Production of alcohols from hydrocarbons catalyzed by chromium

Abstract

Processes for converting a hydrocarbon reactant to an alcohol compound and / or a carbonyl compound are disclosed, which include the steps of irradiating the hydrocarbon reactant and a supported chromium catalyst comprising chromium in the hexavalent oxidation state with a beam of light at a wavelength in the UV-visible spectrum to reduce at least a portion of the supported chromium catalyst to form a reduced chromium catalyst, and hydrolyzing the reduced chromium catalyst to form a reaction product comprising the alcohol compound and / or the carbonyl compound. Further, these processes can further include the step of calcining all or a portion of the reduced chromium catalyst to regenerate the supported chromium catalyst.

Description

[0001] Citation of relevant applications

[0002] This application, filed on September 14, 2020, claims the benefit of priority to U.S. Provisional Patent Application No. 62 / 900,687, filed on September 16, 2019, the disclosure of which is incorporated herein by reference in its entirety. Invention Field

[0003] This disclosure generally relates to methods for converting hydrocarbons into alcohols and / or carbonyl compounds, and more specifically, to performing such methods using supported chromium catalysts. Background of the Invention

[0005] 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

[0006] 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 fundamental features of the claimed subject matter. Nor is it intended to limit the scope of the claimed subject matter.

[0007] Aspects of the present invention relate to processes for converting hydrocarbon reactants into alcohol compounds and / or carbonyl compounds, and such processes may include: (i) irradiating the hydrocarbon reactants and a supported chromium catalyst comprising hexavalent chromium with a light beam of wavelength in the UV-Vis spectrum to reduce at least a portion of the supported chromium catalyst to form a reduced chromium catalyst; and (ii) hydrolyzing the reduced chromium catalyst to form a reaction product comprising an alcohol compound and / or a carbonyl compound. Optionally, these processes may further include (iii) the step of calcining all or part of the reduced chromium catalyst to regenerate the supported chromium catalyst.

[0008] In step (i), at least a portion of the chromium on the reduced chromium catalyst may have at least one bonding site with a hydrocarbon oxygen group (-O-hydroxyl group), which, upon hydrolysis in step (ii), can release an alcoholic compound and / or a carbonyl compound analogue of the hydrocarbon compound. For example, if the hydrocarbon is cyclohexane (or methane), then the alcoholic compound may be cyclohexanol (or methanol).

[0009] The foregoing summary and the following detailed description are provided as examples and are merely illustrative. 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 set forth herein. For example, certain aspects may relate to various combinations and sub-combinations of features described in the detailed description.

[0010] definition

[0011] To more clearly define the terms used herein, the following definitions are provided. Unless otherwise stated, the following definitions apply to this disclosure. If a term is used in this disclosure but is not specifically defined herein, the definition in 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.

[0012] 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.

[0013] 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, elements in a group may be indicated using the common names 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.

[0014] 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.

[0015] 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, as well as mixtures of stereoisomers, which would be recognized by those skilled in the art. For example, general references to pentane include n-pentane, 2-methyl-butane, and 2,2-dimethylpropane; and general references to butyl include n-butyl, sec-butyl, isobutyl, and tert-butyl.

[0016] Unless otherwise stated, the term "(substituted)" when used to describe a group, such as when referring to a substituted analogue of a particular group, is intended to describe any non-hydrogen portion that formally substitutes for hydrogen in the group, and is intended to be non-limiting. Furthermore, unless otherwise stated, one or more groups may also be referred to herein as "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. Additionally, unless otherwise stated, "(substituted)" is intended to be non-limiting and includes inorganic or organic substituents as understood by those skilled in the art.

[0017] 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.

[0018] 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).

[0019] 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”.

[0020] 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.

[0021] 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 two of these numbers (e.g., C2 to C4 alkane compounds and C...). 12 To C 16 (Alkanes).

[0022] Similarly, another representative example follows the same principle regarding the amount of chromium on a supported chromium catalyst. The disclosure that the amount of chromium can range from about 0.1 wt% to about 15 wt% is intended to enumerate any amount of chromium that can be within this range, and for example, can be equal to about 0.1 wt%, about 0.2 wt%, about 0.3 wt%, about 0.4 wt%, about 0.5 wt%, about 0.6 wt%, about 0.7 wt%, about 0.8 wt%, about 0.9 wt%, about 1 wt%, about 2 wt%, about 3 wt%, about 4 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, about 10 wt%, about 11 wt%, about 12 wt%, about 13 wt%, about 14 wt%, or about 15 wt%. Additionally, the amount of chromium can be in any range from about 0.1 wt% to about 15 wt% (e.g., about 0.1 wt% to about 5 wt%), and this also includes any combination of ranges between about 0.1 wt% and about 15 wt% (e.g., the amount of chromium can be in the range from about 0.5 wt% to about 2.5 wt% or from about 5 wt% to about 15 wt%). Furthermore, in all cases, if a specific value is disclosed as “about”, that value itself is disclosed. Therefore, the disclosure that the amount of chromium can be from about 0.1 wt% to about 15 wt% also discloses an amount of chromium from 0.1 wt% to 15 wt% (e.g., 0.1 wt% to 5 wt%), and this also includes any combination of ranges between 0.1 wt% and 15 wt% (e.g., the amount of chromium can be in the range from 0.5 wt% to 2.5 wt% or from 5 wt% to 15 wt%). Similarly, all other ranges disclosed herein should be interpreted in a manner similar to these examples.

[0023] The term "about" means that a quantity, size, formulation, parameter, or other quantity and characteristic is not, and need not be, precise, but can be approximate, including being larger or smaller as required, reflecting tolerances, conversion factors, rounding, measurement errors, and other factors known to those skilled in the art. Generally, whether explicitly stated as "about" or "approximate," a quantity, size, formulation, parameter, or other quantity or characteristic is "about" or "approximate." The term "about" also covers quantities that vary due to different equilibrium conditions of the composition produced from a particular initial mixture. The claims include equivalent quantities, whether or not modified by the term "about." The term "about" can mean within 10% of the reported value, and often within 5% of the reported value.

[0024] 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.

[0025] All publications and patents mentioned herein are incorporated herein by reference for the purpose of describing and disclosing, for example, the constructs and methods described in the publications, which may be used in conjunction with the inventions described herein. Detailed Implementation

[0026] 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 chromium catalysts, photoreduction, and hydrolysis can efficiently convert hydrocarbons (e.g., alkanes) into similar alcohols and / or carbonyl compounds, advantageously even at ambient temperatures.

[0027] Surprisingly, it was also found that the high calcination / activation temperatures (e.g., 600–900 °C) typically required for supported chromium polymerization catalysts are not necessary for the production of alcohols and / or carbonyl compounds as described herein. Although calcination below these conventionally high temperatures results in poor or inactive supported chromium polymerization catalysts, heat treatment temperatures in the range of 100–500 °C effectively remove free water and / or dry the supported catalyst and / or convert or stabilize chromium (VI), thereby efficiently producing the desired alcohols and / or carbonyl products.

[0028] Surprisingly, chromate compounds (such as potassium chromate, potassium dichromate, etc.), which are completely ineffective in polymerization catalysts, are very effective catalysts for converting hydrocarbons into alcohols and / or carbonyl compounds. Furthermore, it is advantageous that very low heat treatment temperatures can be used because chromium (VI) is already present.

[0029] Generally, supported chromium polymerization catalysts are limited to a chromium loading of about 1 wt%. When chromium (VI) is stabilized by combination with silica or other supports, the loading cannot be too high, otherwise the chromium will degrade into unusable chromium (III). However, advantageously, high chromium loadings of 5-10 wt% and even 20-50 wt% can be readily used in the processes described herein, and these higher loadings result in higher overall yields of alcohols and / or carbonyl products (more chromium equals more product). Conversely, low chromium loadings (e.g., less than 0.5 wt%) have been found to be highly selective for the desired alcohols and / or carbonyl products, although they are not very active for polymerization.

[0030] Processes for converting hydrocarbons into alcohols

[0031] This document discloses processes for converting hydrocarbon reactants into alcohols and / or carbonyl compounds. These processes may include (i) irradiating the hydrocarbon reactants and a supported chromium catalyst containing chromium in a hexavalent oxidation state with a light beam of wavelength in the UV-Vis spectrum to reduce at least a portion of the supported chromium catalyst to form a reduced chromium catalyst, and (ii) hydrolyzing the reduced chromium catalyst to form a reaction product containing an alcohol and / or carbonyl compound. While not wishing to be bound by theory, it is believed that in step (i), at least a portion of the chromium on the reduced chromium catalyst may have at least one bonding site with an alkyl group (-O-alkyl group), which, upon hydrolysis in step (ii), may release an alcohol and / or carbonyl compound analogue containing the hydrocarbon. The average oxidation state of the reduced chromium catalyst is lower than that of the supported chromium catalyst.

[0032] Generally, the characteristics of this process (e.g., hydrocarbon reactants, supported chromium catalyst, reducing chromium catalyst, light beam, and conditions for carrying out the irradiation and hydrolysis steps, etc.) are described independently herein, and these characteristics may be combined in any combination to further describe the disclosed process for producing alcohols and / or carbonyl compounds. Furthermore, unless otherwise stated, additional process steps may be performed before, during, and / or after any step in any process disclosed herein, and these additional process steps may be used without limitation in any combination to further describe these processes. Furthermore, any alcohols and / or carbonyl compounds produced according to the disclosed process are within the scope of this disclosure and are covered herein.

[0033] In this process, 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, linear aliphatic hydrocarbon compounds, branched aliphatic hydrocarbon compounds, and cyclic aliphatic hydrocarbon compounds, as well as combinations thereof. Therefore, hydrocarbon reactants may comprise linear alkane compounds, branched alkane compounds, cyclic alkane compounds, or combinations thereof. Furthermore or alternatively, hydrocarbon reactants may comprise aromatic compounds, such as benzene, toluene, etc., and their substituted variants, and combinations thereof.

[0034] Any hydrocarbon with a suitable number of carbon atoms can be used, so that the hydrocarbon reactants can contain C24 carbon atoms. n Hydrocarbon compounds (and alcohol compounds often contain C) n Alcohol compounds, and carbonyl compounds often contain C. n (Carbonyl compounds). Although not limited to this, the integer n can be 1 to 36 in one aspect, 1 to 18 in another aspect, 1 to 12 in yet another aspect, and 1 to 8 in yet another aspect.

[0035] 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 about 90% by weight, at least about 95% by weight, at least about 98% by weight, or at least about 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 contain 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.

[0036] Similarly, hydrocarbon reactants can contain 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 about 90% by weight, at least about 95% by weight, at least about 98% by weight, or at least about 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.

[0037] Similarly, hydrocarbon reactants can contain aromatic compounds with any suitable number of carbons, such as C6 to C4. 36 Aromatic compounds; alternatively, C6 to C6 18 Aromatic compounds; alternatively, C6 to C6 12Aromatic compounds; or alternatively, C6 to C8 aromatic compounds. As above, if desired, the hydrocarbon reactants may contain a single aromatic compound of relatively high purity, such as at least about 90% by weight, at least about 95% by weight, at least about 98% by weight, or at least about 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 contain 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.

[0038] 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, or isopentane), hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, cyclopentene, cyclohexene, benzene, toluene, ethylbenzene, xylene, mesitylene, etc., and combinations thereof.

[0039] Therefore, the hydrocarbon reactants may comprise a mixture of aliphatic and aromatic hydrocarbons. In a non-limiting aspect, the hydrocarbon reactants may comprise 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. Alternatives: propylene; 1-butene; 1-pentene; 1-hexene; 1-heptene; 1-octene; 1-decene; 1-dodecene; 1-tetradecene; 1-hexadecene; 1-octadecene; cyclopentene; cyclohexene; benzene; toluene; ethylbenzene; xylene; or mesitylene.

[0040] On one hand, the 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, the hydrocarbon (alkane) reactants may include methane, ethane, propane, butane, pentane, hexane, etc., or any combination thereof. On yet another hand, the hydrocarbon (alkene) reactants may include ethylene, propylene, 1-butene, 1-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. On the other hand, hydrocarbon (aromatic) reactants may include benzene, toluene, ethylbenzene, xylene, mesitylene, etc., or any combination thereof.

[0041] Generally, the irradiation step can be performed under any conditions sufficient to accommodate the irradiation of the hydrocarbon reactants and the supported chromium catalyst (containing chromium in the hexavalent oxidation state) with a beam of light to form a reduced chromium catalyst (having a lower oxidation state). For example, the relative amount (or concentration) of the hydrocarbon reactants to the amount of chromium (in the supported chromium catalyst) can alter the efficiency of the reduction process. In some respects, the molar ratio of hydrocarbon reactants to chromium (in the supported chromium catalyst) can be at least about 0.25:1, at least about 0.5:1, at least about 1:1, at least about 10:1, at least about 100:1, at least about 1000:1, or at least about 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.

[0042] 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 chromium catalyst, and on the other hand, keep the hydrocarbons gaseous throughout the reduction process of the supported chromium catalyst. Advantageously, it has been found that, through the irradiation step disclosed herein, supported chromium compounds can be reduced at temperatures lower than those typically required to reduce hexavalent chromium using heat instead of light. In some aspects, the irradiation step can be carried out at temperatures less than about 200°C, less than about 100°C, less than about 70°C, less than about 40°C, from about 0°C to about 200°C, from about -100°C to about 100°C, from about 0°C to about 100°C, or from about 10°C to about 40°C, and can produce a reduced chromium catalyst (e.g., at least a portion of the chromium on the reduced chromium catalyst has at least one bonding site with an alkyl group). 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 a respective temperature range, 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 chromium catalyst are exposed to the light beam. Without being bound by theory, it is believed that exposure to the light beam in the presence of the hydrocarbon reactants is the cause of the reduction of the supported chromium 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 about 15 seconds to about 48 hours, about 15 seconds to about 24 hours, about 1 hour to about 8 hours, about 15 minutes to about 4 hours, about 1 minute to about 6 hours, about 5 minutes to about 1 hour, about 10 minutes to about 2 hours, about 1 minute to about 1 hour, or about 1 minute to about 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(s) of the light beam(s), etc. Stirring, mixing, or other suitable techniques can be used to ensure that the mixture of the supported chromium catalyst (e.g., granules) and the hydrocarbon reactants is uniformly exposed to the light beam irradiation.

[0044] The supported chromium 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 process, a supported chromium catalyst is irradiated with a UV-Vis light beam in the presence of hydrocarbon reactants to produce a chromium catalyst in a reduced oxidation state (e.g., a reduced chromium 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 hexavalent chromium present in the supported chromium catalyst. In some respects, for example, the light can be from any suitable source, such as sunlight, fluorescent white light, LED diodes, and / or UV 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 UV-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 UV 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 less than 600 nm, less than 525 nm, or less than 500 nm; in addition or alternatively, a single wavelength or wavelength range greater than 300 nm, greater than 350 nm, greater than 400 nm, or greater than 450 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 about 500 lumens, at least about 1,000 lumens, at least about 2,000 lumens, at least about 5,000 lumens, at least about 10,000 lumens, at least about 20,000 lumens, at least about 50,000 lumens, or at least about 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 about 50 to about 50,000 lumens, about 50 to about 10,000 lumens, about 100 to about 5,000 lumens, or about 500 to about 2,000 lumens. Furthermore, the light beam is characterized by the amount of light reaching the hydrocarbon reactants and the supported chromium catalyst, i.e., the flux. In some aspects, the hydrocarbon reactants and the supported chromium catalyst containing hexavalent chromium oxide can be irradiated with at least about 100 lux, at least about 500 lux, at least about 1000 lux, at least about 2000 lux, at least about 5000 lux, at least about 10,000 lux, at least about 20,000 lux, at least about 100,000 lux, or in the range of about 10,000 to about 1,000,000 lux, about 50,000 to about 500,000 lux, or about 50,000 to about 200,000 lux. Additionally or alternatively, in some aspects, the hydrocarbon reactants and the supported chromium catalyst containing hexavalent chromium oxide can be irradiated with a beam of power of at least about 50 watts, at least about 100 watts, at least about 200 watts, at least about 500 watts, at least about 1,000 watts, or at least about 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 process may include irradiating the solid supported chromium catalyst in a slurry (e.g., a loop slurry) of the hydrocarbon reactants. In yet another aspect, the disclosed process may include contacting the hydrocarbon reactants with a fluidized bed of solid supported chromium catalyst and irradiating them simultaneously with the contact (fluidization). In yet another aspect, the disclosed process may include contacting the hydrocarbon reactants (e.g., in the gas phase or in the liquid phase) with a fixed bed of solid supported chromium catalyst and irradiating them simultaneously with the contact. As those skilled in the art will recognize, other processes exist for contacting and irradiating hydrocarbon reactants with solid supported chromium catalysts, and the disclosed processes are not limited to those disclosed herein. For example, the hydrocarbon reactants and the supported chromium 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 chromium 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 chromium catalyst, and other considerations.

[0051] Typically, the process for forming a reduced chromium catalyst (and subsequently an alcohol and / or carbonyl compound) can be a flow process and / or a continuous process. In such cases, the hydrocarbon reactant-supported chromium 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 chromium catalyst per unit time (in g / g / hr or hr). -1 ) is used to represent this.

[0052] Although not limited to this, the WHSV used in the disclosed process can have a 0.01hr -1 0.02hr -1 0.05hr -1 0.1hr -1 0.25hr -1 or 0.5hr -1 The minimum value; or alternatively, 500hr -1 400hr -1300hr -1 100hr -1 50hr -1 10hr -1 5hr -1 2hr -1 or 1hr -1 The maximum value. Generally, WHSV can range from any minimum WHSV disclosed herein to any maximum WHSV disclosed herein. In a non-limiting aspect, WHSV can range from approximately 0.01hr. -1 approximately 500hr -1 Alternatively, approximately 0.01hr -1 approximately 10 hours -1 Alternatively, approximately 0.01hr -1 approximately 1 hour -1 Alternatively, approximately 0.02hr -1 approximately 400hr -1 Alternatively, approximately 0.02hr -1 approximately 50 hours -1 Alternatively, approximately 0.05hr -1 Approximately 300 hours -1 Alternatively, approximately 0.05hr -1 approximately 5 hours -1 Alternatively, approximately 0.1hr -1 approximately 400hr -1 Alternatively, approximately 0.25hr -1 approximately 50 hours -1 Alternatively, approximately 0.25hr -1 approximately 2 hours -1 Alternatively, approximately 0.5 hours -1 approximately 400hr -1 Alternatively, approximately 0.5 hours -1 approximately 5 hours -1 Or alternatively, approximately 0.5 hours -1 approximately 2 hours -1 Other WHSV scopes are apparent from this disclosure.

[0053] Referring now to the hydrolysis step, a reduced chromium catalyst (e.g., at least a portion of the chromium on the reduced chromium 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 about 200°C, less than about 100°C, less than about 70°C, less than about 40°C, from about 0°C to about 200°C, from about 0°C to about 100°C, or from about 10°C to about 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.

[0054] Although not limited thereto, the hydrolysis step may include contacting the reduced chromium catalyst with a hydrolyzing agent. Illustrative and non-limiting examples of suitable hydrolyzing 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 hydrolyzing agents. Therefore, the pH of (one or more) hydrolyzing agents can range from acidic to neutral to alkaline, generally covering a pH range of about 1 (or lower) to about 13-13.5.

[0055] Optionally, the hydrolysate may further contain any suitable reducing agent, representative examples of which include ascorbic acid, iron(II) reducing agents, zinc reducing agents, and combinations thereof. These can sometimes be used to prevent unreacted chromium(VI) from causing unwanted secondary oxidation. Furthermore, they can also 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.

[0056] 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 processes 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, and combinations thereof. Here, alcohol compounds encompass monohydric alcohols and diols (e.g., ethylene glycol and hexanediol).

[0057] In addition to or in place of alcohols, reaction products may contain carbonyl compounds, such as aldehydes, ketones, or organic acids, and any combination of aldehydes, ketones, and organic acids. Therefore, enols are covered herein because reaction products may contain alcohols, carbonyl compounds, or both. In some respects, alcohols or carbonyl products may contain unsaturation. For example, one or more carbons adjacent to the alcohol or carbonyl group may contain a double bond. Although not wishing to be bound by theory, allyl CH bonds are believed to be particularly susceptible to attack by chromium (VI). Thus, 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. Therefore, in some respects, the alcohol compound may 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.

[0058] The process described herein results in unexpectedly high conversion rates of hydrocarbon reactants and / or unexpectedly high yields of alcohol compounds (or carbonyl compounds). In one aspect, the minimum conversion rate (or yield) may be at least about 2 wt%, at least about 5 wt%, at least about 10 wt%, at least about 15 wt%, or at least about 25 wt%. Furthermore, the maximum conversion rate (or yield) may be about 50 wt%, about 70 wt%, about 80 wt%, about 90 wt%, about 95 wt%, or about 99 wt%, and may approach 100% conversion rate of hydrocarbon reactants (or yield of alcohol compounds or yield of carbonyl compounds). Generally, the conversion rate (or yield) may range from any minimum conversion rate (or yield) disclosed herein to any maximum conversion rate (or yield) disclosed herein. Non-limiting ranges for conversion rates (or yields) may include about 5 wt% to about 99 wt%, about 10 wt% to about 95 wt%, or about 15 wt% to about 70 wt%. For conversion, the percentage is the amount of hydrocarbon reactants converted from the initial amount of hydrocarbon reactants. Yield values ​​are weight percentages and are based on the weight of the resulting 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 multiple-pass reactors (e.g., fixed-bed reactors). Typically, conversion and yield can be controlled by varying the ratio of the reducing agent hydrocarbon feed to chromium (VI) and by changing other reaction conditions such as time, temperature, and irradiation.

[0059] Equally unexpectedly, the continuous flow process according to the invention for the production of alcohols and / or carbonyl compounds exhibits unexpectedly high single-pass conversion rates of hydrocarbon reactants (or single-pass yields of desired alcohols or carbonyl compounds). In one aspect, the minimum single-pass conversion rate (or yield) can be at least about 2 wt%, at least about 5 wt%, at least about 10 wt%, at least about 15 wt%, or at least about 25 wt%. Additionally, the maximum single-pass conversion rate (or yield) can be about 50 wt%, about 70 wt%, about 80 wt%, about 90 wt%, about 95 wt%, or about 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 about 5% to about 99% by weight, about 10% to about 95% by weight, or about 15% to about 70% by weight.

[0060] The yield of alcohols (or carbonyl compounds) can also be characterized based on the amount of chromium (VI) (in supported chromium catalysts). For example, the molar ratio (molar yield) of alcohols (or carbonyl compounds) based on the number of moles of chromium (VI) can be at least about 0.01 moles, at least about 0.02 moles, at least about 0.05 moles, at least about 0.1 moles, or at least about 0.25 moles (and at most 2 moles, at most about 1.8 moles, at most about 1.6 moles, at most about 1.4 moles, at most about 1.2 moles, or at most about 1 mole) of alcohol (or carbonyl compound) / moles of chromium (VI). 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 chromium (VI).

[0061] The processes disclosed herein for producing alcohols and / or carbonyl compounds typically produce a crude reaction mixture after hydrolysis containing residual hydrocarbon reactants (e.g., methane), the desired alcohol and / or carbonyl compound (e.g., methanol), 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 step (ii). 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).

[0062] Additionally or alternatively, the process 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, such as extraction, filtration, evaporation, distillation, or any combination thereof, may be used. Additionally or alternatively, the process disclosed herein may further include the step of isolating at least a portion (and in some cases, all) of the reduced chromium catalyst from the reaction products following step (ii), and as stated above, any suitable technique(s) may be used.

[0063] 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 chromium catalyst, thereby increasing the overall conversion of the hydrocarbon products after multiple contacts (or multiple passages through a reactor containing a supported chromium catalyst) of the hydrocarbon products with the supported chromium catalyst.

[0064] If desired, the process disclosed herein may further include (iii) a step of calcining at least a portion (and in some cases, all) of the reduced chromium catalyst to regenerate the supported chromium catalyst. Any suitable calcination conditions may be used, for example, subjecting the reduced chromium catalyst to an oxidizing atmosphere at any suitable peak temperature and time condition, such as at peak temperatures of about 300°C to about 1000°C, about 500°C to about 900°C, or about 550°C to about 870°C, for a period of about 1 minute to about 24 hours, about 1 hour to about 12 hours, or about 30 minutes to about 8 hours.

[0065] 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.

[0066] The illustrative and non-limiting examples of the processes disclosed herein follow the case where C1-C6 alkanes are hydrocarbon reactants and C1-C6 alcohols are alcohol products. In this case, the process for converting C1-C6 alkanes to C1-C6 alcohols may include (a) irradiating the C1-C6 alkanes and a supported chromium catalyst containing hexavalent chromium with a light beam of wavelength in the UV-Vis spectrum to reduce at least a portion of the supported chromium catalyst to form a reduced chromium catalyst, and (b) (using any suitable hydrolysate) hydrolyzing the reduced chromium catalyst to form a reaction product containing a C1-C6 alcohol.

[0067] C1-C6 alkanes may contain methane (or ethane, propane, butane, pentane, hexane, cyclopentane, or cyclohexane), and C1-C6 alcohols may contain methanol (or ethanol, propanol, butanol, pentanol, hexanol, cyclopentanol, or cyclohexanol). In some aspects, the reaction products may further contain organic acid compounds. For example, when the reactants contain methane, the reaction products may contain methanol, and in some aspects, may further contain formic acid. When the reactants are ethane or ethylene, the reaction products may contain methanol, ethanol, formic acid, and / or acetic acid. Furthermore, as discussed herein, the process for converting C1-C6 alkanes to C1-C6 alcohols may optionally further include (c) a step of calcining and reducing at least a portion (and in some cases, all) of the chromium catalyst to regenerate the supported chromium catalyst.

[0068] Another illustrative and non-limiting example of the process disclosed herein follows the case where methane is the hydrocarbon reactant and methanol is the alcohol product. In this case, the process for converting methane to methanol may include (a) irradiating methane and a supported chromium catalyst containing hexavalent chromium with a light beam of wavelength in the UV-Vis spectrum to reduce at least a portion of the supported chromium catalyst to form a reduced chromium catalyst (e.g., at least a portion of the chromium on the reduced chromium catalyst has at least one methoxy group bonding site), and (b) hydrolyzing the reduced chromium catalyst to form a reaction product containing methanol. The hydrolysis step may use any suitable hydrolysant.

[0069] In some respects, the reaction products containing methanol may further contain formic acid. As mentioned above, the process for converting methane to methanol may optionally further include (c) a step of calcining and reducing at least a portion (and in some cases, all) of the chromium catalyst to regenerate the supported chromium catalyst.

[0070] Chromium catalyst

[0071] Generally, these disclosed processes are applicable to the reduction of any hexavalent chromium catalyst and are not limited to the reduction of any particular type of supported chromium catalyst containing hexavalent oxidation states of chromium. Therefore, the supported chromium catalysts considered herein include those prepared by contacting a support with a chromium-containing compound (representative and non-limiting examples of chromium compounds include chromium(III) acetate, basic chromium(III) acetate, chromium(III) acetylacetone, Cr₂(SO₄)₃, Cr(NO₃)₃, and CrO₃) and calcining in an oxidizing atmosphere to form a supported chromium catalyst. In these respects, chromium may be impregnated during or before the calcination step, which may be performed at various temperatures and time periods and is generally selected to convert all or part of the chromium to hexavalent chromium. The irradiation methods disclosed herein may include reducing at least a portion of the hexavalent chromium material to a reduced oxidation state—for example, Cr(II) and / or Cr(III) and / or Cr(IV) and / or Cr(V) materials, any of which may be present on the reduced chromium catalyst.

[0072] Any suitable chromium-containing compound (or chromium precursor) can be used as the chromium component for the preparation of supported chromium catalysts. Illustrative and non-limiting examples of chromium (II) compounds may include chromium (II) acetate, chromium (II) chloride, chromium (II) bromide, chromium (II) iodide, chromium (II) sulfate, etc., and combinations thereof. Similarly, illustrative and non-limiting examples of chromium (III) compounds may include chromium (III) carboxylate, chromium (III) naphthenate, chromium (III) halide, chromium (III) sulfate, chromium (III) nitrate, chromium (III) diketoate, etc., and combinations thereof. In some aspects, chromium-containing compounds may include chromium (III) acetate, chromium (III) acetylacetonate, chromium (III) chloride, chromium (III) bromide, chromium (III) sulfate, chromium (III) nitrate, etc., and combinations thereof.

[0073] While not essential, it may be advantageous for the chromium-containing compound to be soluble in hydrocarbon solvents during the preparation of supported chromium catalysts. In this case, the chromium-containing compound may include tert-butyl chromate, diaromatic chromium (0) compounds, dicyclopentadienyl chromium (II), chromium acetylacetone (III), chromium acetate, etc., or any combination thereof. Similarly, but not essential, it may be advantageous for the chromium-containing compound to be soluble in water during the preparation of supported chromium catalysts. In this case, the chromium-containing compound may include chromium trioxide, chromium acetate, chromium nitrate, etc., or any combination thereof.

[0074] Other examples include sodium, potassium, or ammonium chromates or dichromates, which is unexpected because such alkali metal chromates are generally unacceptable for use in polymerization catalysts due to their low activity and the sintering of solid supports. Therefore, chromium precursors can include chromate compounds such as potassium chromate, sodium chromate, ammonium chromate, potassium dichromate, sodium dichromate, ammonium dichromate, etc., and any combinations thereof. Since chromium is already in the hexavalent state for these chromate compounds, heat treatment options other than conventional calcination in an oxidizing atmosphere can be used, such as low temperature (and even inert atmosphere) to dry or remove excess water / moisture before exposing the supported chromium catalyst to light irradiation.

[0075] Various solid supports can be used in supported chromium catalysts (and reduced chromium 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 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.

[0076] 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, wherein more than one metal combines with oxygen to form the 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, silicon dioxide-boron oxide, aluminum phosphate, aluminum phosphate, aluminum phosphate-silica, titanium dioxide-zirconia, etc., or combinations thereof. In some aspects, the solid support may comprise 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, 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, the entire contents of which are incorporated herein by reference.

[0077] The percentage of each oxide in a mixed oxide can vary depending on the individual oxide material. For example, the alumina content in silica-alumina (or silica-coated alumina) is typically from 5 wt% to 95 wt%. According to one aspect, the alumina content in silica-alumina (or silica-coated alumina) can be 50 wt% alumina, or 8 wt% to 30 wt% alumina. On the other hand, 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 65 wt% to 80 wt% alumina.

[0078] 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.

[0079] 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, the solid oxide 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.

[0080] Consistent with certain aspects of the invention, supported chromium catalysts and reduced chromium 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 for treating the solid oxide may be a Lewis or [other component] added to the solid oxide after treatment (compared to a solid oxide not treated with at least one electron-withdrawing anion). Any component of 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) used 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, fluorotitanate, phosphotungstic acid, tungstate, molybdate, etc., including mixtures and combinations thereof. Furthermore, other ionic or nonionic compounds used as sources of these electron-withdrawing anions may also be used.

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

[0082] Chemically treated solid oxides may generally contain electron-withdrawing anions from about 1% to about 30% by weight of the chemically treated solid oxide. In the specific aspects provided herein, chemically treated solid oxides may contain electron-withdrawing anions from about 1% to about 20% by weight, about 2% to about 20% by weight, about 3% to about 20% by weight, about 2% to about 15% by weight, about 3% to about 15% by weight, about 3% to about 12% by weight, or about 4% to about 10% by weight of the total weight of the chemically treated solid oxide.

[0083] On one hand, the chemically treated solid oxide may include 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 acid-coated alumina, and any mixture or combination thereof.

[0084] On the other hand, the chemically treated solid oxides used in supported chromium catalysts and reduced chromium catalysts, as well as the processes described herein, may be or may include 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-zirconia, fluorinated silica-coated alumina, sulfated silica-coated alumina, and combinations thereof. Further information regarding chemically treated solid oxides can be found, for example, in U.S. Patent Nos. 7,294,599, 7,601,665, 7,884,163, 8,309,485, 8,623,973, and 8,703,886, which are incorporated herein by reference in their entirety.

[0085] Representative examples of supported chromium catalysts and reducing chromium catalysts (where the solid oxide is the support) include, but are not limited to, chromium / silica, chromium / silica-titanium dioxide, chromium / silica-titanium dioxide-magnesium oxide, chromium / silica-alumina, chromium / silica-coated alumina, chromium / aluminum phosphate, chromium / alumina, chromium / alumina borate, or any combination thereof. In one aspect, for example, supported chromium catalysts and reducing chromium catalysts may comprise chromium / silica, while in another aspect, supported chromium catalysts and reducing chromium catalysts may comprise chromium / silica-titanium dioxide, and in yet another aspect, supported chromium catalysts and reducing chromium catalysts may comprise chromium / silica-alumina and / or chromium / silica-coated alumina. In the case where the supported chromium catalyst and the reduced chromium catalyst contain chromium / silica-titanium dioxide, any suitable amount of titanium may be present, including about 0.1 to about 20 wt%, about 0.5 to about 15 wt%, about 1 wt% to about 10 wt%, or about 1 wt% to about 6 wt% of titanium based on the total weight of the supported chromium catalyst and the reduced chromium catalyst.

[0086] Representative examples of supported chromium catalysts and reduced chromium catalysts (wherein a chemically treated solid oxide serves as the support) include, but are not limited to, chromium / sulfated alumina, chromium / fluorinated alumina, chromium / fluorinated silica-alumina, chromium / fluorinated silica-coated alumina, and combinations thereof.

[0087] Consistent with certain aspects of the invention, supported chromium catalysts and reduced chromium catalysts may comprise zeolites as supports, i.e., chromium-supported zeolites. Any suitable zeolite can be used, for example, macroporous zeolites and mesoporous zeolites. Macroporous zeolites typically have an average pore size in the range of about 7 angstroms to about 12 angstroms, and non-limiting examples of macroporous zeolites include L-zeolites, Y-zeolites, mordenite, ω-zeolites, β-zeolites, etc. Mesoporous zeolites typically have an average pore size in the range of about 5 angstroms to about 7 angstroms. Combinations of zeolite supports can be used.

[0088] Other representative examples of zeolites that can be used in supported chromium catalysts and reducing chromium 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.

[0089] In supported chromium catalysts and reduced chromium 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 chromium catalyst and reduced chromium 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 chromium catalysts and reduced chromium catalysts may contain zeolite and about 3% to about 35% by weight of binder; alternatively, about 5% to about 30% by weight of binder; or alternatively, about 10% to about 30% by weight of binder. These weight percentages are based on the total weight of the supported chromium catalyst or reduced chromium catalyst.

[0090] It is worth noting that chromium polymerization catalysts typically require a chromium loading within a fairly narrow range, usually from 0.5 to 2% by weight, because higher amounts can lead to polymer degradation, while lower amounts result in low activity. However, the present invention does not have such limitations. Therefore, the amount of chromium in supported chromium catalysts and reduced chromium catalysts can typically be from about 0.01 to about 50% by weight; alternatively, from about 0.01 to about 20% by weight; alternatively, from about 0.01 to about 10% by weight; alternatively, from about 0.05 to about 15% by weight; alternatively, from about 0.1 to about 15% by weight; alternatively, from about 0.2 to about 10% by weight; alternatively, from about 0.1 to about 5% by weight; alternatively, from about 0.5 to about 30% by weight; or alternatively, from about 0.5 to about 2.5% by weight. These weight percentages are based on the amount of chromium relative to the total weight of the supported chromium catalyst or the reduced chromium catalyst. While not wishing to be bound by theory, it is believed, and the following examples appear to suggest, that lower chromium loadings (e.g., 1 wt% and below) can result in higher selectivity for specific alcohol compounds (or carbonyl compounds), while higher chromium loadings (e.g., 5-15 wt% and above) can result in higher alcohol and / or carbonyl yields per gram of catalyst.

[0091] Similarly, the amount of chromium with an average oxidation state of +5 or lower in the reduced chromium catalyst is not particularly limited and can fall within the same range. Therefore, the reduced chromium catalyst may contain about 0.01 to about 50 wt%, about 0.01 to about 20 wt%, about 0.01 to about 10 wt%, about 0.05 to about 15 wt%, about 0.1 to about 15 wt%, about 0.2 to about 10 wt%, about 0.1 to about 5 wt%, about 0.5 to about 30 wt%, or about 0.5 to about 2.5 wt% of chromium with an average oxidation state of +5 or lower, based on the total weight of the reduced chromium catalyst.

[0092] Generally, at least about 10 wt% of chromium in supported chromium catalysts is present in the hexavalent oxidation state prior to the reduction step, and more often as chromium (VI) in at least about 20 wt%. In further aspects, at least about 40 wt%, at least about 60 wt%, at least about 80 wt%, at least about 90 wt%, or at least about 95 wt% of chromium in supported chromium catalysts may be present in the +6 oxidation state. These weight percentages are based on the total amount of chromium. Conventional chromium (VI) catalysts often exhibit an orange, yellow, or brownish hue, indicating the presence of chromium (VI).

[0093] Conversely, in reduced chromium catalysts, less than or equal to about 50% by weight, and more often less than or equal to about 40% by weight, chromium is typically present in the +6 (VI) oxidation state. Further, in reduced chromium catalysts, less than or equal to about 30% by weight or less than or equal to about 15% by weight, chromium may be present in the +6 oxidation state. The minimum amount of chromium (VI) can often be 0% by weight (an unmeasurable amount), at least about 0.5% by weight, at least about 1% by weight, at least about 2% by weight, or at least about 5% by weight. These weight percentages are based on the total amount of chromium. Reduced chromium catalysts are often green, blue, gray, or black.

[0094] Therefore, irradiation of a supported chromium catalyst in the presence of hydrocarbon reactants typically results in the reduction or conversion of at least about 10 wt%, at least about 20 wt%, at least about 40 wt%, at least about 60 wt%, at least about 80 wt%, or at least about 90 wt% of the supported chromium catalyst to form a reduced chromium catalyst.

[0095] Alternatively, the chromium in the reduced chromium catalyst is characterized by an average valence of less than or equal to about 5.25. More commonly, the average valence of chromium in the reduced chromium catalyst is less than or equal to about 5; alternatively, the average valence is less than or equal to about 4.75; alternatively, the average valence is less than or equal to about 4.5; alternatively, the average valence is less than or equal to about 4.25; or alternatively, the average valence is less than or equal to about 4.

[0096] It is important to note that chromium polymerization catalysts require highly porosity supports to allow for catalyst fragmentation and subsequent discharge of polymer chains, which are hundreds of times longer than the pore size in the catalyst. However, such limitations are not present in this invention. Therefore, the total pore volume of the supported chromium catalyst and the reduced chromium catalyst is not particularly limited. For example, the total pore volume of the supported chromium catalyst and the reduced chromium catalyst can range from about 0.1 to about 5 mL / g, about 0.15 to about 5 mL / g, about 0.1 to about 3 mL / g, about 0.5 to about 2.5 mL / g, or about 0.15 to about 2 mL / g. Similarly, the surface area of ​​the supported chromium catalyst and the reduced chromium catalyst is not limited to any particular range. However, generally, the BET surface area of ​​the supported chromium catalyst and the reduced chromium catalyst can range from about 50 to about 2000 m². 2 / g, approximately 50 to approximately 700m 2 / g, approximately 50 to approximately 400m 2 / g, approximately 100 to approximately 1200m 2 / g, approximately 150 to approximately 525m 2 / g or approximately 200 to approximately 400m 2 Within the range of / g.

[0097] Supported chromium catalysts and reduced chromium catalysts can have any suitable shape or form, and this can depend on the type of process 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, supported chromium catalyst particles can be prepared using various methods, including, for example, extrusion, spray drying, granulation, marumerizing, spheroidization, agglomeration, oil drop, etc., and combinations thereof.

[0098] In some respects, supported chromium catalysts and reduced chromium catalysts have relatively small particle sizes, wherein the representative range of the average (d50) particle size of supported chromium catalysts and reduced chromium catalysts may include about 10 to about 500 micrometers, about 25 to about 250 micrometers, about 20 to about 100 micrometers, about 40 to about 160 micrometers, or about 40 to about 120 micrometers.

[0099] In other respects, the supported chromium catalyst and the reduced chromium catalyst can be in the form of pellets or beads, with an average size ranging from about 1 / 16 inch to about 1 / 2 inch, or from about 1 / 8 inch to about 1 / 4 inch. As mentioned above, the size of the particles of the supported chromium catalyst and / or the reduced chromium catalyst can be varied to suit specific processes for converting hydrocarbon reactants into alcohol compounds and / or carbonyl compounds.

[0100] Examples 1-67

[0101] 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. After reading this description, those skilled in the art will conceive of various other aspects, modifications, and equivalents without departing from the spirit of the invention or the scope of the appended claims.

[0102] Catalyst A is a Cr / silica catalyst containing 1% wt% Cr, with a BET surface area of ​​500 m². 2 / g, with a pore volume of 1.6 mL / g and an average particle size of 100 μm. Before use, the catalyst was calcined in air at 650 °C for 3 hours to form a chromium(VI) / silica catalyst containing 0.97 wt% hexavalent Cr.

[0103] Catalyst B is a Cr / silica-titanium dioxide catalyst containing 1 wt% Cr and 4.2 wt% TiO2, with a BET surface area of ​​500 m². 2 / g, pore volume is 2.5mL / g, and average particle size is 130μm. Before use, the catalyst is calcined in air at 850-870℃ for 3 hours to form a chromium(VI) / silica-titanium dioxide catalyst containing 0.95 wt% hexavalent Cr.

[0104] Catalyst C is a Cr / silica containing 10 wt% Cr, and the BET surface area of ​​this silica is 500 m². 2 / g, with a pore volume of 1.6 mL / g and an average particle size of 100 μm. Before use, the catalyst was calcined in air at 400 °C for 3 hours to form a chromium(VI) / silica catalyst containing 5 wt% hexavalent Cr.

[0105] Catalyst D is a Cr / silica-titanium dioxide mixture containing 0.8 wt% Cr and 7.5 wt% TiO2, with a BET surface area of ​​550 m². 2 / g, with a pore volume of 2.5 mL / g and an average particle size of 130 μm. Before use, the catalyst was calcined in air at 850 °C for 3 hours to form a chromium(VI) / silica-titanium dioxide catalyst containing 0.8 wt% hexavalent Cr.

[0106] Catalyst E is a Cr / silica mixture containing 0.28 wt% Cr, with a BET surface area of ​​500 m². 2 / g, with a pore volume of 1.6 mL / g and an average particle size of 100 μm. Before use, the catalyst was calcined in air at 750 °C for 3 hours to form a chromium(VI) / silica catalyst containing 0.28 wt% hexavalent Cr.

[0107] Catalyst F is a Cr / silica containing 5% by weight Cr, with a BET surface area of ​​500 m². 2 / g, with a pore volume of 1.6 mL / g and an average particle size of 100 μm. Before use, the catalyst was calcined in air at 500 °C for 3 hours to form a chromium(VI) / silica catalyst containing 4 wt% hexavalent Cr.

[0108] Catalysts G1-G2 were prepared by dissolving CrO3 in water and then impregnating the resulting solution onto a BET surface with a surface area of ​​300 m². 2The catalyst is prepared by calcining the alumina (boehmite) with a pore volume of 1.3 mL / g to a value of 5 wt% Cr. After drying and before use, the catalyst is calcined in air at 500 °C (G1) or 600 °C (G2) for 3 hours to form a chromium (VI) / alumina catalyst containing 4.5 wt% hexavalent Cr.

[0109] Catalysts H1-H2 were prepared by dissolving CrO3 in water, and then impregnating the resulting solution onto silica-coated alumina (40 wt% silica, BET surface area 450 m²). 2 / g, with a pore volume of 1.4 mL / g and an average particle size of 25 μm, up to 5 wt% Cr. After drying and before use, the catalyst is calcined in air at 500 °C (H1) or 600 °C (H2) for 3 hours to form a chromium (VI) / silica-coated alumina catalyst.

[0110] Catalyst J was prepared by dissolving K₂Cr₂O₇ in water, and then impregnating the resulting solution onto silica (with a BET surface area of ​​500 m²). 2 / g, with a pore volume of 1.6 mL / g and an average particle size of 100 μm) up to or equal to 5 wt% Cr. After drying and before use, the catalyst was calcined in air at 500 °C for 3 hours to form a chromium (VI) / silica catalyst containing 5 wt% hexavalent Cr.

[0111] Catalyst K was prepared by dissolving K₂Cr₂O₇ in water, and then impregnating the resulting solution onto silica (with a BET surface area of ​​500 m²). 2 / g, with a pore volume of 1.6 mL / g and an average particle size of 100 μm) up to or equal to 10 wt% Cr. After removing excess water, the catalyst was heat-treated in air at 100 °C for 3 hours to form a chromium (VI) / silica catalyst containing 10 wt% hexavalent Cr.

[0112] Catalyst L was prepared by dissolving K₂Cr₂O₇ in water, and then impregnating the resulting solution onto silica (BET surface area of ​​500 m²). 2 / g, with a pore volume of 1.6 mL / g and an average particle size of 100 μm) up to or equal to 10 wt% Cr. After removing excess water, the catalyst was heat-treated in air at 200 °C for 3 hours to form a chromium (VI) / silica catalyst containing 10 wt% hexavalent Cr.

[0113] 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.

[0114] Table I summarizes the reactions of Examples 1-67, in which the supported chromium catalyst was first loaded into an airtight glass container at 25°C (or a different temperature if specified), 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 chromium catalyst and hydrocarbon reactants was uniformly exposed to light. The sample exposed to sunlight was removed and placed in direct sunlight. 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 at approximately 3-inch intervals in a plane approximately 2 inches from the bottle. The reduction of the supported chromium catalyst was monitored by the presence of color changes. Each supported chromium catalyst containing hexavalent chromium oxide has an orange color. When the supported chromium catalyst is exposed to light in the presence of hydrocarbon reactants, the orange color darkens significantly and usually appears green or blue, indicating the reduction of the starting material of the supported chromium catalyst and the formation of a reduced chromium catalyst.

[0115] After the required exposure time, the reduced chromium catalyst is mixed with a hydrolysant to cleave the hydrocarbon-containing ligands from the reduced chromium 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.).

[0116] Table I summarizes the results of Examples 1-67 and lists the specific supported chromium catalyst and amounts, hydrocarbon reactants and amounts, light treatment and resulting color, hydrolysate and amounts, acid / Cr (mol), alcohol / Cr (mol), GC-MS / Cr (mol), total / Cr (mol), 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 hydrolysate 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%.

[0117] Carboxylic acid products (and acid / Cr molar ratio) are determined by first neutralizing the product acids with sodium hydroxide solution to make them ionic. A small sample is 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 is used. This assay is particularly sensitive to linear carboxylic acids from C1 to C6, glutarate, and glycolate ions. Results are reported in milligrams of carboxylate per milliliter of solution, which are then converted to moles.

[0118] Lower alcohol products (and alcohol / Cr, in moles) were determined using an Agilent 6890 gas chromatograph with a flame ionization detector (FID) program. It utilized a Restek Stapilwax column (P / N 10658) specifically designed and gated for the separation and detection of light alcohols. The program was gated for acetone, methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, tert-butanol, 2-butanol, 2-butoxyethanol, acetonitrile, and tetrahydrofuran.

[0119] Additional reaction products (and GC-MS / Cr, in moles) were determined using another GC-MS procedure described below. Gas chromatography analysis 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, which was electronically controlled at 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 a rate of 20°C / min, and then maintained at 250°C for 19 min. Spectral values ​​were assigned via mass correlation using an Agilent 5977B mass spectrometer connected to the GC unit with electron ionization at 70 eV. The nominal mass range for scanning is 14-400 m / z, and the scan time is 0.5 seconds. The nominal detector voltage used is 1200 V. For calibration purposes, FID and MS detectors are sometimes used sequentially on the same sample or reference sample.

[0120] 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 this was subtracted from the total / Cr (in moles) 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.

[0121] Referring now to the data in Table I, Examples 1-10 demonstrate the unexpected conversion of methane to methanol at ambient temperature using various supported chromium catalysts, irradiation treatments, and hydrolysants. Note that Examples 1-4 used only one analytical technique and showed product streams of 100% methanol, while Examples 6-10 used all three analytical techniques and resulted in product streams containing 66-97 mol% methanol, with the remainder being formic acid.

[0122] Similar successful results were observed for the conversion of ethane to ethanol, isobutane to tert-butanol / isobutanol, n-pentane to 2-pentanol / 1-pentanol, cyclopentane to cyclopentanol, n-hexane to various hexanols, cyclohexane to cyclohexanol, and toluene to benzaldehyde / benzyl alcohol. When the hydrocarbon reactant was isopentane, the oxygen-containing reaction products contained various alcohols and carbonyl products, while when the reactant was dichloromethane, no conversion to alcohols or carbonyl groups was observed.

[0123] While these examples are not focused on maximizing chromium conversion (or the yield of any particular alcohol or carbonyl compound), the total / Cr molar values ​​in Table I illustrate that fairly high chromium conversion and alcohol / carbonyl yields can be achieved, depending, of course, on the reducing agent, catalyst (and chromium loading), irradiation conditions, and other factors. For example, catalysts with high chromium loadings of 5-10 wt%, such as catalysts C and FL, often have relatively low total / Cr molar yields, but when multiplied by a factor of 5-10, these high-chromium catalysts produce exceptionally high amounts of alcohols and / or carbonyl products compared to catalysts with 1 wt% chromium.

[0124] When the reactants are olefins, GC-MS analysis was found essential for identifying the diol products; therefore, examples not using this technique may give an incomplete representation of oxygen-containing product mixtures. Generally, examples using ethylene as a reducing agent yield reaction products containing ethylene glycol and methanol, ethanol, formic acid, and / or acetic acid after hydrolysis (even when used at -78°C to prevent polymerization). Lower reaction temperatures appear to favor selectivity for diols. Examples using 1-pentene as a reducing agent yield reaction products containing pentanediol (e.g., 1,2-pentanediol) and various acids and other alcohols after hydrolysis (even without light exposure, see Example 44). Examples using 1-hexene or 2-hexene as a reducing agent yield reaction products containing hexanediol (e.g., 1,2-hexanediol and / or 3,4-hexanediol) and various acids and other alcohols after hydrolysis (even without light exposure, see Example 55). Table I shows that these olefins are highly reactive, and therefore the reaction products typically contain mixtures of monohydric alcohols, diols, aldehydes, ketones, and / or carboxylic acids.

[0125]

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142] Examples 68-74

[0143] Examples 68-74 were performed to determine the degree of reduction of hexavalent chromium and the average valence after reduction in representative supported chromium catalysts. Table II summarizes the results. Example 74 was a chromium / silica-titanium dioxide catalyst containing approximately 0.8 wt% chromium and 7 wt% titanium dioxide, with a BET surface area of ​​530 m² / g, a pore volume of 2.6 mL / g, and an average particle size of 130 μm, which was calcined in dry air at 850°C for 3 hours to convert chromium to the hexavalent oxidation state (orange). This converted more than 86 wt% of chromium to the hexavalent state. For Examples 68-69, approximately 2 g of the catalyst sample from Example 74 was loaded into glass reaction vessels, and 0.5 mL of liquid isopentane was added to each vessel. For Examples 70-71, approximately 1.5 atm of gaseous ethane was loaded into glass vials. The bottle was then placed in a light-shielding box under blue fluorescence (approximately twice the intensity predicted by sunlight), and continuously rotated to expose all catalyst to light for 24 hours. The final catalyst color is shown in Table II. Approximately 20 mL of 2M H₂SO₄ solution was then introduced into the bottle along with the catalyst. Five drops of ferroin Fe(+3) indicator were added. This typically turned blue-green, indicating the presence of Fe(III) ions. The solution was then titrated to the ferroin endpoint (red) using ferrous ammonium sulfate solution, which had been pre-calibrated by reacting with a standardized 0.1M sodium dichromate solution. When the solution turned red, an endpoint signal was given, and the titrant volume was recorded to calculate the catalyst's oxidizing power, expressed as % Cr(VI) by weight and the reduction percentage, i.e., the percentage of original Cr(VI) oxidizing power removed by the reduction treatment. The average valence was also calculated by multiplying the reduction percentage by +3 and subtracting this number from +6.

[0144] Of course, this treatment only yields an average oxidation state. Note that although Table II lists the oxidizing power as a percentage of Cr(VI) by weight, virtually all chromium can exist in lower valence states, such as Cr(IV) or Cr(V). Therefore, the Cr(VI) values ​​in Table II only list the maximum amount of Cr(VI) that may be present. More likely, the reduced chromium catalyst has a combination of several valence states that produce the measured oxidizing power. Note that some reduced chromium, especially those catalysts reduced with CO, may be in the divalent state, which will not be detected in this test, which stops at the trivalent state.

[0145] Example 74 shows that the air-calcined chromium catalyst contains chromium that is substantially predominantly in the form of Cr(VI) (0.69 / 0.80 = 86 wt%), and it is this amount of Cr(VI) that is reduced during light treatment. Therefore, this amount of Cr(VI), with an average oxidation state of +6, is used as a starting point and as a reference for comparison with the reduced catalyst. Examples 68-69 are reduced chromium catalysts with an average oxidation state of approximately +3.3, containing no more than 0.06 wt% Cr(VI) and less than 10 wt% of initial hexavalent chromium still in the hexavalent oxidation state. Examples 70-71 are reduced chromium catalysts with an average oxidation state of approximately +4.1, containing no more than 0.26 wt% Cr(VI) and less than 40 wt% of hexavalent chromium. For Examples 72-73, the supported chromium catalyst was reduced in CO using blue light or at high temperature, resulting in no measured oxidation capacity (0 wt% Cr(VI) in the table). Therefore, the average valence must not exceed +3. However, it is known that the supported chromium catalyst for CO reduction by conventional means (Example 73) has a valence of Cr(II) after reduction that is largely undetectable in this test. Therefore, Examples 72 and 73 are listed as less than or equal to +3. It is worth noting that this test cannot distinguish between Cr(II) and Cr(III) substances, but no measurable amount of hexavalent chromium was found in Examples 72-73.

[0146] Table II. Examples 68-74

[0147]

[0148] The invention has been described above with reference to various aspects and specific embodiments. Based on the above detailed description, many variations will occur to those skilled in the art. All such apparent 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 "substantially composed of" or "composed of"):

[0149] Aspect 1. A process for converting hydrocarbon reactants into alcohol compounds and / or carbonyl compounds, said process comprising:

[0150] (i) Irradiating the hydrocarbon reactants and a supported chromium catalyst containing hexavalent chromium with a light beam of wavelength in the UV-Vis spectrum to reduce at least a portion of the supported chromium catalyst to form a reduced chromium catalyst (e.g., at least a portion of the chromium on the reduced chromium catalyst has at least one bonding site with an alkyl group (-O-alkyl group)); and

[0151] (ii) Hydrolyzing the reduced chromium catalyst to form a reaction product comprising the alcohol compound and / or the carbonyl compound.

[0152] Aspect 2. The process as defined in Aspect 1, wherein the hydrocarbon reactants comprise saturated or unsaturated, linear or branched aliphatic hydrocarbons, and include combinations thereof.

[0153] Aspect 3. The process as defined in Aspect 1, wherein the hydrocarbon reactants comprise aromatic compounds (e.g., benzene, toluene, xylene and their substituted variants, and combinations thereof).

[0154] Aspect 4. The process as defined in Aspect 1, wherein the hydrocarbon reactants comprise linear alkane compounds, branched alkane compounds, cyclic alkane compounds, or combinations thereof.

[0155] Aspect 5. The process as defined in Aspect 1, wherein the hydrocarbon reactants comprise linear olefin compounds (e.g., α-olefins), branched olefin compounds, cyclic olefin compounds, or combinations thereof.

[0156] Aspect 6. The process as defined in Aspect 1, 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; and / or the hydrocarbon reactants comprise any suitable number of carbon atoms of an olefin compound or any number of carbon atoms of an olefin compound disclosed herein, such as C2 to C8 alkane compounds. 36 Olefin compounds, C2 to C 18 Olefin compounds, C2 to C 12 An olefin compound or a C2 to C8 olefin compound; and / or the hydrocarbon reactant comprises an aromatic compound with any suitable number of carbons or any aromatic compound with any number of carbons disclosed herein, such as C6 to C8. 36 Aromatic compounds, C6 to C 18 Aromatic compounds, C6 to C 12 Aromatic compounds, or C6 to C8 aromatic compounds.

[0157] Aspect 7. The process as defined in Aspect 1, wherein the hydrocarbon reactants comprise methane, ethane, propane, butane (e.g., n-butane or isobutane), pentane (e.g., n-pentane, neopentane or isopentane), hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, or any combination thereof; or 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.

[0158] Aspect 8. The process as defined in Aspect 1, wherein the hydrocarbon reactants comprise ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, cyclopentene, cyclohexene, or any combination thereof.

[0159] Aspect 9. The process as defined in Aspect 1, wherein the hydrocarbon reactants comprise benzene, toluene, ethylbenzene, xylene, mesitylene, or any combination thereof.

[0160] Aspect 10. The process as defined in Aspect 1, wherein the hydrocarbon reactant comprises a Cn hydrocarbon compound and the alcohol compound comprises C n An alcohol compound, wherein the carbonyl compound comprises C n Carbonyl compounds.

[0161] Aspect 11. The process as defined in aspect 10, 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.

[0162] Aspect 12. The process as defined in Aspect 1, wherein the hydrocarbon reactant comprises methane and the alcohol compound comprises methanol.

[0163] Aspect 13. The process as defined in any of the preceding aspects, wherein the supported chromium catalyst and the reduced chromium catalyst contain any suitable amount or within any range of chromium disclosed herein, such as about 0.01 to about 50 wt%, about 0.01 to about 10 wt%, about 0.05 to about 15 wt%, about 0.1 to about 15 wt%, about 0.2 to about 10 wt%, about 0.1 to about 5 wt%, about 0.5 to about 30 wt%, or about 0.5 to about 2.5 wt% of chromium.

[0164] Aspect 14. The process as defined in any of the preceding aspects, wherein the reduced chromium catalyst comprises any suitable amount or any range of amounts of chromium with an average oxidation state of +5 or lower, for example, about 0.01 to about 50 wt%, about 0.01 to about 10 wt%, about 0.05 to about 15 wt%, about 0.1 to about 15 wt%, about 0.2 to about 10 wt%, about 0.1 to about 5 wt%, about 0.5 to about 30 wt%, or about 0.5 to about 2.5 wt% of chromium with an average oxidation state of +5 or lower.

[0165] Aspect 15. The process as defined in any of the preceding aspects, wherein the amount of hexavalent chromium in the supported chromium catalyst is at least about 10% by weight, at least about 20% by weight, at least about 40% by weight, at least about 60% by weight, at least about 80% by weight, or at least about 90% by weight, based on the total amount of chromium on the supported chromium catalyst, and / or the amount of hexavalent chromium in the reduced chromium catalyst is less than or equal to about 50% by weight, less than or equal to about 40% by weight, less than or equal to about 30% by weight, or less than or equal to about 15% by weight, based on the total amount of chromium on the reduced chromium catalyst (from 0% by weight, from about 0.5% by weight, from about 1% by weight, or from about 2% by weight).

[0166] Aspect 16. The process as defined in any of the preceding aspects, wherein at least about 10 wt%, at least about 20 wt%, at least about 40 wt%, at least about 60 wt%, at least about 80 wt%, or at least about 90 wt% of the supported chromium catalyst is reduced to form the reduced chromium catalyst based on the total amount of the supported chromium catalyst.

[0167] Aspect 17. The process as defined in any of the preceding aspects, wherein the chromium in the reduced chromium catalyst has an average valence of less than or equal to about 5.25, less than or equal to about 5, less than or equal to about 4.75, less than or equal to about 4.5, less than or equal to about 4.25, or less than or equal to about 4.

[0168] Aspect 18. The process as defined in any one of Aspects 1-17, wherein the supported chromium catalyst and the reduced chromium 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, alumina-borate, silica-boron oxide, aluminum phosphate-silica, titanium dioxide-zirconium oxide, or any combination thereof.

[0169] Aspect 19. The process as defined in any one of Aspects 1-17, wherein the supported chromium catalyst and the reduced chromium 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, aluminum phosphate-silica, alumina, alumina borate, or any combination thereof.

[0170] Aspect 20. The process as defined in any one of Aspects 1-17, wherein the supported chromium catalyst and the reduced chromium catalyst comprise chemically treated solid oxides, the chemically treated solid oxides including solid oxides treated with electron-withdrawing anions (e.g., as in Aspects 18 or 19, such as silica, alumina, silica-alumina, silica-titanium dioxide, silica-zirconium oxide, silica-yttrium oxide, aluminum phosphate, zirconium oxide, titanium dioxide, thorium oxide, or strontium oxide).

[0171] Aspect 21. The process as defined in Aspect 20, wherein the electron-withdrawing anion comprises sulfate, hydrogen sulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, trifluoromethanesulfonate, fluorozirconate, fluorotitanate, phosphotungstate, tungstate, molybdate, or any combination thereof.

[0172] Aspect 22. The process as defined in aspect 20 or 21, wherein the chemically treated solid oxide contains about 1 to about 30% by weight, about 2 to about 20% by weight, about 2 to about 15% by weight, about 3 to about 12% by weight, or 4 to 10% by weight of the total weight of the chemically treated solid oxide.

[0173] Aspect 23. The process as defined in any one of Aspects 1-17, wherein the supported chromium catalyst and the reduced chromium catalyst comprise chemically treated 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 acid-coated alumina, or any combination thereof.

[0174] Aspect 24. The process as defined in any one of Aspects 1-17, wherein the supported chromium catalyst and the reduced chromium catalyst comprise chromium / silica, chromium / silica-titanium dioxide, chromium / silica-titanium dioxide-magnesium oxide, chromium / silica-alumina, chromium / silica-coated alumina, chromium / aluminum phosphate, chromium / alumina, chromium / alumina borate, or any combination thereof.

[0175] Aspect 25. The process as defined in any one of Aspects 1-17, wherein the supported chromium catalyst and the reduced chromium catalyst comprise chromium / silica-titanium dioxide, and the supported chromium catalyst and the reduced chromium catalyst comprise any suitable amount or any range of titanium disclosed herein, said amount being, for example, about 0.1 to about 20 wt%, about 0.5 to about 15 wt%, about 1 to about 10 wt%, or about 1 to about 6 wt% based on the weight of the supported chromium catalyst or the reduced chromium catalyst.

[0176] Aspect 26. The process as defined in any one of Aspects 1-17, wherein the supported chromium catalyst and the reduced chromium catalyst comprise chromium / sulfated alumina, chromium / fluorinated alumina, chromium / fluorinated silica-alumina, chromium / fluorinated silica-coated alumina, or any combination thereof.

[0177] Aspect 27. The process as defined in any one of Aspects 1-17, wherein the supported chromium catalyst and the reduced chromium catalyst comprise zeolite.

[0178] Aspect 28. The process as defined in aspect 27, wherein the supported chromium catalyst and the reduced chromium catalyst comprise mesoporous zeolite, macroporous zeolite, or a combination thereof.

[0179] Aspect 29. The process as defined in aspect 27, 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.

[0180] Aspect 30. The process as defined in aspect 27, wherein the supported chromium catalyst and the reduced chromium catalyst comprise L-zeolite, γ-zeolite, mordenite, ω-zeolite and / or β-zeolite.

[0181] Aspect 31. The process as defined in any one of Aspects 27-30, wherein the supported chromium catalyst and the reduced chromium catalyst comprise the zeolite and any suitable amount or within any range disclosed herein of a binder, for example, about 3% to about 35% by weight, or about 5% to about 30% by weight, of the supported chromium catalyst and / or the reduced chromium catalyst.

[0182] Aspect 32. The process as defined in any of the preceding aspects, wherein the supported chromium catalyst and the reduced chromium catalyst have any suitable total pore volume or a total pore volume within any range disclosed herein, the total pore volume being, for example, about 0.1 to about 5 mL / g, about 0.15 to about 5 mL / g, about 0.1 to about 3 mL / g, or about 0.15 to about 2 mL / g.

[0183] Aspect 33. The process as defined in any of the preceding aspects, wherein the supported chromium catalyst and the reduced chromium catalyst have any suitable BET surface area or a BET surface area within any range disclosed herein, wherein the BET surface area is, for example, about 50 to about 2000 m². 2 / g, approximately 50 to approximately 700m 2 / g, approximately 50 to approximately 400m 2 / g, approximately 100 to approximately 1200m 2 / g, or about 150 to about 525m 2 / g.

[0184] Aspect 34. The process as defined in any of the preceding aspects, wherein the supported chromium catalyst and the reduced chromium catalyst are of any suitable shape or form or any shape or form disclosed herein, such as powder, round or spherical (e.g., spheres), elliptical, pellet, bead, cylinder, particle (e.g., regular and / or irregular), trefoil, tetralobite, ring, wheel-shaped, monolithic, or any combination thereof.

[0185] Aspect 35. The process as defined in any of Aspects 1-34, wherein the supported chromium catalyst and the reduced chromium catalyst have any suitable average (d50) particle size or an average (d50) particle size within any range disclosed herein, said average (d50) particle size being, for example, about 10 to about 500 micrometers, about 25 to about 250 micrometers, or about 20 to about 100 micrometers.

[0186] Aspect 36. The process defined in any one of Aspects 1-34, wherein the supported chromium catalyst and the reduced chromium catalyst comprise pellets or beads having any suitable average size or an average size within any range disclosed herein, the average size being, for example, about 1 / 16 inch to about 1 / 2 inch, or about 1 / 8 inch to about 1 / 4 inch.

[0187] Aspect 37. The process as defined in any of Aspects 1-36, wherein the wavelength includes a single wavelength or wavelength range in the visible spectrum (380 nm to 780 nm).

[0188] Aspect 38. The process as defined in any of Aspects 1-36, wherein the wavelength includes a single wavelength or wavelength range in the range of 200 nm to 750 nm.

[0189] Aspect 39. The process defined according to any one of Aspects 1-36, wherein the wavelength includes a single wavelength or wavelength range in the range of 300 nm to 750 nm, 350 nm to 650 nm, 300 nm to 500 nm, or 300 nm to 400 nm.

[0190] Aspect 40. The process as defined in any of Aspects 1-36, wherein the wavelength includes a single wavelength or wavelength range below 600 nm, below 525 nm, or below 500 nm.

[0191] Aspect 41. The process as defined in any one of Aspects 1-40, wherein the wavelength is a single wavelength.

[0192] Aspect 42. The process as defined in any one of Aspects 1-40, 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.

[0193] Aspect 43. The process as defined in any of the preceding aspects, wherein the light beam has any suitable intensity or within any range disclosed herein, said intensity being, for example, at least about 500 lumens, at least about 1000 lumens, at least about 2000 lumens, at least about 5000 lumens, at least about 10,000 lumens, or at least about 20,000 lumens.

[0194] Aspect 44. The process as defined in any of the preceding aspects, wherein the beam has any suitable power or any power disclosed herein, such as at least about 50 watts, at least about 100 watts, at least about 200 watts, at least about 500 watts, at least about 1,000 watts, or at least about 2,000 watts.

[0195] Aspect 45. The process as defined in any of the preceding aspects, wherein the supported chromium catalyst is irradiated with any suitable illuminance or any illuminance disclosed herein, such as at least about 100 lux, at least about 500 lux, at least about 1000 lux, at least about 2000 lux, at least about 5000 lux, at least about 10,000 lux, at least about 20,000 lux, or at least about 100,000 lux.

[0196] Aspect 46. The process as defined in any of the preceding aspects, wherein the irradiation step is performed at any suitable temperature or any temperature disclosed herein, such as less than about 200°C, less than about 100°C, less than about 40°C, about -100°C to about 100°C, about 0°C to about 100°C, or about 10°C to about 40°C.

[0197] Aspect 47. The process as defined in any of the preceding aspects, wherein the irradiation step is performed for any suitable exposure time or any exposure time disclosed herein, such as about 15 seconds to about 48 hours, about 1 minute to about 6 hours, about 1 minute to about 15 minutes, or about 1 hour to about 8 hours.

[0198] Aspect 48. The process as defined in any of the preceding aspects, wherein the molar ratio of the hydrocarbon reactant to chromium (of the supported chromium catalyst) is in any suitable range or in any range disclosed herein, for example, at least about 0.25:1, at least about 0.5:1, at least about 1:1, at least about 10:1, at least about 100:1, at least about 1000:1 or at least about 10,000:1.

[0199] Aspect 49. The process as defined in any one of Aspects 1-48, wherein the hydrocarbon reactants are in the gas phase during the irradiation step.

[0200] Aspect 50. The process as defined in any one of Aspects 1-48, wherein the hydrocarbon reactants are in the liquid phase during the irradiation step.

[0201] Aspect 51. The process as defined in any one of Aspects 1-48, wherein the process includes irradiating the supported chromium catalyst in a slurry of the hydrocarbon reactants.

[0202] Aspect 52. The process as defined in any one of Aspects 1-48, wherein the process includes contacting the hydrocarbon reactants with a fluidized bed of the supported chromium catalyst and irradiating them simultaneously with the contact (fluidization).

[0203] Aspect 53. A process as defined in any one of Aspects 1-48, wherein the process comprises contacting the hydrocarbon reactants (e.g., in the gas phase or in the liquid phase) with a fixed bed of the supported chromium catalyst and irradiating them simultaneously with the contact.

[0204] Aspect 54. The process as defined in any of the preceding aspects, wherein the step of irradiating the hydrocarbon reactants with the supported chromium catalyst is carried out at any suitable WHSV or any range of WHSVs disclosed herein, said WHSV being, for example, about 0.01 hr. -1 approximately 500hr -1 or about 0.1hr -1 approximately 10 hours -1 .

[0205] Aspect 55. The process 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 less than about 200°C, less than about 100°C, less than about 40°C, about 0°C to about 100°C, or about 10°C to about 40°C.

[0206] Aspect 56. The process as defined in any of the preceding aspects, wherein the hydrolysis step includes contacting the reduced chromium catalyst with a hydrolyzing agent.

[0207] Aspect 57. The process as defined in aspect 56, wherein the hydrolysant comprises any suitable hydrolysant or any hydrolysant disclosed herein, such as water, steam, alcohol, acid, alkali or any combination thereof.

[0208] Aspect 58. The process as defined in aspect 57, wherein the hydrolysant further comprises any suitable reducing agent or any reducing agent disclosed herein, such as ascorbic acid, iron(II) reducing agent, zinc reducing agent or any combination thereof.

[0209] Aspect 59. The process 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, an allyl alcohol, or any combination thereof.

[0210] Aspect 60. The process 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 conversion (or yield) disclosed herein, for example at least about 2 wt%, at least about 5 wt%, at least about 10 wt%, or at least about 15 wt% (and at most about 99 wt%, about 95 wt%, about 90 wt%, about 80 wt%, about 70 wt%, or about 50 wt%).

[0211] Aspect 61. The process 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 conversion (or single-pass yield) disclosed herein, for example at least about 2 wt%, at least about 5 wt%, at least about 10 wt%, or at least about 15 wt% (and at most about 99 wt%, about 95 wt%, about 90 wt%, about 80 wt%, about 70 wt%, or about 50 wt%).

[0212] Aspect 62. The process as defined in any of the preceding aspects, wherein the yield of the alcohol compound (or the carbonyl compound) per mole of chromium (VI) in the supported chromium catalyst is any molar ratio of the alcohol compound (or the carbonyl compound) to the number of moles of chromium (VI) disclosed herein, for example at least about 0.01, at least about 0.05, at least about 0.1 or at least about 0.25 moles (and at most 2, at most about 1.8, at most about 1.6, at most about 1.4, at most about 1.2 or at most about 1 mole).

[0213] Aspect 63. The process as defined in any of the preceding aspects further comprises the step of separating at least a portion (and in some cases, all) of the hydrocarbon reactants from the reaction products after step (ii) using any suitable technique or any technique disclosed herein, such as extraction, filtration, evaporation, distillation or any combination thereof, to produce the separated hydrocarbon fraction.

[0214] Aspect 64. The process as defined in aspect 63, wherein the separated hydrocarbon fraction is recycled and irradiated again with the supported chromium catalyst.

[0215] Aspect 65. The process as defined in any of the preceding aspects further comprises 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.

[0216] Aspect 66. The process as defined in any of the preceding aspects further comprises the step of separating at least a portion (and in some cases, all) of the reduced chromium catalyst from the reaction product after step (ii) using any suitable technique or any technique disclosed herein, such as extraction, filtration, evaporation, distillation or any combination thereof, to produce the separated reduced chromium catalyst.

[0217] Aspect 67. The process as defined in any of the preceding aspects further includes (iii) the step of calcining the reduced chromium catalyst or the separated reduced chromium catalyst to regenerate the supported chromium catalyst.

[0218] Aspect 68. The process as defined in aspect 67, wherein calcination comprises subjecting the reduced chromium catalyst or the separated reduced chromium catalyst to an oxidizing atmosphere under any suitable peak temperature and time conditions or any peak temperature and time conditions disclosed herein, for example, to an oxidizing atmosphere at a peak temperature of about 300°C to about 1000°C, about 500°C to about 900°C, or about 550°C to about 870°C, for a period of about 1 minute to about 24 hours, about 1 hour to about 12 hours, or about 30 minutes to about 8 hours.

[0219] Aspect 69. The process as defined in any of the preceding aspects, wherein the hydrocarbon reactant comprises methane and the alcohol compound comprises methanol.

[0220] Aspect 70. A process for converting methane into methanol, the process comprising:

[0221] (a) Irradiating methane and a supported chromium catalyst containing hexavalent chromium with a light beam of wavelength in the UV-Vis spectrum to reduce at least a portion of the supported chromium catalyst to form a reduced chromium catalyst; and

[0222] (b) Hydrolyze the reduced chromium catalyst to form a reaction product containing methanol.

[0223] Aspect 71. The process as defined in aspect 70, further comprising (c) calcining at least a portion (and in some cases, all) of the reduced chromium catalyst to regenerate the supported chromium catalyst.

[0224] Aspect 72. The process as defined in aspect 70 or 71, wherein the reaction product further comprises formic acid.

[0225] Aspect 73. A process for converting C1-C6 alkanes into C1-C6 alcohols, the process comprising:

[0226] (a) Irradiating the C1-C6 alkanes and a supported chromium catalyst containing hexavalent chromium with a light beam of wavelength in the UV-Vis spectrum to reduce at least a portion of the supported chromium catalyst to form a reduced chromium catalyst; and

[0227] (b) Hydrolyze the reduced chromium catalyst to form a reaction product containing the C1-C6 alcohol.

[0228] Aspect 74. The process as defined in aspect 73 further includes (c) calcining at least a portion (and in some cases, all) of the reduced chromium catalyst to regenerate the supported chromium catalyst.

[0229] Aspect 75. The process as defined in aspect 73 or 74, wherein the C1-C6 alkane comprises methane (or ethane, or propane, or butane, or pentane, or hexane), and the C1-C6 alcohol comprises methanol (or ethanol, or propanol, or butanol, or pentanol, or hexanol).

[0230] Aspect 76. The process as defined in any one of Aspects 73-75, wherein the reaction product further comprises an organic acid compound.

Claims

1. A process for converting hydrocarbon reactants into alcohol compounds, the process comprising: (i) Irradiating the hydrocarbon reactant and a supported chromium catalyst containing hexavalent chromium with a light beam of at least 10,000 lux in the UV-Vis spectrum to reduce at least a portion of the supported chromium catalyst to form a reduced chromium catalyst, wherein the hydrocarbon reactant comprises methane or ethane. as well as (ii) Hydrolyzing the reduced chromium catalyst to form a reaction product comprising the alcohol compound, wherein the alcohol compound comprises methanol or ethanol; and The irradiation step is carried out at a temperature below 100°C, and the hydrocarbon reactants and the supported chromium catalyst are exposed to the light beam for a period of 15 seconds to 48 hours.

2. The process as described in claim 1, wherein... The supported chromium catalyst contains 0.01 to 50% by weight of chromium based on the weight of the supported chromium catalyst; and The reduced chromium catalyst contains chromium with an average valence of less than or equal to 5.

25.

3. The process of claim 1, wherein the process comprises: The hydrocarbon reactants are brought into contact with the fluidized bed of the supported chromium catalyst, and irradiated simultaneously during the contact. or The hydrocarbon reactants are brought into contact with the fixed bed of the supported chromium catalyst, and irradiated simultaneously during the contact.

4. The process as described in claim 1, wherein: Hydrolysis is carried out at temperatures ranging from 0°C to 100°C; and Hydrolysis involves contacting the reduced chromium catalyst with a hydrolyzing agent, which includes water, steam, alcohol, acid, alkali, or any combination thereof.

5. The process of claim 1, wherein the hydrocarbon reactants and the supported chromium catalyst are irradiated with 50,000 to 500,000 lux.

6. The process of claim 5, wherein the hydrocarbon reactant comprises ethane and the alcohol compound comprises ethanol.

7. The process of claim 6, wherein: The light beam originates from a blue light source or a UV light source; and The irradiation step is performed at a temperature between 0°C and 100°C.

8. The process of claim 1, wherein the molar yield of the alcohol compound is 0.05 to 1.8 moles of the alcohol compound per mole of chromium (VI) in the supported chromium catalyst.

9. The process of claim 1, further comprising: The step of separating at least a portion of the alcohol compound from the reaction products after step (ii); and / or The step of separating at least a portion of the hydrocarbon reactants from the reaction products after step (ii), wherein the at least a portion of the hydrocarbon reactants is recycled and irradiated again with the supported chromium catalyst.

10. The process of claim 1, wherein the hydrocarbon reactants and the supported chromium catalyst are irradiated with 50,000 to 200,000 lux.

11. The process of claim 1, wherein the hydrocarbon reactant comprises methane and the alcohol compound comprises methanol.

12. A process for converting hydrocarbon reactants into alcohol compounds, the process comprising: (i) Irradiating the hydrocarbon reactant and a supported chromium catalyst containing hexavalent chromium with a light beam of at least 10,000 lux in the UV-Vis spectrum to reduce at least a portion of the supported chromium catalyst to form a reduced chromium catalyst, wherein the hydrocarbon reactant comprises methane or ethane. (ii) Hydrolyzing the reduced chromium catalyst to form a reaction product comprising the alcohol compound, wherein the alcohol compound comprises methanol or ethanol; (iii) Separate at least a portion of the reduced chromium catalyst from the reaction products after step (ii); (iv) Calcination of at least a portion of the reduced chromium catalyst to regenerate the supported chromium catalyst; and The irradiation step is carried out at a temperature below 100°C, and the hydrocarbon reactants and the supported chromium catalyst are exposed to the light beam for a period of 15 seconds to 48 hours.

13. The process of claim 12, wherein: The supported chromium catalyst contains 0.01 to 50% by weight of chromium based on the weight of the supported chromium catalyst; and The reduced chromium catalyst contains chromium with an average valence of less than or equal to 5.

25.

14. The process of claim 13, wherein: Hydrolysis is carried out at temperatures ranging from 0°C to 100°C; and Hydrolysis involves contacting the reduced chromium catalyst with a hydrolyzing agent, which includes water, steam, alcohol, acid, alkali, or any combination thereof.

15. The process of claim 12, wherein the hydrocarbon reactants and the supported chromium catalyst are irradiated with 50,000 to 500,000 lux.

16. The process of claim 15, wherein the hydrocarbon reactant comprises ethane and the alcohol compound comprises ethanol.

17. The process of claim 16, wherein: The light beam originates from a blue light source or a UV light source; and The irradiation step is performed at a temperature between 0°C and 100°C.

18. The process of claim 15, wherein the molar yield of the alcohol compound is 0.05 to 1.8 moles of the alcohol compound per mole of chromium (VI) in the supported chromium catalyst.

19. The process of claim 15, wherein the hydrocarbon reactant comprises methane and the alcohol compound comprises methanol.

20. The process of claim 15, further comprising: The step of separating at least a portion of the alcohol compound from the reaction products after step (ii); and / or The step of separating at least a portion of the hydrocarbon reactants from the reaction products after step (ii), wherein the at least a portion of the hydrocarbon reactants is recycled and irradiated again with the supported chromium catalyst.

21. The process of claim 12, wherein the hydrocarbon reactants and the supported chromium catalyst are irradiated with 50,000 to 200,000 lux.

22. A process for converting hydrocarbon reactants into alcohol compounds, the process comprising: (i) Irradiating the hydrocarbon reactant and a supported chromium catalyst containing hexavalent chromium with a light beam containing wavelengths of 350 nm or more and 500 nm or less to reduce at least a portion of the supported chromium catalyst to form a reduced chromium catalyst, wherein the hydrocarbon reactant contains methane or ethane. (ii) Hydrolyzing the reduced chromium catalyst to form a reaction product comprising the alcohol compound, wherein the alcohol compound comprises methanol or ethanol; (iii) Separating at least a portion of the hydrocarbon reactants from the reaction products, wherein the at least a portion of the hydrocarbon reactants is recycled and irradiated again with the supported chromium catalyst; and The irradiation step is carried out at a temperature below 100°C, and the hydrocarbon reactants and the supported chromium catalyst are exposed to the light beam for a period of 15 seconds to 48 hours.

23. The process of claim 22, wherein the hydrocarbon reactants and the supported chromium catalyst are irradiated with 50,000 to 500,000 lux.

24. The process of claim 22, wherein the light beam originates from a blue light source or a UV light source.

25. The process of claim 22, wherein the hydrocarbon reactant comprises ethane and the alcohol compound comprises ethanol.

26. The process of claim 22, wherein the light beam comprises a wavelength of 350 nm or more and 450 nm or less.

27. The process of claim 22, wherein the supported chromium catalyst contains 0.01 to 50% by weight of chromium based on the weight of the supported chromium catalyst.

28. The process of claim 22, wherein the reduced chromium catalyst contains chromium with an average valence of less than or equal to 5.

25.

29. The process of claim 22, wherein the molar yield of the alcohol compound is 0.05 to 1.8 moles of the alcohol compound per mole of chromium (VI) in the supported chromium catalyst.

30. The process of claim 22, further comprising the step of separating at least a portion of the alcohol compound from the reaction product after step (ii).

31. The process of claim 22, further comprising: Separate at least a portion of the reduced chromium catalyst from the reaction products after step (ii); as well as At least a portion of the reduced chromium catalyst is calcined to regenerate the supported chromium catalyst.

32. The process of claim 22, wherein the hydrocarbon reactant comprises methane and the alcohol compound comprises methanol.

33. The process of claim 22, wherein the process includes contacting the hydrocarbon reactants with a fluidized bed of the supported chromium catalyst and irradiating them simultaneously during the contact.

34. The process of claim 22, wherein the process includes contacting the hydrocarbon reactants with a fixed bed of the supported chromium catalyst and irradiating them simultaneously during contact.

35. The process of claim 22, wherein: Hydrolysis is carried out at temperatures ranging from 0°C to 100°C; and Hydrolysis involves contacting the reduced chromium catalyst with a hydrolyzing agent, which includes water, steam, alcohol, acid, alkali, or any combination thereof.

36. The process of claim 22, wherein the irradiation step is performed at a temperature of 0°C to 100°C.

37. The process of claim 22, wherein: The supported chromium catalyst contains 0.1 to 15% by weight of chromium based on the weight of the supported chromium catalyst; and The light beam contains wavelengths above 350 nm and below 450 nm.

38. The process of claim 36, wherein the hydrocarbon reactant comprises methane.

39. A process for converting hydrocarbon reactants into alcohol compounds, the process comprising: (i) Irradiating the hydrocarbon reactant and a supported chromium catalyst containing hexavalent chromium with a light beam containing wavelengths of 350 nm or more and 500 nm or less to reduce at least a portion of the supported chromium catalyst to form a reduced chromium catalyst, wherein the hydrocarbon reactant contains methane or ethane. (ii) Hydrolyzing the reduced chromium catalyst to form a reaction product comprising the alcohol compound, wherein the alcohol compound comprises methanol or ethanol; wherein: The hydrocarbon reactants and the supported chromium catalyst were irradiated with 50,000 to 500,000 lux. The light beam originates from a blue light source or a UV light source; The irradiation process is carried out at a temperature below 100°C; and The hydrocarbon reactants and the supported chromium catalyst are exposed to the light beam for a period of time ranging from 15 seconds to 48 hours.

40. The process of claim 39, wherein the process comprises: The hydrocarbon reactants are brought into contact with the fluidized bed of the supported chromium catalyst, and irradiated simultaneously during the contact. or The hydrocarbon reactants are brought into contact with the fixed bed of the supported chromium catalyst, and irradiated simultaneously during the contact.

41. The process of claim 39, wherein: The supported chromium catalyst contains 0.1 to 15% by weight of chromium based on the weight of the supported chromium catalyst; and The light beam contains wavelengths above 350 nm and below 450 nm.

Images