WO2025006557A1 - Procédés de conversion d'alcanes en alcènes et catalyseurs de déshydrogénation tolérants à la vapeur - Google Patents

Procédés de conversion d'alcanes en alcènes et catalyseurs de déshydrogénation tolérants à la vapeur Download PDF

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WO2025006557A1
WO2025006557A1 PCT/US2024/035550 US2024035550W WO2025006557A1 WO 2025006557 A1 WO2025006557 A1 WO 2025006557A1 US 2024035550 W US2024035550 W US 2024035550W WO 2025006557 A1 WO2025006557 A1 WO 2025006557A1
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dehydrogenation catalyst
chromium
zirconia
dehydrogenation
catalyst
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Alexey KIRILIN
Eric E. Stangland
Victor J. SUSSMAN
Kevin Blann
Davy L.S. NIESKENS
Glenn POLLEFEYT
Andrzej Malek
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/321—Catalytic processes
    • C07C5/322—Catalytic processes with metal oxides or metal sulfides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/321—Catalytic processes
    • C07C5/324—Catalytic processes with metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of rare earths
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/24—Chromium, molybdenum or tungsten
    • C07C2523/26—Chromium

Definitions

  • the present disclosure relates to the preparation of dehydrogenation catalysts, and more particularly, dehydrogenation catalysts that tolerate steam, and methods of using the dehydrogenation catalysts to achieve a high conversion of alkanes to alkenes in the presence of steam.
  • B ACKGROUND [0003] Alkenes are used for a wide range of industrial applications, including producing plastics, fuels, and various downstream chemicals. Such alkenes include C2 to C4 materials, including ethene, propene, and butenes (also commonly referred to as ethylene, propylene, and butylenes, respectively). A variety of processes for producing these alkenes have been developed, including petroleum cracking and various synthetic processes.
  • alkane dehydrogenation One such process for producing alkenes is alkane dehydrogenation.
  • Conventional alkane dehydrogenation is endothermic and equilibrium limited and produces multiple moles of products per mole of reactants. Therefore, to reach economically feasible levels of alkane-to- alkene conversion, conventional alkane dehydrogenation necessitates the use of low pressures and high temperatures, often in excess of 800 o C, to shift the equilibrium toward the reaction products.
  • radical chemistry that occurs in conventional alkane dehydrogenation processes may produce coke as a byproduct. The coke may cause blockages, which may require periodic shutdowns for decoking operations.
  • Embodiments of the present disclosure address these and other needs by the methods of preparation of dehydrogenation catalysts, and more particularly, dehydrogenation catalysts that are capable of performing dehydrogenation chemistry in the presence of steam, and methods of using such dehydrogenation catalysts.
  • a dehydrogenation catalyst as described herein, comprises zirconia (ZrO2) and chromium (Cr). This dehydrogenation catalyst may then be used for converting alkanes to alkenes. The dehydrogenation catalyst may be able to catalyze the conversion of alkanes to alkenes in the presence of steam.
  • a method for converting alkanes to alkenes may comprise contacting a feed stream comprising alkanes with a dehydrogenation catalyst in a reaction zone under steam conditions, the dehydrogenation catalyst comprising zirconia and chromium, and converting at least a portion of the alkanes to alkenes, thereby yielding a product stream comprising alkanes, alkenes, and hydrogen.
  • a method for forming a dehydrogenation catalyst may comprise obtaining a zirconia support, adding a chromium- containing precursor to the zirconia support to form a chromium-containing zirconia, and calcining and drying the chromium-containing zirconia to form a dehydrogenation catalyst.
  • a reaction might take place under 5 volume percent (v.%) steam conditions wherein 5% of the gas volume of the reaction section would be filled with steam.
  • the steam that leads to steam conditions may come from any source.
  • the steam that leads to steam conditions may be generated in-situ by selective hydrogen combustion materials.
  • dehydrogenation refers to a chemical process by which hydrogen is chemically removed from a chemical compound.
  • ethane may undergo dehydrogenation to be converted to ethylene.
  • dehydrogenation catalyst(s) refers to any substance that increases the rate of a dehydrogenation reaction without itself undergoing any permanent chemical change.
  • background dehydrogenation activity refers to the dehydrogenation activity that occurs in the presence of inert material instead of a catalyst measured under the same process conditions.
  • a dehydrogenation catalyst may have an activity equal to 1.1 times background dehydrogenation activity when the dehydrogenation catalyst performs dehydrogenation at a conversion rate equal to 1.1 times the dehydrogenation activity of quartz chips under the same process conditions.
  • alkane(s) refers to any series of hydrocarbon molecules that consist of carbon-carbon single bonds and where the carbon structure is saturated with hydrogen. Ethane, propane, and butane are examples of alkanes.
  • alkene(s) refers any series of hydrocarbon molecules, where at least two of the carbon atoms are not saturated with hydrogen and share a double bond.
  • Ethylene, propylene, 1-butene, trans-2-butene, and cis-2-butene are examples of alkenes.
  • Alkenes include dienes, which are hydrocarbons where at least two sets of 85055-WO-PCT/DOW 85055 WO two of the carbon molecules, that may or may not be adjacent to each other, are not saturated with hydrogen and share a double bond.
  • chromium-containing zirconia refers to a zirconia where chromium is present on the surface of the zirconia, and/or chromium is present in the pores of the zirconia.
  • the chromium may be present in any form.
  • the chromium may be in the form of a metal oxide.
  • dehydrogenation catalysts is known in the field of hydrocarbon products, such as plastics, fuels, and various downstream chemicals.
  • the Catofin propane dehydrogenation processes from Lummus Technology and the Oleflex propane dehydrogenation processes from Honeywell employ Cr/Al2O3 and Pt-Sn-based dehydrogenation catalysts, respectively.
  • the dehydrogenation catalyst may comprise zirconia (ZrO 2 ).
  • the zirconia used in embodiments disclosed and described herein in the dehydrogenation catalyst may be “phase pure zirconia”, which is defined herein as zirconia to which no other materials have intentionally been added during production.
  • phase pure zirconia includes zirconia with small amounts of components other than zirconium (including oxides other than zirconia) that are 85055-WO-PCT/DOW 85055 WO unintentionally present in the zirconia as a natural part of the zirconia production process, such as, for example, hafnium (Hf). Accordingly, as used herein “zirconia” and “phase pure zirconia” are used interchangeably unless specifically indicated otherwise.
  • the zirconia can be non-phase pure zirconia, such as zirconia doped with calcium (Ca), yttria (Y 2 O 3 ), lanthanum (La), cerium (Ce), or rare earth elements.
  • the zirconia particles may include zirconia particles having a crystalline structure.
  • the zirconia particles may include zirconia particles having monoclinic crystal form (also known as a baddeleyite structure), tetragonal crystal form, cubic crystal form, or combinations thereof.
  • the dehydrogenation catalyst may comprise chromium (Cr) in any suitable oxidation state.
  • the chromium may have an oxidation state of +2, +3, +4, +5, +6, or combinations thereof.
  • the dehydrogenation catalyst may comprise chromium having a single oxidation state or the dehydrogenation catalyst may comprise chromium having different oxidation states.
  • the dehydrogenation catalyst may comprise zirconia, where the zirconia acts as a metal oxide support.
  • the term “metal oxide support” may refer to a support material that supports the other components of the dehydrogenation catalyst, for example, chromium.
  • adding a chromium-containing precursor to the zirconia support to form a chromium-containing zirconia may comprise impregnating the zirconia support with chromium-containing precursor to form a chromium-impregnated zirconia.
  • the dehydrogenation catalyst may be prepared by precipitation.
  • the dehydrogenation catalyst may be prepared by co-precipitating the zirconia support and the chromium-containing precursor.
  • the dehydrogenation catalyst may be prepared by a combination of impregnation and precipitation.
  • adding a chromium-containing precursor to the zirconia support in a fluidized bed operation, wherein the zirconia support is a fluidizable zirconia support may comprise placing the zirconia support in a fluidized bed reactor and adding a chromium- containing precursor to the zirconia support.
  • the chromium-containing precursor may be a dry powder or may be part of a solution or slurry.
  • the chromium- containing zirconia support prepared for use in a fluidized bed operation may be spray dried.
  • the surface area of the zirconia particles may be at least 5 m 2 /g, at least 10 m 2 /g, at least 20 m 2 /g, at least 50 m 2 /g, at least 75 m 2 /g, at least 100 m 2 /g, at least 125 m 2 /g, or at least 150 m 2 /g.
  • the surface area of the zirconia particles may be from 10 m 2 /g to 160 m 2 /g, from 20 m 2 /g to 130 m 2 /g, from 30 m 2 /g to 120 m 2 /g, from 40 m 2 /g to 110 m 2 /g, from 50 m 2 /g to 100 m 2 /g, from 60 m 2 /g to 90 m 2 /g, or from 70 m 2 /g to 80 m 2 /g.
  • the dehydrogenation catalyst may be made by other methods that eventually lead to intimate contact between the chromium- containing precursor and zirconia.
  • the dehydrogenation catalyst may comprise from 0.5 % to 20 % chromium, from 0.1 % to 49 %, 0.2 % to 49 %, 0.3 % to 49 %, 0.4 % to 49 %, 0.5 % to 49 %, 1 % to 49 %, 5 % to 49 %, 10 % to 49 %, 15 % to 49 %, 20 % to 49 %, 25 % to 49 %, 30 % to 49 %, 40 % to 49 %, 0.1 % to 40 %, 0.2 % to 40 %, 0.3 % to 40 %, 0.4 % to 40 %, 0.5 % to 40 %, 1 % to 40 %, 5 % to 40 %, 10 % to 40 %, 15 % to 40 %, 20 % to 40 %, 25 % to 40 %, 30 % to 40 %, 0.1 % to 30 %, 0.1 % to 40 %, 5 %
  • the dehydrogenation catalyst may comprise hafnium.
  • the hafnium may be present in the zirconia as a natural part of the zirconia production process.
  • the dehydrogenation catalyst may comprise 1 wt.% to 5 wt.% chromium metal, and 65 wt.% to 80 wt.% zirconium metal, wherein the weight percent is based on a total weight of the dehydrogenation catalyst (the total weight of the dehydrogenation catalyst including the oxygen in the oxides).
  • the dehydrogenation catalyst may be a promoted dehydrogenation catalyst comprising the formula Cr-Zr-X, wherein X is selected from the group consisting of alkali metals, alkaline earth metals, tin (Sn), chloride (Cl), boron (B), phosphorous (P), sulfur (S), niobium (Nb), bismuth (Bi), antimony (Sb), and combinations thereof.
  • X of the formula Cr-Zr-X may be in any thermodynamically stable oxidation state.
  • X of the formula Cr-Zr-X may be an oxide.
  • Zr of the formula Cr-Zr-X may comprise zirconia (ZrO 2 ).
  • the dehydrogenation catalyst may be a promoted dehydrogenation catalyst comprising the formula Cr-Zr-Q, wherein Q is selected from the group consisting of lanthanum (La), cerium (Ce), neodymium (Nd), samarium (Sm), gadolinium (Gd), dysprosium (Dy), praseodymium (Pr), europium (Eu) and combinations thereof.
  • Q of the formula Cr-Zr-Q may be in any thermodynamically stable oxidation state.
  • Q of the formula Cr-Zr-Q may be an oxide.
  • Zr of the formula Cr- Zr-Q may comprise zirconia (ZrO 2 ).
  • the dehydrogenation catalyst may be a promoted dehydrogenation catalyst comprising the formula of a least one of Cr-Zr-X and Cr-Zr-Q.
  • the dehydrogenation catalyst may be a promoted dehydrogenation catalyst comprising the formula Cr-Zr-Z, wherein Z selected from the group consisting of tungsten (W), vanadium (V), niobium (Nb), and combinations thereof.
  • Z of the formula Cr-Zr- Z may be in any thermodynamically stable oxidation state.
  • Z of the formula Cr- Zr-Z may be an oxide.
  • Zr of the formula Cr-Zr-Z may comprise zirconia (ZrO 2 ).
  • the dehydrogenation catalyst may be a promoted dehydrogenation catalyst, 85055-WO-PCT/DOW 85055 WO wherein the promoter is selected from the group comprising transition metals, lanthanides, and combinations thereof.
  • a method for converting alkanes to alkenes may comprise contacting a feed stream comprising alkanes with a dehydrogenation catalyst in a reaction zone.
  • the feed stream may comprise C 2 -C 4 alkanes.
  • the feed stream may comprise ethane, propane, butanes, or combinations thereof.
  • the feed stream may be contacted with the dehydrogenation catalyst for a controlled time of exposure.
  • the controlled time of exposure may be selected based on the desired catalyst to feed stream mass to mass ratio.
  • the controlled time of exposure may be from 5 seconds (sec) to 1 hour (h).
  • the controlled time of exposure may be from 5 seconds (sec) to 1 h, from 10 sec to 30 minutes (min), from 15 sec to 15 min, from 20 sec to 10 min, from 25 sec to 5 min, from 25 sec to 30 sec, from 30 sec to 1 min, or any combination thereof.
  • the reaction zone may be a zone inside a reactor adapted to allow the feed stream to be contacted with the dehydrogenation catalyst.
  • the reactor may be a fixed-bed reactor, including but not limited to a dual tube fixed-bed reactor.
  • the reactor may be a circulating fluidized bed reactor.
  • the reactor may be two or more reactors in series or parallel, and each reactor in series or parallel may be the same type of reactor as other reactors in the series, or may be a different type of reactor from other reactors in the series.
  • the reaction zone may house a material that converts gaseous hydrogen to water.
  • a method for converting alkanes to alkenes may comprise converting at least a portion of the alkanes to alkenes, thereby yielding a product stream comprising alkanes, alkenes, and hydrogen.
  • the product stream may comprise ethylene, propylene, butylene, hydrogen, or combinations thereof.
  • the product stream may comprise ethane, propane, butane, ethylene, propylene, butylene, hydrogen, or combinations thereof.
  • at least a portion of the hydrogen in the product stream is combusted and yields water.
  • the water may be in the form of steam.
  • the steam may comprise gaseous water, liquid water, aerosolized water, or 85055-WO-PCT/DOW 85055 WO combinations thereof. Because of this hydrogen combustion, water—such as steam—will be present in the reaction zone during dehydrogenation of the alkanes in the feed stream. As mentioned above, many oxidative dehydrogenation catalysts lose conversion and selectivity when they are exposed to water and require a significant amount of oxidative gas to offset the loss of conversion and selectivity. However, the dehydrogenation catalysts disclosed and described herein retain catalytic activity in the presence of water and retain all or some of their conversion or selectivity when the hydrogen is combusted and forms water.
  • the dehydrogenation catalyst may have an alkene selectivity of greater than or equal to 40 carbon mole percent (Cmol%), greater than or equal to 45 Cmol%, greater than or equal to 50 Cmol%, greater than or equal to 55 Cmol %, greater than or equal to 65 Cmol%, greater than or equal to 75 Cmol%, greater than or equal to 85 Cmol%, greater than or equal to 95 Cmol %, greater than or equal to 97 Cmol%, greater than or equal to 98 Cmol%, or greater than or equal to 99 Cmol%.
  • Cmol% carbon mole percent
  • the dehydrogenation catalyst comprises a dehydrogenation activity of greater than or equal to 1.1 times background dehydrogenation activity. In embodiments, the dehydrogenation catalyst comprises a dehydrogenation activity of greater than or equal to 1.1 times, 1.5 times, 2 times, 3 times, 4 times, 5 times, or 10 times background dehydrogenation activity. [0040] In one or more embodiments, the dehydrogenation catalyst retains at least some dehydrogenation activity above background dehydrogenation activity under greater than or equal to 5 v.% steam conditions based on a total volume of gaseous components in the reaction zone.
  • the dehydrogenation catalyst retains at least some dehydrogenation activity above background dehydrogenation activity under greater than or equal to 5 v.%, 10 v.%, 15 v.%, 20 v.%, 25 v.%, 30 v.%, 35 v.%, 40 v.%, 45 v.%, or 50 v.% steam conditions based on a total volume of gaseous components in the reaction zone.
  • the dehydrogenation catalyst comprises a dehydrogenation activity of greater than or equal to 1.1 times, 1.5 times, 2 times, 3 times, 4 times, 5 times, or 10 times background dehydrogenation activity under greater than or equal to 5 v.%, 10 v.%, 15 v.%, 20 85055-WO-PCT/DOW 85055 WO v.%, 25 v.%, 30 v.%, 35 v.%, 40 v.%, 45 v.%, or 50 v.% steam conditions based on a total volume of gaseous components in the reaction zone.
  • the method for converting alkanes to alkenes may further comprise contacting the feed stream comprising alkanes with at least one other catalyst.
  • the at least one other catalyst may comprise a selective hydrogen combustion material (interchangeably called an oxygen carrier material).
  • oxygen-carrier materials such as those disclosed in U.S. App. No. 62/725,504, entitled “METHODS OF PRODUCING HYDROGEN-SELECTIVE OXYGEN-CARRIER MATERIALS,” filed on, August 31, 2018, and U.S. App. No.
  • the dehydrogenation catalyst maintains the conversion of alkanes to alkenes without the presence of a gaseous oxidant in the feed stream or as a co-feed. In some embodiments, the dehydrogenation catalyst maintains the conversion of alkanes to alkenes with the presence of only a small amount of a gaseous oxidant in the feed stream or as a co-feed.
  • the dehydrogenation catalyst maintains the conversion of alkanes to alkenes with the presence of less than 5 v.%, less than 4 v.%, less than 3 v.%, less than 2 v.%, less than 1 v.%, less than 0.5 v.%, less than 0.25 v.%, or less than 0.1 v.% gaseous oxidant in the feed stream or as a co-feed.
  • the dehydrogenation catalyst and the feed stream have a mass to mass ratio that is from 5:1 to 200:1. This mass ratio is defined as the ratio between the mass feed rate of catalyst to the reaction zone and the mass feed rate of alkane to the reaction zone.
  • the dehydrogenation catalyst and the feed stream have a mass to mass ratio that is from 5:1 to 200:1, from 10:1 to 200:1, from 25:1 to 200:1, from 50:1 to 200:1, from 75:1 to 200:1, from 100:1 to 200:1, from 150:1 to 200:1, from 5:1 to 150:1, from 10:1 to 150:1, from 25:1 to 150:1, from 50:1 to 150:1, from 75:1 to 150:1, from 100:1 to 150:1, from 5:1 to 100:1, from 10:1 to 100:1, from 25:1 to 100:1, from 50:1 to 100:1, from 75:1 to 100:1, from 5:1 to 75:1, from 10:1 to 75:1, from 25:1 to 75:1, from 50:1 to 75:1, from 5:1 to 50:1, from 10:1 to 50:1, from 25:1 to 50:1, from 5:1 to 50:1, from 10:1 to 50:1, from 25:1 to 50:1, from 5:1 to 50:1, from 25:
  • the converting at least a portion of the alkanes to alkenes occurs at a pressure that is equal to atmospheric pressure. In embodiments, the converting at least a portion of the alkanes to alkenes occurs at a pressure from 1-20 bar, when measured as an absolute pressure (bara). In embodiments, the converting at least a portion of the alkanes to alkenes occurs at a pressure from 1-20 bara, from 1-15 bara, from 1-10 bara, or from 1-5 bara.
  • the method of converting alkanes to alkenes may further comprise removing spent dehydrogenation catalyst from the reaction zone and introducing the spent dehydrogenation catalyst into a regeneration zone.
  • the regeneration zone may be part of the reactor.
  • the regeneration zone may the separate from the reactor.
  • the method of converting alkanes to alkenes may further comprise regenerating the spent dehydrogenation catalyst, thereby forming regenerated dehydrogenation catalyst.
  • regenerating the dehydrogenation catalyst may comprise contacting the dehydrogenation catalyst with a regeneration stream comprising gaseous oxygen, air, or combinations thereof.
  • the regeneration zone is purged with gaseous nitrogen prior to contacting the dehydrogenation catalyst with the regeneration stream.
  • the dehydrogenation catalyst may be regenerated at a temperature of greater than or equal to 650 °C. In one or more embodiments, the dehydrogenation catalyst may be regenerated for a time of greater than or equal to 1 minute (min), greater than 5 min, greater than 10 min, or greater than 30 min. In embodiments, the dehydrogenation catalyst may be heated prior to sending the dehydrogenation catalyst back to the reaction zone.
  • the method of converting alkanes to alkenes may further comprise regenerating the spent selective hydrogen combustion material, thereby forming regenerated selective hydrogen combustion material.
  • Regenerating the selective hydrogen combustion 85055-WO-PCT/DOW 85055 WO material may comprise contacting the selective hydrogen combustion material with a regeneration stream comprising gaseous oxygen, air, or combinations thereof.
  • the regeneration zone is purged with gaseous nitrogen prior to contacting the selective hydrogen combustion material with the regeneration stream.
  • the selective hydrogen combustion material may be regenerated at a temperature of greater than or equal to 650 °C.
  • the selective hydrogen combustion material may be regenerated for a time of greater than or equal to 1 minute (min), greater than 5 min, greater than 10 min, or greater than 30 min.
  • the selective hydrogen combustion material may be heated prior to sending the selective hydrogen combustion material back to the reaction zone to close heat balance.
  • the selective hydrogen combustion material and the dehydrogenation catalyst may be regenerated together.
  • the method of converting alkanes to alkenes may further comprise returning regenerated dehydrogenation catalyst to the reaction zone where it is contacted with the feed stream.
  • the ZrO2 support was impregnated with 2 mL of 1 M Cr (III) nitrate solution in DI water (prepared from the nonahydrate salt) until the impregnation solution was no longer drawn into the pores of the support and the impregnation solution was homogenously distributed over the support.
  • the impregnated catalyst was dried and calcined under air in the box oven using the following temperature program: room temperature to 177 °C at 5 deg/min, dwell 2 h, 177 to 750°C at 5 deg/min, dwell 1 h, cool down to room temperature.
  • the catalyst was sieved after calcination to remove fine particles smaller than 80 mesh.
  • a Cr/ZrO 2 catalyst was prepared by incipient wetness impregnation method. First, 10 g of zirconium hydroxide Zr(OH)4 (DKKK L30036, pore volume determined by DI water 0.67 g/mL) was impregnated with 6.7 mL of DI water until the water was no longer drawn into the pores of the support and the water was homogenously distributed over the support.
  • the material was dried and calcined under air in the box oven using the following temperature program: room temperature to 120°C at 3 deg/min, dwell 2 h, 120 to 500°C at 3 deg/min, dwell 4 h, cool down to room temperature.
  • the calcined support was compacted and sieved to 40-80 mesh size.
  • 1.5 g of the calcined and sieved ZrO2 support (monoclininc and tetragonal phases) was impregnated with 0.6 mL of 1 M Cr (III) nitrate solution in DI water (prepared from the nonahydrate salt) until the impregnation solution was no longer drawn into the pores of the support and the impregnation solution was homogenously distributed over the support.
  • the impregnated catalyst was dried and calcined under air in the box oven using the following temperature program: room temperature to 177 °C at 5 deg/min, dwell 2 h, 177 to 750 °C at 5 deg/min, dwell 1 h, cool down to room temperature.
  • the catalyst was sieved after calcination to remove fine particles smaller than 80 mesh.
  • XRD x-ray powder diffraction
  • the catalyst showed the presence of monoclinic and tetragonal zirconia.
  • EXAMPLE 3 [0060] A Cr/ZrO2 catalyst was prepared by incipient wetness impregnation method.
  • the ZrO 2 support (1.5 g) was impregnated with 0.6 mL of 1 M Cr (III) nitrate solution in DI water (prepared from the nonahydrate salt) until the impregnation solution was no longer drawn into the pores of the support and the impregnation solution was homogenously distributed over the support.
  • the impregnated catalyst was dried and calcined under air in a box oven using the following temperature program: room temperature to 177 °C at 5 deg/min, dwell 2 h, 177 to 750 °C at 5 deg/min, dwell 1 h, cool down to room temperature.
  • EXAMPLE 4 A Cr/ZrO2 catalyst was prepared by incipient wetness method, as described in Example 3, but used 0.6 mL of 1 M ammonium chromate solution in DI water instead of 1 M Cr (III) nitrate nonahydrate solution to impregnate 1.5 g of pre-calcined ZrO 2 support.
  • EXAMPLE 5 A Cr/ZrO2 catalyst was prepared by co-precipitation and incipient wetness impregnation method.
  • a three neck round bottom flask equipped with a magnetic stir bar, a pH probe, a thermometer, and a dropping funnel was placed in a water bath. The water bath was placed on heating plate. Then, 400 mL of DI water was added to the three neck round bottom flask. The heating plate was set and controlled at a temperature of 60+/-2 °C. Then, 275 mL of zirconyl nitrate 35 percent weight (%wt) in nitric acid was added dropwise along with 14.6 M ammonium hydroxide solution in DI water (base) under continuous stirring at a speed of 500 rpm. The rate of chemical addition was controlled to keep pH constant at 7.0 +/-0.3.
  • the precipitate was dried and calcined under air in a box oven using the following temperature program: room temperature to 120 °C at 5 deg/min, dwell 2 h, 120 to 750 °C at 5 deg/min, dwell 4 h, cool down to room temperature.
  • the as prepared ZrO 2 support was compacted (static press 7 tonnes / 10 min) and then crushed and sieved to 40-80 mesh size.
  • Example 5 When analyzed using x-ray powder diffraction (XRD), the catalyst of Example 5 showed the presence of monoclinic and tetragonal zirconia. [0068] EXAMPLE 6 [0069] A Cr/ZrO2 catalyst was prepared by co-precipitation and incipient wetness impregnation method. First, a ZrO2 support was prepared using the same ZrO2 support preparation method described in Example 5.
  • C OMPARATIVE E XAMPLE 3 [0077] A Cr/SiO 2 -Al 2 O 3 catalyst was prepared by incipient wetness method. Siralox 1 from SASOL in the form of extrudates (1.7/250 M10596 spec Z600200, pore volume determined by DI water 0.5 ml/g) was used as a SiO2-Al2O3 support. The support was crushed and sieved to 40- 80 mesh size prior to use.
  • a Cr/SiO2 catalyst was prepared by incipient wetness method.
  • the SiO2 support was SS61138 from NORPRO in the form of 3 mm extrudates (250 m 2 /g, pore volume determined by DI water 1.0 m 2 /g). The support was crushed and sieved to 40-80 mesh size prior to use. Then, 2 mL of impregnation solution was prepared by mixing 1.2 mL of DI water with 0.8 mL of 1 M Cr (III) nitrate solution in DI water (prepared from the nonahydrate salt).
  • a Cr/Nb 2 O 5 catalyst was prepared by incipient wetness method.
  • the Nb 2 O 5 support was prepared by thermal decomposition of ammonium niobate (V) oxalate hydrate at 500 °C for 4 h under air (BET surface area 50 m 2 /g, pore volume determined by DI water 0.4 mL/g).
  • the support was sized to 40-80 mesh size prior to use.
  • Nb 2 O 5 support was impregnated with 0.34 ml of 1 M Cr (III) nitrate solution in DI water (prepared from the nonahydrate salt) until the impregnation solution was no longer drawn into the pores of the support and the impregnation solution was homogenously distributed over the support.
  • the impregnated catalyst was dried and calcined under air in a box oven using the following temperature program: room temperature to 177 °C at 5 deg/min, dwell 2 h, 177 to 750 °C at 5 deg/min, dwell 1 h, cool down to room temperature.
  • the catalyst was sieved after calcination to remove fine particles smaller than 80 mesh.
  • a Cr/HfO2 catalyst was prepared by incipient wetness method.
  • the HfO2 support was prepared by thermal decomposition of hafnium (IV) nitrate at 500 °C for 4 h under air (32 m 2 /g, pore volume determined by DI water 0.13 mL/g) was compacted and sized to 40-80 mesh size prior to use.
  • HfO2 support was impregnated with 0.11 mL of 1 M Cr (III) nitrate solution in DI water (prepared from the nonahydrate salt) until the impregnation solution was no longer drawn into the pores of the support and the impregnation solution was homogenously distributed over the support.
  • the impregnated catalyst was dried and calcined under air in a box oven using the following temperature program: room temperature to 177 °C at 5 deg/min, dwell 2 h, 177 to 750 °C at 5 deg/min, dwell 1 h, cool down to room temperature.
  • the catalyst was sieved after calcination to remove fine particles smaller than 80 mesh.
  • a Cr/SnO 2 catalyst was prepared by incipient wetness method.
  • the SnO 2 support commercially available from Sigma Aldrich (pore volume determined by DI water 0.31 m 2 /g), was compacted and sieved to 40-80 mesh size prior to use. Then, 1.5 g of SnO2 support was impregnated with 0.47 mL of 1 M Cr (III) nitrate solution in DI water (prepared from the nonahydrate salt) until the impregnation solution was no longer drawn into the pores of the support and the impregnation solution was homogenously distributed over the support.
  • the impregnated 85055-WO-PCT/DOW 85055 WO catalyst was dried and calcined under air in a box oven using the following temperature program: room temperature to 177 °C at 5 deg/min, dwell 2 h, 177 to 750 °C at 5 deg/min, dwell 1 h, cool down to room temperature.
  • the catalyst was sieved after calcination to remove fine particles smaller than 80 mesh.
  • COMPARATIVE EXAMPLE 8 [0087]
  • a Cr/MgO catalyst was prepared by incipient wetness method.
  • the MgO support 13 m 2 /g, pore volume determined by DI water 0.31 mL/g) was compacted and sieved to 40-80 mesh size prior to use.
  • impregnation solution was prepared by mixing 0.19 mL DI water with 0.48 mL of 1 M Cr (III) nitrate solution in DI water (prepared from the nonahydrate salt). Then, 1 g of MgO support was impregnated with the impregnation solution until the impregnation solution was no longer drawn into the pores of the support and the impregnation solution was homogenously distributed over the support. The impregnated catalyst was dried and calcined under air in a box oven using the following temperature program: room temperature to 177 °C at 5 deg/min, dwell 2 h, 177 °C to 750 °C at 5 deg/min, dwell 1 h, cool down to room temperature.
  • X-RAY FLUORESCENCE (XRF) MEASUREMENTS Catalyst composition was determined by X-ray Fluorescence (XRF). XRF data were collected at room temperature (RT) with a PANalytical PW4400 spectrometer using an X- ray tube with a rhodium anode. The catalyst compositions are shown in Table 1. Elements that were below the detection limit or not present are represented as blank in the table. Oxygen represented the balance of the elemental composition.
  • Table 1 Composition of Catalysts in Examples 1-6 and Comparative Examples 1-9 85055-WO-PCT/DOW 85055 WO [0093] C ATALYST P ERFORMANCE T ESTING [0094] The performance of the catalysts of both in the examples and the comparative examples was assess under both wet and dry conditions. The reaction conditions of both the wet and dry conditions are shown in Table 2. Table 2: Reaction Conditions Used to Assess Catalyst Performance [0095] The catalysts of the examples and the comparative examples were tested for selectivity and activity in a dual tube fixed-bed reactor. The catalysts were sized to a 40-80 mesh size.
  • the reactor bed comprised 300 milligrams (mg) of catalyst mixed with 1.5 grams (g) of 40-80 mesh size quartz chips.
  • the catalyst was replaced with quartz chips.
  • the 85055-WO-PCT/DOW 85055 WO reactor pressure was set at 1.08 bara (16 psia) and the catalysts were evaluated under the two sets of conditions summarized in Table 2.
  • N2 nitrogen gas
  • the reactor was purged with nitrogen gas (N2) where the pressure was 16 psia.
  • the temperature was ramped to 400 °C under N 2 flow and then the N 2 flow was switched to 60% ethane – 20% H 2 O – 20% N 2 flow. Water inlet flow was controlled by a high pressure liquid chromatography (HPLC) pump.
  • HPLC high pressure liquid chromatography
  • Feed analysis was performed by analyzing the feed gas composition using online gas chromatography (GC). [0097] Then, the reactor was purged with N2 and the temperature was ramped to 650 °C followed by switching from the N2 to air. The catalyst was regenerated at 650 °C for 6 minutes (min) followed by a N 2 purge step. Then, the feed composition was directed to the reactor at a controlled time of exposure (25-30 seconds (s) on stream corresponding to catalyst to ethane mass to mass ratio of 12-10). This completes a single cycle at a given temperature set point.
  • GC gas chromatography
  • Table 3 Performance Data for the Examples 85055-WO-PCT/DOW 85055 WO
  • Table 4 Performance Data for the Comparative Examples 85055-WO-PCT/DOW 85055 WO 85055-WO-PCT/DOW 85055 WO [00100]
  • Examples 1-6 demonstrate that catalysts containing Cr and ZrO2 demonstrate high activity under “dry” or “wet” ethane dehydrogenation conditions and retain some or all of their activity in the presence of 20% steam by volume.
  • the catalysts of the examples also demonstrate substantial activity above the background dehydrogenation activity (as measured in Comparative Example 1 by using quartz chips in lieu of a catalyst).
  • Comparative Example 2 shows high activity and ethylene selectivity in the absence of steam, its activity is notably suppressed and essentially no different than the background dehydrogenation activity in the presence of 20% steam by volume across all temperatures studied.
  • Comparative Examples 3-8 demonstrate that Cr and ZrO 2 are important elements of a steam tolerant catalyst. Cr supported on alternative supports shows either overall low activity or significant rate suppression in the presence of steam.
  • Comparative Example 9 further demonstrates that Cr and ZrO 2 are important elements of a steam tolerant catalyst by showing that Zn supported by ZrO 2 has significant rate suppression under wet conditions despite having high activity in the absence of steam.
  • the present disclosure includes one or more non-limiting aspects.
  • a first aspect includes a method for converting alkanes to alkenes, the method including contacting a feed stream comprising alkanes with a dehydrogenation catalyst in a reaction zone in the presence of 85055-WO-PCT/DOW 85055 WO steam, the dehydrogenation catalyst comprising zirconia and chromium, and converting at least a portion of the alkanes to alkenes, thereby yielding a product stream comprising alkanes, alkenes, and hydrogen, wherein the dehydrogenation catalyst does not require a gaseous oxidant in the feed stream or as a co-feed to catalyze conversion of alkanes to alkenes.
  • a second aspect of the present disclosure includes the first aspect, further including combusting at least a portion of the hydrogen to yield steam.
  • a third aspect of the present disclosure includes the first or second aspect, wherein the dehydrogenation catalyst comprises an alkene selectivity greater than or equal to 40 Cmol%.
  • a fourth aspect of the present disclosure includes any of the first through third aspects, wherein the dehydrogenation catalyst retains at least some dehydrogenation activity above background dehydrogenation activity under greater than or equal to 5 v.% steam conditions based on a total volume of gaseous components in the reaction zone.
  • a fifth aspect of the present disclosure includes any of the first through fourth aspects, further including contacting the feed stream comprising alkanes with a selective hydrogen combustion material, wherein the dehydrogenation catalyst and the selective hydrogen combustion material are both present in the reaction zone.
  • a sixth aspect of the present disclosure includes any of the first through fifth aspects, wherein the dehydrogenation catalyst comprising zirconia and chromium comprises chromium impregnated zirconia.
  • a seventh aspect of the present disclosure includes any of the first through sixth aspects, wherein the dehydrogenation catalyst comprises from 0.5 % to 20 % chromium metal based on a total weight of the dehydrogenation catalyst.
  • An eighth aspect of the present disclosure includes any of the first through seventh aspects, wherein the dehydrogenation catalyst comprises 1 wt.% to 5 wt.% chromium, and 65 wt.% to 80 wt.% zirconium, wherein the weight percent is based on a total weight of the dehydrogenation catalyst.
  • 85055-WO-PCT/DOW 85055 WO [00112]
  • a ninth aspect of the present disclosure includes any of the first through eighth aspects, wherein the dehydrogenation catalyst is substantially free from silicon.
  • a tenth aspect of the present disclosure includes any of the first through ninth aspects, wherein the dehydrogenation catalyst is a promoted dehydrogenation catalyst comprising the formula of a least one of Cr-Zr-X and Cr-Zr-Q, wherein X is selected from the group consisting of alkali metals, alkaline earth metals, tin, chloride, boron, phosphorous, sulfur, niobium, bismuth, antimony, and combinations thereof, and Q is selected from the group consisting of lanthanum, cerium, neodymium, samarium, gadolinium, dysprosium, praseodymium, europium, and combinations thereof.
  • X is selected from the group consisting of alkali metals, alkaline earth metals, tin, chloride, boron, phosphorous, sulfur, niobium, bismuth, antimony, and combinations thereof
  • Q is selected from the group consisting of lanthanum, cerium, ne
  • An eleventh aspect of the present disclosure includes any of the first through tenth aspects, wherein the dehydrogenation catalyst and the feed stream have a mass to mass ratio that is from 5:1 to 200:1.
  • a twelfth aspect of the present disclosure includes any of the first through eleventh aspects, wherein the converting at least a portion of the alkanes to alkenes occurs at a temperature that is less than or equal to 750 °C, a pressure from 1 bara to 20 bara, and a WHSV of from 1 h -1 to 12 h -1 .
  • a thirteenth aspect of the present disclosure includes any of the first through twelfth aspects, wherein the method further includes removing spent dehydrogenation catalyst from the reaction zone, introducing the spent dehydrogenation catalyst into a regeneration zone, regenerating the spent dehydrogenation catalyst, thereby forming regenerated dehydrogenation catalyst, and returning regenerated dehydrogenation catalyst to the reaction zone where it is contacted with the feed stream.
  • a fourteenth aspect of the present disclosure includes any of the first through thirteenth aspects, wherein the dehydrogenation catalyst comprises a conversion rate of greater than or equal to 1.1 times background dehydrogenation activity.
  • a fifteenth aspect of the present disclosure includes a method for forming a dehydrogenation catalyst, the method including obtaining a zirconia support, adding a chromium- 85055-WO-PCT/DOW 85055 WO containing precursor to the zirconia support to form a chromium-containing zirconia, and calcining and drying the chromium-containing zirconia to form a dehydrogenation catalyst.
  • a sixteenth aspect of the present disclosure includes the fifteenth aspect, wherein adding the chromium-containing precursor to the zirconia support to form a chromium-containing zirconia is a process selected from the group consisting of: adding the chromium-containing precursor to the zirconia support, wherein the zirconia support is a fluidizable zirconia support, adding the chromium-containing precursor to the zirconia support by spray drying, adding the chromium-containing precursor to the zirconia support by granulation, and combinations thereof.
  • adding the chromium-containing precursor to the zirconia support to form a chromium-containing zirconia is a process selected from the group consisting of: adding the chromium-containing precursor to the zirconia support, wherein the zirconia support is a fluidizable zirconia support, adding the chromium-containing precursor to the zirconia support by spray drying, adding the chromium-containing precursor to the
  • first component comprises at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or even at least 99% that second component (where % can be weight % or molar %).
  • 85055-WO-PCT/DOW 85055 WO [00123] It is also noted that recitations herein of “at least one” component, element, etc., should not be used to create an inference that the alternative use of the articles “a” or “an” should be limited to a single component, element, etc.

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Abstract

L'invention concerne un procédé de conversion d'alcanes en alcènes comprenant la mise en contact d'un flux d'alimentation comprenant des alcanes avec un catalyseur de déshydrogénation dans une zone de réaction en présence de vapeur, le catalyseur de déshydrogénation comprenant de la zircone et du chrome. Le procédé comprend en outre la conversion d'au moins une partie des alcanes en alcènes, ce qui permet d'obtenir un flux de produit comprenant des alcanes, des alcènes et de l'hydrogène, le catalyseur de déshydrogénation ne nécessitant pas d'oxydant gazeux dans le flux d'alimentation ou en tant que co-alimentation pour catalyser la conversion d'alcanes en alcènes.
PCT/US2024/035550 2023-06-30 2024-06-26 Procédés de conversion d'alcanes en alcènes et catalyseurs de déshydrogénation tolérants à la vapeur Ceased WO2025006557A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5430209A (en) 1993-08-27 1995-07-04 Mobil Oil Corp. Process for the catalytic dehydrogenation of alkanes to alkenes with simultaneous combustion of hydrogen
US7122495B2 (en) 2003-02-05 2006-10-17 Exxonmobil Chemical Patents Inc. Combined cracking and selective hydrogen combustion for catalytic cracking
US9834496B2 (en) 2011-07-13 2017-12-05 Dow Global Technologies Llc Reactivating propane dehydrogenation catalyst
WO2018232133A1 (fr) 2017-06-15 2018-12-20 North Carolina State University Matériaux porteurs d'oxygène à modification de surface pour catalyse à base d'oxydoréduction et procédés de fabrication et d'utilisation associés

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5430209A (en) 1993-08-27 1995-07-04 Mobil Oil Corp. Process for the catalytic dehydrogenation of alkanes to alkenes with simultaneous combustion of hydrogen
US7122495B2 (en) 2003-02-05 2006-10-17 Exxonmobil Chemical Patents Inc. Combined cracking and selective hydrogen combustion for catalytic cracking
US9834496B2 (en) 2011-07-13 2017-12-05 Dow Global Technologies Llc Reactivating propane dehydrogenation catalyst
WO2018232133A1 (fr) 2017-06-15 2018-12-20 North Carolina State University Matériaux porteurs d'oxygène à modification de surface pour catalyse à base d'oxydoréduction et procédés de fabrication et d'utilisation associés

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
A. ZUBKOV, ET AL.: "Influence of Cr/Zr ratio on activity of Cr-Zr oxide catalysts in non-oxidative propane dehydrogenation", CRYSTALS, vol. 11, no. 11, 1435, 22 November 2021 (2021-11-22), MDPI, Basel, CH, pages 1 - 12, XP093224490, ISSN: 2073-4352, DOI: 10.3390/cryst11111435 *
S. DE ROSSI, ET AL.: "Propane dehydrogenation on chromia/zirconia catalysts", APPLIED CATALYSIS A: GENERAL, vol. 81, no. 1, 30 January 1992 (1992-01-30), Elsevier Science, Amsterdam, NL, pages 113 - 132, XP093224267, ISSN: 0926-860X, DOI: 10.1016/0926-860X(92)80264-D *

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