WO2025006558A1 - Procédés de conversion d'alcanes en alcènes et catalyseurs de déshydrogénation tolérants à la vapeur et sans danger pour l'environnement - Google Patents

Procédés de conversion d'alcanes en alcènes et catalyseurs de déshydrogénation tolérants à la vapeur et sans danger pour l'environnement Download PDF

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WO2025006558A1
WO2025006558A1 PCT/US2024/035551 US2024035551W WO2025006558A1 WO 2025006558 A1 WO2025006558 A1 WO 2025006558A1 US 2024035551 W US2024035551 W US 2024035551W WO 2025006558 A1 WO2025006558 A1 WO 2025006558A1
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dehydrogenation catalyst
zirconia
dehydrogenation
metal
combinations
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Alexey KIRILIN
Miguel Rivera TORRENTE
Glenn POLLEFEYT
Kevin Blann
Adam Chojecki
Andrzej Malek
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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    • 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
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    • 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
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    • 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
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    • C07C2523/24—Chromium, molybdenum or tungsten
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    • C07C2523/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with alkali- or alkaline earth metals or beryllium

Definitions

  • the present disclosure relates to methods for efficiently converting various alkanes to alkenes.
  • the present disclosure relates to the preparation of dehydrogenation catalysts, and more particularly, dehydrogenation catalysts that are environmentally friendly and tolerate steam, and methods of using the dehydrogenation catalysts to achieve a high conversion of alkanes to alkenes in the presence of steam.
  • 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).
  • 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. Therefore, to reach economically feasible levels of alkane-to-alkene conversion, conventional alkane dehydrogenation necessitates the use of low pressures to shift the equilibrium toward producing products and high temperatures, often in excess of 800 °C, to provide thermal energy.
  • conventional alkane dehydrogenation processes suffer from additional undesirable radical chemistry that may produce coke as a byproduct. The formation of coke may cause blockages, which may require periodic process shutdowns for decoking operations.
  • Maintaining the low pressures and high temperatures necessary for economically feasible alkane-to -alkene conversion can be expensive.
  • a dehydrogenation catalyst as described herein, comprises zirconia (ZrC ) and a metal selected from the group consisting of iron (Fe), cobalt (Co), molybdenum (Mo), vanadium (V), and combinations thereof.
  • ZrC zirconia
  • 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 in the presence of steam, the dehydrogenation catalyst comprising zirconia and a metal selected from the group consisting of iron, cobalt, molybdenum, vanadium, and combinations thereof, 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 metal-containing precursor to the zirconia support, wherein the metal-containing precursor is selected from the group consisting of iron, cobalt, molybdenum, vanadium, and combinations thereof to form a metal-containing zirconia, and calcining and drying the metal-containing zirconia to form a dehydrogenation catalyst.
  • steam conditions refers to reaction conditions where at least some amount of steam is present. For example, a reaction might take place under 5 volume percent (v.%) steam conditions wherein 5% of the gas volume of the reaction section would be fdled with steam.
  • the steam that leads to steam conditions may come from any source.
  • the steam that leads to steam conditions may be generated by selective hydrogen combustion materials.
  • dehydrogenation refers to chemical process by which hydrogen is chemically removed from a chemical compound. For example, 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.
  • promoter also commonly referred to as catalytic promoter
  • the activator may increase the catalytic efficiency by improving catalytic selectivity, catalytic activity, or combinations thereof.
  • background dehydrogenation activity refers to the dehydrogenation activity that occurs in the presence of inert material, as measured under the same process conditions.
  • a dehydrogenation catalyst may have an activity equal to 1.1 times background dehydrogenation activity when the conversion rate using the dehydrogenation catalyst is 1.1 times the conversion rate when using quartz chips under the same process conditions.
  • alkane(s) refers to any series of hydrocarbon molecules that consist of carbon single bonds 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 cA-2-butene are examples of alkenes.
  • Alkenes include dienes, which are series of hydrocarbons, where at least two sets of 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.
  • metal-containing zirconia refers to a zirconia where metal selected from the group consisting of iron, cobalt, molybdenum, vanadium, and combinations thereof is present on the surface of the zirconia, and/or metal selected from the group consisting of iron, cobalt, molybdenum, vanadium, and combinations thereof is present in the pores of the zirconia.
  • the metal may be present in any form.
  • the metal may be in the form of a metal oxide.
  • dehydrogenation catalysts are known in the field of hydrocarbon products, such as plastics, fuels, and various downstream chemicals.
  • the Cato fin propane dehydrogenation processes from Eummus Technology and the Oleflex propane dehydrogenation processes from Honeywell employ Cr/AhCh and Pt-Sn-based dehydrogenation catalysts, respectively.
  • zirconia and catalysts are known for use in the oxidative dehydrogenation of alkanes.
  • alkanes are typically cofed with a gaseous oxidant such as oxygen, air, carbon dioxide, or nitrogen oxides, thus shifting the equilibrium constraint of the dehydrogenation reaction towards product formation and alkane conversion.
  • Oxidative dehydrogenation occurs at the surface of the catalyst by a reaction of alkane and oxidant and generates water.
  • the presence of water and alkanes at high temperatures can lead to reduced alkene selectivity through oxidation and reforming reactions that yield methane and carbon oxide products such as carbon monoxide and carbon dioxide.
  • many oxidative dehydrogenation catalysts when used in the absence of a gaseous oxidant in the feed stream or as a co-feed, exhibit significantly reduced activity in the presence of steam. Thus, not every oxidative dehydrogenation catalyst is a steam tolerant alkane dehydrogenation catalyst.
  • the dehydrogenation catalysts disclosed and described herein exhibit steam tolerance, even in the absence of a gaseous oxidant in the feed stream or as a co-feed.
  • the preparation and composition of such promoted dehydrogenation catalysts used in embodiments are discussed below.
  • some dehydrogenation catalysts such as the Cr/AhCh catalyst used in the Catofin propane dehydrogenation process from Lummus Technology, comprise elements and compounds that are dangerous to the environment.
  • chromium may adversely impact plant growth by hampering plant metabolic activities. Chromium may also negatively impact the health and life expectancy of animals and aquatic life. Additionally, chromium may cause damage to soil, water, and air and can harm ecosystems at the micro, macro, and planetary level.
  • the dehydrogenation catalysts disclosed and described herein are substantially free from environmentally unsafe compounds such as chromium. The preparation and composition of such dehydrogenation catalysts used in embodiments are discussed below.
  • the dehydrogenation catalyst may comprise zirconia (ZrC ).
  • ZrC zirconia
  • 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 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, yttria, lanthanum, cerium 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 promoted dehydrogenation catalyst may comprise a metal selected from the group consisting of iron (Fe), cobalt (Co), molybdenum (Mo), vanadium (V), and combinations thereof in any suitable oxidation state.
  • the iron may have an oxidation state of +2, +3, +4, +6, or combinations thereof.
  • the iron in the promoted dehydrogenation catalyst may comprise a single oxidation state or may comprise multiple oxidation states.
  • the cobalt may have an oxidation state of +2, +3, or combinations thereof.
  • the cobalt in the promoted dehydrogenation catalyst may comprise a single oxidation state or may comprise multiple oxidation states.
  • the molybdenum may have an oxidation state of +2, +3, +4, +5, +6, or combinations thereof.
  • the molybdenum in the promoted dehydrogenation catalyst may comprise a single oxidation state or may comprise multiple oxidation states.
  • the vanadium may have an oxidation state of +2, +3, +4, +5, or combinations thereof.
  • the vanadium in the dehydrogenation catalyst may comprise a single oxidation state or may comprise multiple 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, iron.
  • a method for forming a dehydrogenation catalyst may comprise obtaining a zirconia support, adding a metal-containing precursor to the zirconia support, wherein the metal-containing precursor is selected from the group consisting of iron, cobalt, molybdenum, vanadium, and combinations thereof to form a metal-containing zirconia, and calcining and drying the metal-containing zirconia to form a dehydrogenation catalyst.
  • the metal-containing zirconia may be calcined and dried under air at a temperature of less than or equal to 1000 C.
  • a method for forming a dehydrogenation catalyst may further comprise preparing the zirconia support by precipitation reaction.
  • adding a metal-containing precursor to the zirconia support to form a metal-containing zirconia may comprise impregnating the zirconia support with the metal to form a metal-impregnated zirconia.
  • the dehydrogenation catalyst may be prepared by precipitation.
  • the dehydrogenation catalyst may be prepared by co-precipitating the zirconia support and a metal-containing precursor, wherein the metal is selected from the group consisting of iron, cobalt, molybdenum, vanadium, and combinations thereof.
  • the dehydrogenation catalyst may be prepared by a combination of impregnation and precipitation.
  • the zirconia support might first be prepared by precipitation, and then the zirconia support might be impregnated with the metal-containing precursor by precipitation.
  • adding a metal-containing precursor to the zirconia support to form a metal-containing zirconia may comprise any combination of adding a metal-containing precursor to the zirconia support, wherein the zirconia support is a fluidizable zirconia support, adding a metal-containing precursor to the zirconia support by spray drying, or adding a metal-containing precursor to the zirconia support by granulation.
  • adding a metal-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 metal-containing precursor to the zirconia support.
  • the metal-containing precursor may be a dry powder or may be part of a solution or slurry.
  • the metal-containing zirconia support prepared using a fluidized bed operation may be spray dried.
  • adding a metal-containing precursor to the zirconia support by granulation may comprise combining powdered zirconia support with powdered metal-containing precursor and combining the powdered zirconia support and powdered metal-containing precursor to form metal-containing zirconia.
  • the promoted dehydrogenation catalyst may be prepared either by first impregnating the zirconia support with silicon and then impregnating the zirconia support with a metalcontaining precursor, wherein the metal is selected from the group consisting of iron, cobalt, molybdenum, vanadium, and combinations thereof, or by first impregnating the zirconia support with a metal-containing precursor, wherein the metal is selected from the group consisting of iron, cobalt, molybdenum, vanadium, and combinations thereof and then impregnating the zirconia support with silicon.
  • the surface area of the zirconia particles may be greater than or equal to 5 meters squared per gram (m 2 /g).
  • 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 particle may be from 5 m 2 /g to 200 m 2 /g, from 10 m 2 /g to 200 m 2 /g, from 20 m 2 /g to 200 m 2 /g, such as from 30 m 2 /g to 200 m 2 /g, from 40 m 2 /g to 200 m 2 /g, from 50 m 2 /g to 200 m 2 /g, from 60 m 2 /g to 200 m 2 /g, from 70 m 2 /g to 200 m 2 /g, from 80 m 2 /g to 200 m 2 /g, from 90 m 2 /g to 200 m 2 /g, from 100 m 2 /g to 200 m 2 /g, from 110 m 2 /g to 200 m 2 /g, from 120 m 2 /g to 200 m 2 /g, from 130 m 2 /g to 200 m 2 /g
  • the surface area of the zirconia particles may be from 5 m 2 /g to 180 m 2 /g, from 5 m 2 /g to 160 m 2 /g, from 5 m 2 /g to 140 m 2 /g, from 5 m 2 /g to 120 m 2 /g, from 5 m 2 /g to 100 m 2 /g, from 5 m 2 /g to 90 m 2 /g, from 5 m 2 /g to 80 m 2 /g, from 5 m 2 /g to 70 m 2 /g, from 5 m 2 /g to 60 m 2 /g, from 5 m 2 /g to 50 m 2 /g, from 5 m 2 /g to 40 m 2 /g, from 5 m 2 /g to 30 m 2 /g, from 5 m 2 /g to 20 m 2 /g, or from 5 m 2 /g to 10 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 metal from the group consisting of iron, cobalt, molybdenum, vanadium, and combinations thereof, and zirconia.
  • Some examples include vapor phase deposition of metal-containing precursors (either organic or inorganic in nature), followed by their controlled decomposition.
  • the dehydrogenation catalyst comprises from 0.5 % to 20 % metal selected from the group consisting of iron, cobalt, molybdenum, vanadium, or combinations thereof based on a total weight of the dehydrogenation catalyst.
  • the dehydrogenation catalyst may comprise from 0.5 % to 20 % metal selected from the group consisting of iron, cobalt, molybdenum, vanadium, or combinations thereof, 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 49
  • 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 0.5 wt.% to 20 wt.% metal, wherein the metal selected from the group consisting of iron, cobalt, molybdenum, vanadium, and combinations thereof, and 65 wt.% to 80 wt.% zirconium metal, wherein the weight percent is calculated based on a total weight of the dehydrogenation catalyst (the total weight of the dehydrogenation catalyst including the oxygen in the oxides).
  • the metal selected from the group consisting of of the metal selected from the group consisting of iron, cobalt, molybdenum, vanadium, and combinations thereof may be at least partially derived from iron oxide, cobalt oxide, molybdenum oxide, vanadium oxide, or combinations thereof.
  • the dehydrogenation catalyst may be a promoted dehydrogenation catalyst comprising the formula M-Zr-X, wherein M is a metal selected from the group consisting of iron, cobalt, molybdenum, vanadium, and combinations, and X is selected from the group consisting of alkali metals, alkaline earth metals, silicon (Si), platinum (Pt), tin (Sn), chloride (Cl), boron (B), phosphorous (P), sulfur (S), niobium (Nb), bismuth (Bi), antimony (Sb), and combinations thereof.
  • M is a metal selected from the group consisting of iron, cobalt, molybdenum, vanadium, and combinations
  • X is selected from the group consisting of alkali metals, alkaline earth metals, silicon (Si), platinum (Pt), tin (Sn), chloride (Cl), boron (B), phosphorous (P), sulfur (S), niobium (Nb),
  • X of the formula M-Zr-X may be an oxide.
  • Zr of the formula M-Zr-X may comprise zirconia (ZrCh).
  • 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 C2-C4 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. In embodiments, the controlled time of exposure may be from 5 seconds (sec) to 1 hour (h). In embodiments, 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.
  • the water may be in the form of steam.
  • the steam may comprise gaseous water, liquid water, aerosolized water, or 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.
  • 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. Therefore, the catalysts disclosed and described herein can operate in the presence of water without the addition of oxidative gas.
  • 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.
  • 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. In embodiments, 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 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.
  • oxygen-carrier materials such as those disclosed in U.S. App. No. 62/725,504, entitled “METHODS OF PRODUCING HYDROGEN-SELECTIVE OXYGENCARRIER MATERIALS,” fded on, August 31, 2018, and U.S. App. No. 62/725,508, entitled “HYDROGEN-SELECTIVE OXYGEN-CARRIER MATERIALS AND METHODS OF USE,” fded on, August 31, 2018, are contemplated as suitable for the presently disclosed processes, and the teachings of these references are incorporated by reference herein.
  • the oxygen-carrier material may include those of U.S. Pat. No. 5,430,209, U.S. Pat. No. 7,122,495, and/or WO 2018/232133, each of which are incorporated by reference in their entireties.
  • the dehydrogenation catalyst and the selective hydrogen combustion material are both present in the reaction zone.
  • the dehydrogenation catalyst and the selective hydrogen combustion material may be present in a mass to mass ratio of from 10:1 to 1 :10.
  • the dehydrogenation catalyst and the selective hydrogen combustion material may be present in a mass to mass ratio of from 10:1 to 1 :10, from 10:1 to 1 :10, from 2:1 to 1 :10, from 1 :1 to 1 :10, from 10:1 to 1 :5, from 10:1 to 1 :5, from 2:l to 1 :5, from 1 :1 to 1 :5, from 10:1 to 1 :2, from 10:1 to 1 :2, from 2:1 to 1 :2, from 1 :1 to 1 :2, from 10:1 to 1 :1, from 10:1 to 1 :1, from 2: 1 to 1 : 1, or from 1 : 1 to 1 : 1.
  • the dehydrogenation catalyst and the selective hydrogen combustion material may be in contact with each other. In embodiments, the dehydrogenation catalyst and the selective hydrogen combustion material may have been mixed or otherwise combined prior to being placed in the reaction zone. In embodiments, the dehydrogenation catalyst and the selective hydrogen combustion material may be mixed in the reaction zone. In embodiments, the dehydrogenation catalyst and the selective hydrogen combustion material may be separate.
  • gaseous oxidant(s) may refer to a substance or substances other than water that may oxidize hydrogen.
  • 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.
  • 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. In some embodiments, 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 feed rate of catalyst to the reaction zone and the 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 25:1 to 50:1, from 25:1 to 50:1, from 10:1 to 50:1, from 10:1 to 50:1, from 25:
  • the dehydrogenation catalyst and the feed stream may have a weight hourly space velocity (WHSV) of from 1 to 12 per hour (h -1 ), where WHSV is defined as the weight of the feed stream flow per weight of the dehydrogenation catalyst present in the reaction zone per hour.
  • WHSV weight hourly space velocity
  • the dehydrogenation catalyst and the feed stream may have a WHSV of from 1 to 12 h’ 1 , from 1 to 10 h’ 1 , from 1 to 8 h’ 1 , from 1 to 5 h’ 1 , from 1 to 3 h’ 1 , or from 1 to 2 h’ 1 .
  • the converting at least a portion of the alkanes to alkenes occurs at a temperature that is less than or equal to 750 °C. In embodiments, the converting at least a portion of the alkanes to alkenes occurs at a temperature that is less than or equal to 780 °C, less than or equal to 750 °C, less than or equal to 725 °C, less than or equal to 700 °C, less than or equal to 675 °C, or less than or equal to 650 °C. [0048] In one or more embodiments, the converting at least a portion of the alkanes to alkenes occurs at a pressure that is equal to atmospheric pressure.
  • 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. In embodiments, 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.
  • 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 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. In embodiments, the selective hydrogen combustion material prior to sending the selective hydrogen combustion material back to the reaction zone to close heat balance. In embodiments, 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.
  • a Fe/ZrCh catalyst was prepared by incipient wetness impregnation method.
  • 3 g of ZrCh support was impregnated with 0.6 milliliters (mE) of 1 M ammonium iron (III) citrate solution in DI water 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 °C 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 promoted dehydrogenation catalyst was made by first preparing an impregnated Si- ZrCh support, and then by impregnating the Si-ZrCb support with iron.
  • 5 g of ZrO2 support was impregnated with 2 mF of tetraethylorthosilicate (TEOS) until the impregnation solution was no longer drawn into the pores of the support and the impregnation solution was homogenously distributed over the support.
  • TEOS tetraethylorthosilicate
  • the material 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.
  • the support was sieved after calcination to remove fine particles smaller than 80 mesh.
  • NORPRO SZ31164 3 mm extrudates, BET 100 m 2 /g, pore volume determined by DI water 0.4 mE/g
  • NORPRO SZ31164 3 mm extrudates, BET 100 m 2 /g, pore volume determined by DI water 0.4 mL/g
  • the resulting peroxo-citrate vanadium solution stopped foaming and was cooled to room temperature (approximately 20 °C to 25 °C). More DI water was added to make the solution a volumetric 100 mL and achieve the nominal 1 mol (V-metal)-dnT 3 . Finally, 1.589 g of ZrCh support was impregnated with 0.635 mL of the prepared peroxo-citrate vanadium solution and until the prepared peroxo-citrate vanadium 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 400 °C at 5 deg/min, dwell 4 h, cool down to room temperature.
  • the catalyst was sieved after calcination to remove fine particles smaller than 80 mesh and then recalcined under air in the 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.
  • the resulting peroxo-citrate vanadium solution stopped foaming and was cooled to room temperature (approximately 20 °C to 25 °C). More DI water was added to make the solution a volumetric 100 mL and achieve the nominal 1 mol(V- metal)-dnT 3 . Finally, 1.614 g of ZrCh support was impregnated with 0.646 mL of the prepared peroxo-citrate vanadium solution until the prepared peroxo-citrate vanadium solution was no longer drawn into the pores of the support and the prepared peroxo-citrate vanadium 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 400 °C at 5 deg/min, dwell 4 h, cool down to room temperature.
  • the catalyst was sieved after calcination to remove fine particles smaller than 80 mesh and then recalcined 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
  • quartz chips Panatics part # 7359-05010 were used to determine background dehydrogenation activity.
  • a dehydrogenation catalyst that is known to effectively perform the dehydrogenation of propylene to propane under the conditions described in US patent number 9834496. the enti rety of which is hereby incorporated by reference, was used in the form of 70 micron particles.
  • a Cr/SiCh-AhOs 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-AbO3 support.
  • the support was crushed and sieved to 40- 80 mesh size prior to use.
  • 1.5 g of SiO2-AbO3 support was impregnated with 0.6 mL of 1 M chromium (III) nitrate nonahydrate solution in DI water 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
  • a Zn/ZrO2 catalyst was prepared by incipient wetness method.
  • 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 1-4
  • 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 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.
  • the reactor was purged with nitrogen gas (N2) where the pressure was 16 psia.
  • N2 nitrogen gas
  • the temperature was ramped to 400 °C under N2 flow and then the N2 flow was switched to 60% ethane - 20% H2O - 20% N2 flow.
  • Water inlet flow was controlled by a high pressure liquid chromatography (HPEC) pump.
  • HPEC high pressure liquid chromatography
  • An evaporator was used to evaporate water to the gas phase.
  • Feed analysis was performed by analyzing the feed gas composition using online gas chromatography (GC).
  • 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 N2 purge step.
  • 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.
  • Ethane Conversion (%) [(qc 2 H 6 , in - qc 2 H 6 , out)/ qc 2 H 6 , in] ⁇ 100
  • Equation 4 where r
  • Examples 1-3 demonstrate that catalysts comprising iron and zirconia demonstrate high activity under “dry” or “wet” ethane dehydrogenation conditions and retain their activity in the presence of 20% steam by volume.
  • the catalysts of Example 1-3 also demonstrate that metals impregnated on a zirconia support has substantial activity over metals impregnated on other supports, such as the catalyst of Comparative Example 3 which comprised a silica-alumina support.
  • Examples 4-6 demonstrate that catalysts comprising Co, V, or Mo, and ZrCh reach high activity under “dry” or “wet” alkane dehydrogenation conditions and retain their activity in the presence of 20% steam.
  • Comparative Example 4 demonstrates that not all metals can be used as steam tolerant dehydrogenation catalyst, as not all metal impregnated zirconia exhibit significant activity under 20% steam conditions.
  • 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 steam, the dehydrogenation catalyst comprising: zirconia and a metal selected from the group consisting of iron, cobalt, molybdenum, vanadium, and combinations thereof, 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 either the first aspect or the 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 a metal selected from the group consisting of iron, cobalt, molybdenum, vanadium, and combinations thereof, comprises zirconia impregnated with a metal selected from the group consisting of iron, cobalt, molybdenum, vanadium, and combinations thereof.
  • a seventh aspect of the present disclosure includes any of the first through sixth aspects, wherein the dehydrogenation catalyst comprises from 0.5 wt.% to 20 wt.% iron, cobalt, molybdenum, vanadium, or combinations thereof 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: 0.5 wt.% to 20 wt.% of the metal selected from the group consisting of iron, cobalt, molybdenum, vanadium, and combinations thereof, and 65 wt.% to 80 wt.% zirconium, wherein the weight percent is based on a total weight of the dehydrogenation catalyst.
  • the dehydrogenation catalyst comprises: 0.5 wt.% to 20 wt.% of the metal selected from the group consisting of iron, cobalt, molybdenum, vanadium, and combinations thereof, and 65 wt.% to 80 wt.% zirconium, wherein the weight percent is based on a total weight of the dehydrogenation catalyst.
  • a ninth aspect of the present disclosure includes any of the first through eighth aspects, wherein the iron, cobalt, molybdenum, vanadium, or combinations thereof are at least partially derived from iron oxide, cobalt oxide, molybdenum oxide, vanadium oxide, or combinations thereof.
  • 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 M-Zr-X, wherein M is a metal selected from the group consisting of iron, cobalt, molybdenum, vanadium, and combinations, and X is selected from the group consisting of alkali metals, alkaline earth metals, silicon, platinum, tin, chloride, boron, phosphorous, sulfur, niobium, bismuth, antimony, and combinations thereof.
  • M is a metal selected from the group consisting of iron, cobalt, molybdenum, vanadium, and combinations
  • X is selected from the group consisting of alkali metals, alkaline earth metals, silicon, platinum, tin, chloride, boron, phosphorous, sulfur, niobium, bismuth, antimony, and combinations thereof.
  • 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 comprises: 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 promoted dehydrogenation catalyst, and returning the 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 metalcontaining precursor to the zirconia support, wherein the metal-containing precursor is selected from the group consisting of iron, cobalt, molybdenum, vanadium, and combinations thereof to form a metal-containing zirconia, and calcining and drying the metal-containing zirconia to form a dehydrogenation catalyst.
  • a sixteenth aspect of the present disclosure includes the fiftieth aspect wherein contacting the zirconia support with the metal to form a metal-containing zirconia is a process selected from the group consisting of: adding the metal-containing precursor to the zirconia support, wherein the zirconia support is a fluidizable zirconia support, adding the metal-containing precursor to the zirconia support by spray drying, adding the metal-containing precursor to the zirconia support by granulation; and combinations thereof.
  • first component is described as “comprising” a second component, it is contemplated that, in embodiments, the first component “consists” or “consists essentially of’ that second component. It should further be understood that where a first component is described as “comprising” a second component, it is contemplated that, in embodiments, 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 %).

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Abstract

Un procédé de conversion d'alcanes en alcènes comprend 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 un métal choisi dans le groupe constitué par le fer, le cobalt, le molybdène, le vanadium et des combinaisons de ceux-ci. 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/US2024/035551 2023-06-30 2024-06-26 Procédés de conversion d'alcanes en alcènes et catalyseurs de déshydrogénation tolérants à la vapeur et sans danger pour l'environnement Ceased WO2025006558A1 (fr)

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