WO2018213183A1 - Catalyseurs à oxydes mixtes pour couplage oxydant du méthane - Google Patents

Catalyseurs à oxydes mixtes pour couplage oxydant du méthane Download PDF

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Publication number
WO2018213183A1
WO2018213183A1 PCT/US2018/032556 US2018032556W WO2018213183A1 WO 2018213183 A1 WO2018213183 A1 WO 2018213183A1 US 2018032556 W US2018032556 W US 2018032556W WO 2018213183 A1 WO2018213183 A1 WO 2018213183A1
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rare earth
earth element
ocm
ocm catalyst
catalyst composition
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PCT/US2018/032556
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English (en)
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Wugeng Liang
Vidya Sagar Reddy SARSANI
Aghaddin Mamedov
David West
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Sabic Global Technologies, B.V.
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Publication of WO2018213183A1 publication Critical patent/WO2018213183A1/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
    • C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
    • C07C2/84—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling catalytic
    • 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
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C07C2521/08—Silica
    • 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
    • C07C2523/30—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
    • C07C2523/16—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
    • C07C2523/32—Manganese, technetium or rhenium
    • C07C2523/34—Manganese
    • 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
    • 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
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the present disclosure relates to catalyst compositions for oxidative coupling of methane (OCM), more specifically catalyst compositions for OCM based on oxides of rare earth elements and Mn/Na 2 WO 4 , and methods of making and using same.
  • OCM oxidative coupling of methane
  • Hydrocarbons and specifically olefins such as ethylene, are typically building blocks used to produce a wide range of products, for example, break-resistant containers and packaging materials.
  • ethylene is produced by heating natural gas condensates and petroleum distillates, which include ethane and higher hydrocarbons, and the produced ethylene is separated from a product mixture by using gas separation processes.
  • Oxidative coupling of the methane (OCM) has been the target of intense scientific and commercial interest for more than thirty years due to the tremendous potential of such technology to reduce costs, energy, and environmental emissions in the production of ethylene (C 2 H 4 ).
  • methane (CH 4 ) and oxygen (O 2 ) react exothermically over a catalyst to form C 2 H 4 , water (H 2 O) and heat.
  • Ethylene can be produced by OCM as represented by Equations (I) and (II):
  • CH 4 is first oxidatively converted into ethane (C 2 H 6 ), and then into C 2 H 4 .
  • CH 4 is activated heterogeneously on a catalyst surface, forming methyl free radicals (e.g., CH 3 ⁇ ), which then couple in a gas phase to form C 2 H 6 .
  • C 2 H 6 subsequently undergoes dehydrogenation to form C 2 H 4 .
  • An overall yield of desired C 2 hydrocarbons is reduced by non-selective reactions of methyl radicals with oxygen on the catalyst surface and/or in the gas phase, which produce (undesirable) carbon monoxide and carbon dioxide.
  • an oxidative coupling of methane (OCM) catalyst composition characterized by the general formula (E a D b O x )-Mn/Na 2 WO 4 ; wherein E is a first rare earth element; wherein D is a second rare earth element; wherein the first rare earth element and the second rare earth element are different; wherein a is 1.0; wherein b is from about 0 to about 10.0; wherein when b is 0, the first rare earth element is not lanthanum (La) alone or cerium (Ce) alone; and wherein x balances the oxidation states.
  • OCM methane
  • Also disclosed herein is a method of making an oxidative coupling of methane (OCM) catalyst composition
  • OCM methane
  • the OCM catalyst precursor mixture comprises one or more compounds comprising a first rare earth element cation, one or more compounds comprising a second rare earth element cation, one or more compounds comprising a Mn cation, and Na 2 WO 4 ; wherein the first rare earth element cation and the second rare earth element cation are different; wherein the OCM catalyst precursor mixture is characterized by a molar ratio of second rare earth element to first rare earth element of b:1; and wherein b is from about 0 to about 10.0, and wherein when b is 0, the first rare earth element is not lanthanum (La) alone or cerium (Ce) alone, and (b) calcining the OCM catalyst precursor mixture at a temperature of equal to or greater than about 700 o C to form the OCM catalyst composition.
  • a method for producing olefins comprising (a) introducing a reactant mixture to a reactor comprising an oxidative coupling of methane (OCM) catalyst composition; wherein the reactant mixture comprises methane (CH 4 ) and oxygen (O 2 ); wherein the OCM catalyst composition is characterized by the general formula (E a D b O x )-Mn/Na 2 WO 4 ; wherein E is a first rare earth element; wherein D is a second rare earth element; wherein the first rare earth element and the second rare earth element are different; wherein a is 1.0; wherein b is from about 0 to about 10.0; wherein when b is 0, the first rare earth element is not lanthanum (La) alone or cerium (Ce) alone; and wherein x balances the oxidation states, (b) allowing at least a portion of the reactant mixture to contact at least a portion of the OCM catalyst composition and react via an OCM reaction to
  • Figures 1 and 2 display graphs of O 2 conversion in an OCM reaction over time for different catalysts.
  • an OCM catalyst composition can be characterized by the general formula (E a D b O x )-Mn/Na 2 WO 4 ; wherein E is a first rare earth element; wherein D is a second rare earth element; wherein the first rare earth element and the second rare earth element are different; wherein a is 1.0; wherein b is from about 0 to about 10.0; wherein when b is 0, the first rare earth element is not lanthanum (La) alone or cerium (Ce) alone; and wherein x balances the oxidation states.
  • a method of making an OCM catalyst composition as disclosed herein can generally comprise the steps of (a) forming an OCM catalyst precursor mixture; wherein the OCM catalyst precursor mixture comprises one or more compounds comprising a first rare earth element cation, one or more compounds comprising a second rare earth element cation, one or more compounds comprising a Mn cation, and Na 2 WO 4 ; wherein the first rare earth element cation and the second rare earth element cation are different; and wherein the OCM catalyst precursor mixture is characterized by a molar ratio of second rare earth element to first rare earth element of b:1, wherein b is from about 0 to about 10.0; and (b) calcining the OCM catalyst precursor mixture to form the OCM catalyst composition, wherein the OCM catalyst composition can be characterized by the general formula (E a D b O x )-Mn/Na 2 WO 4 ; wherein E is a first rare earth element; wherein D is a second rare earth element; wherein the first
  • the one or more compounds comprising a first rare earth element cation comprises a first rare earth element nitrate, a first rare earth element oxide, a first rare earth element hydroxide, a first rare earth element chloride, a first rare earth element acetate, a first rare earth element carbonate, and the like, or combinations thereof;
  • the one or more compounds comprising a second rare earth element cation comprises a second rare earth element nitrate, a second rare earth element oxide, a second rare earth element hydroxide, a second rare earth element chloride, a second rare earth element acetate, a second rare earth element carbonate, and the like, or combinations thereof;
  • the one or more compounds comprising a Mn cation comprises a Mn nitrate, a Mn oxide, a Mn hydroxide, a Mn chloride, a Mn acetate, a Mn carbonate, and the like, or combinations thereof.
  • “combinations thereof” is inclusive of one or more of the recited elements, optionally together with a like element not recited, e.g., inclusive of a combination of one or more of the named components, optionally with one or more other components not specifically named that have essentially the same function.
  • the term“combination” is inclusive of blends, mixtures, alloys, reaction products, and the like.
  • references throughout the specification to“an aspect,”“another aspect,”“other aspects,”“some aspects,” and so forth, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the aspect is included in at least an aspect described herein, and may or may not be present in other aspects.
  • a particular element e.g., feature, structure, property, and/or characteristic
  • the described element(s) can be combined in any suitable manner in the various aspects.
  • the terms“inhibiting” or“reducing” or“preventing” or“avoiding” or any variation of these terms include any measurable decrease or complete inhibition to achieve a desired result.
  • the term“effective,” means adequate to accomplish a desired, expected, or intended result.
  • the terms“comprising” (and any form of comprising, such as“comprise” and “comprises”),“having” (and any form of having, such as“have” and“has”),“including” (and any form of including, such as“include” and“includes”) or“containing” (and any form of containing, such as“contain” and“contains”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.
  • a method for producing olefins as disclosed herein can comprise introducing a reactant mixture to a reactor comprising an oxidative coupling of methane (OCM) catalyst composition to form a product mixture comprising olefins, wherein the reactant mixture comprises methane (CH 4 ) and oxygen (O 2 ), and wherein the OCM catalyst composition can be characterized by the general formula (E a D b O x )-Mn/Na 2 WO 4 ; wherein E is a first rare earth element; wherein D is a second rare earth element; wherein the first rare earth element and the second rare earth element are different; wherein a is 1.0; wherein b is from about 0 to about 10.0; wherein when b is 0, the first rare earth element is not lanthanum (La) alone or cerium (Ce) alone; and wherein x balances the oxidation states.
  • OCM methane
  • the reactant mixture can be a gaseous mixture.
  • the reactant mixture can comprise a hydrocarbon or mixtures of hydrocarbons, and oxygen.
  • the hydrocarbon or mixtures of hydrocarbons can comprise natural gas (e.g., CH 4 ), liquefied petroleum gas comprising C 2 -C 5 hydrocarbons, C 6 + heavy hydrocarbons (e.g., C 6 to C 24 hydrocarbons such as diesel fuel, jet fuel, gasoline, tars, kerosene, etc.), oxygenated hydrocarbons, biodiesel, alcohols, dimethyl ether, and the like, or combinations thereof.
  • the reactant mixture can comprise CH 4 and O 2 .
  • the O 2 used in the reactant mixture can be oxygen gas (which may be obtained via a membrane separation process), technical oxygen (which may contain some air), air, oxygen enriched air, and the like, or combinations thereof.
  • the reactant mixture can further comprise a diluent.
  • the diluent is inert with respect to the OCM reaction, e.g., the diluent does not participate in the OCM reaction.
  • the diluent can comprise water, nitrogen, inert gases, and the like, or combinations thereof.
  • the diluent can provide for heat control of the OCM reaction, e.g., the diluent can act as a heat sink.
  • an inert compound e.g., a diluent
  • the diluent can be present in the reactant mixture in an amount of from about 0.5% to about 80%, alternatively from about 5% to about 70%, or alternatively from about 10% to about 60%, based on the total volume of the reactant mixture.
  • a method for producing olefins can comprise introducing the reactant mixture to a reactor, wherein the reactor comprises the OCM catalyst composition disclosed herein.
  • the reactor can comprise an adiabatic reactor, an autothermal reactor, an isothermal reactor, a tubular reactor, a cooled tubular reactor, a continuous flow reactor, a fixed bed reactor, a fluidized bed reactor, a moving bed reactor, and the like, or combinations thereof.
  • the reactor can comprise an adiabatic reactor.
  • the reactor can comprise a catalyst bed comprising the OCM catalyst composition disclosed herein.
  • the reactant mixture can be introduced to the reactor at a temperature of from about 150 o C to about 1,000 o C, alternatively from about 225 o C to about 900 o C, or alternatively from about 250 o C to about 800 o C.
  • a temperature of from about 150 o C to about 1,000 o C, alternatively from about 225 o C to about 900 o C, or alternatively from about 250 o C to about 800 o C.
  • the reactant mixture can be introduced to the reactor at a temperature effective to promote an OCM reaction.
  • the reactor can be characterized by a temperature of from about 400 o C to about 1,200 o C, alternatively from about 500 o C to about 1,100 o C, or alternatively from about 600 o C to about 1,000 o C.
  • the reactor can be characterized by a pressure of from about ambient pressure (e.g., atmospheric pressure) to about 500 psig, alternatively from about ambient pressure to about 200 psig, or alternatively from about ambient pressure to about 150 psig.
  • the method for producing olefins as disclosed herein can be carried out at ambient pressure.
  • the reactor can be characterized by a gas hourly space velocity (GHSV) of from about 500 h -1 to about 10,000,000 h -1 , alternatively from about 500 h -1 to about 1,000,000 h -1 , alternatively from about 500 h -1 to about 500,000 h -1 , alternatively from about 1,000 h -1 to about 500,000 h -1 , alternatively from about 1,500 h -1 to about 500,000 h -1 , alternatively from about 2,000 h -1 to about 500,000 h -1 , alternatively from about 5,000 h -1 to about 500,000 h -1 , alternatively from about 10,000 h -1 to about 500,000 h -1 , or alternatively from about 50,000 h -1 to about 500,000 h -1 .
  • the GHSV relates a reactant (e.g., reactant mixture) gas flow rate to a reactor volume.
  • GHSV is usually measured at standard temperature and pressure.
  • the reactor can comprise an OCM catalyst composition as disclosed herein characterized by the general formula (E a D b O x )-Mn/Na 2 WO 4 ; wherein E is a first rare earth element; wherein D is a second rare earth element; wherein the first rare earth element and the second rare earth element are different; wherein a is 1.0; wherein b is from about 0 to about 10.0, alternatively from about 0.1 to about 8, or alternatively from about 0.5 to about 5; wherein when b is 0, the first rare earth element is not lanthanum (La) alone or cerium (Ce) alone; and wherein x balances the oxidation states.
  • each of the E and D can have multiple oxidation states within the OCM catalyst composition (e.g., within a (E a D b O x ) portion of the OCM catalyst composition), and as such x can have any suitable value that allows for the oxygen anions to balance all the E and D cations within the (E a D b O x ) portion of the OCM catalyst composition.
  • the different metals (E, D, Na, Mn, W) present in the OCM catalyst compositions as disclosed herein can display synergetic effects in terms of stability, conversion and selectivity.
  • the OCM catalyst composition can be regarded as a composite comprising a (E a D b O x ) portion or phase and a Mn/Na 2 WO 4 portion or phase, wherein the (E a D b O x ) portion and the Mn/Na 2 WO 4 portion can be interspersed.
  • the OCM catalyst composition can comprise a continuous phase comprising Mn/Na 2 WO 4 ; having a discontinuous phase comprising (E a D b O x ) dispersed therein.
  • the OCM catalyst composition can comprise a continuous phase comprising (E a D b O x ); having a discontinuous phase comprising Mn/Na 2 WO 4 dispersed therein.
  • the OCM catalyst composition can comprise both a continuous phase comprising Mn/Na 2 WO 4 and a continuous phase comprising (E a D b O x ), wherein the phase comprising Mn/Na 2 WO 4 and the phase comprising (E a D b O x ) contact each other.
  • the OCM catalyst composition can comprise regions of a phase comprising Mn/Na 2 WO 4 and regions of a phase comprising (E a D b O x ), wherein at least a portion the regions of the phase comprising Mn/Na 2 WO 4 contact at least a portion of the regions of the phase comprising (E a D b O x ).
  • each Mn/Na 2 WO 4 and (E a D b O x ) present in the OCM catalyst composition contribute to the distribution of the phase comprising Mn/Na 2 WO 4 and the phase comprising (E a D b O x ) within the OCM catalyst composition.
  • the OCM catalyst composition as disclosed herein can comprise a first rare earth element (E), and optionally a second rare earth element (D), wherein E and D are different.
  • the first rare earth element (E) and the second rare earth element (D) can each independently be selected from the group consisting of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), scandium (Sc), yttrium (Y), and combinations thereof.
  • the first rare earth element (E) and the second rare earth element (D) can each independently be selected from the group consisting of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), gadolinium (Gd), and combinations thereof.
  • the first rare earth element (E), the second rare earth element (D), or both can be basic (e.g., can exhibit some degree of basicity; can have affinity for hydrogen; can exhibit some degree of affinity for hydrogen).
  • the first rare earth element (E) is basic.
  • the second rare earth element (D) is basic.
  • both the first rare earth element (E) and the second rare earth element (D) are basic.
  • Nonlimiting examples of rare earth elements that can be considered basic for purposes of the disclosure herein include lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), scandium (Sc), yttrium (Y), or combinations thereof.
  • the OCM reaction is a multi-step reaction, wherein each step of the OCM reaction could benefit from specific OCM catalytic properties.
  • an OCM catalyst should exhibit some degree of basicity to abstract a hydrogen from CH 4 to form hydroxyl groups [OH] on the OCM catalyst surface, as well as methyl radicals (CH 3 ⁇ ).
  • an OCM catalyst should exhibit oxidative properties for the OCM catalyst to convert the hydroxyl groups [OH] from the catalyst surface to water, which can allow for the OCM reaction to continue (e.g., propagate).
  • an OCM catalyst could also benefit from properties like oxygen ion conductivity and proton conductivity, which properties can be critical for the OCM reaction to proceed at a very high rate (e.g., its highest possible rate).
  • an OCM catalyst comprising a single metal might not provide all the necessary properties for an optimum OCM reaction (e.g., best OCM reaction outcome) at the best level, and as such conducting an optimum OCM reaction may require an OCM catalyst with tailored composition in terms of metals present, wherein the different metals can have optimum properties for various OCM reaction steps, and wherein the different metals can provide synergistically for achieving the best performance for the OCM catalyst in an OCM reaction.
  • Mn/Na 2 WO 4 (e.g., a Mn/Na 2 WO 4 portion of the OCM catalyst composition) is a catalyst for an OCM reaction in the absence of the (E a D b O x ) (e.g., the (E a D b O x ) portion of the OCM catalyst composition).
  • the Mn/Na 2 WO 4 portion of the OCM catalyst composition can display catalytic activity in an OCM reaction by itself (e.g., without the (E a D b O x ) portion).
  • the Mn/Na 2 WO 4 portion of the OCM catalyst composition can stand (e.g., act, operate, etc.) by itself (e.g., without the (E a D b O x ) portion) to catalyze an OCM reaction.
  • (E a D b O x ) (e.g., the (E a D b O x ) portion of the OCM catalyst composition) is a catalyst for an OCM reaction in the absence of Mn/Na 2 WO 4 (e.g., the Mn/Na 2 WO 4 portion of the OCM catalyst composition).
  • the (E a D b O x ) portion of the OCM catalyst composition can display catalytic activity in an OCM reaction by itself (e.g., without the Mn/Na 2 WO 4 portion).
  • the (E a D b O x ) portion of the OCM catalyst composition can stand (e.g., act, operate, etc.) by itself (e.g., without the Mn/Na 2 WO 4 portion) to catalyze an OCM reaction.
  • (E a D b O x ) (e.g., the (E a D b O x ) portion of the OCM catalyst composition) is a high performance catalyst for an OCM reaction in the absence of Mn/Na 2 WO 4 (e.g., the Mn/Na 2 WO 4 portion of the OCM catalyst composition).
  • a“high performance catalyst” for an OCM reaction refers to a catalyst that displays a higher conversion, a higher selectivity, a higher stability, and the like, or combinations thereof, in an OCM reaction, when compared to a conventional OCM catalyst.
  • Nonlimiting examples of conventional OCM catalysts include CeO 2 , La 2 O 3 - CeO 2 , Ca/CeO 2 , Mn/Na 2 WO 4 , Li 2 O, Na 2 O, Cs 2 O, WO 3 , Mn 3 O 4 , CaO, MgO, SrO, BaO, CaO-MgO, CaO- BaO, Li/MgO, MnO, W 2 O 3 , SnO 2 , Yb 2 O 3 , Sm 2 O 3 , MnO-W 2 O 3 , MnO-W 2 O 3 -Na 2 O, MnO-W 2 O 3 -Li 2 O, SrO/La 2 O 3 , Ce 2 O 3 , La/MgO, La 2 O 3 -CeO 2 -Na 2 O, La 2 O 3 -CeO 2 -CaO, La 2 O 3 -CeO 2 -MnO-WO 3 -SrO, Na
  • deactivation of OCM catalysts can be due to the over-reduction of the OCM catalyst; leaching of active components (e.g., metals, such as Na) from the OCM catalyst; or other reasons.
  • deactivation of an OCM catalyst can be decreased or minimized by increasing the basicity (e.g., basic properties) of the OCM catalyst, for example by incorporating basic elements (e.g., first rare earth element (E); second rare earth element (D); or both) in the OCM catalyst composition, as disclosed herein.
  • rare earth element oxides can increase the basicity of an OCM catalyst, as well as display catalytic activity in an OCM reaction by participating in a methane activation process for the production of methyl radicals.
  • the OCM catalyst composition as disclosed herein can display two parallel routes of methane activation for the production of methyl radicals involving (i) the participation of the (E a D b O x ) portion of the OCM catalyst composition for methane activation via catalytically active rare earth element oxide centers, such as E-O-D-O catalytically active sites; (ii) the participation of the Mn/Na 2 WO 4 portion of the OCM catalyst composition for methane activation via catalytically active metal oxide centers, such as Na-Mn/W-O catalytically active sites; or both (i) and (ii).
  • the production of methyl radicals involves both (i) the participation of the (E a D b O x ) portion of the OCM catalyst composition, and (ii) the participation of the Mn/Na 2 WO 4 portion of the OCM catalyst composition
  • the (E a D b O x ) portion and the Mn/Na 2 WO 4 portion can display an additive effect, a synergistic effect, or both with respect to conversion, selectivity, stability, and the like, or combinations thereof, in an OCM reaction.
  • deactivation of a catalyst in an OCM reaction can be avoided or minimized by employing an OCM catalyst composition as disclosed herein.
  • deactivation of the (E a D b O x ) portion of the OCM catalyst composition can be avoided or minimized owing to the first rare earth element (E); the second rare earth element (D); or both displaying stable performance under the OCM reaction conditions disclosed herein.
  • only a portion (as opposed to all) of the first rare earth element (E) is deactivated under the OCM reaction conditions disclosed herein.
  • the first rare earth element (E) is substantially not deactivated under the OCM reaction conditions disclosed herein.
  • the second rare earth element (D) is deactivated under the OCM reaction conditions disclosed herein. In still yet other aspects, the second rare earth element (D) is substantially not deactivated under the OCM reaction conditions disclosed herein. In still yet other aspects, both the first rare earth element (E) and the second rare earth element (D) are substantially not deactivated under the OCM reaction conditions disclosed herein.
  • the catalytic route of methane activation for the production of methyl radicals involving the participation of the (E a D b O x ) portion of the OCM catalyst composition can further decrease the formation of NaOH, thereby leading to a decrease in Na leaching from the OCM catalyst composition disclosed herein, which in turn confers to the OCM catalyst composition disclosed herein an increased stability and life time.
  • the OCM catalyst composition as disclosed herein can comprise one or more oxides of E; one or more oxides of D; or both.
  • the OCM catalyst composition can comprise one or more oxides of a rare earth element, wherein the rare earth element comprises E, and optionally D.
  • the (E a D b O x ) portion of the OCM catalyst composition can comprise, consist of, or consist essentially of the one or more oxides of a rare earth element, wherein the rare earth element comprises E, and optionally D.
  • the one or more oxides of a rare earth element can be present in the OCM catalyst composition in an amount of from about 0.01 wt.% to about 90 wt.%, alternatively from about 10.0 wt.% to about 80 wt.%, or alternatively from about 25.0 wt.% to about 70 wt.%, based on the total weight of the OCM catalyst composition.
  • the OCM catalyst composition can further comprise a support, as disclosed herein.
  • a portion of the one or more oxides of a rare earth element, in the presence of water, such as atmospheric moisture, can convert to hydroxides, and it is possible that the OCM catalyst composition will comprise some hydroxides, due to exposing the OCM catalyst composition comprising the one or more oxides of a rare earth element to water (e.g., atmospheric moisture).
  • a portion of the one or more oxides of a rare earth element, in the presence of carbon dioxide, such as atmospheric carbon dioxide, can convert to carbonates, and it is possible that the OCM catalyst composition will comprise some carbonates, due to exposing the OCM catalyst composition comprising the one or more oxides of a rare earth element to carbon dioxide (e.g., atmospheric carbon dioxide).
  • carbon dioxide e.g., atmospheric carbon dioxide
  • the one or more oxides of a rare earth element can comprise a single rare earth element oxide, mixtures of single rare earth element oxides, a mixed rare earth element oxide, mixtures of mixed rare earth element oxides, mixtures of single rare earth element oxides and mixed rare earth element oxides, or combinations thereof.
  • the single rare earth element oxide comprises one rare earth element selected from the group consisting of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc, and Y.
  • a single rare earth element oxide can be characterized by the general formula R r O y ; wherein R is a rare earth element selected from the group consisting of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc, and Y; and wherein r and y are integers from 1 to 7, alternatively from 1 to 5, or alternatively from 1 to 3.
  • a single rare earth element oxide contains one and only one rare earth element cation.
  • Nonlimiting examples of single rare earth element oxides suitable for use in the OCM catalyst compositions of the present disclosure include La 2 O 3 , Sc 2 O 3 , Y 2 O 3 , CeO 2 , Ce 2 O 3 , Pr 2 O 3 , PrO 2 , Nd 2 O 3 , Pm 2 O 3 , Sm 2 O 3 , Eu 2 O 3 , Gd 2 O 3 , Tb 2 O 3 , Dy 2 O 3 , Ho 2 O 3 , Er 2 O 3 , Lu 2 O 3 , Yb 2 O 3 , Tm 2 O 3 , and the like, or combinations thereof.
  • mixtures of single rare earth element oxides can comprise two or more different single rare earth element oxides, wherein the two or more different single rare earth element oxides have been mixed together to form the mixture of single rare earth element oxides.
  • Mixtures of single rare earth element oxides can comprise two or more different single rare earth element oxides, wherein each single rare earth element oxide can be selected from the group consisting of La 2 O 3 , Sc 2 O 3 , Y 2 O 3 , CeO 2 , Ce 2 O 3 , Pr 2 O 3 , PrO 2 , Nd 2 O 3 , Pm 2 O 3 , Sm 2 O 3 , Eu 2 O 3 , Gd 2 O 3 , Tb 2 O 3 , Dy 2 O 3 , Ho 2 O 3 , Er 2 O 3 , Lu 2 O 3 , Yb 2 O 3 , and Tm 2 O 3 .
  • Nonlimiting examples of mixtures of single rare earth element oxides suitable for use in the OCM catalyst compositions of the present disclosure include Yb 2 O 3 -La 2 O 3 , Er 2 O 3 -La 2 O 3 , CeO 2 -La 2 O 3 , CeO 2 -Ce 2 O 3 - La 2 O 3 , CeO 2 -Er 2 O 3 , CeO 2 -Ce 2 O 3 -Er 2 O 3 , Tm 2 O 3 -La 2 O 3 , Sm 2 O 3 -La 2 O 3 , PrO 2 -Pr 2 O 3 -La 2 O 3 , and the like, or combinations thereof.
  • the mixed rare earth element oxide comprises two or more different rare earth elements, wherein each rare earth element can be independently selected from the group consisting of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc, and Y.
  • a mixed rare earth element oxide can be characterized by the general formula R 1
  • R 1 and R 2 are rare earth elements; wherein each of the R 1 and R 2 can be independently selected from the group consisting of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc, and Y; and wherein r1, r2 and y are integers from 1 to 15, alternatively from 1 to 10, or alternatively from 1 to 7.
  • R 1 and R 2 can be rare earth element cations of different chemical elements, for example R 1 can be a lanthanum cation and R 2 can be an ytterbium cation.
  • R 1 and R 2 can be different cations of the same chemical element, wherein R 1 and R 2 can have different oxidation states.
  • Nonlimiting examples of mixed rare earth element oxides suitable for use in the OCM catalyst compositions of the present disclosure include LaYbO 3 ; Sm 2 Ce 2 O 7 ; Er 2 Ce 2 O 7 ; and the like; or combinations thereof.
  • mixtures of mixed rare earth element oxides can comprise two or more different mixed rare earth element oxides, wherein the two or more different mixed rare earth element oxides have been mixed together to form the mixture of mixed rare earth element oxides.
  • Mixtures of mixed rare earth element oxides can comprise two or more different mixed rare earth element oxides, such as LaYbO 3 ; Sm 2 Ce 2 O 7 ; Er 2 Ce 2 O 7 ; or combinations thereof.
  • mixtures of single rare earth element oxides and mixed rare earth element oxides can comprise at least one single rare earth element oxide and at least one mixed rare earth element oxide, wherein the at least one single rare earth element oxide and the at least one mixed rare earth element oxide have been mixed together to form the mixture of single rare earth element oxides and mixed rare earth element oxides.
  • the OCM catalyst composition as disclosed herein can comprise one or more oxides of Mn; one or more oxides of Na; one or more oxides of W; or combinations thereof.
  • the OCM catalyst composition can comprise one or more oxides of a metal (e.g., one or more metal oxides), wherein the metal comprises Mn, Na, W, or combinations thereof.
  • the Mn/Na 2 WO 4 portion of the OCM catalyst composition can comprise, consist of, or consist essentially of the one or more metal oxides, wherein the metal comprises Mn, Na, W, or combinations thereof.
  • the one or more metal oxides (e.g., the Mn/Na 2 WO 4 portion of the OCM catalyst composition), wherein the metal comprises Mn, Na, W, or combinations thereof, can be present in the OCM catalyst composition in an amount of from about 0.1 wt.% to about 90.0 wt.%, alternatively from about 1.0 wt.% to about 80.0 wt.%, or alternatively from about 10.0 wt.% to about 70.0 wt.%, based on the total weight of the OCM catalyst composition.
  • the OCM catalyst composition can further comprise a support, as disclosed herein.
  • Mn is present in the OCM catalyst composition in an amount of from about 0.5 wt.% to about 20 wt.%, alternatively from about 1 wt.% to about 10 wt.%, or alternatively from about 2 wt.% to about 5 wt.%, based on a total weight of the OCM catalyst composition.
  • a portion of the one or more metal oxides, wherein the metal comprises Mn, Na, W, or combinations thereof, in the presence of water, such as atmospheric moisture, can convert to hydroxides, and it is possible that the OCM catalyst composition will comprise some hydroxides, due to exposing the OCM catalyst composition comprising the one or more metal oxides to water (e.g., atmospheric moisture).
  • a portion of the one or more metal oxides, in the presence of carbon dioxide, such as atmospheric carbon dioxide, can convert to carbonates, and it is possible that the OCM catalyst composition will comprise some carbonates, due to exposing the OCM catalyst composition comprising the one or more metal oxides to carbon dioxide (e.g., atmospheric carbon dioxide).
  • carbon dioxide e.g., atmospheric carbon dioxide
  • the one or more metal oxides wherein the metal comprises Mn, Na, W, or combinations thereof, can comprise a single metal oxide, mixtures of single metal oxides, a mixed metal oxide, mixtures of mixed metal oxides, mixtures of single metal oxides and mixed metal oxides, or combinations thereof.
  • the single metal oxide comprises one metal selected from the group consisting of Na, W, and Mn.
  • a single metal oxide can be characterized by the general formula M m O y ; wherein M is the metal selected from the group consisting of Na, W, and Mn; and wherein m and y are integers from 1 to 7, alternatively from 1 to 5, or alternatively from 1 to 3.
  • a single metal oxide contains one and only one metal cation.
  • Nonlimiting examples of single metal oxides suitable for use in the OCM catalyst compositions of the present disclosure include WO 3 , MnO 2 , W 2 O 3 , and the like, or combinations thereof.
  • mixtures of single metal oxides can comprise two or more different single metal oxides, wherein the two or more different single metal oxides have been mixed together to form the mixture of single metal oxides.
  • Mixtures of single metal oxides can comprise two or more different single metal oxides, wherein each single metal oxide can be selected from the group consisting of WO 3 , MnO 2 , and W 2 O 3 .
  • Nonlimiting examples of mixtures of single metal oxides suitable for use in the OCM catalyst compositions of the present disclosure include MnO 2 -W 2 O 3 , WO 3 -W 2 O 3 , MnO 2 -WO 3 , MnO 2 -WO 3 -W 2 O 3 , and the like, or combinations thereof.
  • the mixed metal oxide comprises two or more different metals, wherein each metal can be independently selected from the group consisting of Na, W, and Mn.
  • a mixed metal oxide can be characterized by the general formula M 1
  • M 1 and M 2 are metals; wherein each of the M 1 and M 2 can be independently selected from the group consisting of Na, W, and Mn; and wherein m1, m2 and y are integers from 1 to 15, alternatively from 1 to 10, or alternatively from 1 to 7.
  • M 1 and M 2 can be metal cations of different chemical elements, for example M 1 can be a sodium cation and M 2 can be a manganese cation.
  • M 1 and M 2 can be different cations of the same chemical element, wherein M 1 and M 2 can have different oxidation states.
  • the mixed metal oxide can comprise Mn 3 O 4 , wherein M 1 can be a Mn (II) cation and M 2 can be a Mn (III) cation.
  • M 1 can be a Mn (II) cation
  • M 2 can be a Mn (III) cation.
  • Nonlimiting examples of mixed metal oxides suitable for use in the OCM catalyst compositions of the present disclosure include Na/Mn/O; Mn 3 O 4 ; Na 2 WO 4 ; Mn/Na 2 WO 4 ; Na 2 WO 4 /Mn; MnWO 4 ; Mn/WO 4 ; and the like; or combinations thereof.
  • mixtures of mixed metal oxides can comprise two or more different mixed metal oxides, wherein the two or more different mixed metal oxides have been mixed together to form the mixture of mixed metal oxides.
  • Mixtures of mixed metal oxides can comprise two or more different mixed metal oxides, such as Na/Mn/O; Mn 3 O 4 ; Na 2 WO 4 ; Mn/Na 2 WO 4 ; Na 2 WO 4 /Mn; MnWO 4 ; Mn/WO 4 ; and the like; or combinations thereof.
  • mixtures of single metal oxides and mixed metal oxides can comprise at least one single metal oxide and at least one mixed metal oxide, wherein the at least one single metal oxide and the at least one mixed metal oxide have been mixed together to form the mixture of single metal oxides and mixed metal oxides.
  • the Mn/Na 2 WO 4 portion of the OCM catalyst composition can comprise Mn/Na 2 WO 4 , Na/Mn/O, Na 2 WO 4 , Mn 2 O 3 /Na 2 WO 4 , Mn 3 O 4 /Na 2 WO 4 , MnWO 4 /Na 2 WO 4 , Mn/WO 4 , Na 2 WO 4 /Mn, and the like, or combinations thereof.
  • the Mn/Na 2 WO 4 portion of the OCM catalyst composition can comprise, consist of, or consist essentially of Mn/Na 2 WO 4 .
  • the OCM catalyst composition can comprise one or more oxides of a rare earth element (e.g., one or more oxides of the (E a D b O x ) portion of the OCM catalyst composition) and one or more metal oxides (e.g., one or more oxides of the Mn/Na 2 WO 4 portion of the OCM catalyst composition); such as MnO-Yb 2 O 3 -La 2 O 3 , Mn 2 O 3 -Er 2 O 3 -La 2 O 3 , Na 2 WO 4 -CeO 2 -La 2 O 3 , MnWO 4 -Na 2 WO 4 -CeO 2 -Ce 2 O 3 - La 2 O 3 , Na 2 O-CeO 2 -Er 2 O 3 , Na/Mn/O-CeO 2 -Ce 2 O 3 -Er 2 O 3 , Mn 2 O 3 /Na 2 WO 4 -Tm 2 O 3 -La 2 O 3 ,
  • the OCM catalyst compositions suitable for use in the present disclosure can be supported OCM catalyst compositions and/or unsupported OCM catalyst compositions.
  • the supported OCM catalyst compositions can comprise a support, wherein the support can be catalytically active (e.g., the support can catalyze an OCM reaction, such as MgO).
  • the supported OCM catalyst compositions can comprise a support, wherein the support can be catalytically less active (e.g., the support cannot catalyze an OCM reaction, such as SiO 2 ), for example a support that is less active than a catalytically active support, such as MgO.
  • the supported OCM catalyst compositions can comprise a catalytically active support and a catalytically less active support (e.g., a support that is less active than a catalytically active support).
  • a support suitable for use in the present disclosure include MgO, Al 2 O 3 , SiO 2 , ZrO 2 , TiO 2 , and the like, or combinations thereof.
  • the support can be purchased or can be prepared by using any suitable methodology, such as for example precipitation/co-precipitation, sol- gel techniques, templates/surface derivatized metal oxides synthesis, solid-state synthesis of mixed metal oxides, microemulsion techniques, solvothermal techniques, sonochemical techniques, combustion synthesis, etc.
  • the OCM catalyst composition can further comprise a support, wherein at least a portion of the OCM catalyst composition contacts, coats, is embedded in, is supported by, and/or is distributed throughout at least a portion of the support.
  • the support can be in the form of a powder, a particle, a pellet, a monolith, a foam, a honeycomb, and the like, or combinations thereof.
  • support particle shapes include cylindrical, discoidal, spherical, tabular, ellipsoidal, equant, irregular, cubic, acicular, and the like, or combinations thereof.
  • the OCM catalyst composition can further comprise a porous support.
  • a porous material e.g., support
  • a porous material can provide for an enhanced surface area of contact between the OCM catalyst composition and the reactant mixture, which in turn would result in a higher CH 4 conversion to
  • the OCM catalyst composition can be made by using any suitable methodology.
  • a method of making an OCM catalyst composition can comprise a step of forming an OCM catalyst precursor mixture, wherein the OCM catalyst precursor mixture comprises one or more compounds comprising a first rare earth element cation, optionally one or more compounds comprising a second rare earth element cation, one or more compounds comprising a Mn cation, and Na 2 WO 4 ; and wherein the first rare earth element cation and the second rare earth element cation are different.
  • the OCM catalyst precursor mixture can be characterized by a molar ratio of second rare earth element to first rare earth element of b:1, wherein b is from about 0 to about 10.0, alternatively from about 0.1 to about 8, or alternatively from about 0.5 to about 5; and wherein when b is 0, the first rare earth element is not lanthanum (La) alone or cerium (Ce) alone.
  • the one or more compounds comprising a first rare earth element cation comprises a first rare earth element nitrate, a first rare earth element oxide, a first rare earth element hydroxide, a first rare earth element chloride, a first rare earth element acetate, a first rare earth element carbonate, and the like, or combinations thereof.
  • the one or more compounds comprising a second rare earth element cation comprises a second rare earth element nitrate, a second rare earth element oxide, a second rare earth element hydroxide, a second rare earth element chloride, a second rare earth element acetate, a second rare earth element carbonate, and the like, or combinations thereof.
  • the one or more compounds comprising a Mn cation comprises a Mn nitrate, a Mn oxide, a Mn hydroxide, a Mn chloride, a Mn acetate, a Mn carbonate, and the like, or combinations thereof.
  • the step of forming the OCM catalyst precursor mixture can comprise forming one or more aqueous solutions, such as a Mn precursor aqueous solution, a rare earth element precursor aqueous solution, a Na 2 WO 4 aqueous solution, etc.
  • aqueous solution encompasses both a homogeneous solution, such as a solution wherein a solute is completely dissolved in water; as well as a heterogeneous solution, such as slurries (e.g., aqueous slurry solution), suspensions (e.g., aqueous slurry solution), dispersions (e.g., aqueous dispersion solution), etc., such as a solution wherein a solute is suspended in water and/or partially dissolved in water.
  • slurries e.g., aqueous slurry solution
  • suspensions e.g., aqueous slurry solution
  • dispersions e.g., aqueous dispersion solution
  • Aqueous solutions used in a step of forming the OCM catalyst precursor mixture can be formed by solubilizing (e.g., dissolving, dispersing, slurrying, suspending, etc.) one or more compounds (e.g., a one or more compounds comprising a Mn cation for forming a Mn precursor aqueous solution; one or more compounds comprising a first rare earth element cation and optionally one or more compounds comprising a second rare earth element cation for forming a rare earth element precursor aqueous solution; Na 2 WO 4 for forming a Na 2 WO 4 aqueous solution) in an aqueous medium to form the aqueous solution.
  • solubilizing e.g., dissolving, dispersing, slurrying, suspending, etc.
  • one or more compounds e.g., a one or more compounds comprising a Mn cation for forming a Mn precursor aqueous solution; one or more compounds comprising a
  • the aqueous medium can be water, or any other suitable aqueous medium.
  • the aqueous solutions used in a step of forming the OCM catalyst precursor mixture can be formed by dissolving the one or more compounds in water or any suitable aqueous medium.
  • the compounds when more than one compound is used for making an aqueous solution (e.g., one or more compounds comprising a first rare earth element cation and optionally one or more compounds comprising a second rare earth element cation), the compounds can be dissolved in an aqueous medium in any suitable order. In aspects where more than one compound is used for making an aqueous solution, such compounds can be first mixed together and then dissolved in an aqueous medium.
  • the step of forming the OCM catalyst precursor mixture can comprise forming a rare earth element precursor aqueous solution comprising one or more compounds comprising a first rare earth element cation and optionally one or more compounds comprising a second rare earth element cation; wherein the first rare earth element cation and the second rare earth element cation are different; wherein the rare earth element precursor aqueous solution is characterized by a molar ratio of second rare earth element to first rare earth element of b:1, wherein b is from about 0 to about 10.0; and wherein when b is 0, the first rare earth element is not La alone or Ce alone.
  • the step of forming the OCM catalyst precursor mixture can comprise forming a Mn precursor (e.g., a Mn precursor aqueous solution, a supported Mn precursor, a dried supported Mn precursor) comprising one or more compounds comprising a Mn cation.
  • the Mn precursor aqueous solution can be further contacted with a support to form a supported Mn precursor.
  • the supported Mn precursor can be dried to form a dried supported Mn precursor.
  • the supported Mn precursor can be dried at a temperature of equal to or greater than about 75 o C, alternatively equal to or greater than about 100 o C, or alternatively equal to or greater than about 125 o C, to yield the dried supported Mn precursor.
  • the supported Mn precursor can be dried for a time period of equal to or greater than about 4 hours, alternatively equal to or greater than about 8 hours, or alternatively equal to or greater than about 12 hours.
  • the step of forming the OCM catalyst precursor mixture can comprise forming a Na 2 WO 4 aqueous solution.
  • the Mn precursor e.g., Mn precursor aqueous solution, supported Mn precursor, dried supported Mn precursor
  • the Na 2 WO 4 aqueous solution can be contacted with the Na 2 WO 4 aqueous solution to form a Mn/Na 2 WO 4 precursor (e.g., Mn/Na 2 WO 4 precursor aqueous solution, supported Mn/Na 2 WO 4 precursor, dried supported Mn/Na 2 WO 4 precursor, calcined supported Mn/Na 2 WO 4 precursor).
  • the Mn/Na 2 WO 4 precursor comprises a Mn/Na 2 WO 4 precursor aqueous solution
  • the Mn/Na 2 WO 4 precursor aqueous solution can be contacted with a support to form a supported Mn/Na 2 WO 4 precursor.
  • the Mn precursor comprises a supported Mn precursor and/or dried supported Mn precursor
  • the Mn/Na 2 WO 4 precursor can comprise a supported Mn/Na 2 WO 4 precursor.
  • the supported Mn/Na 2 WO 4 precursor can be further dried to form a dried supported Mn/Na 2 WO 4 precursor.
  • the supported Mn/Na 2 WO 4 precursor can be dried at a temperature of equal to or greater than about 75 o C, alternatively equal to or greater than about 100 o C, or alternatively equal to or greater than about 125 o C, to yield the dried supported Mn/Na 2 WO 4 precursor.
  • the supported Mn/Na 2 WO 4 precursor can be dried for a time period of equal to or greater than about 4 hours, alternatively equal to or greater than about 8 hours, or alternatively equal to or greater than about 12 hours.
  • the dried supported Mn/Na 2 WO 4 precursor can be further calcined at a temperature of equal to or greater than about 700 o C, alternatively equal to or greater than about 750 o C, or alternatively equal to or greater than about 800 o C, to yield a calcined supported Mn/Na 2 WO 4 precursor.
  • the dried supported Mn/Na 2 WO 4 precursor can be calcined for a time period of equal to or greater than about 2 hours, alternatively equal to or greater than about 4 hours, or alternatively equal to or greater than about 6 hours.
  • the rare earth element precursor aqueous solution can be contacted with the Mn/Na 2 WO 4 precursor (e.g., Mn/Na 2 WO 4 precursor aqueous solution, supported Mn/Na 2 WO 4 precursor, dried supported Mn/Na 2 WO 4 precursor, calcined supported Mn/Na 2 WO 4 precursor) to form the OCM catalyst precursor mixture (e.g., OCM catalyst precursor mixture aqueous solution, supported OCM catalyst precursor mixture, dried supported OCM catalyst precursor mixture).
  • Mn/Na 2 WO 4 precursor e.g., Mn/Na 2 WO 4 precursor aqueous solution, supported Mn/Na 2 WO 4 precursor, dried supported Mn/Na 2 WO 4 precursor, calcined supported Mn/Na 2 WO 4 precursor
  • the OCM catalyst precursor mixture e.g., OCM catalyst precursor mixture aqueous solution, supported OCM catalyst precursor mixture, dried supported OCM catalyst precursor mixture.
  • the Mn/Na 2 WO 4 precursor comprises a supported Mn/Na 2 WO 4 precursor, a dried supported Mn/Na 2 WO 4 precursor, a calcined supported Mn/Na 2 WO 4 precursor, or combinations thereof;
  • the OCM catalyst precursor mixture can comprise a supported OCM catalyst precursor mixture.
  • the rare earth element precursor aqueous solution can be contacted with the Mn precursor (e.g., Mn precursor aqueous solution, supported Mn precursor, dried supported Mn precursor) to form a Mn-rare earth element precursor (e.g., Mn-rare earth element precursor aqueous solution, supported Mn-rare earth element precursor, dried supported Mn-rare earth element precursor).
  • the Mn-rare earth element precursor comprises a Mn-rare earth element precursor aqueous solution
  • the Mn-rare earth element precursor aqueous solution can be contacted with a support to form a supported Mn-rare earth element precursor.
  • the Mn precursor comprises a supported Mn precursor and/or a dried supported Mn precursor
  • the Mn-rare earth element precursor can comprise a supported Mn-rare earth element precursor.
  • the supported Mn-rare earth element precursor can be further dried to form a dried supported Mn-rare earth element precursor.
  • the supported Mn-rare earth element precursor can be dried at a temperature of equal to or greater than about 75 o C, alternatively equal to or greater than about 100 o C, or alternatively equal to or greater than about 125 o C, to yield the dried supported Mn-rare earth element precursor.
  • the supported Mn-rare earth element precursor can be dried for a time period of equal to or greater than about 4 hours, alternatively equal to or greater than about 8 hours, or alternatively equal to or greater than about 12 hours.
  • the Mn-rare earth element precursor e.g., Mn-rare earth element precursor aqueous solution, supported Mn-rare earth element precursor, dried supported Mn-rare earth element precursor
  • the OCM catalyst precursor mixture e.g., OCM catalyst precursor mixture aqueous solution, supported OCM catalyst precursor mixture, dried supported OCM catalyst precursor mixture.
  • the OCM catalyst precursor mixture can comprise a supported OCM catalyst precursor mixture.
  • the OCM catalyst precursor mixture comprises an OCM catalyst precursor mixture aqueous solution
  • the OCM catalyst precursor mixture aqueous solution can be contacted with a support to form a supported OCM catalyst precursor mixture.
  • the OCM catalyst precursor mixture can be further dried to form a dried OCM catalyst precursor mixture.
  • the OCM catalyst precursor mixture can be dried at a temperature of equal to or greater than about 75 o C, alternatively equal to or greater than about 100 o C, or alternatively equal to or greater than about 125 o C, to yield the dried OCM catalyst precursor mixture.
  • the OCM catalyst precursor mixture can be dried for a time period of equal to or greater than about 4 hours, alternatively equal to or greater than about 8 hours, or alternatively equal to or greater than about 12 hours.
  • the supported OCM catalyst precursor mixture can be further dried to form a dried supported OCM catalyst precursor mixture.
  • the supported OCM catalyst precursor mixture can be dried at a temperature of equal to or greater than about 75 o C, alternatively equal to or greater than about 100 o C, or alternatively equal to or greater than about 125 o C, to yield the dried supported OCM catalyst precursor mixture.
  • the supported OCM catalyst precursor mixture can be dried for a time period of equal to or greater than about 4 hours, alternatively equal to or greater than about 8 hours, or alternatively equal to or greater than about 12 hours.
  • a method of making an OCM catalyst composition can comprise a step of calcining the OCM catalyst precursor mixture (e.g., dried OCM catalyst precursor mixture, supported OCM catalyst precursor mixture, dried supported OCM catalyst precursor mixture) to form the OCM catalyst composition, wherein the OCM catalyst composition is characterized by the general formula (E a D b O x )- Mn/Na 2 WO 4 ; wherein E is a first rare earth element; wherein D is a second rare earth element; wherein the first rare earth element and the second rare earth element are different; wherein a is 1.0; wherein b is from about 0 to about 10.0; wherein when b is 0, the first rare earth element is not La alone or Ce alone; and wherein x balances the oxidation states.
  • the OCM catalyst precursor mixture e.g., dried OCM catalyst precursor mixture, supported OCM catalyst precursor mixture, dried supported OCM catalyst precursor mixture
  • the OCM catalyst composition is characterized by the general formula (E a D b O x )
  • the OCM catalyst precursor mixture can be calcined at a temperature of equal to or greater than about 700 o C, alternatively equal to or greater than about 750 o C, or alternatively equal to or greater than about 800 o C, to yield the OCM catalyst composition.
  • the OCM catalyst precursor mixture can be calcined for a time period of equal to or greater than about 2 hours, alternatively equal to or greater than about 4 hours, or alternatively equal to or greater than about 6 hours.
  • At least a portion of the OCM catalyst precursor mixture can be calcined in an oxidizing atmosphere (e.g., in an atmosphere comprising oxygen, for example in air) to form the OCM catalyst composition.
  • an oxidizing atmosphere e.g., in an atmosphere comprising oxygen, for example in air
  • the oxygen in the (E a D b O x ) portion of the OCM catalyst compositions characterized by the general formula (E a D b O x )-Mn/Na 2 WO 4 can originate in the oxidizing atmosphere used for calcining the OCM catalyst precursor mixture.
  • the oxygen in the (E a D b O x ) portion of the OCM catalyst compositions characterized by the general formula (E a D b O x )-Mn/Na 2 WO 4 can originate in the one or more compounds comprising a first rare earth element cation, one or more compounds comprising a second rare earth element cation, or both; provided that at least one of these compounds comprises oxygen in its formula, as is the case with nitrates, oxides, hydroxides, acetates, carbonates, etc.
  • the method of making an OCM catalyst composition can comprise forming the OCM catalyst composition in the presence of the support, as previously described herein, such that the resulting OCM catalyst composition (after the calcining step) comprises the support.
  • the method of making an OCM catalyst composition can further comprise contacting the OCM catalyst composition with a support to yield a supported catalyst (e.g., an OCM supported catalyst, an OCM supported catalyst composition, etc.).
  • a method for producing olefins can comprise allowing at least a portion of the reactant mixture to contact at least a portion of the OCM catalyst composition and react via an OCM reaction to form a product mixture comprising olefins.
  • the product mixture comprises coupling products, partial oxidation products (e.g., deep oxidation products, partial conversion products, such as CO, H 2 , CO 2 ), and unreacted methane.
  • the coupling products can comprise olefins (e.g., alkenes, characterized by a general formula C n H 2n ) and paraffins (e.g., alkanes, characterized by a general formula C n H 2n+2 ).
  • the product mixture can comprise C 2+ hydrocarbons, wherein the C 2+ hydrocarbons can comprise C 2 hydrocarbons and C 3 hydrocarbons.
  • the C 2+ hydrocarbons can further comprise C 4 hydrocarbons (C 4 s), such as for example butane, iso-butane, n-butane, butylene, etc.
  • the C 2 hydrocarbons can comprise ethylene (C 2 H 4 ) and ethane (C 2 H 6 ).
  • the C 2 hydrocarbons can further comprise acetylene (C 2 H 2 ).
  • the C 3 hydrocarbons can comprise propylene (C 3 H 6 ) and propane (C 3 H 8 ).
  • an O 2 conversion for the OCM as disclosed herein can be equal to or greater than about 90%, alternatively equal to or greater than about 95%, alternatively equal to or greater than about 99%, alternatively equal to or greater than about 99.9%, or alternatively about 100%.
  • a conversion of a reagent or reactant refers to the percentage (usually mol%) of reagent that reacted to both undesired and desired products, based on the total amount (e.g., moles) of reagent present before any reaction took place.
  • the conversion of a reagent is a % conversion based on moles converted.
  • the reactant mixture in OCM reactions is generally characterized by a methane to oxygen molar ratio of greater than 1:1, and as such the O 2 conversion is fairly high in OCM processes, most often approaching 90%-100%.
  • oxygen is usually a limiting reagent in OCM processes.
  • the oxygen conversion can be calculated by using equation (1):
  • OCM catalyst deactivation can be due to leaching out catalyst components over time, such as Na, as disclosed herein.
  • the OCM catalyst composition can be characterized by an O 2 conversion that decreases by less than about 10%, alternatively less than about 7.5%, or alternatively less than about 5%, over a period of time of equal to or greater than about 50 hours, alternatively equal to or greater than about 100 hours, alternatively equal to or greater than about 200 hours, alternatively equal to or greater than about 300 hours, alternatively equal to or greater than about 400 hours, alternatively equal to or greater than about 500 hours, alternatively equal to or greater than about 750 hours, or alternatively equal to or greater than about 1,000 hours.
  • the OCM catalyst composition can be characterized by a deactivation rate of less than about 0.5 %/hr, alternatively less than about 0.25 %/hr, or alternatively less than about 0.1 %/hr over a period of time of equal to or greater than about 50 hours, alternatively equal to or greater than about 100 hours, alternatively equal to or greater than about 200 hours, alternatively equal to or greater than about 300 hours, alternatively equal to or greater than about 400 hours, alternatively equal to or greater than about 500 hours, alternatively equal to or greater than about 750 hours, or alternatively equal to or greater than about 1,000 hours.
  • the deactivation rate of an OCM catalyst composition refers to the reduction of reaction rate constant, more specifically, the reduction of oxygen conversion rate constant.
  • the OCM catalyst composition can be characterized by a deactivation rate that is decreased by equal to or greater than about 50%, alternatively equal to or greater than about 60%, alternatively equal to or greater than about 75%, when compared to a deactivation rate of an otherwise similar OCM catalyst composition comprising (i) Mn/Na 2 WO 4 without (E a D b O x ); or (ii) (E a D b O x ) without Mn/Na 2 WO 4 .
  • the OCM catalyst composition can be characterized by a life time of equal to or greater than about 1,000 h, alternatively equal to or greater than about 1,500 h, or alternatively equal to or greater than about 2,000 h.
  • the catalyst life of a catalyst refers to the amount of time that the catalyst provides its catalytic performance (e.g., O 2 conversion, CH 4 conversion, selectivity) without losing it.
  • the OCM catalyst composition can be characterized by a life time that is increased by equal to or greater than about 50%, alternatively equal to or greater than about 60%, alternatively equal to or greater than about 75%, when compared to a life time of an otherwise similar OCM catalyst composition comprising (i) Mn/Na 2 WO 4 without (E a D b O x ); or (ii) (E a D b O x ) without Mn/Na 2 WO 4 .
  • a method for producing olefins can comprise recovering at least a portion of the product mixture from the reactor.
  • a method for producing olefins can comprise recovering at least a portion of the C 2 hydrocarbons from the product mixture.
  • the product mixture can comprise C 2+ hydrocarbons (including olefins), unreacted methane, and optionally a diluent.
  • the water produced from the OCM reaction and the water used as a diluent can be separated from the product mixture prior to separating any of the other product mixture components. For example, by cooling down the product mixture to a temperature where the water condenses (e.g., below 100 o C at ambient pressure), the water can be removed from the product mixture, by using a flash chamber for example.
  • At least a portion of the C 2+ hydrocarbons can be separated (e.g., recovered) from the product mixture to yield recovered C 2+ hydrocarbons.
  • the C 2+ hydrocarbons can be separated from the product mixture by using any suitable separation technique.
  • at least a portion of the C 2+ hydrocarbons can be separated from the product mixture by distillation (e.g., cryogenic distillation).
  • At least a portion of the recovered C 2+ hydrocarbons can be used for ethylene production.
  • at least a portion of ethylene can be separated from the product mixture (e.g., from the C 2+ hydrocarbons, from the recovered C 2+ hydrocarbons) to yield recovered ethylene and recovered hydrocarbons, by using any suitable separation technique (e.g., distillation).
  • at least a portion of the recovered hydrocarbons e.g., recovered C 2+ hydrocarbons after olefin separation, such as separation of C 2 H 4 and C 3 H 6
  • a method for producing olefins can comprise recovering at least a portion of the olefins from the product mixture.
  • at least a portion of the olefins can be separated from the product mixture by distillation (e.g., cryogenic distillation).
  • the olefins are generally individually separated from their paraffin counterparts by distillation (e.g., cryogenic distillation).
  • ethylene can be separated from ethane by distillation (e.g., cryogenic distillation).
  • propylene can be separated from propane by distillation (e.g., cryogenic distillation).
  • At least a portion of the unreacted methane can be separated from the product mixture to yield recovered methane.
  • Methane can be separated from the product mixture by using any suitable separation technique, such as for example distillation (e.g., cryogenic distillation).
  • At least a portion of the recovered methane can be recycled to the reactant mixture.
  • the OCM catalyst composition can be characterized by the general formula (La a Ce b O x )-Mn/Na 2 WO 4 ; wherein a is 1.0; wherein b is from about 0.01 to about 10.0, alternatively from about 0.1 to about 8, or alternatively from about 0.5 to about 5; and wherein x balances the oxidation states.
  • At least one of the La and Ce can have multiple oxidation states within the OCM catalyst composition (e.g., within a (La a Ce b O x ) portion of the OCM catalyst composition), and as such x can have any suitable value that allows for the oxygen anions to balance all the cations within the (La a Ce b O x ) portion of the OCM catalyst composition.
  • the OCM catalyst composition can be characterized by the general formula (Sm a O x )-Mn/Na 2 WO 4 ; wherein a is 1.0; and wherein x balances the oxidation states (e.g., x balances the oxidation state of Sm cations).
  • the (Sm a O x ) portion of the OCM catalyst composition can comprise Sm 2 O 3 .
  • the (Sm a O x ) portion of the OCM catalyst composition can comprise, consist of, or consist essentially of Sm 2 O 3 .
  • a method of making an OCM catalyst composition can comprise the steps of (a) forming a Mn precursor aqueous solution comprising a Mn nitrate; (b) contacting the Mn precursor aqueous solution with a support to form a supported Mn precursor; (c) optionally drying the supported Mn precursor at a temperature of equal to or greater than about 100 o C to form a dried supported Mn precursor; (d) forming a rare earth element precursor aqueous solution comprising a first rare earth element nitrate and a second rare earth element nitrate; wherein the first rare earth element nitrate and the second rare earth element nitrate are different; wherein the rare earth element precursor aqueous solution is characterized by a molar ratio of second rare earth element to first rare earth element of b:1, wherein b is from about 0 to about 10.0; and wherein when b is 0, the first rare earth element is not La alone or Ce alone; (e) contacting the rare earth element
  • the OCM catalyst composition can be characterized by the general formula (E a D b O x )-Mn/Na 2 WO 4 ; wherein E is a first rare earth element; wherein D is a second rare earth element; wherein the first rare earth element and the second rare earth element are different; wherein a is 1.0; wherein b is from about 0 to about 10.0; wherein when b is 0, the first rare earth element is not La alone or Ce alone; and wherein x balances the oxidation states.
  • a method of making an OCM catalyst composition can comprise the steps of (a) forming a Mn precursor aqueous solution comprising a Mn nitrate; (b) contacting the Mn precursor aqueous solution with a support to form a supported Mn precursor; (c) optionally drying the supported Mn precursor at a temperature of equal to or greater than about 100 o C to form a dried supported Mn precursor; (d) forming a Na 2 WO 4 aqueous solution; (e) contacting the Na 2 WO 4 aqueous solution with the supported Mn precursor and/or the dried supported Mn precursor to form a supported Mn/Na 2 WO 4 precursor; (f) optionally drying the supported Mn/Na 2 WO 4 precursor at a temperature of equal to or greater than about 100 o C to form a dried supported Mn/Na 2 WO 4 precursor; (g) optionally calcining the supported Mn/Na 2 WO 4 precursor and/or the dried supported M
  • the OCM catalyst composition can be characterized by the general formula (E a D b O x )-Mn/Na 2 WO 4 ; wherein E is a first rare earth element; wherein D is a second rare earth element; wherein the first rare earth element and the second rare earth element are different; wherein a is 1.0; wherein b is from about 0 to about 10.0; wherein when b is 0, the first rare earth element is not La alone or Ce alone; and wherein x balances the oxidation states.
  • a method for producing ethylene can comprise the steps of (a) introducing a reactant mixture to a reactor comprising an OCM catalyst composition; wherein the reactant mixture comprises CH 4 and O 2 ; wherein the OCM catalyst composition is characterized by the general formula (E a D b O x )-Mn/Na 2 WO 4 ; wherein E is a first rare earth element; wherein D is a second rare earth element; wherein the first rare earth element and the second rare earth element are different; wherein a is 1.0; wherein b is from about 0 to about 10.0; wherein when b is 0, the first rare earth element is not La alone or Ce alone; and wherein x balances the oxidation states; (b) allowing at least a portion of the reactant mixture to contact at least a portion of the OCM catalyst composition and react via an OCM reaction to form a product mixture comprising olefins, wherein the olefins comprise ethylene; (c) recovering at
  • the OCM catalyst compositions characterized by the general formula (E a D b O x )- Mn/Na 2 WO 4 ; wherein E is a first rare earth element; wherein D is a second rare earth element; wherein the first rare earth element and the second rare earth element are different; wherein a is 1.0; wherein b is from about 0 to about 10.0; wherein when b is 0, the first rare earth element is not La alone or Ce alone; and wherein x balances the oxidation states; and methods of making and using same, as disclosed herein can advantageously display improvements in one or more composition characteristics when compared to an otherwise similar OCM catalyst composition comprising (i) Mn/Na 2 WO 4 without (E a D b O x ); or (ii) (E a D b O x ) without Mn/Na 2 WO 4 .
  • the composition of OCM catalyst compositions characterized by the general formula (E a D b O x )-Mn/Na 2 WO 4 ; wherein E is a first rare earth element; wherein D is a second rare earth element; wherein the first rare earth element and the second rare earth element are different; wherein a is 1.0; wherein b is from about 0 to about 10.0; wherein when b is 0, the first rare earth element is not La alone or Ce alone; and wherein x balances the oxidation states; as disclosed herein can be advantageously adjusted as necessary, based on the needs of the OCM reaction, to meet target criteria, such as a target selectivity and/or a target conversion, owing to a broad range of Mn, Na, W, E and D content; and as such the OCM catalyst compositions as disclosed herein can display better performance when compared to otherwise similar OCM catalyst compositions comprising (i) Mn/Na 2 WO 4 without (E a D b O x
  • the composition of OCM catalyst compositions characterized by the general formula (E a D b O x )-Mn/Na 2 WO 4 ; wherein E is a first rare earth element; wherein D is a second rare earth element; wherein the first rare earth element and the second rare earth element are different; wherein a is 1.0; wherein b is from about 0 to about 10.0; wherein when b is 0, the first rare earth element is not La alone or Ce alone; and wherein x balances the oxidation states; as disclosed herein can be advantageously characterized by a reaction temperature that is lower when compared to a reaction temperature of an otherwise similar OCM catalyst composition comprising (i) Mn/Na 2 WO 4 without (E a D b O x ); or (ii) (E a D b O x ) without Mn/Na 2 WO 4 .
  • OCM catalyst compositions characterized by the general formula (E a D b O x )-Mn/Na 2 WO 4 , as disclosed herein, can reach the same oxygen conversion at a lower temperature when compared to a temperature necessary for reaching the same oxygen conversion of an otherwise similar OCM catalyst composition comprising (i) Mn/Na 2 WO 4 without (E a D b O x ); or (ii) (E a D b O x ) without Mn/Na 2 WO 4 .
  • the presence of both the (E a D b O x ) portion and the Mn/Na 2 WO 4 portion in the OCM catalyst compositions characterized by the general formula (E a D b O x )- Mn/Na 2 WO 4 , as disclosed herein, can broaden the useful temperature range for such OCM catalyst compositions, by providing increased catalyst activity at lower temperatures, and by facilitating reaching the same conversion (e.g., oxygen conversion, methane conversion, etc.) at lower temperatures.
  • OCM catalyst compositions characterized by the general formula (E a D b O x )- Mn/Na 2 WO 4 , as disclosed herein, can advantageously maintain high selectivity at lower temperatures; e.g., higher selectivity at lower temperatures when compared to a selectivity at the same lower temperatures of an otherwise similar OCM catalyst composition comprising (i) Mn/Na 2 WO 4 without (E a D b O x ); or (ii) (E a D b O x ) without Mn/Na 2 WO 4 .
  • OCM catalyst compositions characterized by the general formula (E a D b O x )-Mn/Na 2 WO 4 , as disclosed herein, can be advantageously characterized by a lower ignition temperature when compared to an ignition temperature of an otherwise similar OCM catalyst composition comprising (i) Mn/Na 2 WO 4 without (E a D b O x ); or (ii) (E a D b O x ) without Mn/Na 2 WO 4 .
  • a decrease in the ignition temperature for the OCM reaction and/or a decrease in the temperature needed to achieve a 100% oxygen conversion can lead to a decrease in the overall OCM reaction temperature and to a decreased catalyst bed temperature, which can further lead to a lower temperature of hot spots within a catalyst bed, which can enhance catalyst stability.
  • the ability to use very low temperatures in OCM processes can advantageously result in saving costs, due to savings in energy costs, savings in costs associated with manufacturing materials used in OCM reactors and associated equipment, etc.
  • the OCM catalyst compositions characterized by the general formula (E a D b O x )-Mn/Na 2 WO 4 ; wherein E is a first rare earth element; wherein D is a second rare earth element; wherein the first rare earth element and the second rare earth element are different; wherein a is 1.0; wherein b is from about 0 to about 10.0; wherein when b is 0, the first rare earth element is not La alone or Ce alone; and wherein x balances the oxidation states; can advantageously display an enhanced stability of performance (e.g., in terms of conversion and selectivity) over time when compared to the stability of performance of an otherwise similar OCM catalyst composition comprising (i) Mn/Na 2 WO 4 without (E a D b O x ); or (ii) (E a D b O x ) without Mn/Na 2 WO 4 .
  • E is a first rare earth element
  • D is a second rare earth element
  • the OCM catalyst compositions characterized by the general formula (E a D b O x )- Mn/Na 2 WO 4 as disclosed herein can maintain improved conversion and selectivity over a time frame that is greater than a time frame where an otherwise similar OCM catalyst composition comprising (i) Mn/Na 2 WO 4 without (E a D b O x ); or (ii) (E a D b O x ) without Mn/Na 2 WO 4 , can maintain its conversion and selectivity values.
  • the OCM catalyst compositions characterized by the general formula (E a D b O x )-Mn/Na 2 WO 4 as disclosed herein can have a life time that is greater than a life time of an otherwise similar OCM catalyst composition comprising (i) Mn/Na 2 WO 4 without (E a D b O x ); or (ii) (E a D b O x ) without Mn/Na 2 WO 4 .
  • the performance of catalysts can degrade (e.g., decay), owing to catalyst deactivation (e.g., Na leaching); and the longer a catalyst can maintain a desired performance (e.g., in terms of conversion and selectivity), the better the catalyst is.
  • catalyst deactivation e.g., Na leaching
  • OCM catalyst compositions characterized by the general formula (E a D b O x )- Mn/Na 2 WO 4 ; wherein E is a first rare earth element; wherein D is a second rare earth element; wherein the first rare earth element and the second rare earth element are different; wherein a is 1.0; wherein b is from about 0 to about 10.0; wherein when b is 0, the first rare earth element is not La alone or Ce alone; and wherein x balances the oxidation states; and methods of making and using same, as disclosed herein can be apparent to one of skill in the art viewing this disclosure.
  • Oxidative coupling of methane (OCM) catalyst compositions were prepared as follows.
  • a reference catalyst composition following the general formula Mn/Na 2 WO 4 /SiO 2 was prepared as follows. Silica gel (18.6 g, Davisil ® Grade 646) was used after drying overnight. Mn(NO 3 ) 2 ⁇ 4H 2 O (1.73 g) was dissolved in deionized water (18.6 mL), and then added dropwise onto the silica gel. The resulting manganese impregnated silica material was dried overnight. Na 2 WO 4 ⁇ 4H 2 O (1.13 g) was dissolved in deionized water (18.6 mL), and the solution obtained was added onto the dried manganese silica material above. The resulting material obtained was dried overnight at 125°C, and then calcined at 800°C for 6 hours under airflow to obtain the Mn/Na 2 WO 4 /SiO 2 reference catalyst.
  • a catalyst composition containing both La and Ce (catalyst #1) and following the general formula (La 10 Ce 1 O x )-Mn/Na 2 WO 4 /SiO 2 was prepared as follows. Silica gel (17.6 g, Davisil ® Grade 646) was used after drying overnight. Mn(NO 3 ) 2 ⁇ 4H 2 O (1.74 g) was dissolved in deionized water (17.6 mL), and then added dropwise onto the silica gel. The resulting manganese impregnated silica material was dried overnight.
  • a catalyst composition containing Sm (catalyst #2) and following the general formula (Sm 2 0 3 )-Mn/Na 2 W0 4 /Si0 2 was prepared as follows. 0.1 1 g of Sm 2 0 3 (with a particle size of about 15-45 nm) was mixed with deionized water (6.0 ml) to obtain an aqueous slurry solution.
  • OCM reactions were conducted by using catalysts prepared as described in Example 1 as follows.
  • a mixture of methane and oxygen along with an internal standard, an inert gas (neon) were fed to a quartz reactor with an internal diameter (I.D.) of 5.0 mm heated by traditional clamshell furnace.
  • a catalyst (e.g., catalyst bed) loading was 0.5 ml, and a total flow rate of reactants was 66.7 or 100.0 standard cubic centimeters per minute (seem).
  • the reactor was first heated to a desired temperature under an inert gas flow and then a desired gas mixture was fed to the reactor.
  • a selectivity to a desired product or products refers to how much desired product was formed divided by the total products formed, both desired and undesired.
  • the selectivity to a desired product is a % selectivity based on moles converted into the desired product.
  • a C x selectivity (e.g., C 2 selectivity, C 2+ selectivity, etc.) can be calculated by dividing a number of moles of carbon (C) from CH 4 that were converted into the desired product (e.g., C C2H4 , C C2H6 , etc.) by the total number of moles of C from CH 4 that were converted to any products, both desired and undesired (e.g., C C2H4 , C C2H6 , C C2H2 , C C3H6 , C C3H8 , C C4s , C CO2 , C CO , etc.).
  • C C2H4 number of moles of C from CH 4 that were converted into C 2 H 4 ;
  • C C2H6 number of moles of C from CH 4 that were converted into C 2 H 6 ;
  • C C2H2 number of moles of C from CH 4 that were converted into C 2 H 2 ;
  • C C3H6 number of moles of C from CH 4 that were converted into C 3 H 6 ;
  • C C3H8 number of moles of C from CH 4 that were converted into C 3 H 8 ;
  • C C4s number of moles of C from CH 4 that were converted into C 4 hydrocarbons (C 4 s);
  • C CO2 number of moles of C from CH 4 that were converted into CO 2 ;
  • C CO number of moles of C from CH 4 that were converted into CO; etc.
  • a C 2+ selectivity refers to how much C 2 H 4 , C 3 H 6 , C 2 H 2 , C 2 H 6 , C 3 H 8 , and C 4 s were formed divided by the total products formed, including C 2 H 4 , C 3 H 6 , C 2 H 2 , C 2 H 6 , C 3 H 8 , C 4 s, CO 2 and CO.
  • the data in Table 1 demonstrate that the addition of rate earth elements (La and Ce) to the Mn/Na 2 WO 4 /SiO 2 in catalyst #1 allows for maintaining the same high selectivity and conversions as for the reference catalyst.
  • the data in Table 2 demonstrate that the addition of a rare earth element (Sm) to the Mn/Na 2 WO 4 /SiO 2 in catalyst #2 allows for maintaining the same high selectivity and conversions as for the reference catalyst.
  • the deactivation rate of the reference catalyst for the data shown in Figure 1 was 0.63%/hr; and the deactivation rate of catalyst #1 for the data shown in Figure 1 was 0.32%/hr.
  • the data indicate that when the OCM catalyst contains (e.g., is promoted with) rare earth element oxides, such as (La 10 Ce 1 O x ), in addition to the Mn/Na 2 WO 4 /SiO 2 , the deactivation rate is reduced and the stability over time for the resulting catalyst (catalyst #1) is improved significantly.
  • the reference catalyst in Figure 1 has a deactivation rate that is about twice as large as the deactivation rate of the catalyst #1 that contains rare earth element oxides, such as (La 10 Ce 1 O x ), in addition to the Mn/Na 2 WO 4 /SiO 2 .
  • the presence of the rare earth element oxides (e.g., (La 10 Ce 1 O x )) in the catalyst composition of catalyst #1 can increase the overall basicity of the catalyst composition, consequently increasing catalyst activity (e.g., ability of the catalyst to promote methyl radical formation); lowering the deactivation rate of the catalyst; and increasing catalyst stability over time.
  • the data indicate that when the OCM catalyst contains (e.g., is promoted with) rare earth element oxides, such as (Sm 2 O 3 ), in addition to the Mn/Na 2 WO 4 /SiO 2 , the deactivation rate is reduced and the stability over time for the resulting catalyst (catalyst #2) is improved significantly.
  • the reference catalyst in Figure 2 has a deactivation rate that is almost twice as large as the deactivation rate of the catalyst #2 that contains rare earth element oxides, such as (Sm 2 O 3 ), in addition to the Mn/Na 2 WO 4 /SiO 2 .
  • the presence of the rare earth element oxides (e.g., (Sm 2 O 3 )) in the catalyst composition of catalyst #2 can increase the overall basicity of the catalyst composition, consequently increasing catalyst activity (e.g., ability of the catalyst to promote methyl radical formation); lowering the deactivation rate of the catalyst; and increasing catalyst stability over time.
  • the rare earth element oxides e.g., (Sm 2 O 3 )
  • a first aspect which is an oxidative coupling of methane (OCM) catalyst composition characterized by the general formula (E a D b O x )-Mn/Na 2 WO 4 ; wherein E is a first rare earth element; wherein D is a second rare earth element; wherein the first rare earth element and the second rare earth element are different; wherein a is 1.0; wherein b is from about 0 to about 10.0; wherein when b is 0, the first rare earth element is not lanthanum (La) alone or cerium (Ce) alone; and wherein x balances the oxidation states.
  • OCM methane
  • a second aspect which is the OCM catalyst composition of the first aspect, wherein the first rare earth element and the second rare earth element can each independently be selected from the group consisting of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), scandium (Sc), yttrium (Y), and combinations thereof.
  • La lanthanum
  • Ce cerium
  • Pr praseodymium
  • Nd neodymium
  • promethium Pm
  • Sm samarium
  • Eu europium
  • Gd gadolinium
  • Tb terbium
  • Dy dyspros
  • a third aspect which is the OCM catalyst composition of any one of the first and the second aspects, wherein the first rare earth element is basic; the second rare earth element is basic; or both.
  • a fourth aspect which is the OCM catalyst composition of any one of the first through the third aspects comprising one or more oxides of E; one or more oxides of D; or both.
  • a fifth aspect which is the OCM catalyst composition of any one of the first through the fourth aspects comprising a single rare earth element oxide, mixtures of single rare earth element oxides, a mixed rare earth element oxide, mixtures of mixed rare earth element oxides, mixtures of single rare earth element oxides and mixed rare earth element oxides, or combinations thereof.
  • a sixth aspect which is the OCM catalyst composition of any one of the first through the fifth aspects, wherein (E a D b O x ) is a catalyst for an OCM reaction in the absence of Mn/Na 2 WO 4 .
  • a seventh aspect which is the OCM catalyst composition of any one of the first through the sixth aspects having the general formula (La a Ce b O x )-Mn/Na 2 WO 4 ; wherein a is 1.0; wherein b is from about 0.01 to about 10.0; and wherein x balances the oxidation states.
  • An eighth aspect which is the OCM catalyst composition of any one of the first through the sixth aspects having the general formula (Sm a O x )-Mn/Na 2 WO 4 ; wherein a is 1.0; and wherein x balances the oxidation states.
  • a ninth aspect which is the OCM catalyst composition of the eighth aspect comprising Sm 2 O 3 .
  • a tenth aspect which is the OCM catalyst composition of any one of the first through the ninth aspects further comprising a support, wherein at least a portion of the OCM catalyst composition contacts, coats, is embedded in, is supported by, and/or is distributed throughout at least a portion of the support.
  • An eleventh aspect which is the OCM catalyst composition of the tenth aspect, wherein the support comprises MgO, Al 2 O 3 , SiO 2 , ZrO 2 , TiO 2 , or combinations thereof.
  • a twelfth aspect which is the OCM catalyst composition of any one of the first through the eleventh aspects, wherein the support is in the form of a powder, a particle, a pellet, a monolith, a foam, a honeycomb, or combinations thereof.
  • a thirteenth aspect which is the OCM catalyst composition of any one of the first through the twelfth aspects, wherein Mn is present in the OCM catalyst composition in an amount of from about 0.5 wt.% to about 20 wt.%, based on a total weight of the OCM catalyst composition.
  • a fourteenth aspect which is the OCM catalyst composition of any one of the first through the thirteenth aspects, wherein the OCM catalyst composition is characterized by an O 2 conversion that decreases by less than about 10% over a period of time of equal to or greater than about 50 hours.
  • a fifteenth aspect which is the OCM catalyst composition of any one of the first through the fourteenth aspects, wherein the OCM catalyst composition is characterized by a deactivation rate of less than about 0.5 %/hr over a period of time of equal to or greater than about 50 hours.
  • a sixteenth aspect which is the OCM catalyst composition of any one of the first through the fifteenth aspects, wherein the OCM catalyst composition is characterized by a deactivation rate that is decreased by equal to or greater than about 50% when compared to a deactivation rate of an otherwise similar OCM catalyst composition comprising (i) Mn/Na 2 WO 4 without (E a D b O x ); or (ii) (E a D b O x ) without Mn/Na 2 WO 4 .
  • a seventeenth aspect which is the OCM catalyst composition of any one of the first through the sixteenth aspects, wherein the OCM catalyst composition is characterized by a life time of equal to or greater than about 1,000 h.
  • An eighteenth aspect which is the OCM catalyst composition of any one of the first through the seventeenth aspects, wherein the OCM catalyst composition is characterized by a life time that is increased by equal to or greater than about 50% when compared to a life time of an otherwise similar OCM catalyst composition comprising (i) Mn/Na 2 WO 4 without (E a D b O x ); or (ii) (E a D b O x ) without Mn/Na 2 WO 4 .
  • a nineteenth aspect which is a method of making an oxidative coupling of methane (OCM) catalyst composition
  • OCM methane
  • the OCM catalyst precursor mixture comprises one or more compounds comprising a first rare earth element cation, one or more compounds comprising a second rare earth element cation, one or more compounds comprising a Mn cation, and Na 2 WO 4 ; wherein the first rare earth element cation and the second rare earth element cation are different; wherein the OCM catalyst precursor mixture is characterized by a molar ratio of second rare earth element to first rare earth element of b:1; and wherein b is from about 0 to about 10.0, and wherein when b is 0, the first rare earth element is not lanthanum (La) alone or cerium (Ce) alone; and (b) calcining the OCM catalyst precursor mixture to form the OCM catalyst composition.
  • a twentieth aspect which is the method of the nineteenth aspect, wherein the OCM catalyst composition is characterized by the general formula (E a D b O x )-Mn/Na 2 WO 4 ; wherein E is a first rare earth element; wherein D is a second rare earth element; wherein the first rare earth element and the second rare earth element are different; wherein a is 1.0; wherein b is from about 0 to about 10.0; wherein when b is 0, the first rare earth element is not lanthanum (La) alone or cerium (Ce) alone; and wherein x balances the oxidation states.
  • a twenty-first aspect which is the method of any one of the nineteenth and the twentieth aspects, wherein the OCM catalyst composition comprises Mn in an amount of less than about 20 wt.%, based on a total weight of the OCM catalyst composition.
  • a twenty-second aspect which is the method of any one of the nineteenth through the twenty-first aspects further comprising (i) drying at least a portion of the OCM catalyst precursor mixture to form a dried OCM catalyst precursor mixture; and (ii) calcining the dried OCM catalyst precursor mixture to form the OCM catalyst composition.
  • a twenty-third aspect which is the method of the twenty-second aspect, wherein the OCM catalyst precursor mixture is dried at a temperature of equal to or greater than about 75 o C.
  • a twenty-fourth aspect which is the method of any one of the nineteenth through the twenty- third aspects, wherein at least a portion of the OCM catalyst precursor mixture is contacted with a support to yield a supported OCM catalyst precursor mixture.
  • a twenty-fifth aspect which is the method of the twenty-fourth aspect, wherein at least a portion of the supported OCM catalyst precursor mixture is further dried and calcined to form the OCM catalyst composition.
  • a twenty-sixth aspect which is the method of any one of the nineteenth through the twenty- fifth aspects, wherein the OCM catalyst precursor mixture is calcined at a temperature of equal to or greater than about 700 o C.
  • a twenty-seventh aspect which is the method of any one of the nineteenth through the twenty-sixth aspects, wherein the one or more compounds comprising a first rare earth element cation comprises a first rare earth element nitrate, a first rare earth element oxide, a first rare earth element hydroxide, a first rare earth element chloride, a first rare earth element acetate, a first rare earth element carbonate, or combinations thereof; wherein the one or more compounds comprising a second rare earth element cation comprises a second rare earth element nitrate, a second rare earth element oxide, a second rare earth element hydroxide, a second rare earth element chloride, a second rare earth element acetate, a second rare earth element carbonate, or combinations thereof; and wherein the one or more compounds comprising a Mn cation comprises a Mn nitrate, a Mn oxide, a Mn hydroxide, a Mn chloride, a Mn acetate, a Mn carbonate, or combinations thereof; and
  • a twenty-eighth aspect which is an OCM catalyst produced by the method of any one of the nineteenth through the twenty-seventh aspects.
  • a twenty-ninth aspect which is a method of making an oxidative coupling of methane (OCM) catalyst composition
  • OCM methane
  • a Mn precursor comprising a Mn nitrate
  • a rare earth element precursor aqueous solution comprising a first rare earth element nitrate and a second rare earth element nitrate; wherein the first rare earth element nitrate and the second rare earth element nitrate are different; wherein the rare earth element precursor aqueous solution is characterized by a molar ratio of second rare earth element to first rare earth element of b:1, wherein b is from about 0 to about 10.0; and wherein when b is 0, the first rare earth element is not lanthanum (La) alone or cerium (Ce) alone; (c) contacting the rare earth element precursor aqueous solution with the Mn precursor to form a Mn-rare earth element precursor; (d) forming a Na 2 WO 4 aqueous solution;
  • a thirtieth aspect which is the method of the twenty-ninth aspect, wherein wherein the OCM catalyst composition is characterized by the general formula (E a D b O x )-Mn/Na 2 WO 4 ; wherein E is a first rare earth element; wherein D is a second rare earth element; wherein the first rare earth element and the second rare earth element are different; wherein a is 1.0; wherein b is from about 0 to about 10.0; wherein when b is 0, the first rare earth element is not lanthanum (La) alone or cerium (Ce) alone; and wherein x balances the oxidation states.
  • a thirty-first aspect which is a method of making an oxidative coupling of methane (OCM) catalyst composition
  • OCM methane
  • a method of making an oxidative coupling of methane (OCM) catalyst composition comprising (a) forming a Mn precursor comprising a Mn nitrate; (b) forming a Na 2 WO 4 aqueous solution; (c) contacting the Na 2 WO 4 aqueous solution with the Mn precursor to form a Mn/Na 2 WO 4 precursor; (d) forming a rare earth element precursor aqueous solution comprising a first rare earth element nitrate, and a second rare earth element nitrate; wherein the first rare earth element nitrate and the second rare earth element nitrate are different; wherein the rare earth element precursor aqueous solution is characterized by a molar ratio of second rare earth element to first rare earth element of b:1, wherein b is from about 0 to about 10.0; and wherein
  • a thirty-second aspect which is the method of the thirty-first aspect, wherein the OCM catalyst composition is characterized by the general formula (E a D b O x )-Mn/Na 2 WO 4 ; wherein E is a first rare earth element; wherein D is a second rare earth element; wherein the first rare earth element and the second rare earth element are different; wherein a is 1.0; wherein b is from about 0 to about 10.0; wherein when b is 0, the first rare earth element is not lanthanum (La) alone or cerium (Ce) alone; and wherein x balances the oxidation states.
  • a thirty-third aspect which is an oxidative coupling of methane (OCM) catalyst composition produced by (a) forming an OCM catalyst precursor mixture; wherein the OCM catalyst precursor mixture comprises a first rare earth element nitrate, a second rare earth element nitrate, a Mn nitrate, and Na 2 WO 4 ; wherein the first rare earth element nitrate and the second rare earth element nitrate are different; wherein the OCM catalyst precursor mixture is characterized by a molar ratio of second rare earth element to first rare earth element of b:1, wherein b is from about 0 to about 10.0; and wherein when b is 0, the first rare earth element is not lanthanum (La) alone or cerium (Ce) alone; (b) drying at least a portion of the OCM catalyst precursor mixture at a temperature of equal to or greater than about 75 o C to form a dried OCM catalyst precursor mixture; and (c) calcining the dried OCM catalyst precursor mixture at a temperature of
  • a thirty-fourth aspect which is the OCM catalyst composition of the thirty-third aspect, wherein the OCM catalyst composition is characterized by the general formula (E a D b O x )-Mn/Na 2 WO 4 ; wherein E is a first rare earth element; wherein D is a second rare earth element; wherein the first rare earth element and the second rare earth element are different; wherein a is 1.0; wherein b is from about 0 to about 10.0; wherein when b is 0, the first rare earth element is not lanthanum (La) alone or cerium (Ce) alone; and wherein x balances the oxidation states.
  • a thirty-fifth aspect which is a method for producing olefins comprising (a) introducing a reactant mixture to a reactor comprising an oxidative coupling of methane (OCM) catalyst composition; wherein the reactant mixture comprises methane (CH 4 ) and oxygen (O 2 ); wherein the OCM catalyst composition is characterized by the general formula (E a D b O x )-Mn/Na 2 WO 4 ; wherein E is a first rare earth element; wherein D is a second rare earth element; wherein the first rare earth element and the second rare earth element are different; wherein a is 1.0; wherein b is from about 0 to about 10.0; wherein when b is 0, the first rare earth element is not lanthanum (La) alone or cerium (Ce) alone; and wherein x balances the oxidation states; (b) allowing at least a portion of the reactant mixture to contact at least a portion of the OCM catalyst composition and react via
  • a thirty-sixth aspect which is the method of the thirty-fifth aspect, wherein the first rare earth element and the second rare earth element can each independently be selected from the group consisting of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), scandium (Sc), yttrium (Y), and combinations thereof.
  • La lanthanum
  • Ce cerium
  • Pr praseodymium
  • Nd neodymium
  • promethium Pm
  • Sm samarium
  • Eu europium
  • Gd gadolinium
  • Tb terbium
  • a thirty-seventh aspect which is the method of any one of the thirty-fifth and the thirty-sixth aspects, wherein the first rare earth element and the second rare earth element can each independently be selected from the group consisting of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), gadolinium (Gd), and combinations thereof.
  • the first rare earth element and the second rare earth element can each independently be selected from the group consisting of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), gadolinium (Gd), and combinations thereof.
  • a thirty-eighth aspect which is the method of any one of the thirty-fifth through the thirty- seventh aspects, wherein the OCM catalyst composition is characterized by a life time that is increased by equal to or greater than 50% when compared to a life time of an otherwise similar OCM catalyst composition comprising (i) Mn/Na 2 WO 4 without (E a D b O x ); or (ii) (E a D b O x ) without Mn/Na 2 WO 4 .

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Cette invention concerne une composition de catalyseur pour couplage oxydant du méthane (OCM), caractérisée par la formule générale (EaDbOx)-Mn/Na2WO4, où E est un premier élément de terres rares ; où D est un second élément de terres rares, le premier élément de terres rares et le second élément de terres rares étant différents ; où a est égal à 1,0 ; où b va d'environ 0 à environ 10,0 ; lorsque b est égal à 0, le premier élément de terres rares n'est pas du lanthane (La) seul ou du cérium (Ce) seul ; et où x équilibre les états d'oxydation.
PCT/US2018/032556 2017-05-15 2018-05-14 Catalyseurs à oxydes mixtes pour couplage oxydant du méthane WO2018213183A1 (fr)

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CN109663587A (zh) * 2018-11-30 2019-04-23 中国科学院山西煤炭化学研究所 一种纳米甲烷氧化偶联催化剂及其制备方法和应用
CN111167281A (zh) * 2020-01-09 2020-05-19 珠海格力电器股份有限公司 用于甲醛分解的锰铈氧化物/活性炭复合材料及其制备方法
CN112536029A (zh) * 2019-09-23 2021-03-23 中国石油化工股份有限公司 甲烷氧化偶联制乙烯催化剂及其制备方法和甲烷氧化偶联制乙烯的方法
CN112536028A (zh) * 2019-09-20 2021-03-23 中国石油化工股份有限公司 用于甲烷直接转化制烯烃的催化剂及其制备方法和应用
CN112547049A (zh) * 2019-09-26 2021-03-26 中国石油化工股份有限公司 负载型催化剂及其制备方法和甲烷氧化偶联制乙烯的方法
CN112547048A (zh) * 2019-09-26 2021-03-26 中国石油化工股份有限公司 转化甲烷的催化剂及其制备方法和转化甲烷的方法
WO2021080717A1 (fr) * 2019-10-22 2021-04-29 Sabic Global Technologies, B.V. Catalyseur supporté d'oxyde mixte multicouche pour le couplage par oxydation du méthane
CN112871152A (zh) * 2019-11-29 2021-06-01 中国石油化工股份有限公司 甲烷氧化偶联催化剂及其制备方法和甲烷氧化偶联制乙烯的方法
CN112934215A (zh) * 2019-12-10 2021-06-11 中国石油化工股份有限公司 转化甲烷的催化剂及其制备方法和应用
CN112934216A (zh) * 2019-12-10 2021-06-11 中国石油化工股份有限公司 甲烷氧化偶联催化剂及其制备方法和甲烷氧化偶联制碳二烃的方法
CN113398947A (zh) * 2020-03-16 2021-09-17 华东师范大学 一种用于化学链甲烷氧化偶联反应的催化剂及其制备方法和应用
RU2783516C1 (ru) * 2019-10-22 2022-11-14 Сабик Глоубл Текнолоджиз, Б.В. Многослойный смешанный оксидный катализатор, нанесенный на носитель, для окислительной конденсации метана
US11753357B2 (en) 2019-10-22 2023-09-12 Sabic Global Technologies B.V. Multilayer mixed oxide supported catalyst for oxidative coupling of methane
US11986800B2 (en) 2019-12-18 2024-05-21 Sabic Global Technologies, B.V. OCM catalyst composition having improved stability and carbon efficiency

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CN109663587B (zh) * 2018-11-30 2021-08-06 中国科学院山西煤炭化学研究所 一种纳米甲烷氧化偶联催化剂及其制备方法和应用
CN109663587A (zh) * 2018-11-30 2019-04-23 中国科学院山西煤炭化学研究所 一种纳米甲烷氧化偶联催化剂及其制备方法和应用
CN112536028A (zh) * 2019-09-20 2021-03-23 中国石油化工股份有限公司 用于甲烷直接转化制烯烃的催化剂及其制备方法和应用
CN112536028B (zh) * 2019-09-20 2022-08-19 中国石油化工股份有限公司 用于甲烷直接转化制烯烃的催化剂及其制备方法和应用
CN112536029B (zh) * 2019-09-23 2022-08-19 中国石油化工股份有限公司 甲烷氧化偶联制乙烯催化剂及其制备方法和甲烷氧化偶联制乙烯的方法
CN112536029A (zh) * 2019-09-23 2021-03-23 中国石油化工股份有限公司 甲烷氧化偶联制乙烯催化剂及其制备方法和甲烷氧化偶联制乙烯的方法
CN112547048A (zh) * 2019-09-26 2021-03-26 中国石油化工股份有限公司 转化甲烷的催化剂及其制备方法和转化甲烷的方法
CN112547049A (zh) * 2019-09-26 2021-03-26 中国石油化工股份有限公司 负载型催化剂及其制备方法和甲烷氧化偶联制乙烯的方法
WO2021080717A1 (fr) * 2019-10-22 2021-04-29 Sabic Global Technologies, B.V. Catalyseur supporté d'oxyde mixte multicouche pour le couplage par oxydation du méthane
RU2783516C1 (ru) * 2019-10-22 2022-11-14 Сабик Глоубл Текнолоджиз, Б.В. Многослойный смешанный оксидный катализатор, нанесенный на носитель, для окислительной конденсации метана
US11633721B2 (en) 2019-10-22 2023-04-25 Sabic Global Technologies, B.V. Multilayer mixed oxide supported catalyst for oxidative coupling of methane
US11753357B2 (en) 2019-10-22 2023-09-12 Sabic Global Technologies B.V. Multilayer mixed oxide supported catalyst for oxidative coupling of methane
CN112871152A (zh) * 2019-11-29 2021-06-01 中国石油化工股份有限公司 甲烷氧化偶联催化剂及其制备方法和甲烷氧化偶联制乙烯的方法
CN112934215B (zh) * 2019-12-10 2023-05-30 中国石油化工股份有限公司 转化甲烷的催化剂及其制备方法和应用
CN112934215A (zh) * 2019-12-10 2021-06-11 中国石油化工股份有限公司 转化甲烷的催化剂及其制备方法和应用
CN112934216A (zh) * 2019-12-10 2021-06-11 中国石油化工股份有限公司 甲烷氧化偶联催化剂及其制备方法和甲烷氧化偶联制碳二烃的方法
US11986800B2 (en) 2019-12-18 2024-05-21 Sabic Global Technologies, B.V. OCM catalyst composition having improved stability and carbon efficiency
CN111167281A (zh) * 2020-01-09 2020-05-19 珠海格力电器股份有限公司 用于甲醛分解的锰铈氧化物/活性炭复合材料及其制备方法
CN113398947B (zh) * 2020-03-16 2023-05-02 华东师范大学 一种用于化学链甲烷氧化偶联反应的催化剂及其制备方法和应用
CN113398947A (zh) * 2020-03-16 2021-09-17 华东师范大学 一种用于化学链甲烷氧化偶联反应的催化剂及其制备方法和应用

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