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WO2014191874A1 - Composition catalytique à base de molybdène promue pour production d'hydrocarbure aromatique à partir de méthane - Google Patents

Composition catalytique à base de molybdène promue pour production d'hydrocarbure aromatique à partir de méthane Download PDF

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Publication number
WO2014191874A1
WO2014191874A1 PCT/IB2014/061614 IB2014061614W WO2014191874A1 WO 2014191874 A1 WO2014191874 A1 WO 2014191874A1 IB 2014061614 W IB2014061614 W IB 2014061614W WO 2014191874 A1 WO2014191874 A1 WO 2014191874A1
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WIPO (PCT)
Prior art keywords
composition
catalyst composition
promoter
benzene
molybdenum
Prior art date
Application number
PCT/IB2014/061614
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English (en)
Inventor
Wei CHU
Mohammed Al-Hazmi
Majed MUSSA
Taiwo Odedairo
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Saudi Basic Industries Corporation
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Publication date
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Publication of WO2014191874A1 publication Critical patent/WO2014191874A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6525—Molybdenum
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    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
    • B01J23/686—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of zinc, cadmium or mercury
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of rare earths
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/24—Chromium, molybdenum or tungsten
    • C07C2523/28—Molybdenum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/56—Platinum group metals
    • C07C2523/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tatalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/652—Chromium, molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/66—Silver or gold
    • C07C2523/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tatalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/85—Chromium, molybdenum or tungsten
    • C07C2523/88—Molybdenum
    • C07C2523/881—Molybdenum and iron
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/85—Chromium, molybdenum or tungsten
    • C07C2523/88—Molybdenum
    • C07C2523/882—Molybdenum and cobalt
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/85—Chromium, molybdenum or tungsten
    • C07C2523/88—Molybdenum
    • C07C2523/883—Molybdenum and nickel
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/85—Chromium, molybdenum or tungsten
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • 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.
  • the present invention relates to the catalyst composition having a high productivity and/or a high activity preservation ratio.
  • 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.
  • Aromatic hydrocarbons for example, benzene, toluene, ethylbenzene, xylenes, or polyaromatic hydrocarbons such as naphthalene, are potentially important commodity chemicals in the petrochemical industry.
  • aromatics are mostly produced from the petroleum-based feedstock by a variety of processes, including catalytic reforming and/or catalytic cracking.
  • catalytic reforming and/or catalytic cracking As the world supplies of petroleum feedstock decrease, there is a growing need to find alternative resources for aromatic hydrocarbons.
  • 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.
  • 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 glared 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.
  • the invention in one aspect, relates to a catalyst composition
  • a catalyst composition comprising: a. an inorganic support;
  • At least one promoter selected from the group consisting of copper, iron, silver, zinc, calcium, cobalt, nickel, platinum, lanthanum, and cerium;
  • the total amount of the promoter 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 when the at least one promoter is zinc, the molybdenum is not in the form of molybdenum oxalate; and
  • catalyst composition converts methane to an aromatic compound.
  • a method for preparing a catalyst composition comprising: a. loading molybdenum and at least one promoter 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 promoter 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 when the at least one promoter is zinc, the molybdenum is not in the form of molybdenum oxalate; and
  • Ranges can be expressed herein as from one particular value, and/or to 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. 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 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.
  • 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.
  • 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.
  • a weight percent (wt. %) of a component is based on the total weight of the formulation or composition in which the component is included.
  • 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.
  • the term "substituted" is contemplated to include all permissible substituents of organic compounds.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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.
  • 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.
  • the alkyl group is acyclic.
  • the alkyl group can be branched or unbranched.
  • the alkyl group can also be substituted or unsubstituted.
  • 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.
  • alkyl group can also be a CI alkyl, C1-C2 alkyl, C1-C3 alkyl, C1-C4 alkyl, C1-C5 alkyl, C1-C6 alkyl, C1-C7 alkyl, C1-C8 alkyl, C1-C9 alkyl, C1-C10 alkyl, C1-C12 alkyl and the like up to and including a C1-C24 alkyl.
  • 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.
  • 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.
  • halogenated alkyl specifically refers to an alkyl group that is substituted with one or more halide, e.g., fluorine, chlorine, bromine, or iodine.
  • haloalkyl specifically refers to an alkyl group that is substituted with a single halide, e.g. fluorine, chlorine, bromine, or iodine.
  • 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.
  • alkoxyalkyl specifically refers to an alkyl group that is substituted with one or more alkoxy groups, as described below.
  • aminoalkyl specifically refers to an alkyl group that is substituted with one or more amino groups.
  • hydroxyalkyl specifically refers to an alkyl group that is substituted with one or more hydroxy groups.
  • 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.
  • 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.
  • 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 here
  • alkynyl 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.
  • 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
  • aromatic group refers to a ring structure having cyclic clouds of delocalized ⁇ electrons above and below the plane of the molecule, where the ⁇ clouds contain (4n+2) ⁇ electrons.
  • aromaticity is found in Morrison and Boyd, Organic Chemistry, (5th Ed., 1987), Chapter 13, entitled “Aromaticity,” pages 477-497, incorporated herein by reference.
  • aromatic group is inclusive of both aryl and heteroaryl groups.
  • 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,— N3 ⁇ 4, carboxylic acid, ester, ether, halide, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or thiol as described herein.
  • biaryl is a specific type of aryl group and is included in the definition of "aryl.”
  • 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.
  • 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.
  • 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.
  • halo halogen
  • halide halogen
  • heteroalkyl 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.
  • sil as used herein is represented by the formula— SiA 1 A2 A 3 , 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.
  • sulfo-oxo is represented by the formulas— S(0)A 1 , — S(0) 2 A 1 , or— OS(0) 2 OA 1 , where A 1 can be hydrogen or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.
  • a 1 can be hydrogen or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.
  • sulfonyl is used herein to refer to the sulfo-oxo group represented by the formula— where A 1 can be hydrogen or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.
  • sulfone as used herein is represented by the formula A 1 S(0) 2 A2 , where A 1 and A2 can be, independently, an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.
  • sulfoxide as used herein is represented by the formula
  • a 1 1 S(0)A2 where A 1 and A2" can be, independently, an alkyl, cycloalkyl, alkenyl,
  • cycloalkenyl alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.
  • R 1 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.
  • a first group can be incorporated within second group or, alternatively, the first group can be pendant (i.e., attached) to the second group.
  • an alkyl group comprising an amino group the amino group can be incorporated within the backbone of the alkyl group.
  • 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.
  • the terms "coke” is used to mean carbon containing solid materials, which are essentially non-volatile solids at the reaction conditions.
  • 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.
  • 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.
  • compounds of the invention may contain "optionally substituted” moieties.
  • 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.
  • 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.
  • individual substituents can be further optionally substituted (i.e., further substituted or unsubstituted).
  • GHSV Gas Hourly Space Velocity
  • a GHSV is measured at a standard temperature and pressure, and indicates how many catalyst bed volumes can be treated in a unit time.
  • the GHSV can be 750 ml/g/hr.
  • the GHSV can be 1050 ml/g/hr.
  • time-on-Stream refers to the length of time the catalyst composition is in use for a catalytic reaction in a defined reactor volume or a catalyst bed volume.
  • APR Activity Preservation Ratio
  • 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.
  • 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.
  • compositions of the invention 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.
  • % as used herein with respect to a component, is intended to mean weight percent.
  • 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.
  • a catalyst composition comprising: a. an inorganic support; b. a molybdenum; and c. at least one promoter selected from the group consisting of copper, iron, silver, zinc, calcium, cobalt, nickel, platinum, lanthanum, and cerium; wherein the total amount of promoter 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 when the at least one promoter is zinc, the molybdenum is not in the form of molybdenum oxalate; and wherein the catalyst converts methane to an aromatic compound.
  • the aromatic compound comprises benzene, toluene, naphthalene, or xylenes, or a combination thereof.
  • the aromatic compound further comprises traces of C 2 H 4 , C 2 H 6 , or C 3 H 6 , or a combination thereof.
  • the aromatic compound substantially comprises benzene.
  • 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).
  • the disclosed catalyst composition generally comprises an inorganic support; a molybdenum; and at least one promoter 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.
  • molybdenum can come from any commercially available molybdenum source.
  • any commercially available molybdenum compounds can be used, including, but not limited to molybdenum oxide, ammonium molybdate, ammonium heptamolybdate, ammonium hexamolybdate, ammonium paramolybdate, or molybdenum oxalate, or a combination thereof.
  • the at least one promoter is zinc, the molybdenum is not in the form of molybdenum oxalate
  • the catalyst composition can comprise an inorganic support as a support, a molybdenum, and at least one promoter.
  • the catalyst composition can be homogeneous or heterogeneous.
  • 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 promoter.
  • the catalyst composition is useful in connection with a high selectivity conversion of methane to an aromatic compound.
  • the inorganic support can be any support that, when combined with a molybdenum and a promoter contributes significantly to an overall catalyst composition performance exhibiting a high selectivity conversion of methane to an aromatic compound.
  • the support is suitable for treating or impregnating with molybdenum or solution thereof, and a precursor compound of the promoter or solution thereof.
  • the inorganic support can be either amorphous or crystalline.
  • 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.
  • 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.
  • a microporous crystalline material including, but not limited to, silicates, aluminosilicates, titanosilicates, aluminophosphates, metallophosphates, or silicoaluminophosphates, or a combination thereof.
  • the inorganic support comprises a zeolite support.
  • Microporous aluminosilicate zeolites useful in the conversion methane to an aromatic compound are well known in the art.
  • the zeolite is a medium pore size zeolite having a pore size of 4.5 to 6.5 Angstrom.
  • suitable homogeneous medium-pore size zeolites are 10- ring zeolites, wherein the pore is formed by a ring consisting of 10 Si0 4 tetrahedral.
  • the zeolite is selected from the group of ZSM-5, ZSM-22, ZSM-8, ZSM-11, ZSM-12, or ZSM-35 zeolite structure type.
  • the zeolite is ZSM-5.
  • the zeolite is in a hydrogen form (HZSM-5), having at least a portion of the original cations associated therewith replaced by hydrogen.
  • HZSM-5 a hydrogen form
  • 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.
  • the inorganic support is HZSM-5.
  • the inorganic support comprises HZSM-5.
  • the zeolite of the present invention can be dealuminated.
  • the zeolite can have a S1O 2 /AI 2 O 3 (hereinafter "Si/2A1") ratio of 10 to 100, including exemplary Si/2A1 ratios of 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 and 95.
  • the zeolite can have a Si/2A1 ratio of 15 to 80.
  • 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).
  • 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.
  • the catalyst composition further comprises at least one promoter.
  • the at least one promoter can comprise any metal that exhibits catalytic activity when contacted with a gas stream comprising a hydrocarbon under conditions suitable to the conversion of the hydrocarbon to an aromatic compound.
  • the exemplarily metals used as the active metals include but not limited to, vanadium, chromium, manganese, iron, cobalt, nickel, copper, gallium, germanium, niobium, molybdenum, ruthenium, rhodium, silver, tantalum, tungsten, rhenium, platinum, lead, or a combination thereof.
  • the catalyst composition comprises one promoter selected from the group consisting of copper, iron, silver, zinc, calcium, cobalt, nickel, platinum, lanthanum, and cerium.
  • the catalyst composition comprises one promoter selected from the group consisting of copper, iron, silver, zinc, calcium, cobalt, nickel, platinum, lanthanum, and cerium and one or more promoters that can comprise any metal that exhibits catalytic activity when contacted with a gas stream comprising a hydrocarbon under conditions suitable to the conversion of the hydrocarbon to an aromatic compound.
  • the catalyst composition comprises at least one promoter selected from the group consisting of copper, iron, silver, zinc, calcium, cobalt, nickel, platinum, lanthanum, and cerium and one or more promoters that can comprise any metal that exhibits catalytic activity when contacted with a gas stream comprising a hydrocarbon under conditions suitable to the conversion of the hydrocarbon to an aromatic compound.
  • the catalyst composition comprises one or more promoters selected from the group consisting of copper, iron, silver, zinc, calcium, cobalt, nickel, platinum, lanthanum, and cerium.
  • the catalyst composition comprises one or more promoters selected from the group consisting of copper, iron, silver, zinc, calcium, cobalt, nickel, platinum, lanthanum, and cerium and one or more promoters that can comprise any metal that exhibits catalytic activity when contacted with a gas stream comprising a hydrocarbon under conditions suitable to the conversion of the hydrocarbon to an aromatic compound.
  • the amount of molybdenum in the catalyst composition is in the range from 1 wt. % to 20 wt. %, based on the total weight of the catalyst composition.
  • the range can include any two exemplary values.
  • the amount of molybdenum in the catalyst composition can range from 2 wt. % to 15 wt. %, based on the total weight of the catalyst composition.
  • 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.
  • the catalyst composition comprises at least one promoter, wherein the promoter comprises a substance that increases the activity of the catalyst composition.
  • the promoter can be a part of the catalyst composition or can be added separately.
  • the promoter that can comprise any metal that exhibits catalytic activity when contacted with a gas stream comprising a hydrocarbon under conditions suitable to the conversion of the hydrocarbon to an aromatic compound can comprise but is not limited to titanium, vanadium, chromium, manganese, aluminum, gallium, yttrium, zirconium, hafnium, ruthenium, rhodium, palladium, lead, neodymium, samarium, tungsten, rhenium, iridium, silicon, strontium, ytterbium, tin, gold, or a combination thereof.
  • the promoter is selected from the group consisting of copper, iron, silver, zinc, calcium, cobalt, nickel, platinum, lanthanum, and cerium. In a yet another aspect, the promoter is selected from the group consisting of copper, iron, nickel and zinc. In a further aspect, the promoter can be in the form of an oxide, a complex, or in its elemental form, or a combination thereof.
  • the composition comprises only one promoter.
  • the only promoter is selected from the group consisting of copper, iron, silver, zinc, calcium, cobalt, nickel, platinum, lanthanum, and cerium.
  • the promoter does 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.
  • the promoter in the catalyst composition is in an amount that ranges from greater than 0.01 wt.
  • the range can include any two exemplary values.
  • the promoter 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 promoter is 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.
  • a high selectivity conversion can refer to a high selectivity conversion of methane to benzene.
  • the percentage of benzene yield refers to a carbon-based mole amount of methane that is converted to benzene over an amount of a methane feed that was introduced into the system.
  • the percentage of coke ratio refers to a carbon-base mole amount of formed coke over a total carbon-based mole amount of the products.
  • benzene selectivity of the disclosed catalyst composition refers to the carbon-based molar ratio amount of benzene produced from the methane conversion over the total carbon-based amount of the products.
  • a 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).
  • the benzene selectivity of the disclosed catalyst composition is in a range between 75% to 98 %, when measured at the temperatures between 700°C to 760°C. In further aspects, the range can include any two exemplary values. In another aspect, the benzene selectivity of the disclosed catalyst composition is at least 75 % or greater, when measured at the temperatures between 700°C to 760°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 700°C to 760°C.
  • the benzene selectivity of the disclosed catalyst composition is at least 85 % or greater, when measured at the temperatures between 700°C to 760°C. In a yet even further aspect, the benzene selectivity of the disclosed catalyst composition is at least 90 % or greater, when measured at the temperatures between 700°C to 760°C.
  • a benzene yield of the catalyst composition is in a range between 6.0 % to 12 %, when measured at the temperatures between 700°C to 760°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 temperatures between 700°C to 760°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 700°C to 760°C. In a yet further aspect, the benzene yield of the disclosed catalyst composition is at least 9.0 % or greater, when measured at the temperatures between 700°C to 760°C. In a yet even further aspect, the benzene yield of the disclosed catalyst composition is at least 11.7 % or greater, when measured at the temperatures between 700°C to 760°C.
  • an Activity Preservation Ratio (APR) of the catalyst composition in the conversion of methane to an aromatic compound, at TOS of 24 hours is in the range from 90 % to 100%.
  • the range can include any two exemplary values.
  • the APR can range from 93% to 99%.
  • the APR of the catalyst composition in the conversion of methane to the aromatic compound is at least 95 % or greater at TOS of 10 hours.
  • the APR of the catalyst composition in the conversion of methane to the aromatic compound is at least 97 % or greater at TOS of 10 hours.
  • the APR of the catalyst composition in the conversion of methane to the aromatic compound is 98.3 % at TOS of 10 hours.
  • 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.
  • TOS time-on- stream
  • the range can include any two exemplary values.
  • the TOS can range from 1 hour to 15 hours.
  • a benzene productivity of the disclosed catalyst composition is in a range from 1650 to 3000 ⁇ ⁇ - ⁇ / ⁇ measured at the temperatures between 700°C to 760°C.
  • the range can include any two exemplary values.
  • the benzene productivity can range from 1700 to 2700 ⁇ ⁇ / ⁇ measured at the temperatures between 700°C to 760°C.
  • a methane gas used for converting to an aromatic compound is obtained from including but not limited to a natural gas, methane hydrates, coal bed methane, synthetic gas, or biogas, or a mixture thereof.
  • the catalyst compositions disclosed herein can be prepared by the methods of making disclosed herein or used by the methods of using disclosed herein.
  • 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.
  • a method for preparing a catalyst composition comprising: a. loading molybdenum and at least one promoter 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 promoter 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 when the at least one promoter is zinc, the molybdenum is not in the form of molybdenum oxalate; and
  • a method of preparing a catalyst composition comprising a) loading molybdenum and at least one promoter 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 promoter 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 6,000 min.
  • molybdenum can come from any commercially available molybdenum source.
  • any commercially available molybdenum compounds can be used, including, but not limited to molybdenum oxide, ammonium molybdate, ammonium heptamolybdate, ammonium hexamolybdate, ammonium paramolybdate, and molybdenum oxalate.
  • the at least one promoter is zinc, the molybdenum is not in the form of molybdenum oxalate.
  • the amount of molybdenum in the catalyst composition is in the range from 1 wt. % to 20 wt.
  • the amount of molybdenum in the catalyst composition is in the range from 2 wt. % to 15 wt. %, based on the total weight of 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.
  • the at least one promoter is selected from the group consisting of copper, iron, silver, zinc, calcium, cobalt, nickel, platinum, lanthanum, and cerium. In a yet another aspect, the promoter is selected from the group consisting of copper, iron, nickel, and zinc.
  • the at least one promoter does 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.
  • At least one promoter is loaded in its precursor form comprising nitrate, chloride, oxychloride, acetate, acetylacetonate, alkoxide, oxide, or oxalate salts of the promoter, or a combination thereof.
  • the at least one promoter is loaded in its 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,
  • the at least one promoter in the catalyst composition is loaded in an amount that ranges from greater than 0.01 wt. % to 10 wt. %, based on the total weight of the catalyst composition.
  • the range can include any two exemplary values.
  • the at least one promoter can be present in the amount ranges from 0.1 wt. % to 8 wt. % based on the total weight of the catalyst composition.
  • the promoter is present in the amount ranges from 0.2 wt. % to 7 wt. %, based on the total weight of the catalyst composition.
  • the promoter is present in the amount ranges from 0.2 wt. % to 5 wt. %, based on the total weight of the catalyst composition.
  • the loading of the molybdenum and at least one promoter selected from the group of copper, iron, silver, zinc, calcium, cobalt, nickel, platinum, lanthanum, and cerium can be done by any means well known in the art such as incipient wetness, evaporation, impregnation, spray-drying, ion-exchange, and physical mixing.
  • the molybdenum and at least one promoter 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 a soluble salt comprising at least one additional promoter.
  • the molybdenum and at least one promoter can be loaded onto an inorganic support subsequently by contacting the zeolite with a solution comprising the 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.
  • at least one promoter is loaded by an impregnation method.
  • the impregnation method is performed by co-impregnation or two step impregnation.
  • the molybdenum can be loaded first. In a further aspect, the molybdenum can be loaded last. In a yet further aspect, no specific order of addition of the molybdenum and at least one promoter is required. In a yet even further aspect, the molybdenum and the at least one promoter are loaded in any order suitable to the specific conditions and can be easily determined by one of ordinary skills in the art. [0094] In one aspect, wet impregnation can be used for the catalyst composition and at least one promoter loading. In another aspect, the catalyst composition is not prepared using the shock frozen method by pouring liquid nitrogen over the sample precursor.
  • the catalyst composition is calcinated at a temperature in a range from 450°C to 750°C.
  • the calcining temperature can be in a range from 500°C to 700°C, or 520°C to 680°C.
  • the 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, the calcining the catalyst composition continues in a time range from 2 h to 80 hours. In a yet another aspect, the calcining the catalyst composition continues in a time range from 10 h to 70 hours.
  • 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.
  • a method of preparing a catalyst composition comprising a) loading the molybdenum and at least one promoter 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 promoter 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 6,000 min.
  • promoter selected from the group consisting of copper, iron, silver, zinc, calcium, cobalt, nickel, platinum, lanthanum, and cerium
  • the method of preparing the catalyst composition wherein the catalyst composition has an Activity Preservation Ration (APR) in the conversion of methane to benzene of at least 90% or greater at a steady state of TOS of 10 hours over a temperature range from 700°C to 760°C.
  • APR Activity Preservation Ration
  • the method of preparing the catalyst composition wherein the catalyst composition has the Activity Preservation Ration (APR) in the conversion of methane to benzene of at least 97% or greater at a steady state of TOS of 10 hours over a temperature range from 700°C to 760°C.
  • the method of preparing the catalyst composition wherein the catalyst composition has the Activity Preservation Ration (APR) in the conversion of methane to benzene of at least 98.3 % at a steady state of TOS of 10 hours over a temperature range from 700°C to 760°C.
  • APR Activity Preservation Ration
  • the method of making can be used to prepare the composition disclosed herein or used by the method disclosed herein.
  • the catalyst composition disclosed herein provides an enhanced catalytic performance when used as a catalyst composition in methane conversion to an aromatic compound.
  • a method of using the disclosed catalyst composition comprising contacting the composition of the catalyst with a methane feed to produce an aromatic compound.
  • a method of using the catalyst composition comprising contacting the catalyst composition with methane to produce an aromatic compound, wherein the aromatic compound comprises benzene, toluene, naphthalene, or xylenes, or a combination thereof.
  • the aromatic compound further comprises traces of C 2 H 4 , C 2 3 ⁇ 4, or C 3 H 6 , or a combination thereof.
  • the aromatic compound comprises substantially benzene.
  • the aromatic compound is produced under reaction conditions at a temperature range from 700°C to 760°C.
  • the range can include any two exemplary values.
  • the temperature can range from 710°C to 750°C, for example, 720°C to 750°C.
  • the aromatic compound is produced under reaction conditions at a GHSV range from 300 ml/g/h to 2050 ml/g/h°C.
  • the GHSV can be in a range derived from any two exemplary values.
  • the GHSV can range from 400 ml/g/h to 1500 ml/g/h, or, 500 ml/g/h to 1050 ml/g/h.
  • compositions and methods include at least the following aspects.
  • a catalyst composition comprising:
  • the total amount of the promoter 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 when the at least one promoter is zinc, the molybdenum is not in the form of molybdenum oxalate; and
  • catalyst composition converts methane to an aromatic compound.
  • a catalyst composition for converting methane to an aromatic compound comprising:
  • At least one promoter selected from the group consisting of copper, iron, silver, zinc, calcium, cobalt, nickel, platinum, lanthanum, and cerium;
  • the total amount of the promoter 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 when the at least one promoter is zinc, the molybdenum is not in the form of molybdenum oxalate.
  • Aspect 2 The composition of aspect 1, wherein the inorganic support comprises a HZSM-5 support comprising a Si/2A1 ratio from 10 to 100.
  • Aspect 3 The composition of any one of aspects 1-2, wherein the inorganic support comprises a HZSM-5 support comprising a Si/2A1 ratio from 15 to 80.
  • Aspect 4 The composition of any one of aspects 1-3, wherein the inorganic support comprises the HZSM-5 support comprising a Si/2A1 ratio from 20 to 60.
  • Aspect 5 The composition of any one 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.
  • Aspect 6 The composition of any one 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.
  • Aspect 7 The composition of any one of aspects 1-6, wherein the
  • Aspect 8 The composition of any one of aspects 1-7, wherein the inorganic support is comprises HZSM-5.
  • Aspect 9 The composition of any one of aspects 1-8, wherein the promoter is in the form of an oxide, a complex, or in its elemental form or a combination thereof.
  • Aspect 10 The composition of any one of aspects 1-9, wherein the
  • molybdenum comprises molybdenum oxide, ammonium molybdate, ammonium
  • heptamolybdate ammonium hexamolybdate, or ammonium paramolybdate or a combination thereof.
  • Aspect 11 The composition of any of aspects 1-10, wherein a benzene selectivity is in a range between 75 % to 98% measured at the temperatures between 700°C to 760°C.
  • Aspect 12 The composition of any of aspects 1-11, wherein the benzene selectivity is at least 75 % measured at the temperatures between 700°C to 760°C.
  • Aspect 13 The composition of any of aspects 1-12, wherein the benzene selectivity is at least 80 % measured at the temperatures between 700°C to 760°C.
  • Aspect 14 The composition of any of aspects 1-13, wherein the benzene selectivity is at least 85 % measured at the temperatures between 700°C to 760°C.
  • Aspect 15 The composition of any of aspects 1-14, wherein the benzene selectivity is at least 90 % measured at the temperatures between 700°C to 760°C.
  • Aspect 16 The composition of any of aspects 1-15, wherein a benzene yield is in a range between 6.0 % to 12.0 % measured at the temperatures between 700°C to 760°C.
  • Aspect 17 The composition of any one of aspects 1-16, wherein the benzene yield is at least 6.5 % or greater, measured at the temperatures between 700°C to 760°C.
  • Aspect 18 The composition of any one of aspects 1-17, wherein the benzene yield is at least 7.2 % or greater, measured at the temperatures between 700°C to 760°C.
  • Aspect 19 The composition of any one of aspects 1-18, wherein the benzene yield is at least 9.0 % or greater, measured at the temperatures between 700°C to 760°C.
  • Aspect 20 The composition of any one of aspects 1-19, wherein the benzene yield is at least 11.7 % or greater, measured at the temperatures between 700°C to 760°C.
  • Aspect 21 The composition of any one of aspects 1-20, wherein an Activity Preservation Ratio (APR) of the catalyst composition in the conversion of methane to the aromatic compound is at least 95 % or greater at TOS of 10 hours.
  • Aspect 22 The composition of any one of aspects 1-21, wherein the Activity Preservation Ration (APR) of the catalyst composition in the conversion of methane to the aromatic compound is at least 97 % at TOS of 10 hours.
  • Aspect 23 The composition of any one of aspects 1-22, wherein the Activity Preservation Ratio (APR) of the catalyst composition in the conversion of methane to the aromatic compound is 98.3 % at TOS of 10 hours.
  • APR Activity Preservation Ratio
  • Aspect 24 The composition of any one of aspects 1-23, wherein the Activity Preservation Ration (APR) of the catalyst composition in the conversion of the methane to the aromatic compound is at least 98.3 % at TOS of 10 hours.
  • APR Activity Preservation Ration
  • Aspect 25 The composition of any one of aspects 1-24, wherein a benzene productivity is in a range between 1650 to 3000 ⁇ ⁇ / ⁇ measured at the temperatures between 700°C to 760°C.
  • Aspect 26 The composition of any one of aspects 1-25, wherein the at least one promoter is selected from the group consisting of copper, nickel, iron, and zinc.
  • Aspect 27 A method of using the composition of any one of claims 1-26, comprising contacting the composition of any one of claims 1-26 with a methane feed to produce an aromatic compound.
  • Aspect 28 The method of aspect 27, wherein the aromatic compound comprises benzene, toluene, naphthalene, or xylene or a combination thereof.
  • Aspect 29 The method of any one of aspects 27-28, further comprising traces of C 2 H 4 , C 2 H 6 , or C 3 H 6 , or a combination thereof.
  • Aspect 30 The method of any one of aspects 27-29, wherein the aromatic compound comprises substantially benzene.
  • Aspect 31 The method of any one of aspects 27-30, wherein the aromatic compound is produced under reaction conditions at a temperature range from 700°C to 760°C.
  • Aspect 32 The method of any one of aspects 27-31, wherein the aromatic compound is produced under reaction conditions with GHSV ranging from 300 ml/g/h to 2000 ml/g/h.
  • Aspect 33 The method of aspect 32, wherein the aromatic compound is produced under reaction conditions with GHSV ranging from 500 ml/g/h to 1050 ml/g/h.
  • a method for preparing a catalyst composition comprising: a. loading molybdenum and at least one promoter 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 promoter 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 when the at least one promoter is zinc, the molybdenum is not in the form of molybdenum oxalate; and
  • Aspect 35 The method of aspect 34, wherein molybdenum is loaded as ammonium heptamolybdate tetrahydrate.
  • Aspect 36 The method of any of aspects 34-35, wherein the calcining comprises heating the catalyst composition in air or in nitrogen, or both sequentially.
  • Aspect 37 The method of any one of aspects 34-36, wherein at least one promoter is selected from the group consisting of copper, iron, nickel, and zinc.
  • Aspect 38 The method of any one of aspects 34-37, wherein at least one promoter is loaded in its precursor form.
  • Aspect 39 The method of any one of aspects 34-38, wherein at least one promoter is loaded by an impregnation method.
  • Aspect 40 The method of any one of aspects 34-39, wherein the impregnation method is performed by co-impregnation.
  • Aspect 41 The method of any one of aspects 34-40, wherein the catalyst composition has an Activity Preservation Ratio (APR) in the conversion of methane to benzene of at least 90 % or greater at TOS of 24 hours over a temperature range from 700°C to 760°C.
  • APR Activity Preservation Ratio
  • Aspect 42 The method of any one of aspects 34-41, wherein the catalyst composition has an Activity Preservation Ratio (APR) in the conversion of methane to benzene of at least 97 % or greater at TOS of 24 hours over a temperature range from 700°C to 760°C.
  • APR Activity Preservation Ratio
  • Aspect 43 The method of any one of aspects 34-42, wherein the catalyst composition has an Activity Preservation Ratio (APR) in the conversion of methane to benzene of at least 98.3 % at TOS of 24 hours over a temperature range from 700°C to 760°C.
  • APR Activity Preservation Ratio
  • the inorganic support comprises HZSM-5.
  • Aspect 45 The composition of any one of claims 1-26, wherein the only promoter is selected from the group consisting of copper, iron, silver, zinc, calcium, cobalt, nickel, platinum, lanthanum, and cerium.
  • Aspect 46 The method of any one of claims 24-44, wherein the only promoter is selected from the group consisting of copper, iron, silver, zinc, calcium, cobalt, nickel, platinum, lanthanum, and cerium.
  • the catalyst composition for converting methane to aromatic compounds is formed by loading MFI-type zeolite support with molybdenum and a singular promoter.
  • the MFI-type support, 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.
  • the methane conversion, in % was calculated as a methane mole amount converted to the products over an inlet total C-amount, and the coke ratio, in %, was calculated as a formed coke mole amount on a carbon-mole over a total mole amount of the products on a carbon-mole base, using an external standard method.
  • HZSM-5 zeolites having Si/2A1 (Si0 2 /Al 2 0 3 ) ratios of 23, 50, and 80 were employed as a metallo-silicate support material in the catalyst composition preparation.
  • the prepared exemplarily molybdenum-zinc impregnation solution was added to the above 10 gram of HZSM-5 support, for example, having a Si/2A1 of 80, and the mixture of the support and the impregnation solution was stirred for 60 minutes using a magnetic agitation. 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 500°C for 6 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. The impregnation can be also performed in a two step process.
  • Comparator example Cpl was prepared using a method described above without adding of any of the promoter precursors. Molybdenum alone was loaded on the metallo-silicate, having a Si/2A1 ratio of 50, thereby obtaining the catalyst composition of comparator example Cpl. Comparator example Cp2 was prepared using a similar method of preparation, wherein the metallo-silicate carries has a Si/2A1 ratio of 23. [0164] Examples 2-10 were prepared accordingly to a method of preparation of the singular promoted molybdenum-based catalyst compositions as described above.
  • 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 CH 4 , C 2 H 4 , C 2 H 6 , C 3 H 6 , C 3 H 8 , C 6 H 6 , C 7 H 8 , and CioHs; and a Molecular Sieve column and a thermal conductivity detector (TCD) for the separation and analysis of H 2 , N 2 , CH 4 , CO, C0 2 , C 2 H 4 , and C 2 H 6 .
  • FID flame ionization detector
  • the data were calculated by using an exterior standard method utilizing three mixture gas cylinders of ten components (CH 4 , C 2 H 4 , C 2 3 ⁇ 4, C 3 H 6 , C 3 H 8 , Benzene, CO, H 2 , N 2 , C0 2 ), the benzene content in the three cylinders was 0.1 wt%, 0.4 wt%, and 0.9 wt% respectively.
  • Table 2 shows the catalytic performance of comparator example Cpl versus TOS, wherein the MTB reaction conditions were kept as following: 700°C, 1 bar, and GHSV of 1050 ml/g/h.
  • the measured benzene yield was 3.46 %, and the measured benzene selectivity excluding coke was 86.7%, with the benzene productivity of 1622 ⁇ ⁇ - ⁇ / ⁇ .
  • benzene yield dropped to 2.48%, with decrease in a benzene selectivity and productivity to 71.1% and 1162 ⁇ ⁇ / ⁇ respectively.
  • the Activity Preservation Ratio i.e. the benzene productivity stabilizer indicator, was calculated as the ratio of the benzene productivity at the 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 % (Bz. Productivity (180)/Bz. Productivity (60)), at 300 minutes TOS, the measured APR dropped to 71.7%, showing a poor stability of Cpl.
  • Table 3 shows the catalytic performance of the singular promoted catalyst compositions labeled as Example 1 to Example 4.
  • the MTB reaction conditions were kept as following: 700°C, 1 bar, and GHSV of 525 ml/g/h, TOS at steady state 180 to 300 min.
  • Table 4 shows the catalytic performance of the singular promoted catalyst compositions labeled as Example 5 to Example 10.
  • the MTB reaction conditions were kept as following: 710°C, 1 bar, and GHSV of 525 ml/g/h, TOS at steady state 180 to 300 min. It was demonstrated that the benzene yield and benzene productivity depend significantly on a type of the promoter used. For example, it was shown that use of a Fe promoted catalyst composition that was calcined at 700°C (Example 10) did not improve the benzene selectivity, yield and productivity, but in fact, resulted in the poorer catalytic performance when compared to comparator example Cp2.
  • a Zn promoted catalyst composition when calcined at a slightly higher temperature and a longer period of time demonstrated a slight improvement in the catalytic performance when compared to an identical sample that was calcined at a lower temperature and a shorter period of time (Example 6). It was also demonstrated that copper when used as a promoter improves significantly the performance of the catalyst composition.
  • Table 6 shows the catalytic performance of Example 8 as a function of the reaction TOS.
  • the reaction's conditions were kept as following: #a: temperature of 700°C, pressure of 1 bar, and GHSV of 525 ml/g/h; #b: temperature of 710 oC, pressure of 1 bar, and GHSV of 750 ml/g/h. It can be observed that the high benzene yield and benzene productivity were obtained at a higher reaction temperature and higher GHSV.
  • Benzene productivity, benzene yield and selectivity were also measured for Example 5 at various GHSV conditions are discussed in detail herein and in Table 8. The measurements were performed at a constant temperature of 710°C, and a pressure of 1 bar.
  • Fe was used as a singular catalyst promoter and was impregnated into the catalyst composition by two step impregnation process. It was demonstrated that use of a Fe promoter improved the benzene yield and selectivity without coke, and the benzene productivity when GHSV was increased to 750 ml/g/h. However, a further increase in GHSV to 1050 ml/g/h caused the drop of the benzene yield and selectivity without coke, while continuously increased the benzene productivity.

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Abstract

L'invention concerne une composition catalytique présentant une sélectivité élevée pour la transformation du méthane en un composé aromatique. La composition catalytique comprend un support inorganique ; un molybdène ; et au moins un promoteur sélectionné dans le groupe constitué par le cuivre, le fer , l'argent, le zinc, le calcium, le cobalt, le nickel, le platine, le lanthane, et le cérium, la quantité totale de promoteur présent se situant dans une plage allant de plus 0,01 % en poids à 0 % en poids sur la base du poids total de la composition catalytique. Lorsqu'au moins un promoteur est le zinc, le molybdène ne se présente pas sous forme d'oxalate de molybdène, et la composition catalytique transforme le méthane en composé aromatique. L'invention concerne également un procédé pour préparer la composition catalytique et un procédé d'utilisation de cette dernière pour produire un composé aromatique.
PCT/IB2014/061614 2013-05-28 2014-05-22 Composition catalytique à base de molybdène promue pour production d'hydrocarbure aromatique à partir de méthane WO2014191874A1 (fr)

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