Production of alcohols and carbonyl compounds from hydrocarbons by transition metal catalysis

Abstract

Disclosed are methods for converting a hydrocarbon reactant to an alcohol compound and / or a carbonyl compound, wherein the hydrocarbon reactant is irradiated with a light beam having a wavelength in the ultraviolet-visible spectrum, optionally in an oxidizing atmosphere, with a supported transition metal catalyst comprising molybdenum, tungsten, or vanadium to form a reduced transition metal catalyst, followed by hydrolysis of the reduced transition metal catalyst to form a reaction product comprising the alcohol compound and / or the carbonyl compound.

Description

[0001] This application claims priority and benefit to U.S. Provisional Patent Application No. 63 / 077,761, filed on September 9, 2021, as a PCT international application and filed on September 14, 2020, the entire disclosure of which is incorporated herein by reference. Technical Field

[0002] This disclosure generally relates to methods for converting hydrocarbons into alcohols and / or carbonyl compounds, and more specifically, to performing such methods using supported molybdenum, tungsten, or vanadium catalysts. Background Technology

[0003] Alcohols can be prepared from alkanes using various synthetic techniques, but these techniques often require halogens or harsh reaction conditions. Therefore, alternative reaction schemes are needed. Thus, this invention addresses these objectives in general. Summary of the Invention

[0004] This summary is provided to introduce selected concepts in a simplified form, which are further described below in the detailed description. This summary is not intended to identify essential or essential features of the claimed subject matter. Nor is it intended to be used to limit the scope of the claimed subject matter.

[0005] This invention relates to methods for converting hydrocarbon reactants into alcohols and / or carbonyl compounds. In one aspect, a first method may include (i) irradiating the hydrocarbon reactants and a supported transition metal catalyst comprising molybdenum, tungsten, vanadium, or combinations thereof with a light beam in the ultraviolet-visible spectrum to reduce at least a portion of the supported transition metal catalyst, thereby forming a reduced transition metal catalyst; and (ii) hydrolyzing the reduced transition metal catalyst to form a reaction product comprising an alcohol and / or a carbonyl compound. Optionally, step (i) may include irradiating the hydrocarbon reactants and the supported transition metal catalyst in an oxidizing atmosphere.

[0006] On the other hand, a second method for converting hydrocarbon reactants into alcohol compounds and / or carbonyl compounds may include (I) irradiating the hydrocarbon reactants and a supported transition metal catalyst comprising molybdenum, tungsten, vanadium, or combinations thereof with a light beam in the ultraviolet-visible spectrum to reduce at least a portion of the supported transition metal catalyst to form a reduced transition metal catalyst; (II) subjecting the reduced transition metal catalyst to an oxidizing atmosphere; and (III) hydrolyzing the reduced transition metal catalyst to form reaction products comprising alcohol compounds and / or carbonyl compounds.

[0007] This article also provides supported transition metal catalysts containing a solid support, such as a solid oxide (e.g., silica-coated alumina), a chemically treated solid oxide (e.g., alumina sulfate), or a zeolite; and 0.01 to 50 wt% of a transition metal, including molybdenum, tungsten, vanadium, or combinations thereof.

[0008] Both the foregoing summary and the following detailed description provide examples and are illustrative only. Therefore, the foregoing summary and the following detailed description should not be considered limiting. Furthermore, other features or variations may be provided in addition to those listed herein. For example, certain aspects may be addressed with respect to various combinations and sub-combinations of features described in the detailed description.

[0009] definition

[0010] To more clearly define the terms used herein, the following definitions are provided. Unless otherwise specified, the following definitions apply to this disclosure. If a term is used in this disclosure but is not specifically defined herein, the definition in the IUPAC Compendium of Chemical Terminology, 2nd Edition (1997) may be applied, provided that the definition does not conflict with any other disclosure or definition applied herein, or render any claim to which the definition is applied ambiguous or invalid. If any definition or usage provided in any document incorporated herein by reference conflicts with the definition or usage provided herein, the definition or usage provided herein shall prevail.

[0011] In this document, the features of the subject matter are described such that combinations of different features can be conceived within a particular aspect. For each aspect and feature disclosed herein, all combinations are considered, whether explicitly described or not, that will not adversely affect the catalyst, composition, process, or method described herein. Furthermore, unless otherwise expressly stated, any aspect or feature disclosed herein may be combined to describe a catalyst, composition, process, or method of the invention consistent with this disclosure.

[0012] Generally, element groups are indicated using the numbering scheme indicated in the version of the periodic table published in Chemical and Engineering News, 63(5), 27, 1985. In some cases, a group of elements may be indicated using the common name assigned to that group; for example, alkali metals are indicated by Group 1 elements, alkaline earth metals by Group 2 elements, transition metals by Groups 3–12 elements, and halogens or halides by Group 17 elements.

[0013] Whenever used in this specification and claims, the term "hydrocarbon" refers to a compound containing only carbon and hydrogen, whether saturated or unsaturated. Other identifiers may be used to indicate the presence of a specific group in a hydrocarbon (e.g., a halohydrocarbon indicates the presence of halogen atoms in one or more substituted hydrocarbons with an equal amount of hydrogen atoms). Non-limiting examples of hydrocarbons include alkanes (linear, branched, and cyclic), alkenes (olefins), and aromatic compounds, as well as other compounds. In this document, cyclic compounds and aromatic compounds include fused-ring compounds, such as bicyclic and polycyclic compounds.

[0014] For any particular compound or group disclosed herein, unless otherwise stated, any name or structure presented (generally or specifically) is intended to cover all conformational isomers, positional isomers, stereoisomers, and mixtures thereof that can be produced by a particular set of substituents. Unless otherwise specified, the name or structure (generally or specifically) also covers all enantiomers, diastereomers, and other optical isomers (if any) in enantiomeric or racemic forms that would be recognized by those skilled in the art, as well as mixtures of stereoisomers. For example, general references to pentane include n-pentane, 2-methylbutane, and 2,2-dimethylpropane; and general references to butyl include n-butyl, sec-butyl, isobutyl, and tert-butyl.

[0015] Unless otherwise specified, the term “(substituted)” is used to describe a group, for example, when referring to a substituted analogue of a particular group, intended to describe any non-hydrogen portion that formally replaces hydrogen in the group, and is intended to be non-limiting. Furthermore, unless otherwise specified, one or more groups may also refer herein to “unsubstituted” or equivalent terms such as “unreplaced,” which means an original group in which the non-hydrogen portion does not replace hydrogen within the group. Moreover, unless otherwise specified, “(substituted)” is intended to be non-limiting and includes inorganic or organic substituents as understood by one of ordinary skill in the art.

[0016] Unless otherwise stated, the terms “contact” and “combination” are used herein to describe catalysts, compositions, processes, and methods in which materials or components are contacted or combined together in any order, in any manner, and for any duration. For example, materials or components may be blended, mixed, slurried, dissolved, reacted, treated, impregnated, compounded, or otherwise contacted or combined in some other manner or by any suitable method or technique.

[0017] As used herein, “BET surface area” means the surface area as determined by the nitrogen adsorption Brunauer, Emmett, and Teller (BET) method according to ASTM D1993-91, and as described in, for example, Brunauer, S., Emmett, PH, and Teller, E., “Adsorption of gases in multimolecular layers,” J. Am. Chem. Soc., 60, 3, pp. 309-319 (the contents of which are expressly incorporated herein by reference).

[0018] In this disclosure, although catalysts, compositions, processes, and methods are described as “comprising” various components or steps, unless otherwise stated, catalysts, compositions, processes, and methods may also be “substantially composed of various components or steps” or “composed of various components or steps”.

[0019] The terms “a / an” and “the” are intended to include multiple alternatives, such as at least one. For example, unless otherwise stated, the disclosure of “hydrocarbon reactant,” “solid oxide,” etc., is intended to cover one hydrocarbon reactant, solid oxide, etc., or a mixture or combination of more than one hydrocarbon reactant, solid oxide, etc.

[0020] This invention discloses several types of scopes. When any type of scope is disclosed or claimed, it is intended to individually disclose or claim every possible number that such scope could reasonably cover, including the endpoints of the scope and any sub-scopes and combinations thereof covered therein. For example, when a chemical compound having a certain number of carbon atoms is disclosed or claimed, it is intended to individually disclose or claim every possible number that the scope might cover that conforms to the disclosure herein. For example, as used herein, hydrocarbon reactants containing C1 to C2... 18 The disclosure of alkane compounds, or, in alternative language, alkane compounds having 1 to 18 carbon atoms, refers to compounds that may have 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms, and any range between two of these numbers (e.g., C1 to C8 alkane compounds), and also includes any combination of carbon atoms within the range between these two numbers (e.g., C2 to C4 alkane compounds and C...). 12 To C 16 (Alkanes).

[0021] Similarly, the following is another representative example of the amount of transition metal (molybdenum, tungsten, vanadium) on a supported transition metal catalyst consistent with aspects of the present invention. It is disclosed that the amount of transition metal can range from 0.1 to 15 wt%, and it is intended to state that the amount of transition metal can be any amount within this range, and can include, for example, any range or combination of ranges from 0.1 to 15 wt%, such as 0.2 to 10 wt%, 0.1 to 5 wt%, or 0.5 to 2.5 wt%, etc. Likewise, all other ranges disclosed herein should be interpreted in a manner similar to these examples.

[0022] Typically, quantities, sizes, formulations, parameters, ranges, or other quantities or characteristics are expressed as “about” or “approximately,” whether or not explicitly stated otherwise. Claims include equivalents of quantities or characteristics, regardless of whether they are modified by the terms “about” or “approximately.”

[0023] Although any methods, apparatus, and materials similar to or equivalent to those described herein may be used in the practice or testing of this invention, typical methods, apparatus, and materials are described herein.

[0024] All publications and patents mentioned herein are incorporated herein in their entirety by reference for the purpose of describing and disclosing, for example, the constructs and methods described in the publications and patents, which may be used in conjunction with the inventions described herein. Detailed Implementation

[0025] This invention generally relates to the conversion of hydrocarbons into similar alcohols and / or carbonyl compounds. Surprisingly, it has been found that the combined use of supported transition metal catalysts, photoreduction, and hydrolysis can efficiently convert hydrocarbons (e.g., alkanes) into similar alcohols and / or carbonyl compounds, advantageously even at ambient temperatures.

[0026] In some aspects, steps in methods for converting hydrocarbons into alcohol-like compounds and / or carbonyl compounds are carried out in an oxidizing atmosphere. Given the well-known ability of oxygen to terminate polymerization on transition metal-based catalysts, it is expected that carrying out a step in these methods in an oxidizing atmosphere would not result in the formation of alcohol / carbonyl products. However, instead, these methods significantly increase the molar yield of alcohol / carbonyl products (based on the presence of the transition metal in the catalyst) and produce oxygen-containing oligomers.

[0027] Convert hydrocarbons into alcohols and carbonyl compounds

[0028] This document discloses a method for converting hydrocarbon reactants into alcohols and / or carbonyl compounds. In this disclosure, carbonyl compounds include aldehydes, ketones, and carboxylic acids, etc. A first method for converting hydrocarbon reactants into alcohols and / or carbonyl compounds may include (i) irradiating the hydrocarbon reactants and a supported transition metal catalyst comprising molybdenum, tungsten, vanadium, or combinations thereof with a light beam in the ultraviolet-visible spectrum to reduce at least a portion of the supported transition metal catalyst, thereby forming a reduced transition metal catalyst; and (ii) hydrolyzing the reduced transition metal catalyst to form a reaction product comprising alcohols and / or carbonyl compounds. In step (i), at least a portion of the transition metal on the reduced transition metal catalyst may have at least one bonding site with a hydroxyl group (-O-alkyl) such as an alkoxy group, which, upon hydrolysis in step (ii), may release an alcohol and / or carbonyl compound analogue of the hydrocarbon. The reduced transition metal catalyst may have a lower average oxidation state than the supported transition metal catalyst. In a variation of the first method, step (i) may include irradiating the hydrocarbon reactants and the supported transition metal catalyst in an oxidizing atmosphere.

[0029] A second method for converting hydrocarbon reactants into alcohols and / or carbonyl compounds may include (I) irradiating the hydrocarbon reactants and a supported transition metal catalyst comprising molybdenum, tungsten, vanadium, or combinations thereof with a light beam in the ultraviolet-visible spectrum to reduce at least a portion of the supported transition metal catalyst to form a reduced transition metal catalyst; (II) subjecting the reduced transition metal catalyst to an oxidizing atmosphere; and (III) hydrolyzing the reduced transition metal catalyst to form a reaction product comprising alcohols and / or carbonyl compounds.

[0030] Generally, the features of the first and second methods (e.g., hydrocarbon reactants, supported transition metal catalysts, reduced transition metal catalysts, light beams, oxidizing atmospheres, and conditions for performing the irradiation and hydrolysis steps, etc.) are described independently herein, and these features may be combined in any combination to further describe the disclosed methods for producing alcohols and / or carbonyl compounds. Furthermore, unless otherwise stated, additional method steps may be performed before, during, and / or after any step in any of the methods disclosed herein, and may be used without limitation and in any combination to further describe these methods. Further, any alcohols and / or carbonyl compounds produced according to the disclosed methods are within the scope of this disclosure and are covered herein.

[0031] In these methods, a variety of hydrocarbon reactants can be used to form alcohol compounds and / or carbonyl compounds, including saturated aliphatic hydrocarbon compounds, unsaturated aliphatic hydrocarbon compounds, straight-chain aliphatic hydrocarbon compounds, branched-chain aliphatic hydrocarbon compounds, and cyclic aliphatic hydrocarbon compounds, as well as combinations thereof. Therefore, hydrocarbon reactants may include straight-chain alkane compounds, branched-chain alkane compounds, cyclic alkane compounds, or combinations thereof. Additionally or alternatively, hydrocarbon reactants may include straight-chain olefin compounds (e.g., α-olefins), branched-chain olefin compounds, cyclic olefin compounds, etc., and combinations thereof. Additionally or alternatively, hydrocarbon reactants may contain aromatic compounds, such as benzene, toluene, etc., and their substituted variants, and combinations thereof.

[0032] Any hydrocarbon with a suitable number of carbon atoms can be used, such that the hydrocarbon reactants can include C424. n Hydrocarbon compounds (and alcohol compounds often include C) n Alcohol compounds, and carbonyl compounds often include C n (Carbonyl compounds). In some respects, the reaction products may contain alcohols and carbonyl groups with higher carbon numbers, and in such cases, the hydrocarbon reactants may include C46 groups. n Hydrocarbon compounds, and alcohol compounds may include (C n+1 )+ alcohol compounds and / or carbonyl compounds may include (C n+1 )+carbonyl compounds. As a specific example, when C n If it is C2 (n equals 2, for example for ethane or ethylene), then the term "(C n+1 "+alcohol compounds" includes any C3 and above (C4, C5, C6, C7, etc.) alcohol compounds and mixtures of C3 and above (C4, C5, C6, C7, etc.) alcohol compounds. n+1 The )+ carbonyl compounds will be interpreted similarly. Although not limited to this, the integer n can be 1 to 36 in one aspect, 1 to 18 in another, 1 to 12 in yet another, and 1 to 8 in yet another.

[0033] Alternatively, the reaction products may comprise low-carbon alcohols and carbonyl groups, and in such cases, the hydrocarbon reactants may include C4 groups. n Hydrocarbon compounds, and alcohol compounds may include (C n-1 )- Alcohol compounds and / or carbonyl compounds may include (C n-1 )-Carbonyl compounds. As a specific example, when C n If it is C5 (n equals 5, for example for n-pentane or isopentane), then the term "(C5)" is used. n-1 "C-carbonyl compounds" include any carbonyl compounds of C4 and below (C3, C2, and C1) and mixtures of carbonyl compounds of C4 and below (C3, C2, and C1).n-1 )-alcohol compounds will be interpreted similarly. Although not limited to this, the integer n can be 2 to 36 in one aspect, 2 to 18 in another, 2 to 12 in yet another, and 2 to 8 in yet another.

[0034] Therefore, hydrocarbon reactants can contain alkane compounds with any suitable number of carbons, such as C1 to C2. 36 Alkane compounds; alternatively, C1 to C 18 Alkane compounds; alternatively, C1 to C 12 Alkane compounds; or alternatively, C1 to C8 alkane compounds. If desired, the hydrocarbon reactants may contain a single alkane compound of relatively high purity, such as at least 90% by weight, at least 95% by weight, at least 98% by weight, or at least 99% by weight, etc. Alternatively, the hydrocarbon reactants may comprise a mixture of two or more hydrocarbon reactants (such as two or more alkane compounds in any relative proportion). Therefore, the hydrocarbon reactants may include C1 to C8 alkane compounds. 18 Mixtures of alkanes, mixtures of C1 to C4 alkanes, mixtures of C2 to C6 alkanes, mixtures of C6 to C8 alkanes, or C 10 To C 14 Mixtures of alkane compounds, etc.

[0035] Similarly, hydrocarbon reactants can include olefin compounds with any suitable number of carbons, such as C2 to C3. 36 Olefin compounds; alternatively, C2 to C 18 Olefin compounds; alternatively, C2 to C 12 Olefin compounds; or alternatively, C2 to C8 olefin compounds. As above, if desired, the hydrocarbon reactants may contain a relatively high purity of a single olefin compound, such as at least 90% by weight, at least 95% by weight, at least 98% by weight, or at least 99% by weight, etc. Alternatively, the hydrocarbon reactants may comprise a mixture of two or more hydrocarbon reactants (such as two or more olefin compounds in any relative proportion). Thus, the hydrocarbon reactants may contain C2 to C8 olefin compounds. 36 Mixtures of olefin compounds, C2 to C 18 Mixtures of olefin compounds, C2 to C 12 Mixtures of olefin compounds, or mixtures of C2 to C8 olefin compounds, etc.

[0036] Similarly, hydrocarbon reactants can include aromatic compounds with any suitable number of carbons, such as C6 to C4. 36 Aromatic compounds; alternatively, C6 to C6 18Aromatic compounds; alternatively, C6 to C6 12 Aromatic compounds; or alternatively, C6 to C8 aromatic compounds. As above, if desired, the hydrocarbon reactants may contain a relatively high purity of a single aromatic compound, such as at least 90% by weight, at least 95% by weight, at least 98% by weight, or at least 99% by weight, etc. Alternatively, the hydrocarbon reactants may comprise a mixture of two or more hydrocarbon reactants (such as two or more aromatic compounds in any relative proportion). Thus, the hydrocarbon reactants may comprise C6 to C8 aromatic compounds. 36 Mixtures of aromatic compounds, C6 to C 18 Mixtures of aromatic compounds, C6 to C 12 Mixtures of aromatic compounds, or mixtures of C6 to C8 aromatic compounds, etc.

[0037] Illustrative examples of alkane, olefin, and aromatic reactants may include methane, ethane, propane, butane (e.g., n-butane or isobutane), pentane (e.g., n-pentane, neopentane, cyclopentane, or isopentane), hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, ethylene, propylene, 1-butene, 1-pentene, 2-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, cyclopentene, cyclohexene, benzene, toluene, ethylbenzene, xylene, styrene, mesitylene, etc., and combinations thereof.

[0038] Therefore, hydrocarbon reactants may include mixtures of aliphatic and aromatic hydrocarbons. In a non-limiting aspect, hydrocarbon reactants may include methane; alternatively, ethane; alternatively, propane; alternatively, butane; alternatively, pentane; alternatively, hexane; alternatively, heptane; alternatively, octane; alternatively, nonane; alternatively, decane; alternatively, undecane; alternatively, dodecane; alternatively, tridecane; alternatively, tetradecane; alternatively, pentadecane; alternatively, hexadecane; alternatively, heptadecane; alternatively, octadecane; alternatively, ethylene; alternatively, propane Alkenes; alternatively, 1-butene; alternatively, 1-pentene; alternatively, 1-hexene; alternatively, 1-heptene; alternatively, 1-octene; alternatively, 1-decene; alternatively, 1-dodecene; alternatively, 1-tetradecene; alternatively, 1-hexadecene; alternatively, 1-octadecene; alternatively, cyclopentene; alternatively, cyclohexene; alternatively, benzene; alternatively, toluene; alternatively, ethylbenzene; alternatively, xylene; alternatively, styrene; or alternatively, mesitylene.

[0039] On one hand, hydrocarbon (alkane) reactants may include methane, ethane, propane, n-butane, isobutane, n-pentane, neopentane, isopentane, n-hexane, n-heptane, n-octane, n-decane, n-dodecane, etc., or any combination thereof. On the other hand, hydrocarbon (alkane) reactants may include methane, ethane, propane, butane, pentane, hexane, etc., or any combination thereof. On yet another hand, hydrocarbon (alkene) reactants may include ethylene, propylene, 1-butene, 1-pentene, 2-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, cyclopentene, cyclohexene, etc., or any combination thereof, or alternatively ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, or any combination thereof. In another aspect, hydrocarbon (aromatic) reactants may include benzene, toluene, ethylbenzene, xylene, mesitylene, styrene, 4-phenyl-1-butene, or any combination thereof.

[0040] Typically, in both the first and second methods, the irradiation step can be carried out under conditions sufficient to accommodate the irradiation of the hydrocarbon reactants and the supported transition metal catalyst (e.g., containing a transition metal with oxygen bonds) with a light beam and the formation of a reduced transition metal catalyst (e.g., having a lower oxidation state). For example, the relative amount (or concentration) of the hydrocarbon reactants versus the amount of the transition metal (in the supported transition metal catalyst) can alter the efficiency of the reduction process. In some respects, the molar ratio of hydrocarbon reactants to transition metal (in the supported transition metal catalyst) can be at least 0.25:1, at least 0.5:1, at least 1:1, at least 10:1, at least 100:1, at least 1000:1, or at least 10,000:1. Therefore, a large excess of hydrocarbon reactants can be used, and there is no particular limitation on the maximum amount of hydrocarbon reactants.

[0041] Similarly, when using an oxidizing atmosphere, there are no particular restrictions on the molar ratio of elemental oxygen or other oxidants to transition metals (supported or reduced transition metal catalysts, depending on the specific method), but it can typically be at least 0.25:1, at least 0.5:1, at least 1:1, at least 10:1, at least 100:1, at least 1000:1, or at least 10,000:1. Therefore, a large excess of elemental oxygen or other oxidants can be used, and there are no particular restrictions on the maximum amount of elemental oxygen or other oxidants in the oxidizing atmosphere. For example, a large molar excess of air can be used in these methods.

[0042] In the first and second methods, the temperature and pressure of the irradiation step can, on the one hand, keep the hydrocarbon reactants liquid throughout the reduction process of the supported transition metal catalyst, and on the other hand, keep the hydrocarbons gaseous throughout the reduction process of the supported transition metal catalyst. Advantageously, it has been found that, through the irradiation step disclosed herein, it is possible to reduce supported transition metal compounds at temperatures lower than those typically required for the thermal rather than photochemical reduction of high-valence transition metal substances. In some aspects, the irradiation step can be carried out at temperatures below 200°C, below 100°C, below 70°C, below 40°C, 0°C to 200°C, -100°C to 100°C, 0°C to 100°C, or 10°C to 40°C, and can produce a reduced transition metal catalyst. These temperature ranges are also intended to cover cases where irradiation is carried out at a series of different temperatures rather than at a single fixed temperature falling within their respective temperature ranges, wherein at least one temperature is within the listed range.

[0043] A further characteristic of the irradiation step is the amount of time, such as exposure time, that the hydrocarbon reactants and the supported transition metal catalyst are exposed to the light beam. Not bound by theory, it is assumed that exposure to the light beam in the presence of the hydrocarbon reactants is the cause of the reduction of the supported transition metal catalyst; therefore, regardless of whether the conversion occurs very quickly or very slowly, the exposure time must be sufficient for such conversion to occur. Thus, in some respects, though not limited thereto, the exposure time can range from 15 seconds to 48 hours, 15 seconds to 24 hours, 1 hour to 8 hours, 15 minutes to 4 hours, 1 minute to 6 hours, 5 minutes to 1 hour, 10 minutes to 2 hours, 1 minute to 1 hour, or 1 minute to 15 minutes. As those skilled in the art will recognize, the exposure time can vary based on the intensity of the light beam, the wavelength of the light beam, etc. Stirring, mixing, or other suitable techniques can be used to ensure uniform contact and / or exposure of the mixture of the supported transition metal catalyst (e.g., particles) and the hydrocarbon reactants to the light beam.

[0044] The supported transition metal catalyst and hydrocarbon reactants can be continuously irradiated (for the entire exposure time), or the irradiation can be pulsed (such that the total number of pulses equals the exposure time, for example, sixty one-second pulses equal 60 seconds of exposure time). If desired, a combination of continuous and pulsed irradiation cycles can be used.

[0045] In the disclosed method, a supported transition metal catalyst is irradiated with a beam of light in the ultraviolet-visible spectrum in the presence of hydrocarbon reactants to produce a transition metal catalyst in a reduced oxidation state (e.g., a reduced transition metal catalyst). A wide range of wavelengths, light sources, and intensities can be used, provided that these wavelengths, light sources, and intensities are sufficient to reduce at least a portion of the high-valence transition metal material present in the supported transition metal catalyst. In some respects, for example, the light can be from any suitable source, such as sunlight, fluorescent white light, LED diodes, and / or ultraviolet lamps. The distance from non-solar sources can be varied (e.g., minimized) as needed to increase the effectiveness of irradiation.

[0046] The wavelength of light can be any wavelength within the ultraviolet-visible range. In some aspects, the wavelength of a light beam can be a single wavelength or more than one wavelength, such as a wavelength range. For example, the wavelength of a light beam can be a wavelength range spanning at least 25 nm, at least 50 nm, at least 100 nm, at least 200 nm, or at least 300 nm. In one aspect, the wavelength of a light beam can include a single wavelength or wavelength range in the ultraviolet spectrum, the visible spectrum (380 nm to 780 nm), or both. In another aspect, the wavelength of a light beam can include a single wavelength or wavelength range in the range of 200 nm to 750 nm. However, in yet another aspect, the wavelength of a light beam can include a single wavelength or wavelength range in the range of 300 to 750 nm, 350 nm to 650 nm, 300 nm to 600 nm, 300 nm to 500 nm, or 400 nm to 500 nm. In other respects, the wavelength of the light beam may include a single wavelength or wavelength range below 600 nm, below 525 nm, or below 500 nm; additionally or alternatively, above 300 nm, above 350 nm, above 400 nm, or above 450 nm. Advantageously, blue light and ultraviolet light sources are generally more effective, so the wavelength of the light beam may include a single wavelength or a wavelength range below 475 nm; alternatively, below 450 nm; alternatively, below 430 nm; or below 420 nm; and additionally or alternatively, above 350 nm; alternatively, above 370 nm; alternatively, above 380 nm; or alternatively, above 400 nm.

[0047] The light beam in the irradiation step can also be characterized by its intensity (e.g., the total amount of light emitted from the light source). In some aspects, the light beam may have an intensity of at least 500 lumens, at least 1,000 lumens, at least 2,000 lumens, at least 5,000 lumens, at least 10,000 lumens, at least 20,000 lumens, at least 50,000 lumens, or at least 100,000 lumens. Therefore, there may be no upper limit to the intensity of the light source. Alternatively, the light beam may have an intensity in the range of 50 to 50,000 lumens, 50 to 10,000 lumens, 100 to 5,000 lumens, or 500 to 2,000 lumens. Furthermore, the light beam can be characterized by the amount of light reaching the hydrocarbon reactants and the supported transition metal catalyst, i.e., the flux. In some respects, the hydrocarbon reactants and supported transition metal catalysts (including molybdenum, tungsten and / or vanadium) may be irradiated with at least 100 lux, at least 500 lux, at least 1000 lux, at least 2000 lux, at least 5000 lux, at least 10,000 lux, at least 20,000 lux, at least 50,000 lux, at least 100,000 lux, or in the range of 10,000 to 1,000,000 lux, 10,000 to 250,000 lux, 10,000 to 100,000 lux, 20,000 to 200,000 lux, 20,000 to 100,000 lux, 50,000 to 500,000 lux, or 50,000 to 200,000 lux. Alternatively, in some respects, hydrocarbon reactants and supported transition metal catalysts may be irradiated with a beam of power of at least 50 watts, at least 100 watts, at least 200 watts, at least 500 watts, at least 1,000 watts, or at least 2,000 watts.

[0048] Any suitable reactor or vessel may be used to form alcohol compounds and / or carbonyl compounds. Non-limiting examples of said reactor or vessel may include flow reactors, continuous reactors, packed bed reactors, fluidized bed reactors and stirred tank reactors, including more than one reactor in series or parallel, and any combination of reactor types and arrangements.

[0049] In one aspect, the hydrocarbon reactants may be in the gas phase during the irradiation step. In another aspect, the hydrocarbon reactants may be in the liquid phase during the irradiation step. In yet another aspect, the disclosed method may include irradiating the solid supported transition metal catalyst in a slurry (e.g., a loop slurry) of the hydrocarbon reactants. In yet another aspect, the disclosed method may include contacting the hydrocarbon reactants with a fluidized bed of solid supported transition metal catalyst and irradiating them simultaneously with the contact (fluidization). In yet another aspect, the disclosed method may include contacting the hydrocarbon reactants (e.g., in the gas phase or in the liquid phase) with a fixed bed of solid supported transition metal catalyst and irradiating them simultaneously with the contact. As those skilled in the art will recognize, other methods exist for contacting and irradiating hydrocarbon reactants with solid supported transition metal catalysts, and the disclosed methods are not limited to those disclosed herein. For example, the hydrocarbon reactants and the supported transition metal catalyst may be mixed or contacted in a stirred tank, and irradiation may be performed simultaneously with the mixing in the stirred tank.

[0050] Any suitable pressure can be used to contact the hydrocarbon reactants with the supported catalyst to form a reducing transition metal catalyst, and this can depend on the carbon number of the hydrocarbon reactants (and the boiling point of the hydrocarbon reactants), the type of reactor configuration, the desired mode of contacting the hydrocarbon reactants with the (solid) supported transition metal catalyst, and other considerations.

[0051] Typically, methods for forming reduced transition metal catalysts (and subsequently alcohols and / or carbonyl compounds) can be flow-based and / or continuous methods. In such cases, the hydrocarbon reactant-supported transition metal catalyst contact time (or reaction time) can be expressed as the weight hourly space velocity (WHSV) – the weight ratio of hydrocarbon reactants to a given weight of supported transition metal catalyst per unit time (in g / g / h or h⁻¹). -1 ) is used to represent this.

[0052] Although not limited to this, the WHSV used in the disclosed method can have 0.01h -1 0.02h -1 0.05h -1 0.1h -1 0.25h -1 or 0.5h -1 The minimum value; or alternatively, 500h -1 400h -1 300h -1 100h -1 50h -1 10h -1 5h -1 2h -1 or 1 hour -1The maximum value. Generally, WHSV can range from any minimum WHSV disclosed herein to any maximum WHSV disclosed herein. In a non-limiting aspect, the range of WHSV can be 0.01h. -1 Up to 500h -1 Alternatively, 0.01h -1 Up to 10h -1 Alternatively, 0.01h -1 Up to 1 hour -1 Alternatively, 0.02h -1 Up to 400h -1 Alternatively, 0.02h -1 Up to 50h -1 Alternatively, 0.05h -1 Up to 300h -1 Alternatively, 0.05h -1 Up to 5 hours -1 Alternatively, 0.1h -1 Up to 400h -1 Alternatively, 0.25h -1 Up to 50h -1 Alternatively, 0.25h -1 Up to 2 hours -1 Alternatively, 0.5h -1 Up to 400h -1 Alternatively, 0.5h -1 Up to 5 hours -1 Or alternatively, 0.5h -1 Up to 2 hours -1 Other WHSV scopes are obvious from this disclosure.

[0053] Referring now to the second method, step (II) involves subjecting the reduced transition metal catalyst to an oxidizing atmosphere. This step of subjecting the reduced transition metal catalyst to an oxidizing atmosphere can generally be performed independently under the same temperature, pressure, time, and contact method (e.g., fixed bed or fluidized bed) conditions as the irradiation steps described herein (step (i) of the first method and step (I) of the second method).

[0054] There are no particular limitations on the oxidizing atmosphere in the first and second methods. Typical materials used to generate an oxidizing atmosphere include, but are not limited to, oxygen, air, mixtures of air and inert gases (e.g., nitrogen), mixtures of oxygen and inert gases, NO, NO2, N2O, ozone, halide oxides, H2O2, organic peroxides, and combinations thereof. For convenience, air is typically used, and therefore the corresponding transition metal catalysts in the first and second methods can be simply subjected to or exposed to air under any suitable conditions.

[0055] The hydrolysis step is now referred to, in which a reduced transition metal catalyst (e.g., at least a portion of the transition metal on the reduced transition metal catalyst has at least one bonding site with a hydrocarbon oxygen group) is hydrolyzed to form a reaction product comprising an alcohol compound and / or a carbonyl compound. Generally, the temperature, pressure, and time characteristics of the hydrolysis step may be the same as, but not limited to, those disclosed herein with respect to the irradiation step. For example, the hydrolysis step may be carried out at temperatures less than 200°C, less than 100°C, less than 70°C, less than 40°C, 0°C to 200°C, 0°C to 100°C, or 10°C to 40°C, and may result in the formation of a reaction product comprising an alcohol compound and / or a carbonyl compound. These temperature ranges are also intended to cover cases where the hydrolysis step is performed at a series of different temperatures rather than at a single fixed temperature falling within a respective temperature range, wherein at least one temperature is within the listed range.

[0056] Although not limited thereto, the hydrolysis step may include contacting a reduced transition metal catalyst with a hydrolysing agent. Illustrative and non-limiting examples of suitable hydrolysing agents may include water, steam, alcohols, acids, bases, etc., and combinations thereof. Thus, mixtures of water and various alcohols such as C1-C4 alcohols (and / or acids such as hydrochloric acid, sulfuric acid, acetic acid, ascorbic acid, etc.; and / or bases such as sodium hydroxide, ammonium hydroxide, etc.) in any relative proportions can be used as hydrolysing agents. Therefore, the pH of the hydrolysing agent can range from acidic to neutral to alkaline, generally covering a pH range of 1 (or lower) to 13-13.5.

[0057] Optionally, the hydrolysate may further comprise any suitable reducing agent, representative examples of which include ascorbic acid, ferric (II) reducing agents, zinc reducing agents, and combinations thereof. Typically, reducing agents may include sodium bisulfite, sodium thiosulfate, sodium sulfide, ascorbic acid, ferrous (II) ions, and combinations thereof. These can sometimes be used to prevent unwanted secondary oxidation caused by unreacted transition metals. Furthermore, they can be used to tailor the product range by increasing selectivity. For example, in some respects, adding a reducing agent to the hydrolysate can eliminate all carbonyl products, producing only alcohol products. For instance, a reducing agent can be added to the final quenching solution to produce more alcohol products and fewer carbonyl products (e.g., to prevent secondary oxidation of the formed alcohol).

[0058] As disclosed herein, the reaction products may comprise alcohol compounds and / or carbonyl compounds, which may be analogs of hydrocarbon reactants. Therefore, typical alcohol compounds that can be synthesized using the methods disclosed herein may include, for example, methanol, ethanol, isopropanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, benzyl alcohol, phenol, xylenol, etc., and combinations thereof. Here, alcohol compounds encompass monohydric alcohol compounds and diol compounds (e.g., ethylene glycol and hexanediol). Therefore, alcohol compounds may include diols, allyl alcohol, phenol, etc., and any combinations thereof.

[0059] In addition to or in place of alcohols, the reaction products may contain carbonyl compounds, such as aldehydes, ketones, or carboxylic acids, and any combination of aldehydes, ketones, and carboxylic acids. Therefore, enols are covered herein because the reaction products may contain alcohols, carbonyl compounds, or both. Representative carboxylic acids that can be synthesized using the methods disclosed herein may include, for example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, and combinations thereof. In one particular aspect, the reaction products may contain acetic acid (or consist substantially of acetic acid or be composed of acetic acid).

[0060] In some respects, alcohols or carbonyl products can contain unsaturation. For example, the carbon adjacent to the alcohol or carbonyl group can contain a double bond. While not wishing to be bound by theory, it is considered that the allyl CH bond is particularly susceptible to attack by transition metals. Therefore, when the reducing hydrocarbon has a double bond, the typical alcohol product (often one of the most abundant alcohol products) contains a -OH group on the adjacent allyl carbon. Thus, in some respects, the alcohol compound can be allyl alcohol, such as C4-C8 allyl alcohol. Non-limiting examples of allyl alcohols that can be prepared herein include 1-hexen-3-ol, 2-hexen-1-ol, 1-penten-3-ol, 2-penten-1-ol, 1-cyclohexen-3-ol, and combinations thereof.

[0061] The methods described herein result in unexpectedly high conversions of hydrocarbon reactants and / or unexpectedly high yields of alcohols (or carbonyl compounds). In one aspect, the minimum conversion (or yield) may be at least 2 wt%, at least 5 wt%, at least 10 wt%, at least 15 wt%, or at least 25 wt% of the feed hydrocarbon. Furthermore, the maximum conversion (or yield) may be 50 wt%, 70 wt%, 80 wt%, 90 wt%, 95 wt%, or 99 wt%, and may approach 100% conversion of hydrocarbon reactants (or yield of alcohols or carbonyl compounds). Generally, the conversion (or yield) may range from any minimum conversion (or yield) disclosed herein to any maximum conversion (or yield) disclosed herein. Non-limiting ranges for conversion (or yield) may include from 5 wt% to 99 wt%, from 10 wt% to 95 wt%, or from 15 wt% to 70 wt%. For conversion, the percentage is based on the amount of hydrocarbon reactant converted from the initial amount of hydrocarbon reactant. Yield values ​​are weight percentages and are based on the weight of the produced alcohol (or carbonyl) compound relative to the weight of the hydrocarbon reactants. In some respects, these conversions (or yields) can be achieved using batch processes, while in others they can be achieved using flow or continuous processes, such as single-pass or multi-pass reactors (e.g., fixed-bed reactors). Typically, conversion and yield can be controlled by varying the ratio of reducing hydrocarbon feed to transition metal, the amount of oxygen in the oxidizing atmosphere, and by altering other reaction conditions such as time, temperature, and irradiation.

[0062] Equally unexpectedly, the continuous flow method according to the invention for producing alcohols and / or carbonyl compounds exhibits unexpectedly high single-pass conversion rates of hydrocarbon reactants (or single-pass yields of the desired alcohols or carbonyl compounds). In one aspect, the minimum single-pass conversion rate (or yield) can be at least 2 wt%, at least 5 wt%, at least 10 wt%, at least 15 wt%, or at least 25 wt%. Additionally, the maximum single-pass conversion rate (or yield) can be 50 wt%, 70 wt%, 80 wt%, 90 wt%, 95 wt%, or 99 wt%, and can approach 100% hydrocarbon reactant conversion (or alcohol or carbonyl compound yield), depending on the reaction conditions. Generally, the single-pass conversion rate (or yield) can range from any minimum single-pass conversion rate (or yield) disclosed herein to any maximum single-pass conversion rate (or yield) disclosed herein. The non-limiting range of single-pass conversion rate (or yield) may include 5% to 99% by weight, 10% to 95% by weight, or 15% to 70% by weight.

[0063] In both the first and second methods, the yield of the alcohol (or carbonyl compound) can also be characterized based on the amount of transition metal (supported transition metal catalyst). For example, based on the number of moles of transition metal, the molar ratio (molar yield) of the alcohol (or carbonyl compound) can be at least 0.01, at least 0.05, at least 0.1, or at least 0.25 moles, at least 0.5 moles, or at least 0.75 moles. While not limited thereto, the yield, in terms of the number of moles of product per mole of transition metal, can typically be at most 10 moles, at most 8 moles, at most 5 moles, at most 3 moles, at most 2 moles, at most 1.5 moles, or at most 1 mole of alcohol (or carbonyl compound) per mole of transition metal. If more than one alcohol and / or carbonyl compound is produced, the ratio represents the total number of moles of alcohol and / or carbonyl compound produced per mole of transition metal.

[0064] The methods disclosed herein for producing alcohols and / or carbonyl compounds typically produce a crude reaction mixture following hydrolysis, comprising residual hydrocarbon reactants (e.g., alkanes and / or alkenes), the desired alcohol and / or carbonyl compounds (e.g., aldehydes and / or carboxylic acids, such as acetic acid), a solvent (if used), and byproducts. In many cases, it may be desirable to isolate or separate at least a portion (and in some cases, all) of the hydrocarbon reactants from the reaction products following the hydrolysis step. This can be accomplished using any suitable technique, which may include, but is not limited to, extraction, filtration, evaporation, or distillation, and combinations of two or more of these techniques. In a particular aspect of the invention, the isolation or separation step utilizes distillation at any suitable pressure (using one or more distillation columns).

[0065] Additionally or alternatively, the methods disclosed herein may further include the step of isolating at least a portion (and in some cases, all) of the alcohol compound (or carbonyl compound) from the reaction products, and any suitable technique may be used, such as extraction, filtration, evaporation, distillation, or any combination thereof. Additionally or alternatively, the methods disclosed herein may further include the step of isolating at least a portion (and in some cases, all) of the reduced transition metal catalyst from the reaction products following hydrolysis, and as stated above, any suitable technique may be used.

[0066] Optionally, certain components of the reaction products (such as hydrocarbon reactants) can be recovered and recycled back into the reactor. In such cases, at least a portion (and in some cases, all) of the hydrocarbon reactants can be recycled and contacted again with the supported transition metal catalyst, thereby increasing the overall conversion of the hydrocarbon products after multiple contacts (or multiple passages through a reactor containing a supported transition metal catalyst) with the hydrocarbon products.

[0067] If desired, the methods disclosed herein may further include the step of calcining at least a portion (and in some cases, all) of the reduced transition metal catalyst to regenerate the supported transition metal catalyst. Any suitable calcination conditions may be used, for example, at any suitable peak temperature and time conditions, such as 300°C to 1000°C, 500°C to 900°C, or 550°C to 870°C, to subject at least a portion of the reduced transition metal catalyst to an oxidizing atmosphere for a period of 1 minute to 24 hours, 1 hour to 12 hours, or 30 minutes to 8 hours.

[0068] The calcination step can be performed using any suitable technology and equipment, whether batch or continuous. For example, the calcination step can be performed in a belt calciner, or alternatively, in a rotary calciner. In some aspects, the calcination step can be performed in a batch or continuous calcination vessel including a fluidized bed. As those skilled in the art will recognize, other suitable technologies and equipment can be used for the calcination step, and such technologies and equipment are covered herein.

[0069] Optionally, the first and second methods disclosed herein may further include a step of calcining the supported transition metal catalyst (containing molybdenum, tungsten, and / or vanadium) prior to the irradiation step. Any suitable calcination conditions may be used, for example, under any suitable peak temperature and time conditions, such as at peak temperatures of 200°C to 1000°C, 300°C to 800°C, or 450°C to 750°C, to subject the supported transition metal catalyst to an oxidizing atmosphere (in some respects, an inert atmosphere may be used) for a period of 1 minute to 24 hours, 1 hour to 12 hours, or 30 minutes to 8 hours.

[0070] Transition metal catalysts

[0071] Generally, the disclosed methods are applicable to the reduction of supported transition metal catalysts, and are not limited to the reduction of any particular type of supported transition metal catalyst. Typically, a supported transition metal catalyst can be described as containing a transition metal having an oxygen bond (transition metal = O bond). Additionally or alternatively, a supported transition metal catalyst can be described as containing a transition metal in at least a +3 oxidation state. Additionally or alternatively, a supported transition metal catalyst can be described as containing a transition metal in one of its two highest oxidation states. It should be noted that the transition metal can have more than one oxygen bond. In aspects of the invention, the supported transition metal catalyst may contain molybdenum, tungsten, vanadium, or combinations thereof (e.g., two or more transition metals may be present on the supported transition metal catalyst); alternatively, molybdenum; alternatively, tungsten; or alternatively, vanadium.

[0072] While not limited thereto, the supported transition metal catalysts considered herein include those prepared by contacting a support with a transition metal-containing compound and calcining it in an oxidizing atmosphere to form a supported transition metal catalyst. In these respects, the transition metal may be impregnated during or before the calcination step, which may be carried out at various temperatures and time periods and is generally selected to convert all or part of the transition metal to at least a +3 oxidation state and / or one of its two highest oxidation states. The irradiation methods disclosed herein may include reducing at least a portion of the transition metal material in a reduced transition metal catalyst to a reduced oxidation state (or multiple oxidation states).

[0073] Any suitable transition metal-containing compound (or transition metal precursor) can be used as a transition metal component in the preparation of supported catalysts. In some respects, it may be advantageous for the transition metal-containing compound to be soluble in hydrocarbon solvents during the preparation of supported catalysts, while in other respects, it may be advantageous for the transition metal-containing compound to be soluble in water during the preparation of supported catalysts.

[0074] Various solid supports can be used in supported transition metal catalysts (and reduced transition metal catalysts), such as conventional solid oxides and zeolites. Generally, solid oxides may contain oxygen and one or more elements selected from groups 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 of the periodic table, or contain oxygen and one or more elements selected from lanthanides or actinides (see: Hawley's Condensed Chemical Dictionary, 11th edition, John Wiley & Sons, 1995; Cotton, FA; Wilkinson, G.; Murillo, CA; and Bochmann, M., Advanced Inorganic Chemistry, 6th edition, Wiley-Interscience, 1999). For example, solid oxides may contain oxygen and one or more elements selected from Al, B, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V, W, P, Y, Zn, and Zr. Illustrative examples of solid oxide materials or compounds that can be used as solid supports may include, but are not limited to, Al2O3, B2O3, BeO, Bi2O3, CdO, Co3O4, Cr2O3, CuO, Fe2O3, Ga2O3, La2O3, Mn2O3, MoO3, NiO, P2O5, Sb2O5, SiO2, SnO2, SrO, ThO2, TiO2, V2O5, WO3, Y2O3, ZnO, ZrO2, etc., including mixed oxides thereof, and combinations thereof.

[0075] Solid oxides can encompass oxide materials (such as silicon dioxide), their "mixed oxide" compounds (such as silicon dioxide-titanium dioxide), and combinations or mixtures of more than one solid oxide material. Mixed oxides (such as silicon dioxide-titanium dioxide) can be a single or multiple chemical phases in which more than one metal combines with oxygen to form a solid oxide. Examples of mixed oxides that can be used as solid oxides include, but are not limited to, silicon dioxide-alumina, silicon dioxide-coated alumina, silicon dioxide-titanium dioxide, silicon dioxide-zirconia, alumina-titanium dioxide, alumina-zirconia, zinc aluminate, alumina-boron oxide, alumina borate, silicon dioxide-boron oxide, aluminum phosphate, aluminum phosphate, aluminum dioxide-silica, titanium dioxide-zirconia, etc., or combinations thereof. In some aspects, the solid support may include silica, silica-alumina, silica-coated alumina, silica-titanium dioxide, silica-titanium dioxide-magnesium oxide, silica-zirconium oxide, silica-magnesium oxide, silica-boron oxide, aluminum phosphate-silica, alumina, aluminate borate, etc., or any combination thereof. Silica-coated alumina is covered herein; such oxide materials are described, for example, in U.S. Patent Nos. 7,884,163 and 9,023,959, which are incorporated herein by reference in their entirety.

[0076] The percentage of each oxide in the mixed oxide can vary depending on the respective oxide material. As an example, silica-alumina (or silica-coated alumina) typically has an alumina content ranging from 5 wt% to 95 wt%. According to one aspect, the alumina content of silica-alumina (or silica-coated alumina) can be from 5 wt% to 50 wt% alumina, or from 8 wt% to 30 wt% alumina. In another aspect, silica-alumina (or silica-coated alumina) with high alumina content can be used, wherein the alumina content of these materials is typically in the range of 60 wt% to 90 wt% alumina, or from 65 wt% to 80 wt% alumina.

[0077] In one aspect, the solid oxide may comprise silica-alumina, silica-coated alumina, silica-titanium dioxide, silica-zirconia, alumina-titanium dioxide, alumina-zirconia, zinc aluminate, alumina-boron oxide, silica-boron oxide, aluminum phosphate, aluminum phosphate, aluminum phosphate-silica, titanium dioxide-zirconia, or combinations thereof; alternatively, silica-alumina; alternatively, silica-coated alumina; alternatively, silica-titanium dioxide; alternatively, silica-zirconia; alternatively, alumina-titanium dioxide; alternatively, alumina-zirconia; alternatively, zinc aluminate; alternatively, alumina-boron oxide; alternatively, silica-boron oxide; alternatively, aluminum phosphate; alternatively, aluminum phosphate-silica; or alternatively, titanium dioxide-zirconia.

[0078] On the other hand, the solid oxide may comprise silicon dioxide, aluminum oxide, titanium dioxide, thorium oxide, strontium oxide, zirconium oxide, magnesium oxide, boron oxide, zinc oxide, mixed oxides thereof, or any mixture thereof. In yet another aspect, the solid support may comprise silicon dioxide, aluminum oxide, titanium dioxide, or combinations thereof; alternatively, silicon dioxide; alternatively, aluminum oxide; alternatively, titanium dioxide; alternatively, zirconium oxide; alternatively, magnesium oxide; alternatively, boron oxide; or alternatively, zinc oxide. In another aspect, solid oxides may include silicon dioxide, aluminum oxide, silicon dioxide-alumina, silicon dioxide-coated aluminum oxide, aluminum phosphate, aluminum phosphate, heteropolytungstate, titanium dioxide, zirconium oxide, magnesium oxide, boron oxide, zinc oxide, silicon dioxide-titanium dioxide, silicon dioxide-yttrium oxide, silicon dioxide-zirconia, aluminum oxide-titanium dioxide, aluminum oxide-zirconia, zinc aluminate, aluminum oxide-boron oxide, silicon dioxide-boron oxide, aluminum phosphate-silica, titanium dioxide-zirconia, etc., or any combination thereof.

[0079] In the case where the supported transition metal catalyst and the reduced transition metal catalyst contain silica-titanium dioxide, any suitable amount of titanium may be present based on the total weight of the supported catalyst and the reduced catalyst, including 0.1 to 20 wt%, 0.5 to 15 wt%, 1 to 10 wt%, or 1 to 6 wt% titanium.

[0080] Consistent with certain aspects of the invention, supported transition metal catalysts and reduced transition metal catalysts may comprise chemically treated solid oxides as a support, and wherein the chemically treated solid oxides include solid oxides treated with electron-withdrawing anions (any electron-withdrawing anions disclosed herein). The electron-withdrawing component used to treat the solid oxide may be one that increases the Lewis or Brønsted acidity of the solid oxide after treatment (compared to a solid oxide not treated with at least one electron-withdrawing anion). Any component of the acidity. According to one aspect, the electron-withdrawing component can be an electron-withdrawing anion derived from a salt, acid, or other compound (such as a volatile organic compound) that serves as a source or precursor of the electron-withdrawing anion. Examples of electron-withdrawing anions include, but are not limited to, sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, trifluoromethanesulfonate, fluorozirconate, fluorotitanate, phosphotungstic acid, tungstate, molybdate, etc., including mixtures and combinations thereof. Additionally, other ionic or nonionic compounds that serve as sources of these electron-withdrawing anions may also be used.

[0081] In some respects provided herein, electron-withdrawing anions may be or may include fluoride ions, chloride ions, bromide ions, phosphate ions, trifluoromethanesulfonate ions, bisulfate ions, or sulfate ions, or any combination thereof. In other respects, electron-withdrawing anions may include sulfate ions, bisulfate ions, fluoride ions, chloride ions, bromide ions, iodide ions, fluorosulfate ions, fluoroborate ions, phosphate ions, fluorophosphate ions, trifluoroacetate ions, trifluoromethanesulfonate ions, fluorozirconate ions, fluorotitanate ions, or combinations thereof. However, in other respects, electron-withdrawing anions may include fluoride ions and / or sulfate ions.

[0082] Based on the weight of the chemically treated solid oxide, the chemically treated solid oxide may generally contain 1% to 30% by weight of electron-withdrawing anions. In the specific aspects provided herein, based on the total weight of the chemically treated solid oxide, the chemically treated solid oxide may contain, for example, 1% to 20% by weight, 2% to 20% by weight, 3% to 20% by weight, 2% to 15% by weight, 1% to 10% by weight, 2% to 10% by weight, or 3% to 10% by weight of electron-withdrawing anions.

[0083] In one aspect, the chemically treated solid oxide may include fluorinated aluminum oxide, chlorinated aluminum oxide, brominated aluminum oxide, sulfated aluminum oxide, fluorinated silica-alumina, chlorinated silica-alumina, brominated silica-alumina, sulfated silica-alumina, fluorinated silica-zirconia, chlorinated silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titanium dioxide, fluorinated silica-coated aluminum oxide, fluorinated-chlorinated silica-coated aluminum oxide, sulfated silica-coated aluminum oxide, phosphoric silica-coated aluminum oxide, and any mixture or combination thereof.

[0084] On the other hand, the chemically treated solid oxides used in supported transition metal catalysts and reduced transition metal catalysts, as well as the methods described herein, may be or may comprise fluorinated solid oxides and / or sulfated solid oxides. Non-limiting examples may include fluorinated alumina, sulfated alumina, fluorinated silica-alumina, sulfated silica-alumina, fluorinated silica-zirconium oxide, fluorinated silica-coated alumina, sulfated silica-coated alumina, and combinations thereof. Additional information regarding chemically treated solid oxides can be found, for example, in U.S. Patents 7,294,599, 7,601,665, 7,884,163, 8,309,485, 8,623,973, and 8,703,886, all of which are incorporated herein by reference in their entirety.

[0085] Consistent with certain aspects of this invention, supported transition metal catalysts and reduced transition metal catalysts may comprise zeolites as a support, i.e., transition metal supported zeolites. Any suitable zeolite can be used, for example, macroporous zeolites and mesoporous zeolites. Macroporous zeolites typically have... to The average pore size is within a certain range, and non-limiting examples of macroporous zeolites include L-zeolites, Y-zeolites, mordenite, ω-zeolites, β-zeolites, etc. Mesoporous zeolites typically possess... to Average pore size within the specified range. Combinations of zeolite carriers can be used.

[0086] Other representative examples of zeolites that can be used in supported transition metal catalysts and reduced transition metal catalysts include, for example, ZSM-5 zeolite, ZSM-11 zeolite, EU-1 zeolite, ZSM-23 zeolite, ZSM-57 zeolite, ALPO4-11 zeolite, ALPO4-41 zeolite, magnesium-alkali zeolite framework zeolites, or any combination thereof.

[0087] In supported transition metal catalysts and reduced transition metal catalysts, zeolite can be bonded to a support matrix (or binder). Non-limiting examples of the support matrix (or binder) may include silica, alumina, magnesium oxide, boron oxide, titanium dioxide, zirconium oxide, various clays, including mixed oxides thereof, and mixtures thereof. For example, the supported transition metal catalyst and reduced transition metal catalyst support may contain a binder comprising alumina, silica, mixed oxides thereof, or mixtures thereof. Zeolite can be bonded to the binder using any method known in the art. Although not limited thereto, supported transition metal catalysts and reduced transition metal catalysts may contain zeolite and 3% to 35% by weight of binder; alternatively, 5% to 30% by weight of binder; or alternatively, 10% to 30% by weight of binder. These weight percentages are based on the total weight of the supported transition metal catalyst or reduced transition metal catalyst.

[0088] There are no particular limitations on the amount of transition metal in supported and reduced transition metal catalysts. However, the range of transition metal amount in supported and reduced transition metal catalysts is typically 0.01 to 50 wt%; alternatively, 0.01 to 20 wt%; alternatively, 0.01 to 10 wt%; alternatively, 0.05 to 15 wt%; alternatively, 0.1 to 15 wt%; alternatively, 0.2 to 10 wt%; alternatively, 0.1 to 5 wt%; alternatively, 0.5 to 30 wt%; or alternatively, 0.5 to 2.5 wt%. These weight percentages are based on the amount of transition metal relative to the total weight of the supported or reduced transition metal catalyst. While not wishing to be bound by theory, it is believed that lower transition metal loadings (e.g., 1 wt% and below) can lead to higher selectivity for specific alcohol (or carbonyl) compounds, while higher transition metal loadings (e.g., 5–15 wt% and above) can lead to higher alcohol and / or carbonyl yields per gram of catalyst.

[0089] In the presence of hydrocarbon reactants, irradiation of the supported transition metal catalyst typically results in at least 10 wt%, at least 20 wt%, at least 40 wt%, at least 60 wt%, at least 80 wt%, or at least 90 wt% of the supported transition metal catalyst being reduced or transformed in the first and second methods to form a reduced transition metal catalyst.

[0090] There are no particular limitations on the total pore volume of supported and reduced transition metal catalysts. For example, supported and reduced transition metal catalysts can have a total pore volume in the range of 0.1 to 5 mL / g, 0.15 to 5 mL / g, 0.1 to 3 mL / g, 0.5 to 2.5 mL / g, 0.15 to 2 mL / g, 0.3 to 1.5 mL / g, or 0.5 to 1.0 mL / g. Similarly, the surface area of ​​supported and reduced transition metal catalysts is not limited to any specific range. However, typically, supported and reduced transition metal catalysts can have a surface area of ​​50 to 2000 m². 2 / g, 50 to 700m 2 / g, 50 to 400m 2 / g, 100 to 1200m 2 / g, 150 to 525m 2 / g or 200 to 400m 2 BET surface area within the range of / g.

[0091] Supported transition metal catalysts and reduced transition metal catalysts can have any suitable shape or form, and this can depend on the type of method used to convert hydrocarbon reactants into alcohols and / or carbonyl compounds (e.g., fixed bed versus fluidized bed). Illustrative and non-limiting shapes and forms include powders, spherical or round (e.g., spheres), elliptical, pellets, beads, cylinders, particles (e.g., regular and / or irregular), trilobes, quadrilobes, rings, wagon wheels, monoliths, etc., and any combination thereof. Therefore, various methods can be used to prepare supported transition metal catalyst particles, including, for example, extrusion, spray drying, granulation, marumerizing, spheroidization, agglomeration, droplets, etc., and combinations thereof.

[0092] In some respects, supported transition metal catalysts and reduced transition metal catalysts have relatively small particle sizes, with representative ranges of average (d50) particle sizes for supported and reduced transition metal catalysts including 10 to 500 micrometers, 25 to 250 micrometers, 20 to 100 micrometers, 40 to 160 micrometers, or 40 to 120 micrometers.

[0093] In other respects, supported transition metal catalysts and reduced transition metal catalysts can be in the form of pellets or beads with an average size ranging from 1 / 16 inch to 1 / 2 inch or 1 / 8 inch to 1 / 4 inch. As mentioned above, the size of the particles of supported transition metal catalysts and / or reduced transition metal catalysts can be varied to suit specific methods for converting hydrocarbon reactants into alcohol compounds and / or carbonyl compounds.

[0094] Supported transition metal catalysts consistent with aspects of the present invention may comprise silica-coated alumina and 0.01 to 50% by weight of a transition metal, including molybdenum, tungsten, vanadium, or combinations thereof, based on the weight of the catalyst. Thus, the transition metal may include molybdenum; alternatively, tungsten; or alternatively, vanadium.

[0095] The silica-coated alumina can have any suitable weight ratio of alumina to silica. While not limited thereto, the weight ratio can range from 1:20 to 20:1, for example, 1:5 to 5:1, 3:1 to 1:3, 1:1 to 3:1, 1:1 to 2:1, or 1.2:1 to 1.8:1. Based on the weight of the supported transition metal catalyst, the supported transition metal catalyst can contain 0.01 to 50 wt% of transition metal, and more typically, it contains 0.01 to 10 wt%, 0.05 to 15 wt%, 0.1 to 15 wt%, 0.2 to 10 wt%, 0.1 to 5 wt%, 0.5 to 30 wt%, or 0.5 to 2.5 wt% of transition metal.

[0096] Another supported transition metal catalyst consistent with this invention may comprise a solid support and 0.01 to 50% by weight of a transition metal, including molybdenum, tungsten, vanadium, or combinations thereof, based on the weight of the catalyst. Furthermore, at least one bonding site on the transition metal has a ligand characterized by one of the following formulas: an -O-alkyl group or an -O-haloalkyl group. The solid support for such a supported transition metal catalyst may be any solid support disclosed herein, such as any solid oxide, any chemically treated solid oxide, or any zeolite disclosed herein.

[0097] As described above, based on the weight of the supported transition metal catalyst, the supported transition metal catalyst may contain 0.01 to 50 wt% of transition metal, and more typically, the supported transition metal catalyst contains 0.01 to 10 wt%, 0.05 to 15 wt%, 0.1 to 15 wt%, 0.2 to 10 wt%, 0.1 to 5 wt%, 0.5 to 30 wt%, or 0.5 to 2.5 wt% of transition metal.

[0098] Although not limited thereto, the molar ratio of hydrocarbon groups to transition metals can typically range from 0.25:1 to 2:1 in one aspect, from 0.5:1 to 2:1 in another aspect, from 0.5:1 to 1.5:1 in yet another aspect, from 0.75:1 to 1.75:1 in yet another aspect, and from 0.75:1 to 1.25:1 in yet another aspect.

[0099] Examples 1-23

[0100] The present invention is further illustrated by the following embodiments, which should not be construed as limiting the scope of the invention in any way. Various other aspects, modifications, and equivalents will arise in those skilled in the art upon reading this description without departing from the spirit of the invention or the scope of the appended claims.

[0101] Ammonium metatungstate was dissolved in water and deposited onto a silica support (BET 500m). 2 Catalysts A1-A3 were prepared in silica (with a pore volume of 1.6 mL / g). After drying, the transition metal loading was 0.9-2.5 mmol W / g silica. Before use, the catalysts were calcined in dry air at 500 °C (A1), 650 °C (A2), or 700 °C (A3) for 3 hours.

[0102] Ammonium molybdate was dissolved in water and deposited onto a silica support (BET 500m). 2 Catalyst B1 was prepared in a silica mixture with a pore volume of 1.6 mL / g. After drying, the transition metal loading was 2.0 mmol Mo / g silica. Before use, the catalyst was calcined in dry air at 600 °C for 3 hours. Catalyst B2 was impregnated with an aqueous solution of the same molybdenum compound until the loading reached 1.0 mmol Mo / g silica. It was then dried and calcined in dry air at 700 °C for 3 hours.

[0103] Catalyst C was prepared by dissolving titanium isopropoxide in water containing 2 moles of oxalic acid per mole of titanium and 3 moles of dimethylformamide per mole of titanium. The solution was then deposited on a silica support (BET 500m). 2 / g (pore volume 1.6 mL / g). After drying, the transition metal loading is 1.02 mmol Ti / g silica. Before use, the catalyst was calcined in dry air at 650 °C for 3 hours.

[0104] By combining vanadium acetylacetonate (IV)(VO(AcAc)2) with silicon dioxide (BET 500m) 2Catalyst D1 was prepared by dry mixing of silica (with a pore volume of 1.6 mL / g) to a concentration equal to 2.0 mmol V / g silica. Before use, the dried mixture was calcined in dry air at 500°C for 3 hours. Catalyst D2 was impregnated with a methanol solution of the same vanadium compound to a concentration equal to 1.26 mmol V / g silica. It was then dried and calcined in dry air at 500°C for 3 hours. Catalyst D3 was impregnated with a methanol solution of the same vanadium compound to a concentration equal to 1.0 mmol V / g silica. It was then dried and calcined in dry air at 700°C for 3 hours.

[0105] Similar to the preparation of catalyst E using D2, except that the support is silica-coated alumina (BET is 450m). 2 / g, pore volume of 1.4mL / g, 40% by weight silica), up to 1.26 mmol V / g silica-coated alumina. Before use, calcine the dried mixture in dry air at 500°C for 3 hours.

[0106] The BET surface area can be determined using the BET nitrogen adsorption method as described in Brunauer et al., J. Am. Chem. Soc., 60, 309 (1938), as per ASTM D1993-91. Total pore volume can be determined according to Halsey, GD, J. Chem. Phys. (1948), 16, p. 931. The d50 particle size, or median or average particle size, refers to the particle size in which 50% by volume of the sample has smaller dimensions and 50% by volume of the sample has larger dimensions, and can be determined using laser diffraction according to ISO 13320.

[0107] Table I summarizes the reactions of Examples 1-14, in which the supported transition metal catalyst was first loaded into a hermetically sealed 100-mL glass container at 25°C, followed by the addition of hydrocarbon reactants. The glass container was then exposed to the light source indicated in Table I. For all examples where the glass container was exposed to light, the container was slowly rotated at 5-10 rpm to rotate the catalyst particles in the bottle, ensuring that the mixture of the supported transition metal catalyst and hydrocarbon reactants was uniformly exposed to light. For examples where the glass container was exposed to artificial light, the sample was placed in a box containing fluorescent or LED lights, in which three 15-watt bulbs were placed on a flat surface approximately 3 inches apart and approximately 2 inches away from the bottle. The reduction of the supported transition metal catalyst was monitored by the presence of color changes. The light sources used in Table I are blue fluorescent (425-475nm) or blue LED (400-450nm) with an illuminance of about 54,000-73,000 lux, and ultraviolet LED (380-405nm) with an illuminance of about 75,000-80,000 lux.

[0108] After the required exposure time, the reduced transition metal catalyst is mixed with a hydrolysant to cleave the hydrocarbon-containing ligands from the reduced transition metal catalyst. The mixture is stirred for several minutes. The hydrolysant used is generally selected to not interfere with the analysis of the reaction products (e.g., methanol is not used as a hydrolysant when the hydrolyzed reaction products may contain methanol, etc.).

[0109] Table I summarizes the results of Examples 1-14 and lists the specific supported transition metal catalysts and amounts, hydrocarbon reactants and amounts, light treatment and resulting colors, hydrolysants and amounts, acid / metal (moles), alcohol / metal (moles), GC-MS / metal (moles), total / metal (moles), and analysis of post-hydrolysis reaction products (oxygen-containing products). The reaction product analysis includes only oxygen-containing products obtainable from the reducing agent / reactants, excluding substances such as those obtained from the hydrolysant or its byproducts, or oligomers obtained from polymerization. For oxygen-containing reaction products, the area % from the analytical procedures listed below is approximately equal to mol%, therefore the results in Table I are expressed as mol%.

[0110] Carboxylic acid products (and molar acid / metal ratios) were determined by first neutralizing the product acids with sodium hydroxide solution, converting them to ionic form. A small sample was then injected into an ion column designed to separate the anions from weak organic acids by ion chromatography. A Dionex IC-3000 instrument with an ICE-AS1 column and protection device was used. The assay is particularly sensitive to C1-C6 linear carboxylic acids, glutarate, and glycolate ions. Results are reported in milligrams of carboxylate per milliliter of solution, which are then converted to moles.

[0111] Lower alcohol products (and molar-based alcohol / metal products) were determined using a GC-MS program on an Agilent 6890 gas chromatograph with a flame ionization detector (FID). A Restek Stapilwax column (P / N 10658) specifically designed and gated for the separation and detection of lower alcohols was used. The program was gated for acetone, methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, tert-butanol, 2-butanol, 2-butoxyethanol, acetonitrile, and tetrahydrofuran.

[0112] Additional reaction products (and molar-based GC-MS / metals) were determined using a separate GC-MS procedure as follows. Gas chromatography was performed using an Agilent 7890B GC equipped with flame ionization and mass spectrometry. A universal capillary column (Agilent J&W VF-5ms, 30m x 0.25mm x 0.25μm) was used at variable temperatures. Approximately 0.5μL of sample was aliquoted into the GC port maintained at 250°C using a 10:1 split ratio. The carrier gas was ultra-high purity helium, electronically controlled to a constant flow rate of 1.2mL / min throughout the run. The initial column temperature was maintained at 50°C for 5 min, ramped to 250°C at 20°C / min, and then maintained at 250°C for 19 min. Spectral assignments were performed using electron ionization at 70 eV via mass correlation on an Agilent 5977B mass spectrometer connected to the GC unit. A scan time of 0.5 seconds was used, with a nominal mass range of 14–400 m / z. The nominal detector voltage used was 1200 V. For calibration purposes, the FID and MS detectors were sometimes used sequentially on the same sample or reference sample.

[0113] Because the range of oxygen-containing products generated in this study is broad, one or all of these three procedures were used to characterize the reaction products after hydrolysis. In some cases, the same compound was detected by more than one technique and subtracted from the total / metal (molar) count to prevent duplicate counting of the same compound by more than one analytical technique. However, in most cases, there is little overlap between the three analytical procedures.

[0114] Referring now to the data in Table I, although none of the catalysts in Examples 1-14 exhibited any (ethylene) polymerization activity, alcohols and / or carbonyl (e.g., aldehydes, carboxylic acids) products were unexpectedly generated in these examples, except for Examples 1 and 8-9. Surprisingly, the tungsten catalyst in Example 2 converted isopentane (alkanes) to a reaction product containing 96% acetic acid, while the tungsten catalysts in Examples 4-6 converted methane (alkanes) to a reaction product primarily composed of methanol or primarily composed of formic acid. Using olefin reactants, the tungsten catalyst in Example 3 converted 1-hexene to a reaction product containing 98% acetic acid, while the tungsten catalyst in Example 7 converted ethylene to a reaction product containing 90% methanol.

[0115] Example 9 uses a titanium catalyst. Although titanium is known to be photosensitive using different mechanisms, no alcohol or carbonyl products were produced using this procedure.

[0116] The vanadium catalysts of Examples 10-11 and 14 convert n-pentane (alkanes) into reaction products containing 90-100% pentanol. Using olefin reactants, the vanadium catalyst of Example 12 converts 1-hexene into reaction products containing a variety of oxygen-containing products, including various hexanols, while the vanadium catalyst of Example 13 converts ethylene into reaction products mainly containing lower alcohols, primarily ethanol and methanol.

[0117] Table II summarizes the reactions of Examples 15-23, which are similar to those of Examples 1-14. However, in Examples 15-23, an oxidizing atmosphere is provided by adding dry air (1 atm) to the 100-mL glass container during the reduction “period” (when the catalyst and hydrocarbon reactants are in contact and irradiated) or at the reduction “end” (after irradiation but before hydrolysis). This is achieved by injecting a stream of dry air into the container over approximately 30 seconds, which typically results in immediate discoloration. The total exposure time to air before hydrolysis is approximately 1 minute. The light source used in Examples 15-17 of Table II is a UV LED (380-405 nm) of approximately 75,000-80,000 lux. For Examples 18-23, two ZMHA 60-watt LED UV lamps (380-420 nm) are used as the light source, with an output of approximately 250,000 lux (catalyst sample placed 2 inches from the lamp).

[0118] Referring now to the data in Table II, Examples 15-23 demonstrate the conversion of alkanes (n-pentane) and alkenes (ethylene and 1-hexene) to similar alcohols and carbonyl products at ambient temperatures using vanadium, tungsten, or molybdenum catalysts under various irradiation treatments, oxygen exposure, and hydrolyzing agents. Generally, the use of oxygen during or at the end of the reduction process (but prior to hydrolysis) results in an unexpectedly increased yield of oxygen-containing products compared to Table I, as quantified by GC-MS products based on molar amounts per transition metal. In some embodiments, the molar amount of redox product / metal exceeds 2, for example, from 2.2 to 3.3. Among vanadium, tungsten, or molybdenum-supported catalysts, vanadium catalysts typically produce the largest amount of alcohol / carbonyl products based on molar amounts.

[0119]

[0120]

[0121]

[0122]

[0123]

[0124]

[0125]

[0126] The invention has been described above with reference to various aspects and specific embodiments. Many variations will occur to those skilled in the art based on the foregoing specific embodiments. All such obvious variations are within the full scope of the appended claims. Other aspects of the invention may include, but are not limited to, the following aspects (an aspect is described as "comprising," but alternatively, may be "consistent with" or "component with"):

[0127] Aspect 1. A method for converting hydrocarbon reactants into alcohol compounds and / or carbonyl compounds, the method comprising:

[0128] (i) Irradiating the hydrocarbon reactants and a supported transition metal catalyst comprising molybdenum, tungsten, vanadium, or a combination thereof with a light beam in the ultraviolet-visible spectrum to reduce at least a portion of the supported transition metal catalyst, thereby forming a reduced transition metal catalyst; and

[0129] (ii) Hydrolyzing the reduced transition metal catalyst to form a reaction product comprising the alcohol compound and / or the carbonyl compound.

[0130] Aspect 2. The method as defined in aspect 1, wherein step (i) comprises irradiating the hydrocarbon reactant and the supported transition metal catalyst in an oxidizing atmosphere.

[0131] Aspect 3. A method for converting hydrocarbon reactants into alcohol compounds and / or carbonyl compounds, the method comprising:

[0132] (I) Irradiate the hydrocarbon reactants and the supported transition metal catalyst containing molybdenum, tungsten, vanadium or a combination thereof with a light beam in the ultraviolet-visible spectrum to reduce at least a portion of the supported transition metal catalyst, thereby forming a reduced transition metal catalyst.

[0133] (II) subjecting the reduced transition metal catalyst to an oxidizing atmosphere; and

[0134] (III) Hydrolyze the reduced transition metal catalyst to form a reaction product comprising the alcohol compound and / or the carbonyl compound.

[0135] 4. The method as defined in any one of aspects 1-3, wherein the hydrocarbon reactants comprise saturated or unsaturated, straight-chain or branched or cyclic aliphatic hydrocarbons, and combinations thereof.

[0136] Aspect 5. The method as defined in any one of Aspects 1-3, wherein the hydrocarbon reactants include straight-chain alkane compounds, branched-chain alkane compounds, cyclic alkane compounds, or combinations thereof.

[0137] Aspect 6. The method as defined in any one of Aspects 1-3, wherein the hydrocarbon reactants comprise any alkane compound with a suitable number of carbons or any alkane compound with a number of carbons disclosed herein, such as C1 to C2. 36 Alkane compounds, C1 to C 18 Alkane compounds, C1 to C 12 Alkane compounds or C1 to C8 alkane compounds.

[0138] Aspect 7. The method as defined in any one of Aspects 1-3, wherein the hydrocarbon reactants include methane, ethane, propane, butane (e.g., n-butane or isobutane), pentane (e.g., n-pentane, neopentane, cyclopentane or isopentane), hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, or any combination thereof.

[0139] Aspect 8. The method as defined in any one of Aspects 1-3, wherein the hydrocarbon reactants comprise methane, ethane, propane, n-butane, isobutane, n-pentane, neopentane, isopentane, n-hexane, n-heptane, n-octane, n-decane, n-dodecane, or any combination thereof; or the hydrocarbon reactants comprise methane, ethane, propane, butane, pentane, hexane, or any combination thereof.

[0140] Aspect 9. The method as defined in any one of Aspects 1-3, wherein the hydrocarbon reactants include straight-chain olefin compounds (e.g., α-olefins), branched-chain olefin compounds, cyclic olefin compounds, or combinations thereof.

[0141] Aspect 10. The method as defined in any one of Aspects 1-3, wherein the hydrocarbon reactant comprises an olefin compound with any suitable number of carbons or any olefin compound with any number of carbons disclosed herein, such as C2 to C4. 36 Olefin compounds, C2 to C 18 Olefin compounds, C2 to C 12 Olefin compounds or C2 to C8 olefin compounds.

[0142] Aspect 11. The method as defined in any one of Aspects 1-3, wherein the hydrocarbon reactants comprise ethylene, propylene, 1-butene, 1-pentene, 2-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, cyclopentene, cyclohexene, or any combination thereof.

[0143] Aspect 12. The method as defined in any one of Aspects 1-3, wherein the hydrocarbon reactants include aromatic compounds (e.g., benzene, toluene, xylene, styrene and their substituted forms, and combinations thereof).

[0144] Aspect 13. The method as defined in any one of Aspects 1-3, wherein the hydrocarbon reactants comprise any aromatic compound with a suitable number of carbons or any aromatic compound with a number of carbons disclosed herein, such as C6 to C4. 36 Aromatic compounds, C6 to C 18 Aromatic compounds, C6 to C 12 Aromatic compounds or C6 to C8 aromatic compounds.

[0145] Aspect 14. The method as defined in any one of Aspects 1-3, wherein the hydrocarbon reactants include benzene, toluene, ethylbenzene, xylene, styrene, mesitylene, or any combination thereof.

[0146] Aspect 15. The method as defined in any one of Aspects 1-3, wherein the hydrocarbon reactants comprise C n Hydrocarbon compounds, the alcohol compounds including C n Alcohol compounds, and the carbonyl compounds include C n Carbonyl compounds.

[0147] Aspect 16. The method as defined in aspect 15, wherein n is any suitable integer or an integer within any range disclosed herein, such as 1 to 36, 1 to 18, 1 to 12, or 1 to 8.

[0148] Aspect 17. The method as defined in any one of Aspects 1-3, wherein the hydrocarbon reactants comprise C n Hydrocarbon compounds, the alcohol compounds including (C n+1 ) + alcohol compounds, and / or the carbonyl compounds include (C n+1 )+carbonyl compounds.

[0149] Aspect 18. The method as defined in aspect 17, wherein n is any suitable integer or any integer within any range disclosed herein, such as 1 to 36, 1 to 18, 1 to 12 or 1 to 8.

[0150] Aspect 19. The method as defined in any one of Aspects 1-3, wherein the hydrocarbon reactants comprise C n Hydrocarbon compounds, the alcohol compounds including (C n-1 )-alcohol compounds, and / or the carbonyl compounds including (C n-1 )-carbonyl compounds.

[0151] Aspect 20. The method as defined in aspect 19, wherein n is any suitable integer or an integer within any range disclosed herein, such as 2 to 36, 2 to 18, 2 to 12, or 2 to 8.

[0152] Aspect 21. The method as defined in any of the preceding aspects, wherein the supported transition metal catalyst comprises molybdenum; alternatively, tungsten; or alternatively, vanadium.

[0153] Aspect 22. The method as defined in any of the preceding aspects, wherein the supported transition metal catalyst and the reduced transition metal catalyst comprise any suitable amount of transition metal or any range of amounts of transition metal disclosed herein, for example, based on the weight of the supported transition metal catalyst or the reduced transition metal catalyst, 0.01 to 50 wt%, 0.01 to 10 wt%, 0.05 to 15 wt%, 0.1 to 15 wt%, 0.2 to 10 wt%, 0.1 to 5 wt%, 0.5 to 30 wt%, or 0.5 to 2.5 wt% of transition metal.

[0154] Aspect 23. The method as defined in any of the preceding aspects, wherein in step (i) or step (I), at least 10 wt%, at least 20 wt%, at least 40 wt%, at least 60 wt%, at least 80 wt%, or at least 90 wt% of the supported transition metal catalyst is reduced to form the reduced transition metal catalyst based on the total amount of the supported transition metal catalyst.

[0155] Aspect 24. The method as defined in any one of Aspects 1-23, wherein the supported transition metal catalyst and the reduced transition metal catalyst comprise any suitable solid oxide or any solid oxide disclosed herein, such as silica, alumina, silica-alumina, silica-coated alumina, aluminophosphate, aluminum phosphate, heteropolytungstate, titanium dioxide, zirconium oxide, magnesium oxide, boron oxide, zinc oxide, silica-titanium dioxide, silica-zirconium oxide, alumina-titanium dioxide, alumina-zirconium oxide, zinc aluminate, alumina-boron oxide, aluminoborate, silica-boron oxide, aluminum phosphate-silica, titanium dioxide-zirconium oxide, or any combination thereof.

[0156] Aspect 25. The method as defined in any one of Aspects 1-23, wherein the supported transition metal catalyst and the reduced transition metal catalyst comprise silica, silica-alumina, silica-coated alumina, silica-titanium dioxide, silica-titanium dioxide-magnesium oxide, silica-zirconium oxide, silica-magnesium oxide, silica-boron oxide, aluminophosphate-silica, alumina, alumina borate, or any combination thereof.

[0157] Aspect 26. The method as defined in any one of Aspects 1-23, wherein the supported transition metal catalyst and the reduced transition metal catalyst comprise chemically treated solid oxides, the solid oxides including solid oxides treated with electron-withdrawing anions (e.g., as described in Aspects 24 or 25, such as silica, alumina, silica-alumina, silica-titanium dioxide, silica-zirconium oxide, silica-yttrium oxide, aluminum phosphate, zirconium oxide, titanium dioxide, thorium oxide, or tantalum oxide).

[0158] Aspect 27. The method as defined in aspect 26, wherein the electron-withdrawing anion includes sulfate, hydrogen sulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, trifluoromethanesulfonate, fluorozirconate, fluorotitanate, phosphotungstate, tungstate, molybdate, or any combination thereof.

[0159] Aspect 28. The method as defined in aspect 26 or 27, wherein, based on the total weight of the chemically treated solid oxide, the chemically treated solid oxide contains 1 to 30 wt%, 2 to 20 wt%, 2 to 15 wt%, 3 to 12 wt%, or 4 to 10 wt% of electron-withdrawing anions.

[0160] Aspect 29. The method as defined in any one of Aspects 1-23, wherein the supported transition metal catalyst and the reduced transition metal catalyst comprise chemically treated solid oxides, said solid oxides including fluorinated alumina, chlorinated alumina, brominated alumina, sulfated alumina, fluorinated silica-alumina, chlorinated silica-alumina, brominated silica-alumina, sulfated silica-alumina, fluorinated silica-zirconia, chlorinated silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titanium dioxide, fluorinated silica-coated alumina, fluorinated-chlorinated silica-coated alumina, sulfated silica-coated alumina, phosphoric silica-coated alumina, or any combination thereof.

[0161] Aspect 30. The method as defined in any one of Aspects 1-23, wherein the supported transition metal catalyst and the reduced transition metal catalyst comprise zeolite.

[0162] Aspect 31. The method as defined in aspect 30, wherein the supported transition metal catalyst and the reduced transition metal catalyst comprise mesoporous zeolite, macroporous zeolite, or a combination thereof.

[0163] Aspect 32. The method as defined in aspect 30, wherein the zeolite comprises ZSM-5 zeolite, ZSM-11 zeolite, EU-1 zeolite, ZSM-23 zeolite, ZSM-57 zeolite, ALPO4-11 zeolite, ALPO4-41 zeolite, magnesium alkali zeolite framework zeolite or combinations thereof.

[0164] Aspect 33. The method as defined in aspect 30, wherein the supported transition metal catalyst and the reduced transition metal catalyst comprise L-zeolite, γ-zeolite, mordenite, ω-zeolite and / or β-zeolite.

[0165] Aspect 34. The method as defined in any one of Aspects 30-33, wherein the supported transition metal catalyst and the reduced transition metal catalyst comprise zeolite and any suitable amount of binder or binder within any range disclosed herein, for example, 3% to 35% or 5% to 30% binder based on the weight of the supported transition metal catalyst and / or the reduced transition metal catalyst.

[0166] Aspect 35. The method as defined in any of the preceding aspects, wherein the supported transition metal catalyst and the reduced transition metal catalyst have any suitable pore volume (total) or any range of pore volumes (total) disclosed herein, such as 0.1 to 5 mL / g, 0.15 to 5 mL / g, 0.1 to 3 mL / g, 0.15 to 2 mL / g, 0.3 to 1.5 mL / g or 0.5 to 1.0 mL / g.

[0167] Aspect 36. The method as defined in any of the preceding aspects, wherein the supported transition metal catalyst and the reduced transition metal catalyst have any suitable BET surface area or any range of BET surface areas disclosed herein, for example, 50 to 2000 m². 2 / g, 50 to 700m 2 / g, 50 to 400m 2 / g, 100 to 1200m 2 / g or 150 to 525m 2 / g.

[0168] Aspect 37. The method as defined in any of the preceding aspects, wherein the supported transition metal catalyst and the reduced transition metal catalyst are any suitable shape or form or any shape or form disclosed herein, such as powder, round or spherical (e.g., spherical), elliptical, pellet, bead, cylindrical, granular (e.g., regular and / or irregular), trefoil, tetralobed, annular, wheel-shaped, block, or any combination thereof.

[0169] Aspect 38. The method as defined in any of Aspects 1-37, wherein the supported transition metal catalyst and the reduced transition metal catalyst have any suitable average (d50) particle size or an average (d50) particle size within any range disclosed herein, such as 10 to 500 micrometers, 25 to 250 micrometers or 20 to 100 micrometers.

[0170] Aspect 39. The method as defined in any one of Aspects 1-37, wherein the supported transition metal catalyst and the reduced transition metal catalyst comprise pellets or beads having any suitable average size or an average size within any range disclosed herein, such as 1 / 16 inch to 1 / 2 inch or 1 / 8 inch to 1 / 4 inch.

[0171] Aspect 40. The method as defined in any one of Aspects 1-39, wherein the wavelength includes a single wavelength or wavelength range (380 nm to 780 nm) in the visible spectrum.

[0172] Aspect 41. The method as defined in any one of Aspects 1-39, wherein the wavelength includes a single wavelength or a wavelength range in the range of 200 nm to 750 nm.

[0173] Aspect 42. The method as defined in any one of Aspects 1-39, wherein the wavelength comprises a single wavelength or a wavelength range of 300 to 750 nm, 350 to 650 nm, 300 to 500 nm or 300 to 400 nm.

[0174] Aspect 43. The method as defined in any one of Aspects 1-39, wherein the wavelength includes a single wavelength or a wavelength range of less than 600 nm, less than 500 nm, less than 475 nm, less than 450 nm, less than 430 nm or less than 420 nm.

[0175] Aspect 44. The method as defined in any of aspects 1-43, wherein the wavelength is a single wavelength.

[0176] Aspect 45. The method as defined in any one of Aspects 1-43, wherein the wavelength is a wavelength range spanning at least 25 nm, at least 50 nm, at least 100 nm or at least 200 nm.

[0177] Aspect 46. The method as defined in any of the preceding aspects, wherein the light beam has any suitable intensity or any range of intensity disclosed herein, such as at least 500 lumens, at least 1,000 lumens, at least 2,000 lumens, at least 5,000 lumens, at least 10,000 lumens, or at least 20,000 lumens.

[0178] Aspect 47. The method as defined in any of the preceding aspects, wherein the light beam originates from a light source having any suitable power or any power disclosed herein, such as at least 50 watts, at least 100 watts, at least 200 watts, at least 500 watts, at least 1000 watts, or at least 2000 watts.

[0179] Aspect 48. The method as defined in any of the preceding aspects, wherein the hydrocarbon reactants and the supported transition metal catalyst are irradiated with any suitable illuminance or any illuminance disclosed herein, such as at least 100 lux, at least 500 lux, at least 1000 lux, at least 2000 lux, at least 5000 lux, at least 10,000 lux, at least 20,000 lux, at least 50,000 lux, or at least 100,000 lux.

[0180] Aspect 49. The method as defined in any of the preceding aspects, wherein the irradiation step (or the subjecting step) is performed at any suitable temperature or any temperature disclosed herein, such as below 200°C, below 100°C, below 40°C, -100°C to 100°C, 0°C to 100°C, or 10°C to 40°C.

[0181] Aspect 50. The method as defined in any of the preceding aspects, wherein the irradiation step (or the exposure step) is performed for any suitable exposure time or any exposure time disclosed herein, such as 15 seconds to 48 hours, 1 minute to 6 hours, 1 minute to 15 minutes, or 1 hour to 8 hours.

[0182] Aspect 51. The method as defined in any of the preceding aspects, wherein the molar ratio of the hydrocarbon reactant to the transition metal (of the supported transition metal catalyst) is in any suitable range or any range disclosed herein, for example at least 0.25:1, at least 0.5:1, at least 1:1, at least 10:1, at least 100:1, at least 1000:1 or at least 10,000:1.

[0183] Aspect 52. The method as defined in any one of Aspects 1-51, wherein the hydrocarbon reactants are in the gas phase during the irradiation step.

[0184] Aspect 53. The method as defined in any one of Aspects 1-51, wherein the hydrocarbon reactants are in the liquid phase during the irradiation step.

[0185] Aspect 54. The method as defined in any one of Aspects 1-51, wherein the method comprises irradiating the supported transition metal catalyst in a slurry of the hydrocarbon reactants.

[0186] Aspect 55. The method as defined in any one of Aspects 1-51, wherein the method comprises contacting the hydrocarbon reactant with a fluidized bed of the supported transition metal catalyst and irradiating it simultaneously with the contact (fluidization).

[0187] Aspect 56. The method as defined in any one of Aspects 1-51, wherein the method comprises contacting the hydrocarbon reactants (e.g., in the gas phase or in the liquid phase) with a fixed bed of the supported transition metal catalyst and irradiating them simultaneously with the contact.

[0188] Aspect 57. The method as defined in any of the preceding aspects, wherein the step of contacting the hydrocarbon reactant with the supported transition metal catalyst is carried out at any suitable WHSV or within any range of WHSVs disclosed herein, for example, 0.01 h. -1 Up to 500h -1 or 0.1h -1 Up to 10h -1 .

[0189] Aspect 58. The method as defined in any of the preceding aspects, wherein the hydrolysis step is carried out at any suitable temperature or any temperature disclosed herein, such as below 200°C, below 100°C, below 40°C, 0°C to 100°C, or 10°C to 40°C.

[0190] Aspect 59. The method as defined in any of the preceding aspects, wherein the hydrolysis step comprises contacting the reduced transition metal catalyst with a hydrolysant.

[0191] Aspect 60. The method as defined in aspect 59, wherein the hydrolyzing agent comprises any suitable hydrolyzing agent or any hydrolyzing agent disclosed herein, such as water, steam, alcohol, acid, alkali or any combination thereof.

[0192] Aspect 61. The method as defined in aspect 59 or 60, wherein the hydrolysant further comprises any suitable reducing agent or any reducing agent disclosed herein, such as ascorbic acid, ferric(II) reducing agent, ferrous(II) ion, zinc reducing agent, sodium bisulfite, sodium thiosulfate, sodium sulfide, or any combination thereof.

[0193] Aspect 62. The method as defined in any of the preceding aspects, wherein the carbonyl compound comprises an aldehyde compound, a ketone compound, an organic acid compound, or any combination thereof; furthermore or alternatively, the alcohol compound comprises a diol, allyl alcohol, phenol, or any combination thereof.

[0194] Aspect 63. The method as defined in any of the preceding aspects, wherein the conversion of said hydrocarbon reactant (or the yield of said alcohol compound or the yield of said carbonyl compound) is any percentage conversion (or yield) disclosed herein, such as at least 2 wt%, at least 5 wt%, at least 10 wt%, or at least 15 wt% (and up to 99 wt%, 95 wt%, 90 wt%, 80 wt%, 70 wt%, or 50 wt%).

[0195] Aspect 64. The method as defined in any of the preceding aspects, wherein the single-pass conversion of said hydrocarbon reactant (or the single-pass yield of said alcohol compound or the single-pass yield of said carbonyl compound) is any single-pass percentage conversion (or single-pass yield) disclosed herein, such as at least 2 wt%, at least 5 wt%, at least 10 wt%, or at least 15 wt% (and up to 99 wt%, 95 wt%, 90 wt%, 80 wt%, 70 wt%, or 50 wt%).

[0196] Aspect 65. The method as defined in any of the preceding aspects, wherein the yield of the alcohol compound (or the carbonyl compound) per mole of the transition metal in the supported transition metal catalyst is based on any molar ratio of the number of moles of the transition metal disclosed herein, for example, at least 0.01, at least 0.05, at least 0.1 or at least 0.25 moles (and at most 10, at most 8, at most 5, at most 3, at most 2, at most 1.5 or at most 1 mole) of the alcohol compound (or the carbonyl compound).

[0197] Aspect 66. The method as defined in any of the preceding aspects further includes, after the hydrolysis step, the step of separating at least a portion (in some cases, all) of the hydrocarbon reactants from the reaction products using any suitable technique or any technique disclosed herein, such as extraction, filtration, evaporation, distillation, or any combination thereof, to produce a separated hydrocarbon fraction.

[0198] Aspect 67. The method as defined in aspect 66, wherein the separated hydrocarbon fraction is recycled and irradiated again with a supported transition metal catalyst.

[0199] Aspect 68. The method as defined in any of the preceding aspects further includes the step of separating at least a portion (and in some cases, all) of the alcohol compound and / or the carbonyl compound from the reaction product using any suitable technique or any technique disclosed herein, such as extraction, filtration, evaporation, distillation or any combination thereof.

[0200] Aspect 69. The method as defined in any of the preceding aspects further includes, after the hydrolysis step, the step of separating at least a portion (in some cases, all) of the reduced transition metal catalyst from the reaction product using any suitable technique or any technique disclosed herein, such as extraction, filtration, evaporation, distillation, or any combination thereof, to produce a separated reduced transition metal catalyst.

[0201] Aspect 70. The method as defined in any of the preceding aspects further includes the step of calcining the reduced transition metal catalyst or the separated reduced transition metal catalyst to regenerate the supported transition metal catalyst.

[0202] Aspect 71. The method as defined in aspect 70, wherein the calcination comprises subjecting the reduced transition metal catalyst or the isolated reduced transition metal catalyst to an oxidizing atmosphere, for a period of time of 1 minute to 24 hours, 1 hour to 12 hours or 30 minutes to 8 hours, at any suitable peak temperature and time condition or any peak temperature and time condition disclosed herein, such as 300°C to 1000°C, 500°C to 900°C or 550°C to 870°C.

[0203] Aspect 72. The method as defined in any one of Aspects 2-71, wherein the oxidizing atmosphere comprises any suitable oxidizing atmosphere or any oxidizing atmosphere disclosed herein, such as oxygen, air, a mixture of air and an inert gas (e.g., nitrogen), a mixture of oxygen and an inert gas, NO, NO2, N2O, ozone, halide oxides, H2O2, organic peroxides, and combinations thereof.

[0204] Aspect 73. A supported transition metal catalyst comprising:

[0205] Silica-coated aluminum oxide; and

[0206] Based on 0.01 to 50% by weight of the catalyst, a transition metal, including molybdenum, tungsten, vanadium, or combinations thereof.

[0207] Aspect 74. The catalyst as defined in aspect 73, wherein the transition metal comprises molybdenum; alternatively, tungsten; or alternatively, vanadium.

[0208] Aspect 75. The catalyst as defined in Aspect 73 or 74, wherein the supported transition metal catalyst comprises any suitable amount of transition metal or any amount of transition metal within any range disclosed herein, for example, 0.01 to 10 wt%, 0.05 to 15 wt%, 0.1 to 15 wt%, 0.2 to 10 wt%, 0.1 to 5 wt%, 0.5 to 30 wt%, or 0.5 to 2.5 wt% of transition metal based on the weight of the supported transition metal catalyst.

[0209] Aspect 76. The catalyst as defined in any of Aspects 73-75, wherein the silica-coated alumina has any suitable alumina to silica weight ratio or any range of weight ratios disclosed herein, such as 1:20 to 20:1, 1:5 to 5:1, 3:1 to 1:3, 1:1 to 3:1, 1:1 to 2:1 or 1.2:1 to 1.8:1.

[0210] Aspect 77. A catalyst as defined in any one of Aspects 73-76, wherein the supported transition metal catalyst comprises a transition metal having an oxygen bond, or a transition metal comprising at least a +3 oxidation state, or a transition metal comprising one of its two highest oxidation states, or any combination thereof.

[0211] Aspect 78. A supported transition metal catalyst comprising:

[0212] solid carrier; and

[0213] Based on 0.01 to 50% by weight of a transition metal, including molybdenum, tungsten, vanadium, or combinations thereof, in the catalyst; wherein:

[0214] At least one bonding site on the transition metal has a ligand characterized by one of the following formulas: -O-hydrocarbon group or -O-halohydrocarbon group.

[0215] Aspect 79. The catalyst as defined in aspect 78, wherein the molar ratio of the hydrocarbon group to the transition metal is in any suitable range or in any range disclosed herein, for example 0.25:1 to 2:1, 0.5:1 to 2:1, 0.5:1 to 1.5:1, 0.75:1 to 1.75:1 or 0.75:1 to 1.25:1.

[0216] Aspect 80. The catalyst as defined in Aspect 78 or 79, wherein the supported transition metal catalyst comprises any suitable amount of transition metal or any amount of transition metal within any range disclosed herein, such as 0.01 to 10 wt%, 0.05 to 15 wt%, 0.1 to 15 wt%, 0.2 to 10 wt%, 0.1 to 5 wt%, 0.5 to 30 wt%, or 0.5 to 2.5 wt% of transition metal based on the weight of the supported transition metal catalyst.

[0217] Aspect 81. A catalyst as defined in any of aspects 78-80, wherein the solid support comprises any suitable solid support or any solid support disclosed herein, such as solid oxides, chemically treated solid oxides, zeolites or any combination thereof.

Claims

1. A method for converting hydrocarbon reactants into alcohol compounds and / or carbonyl compounds, the method comprising: (i) Irradiating the hydrocarbon reactants and a supported transition metal catalyst containing molybdenum, tungsten, vanadium or a combination thereof with a light beam in the ultraviolet-visible spectrum to reduce at least a portion of the supported transition metal catalyst, thereby forming a reduced transition metal catalyst; and (ii) Hydrolyzing the reduced transition metal catalyst to form a reaction product comprising the alcohol compound and / or the carbonyl compound.

2. The method of claim 1, wherein step (i) comprises irradiating the hydrocarbon reactants and the supported transition metal catalyst in an oxidizing atmosphere.

3. A method for converting hydrocarbon reactants into alcohol compounds and / or carbonyl compounds, the method comprising: (I) Irradiate the hydrocarbon reactants and the supported transition metal catalyst containing molybdenum, tungsten, vanadium or a combination thereof with a light beam in the ultraviolet-visible spectrum to reduce at least a portion of the supported transition metal catalyst, thereby forming a reduced transition metal catalyst. (II) subject the reduced transition metal catalyst to an oxidizing atmosphere; and (III) Hydrolyze the reduced transition metal catalyst to form a reaction product comprising the alcohol compound and / or the carbonyl compound.

4. The method according to any one of claims 1-3, wherein the hydrocarbon reactants comprise C1 to C2. 36 Straight-chain, branched-chain, or cyclic alkane compounds.

5. The method according to any one of claims 1-3, wherein the hydrocarbon reactants comprise C2 to C3. 36 Olefin compounds, C6 to C 36 Aromatic compounds or any combination thereof.

6. The method of any one of claims 1-3, wherein the supported transition metal catalyst comprises 0.01 to 50% by weight of molybdenum, tungsten, vanadium, or combinations thereof, based on the weight of the supported transition metal catalyst.

7. The method according to any one of claims 1-3, wherein: The supported transition metal catalyst comprises solid oxides, chemically treated solid oxides, zeolites, or combinations thereof; The supported transition metal catalyst has a pore volume of 0.1 to 5 mL / g and a pore size of 50 to 2000 m³ / g. 2 / g of BET surface area; and The irradiation step is performed at a temperature ranging from -100°C to 100°C.

8. The method according to any one of claims 1-3, wherein: The light beam originates from a blue light source or an ultraviolet light source; The light beam includes wavelengths higher than 350 nm and lower than 500 nm; The hydrocarbon reactants and the supported transition metal catalyst are irradiated with an illuminance of at least 5000 lux; or Any combination of them.

9. The method of any one of claims 1-3, wherein the method comprises: The hydrocarbon reactants are brought into contact with the fluidized bed of the supported transition metal catalyst, and irradiated simultaneously during the contact. or The hydrocarbon reactants are brought into contact with a fixed bed of the supported transition metal catalyst, and irradiated simultaneously during the contact.

10. The method according to any one of claims 1-3, wherein: Hydrolysis is carried out at temperatures ranging from 0°C to 100°C; and Hydrolysis involves contacting the reduced transition metal catalyst with a hydrolyzing agent, which includes water, steam, alcohol, acid, alkali, or any combination thereof.

11. The method according to any one of claims 1-3, further comprising the step of separating at least a portion of the alcohol compound and / or the carbonyl compound from the reaction product after the hydrolysis step.

12. The method of any one of claims 1-3, further comprising the step of separating at least a portion of the hydrocarbon reactants from the reaction products after the hydrolysis step, wherein the at least a portion of the hydrocarbon reactants is recycled and irradiated again with the supported transition metal catalyst.

13. The method according to any one of claims 1-3, further comprising: At least a portion of the reduced transition metal catalyst is separated from the reaction product after the hydrolysis step; and At least a portion of the reduced transition metal catalyst is calcined to regenerate the supported transition metal catalyst.

14. The method according to any one of claims 1-3, wherein: The conversion rate of the hydrocarbon reactants is at least 10% by weight; and / or The molar yield of the alcohol compound and / or the carbonyl compound is from 0.01 to 5 moles of the alcohol compound and / or the carbonyl compound per mole of transition metal in the supported transition metal catalyst.

15. The method of any one of claims 1-3, wherein the supported transition metal catalyst comprises vanadium.

16. The method of any one of claims 1-3, wherein the supported transition metal catalyst comprises tungsten.

17. The method of any one of claims 1-3, wherein the supported transition metal catalyst comprises molybdenum.

18. A supported transition metal catalyst, comprising: Silica-coated aluminum oxide; and Based on 0.01 to 50% by weight of a transition metal, including molybdenum, tungsten, vanadium, or combinations thereof, the catalyst... in: At least one bonding site on the transition metal has a ligand characterized by one of the following formulas: -O-hydrocarbon group or -O-halohydrocarbon group.

19. The catalyst of claim 18, wherein: Based on the weight of the supported transition metal catalyst, the supported transition metal catalyst comprises 0.2 to 10% by weight of a transition metal; and The weight ratio of aluminum oxide to silicon dioxide in the silica-coated aluminum oxide is 1:5 to 5:

1.

20. A supported transition metal catalyst, comprising: solid carrier; and Based on 0.01 to 50% by weight of a transition metal in the catalyst, including molybdenum, tungsten, vanadium, or combinations thereof; wherein: At least one bonding site on the transition metal has a ligand characterized by one of the following formulas: -O-hydrocarbon group or -O-halohydrocarbon group.

21. The catalyst of claim 20, wherein: The molar ratio of the hydrocarbon group to the transition metal is in the range of 0.25:1 to 2:1; and Based on the weight of the supported transition metal catalyst, the supported transition metal catalyst contains 0.1 to 5% by weight of transition metal.

22. The catalyst of claim 20 or 21, wherein the solid support comprises a solid oxide, a chemically treated solid oxide, a zeolite, or any combination thereof.

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