WO2018015473A1 - Catalyseur à base de manganèse-alcali sur support de silice mésoporeuse ordonnée pour le couplage oxydatif du méthane et sa préparation - Google Patents

Catalyseur à base de manganèse-alcali sur support de silice mésoporeuse ordonnée pour le couplage oxydatif du méthane et sa préparation Download PDF

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WO2018015473A1
WO2018015473A1 PCT/EP2017/068307 EP2017068307W WO2018015473A1 WO 2018015473 A1 WO2018015473 A1 WO 2018015473A1 EP 2017068307 W EP2017068307 W EP 2017068307W WO 2018015473 A1 WO2018015473 A1 WO 2018015473A1
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catalyst composition
methane
manganese
catalyst
composition according
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PCT/EP2017/068307
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English (en)
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Kartick Chandra Mondal
Onen Amiruddin ATTARWALA
Mohmedasif Iqbalhusain QURAISHI
Andrew David Horton
Evalyn Mae ALAYON
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Shell Internationale Research Maatschappij B.V.
Shell Oil Company
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Publication of WO2018015473A1 publication Critical patent/WO2018015473A1/fr

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    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/612—Surface area less than 10 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding
    • 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
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • 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
    • C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
    • C07C2523/04—Alkali metals
    • 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

Definitions

  • the present invention relates to a mesoporous silica-supported catalyst, a method of preparing such a catalyst, and a process for the oxidative coupling of methane .
  • Methane is a valuable resource which is used not only as a fuel, but is also used in the synthesis of chemical compounds such as higher hydrocarbons .
  • the conversion of methane to other chemical compounds can take place via indirect conversion wherein methane is reformed to synthesis gas (hydrogen and carbon monoxide) , followed by reaction of the synthesis gas in a Fischer-Tropsch process.
  • synthesis gas hydrogen and carbon monoxide
  • reaction of the synthesis gas in a Fischer-Tropsch process is costly and consumes a lot of energy.
  • the oxidative coupling of methane converts methane into saturated and unsaturated, non-aromatic hydrocarbons having 2 or more carbon atoms, including ethylene.
  • a gas stream comprising methane is contacted with an OCM catalyst and with an oxidant, such as oxygen or air.
  • an oxidant such as oxygen or air.
  • two methane molecules are first coupled into one ethane molecule, which is then dehydrogenated into ethylene.
  • Said ethane and ethylene (“C2 compounds”) may further react into saturated and unsaturated hydrocarbons having 3 or more carbon atoms (C3+ ) , including propane, propylene, butane, butene, etc.
  • the gas stream leaving an OCM process may contain a mixture of water, hydrogen, carbon monoxide, carbon dioxide and saturated and unsaturated hydrocarbons having 5 or more carbon atoms.
  • the conversion to saturated and unsaturated hydrocarbons having 2 or more carbon atoms (“C2+”) compounds that can be achieved in an OCM process is relatively low.
  • the selectivity decreases so that it is generally desired to keep the conversion relatively low.
  • a large amount of unconverted methane leaves the OCM process.
  • the proportion of unconverted methane in the OCM product gas stream may be as high as 50 to 60 mol% based on the total molar amount of the gas stream. This unconverted methane has to be recovered from the desired products, such as ethylene and other saturated and unsaturated hydrocarbons having 2 or more carbon atoms, thus
  • a further difficulty with OCM processes is that a competing reaction that takes place is the oxidation of methane to carbon monoxide, carbon dioxide and water, as well as further oxidation of ethane and ethylene to carbon monoxide, carbon dioxide.
  • the currently best-performing catalysts in the OCM field typically comprise manganese, tungsten and sodium impregnated onto an amorphous silica (Si0 2 ) carrier (Mn- Na 2 W0 4 /Si0 2 ) .
  • US 2013/0023709A describes the high throughput screening of catalyst libraries for the oxidative coupling of methane and tests on various catalysts including catalysts comprising sodium, manganese and tungsten on silica and zirconia carriers .
  • a mesoporous silica-supported catalyst composition comprising manganese and one or more alkali metals prepared in situ by a template- assisted one-pot synthesis method exhibits improved performance and stability relative to analogous
  • catalysts prepared by post-impregnation on amorphous or mesoporous silica supports are prepared by post-impregnation on amorphous or mesoporous silica supports .
  • a catalyst composition comprising manganese and one or more alkali metals supported on an ordered mesoporous silica carrier.
  • a catalyst composition comprising manganese, one or more alkali metals, optionally another transition metal and an ordered mesoporous silica carrier material.
  • a method of preparing a catalyst composition comprising manganese and one or more alkali metals and an ordered mesoporous silica carrier material, wherein said method comprises - providing a solution comprising (i) template material, (ii) silica precursor, (iii) manganese precursor, alkali metal precursor, and optionally other metal precursors, and (iv) solvent;
  • a process for the oxidative coupling of methane comprising converting methane to one or more C2+ hydrocarbons, wherein said process comprises contacting a reactor feed comprising methane and oxygen with the afore-mentioned catalyst composition.
  • the in situ template-assisted mesoporous silica-supported catalyst according to the present invention was shown by low angle XRD to exhibit ordered
  • mesoporous structure of the catalyst composition as defined herein is better capable of retaining the active metal inside the mesoporous matrix, thus preventing leaching out of active metals from the catalyst support.
  • Figure 1 shows a low-angle XRD graph of a
  • Figure 2 shows comparative catalytic performance data .
  • methane (CH 4 ) conversion means the mole fraction of methane converted to product (s) .
  • C x selectivity refers to the percentage of converted reactants that went to product (s) having carbon number x and "C x+ selectivity” refers to the percentage of converted reactants that went to the specified product (s) having a carbon number x and higher.
  • C 2 selectivity refers to the percentage of converted methane that formed ethane and ethylene.
  • C 2+ selectivity means the percentage of converted methane that formed compounds having carbon numbers of 2 and higher.
  • C x yield is used to define the percentage of products obtained with carbon number x relative to the theoretical maximum product obtainable.
  • the C x yield is calculated by dividing the amount of obtained product having carbon number x in moles by the theoretical yield in moles and multiplying the result by 100.
  • C 2 yield refers to the total combined yield of ethane and ethylene.
  • the C x yield may be calculated by multiplying the methane conversion by the C x selectivity.
  • reactor temperature or “reaction temperature” should be interpreted to refer to the temperature as measured at the entrance of the catalyst bed, i.e. the temperature of the reactor feed gas just before entering the catalyst bed.
  • reaction temperature the temperature as measured at the entrance of the catalyst bed, i.e. the temperature of the reactor feed gas just before entering the catalyst bed.
  • the temperature of the reactor feed gas just before entering the catalyst bed is not necessarily the same as the temperature of the feed gas at the inlet of the reactor, i.e., it may for example be somewhat or substantially higher.
  • the term "mesoporous” refers to a material containing pores, wherein the pores have a diameter from 2 to 50 nm.
  • the porous structure provides for a large internal surface area with adsorptive capacity for molecular or ionic species, which are capable of entering therein.
  • the mesoporous silica support material of the catalyst composition according to the present invention has pores with a diameter ranging from 2 to 50 nm, more preferably in the range of from 3 to 15 nm, more preferably in the range of from 6 to 12 nm.
  • the mesoporous silica support material typically has a pore diameter larger than 7 nm. Typically, less than 10 % by volume of the mesoporous silica support material has a pore diameter smaller than 5 nm.
  • ordered mesoporous used herein in the context of the silica support material, is well known in the art and generally refers to a mesoporous material comprising extended regions having a narrow pore-size distribution, as described in detail in, for example, F. Liebau, Microporous and Mesoporous Materials 58 (2003) pp. 15-72.
  • the ordered mesoporous silica support material of the catalyst compositions of the present invention are characterized by comprising at least 50 wt%, and/or at least 10 vol% of regions in which the pores have a very narrow size distribution (standard deviation ⁇ 1%) and a high long-range (> 7 nm) order .
  • the pore size and pore size distribution can be determined by a variety of nanoscale characterization techniques, including transmission electron microscopy
  • TEM small-angle X-ray scattering
  • SAXS small-angle X-ray scattering
  • XRD low-angle X- ray diffraction
  • gas adsorption-desorption and mercury intrusion porosimetry combined with analysis techniques including Density Functional Theory (DFT) , Horvath-Kawazoe (HK) modeling and Barrett-Joyner-Halenda
  • the term "supported on” used herein in the context of the ordered mesoporous silica carrier refers to the common way of distributing the catalytically active material over the high surface area carrier ("support") material.
  • support high surface area carrier
  • all catalyst constituents, i.e. catalyst carrier and metals, are combined in their precursor state in the presence of a suitable template material, followed by drying, optional comminution steps and calcination in order to provide a carrier material with interspersed active metal.
  • weight percent refers to the ratio of the total weight of the carrier, the metal-containing component or the metal in the dopant to the total weight of the catalyst composition. Said percentages are determined with respect to the weight of the total dry catalyst composition.
  • the weight of the total dry catalyst composition may be measured following drying for at least four hours at temperatures of at least 120, preferably at least 150 °C, more preferably at least 300 °C.
  • Percentages of metals from the metal-containing constituents in the catalyst composition may be any percentage of metals from the metal-containing constituents in the catalyst composition.
  • XRF X-ray fluorescence
  • the metals content of the catalyst composition may also be inferred or controlled via its synthesis.
  • the components of the catalyst composition are to be selected in an overall amount adding up to 100 wt . %.
  • the term "compound” refers to the combination of a particular element with one or more different elements by surface and/or chemical bonding, such as ionic and/or covalent and/or coordinate bonding.
  • cationic being positive
  • anion or “anionic” being negative
  • oxyanion or “oxyanionic” being a negatively charged moiety containing at least one oxygen atom in combination with another element (i.e., an oxygen-containing anion) . It is understood that ions do not exist in vacuo, but are found in combination with charge-balancing counter ions when added.
  • oxidic refers to a charged or neutral species wherein an element in question is bound to oxygen and possibly one or more different elements by surface and/or chemical bonding, such as ionic and/or covalent and/or coordinate bonding.
  • an oxidic compound is an oxygen-containing compound which also may be a mixed, double or complex surface oxide.
  • Illustrative oxidic compounds include, but are not limited to, oxides (containing only oxygen as the second element), hydroxides, nitrates, sulfates, carboxylates , carbonates, bicarbonates, oxyhalides, etc. as well as surface species wherein the element in question is bound directly or indirectly to an oxygen either in the substrate or the surface.
  • B.E.T. Brunauer-Emmett-Teller
  • ASTM D4365-95 the general procedure and guidance of ASTM D4365-95 is followed in the application of the "B.E.T. method” to the materials.
  • B.E.T. surface area refers to the surface area of the
  • silicon-containing carrier prior to and after doping with manganese and one or more alkali metals, and optionally other metals.
  • catalyst composition of the present invention has a B.E.T. surface area of greater than 1 m 2 /g, preferably in the range of from 1 to 50 m 2 /g, more preferably in the range of from 2 to 20 m 2 /g and most preferably in the range of from 2 to 10 m 2 /g, according to ASTM D4365-95.
  • the total pore volume may be measured by a
  • the mesoporous silica support material may be conveniently present in the catalyst composition in an amount in the range of from 75 to 96 % by weight, preferably in the range of from 85 to 92 % by weight, relative to the total weight of the catalyst
  • the catalyst composition of the present invention comprises manganese in an amount of in the range of from 1 to 10 % by weight, preferably in the range of from 1 to 5 % by weight, more preferably in the range of from 1.3 to 3 % by weight and most preferably in the range of from 1.7 to 2.5 % by weight, relative to the total weight of the catalyst composition.
  • the manganese is present in the catalyst composition in the form of one or more manganese-containing dopants such as one or more manganese-containing oxides.
  • Said manganese- containing oxides may be reducible oxides of manganese and/or reduced oxides of manganese.
  • the catalyst composition comprises at least one reducible oxide of manganese.
  • reducible oxides include compounds of the general formula Mn x O y wherein x and y designate the relative atomic
  • Particularly preferred reducible oxides of manganese include Mn0 2 , Mn 2 0 3 , Mn 3 0 4 and mixtures thereof.
  • the catalyst composition of the present invention comprises one or more (Group 1) alkali metals.
  • Said alkali metals are typically one or more of lithium, sodium, potassium, rubidium and cesium. In some
  • the alkali metals are sodium and/or lithium.
  • the one or more alkali metals are typically each present in an amount of in the range of from 0.1 to 2.0 % by weight, more preferably in the range of from 0.4 to 1.5 % by weight, and most preferably in the range of from 0.4 to 1.2 % by weight, relative to the total weight of the catalyst composition.
  • the catalyst composition of the present invention may further comprise tungsten.
  • Said tungsten may be present in a preferred amount of in the range of from 1 to 4.5 % by weight, more preferably in the range of from 1.5 to 3.5 % by weight, relative to the total weight of the catalyst composition.
  • the catalyst composition comprises manganese, tungsten and one or more alkali metals.
  • composition comprises manganese, tungsten and sodium, generally denoted in the field as Mn/Na 2 W0 4 .
  • the alkali metal is sodium and the other transition metal is tungsten.
  • the catalyst composition comprises a ternary oxide compound having the
  • composition M 1 M 2 Mn0 3 wherein M 1 and M 2 are the same or different and are alkali metals selected from lithium, sodium and potassium.
  • the ternary oxide compound has the
  • the catalyst composition comprises a ternary oxide compound having the
  • composition Li 2 Mn0 3 Li 2 Mn0 3 .
  • the one or more alkali metals and optionally tungsten may be doped as separate metals and/or metal-containing compounds into said composition. If the catalyst composition also comprises tungsten, in some embodiments, the one or more alkali metals and tungsten may be doped into the catalyst composition in the form of one or more compounds comprising both alkali metal (s) and tungsten therein. Suitable examples of such compounds include sodium tungstate and lithium
  • the specific form of the manganese, one or more alkali metals, optionally other transition metals, and any optional co-promoters and/or additional metal-containing dopants in the catalyst composition may be unknown.
  • the catalyst composition of the present invention comprises one or more of Na 2 W0 4 , Na 2 W 2 0 7 , Mn 2 0 3 and MnW0 4 .
  • the invention relates to a process for preparing a catalyst composition comprising manganese and one or more alkali metals, wherein said method comprises
  • composition of the present invention is prepared in situ by a template-assisted solution-gelation (sol-gel) inorganic polymerization method in a solution also comprising manganese precursor, alkali metal precursor, and optionally other metal precursors.
  • sol-gel solution-gelation
  • the organic template material serves as a structure-directing agent for the formation of ordered mesoporous silica via self-organization of the organic template material (e.g. into micelles) and silica precursor compound (s) into three-dimensional periodic phases, followed by removal of the organic matter by high-temperature calcination to provide a three- dimensional, porous structure with long-range order.
  • Examples of commercially available ordered mesoporous silica compounds are the hexagonal ordered mesoporous molecular sieve known as MCM-41 having a 2-3 nm pore size and SBA-15 comprising ordered hexagonal mesoporous silica particles with a tunable, uniform pore size.
  • Suitable template materials are anionic
  • surfactants non-ionic surfactants and cationic
  • poly (propylene glycol) (poly (propylene oxide)) flanked by two hydrophilic chains of poly (ethylene glycol) (poly (ethylene oxide)) ["PEG-PPG-PEG” or “PEO-PPO-PEO” ] , also known as “poloxamers” .
  • PEG-PPG-PEG poly (ethylene glycol)
  • PEO-PPO-PEO poly (ethylene oxide)
  • PLURONIC F-127 which is a PEG-PPG-PEG triblock copolymer having a molecular weight of approximately 12,500 Da.
  • Suitable cationic surfactants include hexadecyl amine (HDA) , and quaternary ammonium salts such as cetyltrimethyl ammonium chloride (CTAC) , cetyltrimethyl ammonium bromide (CTAB) , dodecyltrimethyl ammonium chloride (DTAC) , cetylpyridinium chloride (CPC) ,
  • HDA hexadecyl amine
  • CPC cetylpyridinium chloride
  • BAC benzalkonium chloride
  • BAC benzethonium chloride
  • DODAB dioctadecyl dimethylammonium bromide
  • preferred cationic surfactant is cetyltrimethyl ammonium bromide (CTAB) .
  • Suitable anionic surfactants include alkyl
  • sulfates alkylbenzene sulfonates, alkyl carboxylates and di-alkyl sulfosuccinates, such as sodium dodecyl sulfate (SDS) , stearic acid and dioctyl sodium
  • sulfosuccinate also known as Aerosol-OT
  • Preferred anionic surfactants are sodium dodecyl sulfate (SDS), sodium dodecylbenzene sulfonate and stearic acid.
  • the silica precursor may be any conventionally known silica or silicate, such as fumed silica,
  • colloidal silica sodium silicate, and organic silicates or a combination thereof.
  • an organic silicate such as quaternary ammonium silicate
  • quaternary ammonium silicate examples are tetramethylammonium silicate (TMAS) , tetramethyl orthosilicate (TMOS) and tetraethyl
  • TEOS orthosilicate
  • TEOS orthosilicate
  • the catalyst composition of the present invention may further comprise one or more additional carriers therein selected from titania (Ti0 2 ) , alumina (A1 2 0 3 ) and zirconia (Zr0 2 ) in amounts of from 2 to 50 wt % based on total weight of the catalyst
  • the catalyst synthesis process involves providing a solution of the template material, or of a combination of template materials, and mixing with one or more silica precursor compounds to create a support material solution.
  • the weight ratio of template compound to silica precursor used in the synthesis process is in the range of 0.1:1 to 5:1, preferably 0.2:1 to 2:1, more preferably 0.3:1 to 1:1.
  • the catalyst synthesis process typically further involves providing one or more solutions of the
  • manganese precursor the alkali metal precursor, and optionally other metal precursors, such as tungsten precursor, either as separate solutions or as solutions comprising two or more of the required metal and alkali metal precursors.
  • solvent this should be understood as a single solvent compound or a mixture of solvent compounds.
  • suitable solvents include water, ethanol, acetone, isopropanol and methanol, and any combination thereof.
  • the alkali metal precursor is a sodium precursor and the optional other transition metal is tungsten.
  • an organic or inorganic acid is added to catalyze hydrolysis of the silica precursor and subsequent polymerization (condensation) into a three- dimensional silica network.
  • Suitable examples of such acids include citric acid, acetic acid, nitric acid and hydrochloric acid, and the skilled person will be capable of selecting a preferred combination of silica precursor and hydrolysis catalyst in the appropriate amounts.
  • acid is added to the silica
  • a chelating agent may be added, such as, for example, ammonium oxalate or citric acid.
  • agitation of the slurry of metal and alkali metal solution (s) and (polymerized) silica is conducted over a period of several hours, for example between 1-20 hours, preferably between 2-15 hours, more preferably between 4-14 hours .
  • the template-containing support material solution is combined with the metal and alkali metal solution (s), and optionally other components, under agitation to form a slurry.
  • the one or more solvents are removed by evaporation, typically at moderately elevated temperatures in the range of 40-140 °C, preferably 50-100 °C, more preferably 60-95 °C, to provide a solid material.
  • the thermal solvent removal step further contributes to the aging (e.g., formation of cross-links, strengthening, stiffening, shrinkage) of the polymerized silica network into the desired solid mesoporous structure.
  • the particle size of the resulting solid material may be reduced (comminuted) by any technique known in the art for reducing the size of catalyst particles, including grinding, milling, crushing, cutting, sieving, etc., and any combination thereof .
  • Calcination of the, optionally comminuted, solid material yields a catalyst composition comprising manganese, one or more alkali metals and optionally other metals supported on an ordered mesoporous silica carrier. Calcination may take place at a temperature in the range of from 600 to 1000 °C, preferably in the range of from 700 to 900 °C, and most preferably in the range of from 800 to 850 °C. While above this
  • calcination is typically conducted over a period of several hours, for example 2-10, preferably 4-8, more preferably 5-7 hours. In some embodiments, calcination is carried out by a step-wise increase of the temperature and intermediate dwelling, for example 0.5 hr dwelling at 600 °C, 2 °C/min until 800 °C and 4 hrs dwelling at 800 °C .
  • any optional co-promoters and/or additional metal- containing dopants are provided is not limited, provided that they can be solubilized in an appropriate solvent, such as a water- and/or alcohol-containing solvent.
  • precursors of the manganese, an alkali metal, optional other transition metal (such as tungsten) and an optional co-promoter and/or additional metal-containing dopant may suitably be provided as dissolved ions (e.g., cation, anion, oxyanion, etc.), or as dissolved compounds (e.g., alkali metal salts, salts of a further co-promoter, etc.) .
  • the present disclosure is not intended to be limited by the exact form of the manganese, the one or more alkali metals, the optional other transition metals, and/or any optional co- promoters and/or additional metal-containing dopants that may ultimately exist on the catalyst composition during use .
  • alkali metal compounds include, but are not limited to, alkali metal salts and oxidic compounds of the alkali metals, such as the nitrates, nitrites, carbonates, bicarbonates , oxalates, carboxylic acid salts, hydroxides, halides, oxyhalides, borates, sulfates, sulfites, bisulfates, acetates, tartrates, lactates, oxides, peroxides, and iso- propoxides, etc.
  • alkali metal salts and oxidic compounds of the alkali metals such as the nitrates, nitrites, carbonates, bicarbonates , oxalates, carboxylic acid salts, hydroxides, halides, oxyhalides, borates, sulfates, sulfites, bisulfates, acetates, tartrates, lactates, oxides, peroxides, and iso- propoxides,
  • the one or more alkali metals may comprise a combination of two or more alkali metal dopants.
  • Non-limiting examples include
  • potassium, lithium and rubidium, lithium and cesium sodium and potassium, sodium and rubidium, sodium and cesium, potassium and rubidium, potassium and cesium and rubidium and cesium.
  • the catalyst compositions of the present invention may further comprise one or more co- promoters and/or additional metal-containing dopants.
  • co-promoters and metal-containing dopants examples include lanthanum, cerium, niobium and tin.
  • the catalyst composition of the present invention may comprise said optional co-promoters and/or metal- containing dopants in a total amount of in the range of from 0.1 to 5 % by weight, and most preferably in the range of from 0.5 to 2 % by weight, relative to the total weight of the catalyst composition.
  • the process of the present invention further comprises utilizing the catalyst composition as
  • the invention relates to process for the
  • oxidative coupling of methane comprising converting methane to one or more C2+ hydrocarbons, wherein said process comprises contacting a reactor feed comprising methane and oxygen with a catalyst composition as defined herein.
  • the reactor may be any suitable reactor, such as a fixed bed reactor with axial or radial flow and with inter-stage cooling or a fluidized bed reactor equipped with internal and external heat exchangers.
  • the catalyst composition may be packed along with an inert packing material, such as quartz, into a fixed bed reactor having an appropriate inner diameter and length.
  • the catalyst composition may be pretreated at high temperature to remove moisture and impurities therefrom. Said pretreatment may take place, for example, at a temperature in the range of from 100- 300 °C for about one hour in the presence of an inert gas such as helium.
  • Suitable processes include those described in EP 0206042 Al, US 4443649 A, CA 2016675 A, US 6596912 Bl, US 2013/0023709 Al, WO 2008/134484 A2 and WO 2013/106771 A2.
  • reactor feed is understood to refer to the totality of the gaseous stream at the inlet of the reactor.
  • the reactor feed is often comprised of a combination of one or more gaseous stream(s), such as a methane stream, an oxygen stream, a recycle gas stream, a diluent stream, etc.
  • a reactor feed comprising methane and oxygen is introduced into the reactor.
  • the reactor feed may further comprise one or more of a diluent gas, together with minor components of the methane feed (ethane, propane etc.) or the methane recycle stream (e.g.
  • the diluent represents the balance of the feed gas and is an inert gas.
  • suitable inert gases are nitrogen, argon and helium.
  • the methane and oxygen are added to the reactor as mixed feed, optionally
  • the methane and oxygen may be added in separate feeds, optionally comprising further components therein, to the reactor at separate inlets.
  • Methane may be present in the reactor feed in a concentration of at least 35 mole-%, and most preferably at least 40 mole-%, relative to the total reactor feed. Similarly, methane may be present in the reactor feed in a concentration of at most 90 mole-%, and most
  • methane may be present in the reactor feed in a
  • concentration in the range of from 35 to 90 mole-%, and most preferably in the range of from 40 to 85 mole-%, relative to the total reactor feed.
  • the reactor feed further comprises oxygen, which may be provided either as pure oxygen or air.
  • oxygen which may be provided either as pure oxygen or air.
  • high-purity at least 95 mole-%) oxygen or very high purity (at least 99.5 mole-%) oxygen is employed.
  • the oxygen concentration in the reactor feed should be less than the concentration of oxygen that would form a flammable mixture at either the reactor inlet or the reactor outlet at the prevailing operating conditions.
  • the oxygen concentration in the reactor feed may be no greater than a pre-defined percentage (e.g., 95%, 90%, etc.) of oxygen that would form a flammable mixture at either the reactor inlet or the reactor outlet at the prevailing operating conditions.
  • the oxygen concentration in the reactor feed may vary over a wide range, the oxygen
  • concentration in the reactor feed is typically at least 7 mole-%, or at least 10 mole-%, relative to the total reactor feed.
  • oxygen concentration of the reactor feed is typically at most 25 mole-%, or at most 20 mole-%, relative to the total reactor feed.
  • oxygen may be present in the reactor feed in a concentration in the range of from 7 to 25 mole-%, and most preferably in the range of from 10 to 20 mole-%, relative to the total reactor feed.
  • the methane : oxygen volume ratio in the process of the present invention is preferably in the range of from 2/1 to 10/1, more preferably in the range of from 3/1 to 6/1.
  • the reactor feed optionally may further comprise a diluent gas, such as helium, argon, nitrogen, or a combination thereof.
  • a diluent gas such as helium, argon, nitrogen, or a combination thereof.
  • the order and manner in which the components of the reactor feed are combined prior to contacting the catalyst composition is not limited, and they may be combined simultaneously or sequentially. However, as will be recognized by one skilled in the art, it may be desirable to combine certain components of the inlet feed gas in a specified order for safety reasons. For example, oxygen may be added to the inlet feed gas after the addition of a dilution gas for safety reasons.
  • the concentration of various feed components present in the inlet feed gas may be adjusted throughout the process, for example, to maintain a desired
  • the ordered mesoporosity of the silica substrate is maintained. This may prevent leaching out of active metals from the silica support matrix, thus improving long-term
  • Figure 1 shows a low-angle X-ray diffraction (XRD) diffractogram of a 2 wt% Mn/2 wt% Na 2 W0 4 /mesoporous Si0 2 catalyst composition prepared using Pluronic P-123 as template and having been calcined at 800 °C for 4 hours.
  • XRD X-ray diffraction
  • the reactor feed comprising methane and oxygen is contacted with a catalyst composition as hereinbefore described in order to effect the conversion of methane to one or more C 2+ hydrocarbons.
  • the reactor temperature is in the range of from 500 to 1000 °C.
  • said conversion is effected at a reactor temperature in the range of from 650 to 1000 °C, more preferably in the range of from 700 to 950 °C, even more preferably in the range of from 750 to 900 °C and most preferably in the range of from 800 to 850 °C.
  • the conversion of methane to one or more C 2+ hydrocarbons is effected at a reactor pressure in the range of from 1 to 25 MPa. More preferably, said reactor pressure is in the range of from 2 to 10 MPa.
  • the gas hourly space velocity (GHSV) in the process of the present invention is the entering volumetric flow rate (m 3 /s) of the reactor feed (at standard conditions) divided by the catalyst bed volume.
  • said gas hourly space velocity is in the range of from 3,000 to 1, 000, 000 h -1 .
  • suitable and favorable space velocities differ markedly between laboratory test reactors and industrial reactors.
  • the GHSV is typically in the range of 10,000 to 300,000 h -1 , preferably in the range of from 20,000 to 150, 000 T 1 . Said GHSV is measured at standard
  • the process of the present invention has a C 2+ hydrocarbon selectivity of greater than 40 %, and most preferably greater than 60 %.
  • Example 1 catalyst samples A-J
  • a mesoporous silica catalyst containing Mn x O y -Na 2 W0 4 was synthesized using a template-assisted method.
  • About 30 grams of template material (samples B, F, G, I: Pluronic P-123 ex Sigma-Aldrich; sample E: cetyltrimethylammonium bromide (CTAB) ex Sigma-Aldrich; sample H: stearic acid ex Sigma-Aldrich) was dissolved in 150 ml ethanol at room temperature, followed by dropwise addition of 69 grams of tetraethyl orthosilicate (TEOS; ex Sigma-Aldrich) to the solution under continuous stirring to provide a support material solution.
  • TEOS tetraethyl orthosilicate
  • a metal and alkali metal precursor solution was prepared separately by dissolving 0.4-3 grams of sodium tungstate dihydrate and 1.5-5 gram of manganese nitrate in the desired metal/alkali metal ratios together in approximately 20 ml of ethanol, followed by addition of 12 ml of concentrated nitric acid (HN0 3 ) .
  • the metal/alkali metal precursor solution was added to the support material solution under
  • demineralized water was topped up with demineralized water to a total volume of 1.8 L. This solution was sprayed onto the Mn-impregnated silica and dried dynamically as before. After further overnight drying, the resulting powder was calcined with a heating rate of 3°C/min until 850°C for 5 hours dwell time.
  • a mesoporous silica support was synthesized using a template-assisted method. The total amount of support synthesized was approximately 20 grams. 30 grams of template material was dissolved in 150 ml ethanol at room temperature, followed by dropwise addition of 69 grams of tetraethyl orthosilicate (TEOS) to the solution under continuous stirring to provide a support material solution .
  • TEOS tetraethyl orthosilicate
  • the mixture was stirred overnight to form a slurry, and subsequently heated in an oven for 7 hours at 90 °C. The temperature was reduced to 50 °C and any remaining ethanol was permitted to evaporate overnight .
  • the obtained solid sample was ground to a fine powder and calcined at 600 °C for 4 h then at 800 °C for 4 hours under static air (ramp 2 °C /min) to produce a solid powderous mesoporous silica support.
  • a metal and alkali metal precursor solution was prepared separately by dissolving 0.4-3 grams of sodium tungstate dihydrate and 1.5-5 gram of manganese nitrate in the desired
  • Table 1 provides pore size and pore volume data of the catalyst samples A-I determined using nitrogen
  • Each of the catalyst compositions A-J prepared according the procedures described above was tested for oxidative methane coupling performance in accordance with the following general testing procedure.
  • the catalysts 250-400 ⁇ sieve fraction
  • the methane (CH 4 ; >99.9 %) and oxygen (0 2 ; 99.9 %) reagents were used without further purification.
  • the reactor feed comprised methane and oxygen in a mole ratio of 4:1, with 5 mol . % of nitrogen as inert gas.
  • the gases were fed each via a mass flow controller and then passed through a manifold.
  • the mixed feed was split by a glass chip with 16 channels and sent individually to each of the 16 reactors.
  • the nanoflow unit is divided in 4 blocks, each block containing 4 reactors.
  • the reactions were carried out in quartz tubes (2 mm inner diameter, 3 mm outer diameter) where the catalyst bed (10 mm bed length) was laid on top of a quartz insert. Downstream, each reactor effluent was diluted with helium (He) , which flowed along the outer side of the reactors walls.
  • He helium
  • the pressure was indirectly monitored by means of pressure indicators (4 per block) allocated in the entrance of the He side diluent lines.
  • the pressure was controlled by the parallel pressure block: the effluent flow is passed through one side of a membrane that is pushed by N 2 (controlled by a pressure controller valve, does NOT mix with the effluent) at the other side of the membrane.
  • Thermoscientific GC, Breda equipped with two TCD detectors and two FID detectors for quantitative analyses of oxygen, nitrogen, carbon monoxide, carbon dioxide, methane, ethane, ethylene, C3, C4 and C5 hydrocarbons .
  • the total off-gas flow of the nanoflow unit was determined by the amount and concentration of nitrogen (in Nl/hr) in the reactor feed and in the off gas
  • the catalyst preparations according to the present invention display similar or improved C 2+ yields (Y C 2 + ) and selectivity (S C 2 + ) behavior over time compared to both analogous catalyst compositions on amorphous (samples A and C; I) or pre-synthesized silica carriers (samples D; II) .
  • the results further show improved conversion of oxygen (X 02 ) and reduced
  • Table 1 Pore size and pore volume of the catalyst samples as measured using nitrogen adsorption-desorption analysis.

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Abstract

L'invention concerne une composition de catalyseur comprenant du manganèse, un ou plusieurs métaux alcalins, et éventuellement un autre métal de transition supporté sur un support de silice mésoporeuse ordonnée ayant une structure mésoporeuse ordonnée qui est conservée lors de la calcination; et un procédé pour le couplage oxydatif du méthane à l'aide de ladite composition de catalyseur. L'invention concerne en outre la préparation in situ de la composition de catalyseur ci-dessus par combinaison de tous les constituants du catalyseur, c'est-à-dire un support de catalyseur et des métaux, dans leur état précurseur en présence d'un matériau modèle.
PCT/EP2017/068307 2016-07-21 2017-07-20 Catalyseur à base de manganèse-alcali sur support de silice mésoporeuse ordonnée pour le couplage oxydatif du méthane et sa préparation WO2018015473A1 (fr)

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CN111203283A (zh) * 2018-11-22 2020-05-29 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备烯烃的方法
CN112387265A (zh) * 2019-08-16 2021-02-23 中国石油化工股份有限公司 条形具有网络结构的介孔二氧化硅载体及其制备方法和催化剂以及应用
CN112387266A (zh) * 2019-08-19 2021-02-23 中国石油化工股份有限公司 条形具有蜂窝孔状二氧化硅载体及其制备方法和催化剂以及应用
CN112403455A (zh) * 2019-08-23 2021-02-26 中国石油化工股份有限公司 条形具有三维有序大孔状二氧化硅载体及其制备方法和催化剂以及应用
CN112774663A (zh) * 2019-11-04 2021-05-11 中国石油天然气股份有限公司 用于甲烷直接制乙烯的多级孔催化剂及其制备方法与应用
CN113072094A (zh) * 2021-03-22 2021-07-06 安徽江淮汽车集团股份有限公司 聚烯烃voc改进填料及其制备方法、聚烯烃复合材料

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CN111203283A (zh) * 2018-11-22 2020-05-29 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备烯烃的方法
CN112387265A (zh) * 2019-08-16 2021-02-23 中国石油化工股份有限公司 条形具有网络结构的介孔二氧化硅载体及其制备方法和催化剂以及应用
CN112387266A (zh) * 2019-08-19 2021-02-23 中国石油化工股份有限公司 条形具有蜂窝孔状二氧化硅载体及其制备方法和催化剂以及应用
CN112403455A (zh) * 2019-08-23 2021-02-26 中国石油化工股份有限公司 条形具有三维有序大孔状二氧化硅载体及其制备方法和催化剂以及应用
CN112774663A (zh) * 2019-11-04 2021-05-11 中国石油天然气股份有限公司 用于甲烷直接制乙烯的多级孔催化剂及其制备方法与应用
CN113072094A (zh) * 2021-03-22 2021-07-06 安徽江淮汽车集团股份有限公司 聚烯烃voc改进填料及其制备方法、聚烯烃复合材料

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