactant (X2) to the halogenation reactor;

[0075] - an effluent recovery system configured to recover an effluent stream from the halogenation reactor and feed the recovered effluent stream to the optional polyhaloalkane removal unit, or to the hydrolysis reactor;

[0076] - a methanol recovery system configured to recover a stream comprising methanol (MeOH) and optionally dimethyl ether (DME) and / or optionally unreacted methane from the hydrolysis reactor;

[0077] - a hydrogen recovery system configured to recover a gaseous hydrogen (H2) stream from the electrolysis unit;

[0078] - a halogen recovery system configured to recover the halogen reactant (X2) from the electrolysis unit;

[0079] - a hydrogen halide transfer system configured to receive an aqueous solution of hydrogen halide (HX) from the hydrolysis reactor; (aq) ), and the collected aqueous solution of hydrogen halide (HX (aq) ) is supplied to an electrolysis unit;

[0080] - optionally, a monohalide transfer system configured to receive a monohalide stream from the polyhaloalkane removal unit and supply the monohalide stream to a hydrolysis reactor,

[0081] - optionally, a water supply line for supplying water, preferably water and at least one catalyst, to the hydrolysis reactor;

[0082] - Optionally, C 2+ An alkyl monohalide removal unit is configured to receive an effluent stream from the halogenation reactor and remove C2+ alkyl monohalides from the effluent stream.

[0083] In particular, the present disclosure also provides a system for producing methanol (MeOH), dimethyl ether (DME) and hydrogen (H2) from methane, comprising:

[0084] - a halogenation reactor configured to react a gaseous feed stream comprising methane with at least one halogen reactant (X2) to form an effluent stream comprising methyl halide (MeX) and hydrogen halide (HX) and optionally unreacted methane, and,

[0085] - a hydrolysis reactor fluidly connected to the halogenation reactor and configured to receive an effluent stream from the halogenation reactor; and, wherein the hydrolysis reactor is configured to react the effluent stream with water and an organic base under reaction conditions effective to produce a stream comprising methanol (MeOH) and dimethyl ether (DME) and optionally unreacted methane; and

[0086] an electrolysis unit comprising at least one electrolysis cell and a power source for supplying electric current to the electrolysis cell, the electrolysis unit being fluidically connected to the hydrolysis reactor and configured to receive an aqueous solution of hydrogen halide (HX (aq) ) and the aqueous solution of the hydrogen halide (HX (aq) ) is decomposed into a gaseous hydrogen (H2) stream and a stream comprising a halogen reactant (X2);

[0087] - a feed stream supply system for supplying a gaseous feed stream comprising methane to the halogenation reactor;

[0088] - a halogen supply system for supplying a halogen reactant (X2) to the halogenation reactor;

[0089] - an effluent recovery system configured to recover an effluent stream from the halogenation reactor and feed the recovered effluent stream to the hydrolysis reactor;

[0090] - a methanol recovery system configured to recover a stream comprising methanol (MeOH) and dimethyl ether (DME) and optionally unreacted methane from the hydrolysis reactor;

[0091] - a hydrogen recovery system configured to recover a gaseous hydrogen (H2) stream from the electrolysis unit;

[0092] - a halogen recovery system configured to recover the halogen reactant (X2) from the electrolysis unit;

[0093] - a hydrogen halide transfer system configured to receive an aqueous solution of hydrogen halide (HX) from the hydrolysis reactor; (aq) ), and the collected aqueous solution of hydrogen halide (HX (aq) ) is supplied to the electrolysis unit.

[0094] The present process advantageously allows the production of a substantially pure stream of methanol, or methanol and DME. The process of the present disclosure avoids any direct CO2 emissions.

[0095] In addition, in some embodiments of the present process, a mixture of methanol and dimethyl ether (DME) can be obtained. The present process further allows such a mixture to be separated into a substantially pure stream of methanol and DME. Both methanol and DME can be further used in a large number of downstream applications.

[0096] Furthermore, the present process also allows obtaining a substantially pure stream of hydrogen gas as a by-product, which can be further used in numerous downstream applications.

[0097] The present disclosure also provides a process for producing methanol and optionally DME without involving synthesis gas. Producing methanol and DME directly from methane is a key reaction that enables the conversion from petroleum resources to renewable resources to produce basic chemicals. The methane used in the process can come from renewable resources, which makes the production of methanol and DME and the basic chemicals made of the methanol and optional DME compounds more environmentally friendly.

[0098] The process is also highly efficient because it allows for the recycling (reuse) of reactants and reaction products in the same process, thereby reducing waste and / or pollution.

[0099] Furthermore, the process also allows the production of hydrogen by electrolytic decomposition of an aqueous hydrogen halide solution stream. Thus, at least part of the energy applied in the present process is based on electrical energy, which can be obtained from renewable sources.

[0100] Independent and dependent claims set out particular and preferred features of the present disclosure. Features in the dependent claims may be combined with features in the independent claim or other dependent claims as appropriate.

[0101] The present disclosure will now be further described. In the following paragraphs, different aspects of the present disclosure will be defined in more detail. Unless otherwise expressly stated, each aspect so defined can be combined with any other one or more aspects. In particular, any feature that is indicated as preferred or advantageous can be combined with any other one or more features that are indicated as preferred or advantageous. BRIEF DESCRIPTION OF THE DRAWINGS

[0102] Figure 1 A process according to one embodiment of the present disclosure and a system according to an embodiment of the present disclosure are depicted.

[0103] Figure 2 A process according to another embodiment of the present disclosure and a system according to an embodiment of the present disclosure are depicted. DETAILED DESCRIPTION

[0104] When describing the present disclosure, the terms used should be interpreted in accordance with the following definitions, unless the context dictates otherwise.

[0105] Unless otherwise defined, all terms, including technical and scientific terms, used in disclosing the present disclosure have the meanings commonly understood by those of ordinary skill in the art to which the present disclosure belongs. Further guidance, including term definitions, is provided to better understand the teachings of the present disclosure.

[0106] In the following paragraphs, different aspects of the present disclosure will be defined in more detail. Unless otherwise explicitly stated, each aspect so defined may be combined with any other one or more aspects. In particular, any feature indicated as being preferred or advantageous may be combined with any other one or more features indicated as being preferred or advantageous.

[0107] References throughout this specification to "one embodiment" or "an embodiment" mean that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the present disclosure. Therefore, the phrases "in one embodiment" or "in an embodiment" appearing in various places throughout this specification do not necessarily all refer to the same embodiment, but may all refer to the same embodiment. In addition, particular features, structures, or characteristics may be combined in one or more embodiments in any suitable manner, as will be apparent to those skilled in the art from this disclosure. In addition, while some embodiments described herein include some features included in other embodiments but not other features, the combination of features of different embodiments should be intended to be within the scope of the present disclosure and to form different embodiments, as will be understood by those skilled in the art.

[0108] As used herein, the terms "comprising," "comprises," and "comprised of" are synonymous with "including," "includes," or "containing," "contains," and are inclusive or open-ended and do not exclude additional, unrecited members, elements, or process steps. It will be understood that the terms "comprising," "comprises," and "comprised of" as used herein include the terms "consisting of," "consists," and "consists of."

[0109] As used in the specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. For example, "a step" means one step or more than one step.

[0110] Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by one of ordinary skill in the art.

[0111] Numerical ranges expressed by endpoints include all integers and, where appropriate, fractions contained within the range (when referring to, for example, the number of elements, 1 to 5 may include 1, 2, 3, 4, 5, and when referring to, for example, measured values, 1.5, 2, 2.75, and 3.80 may also be included). The expression of endpoints also includes the endpoint values ​​themselves (for example, from 1.0 to 5.0 includes both 1.0 and 5.0). Any numerical range recited herein is intended to include all subranges contained therein.

[0112] As used herein, the term "about" when referring to a measurable value (e.g., a parameter, an amount, a duration, etc.) is intended to encompass variations of + / -10% or less, preferably + / -5% or less, and more preferably + / -1% or less, from the specified value, as long as these variations are suitable for implementation in the disclosed disclosure. It should be understood that the value referred to by the modifier "about" itself is also specifically and preferably disclosed.

[0113] The terms "wt %", "vol %" or "mol %" refer to the weight percent of a component, the volume percent of a component or the mole percent of a component, respectively, based on the total weight, total volume, or total number of moles including the component.

[0114] When describing the present disclosure, the terms used should be interpreted according to the following definitions, unless the context dictates otherwise.

[0115] Whenever the term "substituted" is used in this disclosure, it is intended to indicate that one or more hydrogens on the atom indicated by the expression "substituted" are replaced with a group selected from the group indicated, provided that the normal valence of the indicated atom is not exceeded and that the substitution produces a chemically stable compound, i.e., a compound that is sufficiently robust to survive isolation to a useful degree of purity from a reaction mixture.

[0116] The term "alkyl" as a group or part of a group refers to a group of formula C n H 2n+1wherein n is a number greater than or equal to 1. The alkyl group may be linear or branched and may be substituted as described herein. Generally, the alkyl groups of the present disclosure contain 1 to 20 carbon atoms, preferably 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1, 2, 3, 4, 5, 6 carbon atoms. When a subscript is used after a carbon atom herein, the subscript refers to the number of carbon atoms that the named group may contain. For example, the term "C 1 -20 "Alkyl", as a group or part of a group, refers to a group of the formula -C n H 2n+1 wherein n is a number from 1 to 20. Thus, for example, C 1-20 Alkyl includes all linear or branched alkyl groups having 1 to 20 carbon atoms, and thus includes, for example, methyl, ethyl, n-propyl, isopropyl, 2-methylethyl, butyl and isomers thereof (e.g., n-butyl, isobutyl and tert-butyl); pentyl and isomers thereof, hexyl and isomers thereof, heptyl and isomers thereof, octyl and isomers thereof, nonyl and isomers thereof, decyl and isomers thereof, undecyl and isomers thereof, dodecyl and isomers thereof, tridecyl and isomers thereof, tetradecyl and isomers thereof, pentadecyl and isomers thereof, hexadecyl and isomers thereof, heptadecyl and isomers thereof, octadecyl and isomers thereof, etc. For example, C 1-10 Alkyl includes all linear or branched alkyl groups having 1 to 10 carbon atoms, and thus includes, for example, methyl, ethyl, n-propyl, isopropyl, 2-methylethyl, butyl and isomers thereof (e.g., n-butyl, isobutyl and tert-butyl); pentyl and isomers thereof, hexyl and isomers thereof, heptyl and isomers thereof, octyl and isomers thereof, nonyl and isomers thereof, decyl and isomers thereof, etc. For example, C 1-6 Alkyl groups include all linear or branched alkyl groups having 1 to 6 carbon atoms, and thus include, for example, methyl, ethyl, n-propyl, isopropyl, 2-methylethyl, butyl and isomers thereof (e.g., n-butyl, isobutyl and tert-butyl); pentyl and isomers thereof, hexyl and isomers thereof, etc. In some embodiments, non-limiting examples of alkyl groups include, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, 2,2-dimethyl-propyl, hexyl, 2,3-dimethyl-2-butyl, heptyl, 2,2-dimethyl-3-pentyl, 2-methyl-2-hexyl, octyl, 4-methyl-3-heptyl, nonyl, decyl, undecyl and dodecyl.

[0117] As used herein and unless otherwise indicated, the term "halo" or "halogen" as a group or part of a group refers collectively to any atom selected from fluorine (F), chlorine (Cl), bromine (Br), iodine (I) and astatine (At).

[0118] Preferred statements (features) and embodiments and uses of the present disclosure are described below. Unless otherwise expressly stated to the contrary, each statement and embodiment of the present disclosure so defined may be combined with any other statement and / or embodiment. In particular, any feature indicated as preferred or advantageous may be combined with any other one or more features or statements indicated as preferred or advantageous. To this end, the present disclosure is particularly captured (covered) by one or more of the following numbered statements and embodiments and any one or any combination of any other aspects and / or embodiments.

[0119] 1. A process for producing methanol (MeOH) and hydrogen (H2) from methane, comprising the following steps:

[0120] a) providing a gaseous feed stream comprising methane;

[0121] b) reacting the gaseous feed stream with at least one halogen reactant (X2) under reaction conditions effective to produce an effluent stream comprising methyl halide (MeX), hydrogen halide (HX), optionally polyhalogenated alkane, and optionally unreacted methane;

[0122] c) recovering an effluent stream comprising methyl halide (MeX), hydrogen halide (HX), optionally polyhalogenated alkane and optionally unreacted methane;

[0123] d) reacting the effluent stream obtained in step c) with water and at least one catalyst under reaction conditions effective to produce:

[0124] - Aqueous solutions of hydrogen halides (HX (aq) ),and

[0125] - a methanol stream comprising methanol (MeOH) and optionally dimethyl ether (DME) and / or optionally unreacted methane,

[0126] e) decomposing the aqueous solution of hydrogen halide (HX2) by electrolysis under conditions effective to produce a stream of gaseous hydrogen (H2) and a stream comprising a halogen reactant (X2); (aq) );and,

[0127] f) optionally, recovering methanol from said methanol (MeOH) stream.

[0128] More particularly, the present disclosure provides thereto a process for producing methanol (MeOH), dimethyl ether (DME) and hydrogen (H2) from methane, comprising the steps of:

[0129] a) providing a gaseous feed stream comprising methane;

[0130] b) reacting the gaseous feed stream with at least one halogen reactant (X2) under reaction conditions effective to produce an effluent stream comprising methyl halide (MeX), hydrogen halide (HX), optionally polyhalogenated alkane, and optionally unreacted methane;

[0131] c) recovering an effluent stream comprising methyl halide (MeX), hydrogen halide (HX), optionally polyhalogenated alkane and optionally unreacted methane;

[0132] d) reacting the effluent stream obtained in step c) with water and an organic base under reaction conditions effective to produce:

[0133] - Aqueous solutions of hydrogen halides (HX (aq) ),and

[0134] - a methanol stream comprising methanol (MeOH) and dimethyl ether (DME) and optionally unreacted methane, and,

[0135] e) decomposing the aqueous solution of hydrogen halide (HX2) by electrolysis under conditions effective to produce a stream of gaseous hydrogen (H2) and a stream comprising a halogen reactant (X2); (aq) );and

[0136] f) optionally, recovering methanol from the methanol (MeOH) stream and / or recovering dimethyl ether (DME) from the methanol (MeOH) stream.

[0137] 2. Process according to statement 1, wherein said process comprises the step of separating said polyhalogenated alkanes formed in step b) from the effluent stream, preferably before reacting said effluent stream with water and at least one catalyst.

[0138] 3. A process according to any one of statements 1 to 2, wherein the polyhalogenated alkane comprises polyhalogenated methane and optionally polyhalogenated C 2+ Alkane.

[0139] 4. A process for producing methanol (MeOH) and hydrogen (H2) from methane, preferably a process for producing methanol (MeOH) and hydrogen (H2) from methane according to any one of statements 1 to 3, comprising the following steps:

[0140] a) providing a gaseous feed stream comprising methane;

[0141] b) reacting the gaseous feed stream with at least one halogen reactant (X2) under reaction conditions effective to produce an effluent stream comprising methyl halide (MeX), hydrogen halide (HX), optionally polyhalogenated alkane, and optionally unreacted methane;

[0142] c) separating from the effluent stream obtained in step b) the following:

[0143] c1) a monohalide stream comprising methyl halide (MeX) and hydrogen halide (HX), and optionally unreacted methane; and,

[0144] c2) a polyhalogenated alkane stream,

[0145] d) reacting the monohalide stream separated in step c1) with water and at least one catalyst under reaction conditions effective to produce:

[0146] d1) Aqueous solution of hydrogen halide (HX (aq) ),and

[0147] d2) a methanol stream comprising methanol (MeOH) and optionally dimethyl ether (DME) and / or optionally unreacted methane,

[0148] e) decomposing the aqueous solution of hydrogen halide (HX2) produced in step d1) by electrolysis under conditions effective to produce a stream of gaseous hydrogen (H2) and a stream comprising a halogen reactant (X2); (aq) );and,

[0149] f) optionally, recovering methanol from said methanol (MeOH) stream.

[0150] For example, the process comprises the following steps:

[0151] a) providing a gaseous feed stream comprising methane;

[0152] b) reacting the gaseous feed stream with at least one halogen reactant (X2) under reaction conditions effective to produce an effluent stream comprising methyl halide (MeX), hydrogen halide (HX), optionally polyhalogenated alkane, and optionally unreacted methane;

[0153] c. separating from the effluent stream obtained in step b) the following:

[0154] c1) a monohalide stream comprising methyl halide (MeX) and hydrogen halide (HX), and optionally unreacted methane; and,

[0155] c2) a polyhalogenated alkane stream,

[0156] d) reacting the monohalide stream separated in step c1) with water and an organic base under reaction conditions effective to produce:

[0157] d1) Aqueous solution of hydrogen halide (HX (aq) ),and

[0158] d2) a methanol stream comprising methanol (MeOH) and dimethyl ether (DME) and optionally unreacted methane,

[0159] e) decomposing the aqueous solution of hydrogen halide (HX2) produced in step d1) by electrolysis under conditions effective to produce a stream of gaseous hydrogen (H2) and a stream comprising a halogen reactant (X2); (aq) );and,

[0160] Optionally, methanol is recovered from the methanol (MeOH) stream and / or dimethyl ether (DME) is recovered from the methanol (MeOH) stream.

[0161] 5. Process according to any of the preceding statements, wherein the step of separating the polyhalogenated alkanes formed in step b) from the effluent stream is performed before separating the monohalide stream from the effluent stream.

[0162] 6. A process according to any of the preceding statements, wherein the halogen reactant is selected from bromine (Br2), chlorine (Cl2), fluorine (F2), iodine (I2) and astatine (At2).

[0163] 7. A process according to any of the preceding statements, wherein the halogen reactant is bromine (Br2).

[0164] 8. The process according to any of the preceding statements, wherein steps b) and d) are carried out in separate reaction steps, preferably in separate reactors or separate reaction zones.

[0165] 9. A process according to any of the preceding statements, wherein the temperature during step b) is at least 150°C, preferably at least 200°C, preferably at least 250°C, preferably at least 300°C, preferably at least 350°C, preferably at least 380°C.

[0166] 10. The process according to any of the preceding statements, wherein the temperature during step b) is at most 900°C, preferably at most 800°C, preferably at most 700°C, preferably at most 600°C, preferably at most 550°C, preferably at most 520°C.

[0167] 11. Process according to any of the preceding statements, wherein the temperature during step b) is at least 150°C to at most 900°C, preferably at least 200°C to at most 800°C, preferably at least 250°C to at most 700°C, preferably at least 300°C to at most 600°C, preferably at least 350°C to at most 550°C, preferably at least 380°C to at most 520°C.

[0168] 12. A process according to any of the preceding statements, wherein the pressure during step b) is at least 1.0 bar, preferably at least 1.5 bar, preferably at least 2.0 bar, preferably at least 2.5 bar, preferably at least 3.0 bar, preferably at least 5.0 bar, preferably at least 10.0 bar.

[0169] 13. The process according to any of the preceding statements, wherein the pressure during step b) is at most 50.0 bar, preferably at most 45.0 bar, preferably at most 40.0 bar, preferably at most 35.0 bar, preferably at most 30.0 bar, preferably at most 25.0 bar, preferably at most 20.0 bar.

[0170] 14. The process according to any of the preceding statements, wherein the pressure during step b) is at least 1.0 bar to at most 50.0 bar, preferably at least 1.5 bar to at most 45.0 bar, preferably at least 2.0 bar to at most 40.0 bar, preferably at least 2.5 bar to at most 35.0 bar, preferably at least 3.0 bar to at most 30.0 bar, preferably at least 5.0 bar to at most 25.0 bar, preferably at least 10.0 bar to at most 20.0 bar.

[0171] 15. A process according to any of the preceding statements, wherein in step b), the gaseous feed stream is contacted with the halogen reactant (X2) for at least 0.1 minutes to a maximum of 2.0 minutes, preferably at least 0.2 minutes to a maximum of 1.7 minutes, preferably at least 0.5 minutes to a maximum of 1.5 minutes, preferably at least 0.7 minutes to a maximum of 1.2 minutes.

[0172] 16. A process according to any one of the preceding statements, wherein during step b) polyhalogenated alkanes are formed, preferably wherein the polyhalogenated alkanes formed during step b) comprise polyhalogenated methane and optionally polyhalogenated C 2+ Alkane.

[0173] 17. A process according to any of the preceding statements, wherein the polyhalogenated alkanes formed in step b) of the process comprise dihalomethanes (CH2X2).

[0174] 18. A process according to any one of the preceding statements, wherein the polyhalogenated alkanes formed in step b) of the process are separated from the effluent stream by distillation.

[0175] 19. A process according to any of the preceding statements, wherein the polyhalogenated alkanes formed in step b) of the process are used as a polyhalogenated methane stream and as a polyhalogenated C 2+ The alkane stream is separated from the effluent stream, preferably by distillation.

[0176] 20. A process according to any of the preceding statements, wherein C 2+The alkyl monohalide is formed in step b).

[0177] 21. A process according to any one of the preceding statements, wherein the process comprises separating the C formed in step b) of the process from the effluent stream. 2+ Alkyl monohalide step.

[0178] 22. A process according to any one of the preceding statements, wherein the process comprises separating the C formed in step b) from the effluent stream before separating the monohalide stream comprising methyl halide (MeX) and hydrogen halide (HX). 2+ Alkyl monohalides.

[0179] 23. A process according to any one of the preceding statements, wherein the process comprises separating the C2+ alkyl monohalide formed in step b) from the effluent stream after separating the polyhalogenated alkanes from the effluent stream.

[0180] 24. A process for producing methanol (MeOH) and hydrogen from methane, preferably a process for producing methanol (MeOH) and hydrogen (H2) from methane according to any of the preceding statements, comprising the following steps:

[0181] a) providing a gaseous feed stream comprising methane;

[0182] b) reacting the gaseous feed stream with at least one halogen reactant (X2) in an effective manner to produce a product comprising methyl halide (MeX), hydrogen halide (HX), polyhalogenated alkanes, C 2+ reacting an alkyl monohalide and optionally an effluent stream of unreacted methane under reaction conditions;

[0183] c) separating the following substreams from the effluent stream obtained in step b):

[0184] c1) a monohalide stream comprising methyl halide (MeX), hydrogen halide (HX), and optionally unreacted methane; and,

[0185] c2) a polyhalogenated alkane stream; and,

[0186] c2) C 2+ Alkyl monohalide stream;

[0187] d) reacting the monohalide stream separated in step c1) with water and at least one catalyst under reaction conditions effective to produce:

[0188] d1) Aqueous solution of hydrogen halide (HX (aq) ),and

[0189] d2) a methanol stream comprising methanol (MeOH) and optionally dimethyl ether (DME) and / or optionally unreacted methane,

[0190] e) decomposing the aqueous solution of hydrogen halide (HX2) produced in step d1) by electrolysis under conditions effective to produce a stream of gaseous hydrogen (H2) and a stream comprising a halogen reactant (X2); (aq) );and,

[0191] f) optionally, recovering methanol from said methanol (MeOH) stream.

[0192] 25. A process according to any one of the preceding statements, wherein the methanol stream comprising methanol (MeOH) and optionally dimethyl ether (DME) and optionally unreacted methane is separated from the aqueous solution of hydrogen halide by distillation.

[0193] 26. A process according to any of the preceding statements, wherein the stream comprising methanol and / or dimethyl ether recovered after step d) comprises at least 75.0 mol%, e.g. at least 80.0 mol%, or at least 85.0 mol%, or at least 95.0 mol% of a combination of methanol and dimethyl ether, based on the total amount of said stream.

[0194] 27. A process according to any one of the preceding statements, wherein the C formed in step b) of the process 2+ The alkyl monohalide is separated from the effluent stream by distillation.

[0195] 28. A process according to any of the preceding statements, wherein the monohalide stream separated in step c) is a gaseous stream.

[0196] 29. A process according to any of the preceding statements, wherein the monohalide stream recovered in step c) is a gaseous stream.

[0197] 30. A process according to any of the preceding statements, wherein the monohalide stream separated in step c) is substantially free of polyhalogenated alkanes.

[0198] 31. A process according to any of the preceding statements, wherein the monohalide stream separated in step c) is substantially free of C 2+ Alkyl monohalides.

[0199] 32. A process according to any of the preceding statements, wherein step c) comprises separating from the effluent stream:

[0200] c1) a monohalide stream comprising methyl halide (MeX) and hydrogen halide (HX), and optionally unreacted methane; and,

[0201] c2) a polyhalogenated alkane stream comprising a polyhalogenated methane stream and optionally a polyhalogenated C 2+ an alkane stream; and,

[0202] c3) Optional C 2+ Alkyl monohalide stream.

[0203] 33. A process according to any of the preceding statements, wherein the monohalide stream contains unreacted methane.

[0204] 34. A process according to any of the preceding statements, wherein the monohalide stream comprises C 2+ Alkyl monohalides.

[0205] 35. A process according to any of the preceding statements, wherein the gaseous feed stream comprises at least 75.0 volume % methane, preferably at least 80.0 volume % methane, preferably at least 85.0 volume % methane, preferably at least 90.0 volume % methane, preferably at least 95.0 volume % methane, preferably at least 98.0 volume % methane, preferably at least 99.0 volume % methane, preferably at least 99.9 volume % methane, based on the total volume of the gaseous feed stream.

[0206] 36. A process according to any of the preceding statements, wherein the gaseous feed stream comprises natural gas, biogas, refinery gas, or any mixture thereof.

[0207] 37. A process according to any of the preceding statements, wherein the gaseous feed stream used in step a) of the process is substantially free of sulfur species, for example it contains less than 1.0 mol%, or less than 0.5 mol%, or less than 0.1 mol%, or less than 0.01 mol%, or less than 0.001 mol%, or less than 0.0001 mol%, or less than 0.00001 mol% of sulfur species.

[0208] 38. A process according to any of the preceding statements, wherein in step d), the effluent stream or the recovered monohalide stream is reacted with water, wherein the water comprises at least one catalyst.

[0209] 39. A process according to any of the preceding statements, wherein the at least one catalyst is a base, preferably an organic base.

[0210] 40. A process according to any of the preceding statements, wherein the at least one catalyst is a N-containing polymer, and preferably a polymer comprising at least one of the following: an amino group, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a pyrazole ring, an imidazole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, a triazole ring, an oxadiazole ring, or any combination thereof.

[0211] 41. A process according to any of the preceding statements, wherein in step d), the monohalide stream is contacted with water and the catalyst for at least 0.1 minutes to a maximum of 600.0 minutes, preferably at least 0.2 minutes to a maximum of 400.0 minutes, preferably at least 0.5 minutes to a maximum of 200.0 minutes, preferably at least 1.0 minutes to a maximum of 100.0 minutes, preferably at least 2.0 minutes to a maximum of 75.0 minutes, preferably at least 3.0 minutes to a maximum of 60.0 minutes, preferably at least 4.0 minutes to a maximum of 30.0 minutes, preferably at least 5.0 minutes to a maximum of 15.0 minutes.

[0212] 42. A process according to any of the preceding statements, wherein the temperature during step d) is at least 50°C, preferably at least 70°C, preferably at least 80°C, preferably at least 90°C, preferably at least 100°C, preferably at least 120°C.

[0213] 43. A process according to any of the preceding statements, wherein the temperature during step d) is at most 500°C, preferably at most 450°C, preferably at most 400°C, preferably at most 350°C, preferably at most 300°C, preferably at most 250°C.

[0214] 44. A process according to any of the preceding statements, wherein the temperature during step d) is from at least 50°C to at most 500°C, preferably from at least 70°C to at most 450°C, preferably from at least 80°C to at most 400°C, preferably from at least 90°C to at most 350°C, preferably from at least 100°C to at most 300°C, preferably from at least 120°C to at most 250°C.

[0215] 45. A process according to any of the preceding statements, wherein the pressure during step d) is at least 1.0 bar, preferably at least 1.2 bar, preferably at least 1.5 bar, preferably at least 1.7 bar, preferably at least 2.0 bar, preferably at least 5.0 bar, preferably at least 10.0 bar.

[0216] 46. ​​A process according to any of the preceding statements, wherein the pressure during step d) is at most 40.0 bar, preferably at most 35.0 bar, preferably at most 30.0 bar, preferably at most 25.0 bar, preferably at most 20.0 bar, preferably at most 15.0 bar, preferably at most 10.0 bar.

[0217] 47. A process according to any of the preceding statements, wherein the pressure during step d) is at least 1.0 bar to a maximum of 40.0 bar, preferably at least 1.2 bar to a maximum of 35.0 bar, preferably at least 1.5 bar to a maximum of 30.0 bar, preferably at least 1.7 bar to a maximum of 25.0 bar, preferably at least 2.0 bar to a maximum of 20.0 bar, preferably at least 5.0 bar to a maximum of 20.0 bar, preferably at least 10.0 bar to a maximum of 15.0 bar.

[0218] 48. A process according to any one of the preceding statements, wherein the polyhalogenated alkane is converted to its corresponding alcohol, preferably by hydrogenating the polyhalogenated alkane to a monohalide and subsequently reacting the monohalide with a solid metal hydroxide (MOH (s) ) under reaction conditions effective to produce the corresponding alcohol.

[0219] 49. A process according to any of the preceding statements, wherein C 2+ The alkyl monohalide stream is converted into its corresponding alcohol, preferably by subjecting the C 2+ Alkyl monohalides and solid metal hydroxides (MOH (s) ) under reaction conditions effective to produce the corresponding alcohol.

[0220] 50. A process according to any one of the preceding statements, wherein the process further comprises the following steps:

[0221] e) recovering at least a portion of the at least one catalyst after step d) of the process or during step e) and supplying the recovered catalyst to step d) of the process.

[0222] 51. The process according to any one of the preceding statements, further comprising the step of returning the halogen reactant (X2) obtained in step e) to step b) of the process.

[0223] 52. The process according to any of the preceding statements, wherein the halogen reactant (X2) obtained in step e) is purified before being fed into step b), and preferably purified by condensation of the halogen reactant (X2).

[0224] 53. Process according to any of the preceding statements, wherein the halogen reactant (X2) obtained in step e) is dried before feeding into step b), preferably over molecular sieves.

[0225] 54. A process according to any one of the preceding statements, wherein step e) of the process comprises supplying an aqueous solution of hydrogen halide (HX) to an electrolytic cell comprising a positive electrode and a negative electrode, and electrolytically decomposing the hydrogen halide by maintaining a potential of about 0.5 to 2.5 V between the electrodes.

[0226] 55. A process according to any of the preceding statements, wherein step e) of the process comprises supplying an aqueous solution of hydrogen halide (HX) to an electrolytic cell comprising a positive electrode and a negative electrode and reacting the electrolyte by maintaining a current between the electrodes of about 100 to 800 mA / cm 2 The hydrogen halide is electrolytically decomposed by a current density of .

[0227] 56. A process according to any of the preceding statements, wherein the electrolytic cell is a polymer electrolyte membrane cell (PEM) containing at least a proton conducting membrane.

[0228] 57. A process according to any of the preceding statements, wherein the hydrogen halide is decomposed in step e) at a temperature of 20 to 95°C.

[0229] 58. The process according to any of the preceding statements, wherein the hydrogen halide is decomposed in step e) at a pressure of 1 to 50 bar.

[0230] 59. The process according to any of the preceding statements, wherein in step e) the solution comprising the catalyst is recovered, preferably the recovered solution comprising the catalyst is returned to step d).

[0231] 60. A process according to any of the preceding statements, wherein the gaseous hydrogen (H2) stream produced in step e) comprises at least 90.0 mol%, such as at least 95.0 mol%, or at least 99.0 mol%, or at least 99.5 mol%, or at least 99.9 mol% hydrogen.

[0232] 61. A process for producing methanol (MeOH) and hydrogen from methane according to any one of the preceding statements, comprising the steps of:

[0233] a) providing a gaseous feed stream comprising methane,

[0234] b) reacting the gaseous feed stream with a bromide (Br2) under reaction conditions effective to produce an effluent stream comprising: hydrogen bromide (HBr), methyl bromide (MeBr), optionally polybrominated alkanes (e.g., polybrominated methane selected from CH2Br2, CHBr3 and / or CBr4); and optionally unreacted methane,

[0235] c) collecting an effluent stream comprising: methyl bromide (MeBr), hydrogen bromide (HBr), optionally polybrominated alkanes (e.g., polybrominated methane selected from CH2Br2, CHBr3 and / or CBr4); and optionally unreacted methane, optionally polybrominated alkanes and optionally unreacted methane;

[0236] d) reacting the effluent stream obtained in step c) with water and at least one catalyst under reaction conditions effective to produce:

[0237] - Aqueous solution of hydrogen bromide (HBr (aq) ),and

[0238] - a methanol stream comprising methanol (MeOH) and optionally dimethyl ether (DME) and / or optionally unreacted methane,

[0239] e) decomposing said aqueous solution of hydrogen bromide by electrolysis under conditions effective to produce a stream of gaseous hydrogen (H2) and a stream comprising bromine (Br2); and,

[0240] f) optionally, recovering methanol from said methanol (MeOH) stream, and

[0241] g) Optionally, after step d) or during step e) at least part of the catalyst is recovered and the recovered catalyst is provided in step d).

[0242] 62. A process for producing methanol (MeOH) and hydrogen from methane according to any one of the preceding statements, comprising the steps of:

[0243] a) providing a gaseous feed stream comprising methane,

[0244] b) reacting the gaseous feed stream with a bromide (Br2) under reaction conditions effective to produce an effluent stream comprising: hydrogen bromide (HBr), methyl bromide (MeBr), optionally polybrominated alkanes (e.g., polybrominated methane selected from CH2Br2, CHBr3 and / or CBr4); and optionally unreacted methane,

[0245] c) separating from the effluent stream obtained in step b) the following:

[0246] (i) a monobromide stream comprising methyl bromide (MeBr) and hydrogen bromide (HBr), and optionally unreacted methane; and,

[0247] (ii) a polybrominated alkane stream comprising polybrominated methanes;

[0248] d) reacting the monobromide stream separated in step c1) with water and at least one catalyst under reaction conditions effective to produce:

[0249] d1) Aqueous solution of hydrogen bromide (HBr (aq) ),and

[0250] d2) a methanol stream comprising methanol (MeOH) and optionally dimethyl ether (DME) and / or optionally unreacted methane,

[0251] e) decomposing the aqueous solution of hydrogen bromide (HBr) obtained in step d1) by electrolysis under conditions effective to produce a stream of gaseous hydrogen (H2) and a stream comprising bromine (Br2); (aq) );

[0252] f) optionally, recovering methanol from said methanol (MeOH) stream; and,

[0253] g) Optionally, after step d) or during step e) at least part of the catalyst is recovered and the recovered catalyst is provided in step d).

[0254] 63. A process according to any one of the preceding statements, wherein a methanol stream comprising methanol (MeOH) and optionally dimethyl ether (DME) and optionally unreacted methane is separated from an aqueous solution of hydrogen bromide by distillation.

[0255] 64. A process according to any of the preceding statements, wherein the process further comprises a step of removing, preferably distilling, unreacted methane from the effluent stream.

[0256] 65. A process according to any of the preceding statements, wherein the process further comprises the step of removing, preferably distilling, unreacted methane from the monohalide stream.

[0257] 66. A process according to any one of the preceding statements, wherein the process further comprises the step of removing unreacted methane, preferably distilling unreacted methane, from the methanol stream produced in step d2).

[0258] 67. The process according to any of the preceding statements, wherein the removed unreacted methane is recycled or fed into step a) and / or step b).

[0259] 68. A process according to any of the preceding statements, wherein the process is a continuous process.

[0260] 69. A system for producing methanol (MeOH) and hydrogen (H2) from methane, comprising:

[0261] - a halogenation reactor configured to react a gaseous feed stream comprising methane with at least one halogen reactant (X2) into an effluent stream comprising methyl halide (MeX) and hydrogen halide (HX) and optionally unreacted methane,

[0262] - Optionally, a polyhalogenated alkane removal unit configured to receive an effluent stream from said halogenation reactor and configured to separate from said effluent stream:

[0263] (i) a polyhalogenated alkane stream comprising polyhalogenated alkanes; and,

[0264] (ii) a monohalide stream comprising methyl halide (MeX) and hydrogen halide (HX), and optionally unreacted methane; and,

[0265] - A hydrolysis reactor fluidically connected to:

[0266] the halogenation reactor and configured to receive an effluent stream from the halogenation reactor; or,

[0267] the polyhalogenated alkane removal unit and configured to receive a monohalide stream from the polyhalogenated alkane removal unit;

[0268] and wherein the hydrolysis reactor is configured to react the effluent stream or the monohalide stream with water and at least one catalyst under reaction conditions effective to produce: (i) an aqueous solution of hydrogen halide (HX (aq) ) and (ii) a stream comprising methanol (MeOH) and optionally dimethyl ether (DME) and / or optionally unreacted methane; and

[0269] an electrolysis unit comprising at least one electrolysis cell and a power source for supplying electric current to the electrolysis cell, the electrolysis unit being fluidically connected to the hydrolysis reactor and being configured to receive an aqueous solution of hydrogen halide (HX (aq) ) and the aqueous solution of the hydrogen halide (HX (aq) ) is decomposed into a gaseous hydrogen (H2) stream and a stream comprising a halogen reactant (X2);

[0270] - a feed stream supply system for supplying a gaseous feed stream comprising methane to the halogenation reactor;

[0271] - a halogen supply system for supplying a halogen reactant (X2) to the halogenation reactor;

[0272] - an effluent recovery system configured to recover an effluent stream from the halogenation reactor and feed the recovered effluent stream to the optional polyhaloalkane removal unit, or to the hydrolysis reactor;

[0273] - a methanol recovery system configured to recover a stream comprising methanol (MeOH) and optionally dimethyl ether (DME) and / or optionally unreacted methane from the hydrolysis reactor;

[0274] - a hydrogen recovery system configured to recover a gaseous hydrogen (H2) stream from the electrolysis unit;

[0275] - a halogen recovery system configured to recover the halogen reactant (X2) from the electrolysis unit;

[0276] - a hydrogen halide transfer system configured to receive an aqueous solution of hydrogen halide (HX) from the hydrolysis reactor; (aq) ), and the collected aqueous solution of hydrogen halide (HX (aq) ) is supplied to an electrolysis unit;

[0277] - optionally, a monohalide transfer system configured to receive a monohalide stream from the polyhaloalkane removal unit and supply the monohalide stream to a hydrolysis reactor,

[0278] - optionally, a water supply line for supplying water, preferably water and at least one catalyst, to the hydrolysis reactor;

[0279] - Optionally, C 2+ An alkyl monohalide removal unit is configured to receive the effluent stream from the halogenation reactor and remove C2+ alkyl monohalides from the effluent stream.

[0280] In particular, the present disclosure also provides a system for producing methanol (MeOH), dimethyl ether (DME) and hydrogen (H2) from methane, comprising:

[0281] - a halogenation reactor configured to react a gaseous feed stream comprising methane with at least one halogen reactant (X2) to form an effluent stream comprising methyl halide (MeX) and hydrogen halide (HX) and optionally unreacted methane, and,

[0282] - a hydrolysis reactor fluidly connected to the halogenation reactor and configured to receive an effluent stream from the halogenation reactor; and, wherein the hydrolysis reactor is configured to react the effluent stream with water and an organic base under reaction conditions effective to produce: a stream comprising methanol (MeOH) and dimethyl ether (DME) and optionally unreacted methane; and

[0283] an electrolysis unit comprising at least one electrolysis cell and a power source for supplying electric current to the electrolysis cell, the electrolysis unit being fluidically connected to the hydrolysis reactor and being configured to receive an aqueous solution of hydrogen halide (HX (aq) ) and the aqueous solution of the hydrogen halide (HX (aq) ) is decomposed into a gaseous hydrogen (H2) stream and a stream comprising a halogen reactant (X2);

[0284] - a feed stream supply system for supplying a gaseous feed stream comprising methane to the halogenation reactor;

[0285] - a halogen supply system for supplying a halogen reactant (X2) to the halogenation reactor;

[0286] - an effluent recovery system configured to recover an effluent stream from the halogenation reactor and feed the recovered effluent stream to the hydrolysis reactor;

[0287] - a methanol recovery system configured to recover a stream comprising methanol (MeOH) and dimethyl ether (DME) and optionally unreacted methane from the hydrolysis reactor;

[0288] - a hydrogen recovery system configured to recover a gaseous hydrogen (H2) stream from the electrolysis unit;

[0289] - a halogen recovery system configured to recover the halogen reactant (X2) from the electrolysis unit;

[0290] - a hydrogen halide transfer system configured to receive an aqueous solution of hydrogen halide (HX) from the hydrolysis reactor; (aq) ), and the collected aqueous solution of hydrogen halide (HX (aq) ) is supplied to the electrolysis unit.

[0291] In a first aspect, the present disclosure provides a process for producing methanol (MeOH) and hydrogen (H2) from methane.

[0292] The process of the present disclosure comprises the following steps:

[0293] a) providing a gaseous feed stream comprising methane;

[0294] b) reacting the gaseous feed stream with at least one halogen reactant (X2) under reaction conditions effective to produce an effluent stream comprising methyl halide (MeX), hydrogen halide (HX), optionally polyhalogenated alkane, and optionally unreacted methane;

[0295] c) recovering an effluent stream comprising methyl halide (MeX), hydrogen halide (HX), optionally polyhalogenated alkane and optionally unreacted methane;

[0296] d) reacting the effluent stream obtained in step c) with water and at least one catalyst under reaction conditions effective to produce:

[0297] - Aqueous solutions of hydrogen halides (HX (aq) ),and

[0298] - a methanol stream comprising methanol (MeOH) and optionally dimethyl ether (DME) and / or optionally unreacted methane,

[0299] e) decomposing an aqueous solution of hydrogen halide (HX(aq)) by electrolysis under conditions effective to produce a stream of gaseous hydrogen (H2) and a stream comprising a halogen reactant (X2); and

[0300] f) optionally, recovering methanol from said methanol (MeOH) stream.

[0301] For example, the process of the present disclosure includes the following steps:

[0302] a) providing a gaseous feed stream comprising methane;

[0303] b) reacting the gaseous feed stream with at least one halogen reactant (X2) under reaction conditions effective to produce an effluent stream comprising methyl halide (MeX), hydrogen halide (HX), optionally polyhalogenated alkane, and optionally unreacted methane;

[0304] c) recovering an effluent stream comprising methyl halide (MeX), hydrogen halide (HX), optionally polyhalogenated alkane and optionally unreacted methane;

[0305] d) reacting the effluent stream obtained in step c) with water and an organic base under reaction conditions effective to produce:

[0306] - Aqueous solutions of hydrogen halides (HX (aq) ),and

[0307] - a methanol stream comprising methanol (MeOH) and dimethyl ether (DME) and optionally unreacted methane,

[0308] e) decomposing the aqueous solution of hydrogen halide (HX2) by electrolysis under conditions effective to produce a stream of gaseous hydrogen (H2) and a stream comprising a halogen reactant (X2); (aq) );and

[0309] f) optionally, recovering methanol from the methanol (MeOH) stream and / or recovering dimethyl ether (DME) from the methanol (MeOH) stream.

[0310] In some embodiments, the process of the present disclosure for producing methanol (MeOH) and hydrogen (H2) comprises the following steps:

[0311] a) providing a gaseous feed stream comprising methane;

[0312] b) reacting the gaseous feed stream with at least one halogen reactant (X2) under reaction conditions effective to produce an effluent stream comprising methyl halide (MeX), hydrogen halide (HX), optionally polyhalogenated alkane, and optionally unreacted methane;

[0313] c) separating from the effluent stream obtained in step b) the following:

[0314] c1) a monohalide stream comprising methyl halide (MeX) and hydrogen halide (HX), and optionally unreacted methane; and,

[0315] c2) a polyhalogenated alkane stream,

[0316] d) reacting the monohalide stream separated in step c1) with water and at least one catalyst under reaction conditions effective to produce:

[0317] d1) Aqueous solution of hydrogen halide (HX (aq) ),and

[0318] d2) a methanol stream comprising methanol (MeOH) and optionally dimethyl ether (DME) and / or optionally unreacted methane,

[0319] e) decomposing the aqueous solution of hydrogen halide (HX2) produced in step d1) by electrolysis under conditions effective to produce a stream of gaseous hydrogen (H2) and a stream comprising a halogen reactant (X2); (aq) );and,

[0320] f) optionally, recovering methanol from said methanol (MeOH) stream.

[0321] For example, a process of the present disclosure for producing methanol (MeOH), dimethyl ether (DME) and hydrogen (H2) comprises the following steps:

[0322] a) providing a gaseous feed stream comprising methane;

[0323] b) reacting the gaseous feed stream with at least one halogen reactant (X2) under reaction conditions effective to produce an effluent stream comprising methyl halide (MeX), hydrogen halide (HX), optionally polyhalogenated alkane, and optionally unreacted methane;

[0324] c) separating from the effluent stream obtained in step b) the following:

[0325] c1) a monohalide stream comprising methyl halide (MeX) and hydrogen halide (HX), and optionally unreacted methane; and,

[0326] c2) a polyhalogenated alkane stream,

[0327] d) reacting the monohalide stream separated in step c1) with water and an organic base under reaction conditions effective to produce:

[0328] d1) Aqueous solution of hydrogen halide (HX (aq) ),and

[0329] d2) a methanol stream comprising methanol (MeOH) and dimethyl ether (DME) and optionally unreacted methane,

[0330] e) decomposing the aqueous solution of hydrogen halide (HX2) produced in step d1) by electrolysis under conditions effective to produce a stream of gaseous hydrogen (H2) and a stream comprising a halogen reactant (X2); (aq) );and,

[0331] f) optionally, recovering methanol from the methanol (MeOH) stream and / or recovering dimethyl ether (DME) from the methanol (MeOH) stream.

[0332] In some embodiments of the process of the present disclosure, the process comprises the further step of separating the polyhalogenated alkanes formed in step b) from the effluent stream, preferably before reacting the effluent stream with water and at least one catalyst, which is preferably an organic base.

[0333] The polyhalogenated alkane preferably comprises a polyhalogenated methane (as defined herein) and optionally a polyhalogenated C 2+ Alkane (as defined herein).

[0334] In some embodiments, the process of the present disclosure comprises the following steps:

[0335] a) providing a gaseous feed stream comprising methane;

[0336] b) reacting the gaseous feed stream with at least one halogen reactant (X2) under reaction conditions effective to produce an effluent stream, thereby producing an effluent stream comprising hydrogen halide (HX), methyl halide (MeX), optionally polyhalogenated alkanes (e.g. polyhalogenated methane) (as defined herein) and optionally unreacted methane,

[0337] c) optionally, separating from the effluent stream obtained in step b) the following:

[0338] c1) a monohalide stream comprising methyl halide (MeX) and hydrogen halide (HX), optionally comprising unreacted methane; and,

[0339] c2) a polyhalogenated alkane stream comprising polyhalogenated alkanes, such as polyhalogenated methanes, as defined herein,

[0340] d) reacting the effluent stream obtained in step b), or the monohalide stream separated in step c), with water and at least one catalyst under reaction conditions effective to produce:

[0341] d1) Aqueous solution of hydrogen halide (HX (aq) ) logistics, and

[0342] d2) a methanol stream comprising methanol (MeOH) and optionally dimethyl ether (DME) and / or optionally unreacted methane,

[0343] e) decomposing the aqueous solution of hydrogen halide (HX2) produced in step d1) by electrolysis under conditions effective to produce a stream of gaseous hydrogen (H2) and a stream comprising a halogen reactant (X2); (aq) );and,

[0344] f) optionally, recovering methanol from said methanol (MeOH) stream.

[0345] For example, the process of the present disclosure includes the following steps:

[0346] a) providing a gaseous feed stream comprising methane;

[0347] b) reacting the gaseous feed stream with at least one halogen reactant (X2) under reaction conditions effective to produce an effluent stream, thereby producing an effluent stream comprising hydrogen halide (HX), methyl halide (MeX), optionally polyhalogenated alkanes (e.g. polyhalogenated methane) (as defined herein) and optionally unreacted methane,

[0348] c) optionally, separating from the effluent stream obtained in step b) the following:

[0349] c1) a monohalide stream comprising methyl halide (MeX) and hydrogen halide (HX), optionally comprising unreacted methane; and,

[0350] c2) a polyhalogenated alkane stream comprising polyhalogenated alkanes, such as polyhalogenated methanes, as defined herein,

[0351] d) reacting the effluent stream obtained in step b) or the monohalide stream separated in step c) with water and an organic base under reaction conditions effective to produce:

[0352] d1) Aqueous solution of hydrogen halide (HX (aq) ) logistics, and

[0353] d2) a methanol stream comprising methanol (MeOH) and dimethyl ether (DME) and optionally unreacted methane,

[0354] e) decomposing the aqueous solution of hydrogen halide (HX2) produced in step d1) by electrolysis under conditions effective to produce a stream of gaseous hydrogen (H2) and a stream comprising a halogen reactant (X2); (aq) );and,

[0355] f) optionally, recovering methanol from the methanol (MeOH) stream and / or recovering dimethyl ether (DME) from the methanol (MeOH) stream.

[0356] In some embodiments, a process for producing methanol (MeOH) and hydrogen from methane according to an embodiment of the present disclosure comprises the following steps:

[0357] a) providing a gaseous feed stream comprising methane;

[0358] b) reacting the gaseous feed stream with at least one halogen reactant (X2) to produce an effluent stream comprising hydrogen halide (HX), methyl halide (MeX), polyhalogenated alkanes (e.g. polyhalogenated methane) (as defined herein), optionally unreacted methane,

[0359] c) separating from the effluent stream obtained in step b) the following:

[0360] c1) a monohalide stream comprising methyl halide (MeX) and hydrogen halide (HX), optionally comprising unreacted methane; and,

[0361] c2) a polyhalogenated alkane stream comprising polyhalogenated methane;

[0362] d) reacting the monohalide stream separated in step c) with water and at least one catalyst under reaction conditions effective to produce:

[0363] d1) Aqueous solution of hydrogen halide (HX (aq) ) logistics, and

[0364] d2) a methanol stream comprising methanol (MeOH) and optionally dimethyl ether (DME) and / or optionally unreacted methane,

[0365] e) decomposing the aqueous solution of hydrogen halide (HX2) produced in step d1) by electrolysis under conditions effective to produce a stream of gaseous hydrogen (H2) and a stream comprising a halogen reactant (X2); (aq) );and,

[0366] f) optionally, recovering methanol from the methanol (MeOH) stream;

[0367] g) optionally, recovering at least a portion of the at least one catalyst after step d) of the process or during step e) and supplying the recovered catalyst to step d) of the process; and,

[0368] h) Optionally, the halogen reactant (X2) obtained in step e) is returned to step b) of the process.

[0369] For example, a process for producing methanol (MeOH), dimethyl ether (DME), and hydrogen from methane according to an embodiment of the present disclosure includes the following steps:

[0370] a) providing a gaseous feed stream comprising methane;

[0371] b) reacting the gaseous feed stream with at least one halogen reactant (X2) to produce an effluent stream comprising hydrogen halide (HX), methyl halide (MeX), polyhalogenated alkanes (e.g. polyhalogenated methane) (as defined herein), optionally unreacted methane,

[0372] c) separating from the effluent stream obtained in step b) the following:

[0373] c1) a monohalide stream comprising methyl halide (MeX) and hydrogen halide (HX), optionally comprising unreacted methane; and,

[0374] c2) a polyhalogenated alkane stream comprising polyhalogenated methane;

[0375] d) reacting the monohalide stream separated in step c) with water and an organic base under reaction conditions effective to produce:

[0376] d1) Aqueous solution of hydrogen halide (HX (aq) ) logistics, and

[0377] d2) a methanol stream comprising methanol (MeOH) and dimethyl ether (DME) and optionally unreacted methane,

[0378] e) decomposing the aqueous solution of hydrogen halide (HX2) produced in step d1) by electrolysis under conditions effective to produce a stream of gaseous hydrogen (H2) and a stream comprising a halogen reactant (X2); (aq) );and,

[0379] f) optionally, recovering methanol from the methanol (MeOH) stream and / or recovering dimethyl ether (DME) from the methanol (MeOH) stream;

[0380] g) optionally, recovering at least a portion of the organic base after step d) of the process or during step e) and supplying the recovered organic base to step d) of the process; and,

[0381] h) Optionally, the halogen reactant (X2) obtained in step e) is returned to step b) of the process.

[0382] According to the present disclosure, it is preferred that steps b) and d) are carried out in separate reaction steps, preferably in separate reactors or separate reaction zones. The process of the present disclosure is preferably a continuous process.

[0383] The present disclosure provides a process for producing a stream of hydrogen and a stream of methanol and / or dimethyl ether, preferably a stream of hydrogen and a stream of methanol and dimethyl ether, starting from a gaseous feed stream comprising, or consisting essentially of, methane, such as biogas or natural gas. In other words, the present disclosure provides a process for producing methanol and / or dimethyl ether, preferably methanol and dimethyl ether, from a gaseous stream comprising methane (not synthesis gas).

[0384] The process comprises reacting a gaseous feed stream with at least one halogen reactant to form methyl halide and hydrogen halide, and then reacting the produced methyl halide with water and optionally at least one catalyst (preferably an organic base) to form methanol and / or dimethyl ether, preferably methanol and dimethyl ether. The process further produces an aqueous solution of hydrogen halide, which can be electrolytically treated to decompose into separate streams of hydrogen and halogen reactant, thereby producing a valuable by-product, i.e. hydrogen. In addition, the collected halogen reactant can be advantageously reused in the process.

[0385] The present process thus provides an efficient process for converting methane to methanol and / or dimethyl ether, preferably methanol and dimethyl ether, wherein hydrogen is produced as an industrially relevant by-product.

[0386] The first step of the process comprises providing a gaseous feed stream comprising methane.

[0387] The terms "gaseous feed stream" and "reactant gas" are used herein as synonyms and refer to a gaseous stream comprising methane.

[0388] In some embodiments of the process according to the present disclosure, the gaseous feed stream used may also contain C 2+ Alkane.

[0389] The term "alkane" refers to an organic compound that is either a non-cyclic saturated hydrocarbon or a cyclic saturated hydrocarbon. As used herein, an alkane may be straight-chain, branched, or cyclic (but not aromatic). Preferably, the alkane is straight-chain or branched. In a preferred embodiment, the alkane is a non-cyclic saturated hydrocarbon and satisfies the following formula C i H (2i+2) , where i is an integer. Examples are methane, ethane, propane, butane, pentane and hexane.

[0390] As used herein, the term "C 2+ "Alkanes" is intended to mean alkanes having greater than two carbon atoms. In some embodiments, C 2+ Alkanes are C 2-6Alkanes, i.e. alkanes containing two to six carbon atoms, thus for example C2, C3, C4, C5, C6 alkanes, and any mixtures thereof. When a subscript is used after a carbon atom herein, the subscript refers to the number of carbon atoms the named group may contain. 2+ Examples of alkanes are ethane, propane, butane, pentane, hexane, and mixtures of two or more of these.

[0391] For example, in some embodiments, the gaseous feed stream employed may comprise a mixture of methane and ethane, or a mixture of methane and propane, or a mixture of methane, ethane, and propane.

[0392] Preferably, the gaseous feed stream comprising methane used in the present process comprises at least 75.0% by volume of methane, preferably at least 80.0% by volume of methane, preferably at least 85.0% by volume of methane, preferably at least 90.0% by volume of methane, preferably at least 95.0% by volume of methane, preferably at least 98.0% by volume of methane, preferably at least 99.0% by volume of methane, preferably at least 99.9% by volume of methane, based on the total volume of the gaseous feed stream.

[0393] Optionally, the gaseous feed stream used in the process according to the present disclosure may also contain hydrogen. Preferably, the molar ratio of this optional hydrogen to methane in the gaseous feed stream may be in the range of about 1:4 to 0:1.

[0394] Optionally, the gaseous feed stream used in the process according to the present disclosure may also contain small amounts of other components selected from oxygen, nitrogen or carbon dioxide. Preferably, such other components may be present in an amount of less than 2.0 mol%, such as less than 1.5 mol%, or less than 1.0 mol%, or less than 0.5 mol%, based on the total molar content of the gaseous feed stream. In some embodiments, the composition of the gaseous feed stream is comparable to that of natural gas or biogas, or a mixture thereof.

[0395] In some embodiments, the gaseous feed stream used in step a) of the process comprises natural gas, biogas, refinery gas (i.e., a gaseous fraction from a crude oil refinery), or any mixture thereof. Preferably, the gaseous feed stream comprises natural gas and / or biogas.

[0396] In some embodiments of the process according to the present disclosure, the gaseous feed stream gas used in step a) of the process is natural gas. The term "natural gas" refers to a multi-component gas obtained from a crude oil well (associated gas) or from an underground gas-bearing formation (non-associated gas). The composition and pressure of natural gas can vary significantly. A typical natural gas stream contains methane as a significant component. Natural gas may also contain ethane, higher molecular weight hydrocarbons (e.g., C2+ alkanes), acid gases (e.g., carbon dioxide, hydrogen sulfide, carbonyl sulfide, carbon disulfide, and mercaptans), and small amounts of contaminants such as water, nitrogen, iron sulfide, wax, and crude oil. As used herein, "natural gas" may also include gas obtained from the regasification of liquefied natural gas, which has been purified to remove contaminants (e.g., water, acid gases) and most of the higher molecular weight hydrocarbons (e.g., C2+ alkanes). 12+ Conventional methods may be used to remove impurities and / or adjust the relative amounts of hydrocarbon compounds present in the gaseous feed stream.

[0397] In some embodiments of the process according to the present disclosure, the gaseous feed stream gas used in step a) of the process is biogas or biomethane produced from biogas. The term "biogas" refers to a multi-component gas consisting primarily of methane and carbon dioxide, produced by anaerobic digestion or by methanogenesis from feedstocks such as, but not limited to, agricultural waste, manure, municipal waste, plant material, sewage, green waste, or food waste. Biogas can be purified to remove carbon dioxide, oxygen, sulfur, and / or silicon-containing compounds to produce biomethane, which can be used as the gaseous feed stream in the present process.

[0398] In some embodiments, the natural gas may be of fossil origin. In some embodiments, the natural gas may be of renewable origin. Natural gas of renewable origin includes, for example, gas produced from existing waste streams and various renewable and sustainable biomass sources (including but not limited to animal waste, crop residues and food waste, organic waste from cattle farms and farms), and gas produced from the biological decomposition of organic waste that occurs naturally in facilities such as wastewater treatment plants and landfills. In some embodiments, the natural gas may comprise a combination of natural gas from fossil sources and natural gas from renewable sources.

[0399] Preferably, the gaseous feed stream used in step a) of the process is substantially free of sulfur species, for example, it contains less than 1.0 mol%, or less than 0.5 mol%, or less than 0.1 mol%, or less than 0.01 mol%, or less than 0.001 mol%, or less than 0.0001 mol%, or less than 0.00001 mol% of sulfur species, based on the total molar content of the gaseous feed stream. In an example, the gaseous feed stream does not contain sulfur species. For example, sulfur species may, for example, refer to species in the form of H2S, COS, CS2. If desired, desulfurization can be achieved by adsorption and / or absorption.

[0400] In some other embodiments of the processes according to the present disclosure, the gaseous feed stream consists of methane.

[0401] Step b) of the process of the present disclosure comprises reacting a gaseous feed stream as defined herein with at least one halogen reactant (X2) under reaction conditions effective to produce an effluent stream comprising methyl halide (MeX), hydrogen halide (HX) and optionally polyhalogenated alkanes. The effluent stream may optionally contain unreacted methane.

[0402] The halogen reactant used in this step of the present process can be selected from bromine (Br2), chlorine (Cl2), fluorine (F2) and iodine (I2), and is preferably bromine. In particular, the collection of bromine in processes e) and f) requires less energy, reactants and / or equipment.

[0403] Therefore, in a preferred embodiment, the present disclosure provides a process for producing methanol (MeOH) and hydrogen (H2) from methane, comprising the steps of:

[0404] a) providing a gaseous feed stream comprising methane,

[0405] b) reacting the gaseous feed stream with a bromide (Br2), thereby producing an effluent stream comprising: hydrogen bromide (HBr), methyl bromide (MeBr), optionally polybrominated alkanes (e.g. polybrominated methane); and optionally unreacted methane,

[0406] c) optionally, separating from the effluent stream obtained in step b) the following:

[0407] (i) a monobromide stream comprising methyl bromide (MeBr) and hydrogen bromide (HBr), optionally comprising unreacted methane; and,

[0408] (ii) a polybrominated alkane stream including polybrominated methanes;

[0409] d) reacting the effluent stream obtained in step b), or the monobromide stream separated in step c), with water and at least one catalyst under reaction conditions effective to produce:

[0410] d1) Aqueous solution of hydrogen bromide (HBr (aq) ) logistics, and

[0411] d2) a methanol stream comprising methanol (MeOH) and optionally dimethyl ether (DME) and / or optionally unreacted methane,

[0412] e) decomposing the aqueous solution of hydrogen bromide (HBr) obtained in step d1) by electrolysis under conditions effective to produce a stream of gaseous hydrogen (H2) and a stream comprising bromine (Br2); (aq) );

[0413] f) optionally, recovering methanol from said methanol (MeOH) stream; and,

[0414] g) optionally, recovering at least a portion of the at least one catalyst after step d) of the process or during step e) and supplying the recovered catalyst to step d) of the process; and,

[0415] h) Optionally, the bromine (Br2) obtained in step e) is returned to step b) of the process.

[0416] For example, the present disclosure provides a process for producing methanol (MeOH), dimethyl ether (DME) and hydrogen (H2) from methane, comprising the steps of:

[0417] a) providing a gaseous feed stream comprising methane,

[0418] b) reacting the gaseous feed stream with a bromide (Br2) to thereby produce an effluent stream comprising: hydrogen bromide (HBr), methyl bromide (MeBr), optionally polybrominated alkanes (e.g. polybrominated methane); and optionally unreacted methane,

[0419] c) optionally, separating from the effluent stream obtained in step b) the following:

[0420] (i) a monobromide stream comprising methyl bromide (MeBr) and hydrogen bromide (HBr), optionally comprising unreacted methane; and,

[0421] (ii) a polybrominated alkane stream comprising polybrominated methanes;

[0422] d) reacting the effluent stream obtained in step b), or the monobromide stream separated in step c), with water and an organic base under reaction conditions effective to produce:

[0423] d1) Aqueous solution of hydrogen bromide (HBr (aq) ) logistics, and

[0424] d2) a methanol stream comprising methanol (MeOH) and dimethyl ether (DME) and optionally unreacted methane,

[0425] e) decomposing the aqueous solution of hydrogen bromide (HBr) obtained in step d1) by electrolysis under conditions effective to produce a stream of gaseous hydrogen (H2) and a stream comprising bromine (Br2); (aq) );

[0426] f) optionally, recovering methanol from the methanol (MeOH) stream and / or recovering dimethyl ether (DME) from the methanol (MeOH) stream; and

[0427] g) optionally, recovering at least a portion of the organic base after step d) of the process or during step e) and supplying the recovered organic base to step d) of the process; and,

[0428] h) Optionally, the bromine (Br2) obtained in step e) is returned to step b) of the process.

[0429] Preferably, the polybrominated methane is selected from CH2Br2, CHBr3 and CBr4, and combinations thereof.

[0430] Preferably, the halogen reactant, such as bromine, is introduced directly into the reaction zone. The halogen reactant can be introduced into the reaction zone in a liquid state. The halogen reactant can be introduced into the reaction zone in pure form, or dissolved in an aqueous hydrogen halide solution.

[0431] According to the present process, step b) of the process is preferably carried out at a temperature during step b) of at least 150° C., preferably at least 200° C., preferably at least 250° C., preferably at least 300° C., preferably at least 350° C., preferably at least 380° C. According to the present process, step b) of the process is preferably carried out at a temperature during step b) of at most 900° C., preferably at most 800° C., preferably at most 700° C., preferably at most 600° C., preferably at most 550° C., preferably at most 520° C.

[0432] For example, in the present process, preferred temperature conditions for the reaction between the feed stream comprising methane and the halogen reactant are included between 150° C. and 900° C., preferably included between 200° C. and 800° C., preferably included between 250° C. and 700° C., preferably included between 300° C. and 600° C., preferably included between 350° C. and 550° C., preferably included between 380° C. and 520° C. In some embodiments, the exothermic nature of the reaction is sufficient to maintain the temperature during the reaction.

[0433] According to the present process, step b) of the process is carried out at a reaction pressure of at least 1.0 bar, preferably at least 1.5 bar, preferably at least 2.0 bar, preferably at least 2.5 bar, preferably at least 3.0 bar, preferably at least 5.0 bar, preferably at least 10.0 bar. According to the present process, step b) of the process is carried out at a reaction pressure of at most 50.0 bar, preferably at most 45.0 bar, preferably at most 40.0 bar, preferably at most 35.0 bar, preferably at most 30.0 bar, preferably at most 25.0 bar, preferably at most 20.0 bar.

[0434] For example, preferred pressure conditions for the reaction between a feed stream comprising methane and a halogen reactant in the present process include between 1.0 bar and 50.0 bar, preferably between 1.5 bar and 45.0 bar, preferably between 2.0 bar and 40.0 bar, preferably between 2.5 bar and 35.0 bar, preferably between 3.0 bar and 30.0 bar, preferably between 5.0 bar and 25.0 bar, and preferably between 10.0 bar and 20.0 bar.

[0435] In some embodiments of the present process, the feed stream comprising methane and the halogen reactant are applied in a methane / halogen molar ratio comprised between 2 / 1 and 7 / 1, preferably between 3 / 1 and 6 / 1, preferably between 4 / 1 and 5 / 1.

[0436] The time required for the gaseous feed stream to react with the halogen will vary depending on the specific feed material used, the halogen used and the reaction temperature. In an example, the gaseous feed stream is contacted with the halogen reactant (X2) at a temperature between 380°C and 520°C, at a pressure between 10 bar and 20 bar, in step b) for at least 0.1 minute to a maximum of 2.0 minutes.

[0437] The effluent stream obtained from the reaction step b) mainly comprises methyl halides and hydrogen halides. The effluent stream may also contain a certain amount of unreacted methane. At the same time, depending on the composition of the initial gaseous feed stream used in the process, the effluent stream may contain a certain amount of C 2+ Alkyl monohalides and / or a certain amount of polyhalogenated alkanes, such as polyhalogenated methane and / or polyhalogenated C 2+Alkanes, which have been formed during reaction step b).

[0438] In the next step, the process of the present disclosure comprises separating the following from the effluent stream obtained in step b): (i) a monohalide stream comprising methyl halide (MeX) and hydrogen halide (HX), optionally including unreacted methane; and (ii) a polyhalogenated alkane stream comprising polyhalogenated alkanes, such as polyhalogenated methane and optionally polyhalogenated C 2+ Alkanes (if the gaseous feed stream contains C 2+ hydrocarbons).

[0439] The monohalide stream is then further reacted with water and at least one catalyst, preferably an organic base, in (step d) of the process, while the aqueous hydrogen halide stream is electrolyzed in (step e) of the process.

[0440] As used herein, the term "monohalide" refers to a compound comprising a single halogen atom. The term "monohalide" preferably encompasses both organic and inorganic compounds. The example of an organic monohalide is an alkyl monohalide comprising a single halogen atom, such as methyl halide (MeX). The example of an inorganic monohalide is a hydrogen halide (HX). As used herein, the term "monohalide" preferably refers to a compound that is either methyl halide (MeX) or a hydrogen halide (HX).

[0441] Therefore, as used herein, the term "monohalide stream" refers to a stream comprising one or more monohalides, preferably two or more monohalides. Other non-halogenated compounds may be present in the monohalide stream, for example, compounds such as methane. Preferably, the term "monohalide stream" refers to a stream comprising at least methyl halide (MeX) and hydrogen halide (HX); even more preferably, the term "monohalide stream" refers to a stream comprising only methyl halide (MeX) and hydrogen halide (HX) as monohalogenated compounds in addition to non-halogenated compounds. Preferably, the monohalide stream is substantially free of polyhalogenated compounds.

[0442] In a preferred embodiment, the monohalide stream is separated from the effluent stream in step c) by distillation.

[0443] In a preferred embodiment, the polyhalogenated alkane stream is separated from the effluent stream in step c) by distillation.

[0444] In a preferred embodiment, the effluent stream is separated into a monohalide stream and a polyhalogenated alkane stream in a separation column or distillation tower.

[0445] In some embodiments of the process of the present disclosure, the effluent stream may comprise additional components in addition to methyl halide, hydrogen halide and optionally unreacted methane, depending on the composition of the initial gaseous feed stream used in the process.

[0446] In some embodiments of the process of the present disclosure, polyhalogenated alkanes are formed in step b) and are present in the effluent stream obtained after step b).

[0447] The term "polyhalogenated alkane" as used herein is an alkane in which more than one hydrogen atom is replaced by a halogen atom (X), wherein X is preferably selected from Br, Cl, F, I and At, more preferably X is Br. "Polyhalogenated alkane" as used herein preferably refers to polyhalogenated alkanes such as polyhalogenated C1-C6 alkanes, preferably polyhalogenated C1-C4 alkanes, preferably polyhalogenated C1-C3 alkanes. When a subscript is used after a carbon atom herein, the subscript refers to the number of carbon atoms that the named group may contain.

[0448] In some embodiments, the term "polyhalogenated alkane" refers to a compound having the following formula (I):

[0449]

[0450] in:

[0451] -n is an integer, and n≥1, preferably 1≤n≥6; preferably 1≤n≥4; preferably 1≤n≥3;

[0452] - m is an integer, and m≥2; preferably 2≤m≥4, preferably 2≤m≥3; and,

[0453] -X is selected from Br, Cl, F, I and At, preferably X is Br.

[0454] In some embodiments, the polyhalogenated alkane comprises a polyhalogenated C1 alkane.

[0455] In some embodiments, the polyhalogenated alkane comprises a polyhalogenated C 2+ Alkane.

[0456] In some embodiments, the polyhalogenated alkane comprises a polyhalogenated C1 alkane and a polyhalogenated C 2+ Alkane.

[0457] The terms "polyhalogenated C1 alkane" and "polyhalogenated methane" are used interchangeably herein and are intended to mean a C1 alkane in which more than one hydrogen atom is replaced by a halogen atom (X), wherein X is preferably selected from Br, Cl, F, I and At, more preferably wherein X is Br.

[0458] In some embodiments, the terms "polyhalogenated C1 alkane" and "polyhalogenated methane" refer to compounds having the following formula (II):

[0459]

[0460] in:

[0461] - p is an integer, and p≥2; preferably 2≤p≥4, preferably 2≤p≥3; and,

[0462] -X is selected from Br, Cl, F, I and At, and preferably X is Br.

[0463] In some preferred embodiments, "polyhalogenated methane" is selected from CH2X2, CHX2 and CX4, and any mixture thereof, wherein X is as defined above. For example, the polyhalogenated methane formed in step b) of the process includes dihalomethane (CH2X2). Preferred examples of polyhalogenated methane include, but are not limited to, CH2Br2, CHBr3 and CBr4.

[0464] As used herein, the term "polyhalogenated C 2+ "Alkanes" refer to the following C 2+ Alkanes: wherein more than one hydrogen atom is replaced by a halogen atom (X), wherein X is preferably selected from Br, Cl, F, I and At, more preferably X is Br. Preferably, the polyhalogenated C 2+ Alkanes preferably refer to polyhalogenated C 2+ The alkane is, for example, a polyhalogenated C2-C6 alkane, preferably a polyhalogenated C2-C4 alkane, preferably a polyhalogenated C2-C3 alkane.

[0465] In some embodiments, the polyhalogenated C 2+ "Alkanes" refer to compounds having the following formula (III):

[0466]

[0467] in:

[0468] -q is an integer and q≥2, preferably 2≤q≥6; preferably 2≤q≥4; preferably 2≤q≥3;

[0469] - r is an integer and r≥2; preferably 2≤r≥4, preferably 2≤r≥3; and,

[0470] -X is selected from Br, Cl, F, I and At, preferably X is Br.

[0471] For example, the polyhalogenated C 2+ The alkanes may include polyhalogenated C2 alkanes (eg, dibromoethane) and / or polyhalogenated C3 alkanes (eg, dibromopropane).

[0472] In some embodiments of the process of the present disclosure, C 2+ Alkyl monohalides are also formed in step b) and are present in the effluent stream obtained after step b).

[0473] The term "C 2+ Alkyl monohalide" and "monohalogenated C 2+ "Alkanes" are used interchangeably herein and refer to the following C 2+ Alkanes: wherein a single hydrogen atom is replaced by a halogen atom (X), wherein X is preferably selected from Br, Cl, F, I and At, more preferably wherein X is Br. Preferably, the monohalogenated C 2+ Alkanes preferably refer to monohalogenated C 2+ For example, monohalogenated C2-C6 alkane, preferably monohalogenated C2-C4 alkane, preferably monohalogenated C2-C3 alkane.

[0474] In other words, the term “C 2+ Alkyl monohalide" and "monohalogenated C 2+ "Alkanes" refer to compounds having the following formula (IV):

[0475]

[0476] in:

[0477] -s is an integer, and s≥2; preferably 2≤s≥6; preferably 2≤s≥4; preferably 2≤s≥3, and,

[0478] -X is selected from Br, Cl, F, I and At, preferably X is Br.

[0479] For example, the C formed in step b) of the process 2+ The alkyl monohalide may include a C2 alkyl monohalide (eg, ethyl bromide) and / or a C3 alkyl monohalide (eg, n-propyl bromide).

[0480] The process may include separating the polyhalogenated alkanes and / or C 2+ Thus, in some embodiments, step c) in the process of the present disclosure comprises the steps of separating the following from the effluent stream obtained in step b):

[0481] (i) a monohalide stream comprising methyl halide (MeX) and hydrogen halide (HX), optionally comprising unreacted methane;

[0482] (ii) a polyhalogenated alkane stream comprising polyhalogenated alkanes as defined herein; and,

[0483] (iii) optionally, C 2+An alkyl monohalide stream comprising C 2+ Alkyl monohalides.

[0484] In some embodiments, step c) comprises a single separation step of the effluent stream, i.e., the effluent stream is separated in one step. In some embodiments, step c) comprises two separation steps, i.e., a monohalide separation step and a polyhalogenated alkane separation step. In some embodiments, step c) comprises three separation steps, i.e., a monohalide separation step, a polyhalogenated alkane separation step, and a C 2+ Alkyl monohalide separation step.

[0485] In one example, step c) in the process of the present disclosure comprises separating from the effluent stream obtained in step b) the following:

[0486] - a monohalide stream comprising methyl halide (MeX) and hydrogen halide (HX), optionally comprising unreacted methane;

[0487] - a polyhalogenated alkane stream comprising polyhalogenated alkanes as defined herein; and,

[0488] - Optionally, C 2+ An alkyl monohalide stream comprising C 2+ Alkyl monohalides.

[0489] In a further example, step c) in the process of the present disclosure comprises separating from the effluent stream obtained in step b) the following:

[0490] - a monohalide stream comprising methyl halide (MeX) and hydrogen halide (HX);

[0491] - a polyhalogenated alkane stream comprising polyhalogenated alkanes as defined herein;

[0492] -C 2+ an alkyl monohalide stream; and,

[0493] - unreacted methane stream;

[0494] In a further example, step c) in the process of the present disclosure comprises separating from the effluent stream obtained in step b) the following:

[0495] a monohalide stream comprising methyl halide (MeX) and hydrogen halide (HX), optionally comprising unreacted methane;

[0496] - a polyhalogenated methane stream comprising polyhalogenated methanes as defined herein;

[0497] -Polyhalogenated C 2+an alkane stream; which comprises a polyhalogenated C 2+ Alkanes; and,

[0498] -C 2+ An alkyl monohalide stream comprising C 2+ Alkyl monohalides.

[0499] Separation of polyhalogenated alkanes and C 2+ Alkyl monohalides have the advantage of allowing recovery of a purified monohalide stream comprising methyl halide (MeX) and hydrogen halide that contains little or no other polyhalogenated alkanes, such as polyhalogenated methanes and / or polyhalogenated C 2+ Alkanes, and thus such purified monohalide streams can be advantageously converted into streams of methanol and / or dimethyl ether, preferably methanol and dimethyl ether, without producing significant amounts of non-alcohol products other than alkanes and DME. In this way, methanol can be produced: non-alcohol products other than alkanes and DME are less than 10.000 ppm, preferably less than 7.000 ppm, preferably less than 5.000 ppm, preferably less than 3.000 ppm, preferably less than 2.000 ppm, preferably less than 1.000 ppm.

[0500] In particular, a preferred process for producing methanol (MeOH) and hydrogen (H2) from methane according to the present disclosure comprises the following steps:

[0501] a) providing a gaseous feed stream comprising methane;

[0502] b) reacting the gaseous feed stream with at least one halogen reactant (X2) under reaction conditions effective to produce an effluent stream comprising hydrogen halide (HX), methyl halide (MeX), polyhalogenated alkanes (e.g., polyhalogenated methane) (as defined herein), and optionally unreacted methane,

[0503] c) separating from the effluent stream obtained in step b) the following:

[0504] c1) a monohalide stream comprising methyl halide (MeX) and hydrogen halide (HX), optionally comprising unreacted methane; and,

[0505] c2) a polyhalogenated alkane stream comprising polyhalogenated methanes as defined herein;

[0506] c3) C 2+ An alkyl monohalide stream comprising C 2+ Alkyl monohalides.

[0507] d) reacting the monohalide stream separated in step c) with water and at least one catalyst under reaction conditions effective to produce:

[0508] d1) Aqueous solution of hydrogen halide (HX (aq) ) logistics, and

[0509] d2) a methanol stream comprising methanol (MeOH) and optionally dimethyl ether (DME) and / or optionally unreacted methane,

[0510] e) decomposing the aqueous solution of hydrogen halide (HX2) obtained in step d1) by electrolysis under conditions effective to produce a stream of gaseous hydrogen (H2) and a stream comprising a halogen reactant (X2); (aq) );

[0511] f) optionally, recovering methanol from the methanol (MeOH) stream;

[0512] g) optionally, recovering at least a portion of the at least one catalyst after step d) of the process or during step e) and supplying the recovered catalyst to step d) of the process;

[0513] h) optionally, returning the halogen reactant (X2) obtained in step e) to step b) of the process; and,

[0514] i) optionally, the polyhalogenated alkane stream and / or C2 + The alkyl monohalide stream is converted to its corresponding alcohol.

[0515] For example, a process for producing methanol (MeOH), dimethyl ether (DME), and hydrogen (H2) from methane according to the present disclosure comprises the following steps:

[0516] a) providing a gaseous feed stream comprising methane;

[0517] b) reacting the gaseous feed stream with at least one halogen reactant (X2) under reaction conditions effective to produce an effluent stream comprising hydrogen halide (HX), methyl halide (MeX), polyhalogenated alkanes (e.g., polyhalogenated methane) (as defined herein), and optionally unreacted methane,

[0518] c) separating from the effluent stream obtained in step b) the following:

[0519] c1) a monohalide stream comprising methyl halide (MeX) and hydrogen halide (HX), optionally comprising unreacted methane; and,

[0520] c2) a polyhalogenated alkane stream comprising polyhalogenated methanes as defined herein;

[0521] c3) C 2+ An alkyl monohalide stream comprising C 2+ Alkyl monohalides.

[0522] d) reacting the monohalide stream separated in step c) with water and an organic base under reaction conditions effective to produce:

[0523] d1) Aqueous solution of hydrogen halide (HX (aq) ) logistics, and

[0524] d2) a methanol stream comprising methanol (MeOH) and dimethyl ether (DME) and optionally unreacted methane,

[0525] e) decomposing the aqueous solution of hydrogen halide (HX2) obtained in step d1) by electrolysis under conditions effective to produce a stream of gaseous hydrogen (H2) and a stream comprising a halogen reactant (X2); (aq) );

[0526] f) optionally, recovering methanol from the methanol (MeOH) stream and / or recovering dimethyl ether (DME) from the methanol (MeOH) stream;

[0527] g) optionally, recovering at least a portion of the organic base after step d) of the process or during step e) and supplying the recovered organic base to step d) of the process;

[0528] h) optionally, returning the halogen reactant (X2) obtained in step e) to step b) of the process; and,

[0529] i) optionally, the polyhalogenated alkane stream and / or C2 + The alkyl monohalide stream is converted to its corresponding alcohol.

[0530] Preferably, the polyhalogenated alkanes formed in step b) of the process are separated from the effluent stream by distillation. For example, the polyhalogenated alkane stream or the polyhalogenated methane stream and the polyhalogenated C 2+ The alkane stream is separated from the effluent stream. Preferably, distillation may be a preferred separation technique due to the large difference in molecular weight and therefore boiling point between polyhalogenated alkanes and monohalogenated compounds. Preferably, the polyhalogenated alkanes are separated from the effluent stream and then the monohalide stream (i.e., methyl halide, hydrogen halide and optional C 2+ alkyl monohalide) is separated from the effluent stream.

[0531] In some preferred embodiments of the present disclosure, the process comprises the steps of: separating the polyhalogenated alkanes formed in step b) from the effluent stream to produce a polyhalogenated alkanes stream, thereby exist separating the monohalide stream from the effluent stream Before , separating the polyhalogenated alkanes formed in step b) from the effluent stream.

[0532] Preferably, the C formed in step b) of the process is distilled 2+ The alkyl monohalide is separated from the effluent stream. For example, the C 2+ An alkyl monohalide stream is separated from the effluent.

[0533] In some embodiments, the process comprises mixing a polyhalogenated methane stream with a polyhalogenated C 2+ The alkane stream is separated in a separate step and / or in a separate separation column. Alternatively, the process may include separating the polyhalogenated methane stream and the polyhalogenated C 2+ The alkane stream is separated in a single step and / or in a single separation column.

[0534] In some preferred embodiments of the present disclosure, the process comprises the following steps: 2+ Alkyl monohalide is separated from the effluent stream to produce C 2+ alkyl monohalide stream, thereby separating the polyhalogenated alkane stream from the effluent stream after , the C formed in step b) 2+ The alkyl monohalide is separated from the effluent stream, preferably by distillation.

[0535] In some embodiments, the process includes separating the polyhalogenated alkane stream and the monohalide stream in separate steps and / or in separate separation towers. Alternatively, the process may include separating the polyhalogenated alkane stream and the monohalide stream in a single step and / or in a single separation tower.

[0536] The monohalide stream separated in step c) is preferably a gaseous stream.

[0537] In step c) polyhalogenated alkanes and / or C 2+After the alkyl monohalide stream, the present process allows the separation of a monohalide stream mainly comprising methyl halide (MeX) and hydrogen halide (HX). Preferably, the separated monohalide stream comprises at least 75.0 mol%, such as at least 80.0 mol%, or at least 85.0 mol%, or at least 90.0 mol% of monohalide, based on the total molar content of the separated monohalide stream. However, it will be noted that the separated monohalide stream may still contain a certain amount of unreacted methane.

[0538] According to the present disclosure, the monohalide stream separated in step c) is also preferably "substantially free" of polyhalogenated alkanes. In this context, "substantially free of polyhalogenated alkanes" means that the monohalide stream obtained in step c) contains less than 1.0 mol %, such as less than 0.1 mol %, preferably less than 0.5 mol % of polyhalogenated alkanes, as defined herein, based on the total molar content of the monohalide stream obtained in step c).

[0539] According to the present invention, the recovered monohalide stream obtained in step c) is also preferably "substantially free" of C 2+ Alkyl monohalide. In this context, "substantially free of C 2+ "Alkyl monohalide" means that the monohalide stream obtained in step c) contains less than 1.0 mol %, such as less than 0.1 mol %, preferably less than 0.5 mol % of C 2+ Alkyl monohalide, as defined herein, is based on the total molar content of said monohalide stream obtained in step c).

[0540] In a next step, the monohalide stream separated in step c) of the process is reacted with water and at least one catalyst, which is preferably an organic base, in an aqueous solution effective to produce hydrogen halide (HX( aq )) and methanol (MeOH), or preferably an aqueous solution of hydrogen halide (HX (aq) ), methanol (MeOH) and dimethyl ether (DME).

[0541] Step d) of the process of the present disclosure is preferably carried out at a temperature of at least 50°C, preferably at least 70°C, preferably at least 80°C, preferably at least 90°C, preferably at least 100°C, preferably at least 150°C. Step d) of the process of the present disclosure is preferably carried out at a temperature of at most 500°C, preferably at most 450°C, preferably at most 400°C, preferably at most 350°C, preferably at most 300°C, preferably at most 250°C. For example, preferred temperature conditions for reaction step d) include between 50°C and 500°C, preferably between 70°C and 450°C, preferably between 80°C and 400°C, preferably between 90°C and 350°C, preferably between 100°C and 300°C, preferably between 120°C and 250°C. In some embodiments, the temperature in step d) can be achieved by heat integration, for example, using the heat harvested during the exothermic reaction in step b).

[0542] Step d) of the process of the present disclosure is preferably carried out at a reaction pressure of at least 1.0 bar, preferably at least 1.2 bar, preferably at least 1.5 bar, preferably at least 1.7 bar, preferably at least 2.0 bar, preferably at least 5.0 bar, preferably at least 10.0 bar. Step d) of the process of the present disclosure is preferably carried out at a reaction pressure of at most 40.0 bar, preferably at most 35.0 bar, preferably at most 30.0 bar, preferably at most 25.0 bar, preferably at most 20.0 bar, preferably at most 15.0 bar, preferably at most 10.0 bar. For example, preferred pressure conditions for reaction step d) include between 1.0 bar and 40.0 bar, preferably between 1.2 bar and 35.0 bar, preferably between 1.5 bar and 30.0 bar, preferably between 1.7 bar and 25.0 bar, preferably between 2.0 bar and 20.0 bar, preferably between 5.0 bar and 20.0 bar, preferably between 10.0 bar and 15.0 bar.

[0543] Preferably, the process of the present disclosure comprises reacting the monohalide stream with water and at least one catalyst, which is preferably an organic base, in step d) for at least 0.1 minute to at most 600.0 minutes, preferably at least 0.2 minutes to at most 400.0 minutes, preferably at least 0.5 minutes to at most 200.0 minutes, preferably at least 1.0 minutes to at most 100.0 minutes, preferably at least 2.0 minutes to at most 75.0 minutes, preferably at least 3.0 minutes to at most 60.0 minutes, preferably at least 4.0 minutes to at most 30.0 minutes, preferably at least 5.0 minutes to at most 15.0 minutes.

[0544] In an example, in step d), the monohalide stream is contacted with water optionally comprising at least one catalyst, which is preferably an organic base, at a temperature of 50°C to 500°C, at a pressure between 1.0 bar and 40.0 bar, and for at least 0.1 minute to at most 600.0 minutes.

[0545] The reaction product obtained from reaction step d) comprises mainly aqueous hydrogen halide solution and methanol (methanol stream), preferably aqueous hydrogen halide solution, methanol and dimethyl ether. In the reaction output there are also optionally residual amounts of unreacted methane.

[0546] Preferably, a methanol stream comprising methanol and optionally dimethyl ether is recovered after step d).Preferably, the methanol stream comprising methanol and optionally dimethyl ether (DME) obtained in step d2) of the process is separated from the aqueous solution of hydrogen halide by distillation.

[0547] Preferably, the total amount of methanol and optionally dimethyl ether in the separated methanol stream accounts for at least 75.0 mol%, such as at least 80.0 mol%, or at least 85.0 mol%, or at least 95.0 mol%, based on the total molar content of the separated methanol stream. However, it will be noted that the recovered methanol stream may still contain a certain amount of unreacted methane.

[0548] By separating the polyhalogenated alkane stream from the effluent stream obtained after step b) of the process of the present disclosure, the present process has the advantage of subjecting the "purified" monohalide stream to a hydrolysis reaction in the presence of water and at least one catalyst, which is preferably an organic base, in step d). Thus, the separation step applied in step c) allows avoiding the reaction of polyhalogenated alkanes with said water and optionally at least one catalyst, which is preferably an organic base, in step d). Thus, the present process thus avoids the conversion of polyhalogenated alkanes into hydroxylation products other than methanol or dimethyl ether during step d) of said process.

[0549] In some embodiments, the catalyst used in the present process is a base, and preferably an organic base. The base can deprotonate the hydrogen halide during step d).

[0550] As used herein, the term "organic base" refers to non-metallic and alkaline organics. Organic bases can contain amino, pyridyl, carboxylic acid derivatives or mixtures thereof. Non-limiting examples include, for example, pyridine, alkylamine, morpholine, imidazoles, benzimidazoles, triethylamine, triethylenediamine, benzyldiethylamine, dimethylethylamine, diisopropylethylamine (DIPEA), 1,8-diazabicyclo [5.4.0] 11 carbon-7-ene (DBU), 2,6-lutidine (2,6-lutidine), piperidine, salts of carboxylic acids or mixtures thereof. In a preferred embodiment, the catalyst used in this process is pyridine.

[0551] In some preferred embodiments, the catalyst used in the present process is a polymer (or polymeric compound) containing N. Preferably, such a polymer containing N is a polymer containing at least one of the following: an amino group, a pyridine ring, a piperidine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a pyrazole ring, an imidazole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, a triazole ring, an oxadiazole ring, or any combination thereof. For example, the polymer containing N is a polymer containing at least one pyridine ring.

[0552] More preferably, in some embodiments, the catalyst used in the present process is a pyridine-containing polymer, such as, for example, selected from poly(4-vinylpyridine), poly(2-vinylpyridine), poly[2-(4-vinylphenyl)pyridine], poly[5-vinyl-2,2'-bipyridine], poly[3-(4-vinylphenyl)pyridine] and poly[4-(4-vinylphenyl)pyridine]. In some preferred embodiments, the catalyst used in the present process is selected from poly(4-vinylpyridine) or poly[4-(4-vinylphenyl)pyridine].

[0553] In some embodiments, the catalyst used in the present process is preferably soluble in water. For example, it can be used in a concentration of at least 5% by weight, such as 10% by weight, or at least 15% by weight of the aqueous solution of the catalyst.

[0554] In some embodiments, the catalyst used in the process of the present disclosure is in solid form or fixed on a solid support. In some embodiments, the solid catalyst or fixed catalyst is suspended in water. In some embodiments, the solid catalyst or fixed catalyst used in the process can be filled in a bed or attached to a structure in a reactor.

[0555] One of ordinary skill in the art will be able to select a catalyst suitable for use in the present process without undue experimentation.

[0556] The aqueous solution of hydrogen halide (HX) obtained in step d) of the process (aq) ) is subjected to decomposition to release hydrogen and halogen for recovery. The halogen reactant may be recycled to steps a) and / or b) of the process, for example added to the feed stream supplied in step a) and / or supplied separately during reaction step b).

[0557] The preferred way of decomposing the hydrogen halide is electrolysis. Therefore, this step of the process of the present disclosure is preferably carried out in an electrolytic cell, preferably in a polymer electrolyte membrane cell (PEM) containing at least a proton conducting membrane. Polymer electrolyte membrane (PEM) electrolysis is well known in the art and includes a cell equipped with a solid polymer electrolyte (SPE) that is responsible for the conduction of protons, the separation of gaseous products and the electrical insulation of the electrodes.

[0558] In some embodiments of the present disclosure, step e) of the process comprises the steps of supplying an aqueous solution of hydrogen halide to an electrolytic cell (such as defined herein) comprising a positive electrode and a negative electrode, and electrolytically decomposing the hydrogen halide by maintaining a potential of about 0.5 to 2.5 V between the electrodes.

[0559] In some embodiments of the present disclosure, step e) of the process comprises the steps of supplying an aqueous solution of hydrogen halide to an electrolytic cell (as defined herein) comprising a positive electrode and a negative electrode, and electrolytically decomposing the hydrogen halide by maintaining a current density between the electrodes of about 100 to 800 mA / cm2.

[0560] The potential required to decompose the hydrogen halide solution decreases with the increase of the temperature of the aqueous solution. It is particularly preferred to carry out the electrolytic decomposition at a temperature of about 20 to 95° C., and preferably about 40 to 80° C. The pressure in the electrolytic decomposition zone is kept high enough to keep the aqueous hydrogen halide in the liquid phase. Generally, the pressure will be in the range of about 0.1 to 5 MPa (1-50 bar).

[0561] The gaseous hydrogen (H2) stream produced in step e) of the process comprises at least 90.0 mol%, such as at least 95.0 mol%, or at least 99.0 mol%, or at least 99.5 mol%, or at least 99.9 mol% hydrogen. The hydrogen obtained by the process according to the present disclosure can be used for downstream applications. For example, it can be used for ammonia synthesis, for hydrogenation purposes, for chemical synthesis, or by (with or without additional hydrocarbon fuels) in gas turbine combustion to produce energy, etc. The produced hydrogen can also be used as a chemical feedstock to reduce dependence on oil and natural gas.

[0562] The halogen reactant (X2) produced in step e) of the process may be reused in step b) of the process, for example after suitable pretreatment such as purification and / or drying.

[0563] In some preferred embodiments, the halogen reactant (X2) obtained in step e) is purified, for example by condensation, before being returned to step b).

[0564] In some preferred embodiments, the halogen reactant (X2) obtained in step e) is dried before being returned to step b). Preferably, the halogen reactant (X2) is dried with a molecular sieve. Preferably, before the halogen reactant (X2) is returned to step b), the amount of water in the halogen reactant (X2) is at most 2000 ppm, preferably at most 1500 ppm, preferably at most 1000 ppm, preferably at most 750 ppm, preferably at most 500 ppm, wherein ppm is expressed as the weight of water relative to the total weight of the halogen reactant.

[0565] In some embodiments, the process comprises a step of recovering at least a portion of the at least one catalyst, which is preferably an organic base, after step d) or during step e) of the process, and a step of supplying the recovered catalyst in step d) of the process.

[0566] In some embodiments, the aqueous solution of hydrogen halide (HX) obtained in step d1) (aq) ) may contain a catalyst, especially when the catalyst is a water-soluble organic base such as pyridine. In such an embodiment, such a catalyst may remain present after the electrolysis step e). In some embodiments of the process, such a catalyst remaining after the electrolytic decomposition in step e) can be collected and supplied in step d) and reused in the process. In an example, according to the present process, a portion of the catalyst will circulate in the hydrolysis reactor and / or the electrolytic cell.

[0567] In some other embodiments, the catalyst (preferably provided in a solid or immobilized form) may be prevented from reacting with an aqueous solution of hydrogen halide (HX (aq) ) is transferred to an electrolysis unit for decomposition. In an example, this can be achieved by using a suitable filtering device. In such an embodiment, fresh water entering the process will allow the catalyst remaining after step d) to be reused.

[0568] In some embodiments of the process according to the present disclosure, polyhalogenated methane (as defined herein) is formed during step b) and may be separated during step c), as described above. In some embodiments, the process of the present disclosure therefore further comprises the step of converting the polyhalogenated methane (e.g., separated in step c)) into methanol, preferably by hydrogenating the polyhalogenated methane to form methyl halide, followed by reacting the methyl halide with a solid metal hydroxide (MOH (s) ) under reaction conditions effective to produce the corresponding alcohol.

[0569] In some embodiments of the process according to the present disclosure, the polyhalogenated C 2+Alkanes may also be formed during step b) and may be separated during step c), as described above. In some embodiments, the process of the present disclosure therefore further comprises the step of: 2+ Alkanes are converted to their corresponding alcohols, preferably by hydrogenation to the corresponding C 2+ monohalide, then making the C 2+ Monohalide compounds and solid metal hydroxides (MOH (s) ) in the effective production of the corresponding C 2+ contacting under reaction conditions of an alcohol.

[0570] Examples of suitable metal hydroxides for use in the present process include, but for example, metal hydroxides selected from the list comprising or consisting of potassium hydroxide (KOH), sodium hydroxide (NaOH), barium hydroxide (Ba(OH)2), cesium hydroxide (CsOH), strontium hydroxide (Sr(OH)2), calcium hydroxide (Ca(OH)2), lithium hydroxide (LiOH), rubidium hydroxide (RbOH), magnesium hydroxide (Mg(OH)2), and any mixture thereof.

[0571] Preferred examples of solid metal hydroxides may be alkali metal hydroxides, such as potassium hydroxide (KOH), lithium hydroxide (LiOH), sodium hydroxide (NaOH), or any mixture thereof. A particularly preferred example is potassium hydroxide (KOH).

[0572] The term "solid" as used herein refers to a metal hydroxide provided on a solid support, such as a silica or alumina support, more preferably a silica support. Preferably, the solid support is impregnated with the metal hydroxide. Preferably, the solid support is impregnated with a solution of the metal hydroxide and the impregnated solid support is then dried.

[0573] In some embodiments of the present process, unreacted methane may remain present in the effluent stream obtained in step b) of the process. In some embodiments of the present process, unreacted methane may remain present in the monohalide stream obtained in step c) of the process. In some embodiments of the present process, unreacted methane may remain present in the methanol stream obtained in step d) of the process. The remaining unreacted methane may be removed from the stream, for example by distillation. In some preferred embodiments of the present disclosure, such removed unreacted methane may be recycled or fed to step a) and / or step b) of the process.

[0574] The present disclosure provides a system for producing methanol and hydrogen from methane, comprising;

[0575] - a halogenation reactor (1) configured to react a gaseous feed stream comprising methane with at least one halogen reactant (X2) to form an effluent stream comprising methyl halide (MeX) and hydrogen halide (HX) and optionally unreacted methane,

[0576] - Optionally, a polyhalogenated alkane removal unit (13) configured to receive the effluent stream from the halogenation reactor (1) and configured to separate from the effluent stream:

[0577] (i) a polyhalogenated alkane stream comprising polyhalogenated alkanes; and,

[0578] (ii) a monohalide stream comprising methyl halide (MeX) and hydrogen halide (HX), and optionally unreacted methane; and,

[0579] - a hydrolysis reactor (3) which is fluidically connected to the halogenation reactor (1) and configured to receive an effluent stream from the halogenation reactor; or, alternatively, which is fluidically connected to the polyhalogenated alkane removal unit (13) and configured to receive a monohalide stream from the polyhalogenated alkane removal unit (13);

[0580] and wherein the hydrolysis reactor (3) is configured to react the effluent stream or the monohalide stream with water and at least one catalyst under reaction conditions effective to produce: (i) an aqueous solution of hydrogen halide (HX (aq) ) and (ii) a stream comprising methanol (MeOH) and optionally dimethyl ether (DME) and / or optionally unreacted methane; and

[0581] - an electrolysis unit (4) comprising at least one electrolysis cell and a power supply for supplying electric current to the electrolysis cell, the electrolysis unit being fluidically connected to the hydrolysis reactor (3) and being configured to receive an aqueous solution of hydrogen halide (HX (aq) ) and the aqueous solution of the hydrogen halide (HX (aq) ) is decomposed into a gaseous hydrogen (H2) stream and a stream containing a halogen reactant (X2).

[0582] For example, the present disclosure also provides a system for producing methanol (MeOH), dimethyl ether (DME), and hydrogen (H2) from methane, comprising:

[0583] a halogenation reactor (1) configured to react a gaseous feed stream comprising methane with at least one halogen reactant (X2) to form an effluent stream comprising methyl halide (MeX) and hydrogen halide (HX) and optionally unreacted methane, and,

[0584] a hydrolysis reactor (3) fluidly connected to the halogenation reactor (1) and configured to receive an effluent stream from the halogenation reactor (1); and, wherein the hydrolysis reactor (3) is configured to react the effluent stream with water and an organic base under reaction conditions effective to produce a stream comprising methanol (MeOH) and dimethyl ether (DME) and optionally unreacted methane; and

[0585] an electrolysis unit (4) comprising at least one electrolysis cell and a power source for supplying electric current to the electrolysis cell, the electrolysis unit being fluidically connected to the hydrolysis reactor (3) and being configured to receive an aqueous solution of hydrogen halide (HX (aq) ) and the aqueous solution of the hydrogen halide (HX (aq) ) is decomposed into a gaseous hydrogen (H2) stream and a stream containing a halogen reactant (X2).

[0586] More particularly, the present disclosure also provides a system for producing methanol (MeOH), dimethyl ether (DME), and hydrogen (H2) from methane, comprising:

[0587] a halogenation reactor (1) configured to react a gaseous feed stream comprising methane with at least one halogen reactant (X2) to form an effluent stream comprising methyl halide (MeX) and hydrogen halide (HX) and optionally unreacted methane, and,

[0588] a hydrolysis reactor (3) fluidly connected to the halogenation reactor (1) and configured to receive an effluent stream from the halogenation reactor (1); and, wherein the hydrolysis reactor (3) is configured to react the effluent stream with water and an organic base under reaction conditions effective to produce a stream comprising methanol (MeOH) and dimethyl ether (DME) and optionally unreacted methane; and

[0589] an electrolysis unit (4) comprising at least one electrolysis cell and a power source for supplying electric current to the electrolysis cell, the electrolysis unit being fluidically connected to the hydrolysis reactor (3) and being configured to receive an aqueous solution of hydrogen halide (HX (aq) ) and the aqueous solution of the hydrogen halide (HX (aq) ) is decomposed into a gaseous hydrogen (H2) stream and a stream comprising a halogen reactant (X2);

[0590] - a feed stream supply system (5) for supplying a gaseous feed stream comprising methane to the halogenation reactor (1);

[0591] - a halogen supply system (6) for supplying a halogen reactant (X2) to the halogenation reactor (1);

[0592] - an effluent recovery system (10, 15) configured to recover the effluent stream from the halogenation reactor (1) and to feed the recovered effluent stream to the hydrolysis reactor (3);

[0593] a methanol recovery system (7) configured to recover a stream comprising methanol (MeOH) and dimethyl ether (DME) and optionally unreacted methane from the hydrolysis reactor (3);

[0594] - a hydrogen recovery system (8) configured to recover a gaseous hydrogen (H2) stream from the electrolysis unit (4);

[0595] - a halogen recovery system (9) configured to recover the halogen reactant (X2) from the electrolysis unit (4);

[0596] a hydrogen halide transfer system (12) configured to collect an aqueous solution of hydrogen halide (HX) from the hydrolysis reactor (3); (aq) ), and the collected aqueous solution of hydrogen halide (HX (aq) ) is supplied to the electrolysis unit (4).

[0597] Preferably, the system further comprises a polyhalogenated alkane removal unit (13) configured to receive an effluent stream from the halogenation reactor (1) and configured to separate (i) a polyhalogenated alkane stream from the effluent stream, the polyhalogenated alkane stream comprising polyhalogenated alkanes; and, (ii) a monohalide stream, the monohalide stream comprising methyl halide (MeX) and hydrogen halide (HX), and optionally comprising unreacted methane. For example, the hydrolysis reactor (3) is further fluidly connected to the polyhalogenated alkane removal unit (13) and further configured to receive a monohalide stream from the polyhalogenated alkane removal unit (13), and wherein the hydrolysis reactor (3) is configured to react the monohalide stream with water and the organic base in an aqueous solution (HX) effective to produce hydrogen halide. (aq) ) under reaction conditions. Advantageously, the effluent recovery system (10, 15) is further configured to feed the recovered effluent stream to the polyhalogenated alkane removal unit (13). Advantageously, the system further comprises a monohalide transfer system (16) configured to recover the monohalide stream from the polyhalogenated alkane removal unit (13) and supply the monohalide stream to the hydrolysis reactor (3).

[0598] For example, the system further comprises a water supply line (17) for supplying water to the hydrolysis reactor (3). Preferably, the water supply line (17) is used to supply water and an organic base.

[0599] For example, the system further includes C 2+an alkyl monohalide removal unit configured to receive an effluent stream from the halogenation reactor (1) and remove C 2+ Alkyl monohalides.

[0600] As used herein, the term "fluidically connected" or "fluid connection" is used as a synonym in this article and is intended to refer to the connection between two components (or units or devices, etc.) of the system given herein, so that a fluid can flow from one component (e.g., unit, device, reactor, etc.) to another through the connection. Preferably, two fluidly connected components are connected so that the outlet of the first component is connected to the inlet of the second component through a pipe, a conduit or a series of pipes or conduits. Other components (e.g., separators, dryers, condensers, etc.) can be fluidly connected between two fluidly connected components.

[0601] The term "supply device" or "supply system" is used herein as a synonym and refers to a suitable system allowing the supply of streams, or reaction products, or reactants, and includes, for example, pipes, conduits, supply lines, inlet lines, connecting lines, etc.

[0602] The term "recovery device" or "recovery system" is used herein as a synonym and refers to a suitable system that allows for the recovery of a stream or reaction products or reactants and includes, for example, pipes, recovery lines, outlet lines, connecting lines, etc. A "recovery device" or "recovery system" may include a separation device.

[0603] The term "transfer device" or "transfer system" is also used as a synonym in this article and refers to a suitable system that allows the transfer (transport) of logistics or reaction products or reactants (for example, from one unit or reactor to another unit or reactor), and includes, for example, pipes, conduits, collection pipelines, outlet pipelines, connecting pipelines, etc.

[0604] The halogenation reactor (1) used in the system of the present disclosure may be any type of reactor suitable for allowing a gaseous feed stream comprising methane to react with a halogen reactant under appropriate conditions to produce an effluent stream comprising methyl halide (MeX) and hydrogen halide (HX).

[0605] In some embodiments of the present disclosure, polyhalogenated alkanes may be formed in step b) of the process. Such polyhalogenated alkanes may include, for example, dihalomethane (CH2X2). Therefore, the system according to the present disclosure may include, in some embodiments, a polyhalogenated alkane removal unit configured to receive an effluent stream from the halogenation reactor (1) and remove polyhalogenated alkanes from the effluent stream, thereby producing a polyhalogenated alkane stream and a monohalide stream.

[0606] In some preferred embodiments, the polyhalogenated alkane removal unit (13) used in the system of the present disclosure comprises or consists of a separation column.

[0607] Preferably, such a polyhalogenated alkane removal unit is arranged downstream of the halogenation reactor (1) and upstream of the hydrolysis reactor (3), and is connected, preferably fluidly connected, to the halogenation reactor (1) and the hydrolysis reactor (3), for example via connecting lines (15, 16).

[0608] The polyhalogenated alkane removal unit may, for example, comprise:

[0609] - a separation system (13), such as a separation (e.g. distillation) column, configured to receive the effluent stream from the halogenation reactor (1) and to separate a polyhalogenated alkane stream from the effluent stream,

[0610] - a supply system (15), such as a supply line or pipeline, configured to supply the effluent stream from the halogenation reactor (1) to the separation column, and

[0611] - A polyhalogenated alkane recovery system (14), such as an outlet pipeline or conduit, configured to recover the polyhalogenated alkane stream from the separation system (13).

[0612] The polyhalogenated alkane removal unit preferably also includes a device (such as a transfer line or pipeline) for collecting a product stream (e.g., a product stream or a monohalide stream comprising methyl halides and hydrogen halides) wherein the polyhalogenated alkanes as defined herein have been removed. Preferably, such a device is configured to transfer the collected product stream to a downstream separation system for further separation of the product stream, or a hydrolysis reactor (3).

[0613] In some embodiments, the polyhalogenated alkane removal unit is capable of separating polyhalogenated alkanes from the effluent stream into a polyhalogenated methane stream and a polyhalogenated C 2+ In some embodiments, the polyhalogenated alkane removal unit includes a polyhalogenated methane outlet and a polyhalogenated C 2+ Alkane export.

[0614] The hydrolysis reactor (3) used in the system of the present disclosure may be any type of reactor suitable for containing water and at least one catalyst (which is preferably an organic base) (as defined herein) and allowing the (gaseous) monohalide stream to react with said water and optionally at least one catalyst (which is preferably an organic base) under suitable conditions to produce an aqueous solution of hydrogen halide (HX (aq) ) and methanol (MeOH) and / or dimethyl ether (DME).

[0615] In some embodiments, the hydrolysis reactor may include a separation device for:

[0616] - separating methanol and / or dimethyl ether from the hydrolysis reactor; and / or

[0617] - separating the aqueous hydrogen halide solution, optionally comprising a catalyst, from the hydrolysis reactor.

[0618] An example of such a separation device may be one or more distillation columns.

[0619] In some embodiments, the hydrolysis reactor includes a device for retaining a catalyst (preferably a heterogeneous catalyst) within the hydrolysis reactor. An example of such a device is a filter on the reactor outlet, wherein the filter can retain a solid catalyst or a catalyst immobilized on a solid support.

[0620] The electrolysis unit (4) for use in the present disclosure comprises at least one electrolysis cell and a power source for supplying electric current to the electrolysis cell. A particularly suitable electrolysis cell is a polymer electrolyte membrane cell (PEM) comprising at least one proton conducting membrane. One of the greatest advantages of PEM electrolysis is its ability to operate at high current densities. This can result in reduced operating costs. Polymer electrolytes allow PEM electrolysis cells to be operated through very thin membranes (~100-200 μm) while still allowing high pressures, resulting in low ohmic losses, which are mainly caused by proton conduction across the membrane (0.1 S / cm) and compressed hydrogen output. Due to its solid structure, polymer electrolyte membranes advantageously provide very high product gas purity.

[0621] In some embodiments, the electrolysis unit may include a catalyst (which may be reacted via an aqueous solution of hydrogen halide (HX) (aq) ) has entered the electrolysis unit) returns to the hydrolysis reactor.

[0622] The system according to the present disclosure may also include

[0623] - a feed stream supply system (5) for supplying a gaseous feed stream comprising methane to the halogenation reactor (1); and

[0624] - A halogen supply system (6) for supplying halogen reactant to the halogenation reactor (1).

[0625] Such a system for supplying reactants to the halogenation reactor may include an inlet line (conduit), which is optionally equipped with a control device to control the flow rate of the reactant stream to the reaction zone. In a preferred embodiment of the present disclosure, a separate device (separate inlet line or conduit) may be provided for each reactant in the process (i.e., a gaseous feed stream and a halogen reactant alone).

[0626] The system according to the present disclosure may also include an effluent recovery system (10), such as a conduit or pipeline, which is configured to recover the effluent stream from the halogenation reactor (1) and is suitable for feeding the recovered effluent stream to a downstream polyhalogenated alkane removal unit (13) or to a hydrolysis reactor (3).

[0627] The system according to the present disclosure may also include:

[0628] a hydrogen halide transfer system (12) configured to collect an aqueous solution of hydrogen halide (HX) from the hydrolysis reactor (3); (aq) ), and supplying the collected hydrogen halide stream to an electrolysis unit (4); and

[0629] A monohalide transfer system (11) configured to recover a monohalide stream from the polyhalogenated alkane removal unit (13) and to supply the recovered monohalide stream to the hydrolysis reactor (3).

[0630] Such a system for supplying reactants to or withdrawing reactants from the separation system may comprise an inlet line (conduit, pipe, pipeline), optionally provided with control means, for example for controlling the flow rate of the reactants to the reaction zone.

[0631] The system according to the present disclosure may further comprise a water supply line (17) for supplying water, preferably water and a catalyst to the hydrolysis reactor. The water supply line is for example an inlet line for supplying water and optionally a catalyst to the separation zone.

[0632] The system according to the present disclosure may also include a system for separately collecting a gaseous hydrogen stream and a stream containing a halogen reactant from the electrolysis unit. Such a system particularly includes:

[0633] - a hydrogen recovery system (8) configured to recover a gaseous hydrogen stream from the electrolysis unit (4);

[0634] - a halogen recovery system (9) configured to recover the halogen reactant from the electrolysis unit (4);

[0635] Such a system for supplying reactants to or withdrawing reactants from the separation system may comprise an inlet line (conduit, pipe, pipeline), which is optionally provided with control means, for example; for controlling the flow rate of the reactants to the reaction zone.

[0636] Optionally, the system of the present disclosure may be provided with means (20) (e.g., a transfer line or conduit) for returning the stream of halogen reactant collected from the electrolysis unit or at least a portion thereof to the halogenation reactor. This allows the halogen reactant to be reused in the system.

[0637] In some preferred embodiments, the means (20) for returning the stream of halogen reactant withdrawn from the electrolysis unit (4) or a portion thereof to the halogenation reactor (1) comprises one or more connecting lines (connecting pipes).

[0638] In some embodiments, the one or more connecting lines for returning the stream of halogen reactant to the halogenation reactor may be provided with one or more driers (e.g., molecular sieves) suitable for drying the stream of halogen reactant before feeding it to the halogenation reactor.

[0639] In some embodiments, the one or more connecting pipelines for returning the stream of halogen reactant to the halogenation reactor may be provided with one or more purification devices (such as, for example, one or more condensers), which are suitable for purifying the stream of halogen reactant before feeding the stream to the halogenation reactor.

[0640] Furthermore, the system of the present disclosure comprises a methanol and / or dimethyl ether (DME) recovery system (7) configured to recover a stream comprising methanol and / or dimethyl ether (DME) from the hydroxylation reactor (3).

[0641] In some embodiments of the present disclosure, C defined herein 2+ The alkyl monohalide may be formed in step b) of the process. Thus, in some embodiments, the system according to the present disclosure may further include C 2+ an alkyl monohalide removal unit configured to receive an effluent stream from the halogenation reactor (1) and remove C 2+ Alkyl monohalides.

[0642] In some embodiments, such C 2+ The alkyl monohalide removal unit is disposed downstream of the halogenation reactor (1) and upstream of the hydrolysis reactor (3), and is connected, preferably fluidly connected, to the halogenation reactor (1) and the hydrolysis reactor (3), for example, via a connecting line.

[0643] In some embodiments, C 2+ The alkyl monohalide removal unit may include, for example

[0644] a separation system, such as a separation (eg, distillation) column, configured to receive the effluent stream from the halogenation reactor (1) and to separate C from the effluent stream; 2+ Alkyl monohalide stream,

[0645] a supply system, such as a supply line or pipeline, configured to supply the effluent stream from the halogenation reactor (1) to the separation system, and

[0646] -C 2+ An alkyl monohalide recovery system, such as an outlet line or pipeline, configured to extract the alkyl monohalide from the C 2+ Alkyl separation system collects C 2+ Alkyl monohalide stream.

[0647] C 2+ The alkyl monohalide removal unit preferably also includes a 2+ Alkyl monohalide removal means, such as a transfer line or pipeline, for recovering a product stream (eg a monohalide stream as defined herein). Preferably, such means is configured to transfer the recovered product stream to the hydrolysis reactor (3).

[0648] In some embodiments of the present disclosure, unreacted methane may remain present in the effluent stream obtained in step b) of the process. In some embodiments of the present disclosure, unreacted methane may remain present in the monohalide stream obtained in step c) of the process. In some embodiments of the present disclosure, unreacted methane may remain present in the methanol and / or dimethyl ether stream obtained in step d) of the process. The remaining unreacted methane may be removed from the corresponding stream, for example by distillation. Therefore, the present system further provides the following apparatus: such as a distillation tower, etc., for removing, preferably distilling, unreacted methane from the above-mentioned stream. In a particularly preferred embodiment of the present disclosure, the following system is provided: wherein the distillation tower is configured to be fluidically connected to a methanol and / or dimethyl ether collection system (7).

[0649] The following examples are only used to illustrate the present disclosure and should not be construed as limiting the scope thereof in any way. Although the present disclosure is shown only in some of its forms, it will be apparent to those skilled in the art that the present disclosure is not limited thereto, but is susceptible to various changes and modifications without departing from the scope of the present disclosure.

[0650] Example

[0651] Example 1

[0652] refer to Figure 1 , the following examples illustrate embodiments of processes according to the present disclosure, as well as systems for performing such embodiments according to the present disclosure.

[0653] Figure 1 The system shown in FIG. 1 comprises a halogenation reactor ( 1 ), a hydrolysis reactor ( 3 ) and an electrolysis unit ( 4 ).

[0654] According to this embodiment, a gaseous feed stream containing methane is introduced into the halogenation reactor (1) via a feed stream supply line (5). A halogen reactant (e.g., Br2) is also introduced into the halogenation reactor (1) via a separate halogen reactant supply line (6). The gaseous feed stream containing methane reacts with the halogen reactant (X2) in the halogenation reactor to produce an effluent stream containing methyl halide (MeX) and hydrogen halide (HX). Optionally, unreacted methane remains present in the effluent stream.

[0655] The effluent stream obtained leaves the halogenation reactor (1) through a suitable collection line (10) and is fed via said line to the hydrolysis reactor (3). In the hydrolysis reactor (3), the effluent stream reacts with water and optionally at least one catalyst, thereby forming an aqueous solution of hydrogen halide (HX (aq) ), and on the other hand methanol (MeOH) and / or dimethyl ether (DME) are formed. A stream comprising methanol and / or dimethyl ether (DME) can be collected from the hydrolysis reactor (3) via a methanol and / or dimethyl ether (DME) collection line (7). Water and optionally a catalyst can be added to the hydrolysis reactor (3) via a water supply line (17).

[0656] The aqueous solution of hydrogen halide (HX) formed in the hydrolysis reactor (3) (aq) ) is fed to the electrolysis unit (4) via a suitable connecting line (12). In the electrolysis unit (4), the aqueous solution of hydrogen halide (HX) from the hydrolysis reactor (3) is (aq) ) is decomposed into a flow of hydrogen gas (H2) and a flow of halogen reactant (X2); the flow of hydrogen gas (H2) is removed from the electrolysis unit via an outlet pipeline (8), and the flow of halogen reactant (X2) is removed from the electrolysis unit via an outlet pipeline (9).

[0657] Example 2

[0658] refer to Figure 2 , the following example illustrates another embodiment of a process according to the present disclosure, and a system for performing such an embodiment according to the present disclosure.

[0659] Figure 1 The system shown includes a halogenation reactor (1), a polyhalogenated alkane removal unit (13), a hydrolysis reactor (3) and an electrolysis unit (4).

[0660] A gaseous feed stream containing about 100 mol% (CH4) of methane is introduced into the halogenation reactor (1) via a feed stream supply line (5) at a flow rate of about 1604 kg / hr. A halogen reactant (X2), in this case bromine (Br2), is introduced into the halogenation reactor (1) via a halogen reactant supply line (6) at a rate of about 5274 kg / hr. The halogenation reactor (1) is maintained at a temperature of about 300-600°C and a pressure of 5 to 30 bar.

[0661] An effluent stream comprising unreacted methane (CH4), hydrogen halide (HX), methyl halide (MeX) and polyhalogenated alkanes (e.g., CH2X2) is collected from the halogenation reactor (1) via outlet (15) and fed to a polyhalogenated alkane removal unit comprising a separation tower (13). The separation tower separates polyhalogenated alkanes (e.g., CH2X2) (e.g., CH2Br2) from the effluent stream and removes polyhalogenated alkanes (e.g., CH2X2) from the system via a polyhalogenated alkane outlet line (14) at a rate of about 860 kg / hr.

[0662] The residual gaseous stream (i.e., monohalide stream) substantially free of polyhalogenated alkanes (e.g., CH2X2) is withdrawn from the polyhalogenated alkanes removal unit (13) and then fed to the hydrolysis reactor (3) via connecting line (16). In the hydrolysis reactor (3), the effluent stream is reacted with water and at least one catalyst (i.e., 15 vol% aqueous pyridine solution) at a temperature of 80°C.

[0663] This leads to the formation of an aqueous solution of hydrogen halide (HX (aq) ), and on the other hand methanol (MeOH) at a rate of 312 kg / hour and dimethyl ether (DME) at a rate of 250 kg / hour. A stream comprising methanol and dimethyl ether (DME) can be collected from the hydrolysis reactor (3) via a methanol collection line (7). A 15 vol% aqueous pyridine solution is added to the hydrolysis reactor (3) via a water supply line (17) at a rate of 1715 kg / hour.

[0664] The methanol, dimethyl ether and optional unreacted methane recovered from the recovery line (7) can be separated by a technique known in the art (eg, distillation using a distillation column).

[0665] The aqueous solution of hydrogen halide formed in the hydrolysis reactor (3) is fed to the electrolysis unit (4) via a suitable connecting line (12). In the electrolysis unit (4), the aqueous solution of hydrogen halide (HX) from the hydrolysis reactor (3) is (aq)) is decomposed into a stream of hydrogen gas (H2) and a stream of halogen reactant (X2); the stream of hydrogen gas (H2) is removed from the electrolysis unit via an outlet pipeline (8), and the stream of halogen reactant (X2) is removed from the electrolysis unit via an outlet pipeline (9). The produced halogen reactant (X2) can also be collected through the outlet pipeline (9), optionally dried, and returned to the halogenation reactor (1) for reuse.

[0666] Example 3

[0667] This example illustrates a halogenation step that can be applied in the process of the present disclosure.

[0668] In this example, the experimental setup consisted of a quartz reactor and a glass syringe (SigmaAldrich) for liquid bromine supply. A methane (5.0, Praxair) supply with a Bronkhorst mass flow controller was established.

[0669] The feed rate was maintained to give the reactants a residence time of about 0.01 seconds in the heated zone of the reactor and a CH4 / Br2 molar ratio of about 3 / 1. The heated zone of the reactor was maintained at a temperature of about 370°C and a pressure of about 3 bar.

[0670] The effluent from the reactor was then first passed through a cold trap (10° C.) to condense CH 2 Br 2 produced during the reaction and traces of unreacted bromine.

[0671] In this experiment, the effluent from the reactor was passed through an aqueous caustic bubbler to remove the major amount of HBr, and the remaining stream was then sent to an Agilent GC with a SilicaPlot column and a FID detector for analysis.

[0672] Based on the GC data, the conversion of methane to methyl bromide (byproduct is CH2Br2) was calculated using the following formula:

[0673]

[0674]

[0675]

[0676] x(CH4) = 29%, s(CH3Br) = 89%, s(CH2Br2) = 9%;

[0677] Where n = molar mass, x = conversion, and s = selectivity

[0678] Example 4

[0679] The following examples illustrate hydrolysis reaction steps that can be used in the processes of the present disclosure.

[0680] In this embodiment, the experimental setting includes using a batch reactor (300 ml) connected to GC. The reactor is loaded with 200 ml deionized water and 30 ml pyridine dissolved in the water. Methyl bromide (>99.9%, Mebrom) is fed by a piston pump. During the whole experiment, the temperature of the reactor remains on 80 ℃, and keeps violent mixing with a magnetic stirrer. During the experiment, the CH of 5 g / h is used The flow velocity of Br and the N of 70 mL / min Flow velocity. During 3 hours of operation, CHBr seems to be stable to the conversion of methanol and dimethyl ether.

[0681] Based on the GC data, the conversion of methyl bromide to methanol was calculated using the following formula:

[0682]

[0683]

[0684]

[0685] where x (CH3Br) = 14%, s (CH3OH) = 32%, and s (DME) = 68%;

[0686] Where n = molar mass, x = conversion, and s = selectivity

Claims

1. A process for producing methanol (MeOH), dimethyl ether (DME) and hydrogen (H2) from methane, comprising the following steps: a) providing a gaseous feed stream comprising methane; b) reacting the gaseous feed stream with at least one halogen reactant (X2) under reaction conditions effective to produce an effluent stream comprising methyl halide (MeX), hydrogen halide (HX), optionally polyhalogenated alkane, and optionally unreacted methane; c) recovering an effluent stream comprising methyl halide (MeX), hydrogen halide (HX), optionally polyhalogenated alkane and optionally unreacted methane; d) reacting the effluent stream obtained in step c) with water and an organic base under reaction conditions effective to produce: - Aqueous solutions of hydrogen halides (HX (aq) ),and - a methanol stream comprising methanol (MeOH) and dimethyl ether (DME) and optionally unreacted methane, and, e) decomposing the aqueous solution of hydrogen halide (HX2) by electrolysis under conditions effective to produce a stream of gaseous hydrogen (H2) and a stream comprising a halogen reactant (X2); (aq) ).

2. The process according to claim 1, wherein the process comprises the step of separating the polyhalogenated alkanes formed in step b) from the effluent stream.

3. The process according to claim 2, wherein the step of separating said polyhalogenated alkanes is carried out prior to reacting said effluent stream with water and an organic base.

4. The process according to any one of claims 1 to 3, comprising the following steps: a) providing a gaseous feed stream comprising methane; b) reacting the gaseous feed stream with at least one halogen reactant (X2) under reaction conditions effective to produce an effluent stream comprising methyl halide (MeX), hydrogen halide (HX), optionally polyhalogenated alkane, and optionally unreacted methane; c) separating from the effluent stream obtained in step b) the following: c1) a monohalide stream comprising methyl halide (MeX) and hydrogen halide (HX), and optionally unreacted methane; and, c2) a polyhalogenated alkane stream, d) reacting the monohalide stream separated in step c1) with water and an organic base under reaction conditions effective to produce: d1) Aqueous solution of hydrogen halide (HX (aq) ),and d2) a methanol stream comprising methanol (MeOH) and dimethyl ether (DME) and optionally unreacted methane, e) decomposing the aqueous solution of hydrogen halide (HX2) produced in step d1) by electrolysis under conditions effective to produce a stream of gaseous hydrogen (H2) and a stream comprising a halogen reactant (X2); (aq) );and, f) Optionally, recovering methanol from the methanol (MeOH) stream and / or recovering dimethyl ether (DME) from the methanol (MeOH) stream.

5. A process according to any one of claims 1 to 4, wherein the halogen reactant is selected from bromine (Br2), chlorine (Cl2), fluorine (F2), iodine (I2) and astatine (At2).

6. A process according to any one of claims 1 to 5, wherein the halogen reactant is bromine (Br2).

7. The process according to any one of claims 1 to 6, wherein the organic base is a N-containing polymer.

8. The process according to claim 7, wherein the N-containing polymer is a polymer comprising at least one of the following: an amino group, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a pyrazole ring, an imidazole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, a triazole ring, an oxadiazole ring, or any combination thereof.

9. The process according to claim 7 or 8, wherein the N-containing polymer is a polymer comprising at least one pyridine ring.

10. The process according to any one of claims 1 to 9, wherein the polyhalogenated alkane comprises polyhalogenated methane and optionally polyhalogenated C 2+ Alkane.

11. The process according to any one of claims 1 to 10, wherein C 2+ The alkyl monohalide is formed in step b).

12. The process according to any one of claims 1 to 11, wherein the process comprises separating the C formed in step b) of the process from the effluent stream. 2+ Alkyl monohalide step.

13. The process according to claim 12, wherein separating C 2+ The alkyl monohalide step is performed prior to separation of the monohalide stream comprising methyl halide (MeX) and hydrogen halide (HX).

14. The process of any one of claims 1 to 13, wherein the gaseous feed stream comprises at least 75.0 vol. % methane, based on the total volume of the gaseous feed stream.

15. The process of any one of claims 1 to 14, wherein the gaseous feed stream comprises at least 99.9 vol. % methane, based on the total volume of the gaseous feed stream.

16. The process according to any one of claims 1 to 15, wherein the gaseous feed stream used in step a) of the process is substantially free of sulphur species.

17. The process according to any one of claims 1 to 16, wherein the gaseous feed stream used in step a) of the process contains less than 1.0 mol% of sulphur species.

18. The process according to any one of claims 1 to 17, wherein the gaseous feed stream used in step a) of the process contains less than 0.00001 mol% of sulfur species.

19. The process according to any one of claims 1 to 18, further comprising the step of returning the halogen reactant (X2) obtained in step e) of the process to step b).

20. The process according to any one of claims 1 to 19, wherein the methanol stream comprising methanol (MeOH) and dimethyl ether (DME) obtained in step d2) is separated from the aqueous solution of hydrogen halide by distillation.

21. The process according to claim 20, wherein the methanol stream comprising methanol (MeOH) and dimethyl ether (DME) obtained in step d2) comprises at least 75.0 mol% of a combination of methanol and dimethyl ether, based on the total amount of the methanol stream.

22. The process according to claim 20 or 21, wherein the methanol stream comprising methanol (MeOH) and dimethyl ether (DME) obtained in step d2) comprises at least 95.0 mol% of a combination of methanol and dimethyl ether, based on the total amount of the methanol stream.

23. The process according to any one of claims 1 to 22, wherein the gaseous hydrogen (H2) stream produced in step e) comprises at least 90.0 mol% hydrogen.

24. The process according to any one of claims 1 to 23, wherein the gaseous hydrogen (H2) stream produced in step e) comprises at least 99.9 mol% hydrogen.

25. A system for producing methanol (MeOH), dimethyl ether (DME) and hydrogen (H2) from methane, comprising: - a halogenation reactor (1) configured to react a gaseous feed stream comprising methane with at least one halogen reactant (X2) to form an effluent stream comprising methyl halide (MeX) and hydrogen halide (HX) and optionally unreacted methane, and, - a hydrolysis reactor (3) fluidly connected to the halogenation reactor (1) and configured to receive an effluent stream from the halogenation reactor (1); and wherein the hydrolysis reactor (3) is configured to react the effluent stream with water and an organic base under reaction conditions effective to produce a stream comprising methanol (MeOH) and dimethyl ether (DME) and optionally unreacted methane; and - an electrolysis unit (4) comprising at least one electrolysis cell and a power supply for supplying electric current to the electrolysis cell, the electrolysis unit being fluidically connected to the hydrolysis reactor (3) and being configured to receive an aqueous solution of hydrogen halide (HX (aq) ) and the aqueous solution of the hydrogen halide (HX (aq) ) is decomposed into a gaseous hydrogen (H2) stream and a stream comprising a halogen reactant (X2); - a feed stream supply system (5) for supplying a gaseous feed stream comprising methane to the halogenation reactor (1); - a halogen supply system (6) for supplying a halogen reactant (X2) to the halogenation reactor (1); - an effluent collection system (10, 15) configured to collect the effluent stream from the halogenation reactor (1) and feed the collected effluent stream to the hydrolysis reactor (3); - a methanol recovery system (7) configured to recover a stream comprising methanol (MeOH) and dimethyl ether (DME) and optionally unreacted methane from the hydrolysis reactor (3); - a hydrogen recovery system (8) configured to recover a gaseous hydrogen (H2) stream from the electrolysis unit (4); - a halogen recovery system (9) configured to recover the halogen reactant (X2) from the electrolysis unit (4); - a hydrogen halide transfer system (12) configured to collect an aqueous solution of hydrogen halide (HX) from the hydrolysis reactor (3); (aq) ), and the collected aqueous solution of hydrogen halide (HX (aq) ) is supplied to the electrolysis unit (4).

26. The system of claim 25, wherein the system further comprises a polyhalogenated alkane removal unit (13) configured to receive an effluent stream from the halogenation reactor (1) and configured to separate from the effluent stream (i) a polyhalogenated alkane stream comprising polyhalogenated alkanes; and, (ii) a monohalide stream comprising methyl halide (MeX) and hydrogen halide (HX), and optionally unreacted methane.

27. The system of claim 26, wherein the hydrolysis reactor (3) is further fluidly connected to the polyhalogenated alkane removal unit (13) and is further configured to receive a monohalide stream from the polyhalogenated alkane removal unit (13), and wherein the hydrolysis reactor (3) is configured to react the monohalide stream with water and the organic base in an aqueous solution effective to produce hydrogen halide (HH). (aq) ) under the reaction conditions.

28. The system of claim 26 or 27, wherein the effluent recovery system (10, 15) is further configured to feed the recovered effluent stream to the polyhalogenated alkane removal unit (13).

29. The system according to any one of claims 26 to 28, wherein the system further comprises a monohalide transfer system (16) configured to collect a monohalide stream from the polyhalogenated alkane removal unit (13) and supply the monohalide stream to a hydrolysis reactor (3).

30. The system according to any one of claims 25 to 29, wherein the system further comprises a water supply line (17) for supplying water to the hydrolysis reactor (3).

31. The system according to claim 30, wherein the water supply line (17) is used to supply water and an organic base.

32. The system according to any one of claims 25 to 31, wherein the system further comprises C 2+ an alkyl monohalide removal unit configured to receive an effluent stream from the halogenation reactor (1) and to remove C 2+ Alkyl monohalides.

Images