WO2014181241A1

WO2014181241A1 - Promoted molybdenum-based supported catalyst composition for high selectivity for converting by methane to an aromatic compound

Info

Publication number: WO2014181241A1
Application number: PCT/IB2014/061215
Authority: WO
Inventors: Wei CHU; Mohammed Al-Hazmi; Majed MUSSA; Taiwo Odedairo
Original assignee: Saudi Basic Industries Corporation
Priority date: 2013-05-06
Filing date: 2014-05-05
Publication date: 2014-11-13

Abstract

The present disclosure relates to a catalyst composition having a high selectivity converting methane to an aromatic compound. The disclosed catalyst composition comprises an inorganic support; molybdenum; and at least two promoters selected from copper, iron, silver, zinc, calcium, cobalt, nickel, platinum, lanthanum, and cerium. Also disclosed is a method for preparing the catalyst composition and a method of using the same to produce an aromatic compound.

Description

PROMOTED MOLYBDENUM-BASED SUPPORTED CATALYST COMPOSITION FOR HIGH SELECTIVITY FOR CONVERTING BY METHANE TO AN AROMATIC

COMPOUND

FIELD OF THE INVENTION

[0001] The present invention relates to a catalyst composition and in one aspect to a catalyst composition for a high selectivity conversion of methane to an aromatic compound. In another aspect, the present invention relates to the catalyst composition having a high activity preservation ratio. In a further aspect, the present invention relates to the catalyst composition having a higher stability as compared to conventional catalyst compositions. The present invention also relates to a method for preparing the catalyst composition and a method of using the same to produce an aromatic compound.

BACKGROUND

[0002] Aromatic hydrocarbons, for example, benzene, toluene, ethylbenzene, xylenes, and polyaromatic hydrocarbons such as naphthalene, are important commodity chemicals in the petrochemical industry. Currently, aromatics are mostly produced from the petroleum- based feedstock by a variety of processes, including a catalytic reforming and a catalytic cracking. However, as the world supplies of petroleum feedstock decrease, there is a growing need to find alternative resources for aromatic hydrocarbons.

[0003] One possible alternative source for production of aromatic hydrocarbons is methane. Methane is one of the most abundant organic compounds on earth. Methane is the major constituent of natural gas; large amounts of methane are trapped in marine sediments as hydrates, and in coal shale as coal bed methane; it can also be easily derived from a biomass as a biogas. In addition, world reserves of natural gas are constantly being upgraded and more natural gas is currently being discovered than oil. Because of the problems associated with the transportation of large volume of natural gas, most of the natural gas produced along with oil, particularly at remote places, is flared and wasted. Hence, the conversion of alkanes contained in natural gas directly to higher hydrocarbons, such as aromatics, is an attractive method of upgrading natural gas.

[0004] To convert the alkanes in natural gas to the higher hydrocarbons, a number of various processes have been proposed. Some processes involve initial conversion of the methane to the synthesis gas that comprises a blend of ¾ and CO. However, this process has high capital costs and is energy intensive, and thus, more economically attractive routes to produce aromatics from methane are needed.

[0005] A number of alternative processes have been proposed for directly converting methane to higher hydrocarbons. One such process involves catalytic oxidative coupling of methane to olefins followed by the catalytic conversion of the olefins to liquid hydrocarbons, including aromatic hydrocarbons.

[0006] However, these oxidative coupling methods have a serious drawback of involving highly exothermic and potentially hazardous methane combustion reactions and they generally generate large quantities of environmentally sensitive carbon oxides.

[0007] Accordingly, it would be beneficial to provide a catalyst composition having high selectivity converting methane to an aromatic compound while maintaining a high stability and conversion yield. Further, it would be beneficial to provide a method for preparing the catalyst composition and a method of using the same to produce an aromatic compound. This and other needs are satisfied by the various aspects of the present disclosure.

SUMMARY

[0008] In accordance with the purpose of the invention, as embodied and broadly described herein, the invention, in one aspect, to a catalyst composition comprising: a. an inorganic support; b. molybdenum; and c. at least two promoters wherein all of the promoters are selected from the group consisting of copper, iron, silver, zinc, calcium, cobalt, nickel, platinum, lanthanum, and cerium; wherein the total amount of promoters is present in an amount that ranges from greater than 0.01 wt. % to 10 wt. , based on the total weight of the catalyst composition; wherein the catalyst composition converts methane to an aromatic compound.

[0009] In another aspect, the invention relates to a method of using the catalyst composition comprising contacting the composition with a methane feed to produce an aromatic compound.

[0010] Also disclosed is a method for preparing a catalyst composition comprising: a. loading molybdenum and at least two promoters selected from the group consisting of copper, iron, silver, zinc, calcium, cobalt, nickel, platinum, lanthanum, and cerium, onto an inorganic support to produce a first composition, wherein the total amount of promoters is present in an amount that ranges from greater than 0.01 wt. % to 10 wt. , based on the total weight of the catalyst composition; and b. calcining the first composition at a temperature that ranges from 450 °C to 750 °C for a time range of from 6 min to 600 min to form a second composition; wherein the resulting second composition is a catalyst composition for converting methane to an aromatic compound.

[0011] In a further aspect, the invention relates to a method wherein the calcination comprises heating the catalyst composition in air or in nitrogen or both sequentially.

[0012] While aspects of the present invention can be described and claimed in a particular statutory class, such as the system statutory class, this is for convenience only and one of skill in the art will understand that each aspect of the present invention can be described and claimed in any statutory class. Unless otherwise expressly stated, it is in no way intended that any method or aspect set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not specifically state in the claims or descriptions that the steps are to be limited to a specific order, it is no way intended that an order be inferred, in any respect. This holds for any possible non-express basis for interpretation, including matters of logic with respect to arrangement of steps or operational flow, plain meaning derived from grammatical organization or punctuation, or the number or type of aspects described in the specification.

BRIEF DESCRIPTION OF THE FIGURES

[0013] The accompanying figures, which are incorporated in and constitute a part of this specification, illustrate several aspects and together with the description serve to explain the principles of the invention.

[0014] Figure 1 shows the product distribution at 180 min time-on-stream (TOS) for a comparative example Cpl.

[0015] Figure 2 shows the benzene selectivity and the selectivity excluding coke for Methane-to-Benzene (MTB) for double promoted catalyst compositions labeled as Examples 1 to 6.

[0016] Figure 3 shows the benzene productivity versus a reaction TOS for a catalyst composition labeled as Example 1 and a comparative example Cpl.

[0017] Figure 4 shows the benzene productivity versus a reaction TOS for a catalyst composition labeled as Example 2 and a comparative example Cpl.

[0018] Figure 5 shows the benzene productivity versus a reaction TOS for a catalyst composition labeled as Example 6 and a comparative example Cpl. [0019] Additional advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or can be learned by practice of the invention. The advantages of the invention will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.

DESCRIPTION

[0020] The present invention can be understood more readily by reference to the following detailed description of the invention and the Examples included therein.

[0021] Before the present compounds, compositions, articles, systems, devices, and/or methods are disclosed and described, it is to be understood that they are not limited to specific synthetic methods unless otherwise specified, or to particular reagents unless otherwise specified, as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, example methods and materials are now described.

[0022] All publications mentioned herein are incorporated herein by reference to disclose and describe the methods and/or materials in connection with which the publications are cited. The publications discussed herein are provided solely for their disclosure prior to the filing date of the present application. Nothing herein is to be construed as an admission that the present invention is not entitled to antedate such publication by virtue of prior invention. Further, the dates of publication provided herein can be different from the actual publication dates, which can require independent confirmation.

DEFINITIONS

[0023] As used herein, nomenclature for compounds, including organic compounds, can be given using common names, IUPAC, IUBMB, or CAS recommendations for nomenclature. One of skill in the art can readily ascertain the structure of a compound if given a name, either by systemic reduction of the compound structure using naming conventions, or by commercially available software, such as CHEMDRAW (Cambridgesoft Corporation, U.S.A.).

[0024] As used in the specification and the appended claims, the singular forms "a," "an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a functional group," "an alkyl," or "a residue" includes mixtures of two or more such functional groups, alky Is, or residues, and the like.

[0025] Ranges can be expressed herein as from "about" one particular value, and/or to "about" another particular value. When such a range is expressed, a further aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value forms a further aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as "about" that particular value in addition to the value itself. For example, if the value "10" is disclosed, then "10" is also disclosed. It is also understood that each unit between two particular units are also disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed.

[0026] References in the specification and concluding claims to parts by weight of a particular element or component in a composition denotes the weight relationship between the element or component and any other elements or components in the composition or article for which a part by weight is expressed. Thus, in a compound containing 2 parts by weight of component X and 5 parts by weight component Y, X and Y are present at a weight ratio of 2:5, and are present in such ratio regardless of whether additional components are contained in the compound.

[0027] A weight percent (wt. %) of a component, unless specifically stated to the contrary, is based on the total weight of the formulation or composition in which the component is included.

[0028] As used herein, the terms "optional" or "optionally" means that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.

[0029] As used herein, the term "substituted" is contemplated to include all permissible substituents of organic compounds. In a broad aspect, the permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, and aromatic and nonaromatic substituents of organic compounds. Illustrative substituents include, for example, those described below. The permissible substituents can be one or more and the same or different for appropriate organic compounds. For purposes of this disclosure, the heteroatoms, such as nitrogen, can have hydrogen substituents and/or any permissible substituents of organic compounds described herein which satisfy the valences of the heteroatoms. This disclosure is not intended to be limited in any manner by the permissible substituents of organic compounds. Also, the terms "substitution" or "substituted with" include the implicit proviso that such substitution is in accordance with permitted valence of the substituted atom and the substituent, and that the substitution results in a stable compound, e.g., a compound that does not spontaneously undergo transformation such as by rearrangement, cyclization, elimination, etc. It is also contemplated that, in certain aspects, unless expressly indicated to the contrary, individual substituents can be further optionally substituted (i.e., further substituted or unsubstituted).

[0030] In defining various terms, "A 1 ," "A2 ," "A 3 ," and "A 4 " are used herein as generic symbols to represent various specific substituents. These symbols can be any substituent, not limited to those disclosed herein, and when they are defined to be certain substituents in one instance, they can, in another instance, be defined as some other substituents.

[0031] The term "aliphatic" or "aliphatic group," as used herein, denotes a hydrocarbon moiety that may be straight-chain (i.e., unbranched), branched, or cyclic (including fused, bridging, and spirofused polycyclic) and may be completely saturated or may contain one or more units of unsaturation, but which is not aromatic. Unless otherwise specified, aliphatic groups contain 1-20 carbon atoms. Aliphatic groups include, but are not limited to, linear or branched, alkyl, alkenyl, and alkynyl groups, and hybrids thereof such as (cycloalkyl)alkyl, (cycloalkenyl)alkyl or (cycloalkyl)alkenyl.

[0032] The term "alkyl" as used herein is a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n- butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, s-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. It is understood that the alkyl group is acyclic. The alkyl group can be branched or unbranched. The alkyl group can also be substituted or unsubstituted. For example, the alkyl group can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, amino, ether, halide, hydroxy, nitro, silyl, sulfo-oxo, or thiol, as described herein. A "lower alkyl" group is an alkyl group containing from one to six (e.g., from one to four) carbon atoms. The term alkyl group can also be a Q alkyl, Q-C2 alkyl, C₁-C3 alkyl, C₁-C4 alkyl, Q- C₅ alkyl, d-C₆ alkyl, d-C₇ alkyl, d-d alkyl, C₁-C9 alkyl, d-do alkyl, C C₁₂ alkyl and the like up to and including a C₁-C24 alkyl.

[0033] Throughout the specification "alkyl" is generally used to refer to both unsubstituted alkyl groups and substituted alkyl groups; however, substituted alkyl groups are also specifically referred to herein by identifying the specific substituent(s) on the alkyl group. For example, the term "halogenated alkyl" or "haloalkyl" specifically refers to an alkyl group that is substituted with one or more halide, e.g., fluorine, chlorine, bromine, or iodine. Alternatively, the term "monohaloalkyl" specifically refers to an alkyl group that is substituted with a single halide, e.g. fluorine, chlorine, bromine, or iodine. The term

"polyhaloalkyl" specifically refers to an alkyl group that is independently substituted with two or more halides, i.e. each halide substituent need not be the same halide as another halide substituent, nor do the multiple instances of a halide substituent need to be on the same carbon. The term "alkoxyalkyl" specifically refers to an alkyl group that is substituted with one or more alkoxy groups, as described below. The term "aminoalkyl" specifically refers to an alkyl group that is substituted with one or more amino groups. The term "hydroxyalkyl" specifically refers to an alkyl group that is substituted with one or more hydroxy groups. When "alkyl" is used in one instance and a specific term such as "hydroxyalkyl" is used in another, it is not meant to imply that the term "alkyl" does not also refer to specific terms such as "hydroxyalkyl" and the like.

[0034] The term "alkenyl" as used herein is a hydrocarbon group of from 2 to 24 carbon atoms with a structural formula containing at least one carbon-carbon double bond.

Asymmetric structures such as (A 1 A2 )C=C(A 3 A 4 ) are intended to include both the E and Z isomers. This can be presumed in structural formulae herein wherein an asymmetric alkene is present, or it can be explicitly indicated by the bond symbol C=C. The alkenyl group can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or thiol, as described herein.

[0035] The term "alkynyl" as used herein is a hydrocarbon group of 2 to 24 carbon atoms with a structural formula containing at least one carbon-carbon triple bond. The alkynyl group can be unsubstituted or substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or thiol, as described herein.

[0036] As used herein, the term "higher hydrocarbon" means a hydrocarbon having more than one carbon atom per molecule, oxygenate having at least one carbon atom per molecule, e.g., ethane, ethylene, propane, propylene, benzene, toluene, xylenes, naphthalene, and/or methyl naphthalene; and/or an organic compound comprising at least one carbon atom and at least one non-hydrogen atom, e.g., methanol, ethanol, methylamine, and/or ethylamine.

[0037] The term "aromatic group" as used herein refers to a ring structure having cyclic clouds of delocalized π electrons above and below the plane of the molecule, where the π clouds contain (4n+2) π electrons. A further discussion of aromaticity is found in Morrison and Boyd, Organic Chemistry, (5th Ed., 1987), Chapter 13, entitled "Aromaticity," pages 477-497, incorporated herein by reference. The term "aromatic group" is inclusive of both aryl and heteroaryl groups.

[0038] The term "aryl" as used herein is a group that contains any carbon-based aromatic group including, but not limited to, benzene, naphthalene, phenyl, biphenyl, anthracene, and the like. The aryl group can be substituted or unsubstituted. The aryl group can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde,— N¾, carboxylic acid, ester, ether, halide, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or thiol as described herein. The term "biaryl" is a specific type of aryl group and is included in the definition of "aryl." In addition, the aryl group can be a single ring structure or comprise multiple ring structures that are either fused ring structures or attached via one or more bridging groups such as a carbon-carbon bond. For example, biaryl refers to two aryl groups that are bound together via a fused ring structure, as in naphthalene, or are attached via one or more carbon-carbon bonds, as in biphenyl.

[0039] The term "aromatic compound" as used herein means molecules containing one or more aromatic groups. Exemplary representatives of an aromatic hydrocarbon are benzene, toluene, xylenes, naphthalene, and methylnaphthalenes.

[0040] The terms "halo," "halogen," or "halide," as used herein can be used interchangeably and refer to F, CI, Br, or I. [0041] The term "heteroalkyl," as used herein refers to an alkyl group containing at least one heteroatom. Suitable heteroatoms include, but are not limited to, O, N, Si, P and S, wherein the nitrogen, phosphorous and sulfur atoms are optionally oxidized, and the nitrogen heteroatom is optionally quaternized. Heteroalkyls can be substituted as defined above for alkyl groups.

[0042] The term "hydroxyl" or "hydroxy" as used herein is represented by the formula—OH.

1 2 3

[0043] The term "silyl" as used herein is represented by the formula— SiA A A , where A 1 , A2 , and A 3 can be, independently, hydrogen or an alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.

[0044] The term "sulfo-oxo" as used herein is represented by the formulas— S(0)A\ — S(0)₂A¹,— OS(0)₂A¹, or— OS(0)₂OA¹, where A¹ can be hydrogen or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. Throughout this specification "S(O)" is a short hand notation for S=0. The term "sulfonyl" is used herein to refer to the sulfo-oxo group represented by the formula— S(0)₂A¹, where A¹ can be hydrogen or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. The term "sulfone" as used herein is represented by the formula A 1 S(0)₂A2 , where A 1 and A2 can be, independently, an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. The term "sulfoxide" as used herein is represented by the formula

A¹S(0)A², where A¹ and A² can be, independently, an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.

[0045] "R¹," "R²," "R³," "Rⁿ," where n is an integer, as used herein can,

independently, possess one or more of the groups listed above. For example, if R¹ is a straight chain alkyl group, one of the hydrogen atoms of the alkyl group can optionally be substituted with a hydroxyl group, an alkoxy group, an alkyl group, a halide, and the like. Depending upon the groups that are selected, a first group can be incorporated within second group or, alternatively, the first group can be pendant (i.e., attached) to the second group. For example, with the phrase "an alkyl group comprising an amino group," the amino group can be incorporated within the backbone of the alkyl group. Alternatively, the amino group can be attached to the backbone of the alkyl group. The nature of the group(s) that is (are) selected will determine if the first group is embedded or attached to the second group. [0046] As described herein, the terms "coke" is used to mean carbon containing solid materials, which are essentially non-volatile solids at the reaction conditions,

[0047] The term "organic residue" defines a carbon containing residue, i.e., a residue comprising at least one carbon atom, and includes but is not limited to the carbon-containing groups, residues, or radicals defined hereinabove. Organic residues can contain various heteroatoms, or be bonded to another molecule through a heteroatom, including oxygen, nitrogen, sulfur, phosphorus, or the like. Examples of organic residues include but are not limited alkyl or substituted alkyls, alkoxy or substituted alkoxy, mono or di-substituted amino, amide groups, etc. Organic residues can preferably comprise 1-26 carbon atoms, 1 to 18 carbon atoms, 1 to 15, carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms. In a further aspect, an organic residue can comprise 2- 26 carbon atoms, 2 to 18 carbon atoms, 2 to 15 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, 2 to 6 carbon atoms, or 2 to 4 carbon atoms.

[0048] As described herein, compounds of the invention may contain "optionally substituted" moieties. In general, the term "substituted," whether preceded by the term "optionally" or not, means that one or more hydrogens of the designated moiety are replaced with a suitable substituent. Unless otherwise indicated, an "optionally substituted" group may have a suitable substituent at each substitutable position of the group, and when more than one position in any given structure may be substituted with more than one substituent selected from a specified group, the substituent may be either the same or different at every position. Combinations of substituents envisioned by this invention are preferably those that result in the formation of stable or chemically feasible compounds. In is also contemplated that, in certain aspects, unless expressly indicated to the contrary, individual substituents can be further optionally substituted (i.e., further substituted or unsubstituted).

[0049] The term "stable," as used herein, refers to compounds that are not substantially altered when subjected to conditions to allow for their production, detection, and, in certain aspects, their recovery, purification, and use for one or more of the purposes disclosed herein.

[0050] The term "Gas Hourly Space Velocity" or "GHSV," as used herein, in one aspect, refers to a ratio of a reactant gas flow rate to a reactor volume or a catalyst bed volume. In another aspect, it can be also defined as a ratio of an entering volumetric flow rate of a reactant gas to a catalyst bed volume. A GHSV is measured at a standard temperature and pressure, and indicates how many catalyst bed volumes can be treated in a unit time, For example, the GHSV can be 1050 ml/g/hr.

[0051] The term "Time-on-Stream" or "TOS," as used herein, refers to a length of time a catalyst composition is in use for a catalytic reaction in a defined reactor volume or a catalyst bed volume.

[0052] The term "Activity Preservation Ratio" or "APR," as used herein, refers to a benzene productivity indicator, or alternatively, to a yield ratio of an ageing catalyst composition at a certain time-on-stream (TOS) over a higher benzene yield of a catalyst composition at the same initial reaction conditions.

[0053] Certain materials, compounds, compositions, and components disclosed herein can be obtained commercially or readily synthesized using techniques generally known to those of skill in the art. For example, the starting materials and reagents used in preparing the disclosed compounds and compositions are either available from commercial suppliers such as Aldrich Chemical Co., (Milwaukee, Wis.), Acros Organics (Morris Plains, N.J.), Fisher Scientific (Pittsburgh, Pa.), or Sigma (St. Louis, Mo.) or are prepared by methods known to those skilled in the art following procedures set forth in references and incorporated by reference in their entirety for their teaching of synthetic preparation, such as Fieser and Fieser's Reagents for Organic Synthesis, Volumes 1-17 (John Wiley and Sons, 1991); Rodd's Chemistry of Carbon Compounds, Volumes 1-5 and Supplemental (Elsevier Science Publishers, 1989); Organic Reactions, Volumes 1-40 (John Wiley and Sons, 1991); March's Advanced Organic Chemistry, (John Wiley and Sons, 4th Edition); and Larock's

Comprehensive Organic Transformations (VCH Publishers Inc., 1989).

[0054] Unless otherwise expressly stated, it is in no way intended that any method set forth herein be construed as requiring that its steps be performed in a specific order.

Accordingly, where a method claim does not actually recite an order to be followed by its steps or it is not otherwise specifically stated in the claims or descriptions that the steps are to be limited to a specific order, it is no way intended that an order be inferred, in any respect. This holds for any possible non-express basis for interpretation, including: matters of logic with respect to arrangement of steps or operational flow; plain meaning derived from grammatical organization or punctuation; and the number or type of embodiments described in the specification.

[0055] Disclosed are the components to be used to prepare the compositions of the invention as well as the compositions themselves to be used within the methods disclosed herein. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of each various individual and collective combinations and permutation of these compounds cannot be explicitly disclosed, each is specifically contemplated and described herein. For example, if a particular compound is disclosed and discussed and a number of modifications that can be made to a number of molecules including the compounds are discussed, specifically contemplated is each and every combination and permutation of the compound and the modifications that are possible unless specifically indicated to the contrary. Thus, if a class of molecules A, B, and C are disclosed as well as a class of molecules D, E, and F and an example of a combination molecule, A-D is disclosed, then even if each is not individually recited each is individually and collectively

contemplated meaning combinations, A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C-F are considered disclosed. Likewise, any subset or combination of these is also disclosed. Thus, for example, the sub-group of A-E, B-F, and C-E would be considered disclosed. This concept applies to all aspects of this application including, but not limited to, steps in methods of making and using the compositions of the invention. Thus, if there are a variety of additional steps that can be performed it is understood that each of these additional steps can be performed with any specific embodiment or combination of embodiments of the methods of the invention.

[0056] It is understood that the compositions disclosed herein have certain functions. Disclosed herein are certain structural requirements for performing the disclosed functions, and it is understood that there are a variety of structures that can perform the same function that are related to the disclosed structures, and that these structures will typically achieve the same result.

CATALYST COMPOSITION

[0057] As summarized above, the disclosure provides an improved catalyst composition that is useful in connection with a high selectivity conversion of a hydrocarbon to an aromatic compound. In one aspect, the hydrocarbon is methane. In another aspect, the aromatic compound comprises benzene, toluene, naphthalene, or xylene, or a combination thereof. In a further aspect, the aromatic compound further comprises traces of C2H4, C2¾, or C₃H₆, or a combination thereof. In another aspect, the aromatic compound comprises substantially benzene. For example, as described in greater detail below, aspects of the disclosure provide a catalyst composition that is capable of being used in a process of a high selectivity conversion of hydrocarbons to an aromatic compound; and that to provide an enhanced catalytic performance, a high aromatic compound selectivity and a high activity preservation ratio (APR) at longer reaction time-on-stream (TOS). To that end, the disclosed catalyst composition generally comprises an inorganic support; molybdenum; and at least two promoters selected from the group consisting of copper, iron, silver, zinc, calcium, cobalt, nickel, platinum, lanthanum, and cerium. The disclosed catalyst composition can further optionally comprise one or more additional additives.

[0058] As used herein, catalyst compositions comprise an inorganic support as a carrier, molybdenum, and promoters.

[0059] In one aspect, the catalyst composition can be homogeneous or heterogeneous.

[0060] The catalyst composition disclosed herein provides an enhanced catalytic performance, a high aromatic compound selectivity and productivity, a high hydrocarbon conversion, and a high APR, as compared to conventional catalyst compositions without presence of the catalyst promoters.

[0061] According to aspects of the disclosure the catalyst composition is particularly useful in connection with a high selectivity conversion of methane to an aromatic compound.

[0062] In one aspect, the inorganic support can be any support that, when combined with molybdenum and promoters contributes significantly to an overall catalyst performance exhibiting a high selectivity conversion of methane to an aromatic compound. The support is suitable for treating or impregnating with a molybdenum compound or solution thereof, and a precursor compound or solution thereof.

[0063] In one aspect, the inorganic support can be either amorphous or crystalline. In another aspect, the inorganic support can be an oxide, carbide or nitride of boron, aluminum, silicon, phosphorous, titanium, scandium, chromium, vanadium, magnesium, manganese, iron, zinc, gallium, germanium, yttrium, zirconium, niobium, molybdenum, indium, tin, barium, lanthanum, hafnium, cerium, tantalum, tungsten, or other transuranium elements, or a combination thereof. In a further aspect, the inorganic support can be a porous material, including but not limited to a microporous crystalline material or a mesoporous material. As used herein, the term "microporous" refers to pores having a diameter of less than 2 nanometers, whereas the term "mesoporous" refers to pores having a diameter form 2 to 50 nanometers. [0064] In a yet further aspect, disclosed herein a microporous crystalline material including, but not limited to, silicates, aluminosilicates, titanosilicates, aluminophosphates, metallophosphates, or silicoaluminophosphates, or a combination thereof.

[0065] In one aspect, the inorganic support comprises a zeolite carrier. Microporous aluminosilicate zeolites useful in the conversion methane to an aromatic compound are well known in the art. In one aspect, the zeolite is a medium pore size zeolite having a pore size of 4.5 to 6.5 Angstrom.

[0066] In another aspect, suitable homogeneous medium-pore size zeolites are 10- ring zeolites, wherein the pore is formed by a ring consisting of 10 Si0₄ tetrahedral. In a yet further aspect, the zeolite is ZSM-5.

[0067] In one aspect, the zeolite is in a hydrogen form (HZSM-5), having at least a portion of the original cations associated therewith replaced by hydrogen. Methods to convert an aluminosilicate zeolite to the hydrogen form are well known in the art. A first method involves a direct ion exchange employing an acid. A second method involves a base exchange followed by calcinations. In another aspect, the inorganic support is HZSM-5.

[0068] In another aspect, the zeolite of the present invention can be dealuminated. In a yet another aspect, the zeolite can have a S1O2/AI2O₃ (hereinafter "Si/2A1") ratio of 10 to 100, e.g., 10 to 95. In a further aspect, the zeolite can have a Si/2A1 ratio of 15 to 80. In a yet further aspect, the zeolite can have a Si/2A1 ratio of 20 to 60. Means and methods to obtain dealuminated zeolite are well known in the art and include, but not limited to the acid leaching technique; (see e.g. Post-Synthesis Modification I; Molecular Sieves, Volume 3; Eds. H.G. Karge, J. Weitkamp; Year (2002); Pages 204-255 incorporated herein by reference in its entirety for its teaching of methods and compositions for dealuminated zeolites). Means and methods for quantifying the Si/2A1 ratio of a dealuminated zeolite are well known in the art and include, but not limited to AAS (Atomic Adsorption Spectroscopy) or ICP

(Inductively Coupled Plasma Spectrometry) analysis.

[0069] In one aspect, molybdenum can come from any commercially available molybdenum source. In another aspect, any commercially available molybdenum compounds can be used, including, but not limited to molybdenum oxide, ammonium molybdate, ammonium heptamolybdate, ammonium hexamolybdate, or ammonium paramolybdate or a combination thereof.

[0070] In one aspect, the amount of molybdenum in the catalyst composition is in the range from 1 wt. % to 20 wt. %. In further aspects, the range can include any two exemplary values. For example, the amount of molybdenum in the catalyst composition can range from 2 wt. % to 15 wt. %. In a yet further aspect, the amount of molybdenum in the catalyst composition is in the range from 3 wt. % to 10 wt. %.

[0071] In one aspect, the catalyst composition comprises at least two promoters, wherein the promoters comprise a substance that increase the activity of the catalyst composition. In another aspect, the promoters can be a part of the catalyst compositions or can be added separately.

[0072] In another aspect, the promoters are selected from the group consisting of copper, iron, silver, zinc, calcium, cobalt, nickel, platinum, lanthanum, and cerium. In a yet another aspect, the promoters are selected from the group consisting of copper, iron, nickel, and zinc. In a further aspect, the promoter can be in an elemental form, in the form of a compound, or in the form of an oxide or a mixture thereof.

[0073] In a further aspect, the promoters do not include one or more of rhodium, chromium, vanadium, titanium, manganese, aluminum, gallium, yttrium, zirconium, ruthenium, palladium, lead, neodymium, samarium, tungsten, rhenium, iridium, silicon, strontium, ytterbium, tin, and/or gold.

[0074] According to aspects of the disclosure, the promoters in the catalyst composition are in an amount that ranges from greater than 0.01 wt. % to 10 wt. % based on the total weight of the catalyst composition. In further aspects, the range can include any two exemplary values. For example, the promoters can be present in an amount ranging from 0.1 wt. % to 8 wt. % based on the total weight of the catalyst composition. In a further aspect, the promoters are present in the amount ranges from 0.2 wt. % to 7 wt. % based on the total weight of the catalyst composition. In a yet further aspect, the promoters are present in the amount ranges from 0.5 wt. % to 5 wt. % based on the total weight of the catalyst composition. In a further aspect, this amount is the total amount of the promoters. In a yet further aspect, this amount is the total amount of the two promoters.

[0075] According to one aspect of the disclosure, a high selectivity conversion of a hydrocarbon to an aromatic compound using the disclosed catalyst composition refers to a high selectivity conversion of methane to benzene. In further aspects of the disclosure, the percentage of benzene yield refers to a carbon-based mole amount of methane that is converted to benzene over an amount of methane feed that was introduced into the system. In a yet further aspect of the disclosure, the percentage of coke ratio refers to a carbon-based mole amount of formed coke over a total carbon-based mole amount of the products. [0076] In other aspects of the disclosure, benzene selectivity of the disclosed catalyst composition refers to the molar ratio amount of benzene produced from the methane conversion over the total carbon-based amount of the products. In a yet further aspect of the disclosure, benzene productivity refers to the carbon-based mole amount of benzene, produced from the conversion of methane using the disclosed catalyst composition, per gram catalyst composition per unit time ^mole-C/g/hour)

[0077] In one aspect, the benzene selectivity of the disclosed catalyst composition is in a range from 70% to 90 %, when measured at the temperatures in a range from 670 °C to 720 °C. In further aspects, the range can include any two exemplary values. For example, the benzene selectivity of the disclosed catalyst composition is in a range from 75% to 85%, when measured at the temperatures in a range from 670 °C to 720 °C. In another aspect, the benzene selectivity of the disclosed catalyst composition is at least 75 % or greater, when measured at the temperatures between 670 °C to 720 °C. In a further aspect, the benzene selectivity of the disclosed catalyst composition is at least 80 % or greater, when measured at the temperatures between 670 °C to 720 °C. In a yet further aspect, the benzene selectivity of the disclosed catalyst composition is at least 85 % or greater, when measured at the temperatures between 670 °C to 720 °C.

[0078] According to aspects of the disclosure, a benzene yield of the catalyst composition is in a range between 6.0 % to 7.5 %, when measured at the temperatures between 670 °C to 720 °C. In further aspects, the range can include any two exemplary values. In another aspect, the benzene yield of the disclosed catalyst composition is at least 6.5 % or greater when measured at the between 670 °C to 720 °C. In a further aspect, the benzene yield of the disclosed catalyst composition is at least 7.2 % or greater, when measured at the temperatures between 670 °C to 720 °C.

[0079] According to aspects of the disclosure, an Activity Preservation Ratio (APR) of the catalyst composition in the conversion of the methane to an aromatic compound, at TOS of 24 hours, is in the range from 70 % to 97%. In further aspects, the range can include any two exemplary values. For example, the APR can range from 75% to 85% or from 75% to 80%. In another aspect, the APR of the catalyst composition in the conversion of the methane to the aromatic compound is at least 95.6 % or greater at TOS of 24 hours. In a further aspect, the APR of the catalyst composition in the conversion of the methane to the aromatic compound is 97% at TOS of 24 hours. In another aspect, the catalyst composition has the Activity Preservation Ratio (APR) in the conversion of methane to benzene is 97% at TOS of 24 hours in a temperature range from 670 °C to 720 °C.

[0080] According to aspects of the disclosure, the selectivity and productivity of benzene, and APR of the catalyst composition can be measured at time-on-stream (TOS) in the range from 1 hour to 40 hours. For example, the TOS can range from 3 hours to 38 hours, or from 5 hours to 30 hours, or from 8 hours to 25 hours.

[0081] According to aspects of the disclosure, a methane gas used for converting to an aromatic compound can be supplied from a natural gas, methane hydrates, coal bed methane, synthetic gas, or biogas, or a mixture thereof.

[0082] In one aspect, molybdenum can come from any commercially available molybdenum source. In another aspect, any commercially available molybdenum compounds can be used, including, but not limited to molybdenum oxide, ammonium molybdate, ammonium heptamolybdate, ammonium hexamolybdate, or ammonium paramolybdate or a combination thereof.

[0083] The compositions disclosed herein can be prepared or used by the methods disclosed herein.

METHODS OF MAKING THE COMPOUNDS

[0084] Also disclosed herein is a method of preparing a catalyst composition useful in connection with a high selectivity conversion of a hydrocarbon to an aromatic compound. In one aspect, disclosed herein, is a method for preparing a catalyst composition comprising: a. loading molybdenum and at least two promoters selected from the group consisting of copper, iron, silver, zinc, calcium, cobalt, nickel, platinum, lanthanum, and cerium, onto an inorganic support to produce a first composition, wherein the total amount of promoters is present in an amount that ranges from greater than 0.01 wt. % to 10 wt. %, based on the total weight of the catalyst composition; and b. calcining the first composition at a temperature that ranges from 450 °C to 750 °C for a time range of from 6 min to 600 min to form a second composition; wherein the resulting second composition is a catalyst composition for converting methane to an aromatic compound.

[0085] In one aspect, the composition can act as a catalyst composition after step a. In another aspect, the composition can act as a catalyst composition after step b.

[0086] In one aspect, molybdenum can come from any commercially available molybdenum source. In another aspect, any commercially available molybdenum compounds can be used, including, but not limited to molybdenum oxide, ammonium molybdate, ammonium heptamolybdate, ammonium hexamolybdate, or ammonium paramolybdate or a combination thereof.

[0087] In one aspect, the amount of molybdenum in the catalyst composition is present in the range from 1 wt. % to 20 wt. % based on the total weight of the catalyst composition. In further aspects, the range can include any two exemplary values. For example, the amount of molybdenum in the catalyst composition is in the range from 2 wt. % to 15 wt. % in the catalyst composition. In a yet further aspect, the amount of molybdenum in the catalyst composition is in the range from 3 wt. % to 10 wt. % based on the total weight of the catalyst composition.

[0088] In one aspect, the loaded promoters can include but are not limited to titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, aluminum, gallium, yttrium, zirconium, hafnium, ruthenium, rhodium, palladium, silver, lead, lanthanum, neodymium, samarium, tungsten, rhenium, iridium, silicon, platinum, cerium, strontium, ytterbium, tin, and gold.

[0089] In another aspect, the loaded promoters are selected from the group consisting of copper, iron, silver, zinc, calcium, cobalt, nickel, platinum, lanthanum, and cerium. In a yet another aspect, the promoters are selected from the group consisting of copper, iron, nickel, and zinc.

[0090] In a further aspect, the loaded promoters do not include rhodium, chromium, vanadium, titanium, manganese, aluminum, gallium, yttrium, zirconium, ruthenium, palladium, lead, neodymium, samarium, tungsten, rhenium, iridium, silicon, strontium, ytterbium, tin, or gold. In another aspect, the loaded promoters do not include a combination of rhodium, chromium, vanadium, titanium, manganese, aluminum, gallium, yttrium, zirconium, ruthenium, palladium, lead, neodymium, samarium, tungsten, rhenium, iridium, silicon, strontium, ytterbium, tin, or gold.

[0091] In one aspect, at least two promoters are loaded in their precursor form comprising nitrate, chloride, oxychloride, acetate, acetylacetonate, alkoxide, oxide, and oxalate salts of the promoters.

[0092] In one aspect, the at least two promoters are loaded in their precursor form comprising copper nitrate, copper chloride, copper oxychloride, copper acetate, copper acetylacetonate, copper alkoxide, copper oxide, copper oxalate, iron nitrate, iron chloride, iron oxychloride, iron acetate, iron acetylacetonate, iron alkoxide, iron oxide, iron oxalate, silver nitrate, silver chloride, silver oxychloride, silver acetate, silver acetylacetonate, silver alkoxide, silver oxide, silver oxalate, zinc nitrate, zinc chloride, zinc oxychloride, zinc acetate, zinc acetylacetonate, zinc alkoxide, zinc oxide, zinc oxalate, calcium nitrate, calcium chloride, calcium oxychloride, calcium acetate, calcium acetylacetonate, calcium alkoxide, calcium oxide, calcium oxalate, cobalt nitrate, cobalt chloride, cobalt oxychloride, cobalt acetate, cobalt acetylacetonate, cobalt alkoxide, cobalt oxide, cobalt oxalate, nickel nitrate, nickel chloride, nickel oxychloride, nickel acetate, nickel acetylacetonate, nickel alkoxide, nickel oxide, nickel oxalate, platinum nitrate, platinum chloride, platinum oxychloride, platinum acetate, platinum acetylacetonate, platinum alkoxide, platinum oxide, platinum oxalate, lanthanum nitrate, lanthanum chloride, lanthanum oxychloride, lanthanum acetate, lanthanum acetylacetonate, lanthanum alkoxide, lanthanum oxide, lanthanum oxalate, cerium nitrate, cerium chloride, cerium oxychloride, cerium acetate, cerium acetylacetonate, cerium alkoxide, cerium oxide, and cerium oxalate.

[0093] According to aspects of the disclosure, the promoters in the catalyst composition are loaded in an amount that ranges from greater than 0.01 wt. % to 10 wt. , based on the total weight of the catalyst composition. In further aspects, the range can include any two exemplary values. For example, the promoters are present in the amount ranges from 0.1 wt. % to 8 wt. % based on the total weight of the catalyst composition. In a further aspect, the promoters are present in the amount ranges from 0.2 wt. % to 7 wt. %. In a yet further aspect, the promoters are present in the amount ranges from 0.5 wt. % to 5 wt. % based on the total weight of the catalyst composition.

[0094] According to aspects of the disclosure, loading of the molybdenum and the at least two promoters selected from the group of copper, iron, silver, zinc, calcium, cobalt, nickel, platinum, lanthanum, and cerium, can be done by any means known in the art such as, incipient wetness, evaporation, impregnation, spray-drying, ion-exchange, and physical mixing. In one aspect, the molybdenum and the at least two promoters selected from the group of consisting copper, iron, silver, zinc, calcium, cobalt, nickel, platinum, lanthanum, and cerium, can be loaded onto an inorganic support concurrently by contacting the zeolite with a solution comprising both a soluble molybdenum salt and soluble salts comprising at least two additional promoters. In a further aspect, the molybdenum and the at least two promoters can be loaded onto an inorganic support subsequently by contacting the zeolite with a solution comprising molybdenum and a different solution comprising at least one promoter selected from the group consisting of copper, iron, silver, zinc, calcium, cobalt, nickel, platinum, lanthanum, and cerium, and then contacting an additional solution comprising a second promoter selected from the group consisting of copper, iron, silver, zinc, calcium, cobalt, nickel, platinum, lanthanum, and cerium In a yet further aspect, the at least two promoters are loaded by an impregnation method. In a yet even further aspect, the at least two promoters are loaded by co-impregnation or two step impregnation.

[0095] In one aspect, molybdenum can be loaded first. In a further aspect, molybdenum can be loaded last. In a yet further aspect, no specific order of molybdenum and promoters is required. In a yet even further aspect, the molybdenum and promoters are loaded in any order suitable to the specific conditions and the order can be determined by one skilled in the art.

[0096] In one aspect, the catalyst composition is calcinated at a temperature in an amount that ranging from 450 °C to 750 °C. In further aspects, the range can include any two exemplary values. In another aspect the calcining temperature is in a range from 500 °C to 700 °C, or 525°C to 680°C.

[0097] In one aspect, calcining the catalyst composition continues in a time range from 0.1 h to 100 hours. In further aspects, the range can include any two exemplary values. In another aspect, calcining the catalyst composition continues in a time range from 2 h to 80 hours. In a yet another aspect, calcining the catalyst composition continues in a time range from 3 h to 70 hours, 10 h to 60 hours.

[0098] In one aspect, the calcining comprises heating the catalyst composition in air. In another aspect, the calcining comprises heating the catalyst composition in nitrogen. In a further aspect, the calcining comprises heating the catalyst composition in air and nitrogen sequentially.

[0099] In one aspect disclosed herein, a method of preparing a catalyst composition comprising a) loading molybdenum and at least two promoters selected from the group consisting of copper, iron, silver, zinc, calcium, cobalt, nickel, platinum, lanthanum, and cerium, onto an inorganic support to produce the catalyst composition, wherein the total amount of promoters is present in an amount that ranges from greater than 0.01 wt. % to 10 wt. , based on the total weight of the catalyst composition; and b) calcining the catalyst composition at a temperature in an amount that ranging from 450 °C to 750 °C for a time range from 6 min to 600 min.

[0100] In one aspect, disclosed herein the method of preparing the catalyst composition wherein the catalyst composition has the Activity Preservation Ration (APR) in the conversion of methane to benzene is 97% at TOS of 24 hours at a temperature range from 670 °C to 720 °C.

[0101] The method of making can be used to prepare the composition disclosed herein or used by the methods disclosed herein.

METHODS OF USING THE COMPOUNDS AND COMPOSITIONS

[0102] The catalyst composition disclosed herein provides enhanced catalytic performance when used as a catalyst composition in methane conversion to an aromatic compound. In one aspect, disclosed herein, a method of using the disclosed catalyst composition comprises contacting the composition of the catalyst composition with a methane feed to produce an aromatic compound.

[0103] In another aspect, disclosed herein a method of using the catalyst composition comprises contacting the catalyst composition with methane to produce an aromatic compound, wherein the aromatic compound comprises benzene, toluene, naphthalene, or xylene, or a combination thereof. In another aspect, the aromatic compound comprises benzene, toluene, naphthalene, or xylene, or a combination thereof. In a further aspect, the aromatic compound further comprises traces of C2H4, C2¾, or C₃H₆, or a combination thereof. In another aspect, the aromatic compound comprises substantially benzene.

[0104] In a further aspect, disclosed herein, the aromatic compound is produced under reaction conditions at a temperature range from 670 °C to 720 °C. In a further aspect, the temperature range can be derived from any two exemplary temperatures. For example, the temperature can range from 705 °C to 720 °C.

[0105] In a further aspect, disclosed herein, the aromatic compound is produced under reaction conditions at a GHSV range from 300 ml/g/h to 2000 ml/g/h. In a further aspect, the GHSV can be in a range derived from any two exemplary values. For example, the GHSV can range from 400 ml/g/h to to 1500 ml/g/h, or 500 ml/g/h to 1050 ml/g/h.

[0106] The methods of using can be performed using the compositions disclosed herein or made by the methods disclosed herein.

ASPECTS

[0107] The disclosed compositions and methods include at least the following aspects. [0108] Aspect 1: A catalyst composition comprising: a. an inorganic support; b. molybdenum; and c. at least two promoters wherein all of the promoters are selected from the group consisting of copper, iron, silver, zinc, calcium, cobalt, nickel, platinum, lanthanum, and cerium; wherein the total amount of promoters is present in an amount that ranges from greater than 0.01 wt. % to 10 wt. , based on the total weight of the catalyst composition; wherein the catalyst composition converts methane to an aromatic compound.

[0109] Aspect 2: The composition of Aspect 1, wherein the inorganic support comprises a HZSM-5 carrier comprising a Si/2A1 ratio of from 10 to 100.

[0110] Aspect 3: The composition of any of Aspects 1-2, wherein the inorganic support comprises a HZSM-5 carrier comprising a Si/2A1 ratio of from 15 to 80.

[0111] Aspect 4: The composition of any of Aspects 1-3, the inorganic support comprises a HZSM-5 carrier comprising a Si/2A1 ratio of from 20 to 60.

[0112] Aspect 5: The composition of any of Aspects 1-4, wherein the molybdenum is present in an amount ranging from 1 wt. % to 20 wt. % based on the total weight of the catalyst composition.

[0113] Aspect 6: The composition of any of Aspects 1-5, wherein the molybdenum is present in an amount ranging from 2 wt. % to 15 wt. % based on the total weight of the catalyst composition.

[0114] Aspect 7: The composition of any of Aspects 1-6, wherein the molybdenum is present in an amount ranging from 3 wt. % to 10 wt. % based on the total weight of the catalyst composition.

[0115] Aspect 8: The composition of any of Aspects 1-7, wherein a benzene selectivity is in a range of from 75 % to 87 % measured at a temperature of from 670 °C to 720 °C.

[0116] Aspect 9: The composition of Aspect 8, wherein the measured benzene selectivity is at least 75 %.

[0117] Aspect 10: The composition of Aspect 8, wherein the measured benzene selectivity is at least 80 %.

[0118] Aspect 11 : The composition of Aspect 8, wherein the measured benzene selectivity is at least 85 %.

[0119] Aspect 12: The composition of Aspect 8, wherein the measured benzene selectivity is at least 87 %. [0120] Aspect 13: The composition of any of Aspects 1-12, wherein a benzene yield is in a range of from 6.0 % to 7.5 % measured at a temperature of from 670 °C to 720 °C.

[0121] Aspect 14: The composition of Aspect 13, wherein the benzene yield is at least 6.5 % or greater.

[0122] Aspect 15: The composition of Aspect 13, wherein the benzene yield is at least 7.2 % or greater.

[0123] Aspect 16: The composition of Aspect 13, wherein the benzene yield is

7.50%.

[0124] Aspect 17: The composition of any one of Aspects 1-16, wherein an Activity Preservation Ratio (APR) of the catalyst composition in the conversion of the methane to an aromatic compound is at least 95.6 % or greater at TOS of 24 hours.

[0125] Aspect 18: The composition of any one of Aspects 1-17, wherein an Activity Preservation Ratio (APR) of the catalyst composition in the conversion of the methane to the aromatic compound is 97% at TOS of 24 hours.

[0126] Aspect 19: The composition of any one of Aspects 1-18, wherein the at least two promoters are selected from the group consisting of copper, iron, nickel, and zinc.

[0127] Aspect 20: The composition of any one of Aspects 1-19, wherein at least one promoter is zinc.

[0128] Aspect 21 : The composition of any one of Aspects 1-20, wherein at least one promoter is selected from the group consisting of copper, iron, and nickel.

[0129] Aspect 22: The composition of any one of Aspects 1-21, wherein the inorganic support comprises a HZSM-5 carrier.

[0130] Aspect 23: A catalyst composition of any one of Aspects 1-22, wherein the catalyst composition comprises: a. an inorganic support comprising HZSM-5; b.

molybdenum, wherein the molybdenum is present in an amount ranging from 3 wt. % to 10 wt. % based on the total weight of the catalyst composition; and c. at least two promoters wherein all of the promoters are selected from the group consisting of copper, iron, silver, zinc, calcium, cobalt, nickel, platinum, lanthanum, and cerium; wherein the total amount of promoters is present in an amount that ranges from greater than 1 wt. % to 4 wt. %, based on the total weight of the catalyst composition;wherein the catalyst composition converts methane to an aromatic compound.

[0131] Aspect 24: A catalyst composition of any one of Aspects 1-23; wherein the catalyst composition comprises: a. an inorganic support comprising HZSM-5; b. molybdenum, wherein the molybdenum is present in an amount ranging from 3 wt. % to 10 wt. % based on the total weight of the catalyst composition; and c. at least two promoters wherein all of the promoters are selected from the group consisting of copper, zinc, calcium, and nickel; wherein the total amount of promoters is present in an amount that ranges from greater than 1 wt. % to 4 wt. , based on the total weight of the catalyst composition;

wherein the catalyst composition converts methane to an aromatic compound.

[0132] Aspect 25: A method of using the composition of any of Aspects 1-24, comprising contacting the composition of Aspect 1 with a methane feed to produce an aromatic compound.

[0133] Aspect 26: The method of Aspect 25, wherein the aromatic compound comprises benzene, toluene, naphthalene, or xylene; or a combination thereof.

[0134] Aspect 27: The method of any one of Aspects 25-26, further comprising traces of C2H4, C2¾ or C3¾, or a combination thereof.

[0135] Aspect 28: The method of any one of Aspects 25-27, wherein the aromatic compound is produced under reaction conditions with GHSV ranging from 500 ml/g/h to 1050 ml/g/h.

[0136] Aspect 29: The method of any one of Aspects 25-28, wherein the aromatic compound comprises substantially benzene.

[0137] Aspect 30: The method of any one of Aspects 25-29, wherein the aromatic compound is produced under reaction conditions at a temperature range of from 670 °C to 720 °C.

[0138] Aspect 31 : The method of any one of Aspects 25-30, wherein the aromatic compound is produced under reaction conditions with GHSV ranging from 300 ml/g/h to 1200 ml/g/h.

[0139] Aspect 32: A method for preparing the catalyst composition of any of Aspects 1-24 comprising: a. loading the molybdenum and the promoters onto an inorganic support to produce a first composition; and b. calcining the first composition at a temperature that ranges from 450 °C to 750 °C for a time range of from 6 min to 600 min to form a second composition; wherein the resulting second composition is a catalyst composition for converting methane to an aromatic compound.

[0140] Aspect 33: A method for preparing a catalyst composition comprising: a. loading molybdenum and at least two promoters selected from the group consisting of copper, iron, silver, zinc, calcium, cobalt, nickel, platinum, lanthanum, and cerium, onto an inorganic support to produce a first composition, wherein the total amount of promoters is present in an amount that ranges from greater than 0.01 wt. % to 10 wt. , based on the total weight of the catalyst composition; and b. calcining the first composition at a temperature that ranges from 450 °C to 750 °C for a time range of from 6 min to 600 min to form a second composition; wherein the resulting second composition is a catalyst composition for converting methane to an aromatic compound.

[0141] Aspect 34: The method of any of Aspect 32-33, wherein molybdenum is loaded as ammonium hexamolybdate tetrahydrate.

[0142] Aspect 35: The method of any one of Aspects 32-34, wherein the calcining comprises heating the catalyst composition in air or in nitrogen, or both sequentially.

[0143] Aspect 36: The method of any one of Aspects 32-35, wherein at least two promoters are selected from the group consisting of copper, iron, nickel, and zinc.

[0144] Aspect 37: The method of any one of Aspects 32-36, wherein the promoter is loaded in its precursor form.

[0145] Aspect 38: The method of Aspect 37, wherein the precursor form of zinc is zinc nitrate.

[0146] Aspect 39: The method of Aspect 37, wherein the precursor form of copper is copper nitrate.

[0147] Aspect 40: The method of any one of Aspects 32-39, wherein the at least two promoters are loaded by an impregnation method.

[0148] Aspect 41 : The method of Aspect 40, wherein the at least two promoters are loaded by co-impregnation or two step impregnation.

[0149] Aspect 42: The method of any one of Aspects 32-41 , wherein the catalyst composition has the Activity Preservation Ratio (APR) in the conversion of methane to benzene of at least 97% at TOS of 24 hours in a temperature range from 670 °C to 720 °C.

[0150] Aspect 43: The method of any one of Aspects 32-42, wherein the methane is supplied from a natural gas, methane hydrates, coal bed methane, synthetic gas, or biogas, or a combination thereof.

[0151] Aspect 44: The method of any one of Aspects 32-43, wherein the inorganic support comprises a HZSM-5 carrier. EXPERIMENTAL

[0152] The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the compounds, compositions, articles, devices and/or methods claimed herein are made and evaluated, and are intended to be purely exemplary of the invention and are not intended to limit the scope of what the inventors regard as their invention. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, temperature is in °C or is at ambient temperature, and pressure is at or near atmospheric.

[0153] Several methods for preparing the compounds of this invention are illustrated in the following Examples. Starting materials and the requisite intermediates are in some cases commercially available, or can be prepared according to literature procedures or as illustrated herein.

1. GENERAL METHODS

[0154] For the non-limiting Examples described herein, the catalyst composition for converting methane to aromatic compounds is formed by loading MFI-type zeolite carrier with molybdenum and double promoters (A_nA_m). The MFI-type carrier, on which the above- mentioned metal component is loaded, includes a porous metallo-silicate formed with pores of 4.5 to 6.5 angstrom in diameter and marked as HZSM-5.

[0155] Promoters (A_nA_m) are chosen from the following group: Al-Zn, A2- Ag, A3- Cu, A4-Ca, A5-Co, A6-Fe, A7-Pt, A8-Ni, A9-Ce, AlO-La. AO- no promoter is added.

[0156] After loading molybdenum and promoters' precursors on the HZSM-5 type carrier, all samples were thermally treated at calcinations temperatures in the range from 450 °C to 650 °C in an atmosphere of air or nitrogen, for time ranging from 0.1 hour to 90 hours.

[0157] Catalytic methane conversion was measured under the following conditions: 670 °C-720 °C, 1 bar, 300 mg to 1200 mg catalyst loading amount with GHSV of 300 ml/g/h to 2000 ml/g/h. In one aspect, the temperature values were kept at 700 °C or 710 °C. In another aspect, the GHSV was in a range between 500 ml/g/h to 1050 ml/g/h.

[0158] The methane conversion, in , was calculated as a methane mole amount converted to the products over an inlet total carbon-amount and the coke ratio, in , was calculated as a formed coke mole amount on a carbon-mole base over a total mole amount of the products on a carbon mole base.

2. PREPARATION OF CATALYST PRECURSORS AND CATALYST COMPOSITIONS

[0159] For the non-limiting Examples described herein below, the prepared catalyst compositions (labeled as "Example 1," Example 2," and the like) and various comparative samples (labeled as "Cpl," "Cp2," and the like) are further described in Table 1 below.

[0160] H-type ZSM-5 (HZSM-5) zeolites, having Si/2A1 (Si0₂/Al₂0₃) ratios of 23,

50, and 80 were employed as a metallo-silicate carrier material in the catalyst composition preparation.

[0161] To prepare the double promoted catalyst composition, 10 gram of the HZSM-5 carrier was added to a 150 ml beaker. A second beaker was used to dissolve 0.968 gram of ammonium hepta-molybdate tetrahydrate in 12 ml of distilled water; the promoter's precursor, for example, 0.91 gram of zinc nitrate, was then added to form a mixed impregnation solution. The prepared exemplarily molybdenum-zinc impregnation solution was added to the above 10 gram of HZSM-5 carrier, for example, having Si/2A1 = 23, and the mixture of the carrier and the impregnation solution was stirred for 60 minutes using a magnetic agitation. The second promoter's precursor, for example, copper nitrate in an amount of 0.456 gram, was added to the stirred impregnation solution to form an

impregnation solution containing two catalyst's promoters. The stirred substance was evaporated at 60 °C and then dried at 110 °C for two hours to remove any traces of a remaining solvent. Thereafter, the dried material was calcinated, in air, at 510 °C for 16 hours. The molybdenum content in the prepared catalyst composition was 5 wt. % relative to the total weight of the catalyst composition. The obtained sample was labeled as Example 1.

[0162] Comparative example Cpl was prepared using a method described above without adding of any of the promoter precursors. Molybdenum alone was loaded on the HZSM-5 carrier (Si/2A1=50), thereby obtaining the catalyst composition of comparative example Cpl.

[0163] Examples 2-6 were prepared accordingly to a method of preparation of the double promoted catalyst compositions as described above. The catalyst compositions labeled as Example 3 and Example 6 were calcinated in an inert gas medium, such as nitrogen. The composition of the double promoted catalyst composition labeled as Example 3 included Al= Zn (1.2 ), and A3=Cu (1.2 ). The composition of the double promoted catalyst compositions labeled as Example 6 included Al= Zn (1.2 %), and A8=Ni (0.12%)). The catalyst composition labeled as Example 6 underwent two step calcinations process: 1) first, Example 6 was calcinated, in air, at 510 °C for 6 hours; 2) followed by an additional step of calcination, in nitrogen, at 510 °C for 72 hours. For Example 5, the calcination was performed in air at 510 C for 16 hours.

imp = impregnation; co-imp = co-impregnation

3. METHANE CATALYTIC CONVERSION TO BENZENE

[0164] All catalytic compositions were tested to evaluate the methane catalytic conversion to benzene. To compare the catalytic performance of all catalytic compositions, the reactions were carried out in a continuous flow quartz tubular fixed-bed reactor, having an inner diameter (i.d.) of 10 mm, under similar reaction conditions and processes. The following conditions were employed: atmospheric pressure, temperatures of 670 °C to 720 °C, GHSV of 500 ml/g/h to 1050 ml/g/h, and TOS of 30 minutes or 1630 minutes. The methane-to-benzene catalytic performance for various examples is shown in Tables 2-5, wherein the catalyst compositions were disclosed in Table 1.

[0165] The reaction products were analyzed by using an on-line gas chromatograph equipped with a six-way sampling valve allowing sample collection every 60 minutes; a Porapak packed column and flame ionization detector (FID) for the separation and analysis of hydrocarbons such as CH4, C2H2_, CeHe, C₇H₈, and QoHg; and a Molecular Sieve column and a thermal conductivity detector (TCD) for the separation and analysis of H2, N₂, CH4, CO, C2H_4i and C2H₆. A representative methane-to-benzene reaction product distribution at 180 min TOS for comparative example Cpl is shown in Figure 1.

[0166] The data were calculated by using an exterior standard method utilizing three mixture gas cylinders of ten components (CH4, C2H4, C2¾, C₃H₆, C₃H₈, Benzene, CO, I¾, N₂, CO2), the benzene content was 0.1 wt%, 0.4%, and 0.9% for three cylinders respectively.

[0167] Table 2 shows the catalytic performance of comparative example Cpl versus TOS, wherein the methane-to-benzene reaction conditions were kept as following: 700 °C, 1 bar, and GHSV of 1050 ml/g/h. At 60 minutes TOS, the Cpl initial conversion was 5.53%, benzene selectivity excluding coke was 86.7%, with a benzene productivity of 1622 μπιοΐε- °C/g/h. Upon reaching TOS of 300 minutes, Cpl conversion dropped to 3.95%, with decrease in a benzene selectivity and productivity to 71.1 % and 1162 μπιο1ε-⁰0/ η respectively.

[0168] The Activity Preservation Ratio (APR), i.e. the benzene productivity indicator, was calculated as the ratio of benzene productivity at specific TOS to the highest benzene productivity of the catalyst composition at the same conditions. For example, APR at 180 minutes TOS was 85.5 % [benzene (Bz.) Productivity (180)/Bz. Productivity (60] , and it dropped to 71.7% at 300 minutes TOS, showing a poor stability of Cpl .

[0169] The catalytic performance of the double promoted catalyst compositions was studied. Table 3 shows the catalytic performance of the double-promoted catalyst compositions labeled as Example 1 to Example 6. The methane-to-benzene reaction conditions were kept as following: 700 °C, 1 bar, and GHSV of 1050 ml/g/h, TOS at steady state, 180 to 300 min. The benzene and C6 excluding coke selectivity are further demonstrated in Figure 2. [0170] It was demonstrated that the benzene yield and benzene productivity increased significantly as compared to the comparative example Cpl.

[0171] The benzene productivity versus reaction TOS in comparison to comparative example Cpl for Examples 1 and 2 is schematically shown in Figures 3 and 4 respectively. The last two points in both figures demonstrate the catalytic performance of the catalyst composition that underwent a regeneration process in pure hydrogen, in situ, after 24 hours as the catalyst for the methane-to-benzene reaction.

[0172] Table 4 shows the catalytic performance of Example 6 as a function of the reaction TOS. The reaction's conditions were kept as following: temperature of 700 °C, pressure of 1 bar, and GHSV of 525 ml/g/h/. It can be observed that the high benzene yield and benzene productivity can be obtained at longer TOS.

[0173] The benzene productivity measured for Example 6 versus reaction TOS in comparison to comparative example Cpl is schematically shown in Figure 5.

[0174] It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.

Claims

CLAIMS What is claimed is:

1. A catalyst composition comprising:

a. an inorganic support;

b. molybdenum; and

c. at least two promoters wherein all of the promoters are selected from the group consisting of copper, iron, silver, zinc, calcium, cobalt, nickel, platinum, lanthanum, and cerium;

wherein the total amount of promoters is present in an amount that ranges from greater than 0.01 wt. % to 10 wt. , based on the total weight of the catalyst composition; wherein the catalyst composition converts methane to an aromatic compound.

2. The composition of claim 1 , wherein the inorganic support comprises a HZSM-5 carrier comprising a Si/2A1 ratio of from 10 to 100.

3. The composition of any of claims 1-2, wherein the inorganic support comprises a HZSM-5 carrier comprising a Si/2A1 ratio of from 15 to 80.

4. The composition of any of claims 1-3, the inorganic support comprises a HZSM-5 carrier comprising a Si/2A1 ratio of from 20 to 60.

5. The composition of any of claims 1-4, wherein the molybdenum is present in an amount ranging from 1 wt. % to 20 wt. % based on the total weight of the catalyst composition.

6. The composition of any of claims 1-5, wherein the molybdenum is present in an amount ranging from 2 wt. % to 15 wt. % based on the total weight of the catalyst composition.

7. The composition of any of claims 1-6, wherein the molybdenum is present in an amount ranging from 3 wt. % to 10 wt. % based on the total weight of the catalyst composition.

8. The composition of any of claims 1-7, wherein a benzene selectivity is in a range of from 75 % to 87 % measured at a temperature of from 670 °C to 720 °C.

9. The composition of claim 8, wherein the measured benzene selectivity is at least 75 %.

10. The composition of claim 8, wherein the measured benzene selectivity is at least 80 %.

11. The composition of claim 8, wherein the measured benzene selectivity is at least 85 %.

12. The composition of claim 8, wherein the measured benzene selectivity is at least 87 %.

13. The composition of any of claims 1-12, wherein a benzene yield is in a range of from 6.0 % to 7.5 % measured at a temperature of from 670 °C to 720 °C.

14. The composition of claim 13, wherein the benzene yield is at least 6.5 % or greater.

15. The composition of claim 13, wherein the benzene yield is at least 7.2 % or greater.

16. The composition of claim 13, wherein the benzene yield is 7.50 %.

17. The composition of any one of claims 1-16, wherein an Activity Preservation Ratio (APR) of the catalyst composition in the conversion of the methane to an aromatic compound is at least 95.6 % or greater at TOS of 24 hours.

18. The composition of any one of claims 1-17, wherein an Activity Preservation Ratio (APR) of the catalyst composition in the conversion of the methane to the aromatic compound is 97% at TOS of 24 hours.

19. The composition of any one of claims 1-18, wherein the at least two promoters are selected from the group consisting of copper, iron, nickel, and zinc.

20. The composition of any one of claims 1-19, wherein at least one promoter is zinc.

21. The composition of any one of claims 1-20, wherein at least one promoter is selected from the group consisting of copper, iron, and nickel.

22. The composition of any one of claims 1-21, wherein the inorganic support comprises a HZSM-5 carrier.

23. A catalyst composition of any one of claims 1-22, wherein the catalyst composition comprises:

a. an inorganic support comprising HZSM-5;

b. molybdenum, wherein the molybdenum is present in an amount ranging from 3 wt. % to 10 wt. % based on the total weight of the catalyst composition; and

wherein the total amount of promoters is present in an amount that ranges from greater than 1 wt. % to 4 wt. , based on the total weight of the catalyst composition;

wherein the catalyst composition converts methane to an aromatic compound.

24. A catalyst composition of any one of claims 1-23; wherein the catalyst composition comprises:

a. an inorganic support comprising HZSM-5;

c. at least two promoters wherein all of the promoters are selected from the group consisting of copper, zinc, calcium, and nickel;

wherein the catalyst composition converts methane to an aromatic compound.

25. A method of using the composition of any of claims 1-24, comprising contacting the composition of claim 1 with a methane feed to produce an aromatic compound.

26. The method of claim 25, wherein the aromatic compound comprises benzene, toluene, naphthalene, or xylene; or a combination thereof.

27. The method of any one of claims 25-26, further comprising traces of C2H4, C2H_6, or C₃H₆, or a combination thereof.

28. The method of any one of claims 25-27, wherein the aromatic compound is produced under reaction conditions with GHSV ranging from 500 ml/g/h to 1050 ml/g/h.

29. The method of any one of claims 25-28, wherein the aromatic compound comprises substantially benzene.

30. The method of any one of claims 25-29, wherein the aromatic compound is produced under reaction conditions at a temperature range of from 670 °C to 720 °C.

31. The method of any one of claims 25-30, wherein the aromatic compound is produced under reaction conditions with GHSV ranging from 300 ml/g/h to 1200 ml/g/h.

32. A method for preparing the catalyst composition of any of claims 1-24 comprising:

a. loading the molybdenum and the promoters onto an inorganic support to produce a first composition; and

b. calcining the first composition at a temperature that ranges from 450 °C to 750 °C for a time range of from 6 min to 600 min to form a second composition;

wherein the resulting second composition is a catalyst composition for converting methane to an aromatic compound.

33. A method for preparing a catalyst composition comprising:

a. loading molybdenum and at least two promoters selected from the group consisting of copper, iron, silver, zinc, calcium, cobalt, nickel, platinum, lanthanum, and cerium, onto an inorganic support to produce a first composition, wherein the total amount of promoters is present in an amount that ranges from greater than 0.01 wt. % to 10 wt. , based on the total weight of the catalyst composition; and

34. The method of any of claim 32-33, wherein molybdenum is loaded as ammonium hexamolybdate tetrahydrate.

35. The method of any one of claims 32-34, wherein the calcining comprises heating the catalyst composition in air or in nitrogen, or both sequentially.

36. The method of any one of claims 32-35, wherein at least two promoters are selected from the group consisting of copper, iron, nickel, and zinc.

37. The method of any one of claims 32-36, wherein the promoter is loaded in its precursor form.

38. The method of claim 37, wherein the precursor form of zinc is zinc nitrate.

39. The method of claim 37, wherein the precursor form of copper is copper nitrate.

40. The method of any one of claims 32-39, wherein the at least two promoters are loaded by an impregnation method.

41. The method of claim 40, wherein the at least two promoters are loaded by co- impregnation or two step impregnation.

42. The method of any one of claims 32-41, wherein the catalyst composition has the Activity Preservation Ratio (APR) in the conversion of methane to benzene of at least 97% at TOS of 24 hours in a temperature range from 670 °C to 720 °C.

43. The method of any one of claims 32-42, wherein the methane is supplied from a natural gas, methane hydrates, coal bed methane, synthetic gas, or biogas, or a combination thereof.

44. The method of any one of claims 32-43, wherein the inorganic support comprises a HZSM-5 carrier.