WO2020210092A1 - Catalyseurs multicomposants pour conversion de gaz de synthèse en hydrocarbures légers - Google Patents

Catalyseurs multicomposants pour conversion de gaz de synthèse en hydrocarbures légers Download PDF

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WO2020210092A1
WO2020210092A1 PCT/US2020/026069 US2020026069W WO2020210092A1 WO 2020210092 A1 WO2020210092 A1 WO 2020210092A1 US 2020026069 W US2020026069 W US 2020026069W WO 2020210092 A1 WO2020210092 A1 WO 2020210092A1
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catalyst composition
catalytic component
catalyst
syngas
oxygen
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PCT/US2020/026069
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English (en)
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Jeffrey C. BUNQUIN
Wenyih F. Lai
Chuansheng Bai
Paul F. Keusenkothen
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Exxonmobil Chemical Patents Inc.
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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
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • 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
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/26—Chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7015—CHA-type, e.g. Chabazite, LZ-218
    • 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
    • B01J35/19—Catalysts containing parts with different compositions
    • 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
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • 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
    • 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
    • B01J35/615—100-500 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
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/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
    • B01J35/64—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
    • 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
    • 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

Definitions

  • TITLE MULTICOMPONENT CATALYSTS FOR SYNGAS CONVERSION TO LIGHT HYDROCARBONS
  • This disclosure generally relates to processes for preparing lower hydrocarbons and oxygenates from a feedstream, and more particularly to processes for preparing a mixture that includes C2 to C4 olefins from a synthesis gas feedstream in the presence of a multicomponent catalyst.
  • Synthesis gas is a mixture of hydrogen and carbon monoxide generated from the upgrading of chemical feedstocks such as natural gas and coal. Syngas has been used industrially for the production of value-added chemicals including chemical intermediates such as olefins and alcohols, and fuels. Fischer-Tropsch catalysis is one route for syngas conversion to value-added products. Generally, Fischer-Tropsch catalysis involves the use of iron and cobalt catalysts for the production of gasoline range products for transportation fuels, heavy organic products including distillates used in diesel fuels, and high purity wax for a range of applications including food production.
  • Similar catalysts can be used for the production of value-added chemical intermediates including olefins and alcohols that can be used, for example, for the production of polymers and fuels.
  • value-added chemicals includes the production of saturated hydrocarbons including paraffins.
  • the selectivity of Fischer-Tropsch catalysts towards production of value-added chemical intermediates may be adjusted by addition of promoters including group 1 and group 2 cations and transition metals.
  • Fischer-Tropsch catalysts have been prepared as metal oxides or sulfides of iron and cobalt. The iron and cobalt catalysts are frequently supported on solid carriers including oxides such as alumina, silica, or various clays or on carbonaceous materials. Fischer-Tropsch catalysts have been used to produce hydrocarbons in the gasoline range and lighter hydrocarbons.
  • multicomponent catalysts having a first catalytic component that includes a metal oxide or mixed metal oxide (e.g., ZrCL’ZnO or ZnCrAlO x ) and a second catalytic component that includes a solid acid (e.g., a zeolite) can be used for the direct conversion of synthesis gas to lower hydrocarbons (e.g., C2-C4 hydrocarbons).
  • the multicomponent catalysts show selectivity for C2-C4 hydrocarbons, e.g., C2-C4 olefins and paraffins, over methane, C5+ hydrocarbons, oxygenates, carbon dioxide, and water.
  • a second aspect of this disclosure relates to a catalyst composition such as a catalyst composition for converting syngas that includes a first catalytic component and a second catalytic component, the first catalytic component that includes zinc, a metal M 1 selected from Al, Zr, and combinations of Al and Zr at any proportion, optionally Cr, and oxygen, wherein Al, Zr, and Cr, if any, are substantially uniformly distributed in the first catalytic component, and the second catalytic component is a solid acid consisting essentially of a molecular sieve having an 8 -member ring in a crystal structure thereof.
  • a third aspect of this disclosure relates to a catalyst composition such as a catalyst composition for converting syngas that includes a first catalytic component, the first catalytic component that includes zinc, a metal M 1 selected from Al, Zr, and combinations of Al and Zr at any proportion, optionally Cr, and oxygen, wherein Al, Zr, and Cr, if any, are substantially uniformly distributed in the first catalytic component.
  • a fourth aspect of this disclosure relates to a process for making a catalytic composition, the process including contacting a feed that includes syngas with a catalyst composition of the first aspect or second aspect described summarily above under conversion conditions to produce a conversion product mixture.
  • a fifth aspect of this disclosure relates to a process for preparing C2-C4 hydrocarbons that includes introducing a feedstream containing hydrogen gas and carbon monoxide gas into a reactor; introducing a catalyst composition of the present disclosure to the reactor, under reactor conditions effective to produce a product mixture, the reactor conditions including a reactor temperature of from 200°C to 450°C; a pressure of from 0.05 MPa to 6 MPa; and (c) forming the product mixture that includes C2-C4 hydrocarbons.
  • FIG. 1 is a x-ray diffraction (XRD) pattern of an example chabazite according to some embodiments.
  • FIG. 2 is a XRD pattern of an example chabazite according to some embodiments.
  • FIG. 3 is a XRD pattern of an example chabazite according to some embodiments.
  • FIG. 4 is a XRD pattern of an example chabazite according to some embodiments.
  • FIG. 5 is a XRD pattern of an example mordenite according to some embodiments.
  • FIG. 6 is a XRD pattern of an example mordenite according to some embodiments.
  • FIG. 7 is a plot showing the CO conversion of Zn-Cr/A10 x + H-chabazite according to some embodiments.
  • a process is described as including at least one“step.” It should be understood that each step is an action or operation that may be carried out once or multiple times in the process, in a continuous or discontinuous fashion. Unless specified to the contrary or the context clearly indicates otherwise, multiple steps in a process may be conducted sequentially in the order as they are listed, with or without overlapping with one or more other step, or in any other order, as the case may be. In addition, one or more or even all steps may be conducted simultaneously with regard to the same or different batch of material.
  • a second step may be carried out simultaneously with respect to an intermediate material resulting from treating the raw materials fed into the process at an earlier time in the first step.
  • the steps are conducted in the order described.
  • composition includes components of the composition and/or reaction products of two or more components of the composition.
  • indefinite article“a” or“an” shall mean“at least one” unless specified to the contrary or the context clearly indicates otherwise.
  • embodiments comprising“a metal” include embodiments comprising one, two, or more metals, unless specified to the contrary or the context clearly indicates only one metal is included.
  • RT room temperature (and is 23 °C unless otherwise indicated)
  • kPag is kilopascal gauge
  • psig is pound- force per square inch gauge
  • psia is pound- force per square inch absolute
  • WHSV weight hourly space velocity
  • GHSV is gas hourly space velocity
  • phrases, unless otherwise specified,“consists essentially of’ and“consisting essentially of’ do not exclude the presence of other steps, elements, or materials, whether or not, specifically mentioned in this specification, so long as such steps, elements, or materials, do not affect the basic and novel characteristics of this disclosure. Additionally, they do not exclude impurities and variances normally associated with the elements and materials used. “Consisting essentially of’ a component in this disclosure can mean, e.g., comprising, by weight, at least 80 wt%, of the given material, based on the total weight of the composition comprising the component.
  • Soluble refers to, with respect to a given solute in a given solvent at a given temperature, at most 100 mass parts of the solvent is required to dissolve 1 mass part of the solute under a pressure of 1 atmosphere.
  • “Insoluble” refers to, with respect to a given solute in a given solvent at a given temperature, more than 100 mass parts of the solvent is required to dissolve 1 mass part of the solute under a pressure of 1 atmosphere.
  • the term“Cn” compound or group, where n is a positive integer refers to a compound or a group comprising carbon atoms therein at the number of n.
  • the term“Cm” compound or group, where m is a positive integer refers to a compound or a group comprising carbon atoms therein at the number of m.
  • “Cm to Cn” alcohols refers to an alcohol comprising carbon atoms therein at a number in a range from m to n, or a mixture of such alcohols.
  • C1-C2 alcohols refers to methanol, ethanol, or mixtures thereof.
  • conversion refers to the degree to which a given reactant in a particular reaction (e.g., dehydrogenation, hydrogenation, etc.) is converted to products. Thus 100% conversion of carbon monoxide refers to complete consumption of carbon monoxide, and 0% conversion of carbon monoxide refers to no measurable reaction of carbon monoxide.
  • the term“selectivity” refers to the degree to which a particular reaction forms a specific product, rather than another product. For example, for the conversion of syngas, 50% selectivity for C2-C4 olefins refers to that 50% of the products formed are C2-C4 olefins, and 100% selectivity for C2-C4 olefins refers to that 100% of the products formed are C2-C4 olefins.
  • the selectivity is based on the product formed, regardless of the conversion of the particular reaction.
  • the selectivity for a given product produced from a given reactant can be defined as weight percent (wt%) of that product relative to the total weight of the products formed from the given reactant in the reaction.
  • a“catalyst composition of this disclosure” refers to a catalyst composition of the first aspect of this disclosure, a catalyst composition of the second aspect of this disclosure, catalyst composition of the third aspect of this disclosure, or a mixture or a combination thereof.
  • a multicomponent catalyst composition e.g., a metal oxide- solid acid catalyst
  • a metal oxide-solid acid catalyst compositions can demonstrate high activity in converting syngas into organic products, especially C2-C4 olefins and C2-C4 alcohols, which have significantly higher value than syngas.
  • these catalysts can be highly selective toward C2-C4 olefins, C2-C4 alkanes, and C1-C4 alcohols, and particularly toward C2-C4 olefins, among all C2-C4 products produced.
  • the catalyst composition includes a first catalytic component and a second catalytic component.
  • the first catalytic component is a metal oxide or a mixed metal oxide.
  • Metal oxide and mixed metal oxides include materials wherein the bonding between the metal and oxygen is undetermined, e.g., a mixed phase.
  • the second catalytic component is a solid acid.
  • the first catalytic component includes Zn, a metal M 1 selected from Al, Zr, and combinations of A1 and Zr at any proportion, optionally Cr, and oxygen, and having a molar ratio 1 (rl) of M 1 to Zn and a molar ratio 2 (r2) of Cr to Zn indicated by the following formula:
  • the distribution of zinc in the first catalytic component is substantially uniform. Without intending to be bound by a particular theory, it is believed that the uniformity results from the unique process for making the catalyst: co-precipitation of Zr and Zn, instead of supporting Zn on a pre-fabricated ZrCh support.
  • the resulting ZnO/ZrCh first catalytic component may be a mixed oxide, glass, or an intricate atom network, or a mixture of all these different forms.
  • the distribution of M 1 in the first catalytic component is substantially uniform.
  • the distribution of Cr, if any, in the first catalytic component is substantially uniform.
  • Al, Zr, and Cr, if any, are substantially uniformly distributed in the first catalytic component.
  • M 1 is Zr and is free or substantially free of Al.
  • M 1 is Al and is free or substantially free of Zr.
  • the first catalytic component consists essentially of Zn, Zr, and oxygen. In some embodiments, the first catalytic component consists essentially of Al, Cr, Zn, and oxygen. In some embodiments, the first catalytic component consists essentially of Al, Zn, and oxygen.
  • the identification of the presence of an oxide phase in a catalyst composition can be conducted by comparing the XRD data of the catalyst composition against an XRD peak database of known oxides, such as those available from International Center for Diffraction Data (“ICDD”). Without intending to be bound by a particular theory, the presence of oxygen can promote the catalytic effect of the catalyst composition.
  • the oxygen may be present as an oxide of one or more metals of M 1 , Cr, and Zn.
  • the second catalytic component is a solid acid, such as a molecular sieve.
  • the solid acid consists essentially of a molecular sieve having an 8-member ring in a crystal structure thereof.
  • the 8-member ring structure has a zeolite framework type defined by the Structure Commission of the international Zeolite Association (IZA) as chabazite (CHA), mordenite (MOR), aluminophosphate-eighteen (AEI), silico-aluminophosphate-fifty-six SAPO-56 (AFX), erionite (ERI), Linde Type A (LTA), UOP Zeolitic Material - five (UFI), Ruhr University Bochum - thirteen (RTH), and a combination thereof.
  • the 8-member ring structure is meso-mordenite (meso-MOR). Examples of zeolites with 8-membered ring structures include ZSM-35 and ZSM-57.
  • the MOR framework type zeolite has a S1O2 to AI2O3 molar ratio (also abbreviated as“Si/Ah molar ratio”“Si/Ah ratio,” or“S1O2 to AI2O3 ratio” in this disclosure) or of from about 6 to about 2000, such as from about 6 to about 200, such as from about 10 to about 60.
  • the CHA framework type zeolite has a S1O2 to AI2O3 molar ratio that is from about 10 to about 1000, such as from about 10 to about 100, such as from about 10 to about 50.
  • the MOR framework type zeolite has a S1O2 to AI2O3 molar ratio that is from about 10 to about 1000, such as from about 10 to about 100, such as from about 10 to about 50.
  • the meso-MOR framework type zeolite has a S1O2 to AI2O3 molar ratio that is from about 10 to about 1000, such as from about 10 to about 100, such as from about 10 to about 50.
  • the CHA, MOR, and/or meso-MOR may be used in its acid form (also known as protonated form or H-form).
  • acid form also known as protonated form or H-form.
  • charge balancing the framework consists predominantly of proton ions H + .
  • the first catalytic component is supported on the surface of the second catalytic component.
  • the catalyst composition is a physical mixture of particles of the first catalytic component and particles of the second catalytic component.
  • the catalyst compositions of this disclosure may consist essentially of the first and second catalytic components of this disclosure, e.g., including > about 85 wt%, or > about 90 wt%, or > about 95 wt%, or > about 98 wt%, or even > about 99 wt% of the first and second catalytic components, based on a total weight of the catalyst composition.
  • Such catalyst compositions may be considered as a“bulk catalyst” in that they include a minor amount of a carrier or a support material in their compositions, if any at all. Bulk catalysts can be made by procedures described below.
  • the catalyst compositions of this disclosure can include a catalyst support material (which may be called a carrier or a binder), at any suitable quantity, e.g., > about 20 wt%, > about 30 wt%, > about 40 wt%, > about 50 wt%, > about 60 wt%, > about 70 wt%, > about 80 wt%, > about 90 wt%, or even > about 95 wt%, based on a total weight of the catalyst composition.
  • the first and second catalytic components can be desirably disposed on the internal or external surfaces of the catalyst support material.
  • Catalyst support materials may include porous materials that provide mechanical strength and a high surface area.
  • Non-limiting examples of suitable support materials can include oxides (e.g. silica, alumina, titania, zirconia, and mixtures thereof), treated oxides (e.g. sulphated), crystalline microporous materials (e.g. zeolites), non-crystalline microporous materials, cationic clays or anionic clays (e.g. saponite, bentonite, kaoline, sepiolite, hydrotalcite), carbonaceous materials, or combinations and mixtures thereof.
  • Deposition of the first and second catalytic components on a support can be effected by, e.g., incipient impregnation.
  • a support material can be sometimes called a binder in a catalyst composition.
  • the catalyst compositions include a first catalytic component (e.g., a metal oxide or a mixed metal oxide) and a second catalytic component (e.g., a solid acid).
  • the first catalytic component may be prepared prior to combining it with the second catalytic component.
  • the second catalytic component may be prepared prior to combining it with the first catalytic component.
  • the first catalytic component may be prepared by a method that includes (1-1) contacting, in water, a first water soluble compound with a second water soluble compound or mixture and optionally with a third water soluble compound under alkaline conditions (e.g., aqueous sodium carbonate) to obtain a precipitate, wherein the first water soluble compound includes Zn, the second water soluble compound or mixture includes Zr, Al, or a combination of Zr and Al, and the third water soluble compound includes Cr, and the precipitate includes Zn, one or both of Al and Zr, and optionally Cr.
  • alkaline conditions e.g., aqueous sodium carbonate
  • the first water soluble compound may be zinc nitrate hexahydrate
  • the second water soluble compound may be zirconyl nitrate hydrate or chromium nitrate nonahydrate
  • the third water soluble compound, if any, may be aluminum nitrate nonahydrate.
  • the method further includes (l-II) obtaining from the precipitate a first catalytic component that includes zinc, a metal M 1 selected from Al, Zr, and combinations of Al and Zn at any proportion, optionally Cr, and oxygen, with a molar ratio 1 (rl) of M 1 to Zn and a molar ratio 2 (r2) of Cr to Zn indicated by the following formula:
  • operation (l-II) further includes drying and/or calcining the precipitate.
  • the second catalytic component may be prepared by a method that includes (2-1) contacting, in water, a template (e.g., a tetralkylammonium compound such as trimethyl adamantylammonium (TMAA) hydroxide, tetraethylammonium bromide (TEABr), tetrapropylammonium hydroxide (TPAOH), or tetrapropylammonium bromide (TPABr)), a silica source (e.g., silica particles, colloidal silicic acid, or an alkali silicate), an alkali source (a sodium hydroxide solution), and an aluminum source (e.g., an alkali aluminate, such as a sodium aluminate, for example one of a sodium aluminate sol or a sodium aluminate solution) to obtain a precipitate.
  • a template e.g., a tetralkylammonium compound such
  • a material can perform several functions; for example a material can operate as an aluminum source and as an alkali source, or as a silicon source and as an alkali source, or also as an aluminum source, an alkali source, and a silicon source.
  • Operation 2-1 may further include mixing (e.g., by stirring) with a stirring speed from about 100 rpm and about 900 rpm, such as about 350 rpm.
  • Operation 2-1 may be performed at a temperature from about 100°C to about 200°C, such as about 138°C or about 160°C.
  • Operation 2-1 may be performed for a period of time from about 40 h to about 90 h, such as about 48 h or about 72 h.
  • the method of making a second catalytic component may further include (2-II) separating (e.g., filtering) the precipitate, drying the precipitate (at a temperature from about 100°C to about 200°C, such as about 120°C or about 160°C, for a period of time of about 2 h to about 20 h), and/or calcining the precipitate (at a temperature of about 200°C to about 800°C, such as about 540°C, for a period of time of about 2 h to about 20 h) to obtain the second catalytic component.
  • the method may further include (2-III) exchanging the alkali ions of the precipitate in an aqueous medium with a proton-containing substance or a substance that yields protons when heated.
  • operation (2-III) may further include one or more of a washing with water, a drying operation (at a temperature from about 100°C to about 200°C, such as about 120°C or about 160°C, for a period of time of from about 2 h to about 20 h), or a calcining operation (at a temperature of about 200°C to about 800°C, such as about 540°C, for a period of time of from about 2 h to about 20 h) to form the H-form of the second catalytic component.
  • a washing with water at a temperature from about 100°C to about 200°C, such as about 120°C or about 160°C, for a period of time of from about 2 h to about 20 h
  • a calcining operation at a temperature of about 200°C to about 800°C, such as about 540°C, for a period of time of from about 2 h to about 20 h
  • the second catalytic component and/or the H-form of the second catalytic component can be mixed with a binder by techniques known in the art.
  • a method of forming a catalyst composition includes (3-1) combining the first catalytic component with second catalytic component which is a solid acid to form a catalyst composition. Non-limiting characteristics of the catalyst composition are described above.
  • the method of forming a catalyst composition may further include (3-II) disposing the first catalytic component on the surface of the second catalytic component and/or forming a physical mixture of the first catalytic component and the second catalytic component.
  • the thus made catalyst composition can be used as is as a catalyst composition for its intended use (e.g., converting syngas), e.g., as a bulk catalyst.
  • a catalyst support material e.g., a co-catalyst, or a solid diluent material
  • Suitable catalyst support materials for combining with the catalyst composition are described earlier in this disclosure in connection with the catalyst composition.
  • the combination of the support material and the catalyst composition can be processed in any known catalyst forming processes, including but not limited to grinding, milling, sifting, washing, drying, calcination, and the like, to obtain a catalyst composition.
  • the catalyst composition may be then disposed in an intended reactor to perform its intended function, such as a syngas converting reactor in a syngas converting process.
  • the first catalytic component and/or the second catalytic component may be combined with a catalyst support material to obtain a mixture thereof, which is subsequently subject to operation (3-1).
  • the first catalytic component and/or the second catalytic component may be disposed on the internal and/or external surfaces of the support material.
  • the operation (3-1) can be performed in a reactor where the catalyst composition is normally used, such as a syngas converting reactor.
  • operation (3-1) can be performed in a reactor other than the reactor the catalyst composition is intended for to obtain a catalyst composition that includes a support material and the catalytic component(s), which can be stored, shipped, and then disposed in a reactor it is intended for.
  • the first catalytic component and/or the second catalytic component may be combined or formed with a precursor of a support material to obtain a support/catalytic component mixture.
  • Suitable precursors of various support materials can include, e.g., alkali metal aluminates, water glass, a mixture of alkali metal aluminates and water glass, a mixture of sources of a di-, tri-, and/or tetravalent metal, such as a mixture of water-soluble salts of magnesium, aluminum, and/or silicon, chlorohydrol, aluminum sulfate, or mixtures thereof.
  • the support/catalytic component mixture is subsequently subject to operation (3-1) together, resulting in the formation of the catalytic component and the support material substantially in the same operation.
  • operation (3-1) can be performed in a reactor where the catalyst composition is normally used, such as a syngas converting reactor.
  • operation (3-1) can be performed in a reactor other than the reactor the catalyst composition is intended for to obtain a catalyst composition that includes a support material and the catalytic component, which can be stored, shipped, and then disposed in a reactor it is intended for.
  • a catalyst composition of this disclosure can be used in any suitable process where a metal oxide-solid acid catalyst can perform a catalytic function.
  • the catalyst compositions of this disclosure can be advantageously used in processes for converting syngas into various products such as hydrocarbons, for example C2-C4 olefins and/or C1-C4 alcohols, by the Fischer-Tropsch processes.
  • the Fischer-Tropsch process is a collection of chemical reactions that converts a mixture of carbon monoxide and hydrogen into hydrocarbons and/or alcohols. These reactions occur in the presence of metal catalysts, typically at temperatures of from about 100°C to about 500°C (from about 212°F to about 932°F) and pressures of from about one to about several tens of atmospheres.
  • syngas as used herein relates to a gaseous mixture consisting essentially of hydrogen (3 ⁇ 4) and carbon monoxide (CO).
  • the syngas which is used as a feed stream, may include up to about 10 mol% of other components such as CO2 and lower hydrocarbons (lower HC), depending on the source and the intended conversion processes. Said other components may be side-products or unconverted products obtained in the process used for producing the syngas.
  • the syngas may contain such a low amount of molecular oxygen (O2) so that the quantity of O2 present does not interfere with the Fischer-Tropsch synthesis reactions and/or other conversion reactions.
  • O2 molecular oxygen
  • the syngas may include not more than about 1 mol% O2, not more than about 0.5 mol% O2, or not more than about 0.4 mol% O2.
  • the syngas may have a hydrogen (3 ⁇ 4) to carbon monoxide (CO) molar ratio of from about 1:3 to about 3:1, such as from about 0.5:1 to about 3:1.
  • the partial pressures of Fp and CO may be adjusted by introduction of a nonreactive gas (such as N2, Ar, He, or a combination thereof) to the reaction mixture.
  • Syngas can be formed by reacting steam and/or oxygen with a carbonaceous material, for example, natural gas, coal, biomass, or a hydrocarbon feedstock through a reforming process in a syngas reformer.
  • a carbonaceous material for example, natural gas, coal, biomass, or a hydrocarbon feedstock
  • the reforming process can be based on any suitable reforming process, such as Steam Methane Reforming, Auto Thermal Reforming, or Partial Oxidation, Adiabatic Pre Reforming, or Gas Heated Reforming, or a combination thereof.
  • Example steam and oxygen reforming processes are detailed in U.S. Patent No. 7,485,767.
  • the syngas formed from steam or oxygen reforming includes hydrogen and one or more carbon oxides (CO and CO2).
  • the hydrogen to carbon oxide ratio of the syngas produced will vary depending on the reforming conditions used.
  • the syngas reformer product(s) should contain 3 ⁇ 4, CO, and CO2 in amounts and ratios which render the resulting syngas blend suitable for subsequent processing into either oxygenates comprising methanol/dimethyl ether or in Fischer-Tropsch synthesis.
  • a process for converting syngas includes contacting a feed that includes syngas with one or more catalyst compositions of the present disclosure under conversion conditions to produce a product mixture.
  • the product mixture includes a C2-C4 hydrocarbon, e.g., a C2-C4 olefin, a C2-C4 alkane, and/or a C1-C4 alcohol.
  • the product mixture includes C2-C4 hydrocarbons, in aggregate, at a concentration greater than about 30 wt%, such as greater than about 35 wt%, such as from about 35 wt% to about 99 wt%, such as from about 35 wt% to about 90 wt%, such as from about 40 wt% to 80 about wt%, based on a total weight of the product mixture excluding hydrogen (H2), CO, and CO2.
  • the product mixture includes C2-C4 hydrocarbons having an olefins/alkanes weight ratio of from about 0.1 to about 7, such as from about 0.1 to about 6.
  • the product mixture includes methane at a concentration no greater than 15 wt%, such as no greater than 10 wt%, such as no greater than 5 wt%, based on a total weight of the product mixture excluding hydrogen (H2), CO, and CO2.
  • the product mixture includes a combined saturated and unsaturated C5 and higher hydrocarbon content of less than about 50 wt%, such as from about 0.00001 wt% to about 30 wt%, such no greater than about 10 wt%, based on a total weight of the product mixture excluding hydrogen (H2), CO, and CO2.
  • the product mixture includes an oxygenate content of no greater than about 20 wt%, such as no greater than about 10 wt%, based on a total weight of the product mixture excluding hydrogen (H2), CO, and CO2.
  • the product mixture includes (excluding hydrogen (i.e., 3 ⁇ 4), CO, and CO2), a combined C2-C4 alkane content of from about 0.0 wt% to about 90 wt%, such as from about from about 0.1 wt% to about 80 wt%, based on a total weight of the product mixture excluding hydrogen (H2), CO, and CO2.
  • the product mixture includes, a combined C2-C4 alkene (e.g., olefin) content of from about 0.0 wt% to about 90 wt%, such as from about 0.1 wt % to about 80 wt%, based on a total weight of the product mixture excluding hydrogen (H2), CO, and CO2.
  • a combined C2-C4 alkene e.g., olefin
  • the syngas to be used in Fischer-Tropsch synthesis may have a molar ratio of H2 to CO, unrelated to the quantity of CO2, of about 1.9 or greater, such as from about 2.0 to about 2.8, or from about 2.1 to about 2.6.
  • the CO2 content of the syngas may be about 10 mol% or less, such as about 5.5 mol% or less, or from about 2 mol% to about 5 mol%, or from about 2.5 mol% to about 4.5 mol%.
  • CO2 can be recovered from the syngas effluent from a steam reforming unit, and the recovered CO2 can be recycled to a syngas reformer.
  • Suitable Fischer-Tropsch catalysis procedures may be found in: U.S. Patent Nos. 7,485,767, 6,211,255, and 6,476,085, the relevant portions of their contents being incorporated herein by reference.
  • the catalyst composition may be contained in a fixed bed reactor, a fluidized bed reactor, or any other suitable reactor.
  • the reaction conditions may include contacting the catalyst composition with syngas, to provide a reaction mixture, at a pressure of about 0.05 MPa to about 10 MPa, at a temperature of about 150°C to about 450°C, and/or a gas hourly space velocity of about 1000 h -1 to about 10,000 h 1 for a reaction period.
  • the reaction conditions may include a wide range of temperatures.
  • the reaction temperature is from about 100°C to about 450°C, such as from about 200°C to about 450°C, or from about 300°C to about 400°C, or from about 150°C to about 350°C, such as from about 200°C to about 300°C.
  • the reaction conditions may include a wide range of pressures.
  • the absolute reaction pressure is from pi to p2 kilopascal (“kPa”), wherein pi and p2 can be, independently, e.g., about 100 kPa, about 150 kPa, about 200 kPa, about 250 kPa, about 300 kPa, about 350 kPa, about 400 kPa, about 450 kPa, about 500 kPa, about 600 kPa, about 700 kPa, about 800 kPa, about 900 kPa, about 1000 kPa, about 1500 kPa, about 2000 kPa, about 2500 kPa, about 3000 kPa, about 3500 kPa, about 4000 kPa, about 4500 kPa, or about 5,000 kPa, as long as pi ⁇ p2.
  • the absolute reaction pressure is from about 0.05 MPa to about 10 MPa
  • Gas hourly space velocities used for converting the syngas to olefins and/or alcohols can vary depending upon the type of reactor that is used.
  • the gas hourly space velocity of the flow of gas through the catalyst bed is from about 100 hr -1 to about 100,000 hr -1 , such as from about 100 hr -1 to about 50,000 hr -1 , such as from about 500 hr -1 to about 25,000 hr -1 , such as from about 1000 hr -1 to about 20,000 hr -1 , or from about 100 hr -1 to 10,000 hr 1 .
  • Reaction conditions may have an effect on the catalyst performance.
  • selectivity on a carbon basis is a function of the probability of chain growth.
  • Factors affecting chain growth include the temperature of the reaction, the gas composition and the partial pressures of the various gases in contact with the catalyst composition. Altering these factors may lead to a high degree of flexibility in obtaining a type of product in a certain carbon range. Without being limited by theory, an increase in operating temperature shifts the selectivity to lower carbon number products. Desorption of growing surface species is one of the main chain termination steps and since desorption is an endothermic process so a higher temperature should increase the rate of desorption which will result in a shift to lower molecular mass products.
  • the slurry was aged for about 2 h with stirring.
  • the slurry was allowed to cool to a temperature of about room temperature (e.g., from about 15°C to about 25°C).
  • the slurry was filtered, the slurry cake recovered, and the slurry cake was washed thoroughly with distilled water.
  • the sample was dried at about 120°C in air for about 16 h and then grinded to a sample powder. After grinding, the sample powder was placed in a box furnace. The furnace was ramped from room temperature to about 932°F (500°C) at a rate of about 10°F/min (about 5.5°C/min) in air. The air flowing rate was set at about 5 volume/volume catalyst/minute.
  • the sample was held at about 500°C in air for about 5 hr.
  • the molar ratio of Zr/Zn is about 2.
  • Solution C was heated in a water-bath with temperature maintained at 70°C, and Solution D was added to Solution C under vigorous stirring, while maintaining a temperature of about 70°C to form a slurry, and the addition of Solution D was stopped when the pH of the slurry reached a pH of about 7.0. While maintaining the temperature of the slurry at about 70°C, the slurry was aged for about 2 h with stirring. The slurry was allowed to cool to a temperature of about room temperature (e.g., from about 15°C to about 25 °C). The slurry was filtered, the slurry cake recovered, and the slurry cake was washed thoroughly with distilled water.
  • room temperature e.g., from about 15°C to about 25 °C
  • the sample was dried at about 120°C in air for about 16 h, and then grinded to a sample powder. After grinding, the sample powder was placed in a box furnace. The furnace was ramped from room temperature to about 932°F (500°C) at a rate of about 10°F/min (about 5.5°C/min) in air. The air flowing rate was set at about 5 volume/volume catalyst/minute. The sample was held at about 500°C in air for about 3 h. In the sample of ZnCrAlO x , the weight percentage of ZnO is about 69%, and C12O3 is about 19%, and AI2O3 is about 12%.
  • Example 1 Preparation of chabazite crystals and the H-form of the chabazite crystals with SiO/APCh of about 21/1.
  • a mixture of water, a 43% sodium aluminate sol, a 25% trimethyl adamantylammonium (TMAA) hydroxide solution, Ultrasil silica, seeds, and a 50% sodium hydroxide solution was prepared. Amounts of materials were added to give the following molar composition: S1O2/AI2O3 of about 26; H2O/S1O2 of about 16; NaOH/SiCh of about 0.25; and TMAA/S1O2 of about 0.20.
  • TMAA trimethyl adamantylammonium
  • the mixture was reacted at about 320°F (about 160°C) in a 2-liter autoclave with stirring at about 350 rpm for about 72 h.
  • the product was filtered, washed with deionized water and dried at a temperature of about 250°F (about 120°C).
  • the XRD pattern (FIG. 1) of the as-synthesized material showed the typical phase of chabazite topology.
  • the scanning electron microscope (SEM) image of the as-synthesized material showed that the material was composed of crystals mainly with size of less than about 1 micron.
  • the resulting chabazite crystals had a S1O2/AI2O3 molar ratio of about 21/1.
  • the as-synthesized crystals were then calcined and converted into the hydrogen form (H-form, also known as the protonated form) by about three ion exchanges with an ammonium nitrate solution at about room temperature, followed by drying at about 250°F (about 120°C) and calcination at about 1000°F (about 540°C) for about 6 h.
  • the resulting H-form chabazite crystals had a Hexane sorption of about 115.4 mg/g, a total surface area(SA)/(micro pore SA + mesopore SA) of about 687/(675+11.6) m 2 /g, and an Alpha value of about 270.
  • Example 2 Preparation of chabazite crystals and H-form of the chabazite crystals with of about 40/1. A mixture of water, a 43% sodium aluminate sol, a 25%
  • TMAA trimethyl adamantylammonium
  • Ultrasil silica seeds, and a 50% sodium hydroxide solution was prepared. Amounts of materials were added to give the following molar composition: S1O2/AI2O3 of about 45; H2O/S1O2 of about 15; NaOH/SiCF of about 0.2; and TMAA S1O2 of about 0.2.
  • the mixture was reacted at about 320°F (about 160°C) in a 2-liter autoclave with stirring at about 350 rpm for about 48 h.
  • the product was filtered, washed with deionized water and dried at a temperature of about 250°F (about 120°C).
  • the XRD pattern FIG.
  • the as-synthesized material showed the typical phase of chabazite topology.
  • the SEM of the as-synthesized material showed that the material was composed of crystals mainly with size of less than about 1 micron.
  • the resulting chabazite crystals had a S1O2/AI2O3 molar ratio of about 40/1.
  • the as-synthesized crystals were then calcined and converted into the hydrogen form (H-form, also known as the protonated form) by about three ion exchanges with an ammonium nitrate solution at about room temperature, followed by drying at about 250°F (about 120°C) and calcination at about 1000°F (about 540°C) for about 6 h.
  • H-form also known as the protonated form
  • the resulting H-form chabazite crystals had a Hexane sorption of about 119.1 mg/g, a total surface area(SA)/(micro pore SA + mesopore SA) of about 724/(715+8.7) m 2 /g, and an Alpha value of about 85.
  • Example 3 Preparation of chabazite crystals and H-form of the chabazite crystals with about 70/1. A mixture of water, a 43% sodium aluminate sol, a 25%
  • TMAA trimethyl adamantylammonium
  • Ultrasil silica Ultrasil silica, seeds, and a 50% sodium hydroxide solution was prepared. Amounts of materials were added to give the following molar composition: S1O2/AI2O3 of about 80; H2O/S1O2 of about 11.3; NaOH/SiCh of about 0.15; and TMAA/S1O2 of about 0.18.
  • the mixture was reacted at about 320°F (about 160°C) in a 2-liter autoclave with stirring at about 350 rpm for about 48 h.
  • the product was filtered, washed with deionized water and dried at a temperature of about 250°F (about 120°C).
  • the XRD pattern FIG.
  • the as-synthesized material showed the typical phase of chabazite topology.
  • the SEM of the as-synthesized material showed that the material was composed of crystals mainly with size of less than about 1 micron.
  • the resulting chabazite crystals had a S1O2/AI2O3 molar ratio of about 70/1.
  • the as-synthesized crystals were then calcined and converted into the hydrogen form (H-form, also known as the protonated form) by about three ion exchanges with an ammonium nitrate solution at about room temperature, followed by drying at about 250°F (about 120°C) and calcination at about 1000°F (about 540°C) for about 6 h.
  • H-form also known as the protonated form
  • Example 4 Preparation of chabazite crystals and H-form of the chabazite crystals with SiCb/AFOi of about 140/1.
  • a mixture of water, a 43% sodium aluminate sol, a 25% trimethyl adamantylammonium (TMAA) hydroxide solution, Ultrasil silica, seeds, and a 50% sodium hydroxide solution was prepared. Amounts of materials were added to give the following molar composition: S1O2/AI2O3 of about 160; H2O/S1O2 of about 11.3; NaOH/SiCh of about 0.05; and TMAA/S1O2 of about 0.20.
  • TMAA trimethyl adamantylammonium
  • the mixture was reacted at about 320°F (about 160°C) in a 2-liter autoclave with stirring at about 350 rpm for about 48 h.
  • the product was filtered, washed with deionized water and dried at a temperature of about 250°F (about 120°C).
  • the XRD pattern (FIG. 4) of the as-synthesized material showed the typical phase of chabazite topology.
  • the SEM of the as-synthesized material showed that the material was composed of crystals mainly with size of less than about 1 micron.
  • the resulting chabazite crystals had a S1O2/AI2O3 molar ratio of about 140/1.
  • the as-synthesized crystals were then calcined and converted into the hydrogen form (H-form, also known as the protonated form) by about three ion exchanges with an ammonium nitrate solution at about room temperature, followed by drying at about 250°F (about 120°C) and calcination at about 1000°F (about 540°C) for about 6 h.
  • H-form also known as the protonated form
  • Example 5 Preparation of meso-mordenite crystals and H-form of meso-mordenite crystals with of about 20/1.
  • the XRD pattern (FIG. 5) of the as-synthesized material showed the typical pure phase of mordenite topology.
  • the SEM of the as-synthesized material showed that the material was composed of small crystals with size of less than about 0.1 micron.
  • the resulting mordenite crystals had a S1O2/AI2O3 molar ratio of about 20/1.
  • the as-synthesized crystals were then calcined and converted into the hydrogen form (H-form, also known as the protonated form) by about three ion exchanges with an ammonium nitrate solution at about room temperature, followed by drying at about 250°F (about 120°C) and calcination at about 1000°F (about 540°C) for about 6 h.
  • H-form also known as the protonated form
  • the resulting H- form mordenite crystals had a Hexane sorption of about 61.7 mg/g, a total surface area(SA)/(micro pore SA + mesopore SA) of about 603/(558 + 45) m 2 /g, and an Alpha value of about 910.
  • Example 6 Preparation of mordenite Crystals and the H-form of the mordenite Crystals with of about 50/1.
  • the XRD pattern (FIG. 6) of the as-synthesized material showed the typical pure phase of mordenite topology.
  • the SEM of the as-synthesized material showed that the material was composed of small crystals with size of less than about 1 micron.
  • the resulting mordenite crystals had a S1O2/AI2O3 molar ratio of about 50/1.
  • the as-synthesized crystals were then calcined and converted into the hydrogen form (H-form, also known as the protonated form) by about three ion exchanges with an ammonium nitrate solution at about room temperature, followed by drying at about 250°F (about 120°C) and calcination at about 1000°F (about 540°C) for about 6 h.
  • H-form also known as the protonated form
  • the resulting H- form mordenite crystals had a Hexane sorption of about 33.5 mg/g, a total surface area(SA)/(micro pore SA + mesopore SA) of about 512/(468 + 44) m 2 /g, and an Alpha value of about 180.
  • Example Cl Preparation of co-extrusion of alumina bound of mixed ZrZnO x and Chabazite extrudates.
  • About 40 parts of calcined ZrZnO x (Sample 1, Part A) and about 40 parts of calcined H-formed Chabazite crystals (Example 1 , Part B) were mixed with about 20 parts of high surface area alumina oxide and water (an amount of water sufficient to form a slurry) in a muller.
  • the mixture of ZrZnO x , Chabazite, alumina, and water was extruded into a 1/16” cylinder extrudates and then dried at about 121°C overnight.
  • the dried extrudate was calcined in nitrogen at about 400°C for about 2 h before testing.
  • Example C2 Preparation of co-extrusion of alumina bound mixed ZnCrAlO x and Mordenite extrudate.
  • About 40 parts of calcined ZnCrAlO x (Sample 2, Part B) and about 40 parts of calcined H-formed Mordenite crystals (Example 5, Part B) were mixed with about 20 parts of high surface area alumina oxide (an amount of water sufficient to form a slurry) in a muller.
  • the mixture of ZnCrAlO x , Mordenite, alumina, and water was extruded into a 1/16” cylinder extrudates and then dried at about 121°C overnight.
  • the dried extrudate was calcined in nitrogen at about 400°C for about 2 h before testing.
  • Part D General procedure for converting syngas using the metal oxide-solid acid catalyst of this disclosure
  • the catalyst was loaded into a fixed-bed reactor system.
  • a mixture of 3 ⁇ 4 and CO e.g., syngas
  • FIG. 8 shows the C2-C4 selectivity of various example catalysts at various CO conversion levels.
  • FIG. 9 is a plot showing the percentage C2-C4 olefins versus the C2-C4 hydrocarbon selectivity of various example catalysts.
  • the catalyst having Zn-Cr/A10 x + H-mordenite (Si/AF 50) shows that at about 25% C2-C4 hydrocarbon selectivity, the percentage of products is about 80% C2-C4 olefins and about 20% C2-C4 paraffins.
  • the catalytic components of all these catalyst compositions contain oxygen, at least part of which in the form of metal oxide(s).
  • MOR refers to mordenite
  • CHA refers to chabazite.
  • the metal oxide-solid acid catalyst compositions comprising metal oxide(s) demonstrated high activity in converting syngas into organic products, especially C2-C4 olefins and C2-C4 alcohols, which have significantly higher value than syngas.
  • these catalysts are highly selective toward C2-C4 olefins, C2-C4 alkanes, and C1-C4 alcohols, and particularly toward C2-C4 olefins, among all C2-C4 products produced.
  • the C2-C4 product fraction comprises from about 10 wt% to about 90 wt% olefins, from about 10 wt% to about 90 wt% alkanes, from about 0 wt% to about 5 wt% alcohols.
  • the Figures and the Table 2 further show that multicomponent catalysts have very low methane selectivity ( ⁇ 5 %).
  • a catalyst composition for converting syngas comprising a first catalytic component, the first catalytic component comprising zinc, a metal M 1 selected from Al, Zr, and combinations of A1 and Zr at any proportion, optionally Cr, and oxygen, and having a molar ratio of M 1 and Cr to Zn of rl and r2, respectively, indicated by the following formula:
  • A2 The catalyst composition of Al, wherein 0.25 ⁇ rl ⁇ 10, 0 ⁇ r2 ⁇ 2.0, or a combination thereof.
  • A4 The catalyst composition of any of Al to A3, wherein the distribution of M 1 in the first catalytic component is substantially uniform.
  • A5. The catalyst composition of any of Al to A4, wherein the distribution of Cr, if any, in the first catalytic component, is substantially uniform.
  • A6 The catalyst composition of any of Al to A5, wherein M 1 is Zr.
  • A8 The catalyst composition of any of Al to A7, wherein 0.25 ⁇ rl ⁇ 10.
  • A9 The catalyst composition of any of A6 to A8, wherein the first catalytic component consists essentially of Zn, Zr, and oxygen.
  • A10 The catalyst composition of any of Al to A5, wherein M 1 is Al.
  • Al l The catalyst composition of A10, wherein 0.25 ⁇ rl ⁇ 4.0.
  • A12 The catalyst composition of A10 or Al 1, wherein 0.25 ⁇ r2 ⁇ 4.0.
  • A13 The catalyst composition of A10 or Al 1, wherein 0.25 ⁇ r2 ⁇ 2.0.
  • a 14 The catalyst composition of any of A10 to A13, wherein the first catalytic component consists essentially of Al, Cr, Zn, and oxygen.
  • A15 The catalyst composition of any of Al to A 14, further comprising a second catalytic component which is a solid acid, such as a molecular sieve.
  • a 16 The catalyst composition of A15, wherein the solid acid consists essentially of a molecular sieve having an 8-member ring in a crystal structure thereof.
  • A17 The catalyst composition of A15 or A16, wherein the first catalytic component is supported on a surface of the second catalytic component.
  • A18 The catalyst composition of A15 or A16, which is a physical mixture of particles of the first catalytic component and particles of the second catalytic component. [00118] A 19. The catalyst composition of any of A15 to A18, wherein the molecular sieve is selected from zeolites the following frame work types: MOR, CHA, and mixtures and combinations thereof.
  • A20 The catalyst composition of any of A15 to A19, wherein the molecular sieve comprises a MOR framework type zeolite having a S1O2 to AI2O3 molar ratio in the range from 6 to 200.
  • A21 The catalyst composition of any of A15 to A19, wherein the molecular sieve comprises a MOR framework type zeolite having a S1O2 to AI2O3 molar ratio in the range from 10 to 60.
  • A22 The catalyst composition of any of A15 to A21, wherein the molecular sieve comprises a CHA framework type zeolite having a S1O2 to AI2O3 molar ratio in the range from 10 to 200.
  • A23 The catalyst composition of any of A15 to A21, wherein the molecular sieve comprises a CHA framework type zeolite having a S1O2 to AI2O3 molar ratio in the range from 10 to 60.
  • A24 The catalyst composition of any of A1-A23, wherein the first catalytic component and the second catalytic component are co-extruded.
  • a catalyst composition comprising a first catalytic component, the first catalytic component comprising zinc, a metal M 1 selected from Al, Zr, and combinations of A1 and Zr at any proportion, optionally Cr, and oxygen, wherein Al, Zr, and Cr, if any, are substantially uniformly distributed in the first catalytic component.
  • B2 The catalyst composition of Bl, wherein the first catalytic component consists essentially of Zn, Zr, and oxygen.
  • B3 The catalyst composition of Bl, wherein the first catalytic component consists essentially of Al, Zn, and oxygen.
  • B5. The catalyst composition of any of Bl to B4, wherein 0.25 ⁇ rl ⁇ 10, 0 ⁇ r2 ⁇
  • B6 The catalyst composition of any of B 1 to B5, wherein M 1 is Zr.
  • B8 The catalyst composition of any of B1 to B7, wherein M 1 is Al, and 0.25 ⁇ rl
  • B9 The catalyst composition of any of B 1 to B8, wherein 0.25 ⁇ r2 ⁇ 4.0.
  • B 10 The catalyst composition of B 10 or B 11 , wherein 0.25 ⁇ r2 ⁇ 2.0.
  • Bll The catalyst composition of any of B1-B10, wherein the first catalytic component and the second catalytic component are co-extruded.
  • a process for converting syngas comprising contacting a feed comprising syngas with a catalyst composition of any of Al to A19 and/or a catalyst composition of any of B 1 to B 11 under conversion conditions to produce a product mixture.
  • C3 The process of Cl or C2, wherein the conversion conditions comprise a temperature of from 250°C to 450°C, a pressure of from 5 bar (0.5 MPa) to 50 bar (5.0 MPa), and a gas hourly space velocity of from 1,000 hour 1 to 100,000 hour 1 .
  • C4 hydrocarbons in aggregate, at a concentration from 40 wt% to 80 wt%, based on the total weight of the product mixture excluding hydrogen (H2), CO, and CO2.
  • C6 The process of C5, wherein the C2 to C4 hydrocarbons have an olefins/alkanes weight ratio from 0.1 to 6.
  • a process for making a catalyst composition comprising:
  • D4 The process of any of Dl to D3, wherein M 1 is Al.
  • D5. The process of D4, wherein 0.25 ⁇ r2 ⁇ 4.0.
  • D6 The process of any of Dl to D5, wherein operation (II) comprises drying and/or calcining the precipitate.
  • D7 The process of any of Dl to D6, further comprising: (III) combining the first catalytic component with second catalytic component which is a solid acid.
  • D8 The process of D7, wherein the solid acid comprises a molecular sieve having an 8-member ring in a crystal structure thereof.
  • Dl l The process of any of D7 to D10, wherein the molecular sieve is selected from zeolites the following frame work types: MOR, CHA, and mixtures and combinations thereof.
  • MOR framework type zeolite having a S1O2 to AI2O3 molar ratio in the range from 6 to 200.
  • MOR framework type zeolite having a S1O2 to AI2O3 molar ratio in the range from 6 to 60.
  • D14 The process of any of D7 to D13, wherein the molecular sieve comprises a CHA framework type zeolite having a S1O2 to AI2O3 molar ratio in the range from 10 to 200.
  • a catalyst composition for preparing C2 to C4 hydrocarbons comprising: a solid acid that is a molecular sieve having 8-membered ring crystals; and a metal oxide on a support, wherein: (a) the metal oxide comprises ZnO and the support comprises Z1O2, or
  • the metal oxide comprises ZnO and C12O3, and the support comprises AI2O3.
  • E5. The catalyst composition of E4, wherein the solid acid is a chabazite having a molar ratio of S1O2/AI2O3 from 10 to 1000.
  • E6 The catalyst composition of E4, wherein the solid acid is a chabazite having a molar ratio of S1O2/AI2O3 is less than 50.
  • E7 The catalyst composition of E4, wherein the solid acid is a chabazite in protonated form.
  • E8 The catalyst composition of E4, wherein the solid acid is a mordenite having a molar ratio of S1O2/AI2O3 from 10 to 1000.
  • E9 The catalyst composition of E4, wherein the solid acid is a mordenite having a molar ratio of S1O2/AI2O3 is less than 50.
  • E10 The catalyst composition of E4, wherein the solid acid is a mordenite in protonated form.
  • E12 The catalyst composition of E4, wherein the solid acid is a meso-mordenite having a molar ratio of S1O2/AI2O3 is less than 50.
  • E13 The catalyst composition of E4, wherein the solid acid is a meso-mordenite in protonated form.
  • El 4. The catalyst composition of any of El to E13, wherein the solid acid and the metal oxide on support are co-extruded.
  • FI. A process for preparing C2-C4 hydrocarbons comprising: introducing a feedstream comprising hydrogen gas and carbon monoxide gas into a reactor; introducing the catalyst composition of any of paragraphs El -22 to the reactor, under reactor conditions effective to produce a product mixture, the reactor conditions comprising: a reactor temperature of from 200°C to 450°C; a pressure of from 0.1 MPa to 5.0 MPa; and (c) forming the product mixture comprising C2-C4 hydrocarbons.
  • the product mixture comprises a combined C2-C4 alkane content of from 30 wt% to 90 wt%; and a combined C2-C4 alkene content of from 0 wt% to 85 wt%, wherein each wt% is based on the total weight of the product mixture excluding hydrogen (H2), CO, and CO2.
  • F3 The process of FI, wherein the product mixture further comprises a methane content of no greater than 15 wt%; a combined saturated and unsaturated C5 and higher hydrocarbon content of no greater than 50 wt%; and an oxygenate content of no greater than 20 wt%, wherein each wt% is based on the total weight of the product mixture excluding hydrogen (H2), CO, and CO2.
  • F4 The process of any of FI to F3, wherein the reactor temperature is from 300°C to 400°C.
  • F5. The process of any of FI to F4, wherein the pressure is from 1.0 MPa to 3.0
  • F6 The process of any of FI to F5, wherein the reactor conditions further comprise a gas hourly space velocity of from 1,000 h 1 to 10,000 h -1 .
  • F7 The process of any of FI to F8, wherein a molar ratio of the hydrogen gas to the carbon monoxide gas is from 0.5:1 to 3:1.
  • a multicomponent catalyst composition e.g., a metal oxide- solid acid catalyst
  • a metal oxide-solid acid catalyst composition can be used to prepare a mixture that includes C2 to C4 olefins from a synthesis gas feedstream.
  • the metal oxide-solid acid catalyst compositions can demonstrate high activity in converting syngas into organic products, especially C2-C4 olefins and C2-C4 alcohols, which have significantly higher value than syngas.
  • ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as, ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited.
  • ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited.
  • within a range includes every point or individual value between its end points even though not explicitly recited. Thus, every point or individual value may serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited.
  • compositions, an element or a group of elements are preceded with the transitional phrase “comprising,” it is understood that we also contemplate the same composition or group of elements with transitional phrases“consisting essentially of,”“consisting of,”“selected from the group of consisting of,” or“is” preceding the recitation of the composition, element, or elements and vice versa.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne de nouvelles compositions de catalyseur, des procédés de fabrication de compositions de catalyseur, et des procédés de conversion de gaz de synthèse. Les composants catalytiques dans la composition de catalyseur peuvent comprendre un oxyde métallique et un acide solide. Cette invention est particulièrement utile pour convertir un gaz de synthèse par l'intermédiaire des réactions de Fischer-Tropsch afin de fabriquer des oléfines et/ou des alcools.
PCT/US2020/026069 2019-04-10 2020-04-01 Catalyseurs multicomposants pour conversion de gaz de synthèse en hydrocarbures légers WO2020210092A1 (fr)

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WO2023233289A1 (fr) * 2022-05-31 2023-12-07 Nova Chemicals (International) S.A. Catalyseurs et leurs procédés de fabrication et d'utilisation

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* Cited by examiner, † Cited by third party
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WO2023233289A1 (fr) * 2022-05-31 2023-12-07 Nova Chemicals (International) S.A. Catalyseurs et leurs procédés de fabrication et d'utilisation

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