Classifications

• • 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
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with 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
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
  • B01J21/04—Alumina
• • 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
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
• • 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
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/72—Copper
• • 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
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/74—Iron group metals
  • B01J23/745—Iron
• • 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
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/74—Iron group metals
  • B01J23/75—Cobalt
• • 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
  • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
  • B01J29/74—Noble metals
  • B01J29/7415—Zeolite Beta
• • 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
  • B01J37/0009—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
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0201—Impregnation
• • 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
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0201—Impregnation
  • B01J37/0213—Preparation of the impregnating solution
• • 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
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/03—Precipitation; Co-precipitation
• • 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
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/03—Precipitation; Co-precipitation
  • B01J37/031—Precipitation
• • 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
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
  • C10G2/50—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon dioxide with hydrogen
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
  • C10G3/42—Catalytic treatment
  • C10G3/44—Catalytic treatment characterised by the catalyst used
  • C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
  • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
  • C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/40—Characteristics of the process deviating from typical ways of processing
  • C10G2300/4081—Recycling aspects
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/70—Catalyst aspects

Definitions

• Carbon dioxide conversion technologies have the added benefit of producing commodity chemicals on-site, anywhere on the globe, with no cost or hazard risk of transportation when coupled with air capture of CO2.
• renewable electricity generation methods such as solar photovoltaics and wind turbines.
• Techniques like these use intermittent energy sources, such as the sun, which sets in the evening and rises in the morning, and wind, which blows intermittently.
• the supply of electricity from these sources to electrical grids surges at some points, and is low at others. This presents an opportunity for technologies that can intermittently utilize electricity to produce desired products on-site.
• the present disclosure provides catalysts, comprising: copper; zinc; one or more first elements selected from iron or cobalt; oxygen; optionally, aluminum, one or more second elements selected from a Group V, VI, VII, VIII, IX, X, and XI metal (e.g., manganese, silver, niobium, zirconium, molybdenum, ruthenium, or palladium); and optionally, one or more Group IA metals, and wherein the one or more first elements is present in an amount of about 1 to about 50 wt.% (e.g., about 1 to about 10 wt.%, about 25 to about 40 wt.%, about 30 to about 40 wt.%, or about 35 to about 50 wt.%) of the total amount of the copper, zinc, the one or more first elements, the optional second element, and the optional Group I A metal.
• a Group V, VI, VII, VIII, IX, X, and XI metal e.g., manganese,
• the present disclosure provides copper zinc aluminum (CZA) catalysts, comprising: copper; zinc; optionally, one or more first elements selected from cobalt, iron, or nickel; oxygen; optionally, aluminum; optionally, one or more second elements selected from a Group V, VI, VII, VIII, IX, X, and XI metal (e.g., manganese, silver, niobium, zirconium, molybdenum, ruthenium, or palladium); and optionally, one or more Group IA metals; wherein the molar ratio of copper to zinc is from about 1 to about 5.
• CZA copper zinc aluminum
• the present disclosure provides catalysts comprising: one or more metals, preferably wherein the metal is iron; optionally one or more second elements selected from copper and/or zinc; optionally one or more Group VI, VII, VIII, IX, X, or XI metal additives, (e.g., manganese, silver, niobium, zirconium, molybdenum, ruthenium, or palladium); and optionally a Group IA or IIA metal promoter.
• the present disclosure provides catalytic compositions, comprising the catalysts disclosed herein and an optional additional support.
• the present disclosure provides methods of preparing the catalysts or catalytic compositions disclosed herein, such as methods comprising preparing the catalyst by coprecipitation, wet impregnation, or ball milling, or a combination thereof.
• the present disclosure provides methods of reducing CO2, CO, or a mixture of the two to a liquid product mixture, comprising contacting the catalysts or other catalytic compositions disclosed herein with a feed mixture comprising CO2, CO, or a mixture of the two and a reductant gas at a reduction temperature and a reduction pressure, thereby providing the liquid product mixture.
• the present disclosure provides a catalyst comprising: one or more paraffin metal oxides; optionally a support; and optionally one or more metal additives.
• FIG. 1 shows a gas chromatogram identifying the primary individual hydrocarbon compounds in the hydrocarbon mixture produced by an exemplary cobalt copper zinc catalyst, namely straight-chain alkanes.
• FIG. 2 shows a gas chromatogram identifying the primary individual hydrocarbon compounds in the hydrocarbon mixture produced by an exemplary iron copper zinc catalyst, including straight-chain alkanes and primary olefins.
• FIG. 3 shows a zoomed-in gas chromatogram identifying the individual hydrocarbon compounds in the hydrocarbon mixture produced by an exemplary iron copper zinc catalyst, including secondary olefins, aromatics, and cycloalkanes.
• the Fischer-Tropsch (FT) process is one of the most widely used petrochemical process for fuel production today.
• the FT process utilizes a mixture of CO and Hz at elevated temperature and pressure to produce paraffins and other hydrocarbons.
• Nearly all modern FT processes use commercial catalysts that are comprised of cobalt, iron, iron carbide, or ruthenium, deposited on an aluminum oxide (AI2O3) support.
• AI2O3 aluminum oxide
• Thousands of variants of these catalysts have been produced, with the ultimate goal of improving the economics of the FT process.
• Product distribution from the FT process is characterized by the polymerization of CHx reaction intermediates on the surface of the FT catalyst.
• the CH X monomers polymerize on the surface of the FT catalyst into C y H z intermediates of different carbon numbers, which under further hydrogenation or dehydrogenation to form paraffins, olefins, and other hydrocarbon compounds.
• the C-C coupling of active CHx and C y H z species on the surface of the FT catalyst is challenging to control, which leads to a statistical distribution of hydrocarbon products.
• the distribution of hydrocarbon products in FT is predicted by the Anderson-Schulz-Flory (ASF) model, and is typically referred to as the ASF distribution.
• the ASF model depends on a chain growth probability variable, which is influenced by the nucleophilicity the FT catalyst, reductive chemical potential of the active site, the effectiveness of the catalyst for C-C coupling, and the reaction conditions in the FT reactor.
• an industrial FT process that follows the ASF model has a maximum selectivity for products with a carbon number between 10 and 20 of approximately 39%. It is, therefore, desirable to develop gas- to-liquids processes with chemistry that enables deviations from the ASF model.
• Another process that uses synthesis gas (syngas) to produce a commodity chemical is methanol production.
• Catalysts made of copper with zinc oxide on an alumina scaffold, known as copper-zinc-alumina or “CZA” catalysts are typically used for the production of methanol from a synthesis gas comprised of carbon monoxide and hydrogen gases, methanol being a commodity chemical that is produced on the scale of millions of tons per year.
• CZA catalysts are also useful for the hydrogenation of CO2 to methanol due to their high selectivity, but suffer from several other drawbacks such as product purity, methane coproduction, and limited catalyst lifetime. This high selectivity for methanol, however, hinders production of higher alcohols or hydrocarbons for situation where such higher alcohols or hydrocarbons may be desired.
• Catalysts for CO2 conversion specifically, face a major challenge in that CO2 requires a substantial amount of energy to transform into other compounds. This makes stability and activity a key challenge for industrial catalysts for CO2 conversion.
• Some catalysts for thermochemical reduction of CO2 have been demonstrated in academic literature, but none have transitioned to industrial use due to either high cost or poor stability.
• Ni-based catalysts are primarily used to hydrogenate CO2 to CH4. Co, Fe, Ru, Ir, Zn, Pd, Cu, and Rh compounds have also been used as CO2 hydrogenation catalysts for higher hydrocarbon formation.
• the present disclosure provides catalysts made of copper and zinc oxide, optionally further comprising a metal selected from iron or cobalt for CO2 conversion to long-chain hydrocarbons, and optionally including a support material such as alumina, a zeolite, or silica, as well as methods of using such catalysts for production of hydrocarbons from CO2.
• the catalysts of the present disclosure include a first element (Co or Fe) as a metal promoting carbon-carbon bond formation.
• copper-zinc family catalysts such as copper and zinc oxide on alumina (CZA) catalysts had not been demonstrated as competent catalysts for CO2 hydrogenation to multi-carbon products, such as paraffins.
• the modified copper zinc catalysts of the present disclosure catalyze the production of hydrocarbons from carbonaceous feedstocks, CO2, CO, or CPU at a higher rate than any other reported CZA or FT catalysts.
• These catalysts can also be used to inhibit the formation of gaseous byproducts during operation, e.g., CPU, to further enable effective recycle of unreacted gases during product gas recycle in a multi-pass gas to liquids reactor.
• the present disclosure provides catalysts comprising iron oxide, optionally further comprising one or more additional metals selected from copper and/or zinc.
• the one or more additional metals aid in CO2 activation and conversion (e.g., by acting as a metal promoter).
• the catalysts comprising iron oxide further comprise a support including alumina, a zeolite, or silica.
• the catalysts comprising iron oxide are useful for converting CO2 to long-chain hydrocarbons.
• the catalysts of the present disclosure preferably include one of more additional metals (Cu and/or Zn) as a metal promoting CO2 activation.
• additional metals Cu and/or Zn
• iron family catalysts such as iron oxide catalysts have not been demonstrated as competent catalysts for CO2 hydrogenation to multi-carbon products, such as paraffins.
• the present disclosure provides a chemical process to produce long- chain hydrocarbons from CO2 and H2 in a single reactor.
• the process is novel from prior CZA-based processes in that it produces multi-carbon species, and specifically long-chain alkanes with a carbon number between 6 and 20, where prior CZA-based processes produced only products with a carbon number between 1 and about 5.
• the process differs from FT-based processes in that CO2 is a feedstock rather than CO. Increasing concentrations of CO2 in the feedstock stream of typical cobalt-catalyzed FT processes causes the reactor to produce exclusively methane, as known to persons having ordinary skill in the art.
• the present invention thus, represents a significant step forward in gas-to-liquids chemistry by using a catalyst and reaction conditions where little to no methane is produced with a feedstock stream comprised of CO2 and H2.
• the present invention uses cobalt to promote C-C bonding and chain growth while simultaneously preventing the production of CH4 through a combination of reactor conditions, adaptive monitoring of the reaction products, and catalyst composition.
• the present disclosure provides a chemical process to produce long- chain hydrocarbons from CO2 and H2 in a single reactor through an alcohol intermediate.
• alcohols are co-produced with the long-chain hydrocarbons.
• the alcohol co-produced with the long-chain hydrocarbons is primarily methanol.
• the alcohols are an intermediate to the long-chain hydrocarbons in the chemical reaction occurring in the single reactor. In these cases, the production of the long-chain hydrocarbons is achieved by first producing an alcohol, then dehydrating the alcohol to produce either a bound CH X intermediate or a free olefin, such as ethylene or propylene. The bound CH X intermediate or free olefin are further oligomerized to produce the long-chain hydrocarbons.
• the alcohols are a side-product to the long-chain hydrocarbons in the chemical reaction occurring in the single reactor.
• the present disclosure provides a chemical process to produce long- chain hydrocarbons from carbonaceous feedstocks that do not follow an ASF distribution.
• the ASF distribution is deviated from because of mechanistic uniqueness from legacy FT processes.
• the present invention provides for methods to produce a narrower distribution of desired hydrocarbons for diesel and aviation fuel than legacy FT processes.
• the present invention provides for methods to selectively produce linear alkanes with a carbon number between 6 and 26.
• the present invention provides for methods to selectively produce linear alkanes with a carbon number between 8 and 16.
• the present invention provides for methods to selectively produce hydrocarbons with a carbon number between 6 and 30.
• the present disclosure provides catalysts to produce long-chain hydrocarbons from carbonaceous feedstocks with distinct differences between Co- and Fe- promoted catalysts.
• Co-promoted copper zinc catalysts typically fully hydrogenate long-chain hydrocarbons to produce saturated straight-chain alkanes of various carbon numbers between 6 and 30.
• Fe-promoted copper zinc catalysts typically partially hydrogenate long-chain hydrocarbons to produce a mixture of saturated alkanes, olefins, as well as smaller concentrations of branched and cycloalkanes, aromatics, alcohols, and carboxylic acids.
• the present invention uses both Co and Fe in various ratios in a catalyst comprised of copper and zinc oxide to control the degree to which branching occurs or reaction intermediates are hydrogenated.
• the ratio of Co:Fe is 100:1, 50: 1, 20: 1, 10: 1, 5: 1, 2: 1, 1 : 1, 1 :2, 1 :5, 1 :10, 1 :20, 1 :50, or 1 : 100.
• the present disclosure provides methods for adaptive monitoring of reactors to produce long-chain hydrocarbons from CO2 and H2 in a single reactor continuously, without the formation of byproducts.
• the present invention provides for methods of real-time monitoring of the composition of the gaseous recycle loop in a gas-to-liquids reactor system and adaptive adjustment of feed gas ratios and temperatures.
• real-time monitoring of the composition of the gaseous recycle loop is achieved by a syngas analyzer, which uses thermal conductivity detection to determine the relative concentration of H2, and infrared detection to determine the relative concentrations of CO2, CO, CH4, and other hydrocarbons.
• a syngas analyzer uses thermal conductivity detection to determine the relative concentration of H2, and infrared detection to determine the relative concentrations of CO2, CO, CH4, and other hydrocarbons.
• either software or operator intervention is used to adjust the feed ratio of CO2 and H2 based on the outlet composition of the detector to avoid formation of unrecyclable byproducts, such as CFU.
• the present disclosure provides catalysts, comprising: copper; zinc; one or more first elements selected from iron or cobalt; oxygen; optionally, aluminum; optionally, one or more second elements selected from a Group V, VI, VII, VIII, IX, X, and XI metal (e.g., manganese, silver, niobium, zirconium, molybdenum, ruthenium, palladium, platinum, or nickel); and optionally, one or more Group IA metals, and wherein the one or more first elements is present in an amount of about 1 to about 40 wt.% (e.g., about 1 to about 10 wt.%, about 25 to about 40 wt.%, about 30 to about 40 wt.%, or about 35 to about 40 wt.%) of the total amount of the copper, zinc, one or more first elements, the optional second element, and the optional Group IA metal.
• a Group V, VI, VII, VIII, IX, X, and XI metal e.g
• the one or more first elements is present in an amount of about 0.5 wt.%, about 1 wt.%, about 2 wt.%, about 3 wt.%, about 4 wt.%, about 5 wt.%, about 6 wt.%, about 7 wt.%, about 8 wt.%, about 9 wt.%, about 10 wt.%, about 11 wt.%, about 12 wt.%, about 13 wt.%, about 14 wt.%, about 15 wt.%, about 16 wt.%, about 17 wt.%, about 18 wt.%, about 19 wt.%, about 20 wt.%, about 21 wt.%, about 22 wt.%, about 23 wt.%, about 24 wt.%, about 25 wt.%, about 26 wt.%, about 27 wt.%, about 28 wt.%, about 29 wt
• the one or more first elements is present in an amount of 1-10 wt.%, 10-20 wt.%, or 20-30 wt.%, 20-25 wt.%, 22-24 wt.%, 25-40 wt.% 30- 40 wt.%, or 35-40 wt.% of the total amount of the total amount of the copper, zinc, the one or more first elements, the optional second element, and the optional Group IA metal.
• the catalyst comprises a cobalt-embedded interconnected matrix of reduced copper metal nanoparticles and alumina-modified zinc oxide.
• the cobalt is present as cobalt oxide.
• the copper is present as copper oxide.
• the molar ratio of cobalt to copper to zinc (Co:Cu:Zn) is about 0.1-3 in cobalt, 1-4 in copper, and 0.5-1.5 in zinc.
• the Co:Cu:Zn ratio is in the range of 1-2 in cobalt, 1-3 in copper, and 0.5-1 in zinc.
• the Co:Cu:Zn ratio is approximately 1 :2.5: 1.
• the zinc is preferably 0.3 - 1 the molar content of the copper.
• the cobalt is preferably 0.1 - 1 the molar content of the copper.
• the catalyst comprises an iron-embedded interconnected matrix of reduced copper metal nanoparticles and alumina-modified zinc oxide.
• the iron is present as iron oxide.
• the copper is present as copper oxide.
• the molar ratio of iron to copper to zinc (Fe:Cu:Zn) is about 0.05-3 in iron, 1-4 in copper, and 0.5-4 in zinc.
• the Fe:Cu:Zn ratio is in the range of 0.4-2 in iron, 1-3 in copper, and 0.5-3 in zinc.
• the Fe:Cu:Zn ratio is approximately 1 :2.3:2.3.
• the zinc is preferably 0.3 - 1 the molar content of the copper.
• the iron is preferably 0.5 - 5 the molar content of the copper.
• catalysts of the disclosure comprise copper, e.g., reduced copper nanoparticles, and zinc oxide supported on an iron support.
• the iron support is iron oxide.
• the copper is present as copper oxide.
• the catalysts comprise iron, copper, and zinc in an Fe:Cu:Zn ratio that is from about 0.05 to about 3 in iron, about 1 to about 3 in copper, and about 0.5 to about 3 in zinc.
• the Fe:Cu:Zn ratio is from about 0.4 to about 3 in iron, about 0.4 to about 3 in copper, and about 0.4 to about 3 in zinc.
• the Fe:Cu:Zn ratio is about 2.3 : 1 : 1.
• the catalysts comprise a molar content of zinc that is from about 0.3 to about 1 times the molar content of copper. In certain preferred embodiments, the catalysts comprise a molar content of iron that is from about 0.5 to about 5 times the molar content of copper.
• the catalyst comprises one or more elements selected from a transition, or Group VI, VII, VIII, IX, X, or XI metal. In some embodiments, the catalyst comprises one or more second elements selected from a Group VI metal. In some embodiments, the catalyst comprises one or more second elements selected from a Group VII metal. In some embodiments, the catalyst comprises one or more second elements selected from a Group VIII metal. In some embodiments, the catalyst comprises one or more second elements selected from a Group IX metal. In some embodiments, the catalyst comprises one or more second elements selected from a Group X metal. In some embodiments, the catalyst comprises one or more second elements selected from a Group XI metal.
• the one or more second elements comprise manganese, silver, niobium, zirconium, molybdenum, ruthenium, palladium, platinum, or nickel.
• the one or more second elements comprise nickel. In some embodiments, the one or more second elements comprise silver. In some embodiments, the one or more second elements comprise palladium. In some embodiments, the one or more second elements comprise niobium. In some embodiments, the one or more second elements comprise manganese. In some embodiments, the one or more second elements comprise zirconium. In some embodiments, the one or more second elements comprise molybdenum.
• the catalyst comprises the one or more second elements at a molar ratio of about 0.15 to about 2 relative to copper. In some embodiments, the catalyst comprises the one or more second elements at a molar ratio of about 0.15 to about 1.5 relative to copper. In some embodiments, the catalyst comprises the one or more second elements at a molar ratio of about 0.15 to about 1 relative to copper. In some embodiments, the catalyst comprises the one or more second elements at a molar ratio of about 0.15 to about 0.75 relative to copper. In some embodiments, the catalyst comprises the one or more second elements at a molar ratio of about 0.15 to about 0.5 relative to copper. In some embodiments, the catalyst comprises the one or more second elements at a molar ratio of about 0.15 to about 0.25 relative to copper.
• the catalyst comprises copper at a molar ratio of about 0.5 to about 5 relative to the one or more first elements. In some embodiments, the catalyst comprises copper at a molar ratio of about 1 to about 10 relative to the one or more first elements. In some embodiments, the catalyst comprises copper at a molar ratio of about 2 to about 9 relative to the one or more first elements. In some embodiments, the catalyst comprises copper at a molar ratio of about 2.3 to about 8.4 relative to the one or more first elements. In some embodiments, the catalyst comprises copper at a molar ratio of about 2.3 relative to the one or more first elements. In some embodiments, the catalyst comprises copper at a molar ratio of about 8.4 relative to the one or more first elements.
• the catalyst comprises copper at a molar ratio of about 1.5 relative to the one or more first elements. In some embodiments, the catalyst comprises copper at a molar ratio of about 1.0 relative to the one or more first elements. In some embodiments, the catalyst comprises copper at a molar ratio of about 0.75 relative to the one or more first elements. In some embodiments, the catalyst comprises copper at a molar ratio of about 0.5 relative to the one or more first elements.
• the catalyst comprises zinc at a molar ratio of about 0.3 to about 3 relative to copper. In some embodiments, the catalyst comprises zinc at a molar ratio of about 0.3 to about 3 relative to copper. In some embodiments, the catalyst comprises zinc at a molar ratio of about 0.4 to about 1 relative to copper. In some embodiments, the catalyst comprises zinc at a molar ratio of about 1.5 relative to copper. In some embodiments, the catalyst comprises zinc at a molar ratio of about 1.0 relative to copper. In some embodiments, the catalyst comprises zinc at a molar ratio of about 0.75 relative to copper. In some embodiments, the catalyst comprises zinc at a molar ratio of about 0.5 relative to copper. In some embodiments, the catalyst comprises zinc at a molar ratio of about 0.4 relative to copper.
• the one or more second elements comprise niobium. In some embodiments, the one or more second elements consist of niobium. In some embodiments, the niobium is present at a molar ratio of about 0.05 to about 1 relative to copper. In some embodiments, the niobium is present at a molar ratio of about 0.2 relative to copper. In some embodiments, the niobium is present at a molar ratio of about 0.3 relative to copper. In some embodiments, the niobium is present at a molar ratio of about 0.1 relative to copper.
• the catalyst comprises the one or more Group IA metals. In some embodiments, the catalyst comprises the one or more Group IA or IIA metals at a molar ratio from about 0.01 to about 1.0 relative to copper. In some embodiments, the catalyst comprises the one or more Group IA or IIA metals at a molar ratio from about 0.05 to about 0.50 relative to copper. In some embodiments, the catalyst comprises the one or more Group IA or IIA metals at a molar ratio from about 0.20 to about 0.50 relative to copper. In some embodiments, the catalyst comprises the one or more Group IA or IIA metals at a molar ratio from about 0.30 to about 0.50 relative to copper.
• the catalyst comprises the one or more Group IA or IIA metals at a molar ratio from about 0.40 to about 0.50 relative to copper. In some embodiments, the catalyst comprises the one or more Group IA or IIA metals at a molar ratio at about 0.15 relative to copper.
• the catalyst comprises one or more Group IA metals.
• the one or more Group IA or IIA metals comprise potassium, sodium or cesium. In some embodiments, the one or more Group IA or IIA metals consist of potassium, sodium or cesium. In some embodiments, the one or more Group IA or IIA metals comprise potassium. In some embodiments, the one or more Group IA or IIA metals comprise sodium. In some embodiments, the one or more Group IA or IIA metals comprise cesium. In some embodiments, the one or more Group IA or IIA metals consist of potassium. In some embodiments, the one or more Group IA or IIA metals consist of sodium. In some embodiments, the one or more Group IA or IIA metals consist of cesium.
• the catalyst comprises potassium at a molar ratio of about 0.05, about 0.09, about 0.1, about 0.15, about 0.2, about 0.25, about 0.3, about 0.35, about 0.4, about 0.45, or about 0.5 relative to copper. In some embodiments, the catalyst comprises potassium at a molar ratio of about 0.09 relative to copper.
• the catalyst comprises iron at a molar ratio of about 0.1 to about 10 relative to copper. In further embodiments, the catalyst comprises iron at a molar ratio of about 0.1 to about 1 relative to copper. In yet further embodiments, the catalyst comprises iron at a molar ratio of about 0.1 to about 0.2 relative to copper. In certain embodiments, the catalyst comprises iron at a molar ratio of about 0.5 to about 1 relative to copper. In certain embodiments, the catalyst comprises iron at a molar ratio selected from about 0.1, about 0.2, about 2, about 3, about 4, about 5, about 6, about 7, about 8, about 9, and about 10 relative to copper.
• the catalyst comprises aluminum at a molar ratio of about 0.1 to about 10 relative to copper. In some embodiments, the catalyst comprises aluminum at a molar ratio of about 0.1 to about 1 relative to copper. In some embodiments, the catalyst comprises aluminum at a molar ratio of about 0.1 to about 0.2 relative to copper. In some embodiments, the catalyst comprises aluminum at a molar ratio of about 0.5 to about 1 relative to copper. In some embodiments, the catalyst comprises aluminum at a molar ratio of about 0.1 relative to copper. In some embodiments, the catalyst comprises aluminum at a molar ratio of about 0.2 relative to copper.
• the catalyst comprises zinc oxide. In some embodiments, the catalyst comprises copper oxide.
• the catalyst comprises cobalt oxide.
• the catalyst comprises iron oxide.
• the catalyst comprises nickel oxide.
• the catalyst comprises alumina.
• the one or more Group IA or IIA metals comprise or consist of sodium or cesium.
• substituting sodium or cesium for potassium does not substantially affect the catalytic activity, and both sodium and cesium have been found to provide the same stability potassium provides. This is a contrast with known syngas catalysts, where the choice of potassium, sodium or cesium greatly affects activity.
• the catalyst comprises or consists of aluminum oxide (AI2O3) wherein the aluminum is present in a molar ratio of about 0.02 to about 3 relative to copper. In some embodiments, the aluminum is present in a molar ratio of about 0.1 to about 0.8 relative to copper. In some embodiments, the aluminum is present in a molar ratio of about 0.7 relative to copper.
• the alumina can be added as a support to increase the surface area of the copper and zinc, or produced in-situ as a component of the catalyst, e.g. from aluminum nitrate co-precipitation with first element, copper, and zinc precursors.
• the catalyst comprises iron oxide e.g., FesC , Fe2Ch, and/or FeO) and copper.
• the iron is present in a molar ratio from about 0.2 to about 20 relative to copper.
• the iron is present in a molar ratio of about 0.2 to about 10, about 0.2 to about 5, about 0.2 to about 2, about 0.2 to about 1, about 0.2 to about 0.5, about 1 to about 20, about 1 to about 10, or about 1 to about 2 relative to copper.
• the iron is present in a molar ratio selected from about 1, about 2, about 5, about 10, about 15, and about 20, relative to copper.
• the catalyst comprises iron oxide as a support that increases the surface area of the copper and zinc.
• the iron oxide is produced in- situ as a component of the catalyst, for example by co-precipitating iron nitrate with copper and zinc precursors.
• the catalyst comprises copper, zinc oxide, cobalt, and alumina.
• the molar ratios of the components are as described above.
• the catalyst comprises: cobalt; copper at a molar ratio of about 8.4 relative to the cobalt; zinc at a molar ratio of about 3.3 relative to the cobalt, and alumina, with the aluminum at a molar ratio of about 1.8 relative to cobalt.
• the catalyst comprises: copper at a molar ratio of about 8.4 relative to the cobalt; zinc oxide at a molar ratio of about 3.3 relative to the cobalt; and alumina at a molar ratio of about 0.9 relative to the cobalt.
• the catalyst comprises copper, zinc oxide, nickel, and alumina.
• the molar ratios of the components are as described above.
• the catalyst comprises: nickel; copper at a molar ratio of about 2.5 relative to the nickel; zinc at a molar ratio of about 1 relative to the cobalt, and alumina, with the aluminum at a molar ratio of about 0.7 relative to nickel.
• the catalyst comprises: copper at a molar ratio of about 2.5 relative to the nickel; zinc oxide at a molar ratio of about 1 relative to the nickel; and alumina at a molar ratio of about 0.35 relative to the nickel.
• the catalyst comprises copper, zinc oxide, iron, and alumina.
• the molar ratios of the components are as described above.
• the catalyst comprises: iron; copper at a molar ratio of about 2.3 relative to the iron; zinc at a molar ratio of about 2.3 relative to the iron, and alumina, with the aluminum at a molar ratio of about 0.8 relative to iron.
• the catalyst comprises: copper at a molar ratio of about 2.3 relative to the iron; zinc oxide at a molar ratio of about 2.3 relative to the iron; and alumina at a molar ratio of about 0.4 relative to the iron.
• the catalyst comprises copper, zinc oxide, cobalt, alumina, and a Group IA metal.
• the molar ratios of the components are as described above.
• the catalyst comprises: cobalt; copper at a molar ratio of about
• the catalyst comprises: copper at a molar ratio of about 8.4 relative to the cobalt; zinc oxide at a molar ratio of about 3.3 relative to the cobalt; alumina at a molar ratio of about 0.9 relative to the cobalt; and the one or more Group IA or IIA metals at a molar ratio of about 0.14 relative to the cobalt.
• the catalyst comprises copper, zinc oxide, nickel, alumina, and a Group IA metal. In some embodiments, the molar ratios of the components are as described above. In some embodiments, the catalyst comprises: nickel; copper at a molar ratio of about
• the catalyst comprises: copper at a molar ratio of about 2.5 relative to the nickel; zinc oxide at a molar ratio of about 1 relative to the nickel; alumina at a molar ratio of about 0.35 relative to the nickel; and the one or more Group IA or IIA metals at a molar ratio of about 0.1 relative to the nickel.
• the catalyst comprises copper, zinc oxide, iron, alumina, and a Group IA metal.
• the molar ratios of the components are as described above.
• the catalyst comprises: iron; copper at a molar ratio of about 2.3 relative to the iron; zinc at a molar ratio of about 2.3 relative to the iron; alumina, with the aluminum at a molar ratio of about 0.4 relative to the iron; and the one or more Group IA or IIA metals at a molar ratio of about 0.4 relative to the iron.
• the catalyst comprises: copper at a molar ratio of about 2.5 relative to the iron; zinc oxide at a molar ratio of about 1 relative to the iron; alumina at a molar ratio of about 0.35 relative to the iron; and the one or more Group IA or IIA metals at a molar ratio of about 0.1 relative to the iron.
• the catalyst comprises Cu, Zn, Al, O, and an alkali metal. In certain embodiments, the catalyst comprises Cu, Zn, Fe, and O. In some embodiments, the catalyst comprises Cu, Zn, Ni, Al, O, and an alkali metal. In some embodiments, the catalyst comprises Cu, Zn, Fe, Al, O, and an alkali metal. In some embodiments, the catalyst comprises Cu, Zn, Co, Fe, Al, O, and an alkali metal. In some embodiments, the catalyst comprises Cu, Zn, Co, Al, O, and an alkali metal. In some embodiments, the catalyst comprises Cu, Zn, Co, Nb, Al, and O, and an alkali metal. In some embodiments, the catalyst comprises Cu, Zn, Co, Ni, Al, and O, and an alkali metal. In some embodiments, the catalyst comprises Cu, Zn, Co, Mo, Al, and O, and an alkali metal.
• the catalyst comprises Cu, Zn, Al, and O. In some embodiments, the catalyst comprises Cu, Zn, Fe, Al, and O. In some embodiments, the catalyst comprises Cu, Zn, Ni, Al, and O. In some embodiments, the catalyst comprises Cu, Zn, Co, Al, and O. In some embodiments, the catalyst comprises Cu, Zn, Co, Fe, Al, and O. In some embodiments, the catalyst comprises Cu, Zn, Co, Nb, Al, and O. In some embodiments, the catalyst comprises Cu, Zn, Co, Ni, Al, and O. In some embodiments, the catalyst comprises Cu, Zn, Co, Mo, Al, and O.
• the elemental composition of the catalyst material is Cu(ZnO)CoA/Al 2 O 3 , Cu(ZnO)CoFeA/Al 2 O 3 , Cu(ZnO)CoNbA/Al 2 O 3 , Cu(ZnO)CoNiA/Al 2 O 3 , Cu(ZnO)CoMoA/Al 2 O 3 , or Cu(ZnO)A/Fe 3 O4, wherein A is an alkali metal and further wherein the relative amounts of the elemental components are as described above.
• the elemental composition of the catalyst material is Cu(ZnO)Co/Al 2 O 3 , Cu(ZnO)CoFe/Al 2 O 3 , Cu(ZnO)CoNb/Al 2 O 3 , Cu(ZnO)CoNi/Al 2 O 3 , Cu(ZnO)CoMo/Al 2 O 3 , Cu(ZnO)Nb/Fe 3 O4, wherein the relative amounts of the elemental components are as described above.
• the catalyst is selected from one of the following exemplary catalysts: CuO(ZnO), Cu(ZnO)Co, Cu(ZnO)CoK, Cu(ZnO)CoFe, Cu(ZnO)Fe, Cu(ZnO)CoFeK, Cu(ZnO)FeK, Cu(ZnO)CoNi, Cu(ZnO)CoNiK, Cu(ZnO)CoNb, Cu(ZnO)CoNbK, Cu(ZnO)CoMo, Cu(ZnO)CoMoK on A1 2 O 3 , wherein the relative amounts of the elemental components are as described above.
• the catalyst is approximately CuO( 2 )(ZnO)(i), Cu( 2 .5)(ZnO)(i)Co(i), Cu( 2 .5)(ZnO)(i)Co(i)K(o.i), Cu(i)(ZnO)(i)Co(i)Fe(i), Cu(i)(ZnO)(i)Fe(i>, Cu(i)(ZnO)(i)Co(i)Fe(i)K(o.i5), Cu(i)(ZnO)(i)Fe(i)K(o.i5), Cu( 2 )(ZnO)(i)Co(i)Ni(i), Cu( 2 )(ZnO)(i)Co(i)Ni(i)K(o.i5), Cu( 2 )(ZnO)(i)Co(i)Nb(i), Cu( 2 )(ZnO)(i)Co(i)Nb(i), Cu( 2 )(Zn
• catalysts for the production of paraffins comprising: one or more metals; optionally one or more second elements selected from copper and zinc; optionally one or more Group VI, VII, VIII, IX, X, or XI metal additives; optionally a Group IA or IIA metal promoter.
• the one or more metals is selected from elected from cobalt, iron, nickel, indium, yttrium, a lanthanide, and combinations thereof. In further embodiments, the one or more metals is cobalt. In yet further embodiments, the one or more metals is iron. In still further embodiments, the one or more metals is a combination of iron and cobalt.
• the one or more metals is present in the form of an oxide, nitride, or carbide.
• the one or more second elements is copper.
• the one or more second elements is zinc.
• the one or more second elements are copper and zinc.
• the one or more second elements is present in the form of an oxide, nitride, or carbide.
• the one or more Group VI, VII, VIII, IX, X, or XI metal additives when present, is selected from manganese, silver, niobium, zirconium, molybdenum, ruthenium, palladium, platinum, or nickel.
• the Group IA or IIA metal promoter when present, is a Group IA element.
• the Group IA or IIA metal promoter when present, is lithium, sodium, potassium, or cesium.
• the one or more second elements is present in an amount of about 0.5 to about 40 wt.% of the total amount of the one or more metals, the second element, the optional one or more Group VI, VII, VIII, IX, X, or XI metal additives, and the optional Group IA or IIA metal promoter.
• the systems and methods of the present disclosure involve the use of hydrogenation catalysts and isomerization catalysts for isomerizing or hydrogenating percentages of the hydrocarbons produced, respectively.
• the hydrogenation catalysts and isomerization catalysts of the disclosure may be independently selected from the catalysts described below.
• the isomerization catalysts and/or the hydrogenation catalysts of the present disclosure are aluminosilicate catalysts, such as zeolites.
• the isomerization catalyst and/or the hydrogenation catalyst is AlCh.
• the isomerization catalyst and/or the hydrogenation catalyst is doped with a transition metal, such as Pt, Pd, etc.
• the isomerization catalyst and/or the hydrogenation catalyst is Pt on beta-zeolite.
• isomerization catalysts and/or hydrogenation catalysts of the disclosure comprise an isomerization catalyst metal, and a zeolite support.
• the isomerization catalyst metal is selected from Pd, Pt, Ni-Co, Ni-W, and Ni-Mo.
• the zeolite support is selected from SiAlOx, SCh-ZrCh, Y-type zeolites, beta-zeolite, ZSM5, ZSM22, SAPO11, SAPO31, SAPO41, and TiCh.
• the isomerization catalyst and the hydrogenation catalyst are independently selected from Pt/SiAlOx, Pt/SCh-ZrCh, Pt/ZSM5, Pt/ZSM22, Pt/SAPO, Ni-W/SiA10x, Ni-W/SC -ZrCh, Ni- W/ZSM5, Ni-W/ZSM22, and Ni-W/SAPO.
• the isomerization metal comprises from about 0.5 wt% to about 40 wt% of the isomerization catalyst and/or the hydrogenation catalyst. In further embodiments, the isomerization metal comprises about 0.5 wt% of the isomerization catalyst and/or the hydrogenation catalyst. In yet further embodiments, the isomerization metal comprises about 1 wt% of the isomerization catalyst and/or the hydrogenation catalyst. In still further embodiments, the isomerization metal comprises about 10 wt% of the isomerization catalyst and/or the hydrogenation catalyst. In certain embodiments, the isomerization metal comprises about 20 wt% of the isomerization catalyst and/or the hydrogenation catalyst.
• the isomerization metal comprises about 30 wt% of the isomerization catalyst and/or the hydrogenation catalyst. In yet further embodiments, the isomerization metal comprises about 40 wt% of the isomerization catalyst and/or the hydrogenation catalyst.
• the isomerization temperature is about 250 °C and the isomerization pressure is about 750 psi.
• the isomerization temperature is about 300 °C and the isomerization pressure is about 750 psi.
• the present disclosure provides catalytic compositions, comprising one or more of the catalysts disclosed herein and an additional support.
• the additional support may be any suitable material that can serve as a catalyst support.
• the additional support comprises one or more materials selected from an oxide, nitride, fluoride, silicate, or carbide of an element selected from aluminum, silicon, titanium, zirconium, cerium, magnesium, yttrium, lanthanum, zinc, and tin.
• the additional support comprises one or more materials selected from an oxide, nitride, fluoride, silicate, or carbide of an element selected from aluminum, silicon, titanium, zirconium, cerium, magnesium, yttrium, lanthanum, zinc, iron, and tin.
• the additional support comprises y-alumina.
• the additional support is selected from carbon, silica, zeolite, alumina, zirconium oxide, titanium oxide, and silica carbide. In certain embodiments, the additional support is selected from carbon, silica, zeolite, alumina, iron oxide, zirconium oxide, titanium oxide, and silica carbide. In some embodiments, the additional support is an aluminum oxide that is formed in-situ as part of the catalyst. In some embodiments, the additional support is selected from, but not limited to, AI2O3, ZrCh, SnCh, SiCh, ZnO, and TiCh. In some embodiments, the additional support is selected from AI2O3, ZrCh, SnCh, SiCh, ZnO, and TiO2. In some embodiments, the additional support is selected from AI2O3, ZrO2, SnO2, SiO2, ZnO, Fe2O3, Fe3O4, FeO, and TiO2.
• the additional support comprises one or more carbon-based materials.
• the carbon-based material is selected from activated carbon, carbon nanotubes, graphene and graphene oxide.
• the additional support is a mesoporous material. In some embodiments, the additional support has a mesopore volume from about 0.01 to about 3.0 cc/g.
• the additional support has surface area from about 10 m 2 /g to about 1000 m 2 /g.
• the catalytic composition comprising the additional support and a catalyst disclosed herein has a surface area from about 10 m 2 /g to about 1000 m 2 /g.
• the catalytic composition is in a form of particles having an average size from about 10 nm to about 5 pm. In some embodiments, the catalytic composition is in a form of particles having an average size from about 20 nm to about 5 pm. In some embodiments, the catalytic composition is in a form of particles having an average size from about 50 nm to about 1 pm. In some embodiments, the catalytic composition is in a form of particles having an average size from about 100 nm to about 500 nm. In some embodiments, the catalytic composition is in a form of particles having an average size from about 50 nm to about 300 nm.
• the catalytic composition comprises from about 5 wt.% to about 80 wt.% of the catalyst. In some embodiments, the catalytic composition comprises from about 5 wt.% to about 70 wt.% of the catalyst. In some embodiments, the catalytic composition comprises from about 20 wt.% to about 70 wt.% of the catalyst. In some embodiments, the catalytic composition comprises from about 30 wt.% to about 70 wt.% of the catalyst.
• the support is a high surface area scaffold. In some embodiments, the support comprises mesoporous silica. In some embodiments, the support comprises carbon allotropes.
• the catalyst is a nanoparticle catalyst.
• the particle sizes of the catalyst on the surface of the scaffold are about 1 nm to 5 nm. In some embodiments, the particle sizes of the catalyst on the surface of the scaffold are about 5 nm to 100 nm. In some embodiments, the particle sizes of the catalyst on the surface of the scaffold are 100-500 nm. In some embodiments, the particles not subjected to agglomeration are 100-500 nm in particle size.
• the catalysts and catalytic compositions of the present disclosure may be prepared by any suitable method.
• the present disclosure provides methods for preparing the catalysts or the catalytic compositions disclosed herein, comprising preparing the catalyst by coprecipitation, wet impregnation, or ball milling.
• the method comprises the following steps:
• the method comprises the following steps:
• the method comprises the following steps: providing a first solution comprising a source of cobalt, a source of copper, a source of zinc, and a source of aluminum. Combining the first solution with a basic precipitant, such as a carbonate, to increase the pH of the metal salt containing solution thereby precipitating solid particles.
• the solid particles are dried and calcined to form a solid catalyst.
• the base comprises carbonate and a cation selected from potassium, sodium, ammonium, lithium, and cesium. In other embodiments, the base comprises bicarbonate and a cation selected from potassium, sodium, ammonium, lithium, and cesium.
• the method comprises the following steps: providing a first solution comprising a cobalt source and introducing it to a pre-made copper-zinc alumina material via incipient wetness or wet impregnation, followed by drying and calcining to form a solid catalyst.
• the method comprises the following steps: mixing a cobalt source and a support in a mill jar to provide a first mixture; ball milling the first mixture for between 2 hours to 2 weeks to thereby provide a first precipitate; filtering the first precipitate and heating to a first temperature to provide a ball milled cobalt source; mixing the ball milled cobalt source with a source of copper and zinc and a source of the alumina to provide a second mixture; and isolating a solid material from the second mixture.
• the method further comprises combining the solid material with a source of the one or more Group IA metals. In some embodiments, the method further comprises pressing the solid material into pellets. In some embodiments, the method further comprises pressing the solid material into pellets prior to introduction into a flow reactor.
• the present disclosure provides methods of reducing carbonaceous feedstock, namely CO2 to a liquid product mixture, comprising contacting the catalysts of catalytic compositions disclosed herein with a feed mixture comprising CO2 and a reductant gas at a reduction temperature and a reduction pressure, thereby providing the liquid product mixture.
• the reductant gas is H2.
• the reductant gas is a hydrocarbon, such as CH4, ethane, propane, or butane.
• the hydrocarbon is CH4.
• the CH4 is a component of a gas mixture that also comprises other hydrocarbons, such as ethane, propane, or butane.
• the gas mixture used to supply CH4 may be (or may be derived from) flare gas, waste gas, natural gas, or the like.
• the feed mixture further comprises CO. In some embodiments, the feed mixture comprises less than 25% of CO, less than 20% of CO, less than 15% of CO, less than 10% of CO, less than 5% of CO, or less than 1% of CO. In some embodiments, the feed mixture is substantially free of CO.
• the reduction temperature is from about 100 to about 600 °C. In some embodiments, the reduction temperature is from about 275 to about 350 °C. In some embodiments, the reduction temperature is about 275 °C. In some embodiments, the reduction temperature is about 300 °C.
• the reduction pressure is from about 50 to about 3000 psi. In some embodiments, the reduction pressure is from about 900 to about 1100 psi. In some embodiments, the reduction pressure is about 1000 psi. In some embodiments, the partial pressure of CO2 in the feed mixture is from about 20 to about 1500 psi. In some embodiments, the partial pressure of CO2 in the feed mixture is from about 200 to about 800 psi, from about 200 to about 600 psi, from about 200 to about 400 psi, or from about 300 to about 400 psi.
• the partial pressure of CO2 in the feed mixture is about 200 psi, about 250 psi, about 300 psi, about 350 psi, about 400 psi, about 450 psi, about 500 psi, about 550 psi, about 600 psi, about 650 psi, about 700 psi, about 750 psi, about 800 psi, about 850 psi, about 900 psi, about 950 psi, or about 1000 psi.
• the partial pressure of CO2 in the feed mixture is about 330 psi.
• the ratio of reductant gas:CO2 in the feed mixture is about 10: 1 to about 1 : 10. In some embodiments, the ratio of reductant gas:CO2 in the feed mixture is about 5: 1 to about 0.5:1. In some embodiments, the ratio of reductant gas:CO2 in the feed mixture is about 4: 1 to about 1 : 1. In some embodiments, the ratio of reductant gas:CO2 in the feed mixture is about 3: 1.
• the liquid product mixture comprises methanol. In some embodiments, the liquid product mixture comprises methanol, ethanol, and n-propanol. In some embodiments, the liquid product mixture comprises methanol, ethanol, acetic acid, and n-propanol. In some embodiments, the amount of ethanol and higher alcohols is at least 10 wt.% of the total In some embodiments, the amount of ethanol and higher alcohols is at least 7 wt.% of the total amount of liquid product mixture. In some embodiments, the amount of ethanol and higher alcohols is at least 5 wt.% of the total amount of liquid product mixture.
• the amount of ethanol and higher alcohols is at least 2 wt.% of the total amount of liquid product mixture. In some embodiments, the molar ratio of ethanol and higher alcohols to the total amount of methanol and n-propanol in the liquid product mixture is from about 1 :5 to about 1 : 10. In some embodiments, the amount of formic acid in the liquid product mixture is less than 10 ppm. In some embodiments, the amount of isopropanol in the liquid product mixture is less than 10 ppm.
• the liquid product mixture comprises hydrocarbons.
• the liquid product mixture comprises paraffins.
• paraffins refers to hydrocarbons which are preferably linear, but may include branched hydrocarbons. Exemplary paraffins have carbon numbers from 6-20, preferably from 9-16.
• liquid product mixture refers to products which are liquid at atmospheric pressure and temperature.
• the liquid product mixture comprises paraffins, olefins, and other hydrocarbons.
• the amount of paraffins is at least 50 wt.% of the total non-aqueous products. In some embodiments, the amount of paraffins is at least 10 wt.% of the total amount of liquid product mixture. In some embodiments, the amount of paraffins is at least 5 wt.% of the total amount of liquid product mixture. In some embodiments, the amount of paraffins is at least 2 wt.% of the total amount of liquid product mixture. In some embodiments, the molar ratio of paraffins to the total amount of carbon-containing products in the liquid product mixture is from about 1 :2 to about 1 : 10. In some embodiments, the amount of formic acid in the liquid product mixture is less than 1,000 ppm. In some embodiments, the amount of isopropanol in the liquid product mixture is less than 1,000 ppm.
• the method does not produce Cl alkanes or aldehydes such as formaldehyde or methane. In some embodiments, the method produces less than about 0.5 wt% formaldehyde or methane. In some embodiments, the method produces less than about 0.05 wt% formaldehyde or methane. In some embodiments, the method produces less than about 50 ppm formaldehyde or methane. In some embodiments, the method produces less than 5 ppm formaldehyde or methane.
• the GHSV of reactant gases and recycle gases introduced to the reactor is 10. In some embodiments, the GHSV of reactant gases and recycle gases introduced to the reactor is 100. In some embodiments, the GHSV of reactant gases and recycle gases introduced to the reactor is 500. In some embodiments, the GHSV of reactant gases and recycle gases introduced to the reactor is 1,000. In some embodiments, the GHSV of reactant gases and recycle gases introduced to the reactor is 2,000. In some embodiments, the GHSV of reactant gases and recycle gases introduced to the reactor is 5,000. In some embodiments, the GHSV of reactant gases and recycle gases introduced to the reactor is 10,000. In some embodiments, the GHSV of reactant gases and recycle gases introduced to the reactor is 20,000 or higher.
• the GHSV of reactant gases and recycle gases introduced to the reactor is from about 10 to about 20,000. In some embodiments, the GHSV of reactant gases and recycle gases introduced to the reactor is from about 10 to about 10,000. In some embodiments, the GHSV of reactant gases and recycle gases introduced to the reactor is from about 10 to about 5,000. In some embodiments, the GHSV of reactant gases and recycle gases introduced to the reactor is from about 10 to about 2,000. In some embodiments, the GHSV of reactant gases and recycle gases introduced to the reactor is from about 10 to about 1,000. In some embodiments, the GHSV of reactant gases and recycle gases introduced to the reactor is from about 10 to about 500. In some embodiments, the GHSV of reactant gases and recycle gases introduced to the reactor is from about 10 to about 100.
• the GHSV of reactant gases and recycle gases introduced to the reactor is less than about 10. In some embodiments, the GHSV of reactant gases and recycle gases introduced to the reactor is less than about 100. In some embodiments, the GHSV of reactant gases and recycle gases introduced to the reactor is less than about 500. In some embodiments, the GHSV of reactant gases and recycle gases introduced to the reactor is less than about 1,000. In some embodiments, the GHSV of reactant gases and recycle gases introduced to the reactor is less than about 2,000. In some embodiments, the GHSV of reactant gases and recycle gases introduced to the reactor is less than about 5,000. In some embodiments, the GHSV of reactant gases and recycle gases introduced to the reactor is less than about 10,000. In some embodiments, the GHSV of reactant gases and recycle gases introduced to the reactor is less than about 20,000.
• the GHSV of reactant gases and recycle gases introduced to the reactor is 100. In some embodiments, the GHSV of reactant gases and recycle gases introduced to the reactor is 500. In some embodiments, the GHSV of reactant gases and recycle gases introduced to the reactor is 1,000. In some embodiments, the GHSV of reactant gases and recycle gases introduced to the reactor is 2,000. In some embodiments, the GHSV of reactant gases and recycle gases introduced to the reactor is 5,000. In some embodiments, the GHSV of reactant gases and recycle gases introduced to the reactor is 10,000. In some embodiments, the GHSV of reactant gases and recycle gases introduced to the reactor is 20,000.
• the method comprises contacting the catalyst with the feed mixture for at least 8,000 hours. In some embodiments, the method comprises contacting the catalyst with the feed mixture for at least 96 hours. In some embodiments, the method comprises contacting the catalyst with the feed mixture for at least 24 hours.
• methods of the disclosure further comprise contacting the liquid product mixture and a first reduction gas with an isomerization catalyst at an isomerization temperature and an isomerization pressure to afford an isomerized product mixture comprising linear paraffins, branched paraffins, and/or naphthenes.
• the isomerized product mixture comprises: additional Ci-s hydrocarbons; additional C9-15 hydrocarbons including linear paraffins, branched paraffins, and naphthenes; and additional Ci6+ hydrocarbons.
• the numbers used to describe and claim certain embodiments of the disclosure are modified in some instances by the term “about.”
• the numerical parameters should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of some embodiments of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as practicable. The numerical values presented in some embodiments of the invention may contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements.
• the term “about” means within 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2, 1%, 0.5%, or 0.05% of a given value or range.
• Example 1 Elemental composition of exemplary cobalt copper zinc alumina catalyst.
• Example 2 Synthesis of exemplary cobalt copper zinc alumina catalyst by combined coprecipitation and wet impregnation.
• a first solution comprising zinc nitrate (1 molar equivalent), copper nitrate (3 molar equivalents), aluminum nitrate (1.4 molar equivalents), and a second solution comprising sodium carbonate (9.7 molar equivalents) are combined in a reactor.
• the resulting mixture is stirred rapidly and heated at 70-90 °C for 2 hours, then filtered.
• the resulting solid material is dried under air at 110 °C for 12 hours, and the resulting solid material is crushed, heated to 350 °C in air at a heating rate of 2 °C /min, and calcined at 350 °C for 6 h. After calcining, the resulting power is then further ground with a mortar and pestle.
• the powder is pelletized and a liquid comprised of Co(NO3)2 6H2O dissolved in water (8 wt% Co in the aqueous solution) is added to the pelletized catalyst by incipient wetness impregnation and heated, to result in the cobalt copper zinc alumina catalyst (CCZA).
• CCZA cobalt copper zinc alumina catalyst
• a first solution of ferric nitrate (1 molar equivalent), and a base solution comprising sodium carbonate (1.2 molar equivalents) are combined in a reactor at about 60 °C.
• the resulting mixture is stirred rapidly and heated at 70 °C to 90 °C for 2 hours, then filtered and dried.
• the resulting solid material is dried under air at 110 °C for 12 hours, and the resulting solid material is crushed, heated to 350 °C in air at a heating rate of 2 °C /min, and calcined at 350 °C for 6 h. After calcining, the resulting powder is further ground with a mortar and pestle.
• Example 4 Elemental composition of exemplary iron copper zinc catalyst with and without alumina.
• FCZK Iron copper zinc catalyst without alumina
• Example 5 CO2 reduction in the presence of an exemplary cobalt copper zinc catalyst.
• GHSV was approximately 2000 h' 1 ;
• Example 6 Catalytic reduction of CO2 to hydrocarbons using an iron copper zinc catalyst
• GHSV was approximately 5000 h' 1 ; CO2 conversion per pass about 20%;
• Paraffins are fed into an isomerization reactor loaded with a hydro-isomerization catalyst (Pt on beta-zeolite, 0.5 wt% Pt). The reaction is carried out at 750 psi and 250 °C, with a mole ratio of hydrogen over hydrocarbons set at 500, and a liquid weight hourly space velocity of 1.0 h' 1 .
• the paraffins are converted into a mixture of saturated n-paraffins and isoparaffins with a selective range of carbon chain number between Cs and Cis.

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