WO2024000370A1 - Catalyseurs au manganèse pour procédés de conversion inverse de gaz à l'eau - Google Patents

Catalyseurs au manganèse pour procédés de conversion inverse de gaz à l'eau Download PDF

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WO2024000370A1
WO2024000370A1 PCT/CN2022/102723 CN2022102723W WO2024000370A1 WO 2024000370 A1 WO2024000370 A1 WO 2024000370A1 CN 2022102723 W CN2022102723 W CN 2022102723W WO 2024000370 A1 WO2024000370 A1 WO 2024000370A1
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catalyst
oxide
support
range
manganese
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PCT/CN2022/102723
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English (en)
Inventor
Gareth ARMITAGE
John Glenn Sunley
Meiling GUO
Xuebin Liu
Ben DENNIS-SMITHER
Eric Doskocil
Ning Wang
James Paterson
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Bp P.L.C
Bp (China) Holdings Limited
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Priority to PCT/CN2022/102723 priority Critical patent/WO2024000370A1/fr
Priority to PCT/IB2023/056800 priority patent/WO2024003843A1/fr
Publication of WO2024000370A1 publication Critical patent/WO2024000370A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • C10K3/026—Increasing the carbon monoxide content, e.g. reverse water-gas shift [RWGS]
    • 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
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0242—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical
    • B01J8/025—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical in a cylindrical shaped bed
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0278—Feeding reactive fluids

Definitions

  • the present disclosure relates generally to reverse water-gas shift catalysts, methods of making the same, and methods for performing reverse water-gas shift reactions.
  • the reverse water-gas shift reaction is an advantageous route to obtain carbon monoxide from carbon dioxide for further chemical processing.
  • the rWGS converts carbon dioxide and hydrogen to carbon monoxide and water, as shown in Equation (1) .
  • the carbon monoxide and hydrogen so formed is a valuable feedstock for a number of chemical processes, for example, the well-known Fischer-Tropsch process, shown in Equation (2) .
  • acompeting reaction is the Sabatier reaction (Equation (3) ) , which decreases carbon monoxide yield in favor of methane production.
  • the strongly exothermic Sabatier reaction is thermodynamically favored over the endothermic rWGS reaction at lower reaction temperatures. As such, minimizing the methanation during rWGS, especially at low temperatures, can become a significant challenge.
  • the carbon monoxide product from rWGS can be hydrogenated to methane, as shown in Equation (4) .
  • the present disclosure provides for a supported reverse water-gas shift catalyst comprising:
  • a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, and zirconium oxide;
  • manganese present in an amount in the range of 0.5 to 20 wt%of the catalyst, based on the total weight of the catalyst.
  • the present disclosure provides for a method of making the catalyst as described herein, the method comprising:
  • a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, and zirconium oxide;
  • the present disclosure provides for a catalyst as described herein made by the method as described herein.
  • the present disclosure provides a method for performing a reverse water-gas shift reaction, the method comprising contacting at a temperature in the range of 250-800°C a catalyst as described herein with a feed stream comprising CO 2 and H 2 , to provide a product stream comprising CO and H 2 , the product stream having a lower concentration of CO 2 and a higher concentration of CO than the feed stream.
  • FIG. 1 is a schematic of the reverse water-gas shift reaction as described herein.
  • the reverse gas-water shift reaction reacts carbon dioxide with hydrogen to form carbon monoxide and water, and can be useful in providing a feedstock containing carbon monoxide and hydrogen--often called “synthesis gas” --for use in processes such as the Fischer-Tropsch process.
  • synthesis gas a feedstock containing carbon monoxide and hydrogen--often
  • the Sabatier reaction, carbon monoxide methanation, and carbon-producing side reactions can interfere with the rWGS reaction.
  • the Sabatier reaction and CO methanation are exothermic and favored at lower temperatures, while the rWGS and carbon-producing side reactions are endothermic and favored at higher temperatures. Accordingly, there remains a need for rWGS catalysts that can provide good performance in spite of these complicating factors.
  • the present inventors have provided supported reverse water-gas shift catalysts that include a metal oxide support and manganese, that can meet the requirements necessary for a commercially-useful rWGS process.
  • the present disclosure provides a supported reverse water-gas shift catalyst including a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, or a mixed oxide support including a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, and zirconium oxide; and manganese, present in an amount in the range of 0.5 to 20 wt%of the catalyst, based on the total weight of the catalyst.
  • the reverse water-gas shift catalysts of the present disclosure are supported catalysts.
  • the support makes up at least 80 wt%, e.g., at least 85 wt%, or 90 wt%of the catalyst on an oxide basis.
  • the support is a cerium oxide support.
  • a "cerium oxide” support is a support that presents at least a surface layer (e.g., 50 microns in thickness) that is at least 50 wt%cerium oxide, on an oxide basis.
  • at least a surface layer of the cerium oxide support includes at least 60 wt%cerium oxide, e.g., at least 70 wt% cerium oxide, or at least 80 wt%cerium oxide.
  • at least a surface layer of the cerium oxide support includes at least 90 wt%cerium oxide.
  • At least a surface layer of the cerium oxide support includes at least 95 wt%cerium oxide or at least 98 wt%cerium oxide.
  • the cerium oxide support contains cerium oxide substantially throughout, e.g., at least 50 wt%of the cerium oxide support is cerium oxide on an oxide basis.
  • the cerium oxide support includes at least 60 wt%cerium oxide, e.g., at least 70 wt%cerium oxide, or at least 80 wt%cerium oxide.
  • the cerium oxide support includes at least 90 wt%cerium oxide, e.g., at least 95 wt%cerium oxide, or at least 98 wt%cerium oxide.
  • the aluminum oxide support may further include additional metals or metal oxides.
  • the support is a titanium oxide support.
  • a "titanium oxide” support is a support that presents at least a surface layer (e.g., 50 microns in thickness) that is at least 50 wt%titanium oxide, on an oxide basis.
  • at least a surface layer of the titanium oxide support includes at least 60 wt%titanium oxide, e.g., at least 70 wt%titanium oxide, or at least 80 wt%titanium oxide.
  • at least a surface layer of the titanium oxide support includes at least 90 wt%titanium oxide.
  • At least a surface layer of the titanium oxide support includes at least 95 wt%titanium oxide or at least 98 wt%titanium oxide.
  • the titanium oxide support contains titanium oxide substantially throughout, e.g., at least 50 wt%of the titanium oxide support is titanium oxide on an oxide basis.
  • the titanium oxide support includes at least 60 wt%titanium oxide, e.g., at least 70 wt%titanium oxide, or at least 80 wt%titanium oxide.
  • the titanium oxide support includes at least 90 wt%titanium oxide, e.g., at least 95 wt%titanium oxide, or at least 98 wt%titanium oxide.
  • the aluminum oxide support may further include additional metals or metal oxides.
  • the support is an aluminum oxide support.
  • an "aluminum oxide” support is a support that presents at least a surface layer (e.g., 50 microns in thickness) that is at least 50 wt%aluminum oxide, on an oxide basis.
  • at least a surface layer of the aluminum oxide support includes at least 60 wt%aluminum oxide, e.g., at least 70 wt%aluminum oxide, or at least 80 wt%aluminum oxide.
  • at least a surface layer of the aluminum oxide support includes at least 90 wt%aluminum oxide.
  • At least a surface layer of the aluminum oxide support includes at least 95 wt%aluminum oxide or at least 98 wt%aluminum oxide.
  • the aluminum oxide support contains aluminum oxide substantially throughout, e.g., at least 50 wt%of the aluminum oxide support is aluminum oxide on an oxide basis.
  • the aluminum oxide support includes at least 60 wt%aluminum oxide, e.g., at least 70 wt%aluminum oxide, or at least 80 wt%aluminum oxide.
  • the aluminum oxide support includes at least 90 wt%aluminum oxide, e.g., at least 95 wt%aluminum oxide, or at least 98 wt%aluminum oxide. In some embodiments, the aluminum oxide support may further include additional metals or metal oxides.
  • the support is a zirconium oxide support.
  • a "zirconium oxide” support is a support that presents at least a surface layer (e.g., 50 microns in thickness) that is at least 50 wt%zirconium oxide, on an oxide basis.
  • at least a surface layer of the zirconium oxide support includes at least 60 wt%zirconium oxide, e.g., at least 70 wt%zirconium oxide, or at least 80 wt%zirconium oxide.
  • at least a surface layer of the zirconium oxide support includes at least 90 wt%zirconium oxide.
  • At least a surface layer of the zirconium oxide support includes at least 95 wt%zirconium oxide or at least 98 wt%zirconium oxide.
  • the zirconium oxide support contains zirconium oxide substantially throughout, e.g., at least 50 wt%of the zirconium oxide support is zirconium oxide on an oxide basis.
  • the zirconium oxide support includes at least 60 wt%zirconium oxide, e.g., at least 70 wt%zirconium oxide, or at least 80 wt%zirconium oxide.
  • the zirconium oxide support includes at least 90 wt%zirconium oxide, e.g., at least 95 wt%zirconium oxide, or at least 98 wt%zirconium oxide. In some embodiments, the zirconium oxide support may further include additional metals or metal oxides.
  • the support is a mixed oxide support.
  • the mixed oxide support is a mixture of two or more metal oxides, such as cerium oxide, titanium oxide, aluminum oxide, and zirconium oxide.
  • at least a surface layer of the support includes at least 50 wt%total of two or more of cerium oxide, titanium oxide, aluminum oxide, and zirconium oxide, on an oxide basis.
  • At least a surface layer of the mixed oxide support includes at least 60 wt%total, e.g., at least 70 wt%, or at least 80 wt%of two or more of cerium oxide, titanium oxide, aluminum oxide, and zirconium oxide. In some embodiments, at least a surface layer of the mixed oxide support includes at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt%of two or more cerium oxide, titanium oxide, aluminum oxide, and zirconium oxide.
  • the mixed oxide support contains the oxides substantially throughout, e.g., at least 50 wt%of the mixed oxide support is two or more of cerium oxide, titanium oxide, aluminum oxide, and zirconium oxide.
  • the mixed oxide support includes at least 60 wt%total, e.g., at least 70 wt%, or at least 80 wt%of two or more of cerium oxide, titanium oxide, aluminum oxide, and zirconium oxide.
  • the mixed oxide support includes at least 90 wt%total, e.g., at least 95 wt%, or at least 98 wt%of two or more of cerium oxide, titanium oxide, aluminum oxide, and zirconium oxide.
  • the mixed oxide support may further include additional metals or metal oxides.
  • cerium oxide, titanium oxide, aluminum oxide, and zirconium oxide can provide good performance in the absence of substantial amounts of other metals in the support.
  • the support does not include additional metals in a total amount of additional metals in excess of 2 wt%, e.g., in excess of 1 wt%or in excess of 0.5 wt%, on an oxide basis.
  • the support includes at least one additional metal.
  • the total amount of the at least one additional metal is in the range of 0.5-20 wt%, e.g., 1-20 wt%, or 2-20 wt%, or 0.5-15 wt%, or 1-15 wt%, or 2-15 wt%, or 0.5-10 wt%, or 1-10 wt%, or 2-10 wt%, or 0.5-5 wt%, or 1-5 wt%, on an oxide basis.
  • the pore volume is at least 0.05 mL/g, e.g., at least 0.1 mL/g. In various embodiments as otherwise described herein, the pore volume is at most 1.5 mL/g, e.g., at most 1 mL/g. In various embodiments of the present disclosure as described herein, the pore volume is in the range of 0.05-1.5 mL/g, e.g., 0.1 mL/g to 1 mL/g. Pore volumes are measured by mercury porosimetry, for example, as measured according to ASTM D4284-12.
  • the supported reverse water-gas shift catalysts of the disclosure also include manganese.
  • the present inventors have determined that inclusion of manganese in the catalyst can provide improved performance, as described in the Examples below.
  • the amount of manganese present is calculated as a weight percentage of manganese atoms in the catalyst based on the total weight of the catalyst, despite the form in which that manganese may be present.
  • the manganese may be present in the catalyst in a variety of forms; most commonly, manganese is principally present as metal oxide, metal, or a combination thereof.
  • manganese is present in the catalyst in an amount in the range of 0.5 to 20 wt%, based on total weight of the catalyst.
  • manganese is present in the catalyst in an amount in the range of 0.5 to 15 wt%, or 0.5 to 12 wt%, or 0.5 to 10 wt%, based on the total weight of the catalyst.
  • manganese is present in the catalyst in an amount in the range of 1 to 20 wt%, e.g., in the range of 1 to 15 wt%, or 1 to 12 wt%or 1 to 10 wt%, based on the total weight of the catalyst.
  • manganese is present in an amount in the range of 2 to 20 wt%, e.g., in the range of 2 to 15 wt%, or 2 to 12 wt%, or 2 to 10 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, manganese is present in an amount in the range of 4 to 20 wt%, e.g., in the range of 4 to 15 wt%, or 4 to 12 wt%, or 4 to 10 wt%, based on the total weight of the catalyst.
  • suitable reverse water-gas shift catalysts can be formed of one or more of cerium oxide, titanium oxide, aluminum oxide, and zirconium oxide as a support in combination with manganese included in/on the catalyst.
  • the amount of cerium, titanium, aluminum, zirconium, and manganese can be quantified on a metallic basis regardless of the form in which these metals may be present.
  • the amount of these metals can be calculated as a weight percentage based on the total weight of metals in the catalysts (i.e., on a metallic basis) , i.e., without the inclusion of oxygen or non-metallic counterions in the calculation.
  • the total amount of cerium, titanium, aluminum, zirconium, and manganese in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt%of the catalyst, on a metallic basis.
  • the total amount of cerium and manganese in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt%of the catalyst, on a metallic basis.
  • the total amount of titanium and manganese in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt%of the catalyst, on a metallic basis.
  • the total amount of aluminum and manganese in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt%of the catalyst, on a metallic basis.
  • the total amount of zirconium and manganese in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt%of the catalyst, on a metallic basis.
  • the supported catalyst includes manganese.
  • the manganese which will typically be principally present in metallic form and/or oxide form, can be disposed at a variety of different places on the support. For example, it can be found in pores of the support and on the outer surface of the support. Manganese may be found substantially throughout the support, e.g., as when a large volume of impregnation liquid is used, or only in a surface layer of the support, e.g., when impregnation liquid does not infiltrate into the entirety of the support, such as when using an incipient wetness technique.
  • the present inventors believe that the manganese acts to improve the catalytic activity of the support by reducing CO methanation that can occur over the typical reverse water-gas shift reaction temperature range, which impacts CO selectivity.
  • the present inventors believe that the improved activity can be attributed to the manganese interfacing with the support (e.g., cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, or a mixed oxide) .
  • the manganese will typically be provided in oxide form after catalyst preparation and during shipment and storage. As described below, the present inventors contemplate that is may be desirable to activate the catalyst be contacting it with a reductant, e.g., hydrogen gas, to convert a substantial fraction of such oxide to metallic form. However, the person of ordinary skill in the art will appreciate that the present disclosure contemplates the usefulness of a wide variety of manganese forms in its catalysts, as these can provide a promoting effect or can be conveniently transformed to forms that will.
  • a reductant e.g., hydrogen gas
  • the catalysts of the disclosure can be provided in many forms, depending especially on the particular form of the reactor system in which they are to be used, e.g., in a fixed bed or as a fluid bed.
  • the supports themselves can be provided as discrete bodies of material, e.g., as porous particles, pellets or shaped extrudates, with manganese provided thereon to provide the catalyst.
  • a catalyst of the disclosure can itself be formed as a layer on an underlying substrate.
  • the underlying substrate is not particularly limited. It can be formed of, e.g., a metal or metal oxide, and can itself be provided in a number of forms, such as particles, pellets, shaped extrudates, or monoliths.
  • a metal or metal oxide can itself be provided in a number of forms, such as particles, pellets, shaped extrudates, or monoliths.
  • other embodiments may be possible.
  • the method includes providing a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, or a mixed oxide support including a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, and zirconium oxide; contacting the support with one or more liquids each including one or more manganese-containing compounds dispersed in a solvent; allowing the solvent (s) to evaporate to provide a catalyst precursor; and calcining the catalyst precursor.
  • a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, or a mixed oxide support including a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, and zirconium oxide
  • contacting the support with one or more liquids each including one or more manganese-containing compounds dispersed in a solvent
  • allowing the solvent (s) to evaporate to provide a catalyst precursor and calcining the catalyst precursor.
  • contacting the support with the liquid includes adding the liquid in an amount about equal to (i.e., within 25%of, or within 10%of) the pore volume of the support. In other embodiments, contacting the support with the liquid includes adding the liquid in an amount greater than the pore volume of the support. For example, in some embodiments, the ratio of the amount of liquid to the amount of support on a mass basis is in the range of 0.75: 1 to 5: 1, e.g., in the range of 0.9: 1 to 3: 1. In some embodiments, contacting the support with the liquid provides a slurry.
  • allowing the solvent to evaporate is conducted at ambient temperature. In various embodiments, allowing the solvent to evaporate is conducted at an elevated temperature for a drying time.
  • the person of ordinary skill in the art would be able to select appropriate apparatuses or instruments to allow the solvent to evaporate, and such apparatuses or instruments are not particularly limited. Additionally, the person of ordinary skill in the art would understand that the elevated temperature that will allow the solvent to evaporate depends on the boiling point of the solvent. As such, the person of ordinary skill in the art would be able to select an appropriate elevated temperature.
  • the elevated temperature is in the range of 50-150°C, e.g., in the range of 50-120°C, or 50-100°C, or 100-150°C, or 100-120°C.
  • the drying time is in the range of 1 to 48 hours, e.g., in the range of 10 to 36 hours, or 12 to 24 hours. For example, in particular embodiments, the drying time is about 24 hours.
  • allowing the solvent to evaporate is conducted under vacuum and at an elevated temperature for a drying time, as described herein. In some embodiments, allowing the solvent to evaporate is conducted in a stirring drybath at an elevated temperature, for example, in the range of 30-100°C.
  • calcining the catalyst precursor is conducted in a furnace for a calcining time and at a calcining temperature.
  • the calcining time is in the range of 0.5 to 24 hours, or 0.5 to 15 hours, or 0.5 to 10 hours, or 0.5 to 5 hours.
  • the calcining temperature is in the range of 100-600°C, e.g., in the range of 120-500°C.
  • the method of making the catalyst as described herein includes contacting the support with one or more liquids each including one or more manganese-containing compounds dispersed in a solvent.
  • the manganese-containing compounds are not particularly limited and the person of ordinary skill in the art would be able to choose appropriate compounds that are soluble in the solvent.
  • the manganese-containing compounds may be selected from metal salts (e.g., nitrates and acetates) .
  • the solvent is also not particularly limited and the person of ordinary skill in the art would be able to choose an appropriate solvent that can be absorbed by the support.
  • the solvent is water.
  • these metal species are conveniently provided in the same liquid, so that only one step of contacting the support with liquid is required. However, other schemes are possible.
  • the present disclosure provides a catalyst as described herein made by the methods as described herein.
  • the method includes contacting at a temperature in the range of 250-800°C a catalyst as described herein with a feed stream that includes CO 2 and H 2 , to provide a product stream that includes CO and H 2 , the product stream having a lower concentration of CO 2 and a higher concentration of CO than the feed stream.
  • An example of such a method is shown schematically in FIG. 1.
  • the method 100 includes performing a reverse water-gas shift reaction by providing a feed stream 111 comprising H 2 and CO 2 , here, to a reaction zone, e.g., a reactor 110.
  • a reverse water-gas shift catalyst 113 as described herein is contacted at a temperature in the range of 250-800°C with the feed stream 111 to provide a product stream 112 comprising CO and H 2 .
  • the product stream has a lower concentration of CO 2 and a higher concentration of CO than the feed stream.
  • a “feed stream” is used to mean the total material input to a process step, regardless of whether provided in a single physical stream or multiple physical streams, and whether through a single inlet or multiple inlets.
  • H 2 and CO of the feed stream can be provided to the reverse water-gas shift catalyst in a single physical stream (e.g., in a single pipe to reactor 110) , or in multiple physical streams (e.g., separate inlets for CO and H 2 , or one inlet for fresh CO and H2 and another for recycled CO and/or H2) .
  • a “product stream” is used to mean the total material output from a process step, regardless of whether provided in a single physical stream or multiple physical streams, and whether through a single outlet or multiple outlets.
  • the reverse water-gas shift reaction has a CO selectivity of at least 95%, e.g., or at least 96%.
  • a “selectivity” for a given reaction product is the molar fraction of the feed (here, CO 2 ) that is converted to the product (for “CO selectivity, ” CO) .
  • the present inventors have determined that the present catalysts, even when operating at lower temperatures than many conventional reverse water-gas shift catalysts, can provide excellent selectivity for CO, despite the potential for competition by the Sabatier reaction and the methanation of CO.
  • the reverse water-gas shift reaction has a CO selectivity of at least 98%, e.g., or at least 99%.
  • the catalysts described herein can be operated to provide carbon monoxide with only a very minor degree of methane formation.
  • the reverse water-gas shift reaction has a methane selectivity of no more than 5%, e.g., no more than 4%.
  • the reverse water-gas shift reaction has a methane selectivity of no more than 2%, e.g., no more than 1%.
  • the reverse water-gas shift reaction has a methane selectivity of no more than 0.5%, e.g., no more than 0.2%.
  • the catalysts described here can provide desirably high CO selectivity and desirably low methane selectivity at commercially relevant conversion rates.
  • a “conversion” is a molar fraction of a feed that is reacted (be it to desirable products or undesirable species) .
  • the reverse water-gas shift reaction has a CO 2 conversion of at least 5%, e.g., at least 10%, or 20%.
  • the reverse water-gas shift reaction has a CO 2 conversion of at least 30%, e.g., at least 40%, or 50%, or 60%.
  • the reverse water-gas shift reaction has a CO 2 conversion of no more than 80%, e.g., no more than 70%.
  • the reverse water-gas shift reaction has a CO 2 conversion of no more than 65%, e.g., no more than 60%.
  • the CO 2 conversion is in the range of 10-80%, e.g., 10-70%, or 10-60%, or 10-65%, or 20-80%, or 20-70%, or 20-60%, or 20-65%, or 30-80%, or 30-70%, or 30-60%, or 30-65%, or 40-80%, or 40-70%, or 40-60%, or 40-65%.
  • the processes described herein can be performed at temperatures that are lower than temperatures used in many conventional reverse water-gas shift processes.
  • various processes of the disclosure can be performed in a temperature range of 250-800°C.
  • the method for performing the reverse water-gas shift reaction is conducted at a temperature in the range of 250-750°C, or 250-700°C, or 250-650°C, or 250-600°C.
  • the method for performing the reverse water-gas shift reaction is conducted at a temperature in the range of 300-800°C, e.g., in the range of 300-750°C, or 300-700°C, or 300-650°C, or 300-600°C.
  • the method for performing the reverse water-gas shift reaction is conducted at a temperature in the range of 350-800°C, e.g., in the range of 350-750°C, or 350-700°C, or 350-650°C, or 350-600°C.
  • the method for performing the reverse water-gas shift reaction is conducted at a temperature in the range of 400-800°C, e.g., in the range of 400-750°C, or 400-700°C, or 400-650°C, or 400-600°C.
  • the method for performing the reverse water-gas shift reaction is conducted at a temperature in the range of 450-800°C, e.g., in the range of 450-750°C, or 450-700°C, or 450-650°C, or 450-600°C. In some embodiments, the method for performing the reverse water-gas shift reaction is conducted at a temperature in the range of 500-800°C, e.g., in the range of 500-750°C, or 500-700°C, or 500-650°C, or 500-600°C.
  • the method for performing the reverse water-gas shift reaction is conducted at a temperature in the range of 550-800°C, e.g., in the range of 550-750°C, or 550-700°C, or 550-650°C, or 550-600°C.
  • the reverse water-gas shift reaction is conducted at a temperature in the range of 200-500°C, e.g., 200-450°C, or 200-400°C, or 200-350°C, or 250-500°C, or 250-450°C, or 250-400°C, or 250-350°C.
  • 200-500°C e.g., 200-450°C, or 200-400°C
  • 200-350°C e.g., 200-450°C, or 200-400°C, or 200-350°C, or 250-500°C, or 250-450°C, or 250-400°C, or 250-350°C.
  • the feed stream includes CO 2 and H 2 .
  • the present inventors have recognized that both of these can come from renewable or otherwise environmentally responsible sources.
  • at least part of the H 2 can be so-called “green” hydrogen, e.g., produced from the electrolysis of water operated using renewable electricity (such as wind, solar, or hydroelectric power) .
  • at least part of the H 2 may be from a so-called “blue” source, e.g., from a natural gas reforming process with carbon capture.
  • a blue e.g., from a natural gas reforming process with carbon capture.
  • other sources of hydrogen can be used in part or in full.
  • At least a portion of the H 2 of the feed stream is grey hydrogen, black hydrogen, brown hydrogen, pink hydrogen, turquoise hydrogen, yellow hydrogen, and/or white hydrogen.
  • CO 2 can be captured from the environment generally, or more directly from processes that form CO 2 (especially in difficult-to-abate sectors) , making a product that is later made from the CO at least carbon-neutral.
  • at least part of the CO 2 is from direct air capture, or from a manufacturing plant such as a bioethanol plant (e.g., CO 2 produced fermentation) , a steel plant, or a cement plant.
  • the rWGS reaction can be not only carbon neutral, but in some cases a net consumer of carbon dioxide.
  • the feed stream contains both H 2 and CO 2 (e.g., provided to a reaction zone in a single physical stream or multiple physical streams) .
  • the feed stream includes all feeds to the process, regardless of whether provided as a mixture of gases or as gases provided individually to a reaction zone.
  • the molar ratio of H 2 to CO 2 in the feed stream is at least 0.1: 1, e.g., at least 0.5: 1.
  • the molar ratio of H 2 to CO 2 in the feed stream is at least 0.9: 1, e.g., at 1: 1 or least 1.5: 1.
  • the molar ratio of H 2 to CO 2 in the feed stream is at least 2: 1, e.g., at least 2.5: 1. In some embodiments, the molar ratio of H 2 to CO 2 in the feed stream is no more than 100: 1, e.g., no more than 75: 1, or 50: 1. In some embodiments, the molar ratio of H 2 to CO 2 in the feed stream is no more than 20: 1, e.g., no more than 15: 1, or 10: 1. For example, in some embodiments, the molar ratio of H 2 to CO 2 in the feed stream is in the range of 0.5: 1 to 10: 1.
  • the feed stream further comprises CO.
  • the feed stream further comprises one or more inert gases.
  • the feed stream further comprises nitrogen and/or methane.
  • the processes described herein can be performed at a variety of pressures, as would be appreciated by the person of ordinary skill in the art.
  • the method for performing the reverse water-gas shift reaction is conducted at a pressure in the range of 1to 100 barg.
  • the method is conducted at a pressure in the range of 1 to 70 barg, or 1 to 50 barg, or 1 to 40 barg, or 1 to 35 barg, or 5 to 70 barg, or 5 to 50 barg, or 5 to 40 barg, or 5 to 35 barg, or 10 to 70 barg, 10 to 50 barg, or 10 to 40 barg, or 10 to 35 barg, or 20 to 70 barg, 20 to 50 barg, or 20 to 40 barg, or 20 to 35 barg, or 25 to 70 barg, 25 to 50 barg, or 25 to 40 barg, or 25 to 35 barg.
  • the processes described herein can be performed at a variety of GHSV (gas hourly space velocity) , as would be appreciated by the person of ordinary skill in the art.
  • GHSV gas hourly space velocity
  • the GHSV for performing the reverse water-gas shift reaction is not particularly limited.
  • the method for performing the reverse water-gas shift reaction is conducted at a GHSV in the range of 1,000 to 2,000,000 h -1 .
  • the method for performing the reverse water-gas shift reaction is conducted at a GHSV in the range of 1,000 to 1,200,000 h -1 , or 1,000 to 500,000 h -1 , or 1,000 to 100,000 h -1 , or 5,000 to 1,200,000 h -1 , or 5,000 to 500,000 h -1 , or 5,000 to 100,000 h -1 , or 10,000 to 1,200,000 h -1 , or 10,000 to 500,000 h -1 , or 10,000 to 100,000 h -1 .
  • the method for performing the reverse water-gas shift reaction is conducted at a GHSV in the range of 1,000 to 50,000 h -1 , or 2,000 to 50,000 h -1 , or 5,000 to 50,000 h -1 , or 10,000 to 50,000, or 1,000 to 40,000 h -1 , or 2,000 to 40,000 h -1 , or 5,000 to 40,000 h -1 , or 10,000 to 40,000 h -1 , or 1,000 to 30,000 h -1 , or 2,000 to 30,000 h -1 , or 5,000 to 30,000 h -1 , or 10,000 to 30,000 h -1 .
  • the method comprises activating the rWGS catalyst prior to conacting the catalyst with the feed stream.
  • activating the catalyst comprises contacting the catalyst with a reducing stream comprising a reductive gas, e.g., hydrogen.
  • the reducing stream comprises hydrogen in an amount of at least 25 mol%, e.g., at least 50 mol%, or 75 mol%, or 90 mol%. The person of ordinary skill in the art will determine suitable conditions for reductive activation of the rWGS catalyst.
  • activating the catalyst is conducted at a temperature in the range of 200°C to 800°C.
  • activating the catalyst is conducted at a temperature in the range of 250°C to 800°C, or 300°C to 800°C, or 200°C to 700°C, or 250°C to 800°C, or 300°C to 700°C.
  • the present inventors have found that contacting the rWGS catalysts as described herein with a feed stream can provide a product stream with advantageously high CO selectivity and low methane selectivity.
  • the amount of CO in the product stream can be further controlled by the rWGS reaction conditions, as described above.
  • the methods for performing the rWGS reaction as described herein provide a product stream comprising H 2 and CO, with the product stream having a lower concentration of CO 2 and a higher concentration of CO than the feed stream, as is consistent with the degrees of conversion described herein.
  • the product stream includes no more than 95 mol%CO 2 , or no more than 90 mol%CO 2 .
  • the product stream includes no more than 85 mol%CO 2 , or no more than 80 mol%CO 2 . In other examples, the product stream includes no more than 75 mol%, or no more than 70 mol%CO 2 .
  • the present inventors have determined that it can be desirable to perform the processes at intermediate degrees of conversion to provide desirably high CO selectivities and desirably low methane selectivities. Accordingly, in various embodiments as otherwise described herein, the product stream includes an amount of CO 2 together with the CO.
  • the product stream further comprises one or more inert gases. These inert gases may be included from the feed stream or provided from a source other than the feed stream.
  • the product stream further comprises nitrogen and/or methane.
  • the product stream can include H 2 in combination with CO, in a variety of ratios.
  • the ratio of H 2 : CO in the product stream is in the range of 0.1: 1 to 100: 1 (e.g., in the range of 0.1: 1 to 50: 1, or 0.1: 1 to 25: 1, or 0.1: 1 to 10: 1, or 0.1: 1 to 5: 1, or 1: 1 to 100: 1, or 1: 1 to 50: 1, or 1: 1 to 25: 1, or 1: 1 to 10: 1, or 1: 1 to 5: 1) .
  • the product stream may include H 2 , CO, and CO 2 and other components in various amounts. Components of the product stream may be separated and used for various purposes in the rWGS process.
  • the method further comprises separating the product stream to recycle at least a portion (e.g., at least 5 mol%, at least 10 mol%, at least 25 mol%, at least 50 mol%, at least 75 mol%, or at least 90 mol%) of one or more components of the product stream to the feed stream.
  • the method can include recycling at least a portion (e.g., at least 5 mol%, at least 10 mol%, at least 25 mol%, at least 50 mol%, at least 75 mol%, or at least 90 mol%) of the CO 2 of the product stream to the feed stream.
  • the product stream may also include H 2 ; in some embodiments, the method further includes recycling at least a portion of H 2 of the product stream (e.g., at least 5 mol%, at least 10 mol%, at least 25 mol%, at least 50 mol%, at least 75 mol%, or at least 90 mol%) to the feed stream.
  • H 2 of the product stream e.g., at least 5 mol%, at least 10 mol%, at least 25 mol%, at least 50 mol%, at least 75 mol%, or at least 90 mol%
  • Such recycling is shown in the process 100 of FIG. 1.
  • the process 100 includes separating from the product stream 112 at least a portion of CO 2 (stream 114) to recycle to the feed stream 111.
  • the process 100 includes separating from the product stream 112 at least a portion of H 2 (stream 115) to recycle to the product stream 111. While stream 115 is depicted as entering reactor 110 through a different inlet than the rest of the feed stream 111, it is considered to be part of the feed stream, as it is part of the material input to the process step.
  • the product stream comprises one or more light hydrocarbons.
  • the product stream may include one or more of methane, ethane, propane, or combinations thereof.
  • such light hydrocarbons may be inert in further processing of the product stream and so may be acceptable at higher amounts.
  • the person of ordinary skill in the art would be able to select appropriate reaction conditions (e.g., temperature, pressure, feed stream composition) to provide a product stream that includes methane at a desired amount.
  • the product stream includes no more than 20 mol%methane or no more than 15 mol%.
  • the catalysts of the disclosure can provide very low methane selectivity.
  • the product stream includes no more than 10 mol%methane.
  • the product stream includes no more than 5 mol%, or 1 mol%, or 0.5 mol%, or no more than 0.1 mol%methane.
  • the light hydrocarbons of the product stream can be separated and used for other purposes.
  • the method further includes separating at least a portion of one or more light hydrocarbons from the product stream to provide a light hydrocarbon stream.
  • at least a portion of one or more light hydrocarbons are separated from the product stream 112 to provide a light hydrocarbon stream 116.
  • the light hydrocarbon stream for example, can be used to provide other products, can be partially oxidized to form CO, can be steam reformed to provide hydrogen, and/or can be burned to provide heat or other energy (e.g., electricity for electrolysis) for use in the rWGS method or otherwise.
  • the present inventors performed modelling of various equilibrium conditions of the reverse water-gas shift reaction.
  • the predicted carbon dioxide conversion and product composition of the rWGS reaction (Equation 1) in competition with the Sabatier reaction (Equation 3) and the CO methanation reaction (Equation 4) was calculated over the temperature range of 400-800°C, based on thermodynamic equilibrium. From the modeling, the carbon monoxide selectivity increased at temperatures greater than 600°C, while methane selectivity decreased at higher temperatures.
  • a solution of manganese acetate tetrahydrate (purity 99.9%, Fisher Chemicals) was prepared in deionized water.
  • the solution of manganese acetate tetrahydrate solution was added to the support powder.
  • the amount of support added is based on the amount of the water on a mass basis so that the ratio of water: support is 3: 1.
  • the slurry was then stirred at room temperature for 4 hours. Excess water was then evaporated using a stirring drybath at a temperature of 60°C.
  • the resulting catalyst precursor powder was then dried for 24 hours at 90°C in a drying oven.
  • That catalyst precursor powder was then subjected to calcination by evenly spreading out the powder in a crucible.
  • the crucible is placed in a calcination furnace and the temperature is increased from ambient to 120°C at a rate of 10°C per minute.
  • the temperature was then held at 120°C for 1 hour, and then increased from 120°C to 500°C at a rate of 2°C per minute.
  • the temperature was held at 500°C for 4 hours, and then cooled to ambient temperature.
  • the resulting catalysts were then tested for its viability for reverse water-gas shift reactions.
  • Catalysts prepared as explained in Example 2 were then tested for their catalytic performance for reverse water-gas shift reactions.
  • the catalysts tested were ceria supported catalysts with manganese in either 1 wt%, 5 wt%, or 10 wt%.
  • 20 ⁇ L of the catalyst diluted with SiC F100 to provide a ratio of 1: 10 was loaded into a 3mm ID ceramic tube reactor, resulting in a 0.22 mL catalyst bed with a zone height of 31.1 mm.
  • the catalysts Prior to performing the rWGS reaction, the catalysts were activated at 590°C for 5 hours in a 97%hydrogen and 3%argon atmosphere.
  • the catalysts were contacted at a temperature of 600°C with a feed stream including H 2 and CO 2 at a ratio of 2: 1.
  • the total pressure and GHSV were kept at 30 barg and 1,200,000 h -1 , respectively, to conduct the rWGS reaction.
  • the catalytic performance was analyzed by detecting the gas composition of the reactor outlet feed using a multi-detector gas chromatograph.
  • the catalytic performance of these catalysts are shown in Table 2.
  • Table 2 and Tables 3 and 4 below the amount of manganese present in the catalyst is shown in parenthesis. These numbers are in weight percent and based on the total weight of the catalyst.
  • CeO 2 Mn (1) corresponds to a catalyst with 1 wt%Mn and 99 wt%CeO 2 .
  • the catalysts including manganese demonstrate very high CO selectivity, although the CO 2 conversion is low at the conditions tested.
  • the reasonably high selectivity of CO demonstrated at a total pressure of 30 barg with a feed containing hydrogen and carbon dioxide at a mole ratio of 2: 1 at 600°C provides an effluent stream suitable for integration with other processes.
  • Table 3 show that bare ceria (CeO 2 ) is active and highly selective for rWGS with a CO selectivity of greater than 99%.
  • the activity of the ceria can be improved without compromising CO selectivity by including 5 wt%manganese.
  • the addition of 5 wt%manganese to the ceria results in an overall increase in CO 2 conversion.
  • the CO selectivity remains robust (>99%) for both ceria and manganese on ceria catalysts at temperatures between 500-760°C.
  • the impact of the support on catalyst performance was also evaluated by evaluating manganese supported catalysts on a variety of catalytic supports.
  • the catalysts contained 5 wt%manganese. As with the previous examples, these catalysts were prepared by the method as described in Example 2. The reactor setup and catalyst activation as described in Example 3 were also used here. Then, these catalysts were contacted at a temperature of 750°C with a feed stream of H 2 and CO 2 , present at a mole ratio of 3: 1. The reaction was conducted at a pressure of 10 barg and a GHSV of 100,000 h - 1 . The catalytic performance was analyzed by detecting the gas composition of the reactor outlet feed using a multi-detector gas chromatograph. The results are shown in Table 4.
  • Table 4 shows that the manganese effect is still viable on a range of metal oxide supports.
  • the addition of 5 wt%manganese to a variety of metal oxide supports showed high CO selectivity at a high pressure and a high H 2 : CO 2 ratio.
  • the alumina supported manganese catalyst showed the highest CO selectivity and the ceria supported manganese catalyst showed the highest activity and stability.
  • a supported reverse water-gas shift catalyst comprising:
  • a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, and zirconium oxide;
  • manganese present in an amount in the range of 0.5 to 20 wt%of the catalyst, based on the total weight of the catalyst.
  • Embodiment 2 The catalyst of embodiment 1, wherein the support makes up at least 80 wt% (e.g., at least or 85 wt%, or 90 wt%) of the catalyst, on an oxide basis.
  • Embodiment 3 The catalyst of embodiment 1 or embodiment 2, wherein the support is a cerium oxide support.
  • Embodiment 4 The catalyst of embodiment 3, wherein at least a surface layer of the cerium oxide support comprises at least 60 wt%cerium oxide, e.g., at least 70 wt%cerium oxide or at least 80 wt%cerium oxide, on an oxide basis.
  • Embodiment 5 The catalyst of embodiment 3, wherein at least a surface layer of the cerium oxide support comprises at least 90 wt%cerium oxide, e.g., at least 95 wt%cerium oxide, or at least 98 wt%cerium oxide, on an oxide basis.
  • Embodiment 6 The catalyst of any of embodiments 3-5, wherein the cerium oxide support comprises at least 50 wt%cerium oxide, e.g., at least 60 wt%cerium oxide, or at least 70 wt%cerium oxide, or at least 80 wt%cerium oxide, on an oxide basis.
  • the cerium oxide support comprises at least 50 wt%cerium oxide, e.g., at least 60 wt%cerium oxide, or at least 70 wt%cerium oxide, or at least 80 wt%cerium oxide, on an oxide basis.
  • Embodiment 7 The catalyst of any of embodiments 3-5, wherein the cerium oxide support comprises at least 90 wt%cerium oxide, e.g., at least 95 wt%cerium oxide, or at least 98 wt%cerium oxide, on an oxide basis.
  • Embodiment 8 The catalyst of embodiment 1 or embodiment 2, wherein the support is a titanium oxide support.
  • Embodiment 9 The catalyst of embodiment 8, wherein at least a surface layer of the titanium oxide support comprises at least 60 wt%titanium oxide, e.g., at least 70 wt%titanium oxide or at least 80 wt%titanium oxide, on an oxide basis.
  • Embodiment 10 The catalyst of embodiment 8, wherein at least a surface layer of the titanium oxide support comprises at least 90 wt%titanium oxide, e.g., at least 95 wt%titanium oxide, or at least 98 wt%titanium oxide, on an oxide basis.
  • Embodiment 11 The catalyst of any of embodiments 8-10, wherein the titanium oxide support comprises at least 50 wt%titanium oxide, e.g., at least 60 wt%titanium oxide, or at least 70 wt%titanium oxide, or at least 80 wt%titanium oxide, on an oxide basis.
  • the titanium oxide support comprises at least 50 wt%titanium oxide, e.g., at least 60 wt%titanium oxide, or at least 70 wt%titanium oxide, or at least 80 wt%titanium oxide, on an oxide basis.
  • Embodiment 12 The catalyst of any of embodiments 8-10, wherein the titanium oxide support comprises at least 90 wt%titanium oxide, e.g., at least 95 wt%titanium oxide, or at least 98 wt%titanium oxide, on an oxide basis.
  • Embodiment 13 The catalyst of embodiment 1 or embodiment 2, wherein the support is an aluminum oxide support.
  • Embodiment 14 The catalyst of embodiment 13, wherein at least a surface layer of the aluminum oxide support comprises at least 60 wt%aluminum oxide, e.g., at least 70 wt%aluminum oxide or at least 80 wt%aluminum oxide, on an oxide basis.
  • Embodiment 15 The catalyst of embodiment 13, wherein at least a surface layer of the aluminum oxide support comprises at least 90 wt%aluminum oxide, e.g., at least 95 wt%aluminum oxide, or at least 98 wt%aluminum oxide, on an oxide basis.
  • Embodiment 16 The catalyst of any of embodiments 13-15, wherein the aluminum oxide support comprises at least 50 wt%aluminum oxide, e.g., at least 60 wt%aluminum oxide, or at least 70 wt%aluminum oxide, or at least 80 wt%aluminum oxide, on an oxide basis.
  • the aluminum oxide support comprises at least 50 wt%aluminum oxide, e.g., at least 60 wt%aluminum oxide, or at least 70 wt%aluminum oxide, or at least 80 wt%aluminum oxide, on an oxide basis.
  • Embodiment 17 The catalyst of any of embodiments 13-15, wherein the aluminum oxide support comprises at least 90 wt%aluminum oxide, e.g., at least 95 wt%aluminum oxide, or at least 98 wt%aluminum oxide, on an oxide basis.
  • the aluminum oxide support comprises at least 90 wt%aluminum oxide, e.g., at least 95 wt%aluminum oxide, or at least 98 wt%aluminum oxide, on an oxide basis.
  • Embodiment 18 The catalyst of embodiment 1 or embodiment 2, wherein the support is a zirconium oxide support.
  • Embodiment 19 The catalyst of embodiment 18, wherein at least a surface layer of the zirconium oxide support comprises at least 60 wt%zirconium oxide, e.g., at least 70 wt%zirconium oxide or at least 80 wt%zirconium oxide, on an oxide basis.
  • Embodiment 20 The catalyst of embodiment 18, wherein at least a surface layer of the zirconium oxide support comprises at least 90 wt%zirconium oxide, e.g., at least 95 wt%zirconium oxide, or at least 98 wt%zirconium oxide, on an oxide basis.
  • Embodiment 21 The catalyst of any of embodiments 18-20, wherein the zirconium oxide support comprises at least 50 wt%zirconium oxide, e.g., at least 60 wt%zirconium oxide, or at least 70 wt%zirconium oxide, or at least 80 wt%zirconium oxide, on an oxide basis.
  • the zirconium oxide support comprises at least 50 wt%zirconium oxide, e.g., at least 60 wt%zirconium oxide, or at least 70 wt%zirconium oxide, or at least 80 wt%zirconium oxide, on an oxide basis.
  • Embodiment 22 The catalyst of any of embodiments 18-21, wherein the zirconium oxide support comprises at least 90 wt%zirconium oxide, e.g., at least 95 wt%zirconium oxide, or at least 98 wt%zirconium oxide, on an oxide basis.
  • the zirconium oxide support comprises at least 90 wt%zirconium oxide, e.g., at least 95 wt%zirconium oxide, or at least 98 wt%zirconium oxide, on an oxide basis.
  • Embodiment 23 The catalyst of embodiment 1 or embodiment 2, wherein the support is a mixed oxide support having at least a surface layer comprising at least 50 wt%of two or more of cerium oxide, titanium oxide, aluminum oxide, and zirconium oxide, on an oxide basis.
  • Embodiment 24 The catalyst of any of embodiments 1-23, wherein the support does not include additional metal in a total amount of additional metals in excess of 2 wt%, e.g., in excess of 1 wt%or in excess of 0.5 wt%, on an oxide basis.
  • Embodiment 25 The catalyst of any of embodiments 1-23, wherein the support includes at least one additional metal.
  • Embodiment 26 The catalyst of embodiment 25, wherein the total amount of the at least one additional metal is in the range of 0.5-20 wt%, e.g., 1-20 wt%, or 2-20 wt%, or 0.5-15 wt%, or 1-15 wt%, or 2-15 wt%, or 0.5-10 wt%, or 1-10 wt%, or 2-10 wt%, or 0.5-5 wt%, or 1-5 wt%, on an oxide basis.
  • 0.5-20 wt% e.g., 1-20 wt%, or 2-20 wt%, or 0.5-15 wt%, or 1-15 wt%, or 2-15 wt%, or 0.5-10 wt%, or 1-10 wt%, or 2-10 wt%, or 0.5-5 wt%, or 1-5 wt%, on an oxide basis.
  • Embodiment 27 The catalyst of any of embodiments 1-26, wherein the support has a pore volume of at least 0.05 mL/g.
  • Embodiment 28 The catalyst of any of embodiments 1-27, wherein the support has a pore volume of at most 1.5 mL/g.
  • Embodiment 29 The catalyst of any of embodiments 1-28, wherein the support has a pore volume in the range of 0.05-1.5 mL/g.
  • Embodiment 30 The catalyst of any of embodiments 1-29, wherein manganese is present in the catalyst in an amount in the range of 0.5 to 15 wt%, e.g., in the range of 0.5 to 12 wt%or 0.5 to 10 wt%, based on the total weight of the catalyst.
  • Embodiment 31 The catalyst of any of embodiments 1-29, wherein manganese is present in the catalyst in an amount in the range of 1 to 20 wt%, e.g., in the range of 1 to15 wt%, or 1 to 12 wt%, or 1 to 10 wt%, based on the total weight of the catalyst.
  • Embodiment 32 The catalyst of any of embodiments 1-29, wherein manganese is present in the catalyst in an amount in the range of 2 to 20 wt%, e.g., in the range of 2 to15 wt%, or 2 to 12 wt%, or 2 to 10 wt%, based on the total weight of the catalyst.
  • Embodiment 33 The catalyst of any of embodiments 1-29, wherein manganese is present in the catalyst in an amount in the range of 4 to 20 wt%, e.g., in the range of 4 to 15 wt%, or 4 to 12 wt%, or 4 to 10 wt%, based on the total weight of the catalyst.
  • Embodiment 34 The catalyst of any of embodiments 1-33, wherein the total amount of cerium, titanium, aluminum, zirconium, and manganese in the catalyst is at least 90 wt%, e.g., at least 95 wt%or at least 98 wt%of the catalyst, on a metallic basis.
  • Embodiment 35 A method for making the catalyst of any of embodiments 1-34, the method comprising:
  • a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, and zirconium oxide;
  • Embodiment 36 The method of embodiment 35, wherein contacting the support with the liquid comprises adding the liquid in an amount equal to the pore volume of the support.
  • Embodiment 37 The method of embodiment 35, wherein contacting the support with the liquid comprises adding the liquid in an amount greater than the pore volume of the support.
  • Embodiment 38 The method of any of embodiments 35-37, wherein ratio of the amount liquid to the amount of support on a mass basis is in the range of 1: 1 to 5: 1 (e.g., in the range of 1: 1 to 3: 1) .
  • Embodiment 39 The method of any of embodiments 35-38, wherein contacting the support with the liquid provides a slurry.
  • Embodiment 40 The method of any of embodiments 35-39, wherein allowing the solvent to evaporate is conducted at ambient temperature.
  • Embodiment 41 The method of embodiments 35-39, wherein allowing the solvent to evaporate is conducted at an elevated temperature (e.g., in the range of 50-150°C) for a drying time (e.g., 24 hours) .
  • an elevated temperature e.g., in the range of 50-150°C
  • a drying time e.g., 24 hours
  • Embodiment 42 The method of embodiments 35-39, wherein allowing the solvent to evaporate is conducted under vacuum and at an elevated temperature (e.g., in the range of 50-150°C) for a drying time (e.g., 24 hours) .
  • an elevated temperature e.g., in the range of 50-150°C
  • a drying time e.g., 24 hours
  • Embodiment 43 The method of any of embodiments 35-39, wherein allowing the solvent to evaporate is conducted in a stirring drybath at an elevated temperature (e.g., in the range of 30-100°C) .
  • an elevated temperature e.g., in the range of 30-100°C
  • Embodiment 44 The method of any of embodiments 35-43, wherein calcining the catalyst precursor is conducted for a calcining time in the range of 0.5 to 24 hours (e.g., 0.5 to 15 hours, or 0.5 to 10 hours, or 0.5 to 5 hours) .
  • Embodiment 45 The method of any of embodiments 35-44, wherein calcining the catalyst precursor is conducted for a calcining is in the range of 100-600°C (e.g., in the range of 120-500°C) .
  • Embodiment 46 The catalyst of any of embodiments 1-34, made by a method according to embodiments 35-45.
  • Embodiment 47 A method for performing a reverse water-gas shift reaction, the method comprising:
  • Embodiment 48 The method of embodiment 47, wherein the reverse water-gas shift reaction has a CO selectivity of at least 95%, e.g., of at least 96%.
  • Embodiment 49 The method of embodiment 47, wherein the reverse water-gas shift reaction has a CO selectivity of at least 98%, e.g., of at least 99%.
  • Embodiment 50 The method of any of embodiments 47-49, wherein the reverse water-gas shift reaction has a methane selectivity of no more than 5%, e.g., no more than 4%.
  • Embodiment 51 The method of any of embodiments 47-49, wherein the reverse water-gas shift reaction has a methane selectivity of no more than 2%, e.g., no more than 1%.
  • Embodiment 52 The method of any of embodiments 47-49, wherein the reverse water-gas shift reaction has a methane selectivity of no more than 0.5%, e.g., no more than 0.2%.
  • Embodiment 53 The method of any of embodiments 47-52, having a CO 2 conversion of at least 5%, e.g., at least 10%, or 20%.
  • Embodiment 54 The method of any of embodiments 47-52, having a CO 2 conversion of at least 30%, e.g., at least 40%.
  • Embodiment 55 The method of any of embodiments 47-54, having a CO 2 conversion of no more than 80%, e.g., no more than 70%.
  • Embodiment 56 The method of any of embodiments 47-54, having a CO 2 conversion of no more than 65%, e.g., no more than 60%.
  • Embodiment 57 The method of any of embodiments 47-56, conducted at a temperature in the range of 250-750°C, e.g., in the range of 250-700°C, or 250-650°C, or 250-600°C.
  • Embodiment 58 The method of any of embodiments 47-56, conducted at a temperature in the range of 300-800°C, e.g., in the range of 300-750°C, or 300-700°C, or 300-650°C, or 300-600°C.
  • Embodiment 59 The method of any of embodiments 47-56, conducted at a temperature in the range of 350-800°C, e.g., in the range of 350-750°C, or 350-700°C, or 350-650°C, or 350-600°C.
  • Embodiment 60 The method of any of embodiments 47-56, conducted at a temperature in the range of 400-800°C, e.g., in the range of 400-750°C, or 400-700°C, or 400-650°C, or 400-600°C.
  • Embodiment 61 The method of any of embodiments 47-56, conducted at a temperature in the range of 450-800°C, e.g., in the range of 450-750°C, or 450-700°C, or 450-650°C, or 450-600°C.
  • Embodiment 62 The method of any of embodiments 47-56, conducted at a temperature in the range of 500-800°C, e.g., in the range of 500-750°C, or 500-700°C, or 500-650°C, or 500-600°C.
  • Embodiment 63 The method of any of embodiments 47-56, conducted at a temperature in the range of 550-800°C, e.g., in the range of 550-750°C, or 550-700°C, or 550-650°C, or 550-600°C.
  • Embodiment 64 The method of any of embodiments 47-63, wherein at least part of the H 2 of the feed stream is from a renewable source.
  • Embodiment 65 The method of any of embodiments 47-64, wherein at least part of the H 2 of the feed stream is green hydrogen.
  • Embodiment 66 The method of any of embodiments 47-65, wherein at least part of the H 2 of the feed stream is blue hydrogen.
  • Embodiment 67 The method of any of embodiments 47-66, wherein at least a part of the H 2 of the feed stream is grey hydrogen, black hydrogen, brown hydrogen, pink hydrogen, turquoise hydrogen, yellow hydrogen, and/or white hydrogen.
  • Embodiment 68 The method of any of embodiments 47-67, wherein at least part of the CO 2 of the feed stream is from a renewable source.
  • Embodiment 69 The method of any of embodiments 47-68, wherein at least part of the CO 2 of the feed stream is from direct air capture.
  • Embodiment 70 The method of any of embodiments 46-69, wherein at least part of the CO 2 of the feed stream captured from a manufacturing plant, e.g., a bioethanol plant, a steel plant, or a cement plant.
  • a manufacturing plant e.g., a bioethanol plant, a steel plant, or a cement plant.
  • Embodiment 71 The method of any of embodiments 46-70, wherein the molar ratio of H 2 to CO 2 in the feed stream is at least 0.1: 1, e.g., at least 0.5: 1.
  • Embodiment 72 The method of any of embodiments 46-70, wherein the molar ratio of H 2 to CO 2 in the feed stream is at least 0.9: 1, e.g., at least 1: 1 or at least 1.5: 1.
  • Embodiment 73 The method of any of embodiments 46-70, wherein the molar ratio of H 2 to CO 2 in the feed stream is at least 2: 1, e.g., at least 2.5: 1.
  • Embodiment 74 The method of any of embodiments 46-73, wherein the molar ratio of H 2 to CO 2 in the feed stream is no more than 100: 1, e.g., no more than 75: 1, or 50: 1.
  • Embodiment 75 The method of any of embodiments 46-73, wherein the molar ratio of H 2 to CO 2 in the feed stream is no more than 20: 1, e.g., no more than 15: 1, or 10: 1.
  • Embodiment 76 The method of any of embodiments 46-73, wherein the molar ratio of H 2 to CO 2 in the feed stream is in the range of 0.5: 1 to 10: 1.
  • Embodiment 77 The method of any of embodiments 46-76, conducted at a pressure in the range of 1 to 100 barg (e.g., in the range of 1 to 70 barg, or 1 to 50 barg, or 1 to 40 barg, or 1 to 35 barg, or 5 to 80 barg, or 5 to 50 barg, or 5 to 40 barg, or 5 to 35 barg, or 10 to 70 barg, 10 to 50 barg, or 10 to 40 barg, or 10 to 35 barg, or 20 to 70 barg, 20 to 50 barg, or 20 to 40 barg, or 20 to 35 barg, or 25 to 70 barg, 25 to 50 barg, or 25 to 40 barg, or 25 to 35 barg) .
  • 1 to 100 barg e.g., in the range of 1 to 70 barg, or 1 to 50 barg, or 1 to 40 barg, or 1 to 35 barg, or 5 to 80 barg, or 5 to 50 barg, or 5 to 40 barg, or 5 to 35 barg, or 10 to
  • Embodiment 78 The method of any of embodiments 46-77, conducted at a GHSV in the range of 1,000 to 2,000,000 h -1 (e.g., in the range of 1,000 to 1,200,000 h -1 , or 1,000 to 500,000 h -1 , or 1,000 to 100,000 h -1 , or 5,000 to 1,200,000 h -1 , or 5,000 to 500,000 h -1 , or 5,000 to 100,000 h -1 , or 10,000 to 1,200,000 h -1 , or 10,000 to 500,000 h -1 , or 10,000 to 100,000 h -1 ) .
  • 1,000 to 1,200,000 h -1 e.g., in the range of 1,000 to 1,200,000 h -1 , or 1,000 to 500,000 h -1 , or 1,000 to 100,000 h -1 , or 5,000 to 1,200,000 h -1 , or 5,000 to 500,000 h -1 , or 5,000 to 100,000 h -1 , or 10,000 to 1,200,000 h -1 , or 10,000 to 500,000 h -1 ,
  • Embodiment 79 The method of any of embodiments 46-78, wherein the product stream comprises no more than 95 mol%CO 2 (e.g., no more than 90 mol%CO 2 ) .
  • Embodiment 80 The method of any of embodiments 46-78, wherein the product stream comprises no more than 85 mol%CO 2 (e.g., no more than 80 mol%CO 2 ) .
  • Embodiment 81 The method of any of embodiments 46-78, wherein the product stream comprises no more than 75 mol%CO 2 (e.g., no more than 70 mol%CO 2 ) .
  • Embodiment 82 The method of any of embodiments 46-81, wherein the product stream further comprises CO 2 , and wherein the method further comprises recycling at least a portion of the CO 2 of the product stream to the feed stream.
  • Embodiment 83 The method of any of embodiments 46-82, wherein the product stream further comprises hydrogen and wherein the method further comprises recycling at least a portion of the hydrogen of the product stream to the feed stream.
  • Embodiment 84 The method of any of embodiments 46-83, wherein a ratio of H 2 : CO in the product stream is in the range of 0.1: 1 to 100: 1. (e.g., in the range of 0.1: 1 to 50: 1, or 0.1: 1 to 25: 1, or 0.1: 1 to 10: 1, or 0.1: 1 to 5: 1, or 1: 1 to 100: 1, or 1: 1 to 50: 1, or 1: 1 to 25: 1, or 1: 1 to 10: 1, or 1: 1 to 5: 1) .
  • Embodiment 85 The method of any of embodiments 46-84, wherein the product stream comprises no more than 20 mol%methane, e.g., no more than 15 mol%methane.
  • Embodiment 86 The method of any of embodiments 46-84, wherein the product stream comprises no more than 10 mol%methane, e.g., no more than 5 mol%, or 1 mol%, or 0.5 mol%, or 0.1 mol%methane.
  • Embodiment 87 The method of any of embodiments 46-86, wherein the method comprises activating the catalyst prior to contacting the catalyst with the feed stream.
  • Embodiment 88 The method of embodiment 87, wherein activating the catalyst comprises contacting the catalyst with a reducing stream comprising a reductive gas (e.g., hydrogen) .
  • a reductive gas e.g., hydrogen
  • Embodiment 89 The method of embodiment 87 or embodiment 88, wherein the reducing stream comprises hydrogen in an amount of at least 25 mol% (e.g., at least 50 mol%, or 75 mol%, or 90 mol%) .
  • Embodiment 90 The method of any of embodiments 87-89, wherein activating the catalyst is conducted at a temperature in the range of 200 to 800°C. (e.g., in the range of 250°C to 800°C, or 300°C to 800°C, or 200°C to 700°C, or 250°C to 800°C, or 300°C to 700°C) .
  • each embodiment disclosed herein can comprise, consist essentially of or consist of its particular stated element, step, ingredient or component.
  • the transition term “comprise” or “comprises” means includes, but is not limited to, and allows for the inclusion of unspecified elements, steps, ingredients, or components, even in major amounts.
  • the transitional phrase “consisting of” excludes any element, step, ingredient or component not specified.
  • the transition phrase “consisting essentially of” limits the scope of the embodiment to the specified elements, steps, ingredients or components and to those that do not materially affect the embodiment.

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  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
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Abstract

La présente divulgation concerne de manière générale un catalyseur de conversion inverse de gaz à l'eau supporté comprenant : un support qui représente un support d'oxyde de cérium, un support d'oxyde de titane, un support d'oxyde d'aluminium, un support d'oxyde de zirconium, ou un support d'oxyde mixte comprenant un mélange d'au moins deux éléments parmi l'oxyde de cérium, l'oxyde de titane, l'oxyde d'aluminium, et l'oxyde de zirconium ; et du manganèse, présent dans une proportion se situant dans la plage de 0,5 à 20 % en poids du catalyseur, sur la base du poids total du catalyseur.
PCT/CN2022/102723 2022-06-30 2022-06-30 Catalyseurs au manganèse pour procédés de conversion inverse de gaz à l'eau WO2024000370A1 (fr)

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PCT/CN2022/102723 WO2024000370A1 (fr) 2022-06-30 2022-06-30 Catalyseurs au manganèse pour procédés de conversion inverse de gaz à l'eau
PCT/IB2023/056800 WO2024003843A1 (fr) 2022-06-30 2023-06-29 Catalyseurs au manganèse pour conversion eau-gaz inverse et procédés de fischer-tropsch intégrés

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050232833A1 (en) * 2004-04-15 2005-10-20 Hardy Dennis R Process for producing synthetic liquid hydrocarbon fuels
WO2008131898A1 (fr) * 2007-04-27 2008-11-06 Saudi Basic Industries Corporation Hydrogénation catalytique du dioxyde de carbone en un mélange de syngaz
WO2013085861A1 (fr) * 2011-12-08 2013-06-13 Saudi Basic Industries Corporation Catalyseur à base d'un oxyde mixte pour la conversion du dioxyde de carbone en gaz de synthèse, son procédé de préparation et utilisation
WO2017122113A1 (fr) * 2016-01-15 2017-07-20 Sabic Global Technologies B.V. Procédés de production de gaz de synthèse à partir de dioxyde de carbone
WO2017130081A1 (fr) * 2016-01-27 2017-08-03 Sabic Global Technologies B.V. Procédés et systèmes pour augmenter la sélectivité pour des oléfines légères dans l'hydrogénation de co2
US20180093888A1 (en) * 2015-04-29 2018-04-05 Aghaddin Mamedov Methods for conversion of co2 into syngas

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050232833A1 (en) * 2004-04-15 2005-10-20 Hardy Dennis R Process for producing synthetic liquid hydrocarbon fuels
WO2008131898A1 (fr) * 2007-04-27 2008-11-06 Saudi Basic Industries Corporation Hydrogénation catalytique du dioxyde de carbone en un mélange de syngaz
WO2013085861A1 (fr) * 2011-12-08 2013-06-13 Saudi Basic Industries Corporation Catalyseur à base d'un oxyde mixte pour la conversion du dioxyde de carbone en gaz de synthèse, son procédé de préparation et utilisation
US20180093888A1 (en) * 2015-04-29 2018-04-05 Aghaddin Mamedov Methods for conversion of co2 into syngas
WO2017122113A1 (fr) * 2016-01-15 2017-07-20 Sabic Global Technologies B.V. Procédés de production de gaz de synthèse à partir de dioxyde de carbone
WO2017130081A1 (fr) * 2016-01-27 2017-08-03 Sabic Global Technologies B.V. Procédés et systèmes pour augmenter la sélectivité pour des oléfines légères dans l'hydrogénation de co2

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