Dehydrogenation catalyst materials and systems and methods for using same

Abstract

The present disclosure relates dehydrogenation catalyst materials, and their use in the dehydrogenation of alkanes to provide olefins. In one aspect, the disclosure provides a catalyst material comprising: an alumina or silica-alumina carrier; gallium, present in the catalyst material in an amount in the range of 0.5-8 wt%, calculated as Ga2O3 on a calcined basis; and zirconium, present in the catalyst material in an amount in the range of 0.5-30 wt%, calculated as ZrO2 on a calcined basis. Notably, the catalyst material exhibits, in a calcined form, a ratio of a peak height of an infrared absorbance peak at 1595 ± 5 cm-1 to a peak height of an infrared absorbance peak at 1615 ± 5 cm-1 of no more than 0.7 in a pyridine FTIR experiment.

Description

DEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT DEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAMEBACKGROUND OF THE DISCLOSURE1. Field

[0001] The present disclosure relates generally to catalyst materials, processes for making them, catalyst systems including them, and their use in the dehydrogenation of alkanes to provide olefins.2. Technical Background

[0002] Alkane dehydrogenation is a recognized process for production of a variety of useful hydrocarbon products, such as in the dehydrogenation of propane to make propene for use in the polymer industry, dehydrogenation of n-butane to produce n-butene or alkylate and butadiene useful in tire production, and the dehydrogenation of isobutane to make isobutylene suitable for conversion to methyl tert-butyl ether, isooctane, and alkylates to supplement and enrich gasolines. Current commercial catalysts useful for catalytic dehydrogenation of light alkanes include CrOx / AI2O3 and Pt-Sn / AhOs catalysts, which have been in use for decades.

[0003] CrOx / AI2O3 dehydrogenation catalysts typically contain a majority of their chromium in the Cr(lll) oxidation state on the alumina surface. However, there typically remains a small amount of Cr(VI) , which is carcinogenic and thus presents health risks during catalyst handling and operation. They also can cause significant environmental pollution.

[0004] Gallium-based dehydrogenation catalysts have been known for two decades. They are generally not hazardous, and their application presents no significant environmental issue. However, these catalysts have limitations in activity and stability, especially for the commercially important dehydrogenation of propane. For example, the reaction temperature necessary to maintain a desired propylene yield for a gallium-based dehydrogenation catalyst often increases with the number of reaction-regeneration cycles to which the catalyst is subjected.

[0005] Accordingly, there remains a need for improved gallium-based dehydrogenation catalysts.SUMMARY OF THE DISCLOSURE

[0006] In one aspect, the disclosure provides a catalyst material for the dehydrogenation of hydrocarbons, the catalyst material comprising:an alumina or silica-alumina carrier, the catalyst material having in the range of 39- 98.75 wt% aluminum, calculated as AI2Os on a calcined basis, and a ratio of anDEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT amount of silicon to a combined amount of silicon and aluminum of up to 20 wt%, in which silicon and aluminum are respectively calculated as SiC>2 and AI2O3 on a calcined basis;gallium, present in the catalyst material in an amount in the range of 0.5-8 wt%, calculated as Ga2Os on a calcined basis; andzirconium, present in the catalyst material in an amount in the range of 0.5-30 wt%, calculated as Zr©2 on a calcined basis.Notably, the catalyst material exhibits, in a calcined form, a ratio of a peak height of an infrared absorbance peak at 1595 ± 5 cm-1to a peak height of an infrared absorbance peak at 1615 ± 5 cm'1of no more than 0.7 in a pyridine FTIR experiment, which is described in detail below.

[0007] In another aspect, the disclosure provides a method for preparing the catalyst material as disclosed herein, the method comprising:providing an aqueous mixture comprising:a gallium source;a zirconium source; andan aluminum source; andforming a solid from the aqueous mixture; andcalcining the solid so formed.In various desirable embodiments, the gallium source is substantially dissolved in the aqueous mixture. In various desirable embodiments, the zirconium source is substantially dissolved in the aqueous mixture.

[0008] In another aspect, the disclosure provides a catalyst bed for the dehydrogenation of hydrocarbons, the catalyst bed comprising the catalyst material as disclosed herein, present in the catalyst bed (e.g., in an amount in the range of 40-70 vol%, based on the total volume of the catalyst bed).

[0009] In another aspect, the disclosure provides a method for dehydrogenating hydrocarbons, the method comprising:providing a catalyst as disclosed herein in a dehydrogenation reaction zone; and performing a plurality of reaction cycles, each reaction cycle comprising:reducing the catalyst material under a reducing atmosphere comprising H2; contacting a feed stream comprising hydrocarbons with the catalyst bed to provide a deactivated catalyst and a product stream comprising dehydrogenated hydrocarbons, wherein a reaction byproduct comprising coke is formed in the catalyst bed;purging the dehydrogenation reaction zone with a purge stream to substantially remove the product stream thereof;DEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT regenerating the deactivated catalyst under an oxidizing atmosphere comprising O2 to provide the catalyst material; andremoving the oxidizing atmosphere from the dehydrogenation reaction zone.

[0010] Other aspects of the disclosure will be apparent to the person of ordinary skill in the art in view of the discussion herein.BRIEF DESCRIPTION OF THE DRAWINGS

[0011] The accompanying drawings are included to provide a further understanding of the compositions and processes of the disclosure, and are incorporated in and constitute a part of this specification. The drawings are not necessarily to scale, and sizes of various elements may be distorted for clarity. The drawings illustrate one or more embodiment(s) of the disclosure and, together with the description, serve to explain the principles and operation of the disclosure.

[0012] FIG. 1 is a plot of the propylene yield versus dehydrogenation cycle number for catalyst materials A1-A3 and C1-C3.

[0013] FIG. 2 shows Pyridine-FTIR (Py-FTIR) spectra for catalyst materials A1-A3 and C1-C3.

[0014] FIG. 3 shows X-ray Diffraction (XRD) spectra for various catalyst materials.

[0015] FIG. 4 is a schematic of the catalyst beds described herein.DETAILED DESCRIPTION

[0016] One of the main commercial processes for preparing alkenes from the dehydrogenation of alkanes is the Houdry process (also known as the CATOFIN process). The Houdry process is a cyclic dehydrogenation process that involves sequentially regenerating the catalyst bed under oxidative conditions and activating the catalyst under reductive conditions in between each dehydrogenation reaction.

[0017] Conventional Houdry-type processes rely on chromium-based dehydrogenation catalysts, which can be hazardous due to trace amounts of chromium (VI) therein. As such, it can be desirable to replace such dehydrogenation catalysts with gallium-based ones, which are generally non-hazardous and do not present significant environmental issue when used. However, gallium-based dehydrogenation catalysts can have limitations in activity and stability. For example, gallium-based catalysts can have stability issues with steam purges, which are typically used to remove the product stream from the dehydrogenation reaction zone. Gallium-based catalysts can also have stability issues when included in a catalyst bed together with heat-generating materials, which are typically added to a catalyst bed to help maintain sufficiently high temperatures for dehydrogenation. Advantageously, the present inventors have found that that the inclusion of zirconium in the gallium-basedDEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT dehydrogenation catalysts can lead to improvements to their activity and stability during the dehydrogenation processes described above. Notably, the present inventors have found that use of zirconium can reduce the fraction of weak Bronsted acid sites (as measured by pyridine FTIR as described herein) can significantly improve the stability of the catalyst material to the steam purge typically used in cyclic dehydrogenation processes.

[0018] Catalyst Materials

[0019] One aspect of the present disclosure provides a catalyst material that includes: an alumina or silica-alumina carrier, the catalyst material having in the range of 44-98.75 wt% aluminum, calculated as AI2O3 on a calcined basis, and a ratio of an amount of silicon to a combined amount of silicon and aluminum of up to 20 wt%, in which silicon and aluminum are respectively calculated as SiO2 and AI2O3 on a calcined basis; gallium, present in the catalyst material in an amount in the range of 0.5-8 wt%, calculated as Ga2Os on a calcined basis; and zirconium, present in the catalyst material in an amount in the range of 0.5-30 wt%, calculated as ZrC>2 on a calcined basis. Notably, the catalyst material exhibits, in a calcined form, a ratio of a peak height of an infrared absorbance peak at 1595 ± 5 cm'1to an infrared absorbance peak at 1615 ± 5 cm'1of no more than 0.7 in a pyridine FTIR experiment, which is described in detail below.

[0020] The dehydrogenation catalyst materials described herein comprise gallium. As described above, gallium-based catalyst materials can be a safer alternative to chromium-based catalyst materials for Houdry-type dehydrogenation processes. In various embodiments of the present disclosure as described herein, gallium is present in the catalyst material in an amount in the range of 0.5-6 wt%, e.g. in the range of 0.5-4 wt%, or in the range of 0.5-3.5 wt%, or in the range of 0.2-3 wt%, calculated as Ga2Os on a calcined basis. For example, in various embodiments, gallium is present in the catalyst material in an amount in the range of 1-8 wt%, e.g. in the range of 1-6 wt%, or in the range of 1-4 wt%, or in the range of 1-3.5 wt%, or in the range of 1-3 wt%, calculated as Ga2Os on a calcined basis. In some embodiments, gallium is present in the catalyst material in an amount in the range of 1.5-8 wt%, e.g. in the range of 1.5-6 wt%, or in the range of 1.5-4 wt%, or in the range of 1.5-3.5 wt%, or in the range of 1.5-3 wt%, calculated as Ga2Os on a calcined basis. For example, in various embodiments as described herein, gallium is present in the catalyst material in an amount in the range of 2-8 wt%, e.g. in the range of 2-6 wt%, or in the range of 2-4 wt%, or in the range of 2-3.5 wt%, or in the range of 2-3 wt%, calculated as Ga2Os on a calcined basis. For example, in some embodiments, gallium is present in the catalyst material in an amount in the range of 2.5-8 wt%, e.g. in the range of 2.5-6 wt%, or in the range of 2.5-4 wt%, or in the range of 2.5-3.5 wt%, calculated as Ga2Os on a calcined basis.

[0021] The present inventors have discovered that the inclusion of zirconium in the catalyst material can improve the stability and activity of the catalyst, and can provide aDEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT desirable reduced fraction of weak Bronsted acid sites. In various embodiments of the present disclosure as described herein, zirconium is present in the catalyst material in an amount in the range of 0.5-30 wt%, e.g., in the range of 0.5-25 wt%, or in the range of 0.5-20 wt%, or in the range of 0.5-15 wt%, or in the range of 0.5-10 wt%, or in the range of 0.5-8 wt%, or in the range of 0.5-5 wt%, calculated as Zr©2 on a calcined basis. For example, in various embodiments, zirconium is present in the catalyst material in an amount in the range of 1-30 wt%, e.g., in the range of 1-25 wt%, or in the range of 1-20 wt%, or in the range of 1-15 wt%, or in the range of 1 -10 wt%, or in the range of 1 -8 wt%, or in the range of 1 -5 wt%, calculated as ZrC>2 on a calcined basis. In various embodiments, zirconium is present in the catalyst material in an amount in the range of 2-30 wt%, e.g., in the range of 2-25 wt%, or in the range of 2-20 wt%, or in the range of 2-18 wt%, or in the range of 2-15 wt%, or in the range of 2-12 wt%, or in the range of 2-10 wt%, or in the range of 2-8 wt%, or in the range of 2-5 wt%, calculated as Zr©2 on a calcined basis. In some embodiments, zirconium is present in the catalyst material in an amount in the range of 3.5-30 wt%, e.g., in the range of 3.5-25 wt%, or in the range of 3.5-20 wt%, or in the range of 3.5-18 wt%, or in the range of 3.5-15 wt%, or in the range of 3.5-12 wt%, or in the range of 3.5-10 wt%, or in the range of 3.5-8 wt%, calculated as ZrC>2 on a calcined basis. For example, in some embodiments, zirconium is present in the catalyst material in an amount in the range of 5-30 wt%, e.g., in the range of 5-25 wt%, or in the range of 5-20 wt%, or in the range of 5-18 wt%, or in the range of 5-15 wt%, or in the range of 5-12 wt%, or in the range of 5-10 wt% or in the range of 5-8 wt%, calculated as Zr©2 on a calcined basis.

[0022] The gallium and zirconium can present in an amount such that the catalyst material has sufficient activity and stability when used in a dehydrogenation process. As such, the gallium and zirconium can be present in the catalyst material in a particular weight ratio. For example, in various embodiments as described herein, a weight ratio of zirconium to gallium (i.e., as oxides on an as-calcined basis) present in the catalyst material is in the range of 1 :1 to 20:1 , e.g., in the range of 1 :1 to 15:1 , or in the range of 1 :1 to 10:1 , or in the range of 1 :1 to 5:1 , or in the range of 1 :1 to 2:1. In some embodiments, a weight ratio of zirconium to gallium present in the catalyst material is in the range of 1 .5:1 to 20:1 , e.g., in the range of 1.5:1 to 15:1 , or in the range of 1.5:1 to 10:1 , or in the range of 1 .5:1 to 5:1 , or in the range of 1.5:1 to 3:1 . For example, in some embodiments, a weight ratio of zirconium to gallium present in the catalyst material is in the range of 2:1 to 20:1 , e.g., in the range of 2:1 to 15:1 , or in the range of 2:1 to 10:1 , or in the range of 2:1 to 5:1.

[0023] The catalyst material further comprises an alumina or a silica-alumina carrier; in various embodiments, the catalyst material has in the range of 39-98.75 wt% aluminum to the catalyst material, calculated as AI2O3 on a calcined basis. In various embodiments of the present disclosure as described herein, aluminum is present in the catalyst material in anDEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT amount in the range of 39-95 wt%, e.g., in the range of 39-92 wt%, or in the range of 39-90 wt%, or in the range of 39-85 wt%, or in the range of 39-80 wt%, or in the range of 39-75 wt%, calculated as AI2O3 on a calcined basis. For example, in various embodiments, aluminum is present in the catalyst material in an amount in the range of 60-98.75 wt%, e.g., in the range of 60-95 wt%, or in the range of 60-93 wt%, or in the range of 60-90 wt%, or in the range of 60-85 wt%, or in the range of 60-80 wt%, calculated as AI2O3 on a calcined basis. In various embodiments, aluminum is present in the catalyst material in an amount in the range of 75-98.75 wt%, e.g., in the range of 75-95 wt%, or in the range of 75-93 wt%, or in the range of 75-90 wt%, or in the range of 75-85 wt%, or in the range of 75-80 wt%, calculated as AI2O3 on a calcined basis. For example, in some embodiments, aluminum is present in the catalyst material in an amount in the range of 85-98.75 wt%, e.g., in the range of 85-95 wt%, or in the range of 85-93 wt%, or in the range of 85-90 wt%, calculated as AI2O3 on a calcined basis.

[0024] As noted above, the carrier can be an alumina or silica-alumina carrier. The catalyst material can have a ratio of an amount of silicon to a combined amount of silicon and aluminum of up to 20 wt%, in which silicon and aluminum are respectively calculated as SiC>2 and AI2O3 on a calcined basis. In some embodiments, a ratio of an amount of silicon to a combined amount of silicon and aluminum in the catalyst material is up to 15 wt%, e.g., up to 10 wt%, or up to 5 wt%. In some embodiments, a ratio of an amount of silicon to a combined amount of silicon and aluminum is in the range of 1-20 wt%, e.g., in the range of 1-15 wt%, or in the range of 1-10 wt%, or in the range of 1-5 wt%. For example, in various embodiments, a ratio of an amount of silicon to a combined amount of silicon and aluminum is in the range of 2-20 wt%, e.g., in the range of 2-15 wt%, or in the range of 2-10 wt%, or in the range of 2-5 wt%.

[0025] The person of ordinary skill in the art will appreciate that aluminum and silicon can both be provided from a single silica-alumina source . As such, the aluminum and silicon can be present in the catalyst material in a particular ratio. For example, in some embodiments a weight ratio of aluminum to silicon present in the catalyst material, calculated as AI2O3 and SiC>2 on a calcined basis, is in the range of 4:1 to 50:1 , e.g., in the range of 4:1 to 25:1 , or in the range of 4:1 to 20:1 , or in the range of 9:1 to 50:1 , or in the range of 9:1 to 25:1 , or in the range 9:1 to 20:1 , or in the range of 14:1 to 50:1 , or in the range of 14:1 to 25:1 , or in the range of 14:1 to 20:1 .

[0026] The catalyst material as described herein can generally be considered as a gallia-zirconia-alumina matrix. However, the present inventors contemplate that additional metal promoters can be included. In various embodiments as described herein, the catalyst material further comprises platinum. For example, in various embodiments of the present disclosure, platinum is present in the gallium-based catalyst material in an amount up to 250DEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT ppm on a weight basis, e.g., up to 150 ppm, or up to 100 ppm, or up to 50 ppm, calculated as PtO2 on a calcined basis. In some embodiments, platinum is present in the gallium-based catalyst material in an amount in the range of 1-250 ppm, e.g., in the range of 1-150 ppm, or in the range of 1-100 ppm, or in the range of 1-50 ppm, or in the range of 5-250 ppm, or in the range of 5-150 ppm, or in the range of 5-100 ppm or in the range of 5-50 ppm, or in the range of 10-250 ppm, or in the range of 10-150 ppm, or in the range of 10-100 ppm, or in the range of 10-50 ppm, calculated as PtO2 on a calcined basis.

[0027] In various embodiments as described herein, the catalyst material further comprises cerium. For example, in various embodiments of the present disclosure as described herein, cerium is present in the catalyst material in an amount up to 34 wt%, e.g., up to 2 wt%, or up to 1 wt%, or up to 0.5 wt%, or up to 0.2 wt%, or up to 0.1 wt%, or up to 0.05 wt%, calculated as CeO2 on a calcined basis. In some embodiments, cerium is present in the catalyst material in an amount in the range of 0.02-4 wt%, e.g., in the range of 0.02-2 wt%, or in the range of 0.02-1 wt%, or in the range of 0.02-0.5 wt%, or in the range of 0.02-0.2 wt% or in the range of 0.02-0.1 wt%, calculated as CeO2 on a calcined basis. In various embodiments, cerium is present in the catalyst material in an amount in the range of 0.05-4 wt%, e.g., in the range of 0.05-2 wt%, or in the range of 0.05-1 wt%, or in the range of 0.05-0.5 wt%, or in the range of 0.05-0.2 wt% or in the range of 0.05-0.1 wt%, calculated as CeO2 on a calcined basis.

[0028] In various embodiments as described herein, the catalyst material further comprises one or more promoters M1 selected from Group 1 metals and / or one or more promoters M2 selected from Group 2 metals, wherein promoters M1 and M2 are present in the catalyst material in a total amount up to 3 wt%. For example, in some embodiments, the catalyst material further comprises one or more promoters M1. In various embodiments, the one or more promoters M1 are selected from the group consisting of lithium, sodium, potassium, and a combination thereof. In certain embodiments, the one or more promoters M1 are potassium. In various embodiments of the present disclosure, the one or more promoters M1 are present in the catalyst material in a total amount in the range of 0.01-3 wt%, e.g., in the range of 0.01-2.5 wt%, or in the range of 0.01-2 wt%, or in the range of 0.01-1.5 wt%, or in the range of 0.01-1 wt%, calculated as M12O on a calcined basis. In some embodiments, the one or more promoters M1 are present in the catalyst material in a total amount in the range of 0.05-3 wt%, e.g., in the range of 0.05-2.5 wt%, or in the range of 0.05-2 wt%, or in the range of 0.05-1.5 wt%, or in the range of 0.05-1 wt%, calculated as M12O on a calcined basis.

[0029] In various embodiments, the catalyst material further comprises one or more promoters M2. In various embodiments, the one or more promoters M2 are selected from the group consisting of beryllium, magnesium, calcium, and a combination thereof. InDEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT various embodiments of the present disclosure, the one or more promoters M2 are present in the catalyst material in a total amount in the range of 0.01-3 wt%, e.g., in the range of 0.01-2.5 wt%, or in the range of 0.01-2 wt%, or in the range of 0.01-1.5 wt%, or in the range of 0.01-1 wt%, calculated as M2O on a calcined basis. In some embodiments, the one or more promoters M2 are present in the catalyst material in a total amount in the range of 0.05-3 wt%, e.g., in the range of 0.05-2.5 wt%, or in the range of 0.05-2 wt%, or in the range of 0.05-1.5 wt%, or in the range of 0.05-1 wt%, calculated as M2O on a calcined basis.

[0030] For example, in various embodiments of the present disclosure as described herein, a total amount of promoters M1 and M2 present in the catalyst material is up to 2.5 wt%, e.g., up to 2 wt%, or up to 1 .5 wt%, or up to 1 wt%, calculated as M12O and M2O on a calcined basis. In various embodiments of the present disclosure, a total amount of promoters M1 and M2 present in the catalyst material is in the range of 0.01-3 wt%, e.g., in the range of 0.01 -2.5 wt%, or in the range of 0.01 -2 wt%, or in the range of 0.01 -1.5 wt%, or in the range of 0.01-1 wt%, calculated as M12O and M2O on a calcined basis. In some embodiments, a total amount of promoters M1 and M2 present in the catalyst material is in the range of 0.05-3 wt%, e.g., in the range of 0.05-2.5 wt%, or in the range of 0.05-2 wt%, or in the range of 0.05-1.5 wt%, or in the range of 0.05-1 wt%, calculated as M12O and M2O on a calcined basis.

[0031] The elements described hereinabove can comprise a substantial amount of the catalyst materials. For example, in various embodiments as described herein, a total amount of gallium, zirconium, aluminum, silicon, M1 promoter(s), M2 promoter(s), platinum and cerium each calculated as oxide on a calcined basis, is at least 90 wt% of the catalyst material, e.g., at least 95 wt%, or at least 98 wt%, or at least 99 wt%.

[0032] As such, in some embodiments of the present disclosure, other metals are not present in a significant amount in the catalyst material. For example, in some embodiments, the catalyst material does not include a substantial amount of chromium, copper, or cobalt. In various embodiments as described herein, a chromium content of the catalyst material is less than 0.1 wt% chromium, e.g., less than 0.05 wt%, or less than 0.01 wt%, based on the total weight of the catalyst, calculated as Cr2Os on a calcined basis. In some embodiments, a copper content of the catalyst material is less than 0.1 wt% copper, e.g., less than 0.05 wt%, or less than 0.01 wt%, based on the total weight of the catalyst. In various embodiments, a cobalt content of the catalyst material is less than 0.1 wt% cobalt, e.g., less than 0.05 wt%, or less than 0.01 wt%, based on the total weight of the catalyst, calculated as CuO on a calcined basis. In some embodiments, the catalyst material does not include chromium. In some embodiments, the catalyst material does not include copper. In some embodiments, the catalyst material does not include cobalt.DEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT

[0033] The person of ordinary skill in the art will appreciate that the catalyst materials described herein can have a plurality of Lewis acid sites and Bronsted acid sites on the surface thereof. The person of ordinary skill in the art will appreciate that a Lewis acid site is a discrete site on the surface of the catalyst material that can accept electrons from an adsorbent. The person of ordinary skill in the art will also appreciate that a Bronsted acid site is a discrete hydrogen atom-bearing site on the surface of the catalyst material that, upon contact with a Bronsted base, can lead to the transfer of the proton from the Bronsted acid site to the Bronsted base. As used herein, the “total number of acid sites” of a catalyst material refers to the sum of the total number of Lewis acid sites and the total number of Bronsted acid site on the surface thereof. The present inventors have found that reducing the number of weak Bronsted acid sites on the catalyst material (as measured by pyridine FTIR as described herein) can improve the dehydrogenation activity of the catalyst materials described herein. Without intending to be bound by theory, the present inventors believe that the inclusion of zirconium in the gallium catalyst material, can modulate the weak Bronsted acidity of the catalyst material. Such changes to the acid landscape of the catalyst surface can interfere with potential adsorbents from the feed stream or product stream that can poison the catalyst, thus leading to improved dehydrogenation activity and catalyst stability, especially during the steam purging operations typically used in cyclic dehydrogenations.

[0034] As used herein, the term “weak Bronsted acid site” is used to refer to Bronsted acid sites on the surface of the catalyst material that, when contacted with pyridine, give rise to a signal in the range of 1590-1600 cm-1(e.g., a signal of 1595 cm'1) in a Fourier Transform Infrared Spectroscopy (FTIR) spectrum. The present inventors determined a degree of weak Bronsted acid site by obtaining a FTIR spectrum after contacting a given catalyst material with pyridine, and deconvoluting the FTIR spectrum of the pyridine into four Gaussian peaks centered in the ranges of 1570-1580 cm-1(e.g., a signal of 1575 cm'1), 1590-1600 cm'1(e.g., a signal of 1595 cm'1), 1610-1620 cm'1(e.g., a signal of 1615 cm-1), and 1630-1640 cm'1(e.g., a signal of 1635 cm-1). The degree of weak Bronsted acid sites is quantified as a ratio of a peak height of an infrared absorbance peak at 1595 ± 5 cm'1to a peak height of an infrared absorbance peak at 1615 ± 5 cm'1.

[0035] In various embodiments as described herein, the catalyst material exhibits, in a calcined form, a ratio of a peak height of an infrared absorbance peak at 1595 ± 5 cm'1to a peak height of an infrared absorbance peak at 1615 ± 5 cm'1in the range of 0.1 -0.7, e.g., 0.2-0.7, or 0.3-0.7 in a pyridine FTIR experiment. In various embodiments, the catalyst material exhibits, in a calcined form, a ratio of a peak height of an infrared absorbance peak at 1595 ± 5 cm'1to a peak height of an infrared absorbance peak at 1615 ± 5 cm-1of no more than 0.6, e.g., in the range of 0.1 -0.6, e.g., 0.2-0.6, or 0.3-0.6, in a pyridine FTIRDEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT experiment. In various embodiments, the catalyst material exhibits, in a calcined form, a ratio of a peak height of an infrared absorbance peak at 1595 ± 5 cm'1to a peak height of an infrared absorbance peak at 1615 ± 5 cm-1of no more than 0.5, e.g., in the range of 0.1 -0.5, e.g., 0.2-0.5, or 0.3-0.5, in a pyridine FTIR experiment.

[0036] The nature of the zirconium precursor can influence the zirconium dispersion in the final calcined catalyst material. The present inventors found that there can be broad variation in the sharpness of the primary tetragonal Zr©2 reflection observed at 20 = 30.4° when performing Rietveld refinement of x-ray diffraction (XRD) spectra of various catalyst materials. The person of ordinary skill in the art will appreciate that Rietveld refinement of XRD spectra can be used to estimate crystalline domain sizes based on the full-width half maximum (FWHM) value of the corresponding reflection peak. The present inventors have found that smaller Zr©2 crystalline domains can be effective at promoting the catalyst. For example, in various embodiments as described herein, at least 50 wt%, e.g., at least 75 wt%, or at least 90 wt%, of the zirconium present in the catalyst material have crystalline domain sizes of no more than 4 nm (e.g., in the range of 0.5-4 nm, or in the range of 1-4 nm), as determined by Rietveld refinement of the x-ray diffraction spectra of the catalyst material. For example, in some embodiments, at least 50 wt%, e.g., at least 75 wt%, or at least 90 wt%, of the zirconium present in the catalyst material have crystalline Zr©2 domain sizes of no more than 3 nm (e.g., in the range of 0.5-3 nm, or in the range of 1-3 nm), as determined by Rietveld refinement of the x-ray diffraction spectra of the catalyst material. In various embodiments as described herein, at least 50 wt%, e.g., at least 75 wt%, or at least 90 wt%, of the zirconium present in the catalyst material have crystalline Zr©2 domain sizes of no more than 2.5 nm (e.g., in the range of 0.5-2.5 nm, or in the range of 1-2.5 nm), as determined by Rietveld refinement of the x-ray diffraction spectra of the catalyst material. For example, in some embodiments of the present disclosure, at least 50 wt%, e.g., at least 75 wt%, or at least 90 wt%, of the zirconium present in the catalyst material have crystalline Zr©2 domain sizes of no more than 2 nm (e.g., in the range of 0.5-2 nm, or in the range of 1-2 nm), as determined by Rietveld refinement of the x-ray diffraction spectra of the catalyst material. However, the presence of large XRD-observable Zr©2 crystalline domains does not necessarily imply a lack of a zirconium promoter effect.

[0037] Synthesis of Catalyst Materials

[0038] In another aspect, the present disclosure provides a method for preparing the catalyst material as disclosed herein, the method comprising: providing an aqueous mixture comprising: a gallium source; a zirconium source; and an aluminum source; and forming a solid from the aqueous mixture; and calcining the solid so formed. As described below, in some embodiments the gallium source and / or the zirconium source are substantially dissolved in the aqueous mixture.DEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT

[0039] As described above, the catalyst materials described herein can further comprise platinum, cerium, promoters M1 or M2, and / or silicon. As such, in various embodiments of the present disclosure, the method further comprises providing a platinum source, a cerium source, a promoter M1 source, a promoter M2 source, and / or a silicon source in the aqueous mixture. Here, too, in various embodiments the platinum source, cerium source, promoter M1 source, and / or promoter M2 source are substantially dissolved in the aqueous mixture.

[0040] Nitrate salts can be especially useful in synthesis of catalyst materials. In some embodiments of the present disclosure, at least one of the gallium source, the zirconium source, the platinum source, the promoter M1 source, and the promoter M2 source comprises one or more nitrate counterions.

[0041] Aluminum and silicon precursors can be provided in a variety of fashions, e.g., as a particulate silicon-doped alumina.

[0042] As discussed above, the present inventors have found that the zirconium source can affect the crystalline Zr©2 domain sizes of the calcined catalyst material. As smaller crystalline Zr©2 domain sizes can lead to improved dehydrogenation activity and stability, it can be beneficial to ensure that the zirconium source is substantially dissolved or otherwise dispersed in the aqueous mixture during preparation of the catalyst material. A variety of water-soluble zirconium precursors can be used, e.g., salts of zirconium cations with fluoride, chloride, bromide, iodide, nitrate, acetate, sulfate, sulfite, silicate, or citrate as counterions. In various embodiments, the zirconium precursor is a zirconium nitrate, a zirconium acetate, or a zirconium carbonate. The present inventors have also found that decreasing the pH of the aqueous mixture (e.g., with nitric acid) can help ensure that the zirconium source is substantially dissolved therein. For example, in various embodiments of the present disclosure, the aqueous mixture has a pH of no more than 3, e.g., no more than 2, or no more than 1. For example, in various embodiments as described herein, the method further comprises adjusting the pH of the aqueous mixture using nitric acid prior to forming a solid from the aqueous mixture. In certain embodiments, the nitric acid is concentrated nitric acid (i.e., nitric acid having a molarity of about 15.7 M).

[0043] In various embodiments of the present disclosure, at least 70%, e.g., at least 80%, or at least 90% of the zirconium atoms of the catalyst material is provided from the zirconium source.

[0044] Of course, the zirconium precursor can be provided in other forms. It is desirable that even if the zirconium precursor is not fully dissolved in the aqueous mixture, it be well-dispersed so that it can form small domains in the eventual catalyst material. The person of ordinary skill in the art can, based on the disclosure herein, especially based on particle sizeDEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT and acid site measurements, determine other forms of the zirconium precursor suitable for use.

[0045] The particulars for forming a solid from the aqueous mixture and calcining the solid so formed can be determined by the person of ordinary skill in the art. For example, in various embodiments, the aqueous mixture is in the form of a slurry or paste, and forming the solid comprises extruding and drying the slurry or paste to provide a solid. Precipitating solid materials can also be performed, for example, by rapid pH adjustment to less-acidic pH to precipitate salts; precipitation can be performed before an extrusion step, or, in some cases can itself provide a solid material. In some embodiments, calcining the solid is performed at a calcination temperature in the range of 500-1200 °C, e.g., in the range of 500-1000 °C, or in the range of 500-800 °C, or in the range of 700-1200 °C, or in the range of 700-1000 °C, or in the range of 900-1200 °C.

[0046] Various metals can be provided using impregnation techniques; for example, platinum and cerium can be conveniently added to the gallia / zirconia / alumina matrix by impregnation.

[0047] And of course the person of ordinary skill in the art is familiar with a variety of methods for synthesizing catalyst, including precipitation, sol-gel, impregnation, bulk compounding and combinations thereof, and can adapt such processes to make the materials described herein.

[0048] Catalyst Beds

[0049] In another aspect, the disclosure provides a catalyst bed for the dehydrogenation of hydrocarbons, the catalyst bed comprising the catalyst material as disclosed herein, for example, present in the catalyst bed in an amount in the range of 40-70 vol%, based on the total fill volume of the catalyst bed. The amount of catalyst material disposed in the catalyst bed is not particularly limited. For example, in various embodiments of the present disclosure, the catalyst material is present in the catalyst bed in an amount in the range of 40-65 vol%, e.g., in the range of 40-60 vol%, or in the range of 40-55 vol%, or in the range of 40-50 vol%, based on the total fill volume of the catalyst bed. In some embodiments, the catalyst material is present in the catalyst bed in an amount in the range of 45-70 vol%, e.g., in the range of 45-65 vol%, or in the range of 45-60 vol%, or in the range of 45-55 vol%, or in the range of 45-50 vol%, based on the total fill volume of the catalyst bed. For example, in some embodiments, the catalyst material is present in the catalyst bed in an amount in the range of 50-70 vol%, e.g., in the range of 50-65 vol%, or in the range of 50-60 vol%, or in the range of 50-55 vol%, based on the total fill volume of the catalyst bed.

[0050] The catalyst beds of the present disclosure can further comprise an inert material. As used herein, the inert material is a substance that does not undergo any chemical reactions during any of the steps of the plurality of reaction cycles as describedDEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT below. For example, the inert material will not undergo any chemical reactions during the reduction of the catalyst material, during the contacting of the feed stream with the catalyst bed, and during the regeneration of the deactivated catalyst. The person of ordinary skill in the art will appreciate that refractory oxides can be inert to such reactions. In various embodiments of the present disclosure as described herein, the inert material includes (or is) silica, alumina, aluminate, or a mixture thereof. For example, in various embodiments, the inert material includes, or is alumina. The person of ordinary skill in the art will appreciate that alumina can be provided in a variety of forms. For example, in various embodiments of the present disclosure as described herein, the alumina is present in the inert material in the form of a-, y-, q-, 0-, x-, K-, b-alumina, or a combination thereof. In particular embodiments, the inert material includes (or is) alumina in the form of a-alumina.

[0051] The inert material can comprise additional elements provided in the form of various aluminates. As used herein, “aluminate” is used to refer to mixed oxides that contain aluminum. In various embodiments of the present disclosure as described herein, the inert material includes (or is) aluminate. The additional element used to form the aluminate is not particularly limited. For example, in various embodiments as described herein, the aluminate is in the form of Ca-aluminate, Zn-aluminate, or Mg-aluminate.

[0052] The inert material can be substantially formed from refractory oxides. For example, in various embodiments of the present disclosure as described herein, silica, alumina, and aluminate are present in the inert material in an amount of at least 80 wt%, e.g., at least 85 wt%, or at least 90 wt%, or at least 95 wt%, based on the total weight of the inert material.

[0053] In various embodiments of the present disclosure as described herein, the inert material is present in the catalyst bed in an amount in the range of 25-50 vol%, e.g., in the range of 30-50 vol%, or 35-50 vol%, or 40-50 vol%, based on the total fill volume of the catalyst bed. In some embodiments as described herein, the inert material is present in the catalyst bed in an amount in the range of 20-45 vol%, e.g., in the range of 25-45 vol%, or SO-45 vol%, or 35-45 vol%, based on the total fill volume of the catalyst bed.

[0054] The catalyst material and inert material can be provided in a particular volume ratio. For example, in various embodiments as described herein, the volume ratio of the catalyst material to the inert material present in the catalyst bed is in the range of 3:1 to 1 :3, e.g., in the range of 2:1 to 1 :2.

[0055] The person of ordinary skill in the art would appreciate that the dehydrogenation of hydrocarbons is an endothermic reaction. Thus, high temperatures (e.g., reaction temperatures of at least 400 °C) are required in order to shift the reaction equilibrium towards dehydrogenation. As such, in various embodiments of the present disclosure, the catalyst bed further comprises a heat-generating material. Heat-generating materials can beDEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT used to help maintain the required temperatures, wherein the heat-generating materials provide heat to the dehydrogenation reaction zone during any one of the steps of a Houdry-type dehydrogenation process. While gallium-based catalyst materials can have poor stability when used together with heat-generating materials in a catalyst bed, the present inventors have found that the inclusion of zirconium in the gallium-based catalyst material can advantageously improve the stability of the catalyst material in such catalyst bed configurations.

[0056] In various embodiments of the present disclosure as described herein, the heatgenerating material comprises: a heat-generating metal, present in the heat-generating material in an amount in the range of 0.5-60 wt%, based on a total weight of the heatgenerating material; and a carrier, present in the heat-generating material in an amount in the range of 40-99 wt%, based on the total weight of the heat-generating material.

[0057] The heat-generating metal is not particularly limited. In various embodiments of the present disclosure as described herein, the heat-generating metal includes (or is) copper oxide, copper aluminate, calcium sulfate, copper sulfate, zinc oxide, nickel oxide, iron oxide, tin oxide, cobalt oxide, vanadium oxide, lanthanum oxide, cerium oxide, manganese oxide, or a mixture thereof. As described above, the heat-generating metal can provide heat during at least any one of the steps during a dehydrogenation reaction cycle.

[0058] In various embodiments, the heat-generating metal is provided in an oxidized form, and reduction of the heat-generating metal provides heat to the dehydrogenation reaction zone. For example, in some embodiments, the heat-generating metal is reduced and generates heat during the reduction of the catalyst material.

[0059] In various embodiments, the heat-generating metal is provided in a reduced form, and oxidation of the heat-generating metal provides heat to the dehydrogenation reaction zone. For example, in some embodiments, the heat-generating metal is oxidized and generates heat during the regeneration of the deactivated catalyst.

[0060] Importantly, the heat-generating metal should be chemically inert to the dehydrogenation reaction. As discussed above, inert (i.e., chemically inert) is used to describe a substance that does not undergo any chemical reactions for a particular process. Thus, as used herein, a heat-generating metal that is chemically inert to the dehydrogenation reaction does not catalyze the dehydrogenation reaction when the feed stream is contacted with the catalyst bed.

[0061] The amount of the heat-generating metal present in the heat-generating material is not particularly limited and can be determined by the person of ordinary skill in the art. For example, in various embodiments of the present disclosure as described herein, the heatgenerating metal is present in the heat-generating material in an amount in the range of 0.5-50 wt%, e.g., in the range of 0.5-45 wt%, or in the range of 0.5-40 wt%, or in the range ofDEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT 0.5-35 wt%, or in the range of 0.5-30 wt%, or in the range of 0.5-25 wt%, based on the total weight of the heat-generating material. In some embodiments, the heat-generating metal is present in the heat-generating material in an amount in the range of 1-60 wt%, e.g., in the range of 5-60 wt%, or in the range of 10-60 wt%, or in the range of 15-60 wt%, or in the range of 20-60 wt%, or in the range of 25-60 wt%, or in the range of 30-60 wt%, based on the total weight of the heat-generating material.

[0062] The identity of the carrier is not particularly limited, so long as the carrier can adequately support the heat-generating metal. In various embodiments of the present disclosure as described herein, the carrier includes (or is) silica, alumina, aluminate, or a mixture thereof. For example, in various embodiments, the carrier includes, or is alumina. The person of ordinary skill in the art will appreciate that alumina can be provided in a variety of forms. For example, in various embodiments of the present disclosure as described herein, the alumina is present in the carrier in the form of a-, y-, q-, 0-, x-, K-, 5-alumina, or a combination thereof. In particular embodiments, the carrier includes (or is) alumina in the form of a-alumina.

[0063] The carrier can comprise additional elements provided in the form of various aluminates. As described above, “aluminate” as used herein refers to mixed oxides that contain aluminum. In various embodiments of the present disclosure as described herein, the carrier includes (or is) aluminate. The additional element used to form the aluminate is not particularly limited. For example, in various embodiments as described herein, the aluminate is in the form of Ca-aluminate, Zn-aluminate, or Mg-aluminate.

[0064] In various embodiments of the present disclosure as described herein, the carrier is present in the heat-generating material in an amount in the range of 40-95 wt%, e.g., in the range of 40-90 wt%, or in the range of 40-80 wt%, or in the range of 40-70 wt%, or in the range of 40-60 wt%, based on the total weight of the heat-generating material. In some embodiments, the carrier is present in the heat-generating material in an amount in the range of 45-99 wt%, e.g., in the range of 50-99 wt%, or in the range of 55-99 wt%, or in the range of 60-99 wt%, based on the total weight of the heat-generating material.

[0065] In various embodiments of the present disclosure as described herein, the heatgenerating material is comprised mostly of the heat-generating metal and the carrier. For example, in various embodiments, the heat-generating metal and the carrier are present in the heat-generating material in a total amount of at least 80 wt%, e.g., at least 85 wt%, or at least 90 wt%, or at least 95 wt%, based on the total weight of the heat-generating material.

[0066] The person of ordinary skill in the art can determine an appropriate amount of heat-generating material to be used in the catalyst bed. For example, in various embodiments as described herein, the heat-generating material is present in the catalyst bed in an amount in the range of 1-20 vol%, e.g., in the range of 1-18 vol%, or in the rangeDEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT of 1-16 vol%, based on the total fill volume of the catalyst bed. In some embodiments, the heat-generating material is present in the catalyst bed in an amount in the range of 5-20 vol%, e.g., in the range of 5-18 vol%, or in the range of 5-16 vol%, based on the total fill volume of the catalyst bed. In various embodiments, the heat-generating material is present in the catalyst bed in an amount in the range of 10-20 vol%, e.g., in the range of 10-18 vol%, or the range of 10-16 vol%, based on the total fill volume of the catalyst bed.

[0067] The present inventors have found that particular configurations of catalyst bed can be advantageous during dehydrogenation processes. In various embodiments of the present disclosure as described herein, the total volume of the catalyst bed comprises an upstream volume and a downstream volume. As used herein, upstream and downstream are defined relative to the direction of flow of the feed stream.

[0068] The distribution of the volumes within the catalyst bed is not particularly limited. In various embodiments, the upstream volume is in the range of 15-50% of the total fill volume of the catalyst bed, e.g., in the range of 15-40%, or in the range of 15-30%, or in the range of 20-50%, or in the range of 20-40%, or in the range of 20-30%. For example, in various embodiments as described herein, the downstream volume is in the range of 25-75% of the total fill volume of the catalyst bed, e.g., in the range of 25-65%, or in the range of 25-55%, or in the range of 35-75%, or in the range of 35-65%, or in the range of 35-55%, or in the range of 45-75%, or in the range of 45-65%, or in the range of 45-55%.

[0069] While the inclusion of zirconium in the catalyst material can allow for the catalyst material and heat-generating material to be used together in a catalyst bed, it can be advantageous for keep the catalyst material separate from the heat-generating material. As such, the catalyst material and heat-generating material can be disposed in different volumes of the catalyst bed.

[0070] In various embodiments of the present disclosure as described herein, the catalyst material is disposed in the downstream volume and the heat-generating material is disposed in the upstream volume. For example, in some embodiments, at least 80 wt% of the total amount of the heat-generating material in the one or more fixed catalyst beds is located in the upstream volume, e.g., at least 85 wt%, or at least 90 wt%, or at least 95 wt%, or at least 99 wt%. In some embodiments, the upstream volume can comprise substantially of the heat-generating material. For example, in various embodiments, the heat-generating material comprises at least 85 wt% of a total mass of material of the upstream volume, e.g., at least 90 wt%, or at least 95 wt%. In embodiments wherein the heat-generating material is disposed in the upstream volume, the catalyst material can be substantially absent from the upstream volume so as to minimize any direct contact between the catalyst material and the heat-generating material. For example, in various embodiments, no more than 10 wt% of the total amount of catalyst material in the catalyst bed is located in the upstream volume,DEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT e.g., no more than 5 wt%, or no more than 1 wt%. For example, in various embodiments, the catalyst material comprises no more than 10 wt% of the total fill volume of the upstream volume, e.g., no more than 5 wt%, or no more than 1 wt%.

[0071] In various embodiments of the present disclosure as described herein, the catalyst material is disposed in the upstream volume and the heat-generating material is disposed in the downstream volume. For example, in some embodiments, at least 80 wt% of the total amount of the heat-generating material in the one or more fixed catalyst beds is located in the downstream volume, e.g., at least 85 wt%, or at least 90 wt%, or at least 95 wt%, or at least 99 wt%. In some embodiments, the downstream volume can comprise substantially of the heat-generating material. For example, in various embodiments, the heat-generating material comprises at least 85 vol% of the total fill volume of the downstream volume, e.g., at least 90 vol%, or at least 95 vol%. In embodiments wherein the heat-generating material is disposed in the downstream volume, the catalyst material can be substantially absent from the downstream volume so as to minimize any direct contact between the catalyst material and the heat-generating material. For example, in various embodiments, no more than 10 wt% of the total amount of catalyst material in the one or more fixed catalyst beds is located in the downstream volume, e.g., no more than 5 wt%, or no more than 1 wt%. For example, in various embodiments, the catalyst material comprises no more than 10 vol% of the total fill volume of the downstream volume, e.g., no more than 5 vol%, or no more than 1 vol%.

[0072] In various embodiments of the present disclosure as described herein, the catalyst bed can further comprise a middle volume, disposed in between the upstream and downstream volumes. An example of such embodiments is depicted in FIG. 4. In catalyst bed 400, the total volume 401 of the catalyst bed is divided into the downstream volume 411 , the middle volume 412, and the upstream volume 413.

[0073] In various embodiments, the middle volume is in the range of 15-50% of the total volume of the catalyst bed, e.g., in the range of 15-40%, or in the range of 15-30%, or in the range of 20-50%, or in the range of 20-40%, or in the range of 20-30%. In such embodiments, the upstream volume can be decreased to accommodate the middle volume. For example, in some embodiments, the upstream volume is in the range of 1-30% of the total volume of the catalyst bed, e.g., in the range of 1-25%, or in the range of 1-20%, or in the range of 5-30%, or in the range of 5-25%, or in the range of 5-20%, or in the range of 10-30%, or in the range of 10-25%, or in the range of 10-20%.

[0074] The present inventors have found that placing the heat generating material in a middle layer of the catalyst bed can advantageously lead to improved performance during hydrocarbon dehydrogenation. As such, in some embodiments, at least 80 vol% of the total amount of the heat-generating material in the catalyst bed is located in the middle volume,DEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT e.g., at least 85 vol%, or at least 90 vol%, or at least 95 vol%, or at least 99 vol%. In some embodiments, the downstream volume can comprise substantially of the heat-generating material. For example, in various embodiments, the heat-generating material comprises at least 85 vol% of the total volume of the middle volume, e.g., at least 90 vol%, or at least 95 vol%. In embodiments wherein the heat-generating material is disposed in the middle volume, the catalyst material can be substantially absent from the middle volume so as to minimize any direct contact between the catalyst material and the heat-generating material. For example, in various embodiments, no more than 10 vol% of the total amount of catalyst material in the one or more fixed catalyst beds is located in the middle volume, e.g., no more than 5 vol%, or no more than 1 vol%. For example, in various embodiments, the catalyst material comprises no more than 10 vol% of the total volume of the middle volume, e.g., no more than 5 vol%, or no more than 1 vol%.

[0075] Dehydrogenation Processes

[0076] In another aspect, the disclosure provides a method for dehydrogenating hydrocarbons, the method comprising: providing a catalyst bed as disclosed herein in a dehydrogenation reaction zone; and performing a plurality of reaction cycles, each reaction cycle comprising: reducing the dehydrogenation catalyst material under a reducing atmosphere comprising H2; contacting a feed stream comprising hydrocarbons with the catalyst bed to provide a deactivated catalyst and a product stream comprising dehydrogenated hydrocarbons, wherein a reaction byproduct comprising coke is formed in the catalyst bed; purging the dehydrogenation reaction zone with a purge stream (e.g., a steam purge stream) to substantially remove the product stream thereof; regenerating the deactivated catalyst under an oxidizing atmosphere comprising O2to provide the catalyst material; and removing the oxidizing atmosphere from the dehydrogenation reaction zone.

[0077] The dehydrogenation of hydrocarbons is an endothermic process, and thus the dehydrogenation should be conducted at a reaction temperature sufficient for dehydrogenation to occur. For example, in various embodiments as described herein, the plurality of reaction cycles are performed at a reaction temperature in the range of 450-700 °C, e.g., in the range of 500-700 °C, or in the range of 550-700 °C, or in the range of 600-700 °C.

[0078] Reduction of the catalyst material is performed under a reducing atmosphere, e.g., comprising H2. The reduction time is not particularly limited. For example, in various embodiments as described herein, the reduction time is in the range of 0.5-250 seconds, e.g., in the range of 0.5-200 seconds, or in the range of 0.5-150 seconds, or in the range of 0.5-100 seconds, or in the range of 0.5-80 seconds. In some embodiments, the reduction time is in the range of 30-250 seconds, e.g., in the range of 30-200 seconds, or in the range of 30-150 seconds, or in the range of 30-100 seconds, or in the range of 30-80 seconds. InDEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT some embodiments, the reduction time is in the range of 0.1-30 seconds, e.g., in the range of 0.1-20 seconds, or in the range of 0.1-10 seconds, or in the range of 0.1-5 seconds.

[0079] As described above, the reducing atmosphere can comprise hydrogen. In various embodiments as described herein, the reducing atmosphere comprises hydrogen in an amount of at least 10 vol%, e.g., at least 20 vol% or at least 30 vol%. The reducing atmosphere can further comprise additional components. For example, in various embodiments, the reducing atmosphere further comprises inert gases, e.g., N2or Ar. As described above, the reduction time can be short in some embodiments (e.g., in the range of 0.1-30 seconds). As such, in various amendments, the reducing atmosphere can further comprise hydrocarbons, e.g., the hydrocarbons of a product stream of another reactor.

[0080] The dehydrogenation of hydrocarbons is then performed by contacting a feed stream comprising hydrocarbons with the catalyst bed to provide a product stream comprising dehydrogenated hydrocarbons. The dehydrogenated hydrocarbons provided from the dehydrogenation of C3-C5 hydrocarbons are of particular interest as commodity chemicals. For example, in various embodiments as described herein, the feed stream comprises C3-C5 hydrocarbons. In some embodiments, the feed stream comprises one or more of propane, n-butane, isobutene, and n-butylene; and the product stream comprises one or more of propylene, n-butylene, isobutylene, and butadiene. In some embodiments, the feed stream comprises propane, and the product stream comprises propylene.

[0081] As discussed above, the dehydrogenation of hydrocarbons is an endothermic process, and thus the dehydrogenation should be conducted at a reaction temperature sufficient for dehydrogenation to occur. Thus, it can be beneficial to provide the feed stream at an elevated temperature. For example, in various embodiments as described herein, when contacting the feed stream with the one or more fixed catalyst beds, the feed stream is provided at a feed stream temperature in the range of 500-700 °C, e.g., in the range of 550-700 °C, or in the range of 500-650 °C, or in the range of 550-650 °C.

[0082] The person of ordinary skill in the art can determine appropriate parameters for providing the feed stream. For example, in various embodiments of the present disclosure as described herein, when contacting the feed stream with the one or more fixed catalyst beds, the feed stream is provided with a feed stream liquid hourly space velocity in the range of 0.5-3.0 IT1, e.g., in the range of 0.5-2.5 IT1, or in the range of 0.5-2.0 IT1, or in the range of 0.5-1.5 hr1, or in the range of 0.8-3.0 hr1, or in the range of 0.8-2.5 hr1, or in the range of 0.8-2.0 IT1, or in the range of 0.8-1.5 IT1. In various embodiments as described herein, contacting the feed stream with the one or more fixed catalyst beds is performed at a dehydrogenation pressure in the range of 0.1 -2.0 atm.

[0083] In various embodiments, contacting the feed stream with the one or more fixed catalyst beds is performed for a dehydrogenation time in the range of 200-900 seconds. InDEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT some embodiments, the dehydrogenation time is in the range of 200-500 seconds, e.g., in the range of 200-400 seconds, or in the range of 200-300 seconds, or in the range of 250-500 seconds, or in the range of 250-400 seconds, or in the range of 250-300 seconds. In some embodiments, the dehydrogenation time is in the range of 400-900 seconds, e.g., in the range of 400-800 seconds, or in the range of 400-700 seconds, or in the range of 400-600 seconds, or in the range of 500-900 seconds, or in the range of 500-800 seconds, or in the range of 500-700 seconds, or in the range of 500-600 seconds.

[0084] The dehydrogenation of hydrocarbons can lead to the formation of a product stream comprising dehydrogenated hydrocarbons. The product stream can be recovered from the dehydrogenation reaction zone by purging the dehydrogenation reaction zone with a purge stream. In various embodiments, the purge stream comprises nitrogen.Advantageously, the present inventors have found that the inclusion of zirconium in the catalyst material can improve the stability of the catalyst material during contact with steam. As such, in some embodiments, the purge stream comprises steam. Purging the dehydrogenation reaction zone can be performed for a purge time sufficient to remove and recover a sufficient amount of the product stream from the dehydrogenation reaction zone. For example, in various embodiments as described herein, the purge time is in the range of 30-120 seconds, e.g., in the range of 40-120 seconds, or in the range of 50-120 seconds, or in the range of 60-120 seconds, or in the range of 70-120 seconds, or in the range of 80-120 seconds.

[0085] However, the dehydrogenation of hydrocarbons can also lead to the formation of byproducts, such as coke, on the one or more fixed catalyst beds, thus providing a deactivated catalyst. The deactivated catalyst does not necessarily refer to a catalyst that has lost all of its activity. As used herein, the term “deactivated catalyst” is used to describe a catalyst material that has lost at least a portion of its dehydrogenation activity (e.g., hydrocarbon conversion or dehydrogenated hydrocarbon yield, as described below). For example, in various embodiments of the present disclosure as otherwise described herein, the deactivated catalyst exhibits a dehydrogenation activity that is no more than 50%, e.g., no more than 40%, no more than 30%, no more than 20%, or no more than 10% of the dehydrogenation activity exhibited by a catalyst that is not deactivated. In some embodiments, the deactivated catalyst exhibits no dehydrogenation activity.

[0086] The person of ordinary skill in the art will appreciate that the coke can be removed under oxidizing conditions. Thus, in various embodiments of the present disclosure as described herein, the deactivated catalyst can be regenerated under an oxidizing atmosphere comprising O2. In various embodiments, the oxidizing atmosphere includes (or is) air. In some embodiments, regenerating the deactivated catalyst is performed for a regeneration time in the range of 200-500 seconds, e.g., in the range of 200-DEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT 400 seconds, or in the range of 200-300 seconds, or in the range of 250-500 seconds, or in the range of 250-400 seconds, or in the range of 250-300 seconds. In some embodiments, regenerating the deactivated catalyst is performed for a regeneration time in the range of 400-900 seconds, e.g., in the range of 400-800 seconds, or in the range of 400-700 seconds, or in the range of 400-600 seconds, or in the range of 500-900 seconds, or in the range of 500-800 seconds, or in the range of 500-700 seconds, or in the range of 500-600 seconds.

[0087] The regeneration time can be sufficient to provide an amount of air to the dehydrogenation reaction zone in a particular weight ratio to the hydrocarbons provided thereof for each reaction cycle. For example, in various embodiments of the present disclosure as described herein, the weight ratio of air to hydrocarbons provided during each reaction cycle is in the range of 1 :1 to 10:1 , e.g., in the range of 1 :1 to 8:1 , or in the range of 2:1 to 10:1 , or in the range of 2:1 to 8:1 , or in the range of 4:1 to 10:1, or in the range of 4:1 to 8:1.

[0088] The person of ordinary skill in the art will appreciate that the oxidizing atmosphere should be removed from the dehydrogenation reaction zone prior to the re-introduction of the reducing atmosphere. As such, in various embodiments as described herein, each reaction cycle comprises removing (i.e., at least substantially removing) the oxidizing atmosphere from the dehydrogenation zone. Removal of the oxidizing atmosphere can be performed by applying positive pressure to the dehydrogenation reaction zone (i.e., applying a pressure greater than the pressure of the dehydrogenation reaction zone prior to removal of the oxidizing atmosphere). For example, in various embodiments as described herein, removal of the oxidizing atmosphere is performed using the purge stream comprising nitrogen. Removal of the oxidizing atmosphere can also be performed by applying negative pressure to the dehydrogenation reaction zone (i.e., exposing the dehydrogenation reaction zone to a pressure less than the pressure of the dehydrogenation reaction zone prior to removal of the oxidizing atmosphere). For example, in various embodiments as described herein, removal of the oxidizing atmosphere is performed by evacuating the dehydrogenation reaction zone.

[0089] The removal of the oxidizing atmosphere can be performed for a removal time sufficient to allow for the reduction step of the next reaction cycle to proceed safely. For example, in various embodiments as described herein, the removal time is in the range of 30-120 seconds, e.g., in the range of 40-120 seconds, or in the range of 50-120 seconds, or in the range of 60-120 seconds, or in the range of 30-100 seconds, or in the range of 40-100 seconds, or in the range of 50-100 seconds, or in the range of 60-100 seconds.

[0090] It can be desirable to ensure that the dehydrogenation process selectively converts the feed stream into the desired product. As used herein, “selectivity” is the weightDEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT percentage of the product stream that is the desired product (e.g., dehydrogenated products). For example, in various embodiments of the present disclosure as described herein, the dehydrogenation is performed with a dehydrogenated hydrocarbon selectivity in the range of 75-95%, e.g., in the range of 75-90%, or in the range of 80-95%, or in the range of 80-90%, as determined on a weight basis.

[0091] As described above, the dehydrogenation process involves conducting a plurality of reaction cycles. The person of ordinary skill in the art will appreciate that, due to the deactivation of the catalyst every reaction cycle, the efficiency of subsequent dehydrogenation cycles may not have the same efficiency as previous dehydrogenation cycles. For example, in various embodiments of the present disclosure as described herein, the plurality of reaction cycles comprises a first reaction cycle having a first hydrocarbon conversion, a first dehydrogenated hydrocarbon selectivity, and a first dehydrogenated hydrocarbon yield; and a subsequent reaction cycle occurring “n” cycles after the first reaction cycle, having a second hydrocarbon conversion, a second dehydrogenated hydrocarbon selectivity, and a second dehydrogenated hydrocarbon yield.

[0092] As discussed above, the present inventors have found that the inclusion of zirconium in the catalyst materials can advantageously improve the stability of the catalyst material e.g., when contacting the catalyst material with steam during a steam purge, or when adding a heat-generating material to the catalyst bed. As such, the inclusion of zirconium in the catalyst material can advantageously allow for many dehydrogenation reaction cycles to be performed while minimizing any decline in the efficiency of the dehydrogenation process. The number of dehydrogenation cycles that occur before the efficiency of the dehydrogenation process starts to decline can depend on a variety of factors. In some embodiments, the subsequent reaction cycle occurs after at least 100 cycles, e.g., at least 120 cycles, at least 140 cycles, or at least 160 cycles. The subsequent dehydrogenation reaction cycle can have a minimal decrease in the efficiency of the dehydrogenation process. For example, in various embodiments, the second hydrocarbon conversion is at least 60%, e.g., at least 70%, or at least 80% of the first hydrocarbon conversion. In some embodiments, the second dehydrogenated hydrocarbon selectivity is at least 60%, e.g., at least 70%, or at least 80% of the first dehydrogenated hydrocarbon conversion. In various embodiments, the second dehydrogenated hydrocarbon yield is at least 60%, e.g., at least 70%, or at least 80% of the first dehydrogenated hydrocarbon yield.EXAMPLES

[0093] The Examples that follow are illustrative of specific embodiments of the materials of the disclosure. They are set forth for explanatory purposes only, and are not to be taken as limiting the scope of the disclosure.

[0094] Example 1 : Preparation of Zr / Ga Dehydrogenation Catalyst MaterialsDEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT

[0095] Catalyst materials A1 -A8 were prepared as follows:

[0096] Catalyst A1 was prepared by mixing 3 g of aqueous Ga(NOs)3(10 wt% Ga), 0.1 g of aqueous Ce(NOs)3(10 wt% Ce), 0.05 g of aqueous (NH3)4Pt(NO3)2(0.5 wt% Pt), 0.5 g of aqueous KNOs(10 wt% K), 3.62 g of aqueous ZrO(NOs)2 (35 wt% Zr), 2 g deionized water, and 0.5 g of concentrated nitric acid and adding to 13.3 g of pseudoboehmite doped with 5 wt% SiO2. The mixture was blended and extruded. The extrudates were dried in air at 120 °C for 3 h and then calcined in air at 900 °C for 3 h.

[0097] Catalyst A2 was prepared by mixing 3 g of aqueous Ga(NOs)3 (10% Ga), 0.1 g of aqueous Ce(NO3)3(10 wt% Ce), 0.05 g of aqueous (NH3)4Pt(NO3)2(0.5 wt% Pt), 0.5 g of aqueous KNOs(10 wt% K), 1.19 g of solid Zr(OH)2(C2H3O2)2, 2 g deionized water, and 0.5 g of concentrated nitric acid and adding to 13.3 g of pseudoboehmite doped with 5 wt% SiO2. The mixture was blended and extruded. The extrudates were dried in air at 120 °C for 3 h and then calcined in air at 900 °C for 3 h.

[0098] Catalyst A3 was prepared by mixing 3 g of aqueous Ga(NOs)3(10 wt% Ga), 0.1 g of aqueous Ce(NO3)3(10 wt% Ce), 0.05 g of aqueous (NH3)4Pt(NO3)2(0.5 wt% Pt), 0.5 g of aqueous KNOs(10 wt% K), 3.62 g of aqueous Zr(C2H3O2)4 (15 wt% Zr), 2 g deionized water, and 0.5 g of concentrated nitric acid and adding to 13.3 g of pseudoboehmite doped with 5 wt% SiO2. The mixture was blended and extruded. The extrudates were dried in air at 120 °C for 3 h and then calcined in air at 900 °C for 3 h.

[0099] Catalyst A4 was prepared by mixing 3 g of aqueous Ga(NOs)3(10 wt% Ga), 0.1 g of aqueous Ce(NO3)3(10 wt% Ce), 0.05 g of aqueous (NH3)4Pt(NO3)2(0.5 wt% Pt), 0.5 g of aqueous KNO3 (10 wt% K), 1.45 g of aqueous ZrO(NOs)2 (35 wt% Zr), 4 g deionized water, and 0.5 g of concentrated nitric acid and adding to 13.3 g of pseudoboehmite doped with 5 wt% SiO2. The mixture was blended and extruded. The extrudates were dried in air at 120 °C for 3 h and then calcined in air at 900 °C for 3 h.

[0100] Catalyst A5 was prepared by mixing 3 g of aqueous Ga(NOs)3(10 wt% Ga), 0.1 g of aqueous Ce(NO3)3(10 wt% Ce), 0.05 g of aqueous (NH3)4Pt(NO3)2(0.5 wt% Pt), 0.5 g of aqueous KNOs(10 wt% K), 7.24 g of aqueous ZrO(NOs)2 (35 wt% Zr), and 0.5 g of concentrated nitric acid and adding to 13.3 g of pseudoboehmite doped with 5 wt% SiO2. The mixture was blended and extruded. The extrudates were dried in air at 120 °C for 3 h and then calcined in air at 900 °C for 3 h.

[0101] Catalyst A6 was prepared by mixing 3 g of aqueous Ga(NOs)3(10 wt% Ga), 0.1 g of aqueous Ce(NOs)3(10 wt% Ce), 0.05 g of aqueous (NH3)4Pt(NO3)2(0.5 wt% Pt), 0.5 g of aqueous KNOs(10 wt% K), 13.41 g of aqueous ZrO(NOs)2 (35 wt% Zr), and 0.5 g of concentrated nitric acid and adding to 13.3 g of pseudoboehmite doped with 5 wt% SiO2. The mixture was blended and extruded. The extrudates were dried in air at 120 °C for 3 h and then calcined in air at 900 °C for 3 h.DEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT

[0102] Catalyst A7 was prepared by mixing 3 g of aqueous Ga(NOs)3(10 wt% Ga), 0.1 g of aqueous Ce(NOs)3(10 wt% Ce), 0.05 g of aqueous (NH3)4Pt(NO3)2(0.5 wt% Pt), 0.5 g of aqueous KNOs(10 wt% K), 6.67 g of aqueous Zr(C2H3O2)4 (15 wt% Zr), 3 g deionized water, and 0.5 g of concentrated nitric acid and adding to 13.3 g of pseudoboehmite doped with 5 wt% SiO2. The mixture was blended and extruded. The extrudates were dried in air at 120 °C for 3 h and then calcined in air at 900 °C for 3 h.

[0103] Catalyst A8 was prepared by mixing 3 g of aqueous Ga(NOs)3(10 wt% Ga), 0.1 g of aqueous Ce(NO3)3(10 wt% Ce), 0.05 g of aqueous (NH3)4Pt(NO3)2(0.5 wt% Pt), 0.5 g of aqueous KNOs(10 wt% K), 2.38 g of Zr(OH)2(C2H3O2)2(s), and 0.5 g of concentrated nitric acid and adding to 13.3 g of pseudoboehmite doped with 5 wt% SiO2. The mixture was blended and extruded. The extrudates were dried in air at 120 °C for 3 h and then calcined in air at 900 °C for 3 h.

[0104] Example 2: Preparation of Comparative Catalyst Materials

[0105] Comparative catalyst materials C1-C9 were prepared as follows:

[0106] Catalyst C1 was prepared by mixing 3 g of aqueous Ga(NOs)3(10 wt% Ga), 0.1 g of aqueous Ce(NO3)3(10 wt% Ce), 0.05 g of aqueous (NH3)4Pt(NO3)2(0.5 wt% Pt), 0.5 g of aqueous KNOs(10 wt% K), 4 g deionized water, and 0.5 g of concentrated nitric acid and adding to 13.3 g of pseudoboehmite doped with 5 wt% SiO2. The extrudates were dried in air at 120 °C for 3 h and then calcined in air at 900 °C for 3 h.

[0107] Catalyst C2 was prepared by mixing 3 g of aqueous Ga(NOs)3(10 wt% Ga), 0.1 g of aqueous Ce(NO3)3(10 wt% Ce), 0.05 g of aqueous (NH3)4Pt(NO3)2(0.5 wt% Pt), 0.5 g of aqueous KNOs(10 wt% K), 0.85 g of solid ZrO2(~5 micron particle size), 4 g deionized water, and 0.5 g of concentrated nitric acid and adding to 13.3 g of pseudoboehmite doped with 5 wt% SiO2. The mixture was blended and extruded. The extrudates were dried in air at 120 °C for 3 h and then calcined in air at 900 °C for 3 h.

[0108] Catalyst C3 was prepared by mixing 3 g of aqueous Ga(NOs)3(10 wt% Ga), 0.1 g of aqueous Ce(NO3)3(10 wt% Ce), 0.05 g of aqueous (NH3)4Pt(NO3)2(0.5 wt% Pt), 0.5 g of aqueous KNOs(10 wt% K), 2.56 g of liquid Zr(OC3H7)4, 4 g deionized water, and 0.5 g of concentrated nitric acid and adding to 13.3 g of pseudoboehmite doped with 5 wt% SiO2. The mixture was blended and extruded. The extrudates were dried in air at 120 °C for 3 h and then calcined in air at 900 °C for 3 h.

[0109] Catalyst C4 was prepared by mixing 3 g of aqueous Ga(NOs)3(10 wt% Ga), 0.1 g of aqueous Ce(NOs)3(10 wt% Ce), 0.05 g of aqueous (NH3)4Pt(NO3)2(0.5 wt% Pt), 0.5 g of aqueous KNOs(10 wt% K), 1.7 g of ZrO2(Sj (solid, ~5 micron particle size), 4 g deionized water, and 0.5 g of concentrated nitric acid and adding to 13.3 g of pseudoboehmite doped with 5 wt% SiO2. The mixture was blended and extruded. The extrudates were dried in air at 120 °C for 3 h and then calcined in air at 900 °C for 3 h.DEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT

[0110] Catalyst C5 was prepared by mixing 3 g of aqueous Ga(NOs)3(10 wt% Ga), 0.1 g of aqueous Ce(NOs)3(10 wt% Ce), 0.05 g of aqueous (NH3)4Pt(NO3)2(0.5 wt% Pt), 0.5 g of aqueous KNOs(10 wt% K), 5.12 g of liquid Zr(OC3H7)4, 4 g deionized water, and 0.5 g of concentrated nitric acid and adding to 13.3 g of pseudoboehmite doped with 5 wt% SiO2. The mixture was blended and extruded. The extrudates were dried in air at 120 °C for 3 h and then calcined in air at 900 °C for 3 h.

[0111] Catalyst C6 was prepared by mixing 3 g of aqueous Ga(NOs)3(10 wt% Ga), 0.1 g of aqueous Ce(NO3)3(10 wt% Ce), 0.05 g of aqueous (NH3)4Pt(NO3)2(0.5 wt% Pt), 0.5 g of aqueous KNOs(10 wt% K), 0.67 g solid Zr(COs)2, and 0.5 g of concentrated nitric acid and adding to 13.3 g of pseudoboehmite doped with 5% SiO2. The mixture was blended and extruded. The extrudates were dried in air at 120 °C for 3 h and then calcined in air at 900 °C for 3 h.

[0112] Catalyst C7 was made by mixing 3 g of aqueous Ga(NOs)3(10 wt% Ga), 0.1 g of aqueous Ce(NO3)3(10 wt% Ce), 0.05 g of aqueous (NH3)4Pt(NO3)2(0.5 wt% Pt), 0.5 g of aqueous KNO3 (10 wt% K), 1.67 g solid Zr(COs)2, and 0.5 g of concentrated nitric acid and adding to 13.3 g of pseudoboehmite doped with 5 wt% SiO2. The mixture was blended and extruded. The extrudates were dried in air at 120 °C for 3 h and then calcined in air at 900 °C for 3 h.

[0113] Catalyst C8 was prepared by mixing 3 g of aqueous Ga(NOs)3(10 wt% Ga), 0.1 g of aqueous Ce(NO3)3(10 wt% Ce), 0.05 g of aqueous (NH3)4Pt(NO3)2(0.5 wt% Pt), 0.5 g of aqueous KNOs(10 wt% K), 3.85 g Zircosol AC-7 (Daiichi Kigenso Kagaku Kogyo Co., ~13 wt% Zr©2 sol), and 0.5 g of concentrated nitric acid and adding to 13.3 g of pseudoboehmite doped with 5 wt% SiO2. The mixture was blended and extruded. The extrudates were dried in air at 120 °C for 3 h and then calcined in air at 900 °C for 3 h.

[0114] Catalyst C9 was prepared by mixing 3 g of aqueous Ga(NOs)3(10 wt% Ga), 0.1 g of aqueous Ce(NO3)3(10 wt% Ce), 0.05 g of aqueous (NH3)4Pt(NO3)2(0.5 wt% Pt), 0.5 g of aqueous KNOs(10 wt% K), 7.69 g Zircosol AC-7 (Daiichi Kigenso Kagaku Kogyo Co., ~13 wt% Zr©2 sol), and 0.5g of concentrated nitric acid and adding to 13.3 g of pseudoboehmite doped with 5 wt% SiO2. The mixture was blended and extruded. The extrudates were dried in air at 120 °C for 3 h and then calcined in air at 900 °C for 3 h.

[0115] Compositions for the as-calcined materials are in Table 1 below, assuming complete incorporation and conversion to oxide of all species.DEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT

[0116] Table 1> > >

[0117] Example 3: Propylene dehydrogenation with steam purges

[0118] Catalyst materials A1 -A8 and C1 -C9 were subjected to 160 cycles under the following dehydrogenation conditions: 575 °C; LHSVPrOpane = 2 h1; P propane — 0.5 atm, tdehydrogenation = 10 min, tregeneration = 10 min, and treduction=3 min. Prior to testing, catalyst materials were crushed and sieved to achieve a particle diameter range of 90-425 microns. The sized catalysts were volumetrically loaded (0.264 cubic cm) into quartz reactor tubes (5mm O.D.; 3 mm I . D) , and an equal volume of inert alumina was added on top of the bed. The tubes were then loaded into custom isothermal 16-channel parallel fixed bed reactors for performance testing. Each 16-channel reactor system is interfaced with a stand-alone gas chromatography instrument, which are able to evaluate the product stream of a selected channel in less than the time required for one cyclic dehydrogenation cycle. Each 16-channel reactor system is operated with one channel dedicated to monitoring the feed (i.e., blank) and one channel monitoring the performance of a reference Cr catalyst to ensure continuous and reliable data generation.

[0119] The propane conversion (as a percentage) is calculated by dividing the propane consumed in the catalyst channel (difference in propane between the “feed” channel andDEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT catalyst channel, in weight %) by the propane weight % in a “feed” channel, which is a reactor tube loaded only with inert alumina, as shown in the equation below. The propylene selectivity (as a percentage) is calculated by dividing the propylene created by a catalyst channel (difference in propylene between the catalyst channel and feed channel, in mol %) by the propane consumed by the catalyst channel (difference in propane between the feed channel and the catalyst channel, in mol%). Yield is the product of conversion and selectivity.

[0120] The resulting propylene yields are shown below in Table 2.

[0121] Table 2.

[0122] The catalyst materials that did not contain any zirconium (e.g., catalyst material C1 ) or were prepared with a zirconium source that does not substantially disperse in the aqueous mixture during the catalyst synthesis (e.g., ZrC>2, Zr(OC3H7)4, Zr(COs)2, or colloidal Zr in catalyst materials C2-C9) generally provide lower propylene yields under the dehydrogenation conditions described above. The person of ordinary skill in the art will appreciate that materials in which zirconium is well dispersed can be made in other manners.DEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT

[0123] The effects of the steam purge on the dehydrogenation catalyst materials is displayed in FIG. 1, which shows propylene yields provided by catalyst materials A1-A3 and C1-C3 versus the dehydrogenation cycle number. While all six catalyst materials started with similar propylene yields, the propylene yields provided by catalyst materials C1-C3 decreased with additional dehydrogenation cycles, with a relative activity loss in the range of 15-35% as shown in FIG. 3.

[0124] Example 4: Determination of Weak Bronsted Acid Sites

[0125] The percentage of the surface acid sites of the catalyst materials that are weak Bronsted acid sites was determined using pyridine and Fourier Transform Infrared spectroscopy (Py-FTIR). The process described below defines the pyridine FTIR process for the purposes of this disclosure; it was repeated for each catalyst material A1-A3 and CIGS.

[0126] 30 mg of finely powdered catalyst material was pressed into a self-supporting disc and loaded into a Harrick HTC transmission cell fitted with 2 mm ZnSe windows. The sample was heated from room temperature (i.e., 25 °C) under a flow of N2(50 cc / min) and held at 500 °C for 30 min, then lowered to 150 °C. A flow of pyridine saturated N2(50 cc / min) was passed through the self-supporting disc for 5 min, followed by pure N2for 30 min. The FTIR spectrum was collected in transmission mode using a resolution of 2 cm'1under N2at 150 °C. The absorbance spectra for each of catalyst materials A1 -A3 and C1 -C3 were normalized to maximum peak height at 1615 cm-1and deconvoluted using Gaussian peak fitting. A linear baseline over the range 1400-1700 cm-1is determined by the fitting software (OMNIC, Thermo-Fisher) during peak deconvolution, and peak height is determined based on the linear baseline. The pyridine spectra, with 4 main infrared aborbance peaks at around 1575, 1595, 1615, and 1635 cm'1, are shown in FIG. 2.

[0127] The degree of weak Bronsted acid sites was estimated by a ratio of a peak height of an infrared absorbance peak at 1595 ± 5 cm'1to an infrared absorbance peak at 1615 ± 5 cm'1of no more than 0.7 in a pyridine FTIR experiment from the deconvolution of Py-FTIR spectra into four Gaussian peaks centered around 1575, 1595, 1615, and 1635 cm'1. The activity loss for catalyst materials A1-A3 and C1-C3, as described above, versus the 1595 / 1615 ratio is shown in in Table 3 below:DEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT

[0128] Table 3.

[0129] The present inventors found that catalyst materials C1-C3 all have a 1595 / 1615 ratio of well above 0.8, whereas catalyst materials A1-A3 have 1595 / 1615 ratio values of no more than 0.7. As such, the present inventors have unexpectedly found that having a 1595 / 1615 ratio of no more than 0.7 can advantageously improve catalyst stability when performing dehydrogenations with steam purging.

[0130] Example 5: Determination of ZrC>2 crystalline domain sizes

[0131] In addition to impacting catalyst acidity, the present inventors found that the nature of the zirconium source also influenced zirconium dispersion in the final calcined catalyst as observed by x-ray diffraction (XRD) analyses. XRD spectra for the catalyst materials prepared in Examples 1 and 2 were each collected using the following collection parameters: 20 kV, 5 mA, Cu source. The XRD spectra with powder diffraction file (PDF) stick pattern 04-013-6621 are compared in FIG. 4, revealing broad variation in the sharpness of the primary tetragonal ZrO2 reflection observed at 20 = 30.4°. The differences in the full-width half maximum (FWHM) of a reflection peak is indicative of differences in Zr©2 crystalline domain sizes. When compared with the performance and stability results, the data in FIG. 4 show that smaller Zr©2 crystalline domains can be more effective at promoting the catalyst. However, the present inventors note that the presence of XRD-observable Zr©2 crystalline domains does not necessarily imply a lack of a promotion effect from the inclusion of zirconium. Catalyst materials A1 , A5, and A6 were made with the same zirconium precursor (i.e., ZrO(NOs)2), but with different zirconium amounts. Catalyst materials A1 -A8 all demonstrated good performance and stability, suggesting effective zirconium promotion, but catalyst A6, which has the highest zirconium loading (i.e., 18 wt% zirconium) exhibits a clear Zr©2 reflection at 20 = 30.4°.

[0132] To better understand the interplay between the zirconium source, zirconium crystalline domain size, and catalyst performance and stability, the XRD data shown in FIG.3 was analyzed by Rietveld refinement. The Rietveld refinement provides an estimate forDEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT the tetragonal Zr©2 crystalline domain sized in each sample, the results of which are shown in Table 4 below.

[0133] Table 4.

[0134] The results show that the smallest ZrC>2 crystalline domains calculated from the Rietveld refinement (i.e., catalyst materials A1-A3) correlate to the catalyst materials with the greatest stability during dehydrogenation, whereas those with the largest domains (i.e., catalyst materials C2-C3) are the least stable during dehydrogenation with steam purges.

[0135] Other aspects of the disclosure are described with respect to the following enumerated embodiments, which may be combined in any fashion and in any number that is not technically or logically inconsistent.Embodiment 1 . A catalyst material for the dehydrogenation of hydrocarbons, the catalyst material comprising:an alumina or silica-alumina carrier, the catalyst material having in the range of 39- 98.75 wt% aluminum, calculated as AI2O3 on a calcined basis, and a ratio of an amount of silicon to a combined amount of silicon and aluminum of up to 20 wt%, in which silicon and aluminum are respectively calculated as SiC>2 and AI2O3 on a calcined basis;gallium, present in the catalyst material in an amount in the range of 0.5-8 wt%, calculated as Ga2Os on a calcined basis;zirconium, present in the catalyst material in an amount in the range of 0.5-30 wt%, calculated as Zr©2 on a calcined basis,DEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT the catalyst material exhibiting, in a calcined form, a ratio of a peak height of an infrared absorbance peak at 1595 ± 5 cm-1to a peak height of an infrared absorbance peak at 1615 ± 5 cm'1of no more than 0.7 in a pyridine FTIR experiment.Embodiment 2. The catalyst material of embodiment 1 , wherein gallium is present in the catalyst material in an amount in the range of 0.5-6 wt%, e.g. in the range of 0.5-4 wt%, or in the range of 0.5-3.5 wt%, or in the range of 0.5-3 wt%, calculated as Ga2Os on a calcined basis.Embodiment 3. The catalyst material of embodiment 1 , wherein gallium is present in the catalyst material in an amount in the range of 1-8 wt%, e.g. in the range of 1-6 wt%, or in the range of 1-4 wt%, or in the range of 1-3.5 wt%, or in the range of 1-3 wt%, calculated as Ga2Os on a calcined basis.Embodiment 4. The catalyst material of embodiment 1 , wherein gallium is present in the catalyst material in an amount in the range of 1.5-8 wt%, e.g. in the range of 1.5-6 wt%, or in the range of 1.5-4 wt%, or in the range of 1.5-3.5 wt%, or in the range of 1.5-3 wt%, calculated as Ga2Os on a calcined basis.Embodiment 5. The catalyst material of embodiment 1 , wherein gallium is present in the catalyst material in an amount in the range of 2-8 wt%, e.g. in the range of 2-6 wt%, or in the range of 2-4 wt%, or in the range of 2-3.5 wt%, or in the range of 2-3 wt%, calculated as Ga2Os on a calcined basis.Embodiment 6. The catalyst material of embodiment 1 , wherein gallium is present in the catalyst material in an amount in the range of 2.5-8 wt%, e.g. in the range of 2.5-6 wt%, or in the range of 2.5-4 wt%, or in the range of 2.5-3.5 wt%, calculated as Ga2Os on a calcined basis.Embodiment 7. The catalyst material of any of embodiments 1-6, wherein zirconium is present in the catalyst material in an amount in the range of 0.5-25 wt%, e.g., in the range of 0.5-25 wt%, or in the range of 0.5-20 wt%, or in the range of 0.5-15 wt%, or in the range of 0.5-10 wt%, or in the range of 0.5-8 wt%, or in the range of 0.5-5 wt%, calculated as ZrC>2 on a calcined basis.DEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT Embodiment 8. The catalyst material of any of embodiments 1-6, wherein zirconium is present in the catalyst material in an amount in the range of 1-30 wt%, e.g., in the range of 1-25 wt%, or in the range of 1-20 wt%, or in the range of 1-15 wt%, or in the range of 1-10 wt%, or in the range of 1-8 wt%, or in the range of 1-5 wt%, calculated as Zr©2 on a calcined basis, calculated as Zr©2 on a calcined basis.Embodiment 9. The catalyst material of any of embodiments 1-6, wherein zirconium is present in the catalyst material in an amount in the range of 2-30 wt%, e.g., in the range of 2-25 wt%, or in the range of 2-20 wt%, or in the range of 2-18 wt%, or in the range of 2-15 wt%, or in the range of 2-12 wt%, or in the range of 2-10 wt%, or in the range of 2-8 wt%, or in the range of 2-5 wt%, calculated as ZrC>2 on a calcined basis.Embodiment 10. The catalyst material of any of embodiments 1-6, wherein zirconium is present in the catalyst material in an amount in the range of 3.5-30 wt%, e.g., in the range of 3.5-25 wt%, or in the range of 3.5-20 wt%, or in the range of 3.5-18 wt%, or in the range of 3.5-15 wt%, or in the range of 3.5-12 wt%, or in the range of 3.5-10 wt%, or in the range of 3.5-8 wt%, calculated as ZrC>2 on a calcined basis.Embodiment 11. The catalyst material of any of embodiments 1 -6, wherein zirconium is present in the catalyst material in an amount in the range of 5-30 wt%, e.g., in the range of 5-25 wt%, or in the range of 5-20 wt%, or in the range of 5-18 wt%, or in the range of 5-15 wt%, or in the range of 5-12 wt%, or in the range of 5-10 wt%, or in the range of 5-8 wt%, calculated as Zr©2 on a calcined basis.Embodiment 12. The catalyst material of any of embodiments 1-11, wherein the zirconium and gallium are present in a weight ratio of zirconium to gallium in the range of 1 :1 to 20:1 , e.g., in the range of 1 :1 to 15:1 , or in the range of 1 :1 to 10:1 , or in the range of 1 :1 to 5:1 , or in the range of 1 :1 to 2:1 .Embodiment 13. The catalyst material of any of embodiments 1-11, wherein the zirconium and gallium are present in a weight ratio of zirconium to gallium in the range of 1.5:1 to 20:1 , e.g., in the range of 1.5:1 to 15:1 , or in the range of 1.5:1 to 10:1 , or in the range of 1.5:1 to 5:1 , or in the range of 1 .5:1 to 3:1.Embodiment 14. The catalyst material of any of embodiments 1-11, wherein the zirconium and gallium are present in a weight ratio of zirconium to gallium in the range of 2:1DEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT to 20:1 , e.g., in the range of 2:1 to 15:1 , or in the range of 2:1 to 10:1, or in the range of 2:1 to 5:1.Embodiment 15. The catalyst material of any of embodiments 1-14, wherein aluminum is present in the catalyst material in an amount in the range of 39-95 wt%, e.g., in the range of 39-93 wt%, or in the range of 39-90 wt%, or in the range of 39-85 wt%, or in the range of 39-75 wt%, calculated as AI2O3 on a calcined basis.Embodiment 16. The catalyst material of any of embodiments 1-14, wherein aluminum is present in the catalyst material in an amount in the range of 60-98.75 wt%, e.g., in the range of 60-95 wt%, or in the range of 60-93 wt%, or in the range of 60-90 wt%, or in the range of 60-85 wt%, or in the range of 60-80 wt%, calculated as AI2O3 on a calcined basis.Embodiment 17. The catalyst material of any of embodiments 1-14, wherein aluminum is present in the catalyst material in an amount in the range of 75-98.75 wt%, e.g., in the range of 75-95 wt%, or in the range of 75-93 wt%, or in the range of 75-90 wt%, or in the range of 75-85 wt%, or in the range of 75-80 wt%, calculated as AI2O3 on a calcined basis.Embodiment 18. The catalyst material of any of embodiments 1-14, wherein aluminum is present in the catalyst material in an amount in the range of 85-98.75 wt%, e.g., in the range of 85-95 wt%, or in the range of 85-93 wt%, or in the range of 85-90 wt%, calculated as AI2O3 on a calcined basis.Embodiment 19. The catalyst material of any of embodiments 1-18, wherein the catalyst material further comprises silicon.Embodiment 20. The catalyst material of embodiment 19, wherein silicon is present in the catalyst material in an amount up to 20 wt%, e.g., up to up to 15 wt%, or up to 10 wt%, or up to 5 wt%, calculated as silica on a calcined basis.Embodiment 21. The catalyst material of embodiment 19, wherein silicon is present in the catalyst material in an amount in the range of 1-20 wt%, e.g., in the range of 1-15 wt%, or in the range of 1 -10 wt%, or in the range of 1 -5 wt%, calculated as silica on a calcined basis.DEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT Embodiment 22. The catalyst material of embodiment 19, wherein silicon is present in the catalyst material in an amount in the range of 2-20 wt%, e.g., in the range of 2-15 wt%, or 2-10 wt%, or 2-5 wt%, calculated as silica on a calcined basis.Embodiment 23. The catalyst material of any of embodiments 19-22, wherein aluminum and silicon are present in the catalyst material in a weight ratio of aluminum to silicon, calculated as AI2O3 and SiC>2 on a calcined basis, in the range of 4:1 to 50:1 , e.g., in the range of 4:1 to 25:1 , or 4:1 to 20:1 , or 9:1 to 50:1 , or 9:1 to 25:1 , or 9:1 to 20:1 , or 14:1 to 50:1, or 14:1 to 25:1, or 14:1 to 20:1.Embodiment 24. The catalyst material of any of embodiments 1-23, further comprising platinum.Embodiment 25. The catalyst material of embodiment 24, wherein platinum is present in the catalyst material in an amount of up to 250 ppm on a weight basis, e.g., up to 150 ppm, or up to 100 ppm, or up to 50 ppm, calculated as PtO2 on a calcined basis.Embodiment 26. The catalyst material of embodiment 24, wherein platinum is present in the catalyst material in an amount in the range of 1-250 ppm, e.g., in the range of 1-150 ppm, or in the range of 1-100 ppm, or in the range of 1-50 ppm, or in the range of 5-250 ppm, or in the range of 5-150 ppm, or in the range of 5-100 ppm or in the range of 5-50 ppm, or in the range of 10-250 ppm, or in the range of 10-150 ppm, or in the range of 10-100 ppm, or in the range of 10-50 ppm, calculated as PtO2 on a calcined basis.Embodiment 27. The catalyst material of any of embodiments 1-26, further comprising cerium.Embodiment 28. The catalyst material of embodiment 27, wherein cerium is present in the catalyst material in an amount of up to 4 wt%, e.g., up to 2 wt%, or up to 1 wt%, or up to 0.5 wt%, or up to 0.2 wt%, or up to 0.1 wt%, calculated as CeO2 on a calcined basis.Embodiment 29. The catalyst material embodiment 27, wherein cerium is present in the catalyst material in an amount in the range of 0.02-4 wt%, e.g., in the range of 0.02-2 wt%, or in the range of 0.02-1 wt%, or in the range of 0.02-0.5 wt%, or in the range of 0.02-0.2 wt% or in the range of 0.02-0.1 wt%, calculated as CeO2 on a calcined basis.DEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT Embodiment 30. The catalyst material embodiment 27, wherein cerium is present in the catalyst material in an amount in the range of 0.05-4 wt%, e.g., in the range of 0.05-2 wt%, or in the range of 0.05-1 wt%, or in the range of 0.05-0.5 wt%, or in the range of 0.05-0.2 wt% or in the range of 0.05-0.1 wt%, calculated as Ce on a calcined basis.Embodiment 31. The catalyst material of any of embodiments 1 -30, further comprising one or more promoters M1 selected from Group 1 metals and / or one more promoters M2 selected from Group 2 metals, wherein a total amount of promoters M1 and M2 in the catalyst material is up to 3 wt%, calculated as M12O and M2O on a calcined basis.Embodiment 32. The catalyst material of embodiment 31 , wherein one or more promoters M1 are present.Embodiment 33. The catalyst material of embodiment 31 or embodiment 32, wherein the one or more promoters M1 are selected from the group consisting of lithium, sodium, potassium, and a combination thereof.Embodiment 34. The catalyst material of embodiment 31 or embodiment 32, wherein the one or more promoters M1 are potassium.Embodiment 35. The catalyst material of any of embodiments 31-34, wherein the one or more promoters M1 are present in the catalyst material a total amount in the range of 0.01-3 wt%, e.g., in the range of 0.01-2.5 wt%, or in the range of 0.01-2 wt%, or in the range of 0.01-1.5 wt%, or in the range of 0.01-1 wt%, calculated as M12O on a calcined basis.Embodiment 36. The catalyst material of any of embodiments 31-34, wherein the one or more promoters M1 are present in the catalyst material in a total amount in the range of 0.05-3 wt%, e.g., in the range of 0.05-2.5 wt%, or in the range of 0.05-2 wt%, or in the range of 0.05-1.5 wt%, or in the range of 0.05-1 wt%, calculated as M12O on a calcined basis.Embodiment 37. The catalyst material of any of embodiments 31-36, wherein the one or more promoters M2 are present.Embodiment 38. The catalyst material of embodiment 37, wherein the one or more promoters M2 are selected form the group consisting of beryllium, magnesium, calcium, and a combination thereof.DEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT Embodiment 39. The catalyst material of embodiment 37 or embodiment 38, wherein the one or more promoters M2 are present in the catalyst material a total amount in the range of 0.01-3 wt%, e.g., in the range of 0.01-2.5 wt%, or in the range of 0.01-2 wt%, or in the range of 0.01 -1.5 wt%, or in the range of 0.01-1 wt%, calculated as M2O on a calcined basis.Embodiment 40. The catalyst material of embodiment 37 or embodiment 38, wherein the one or more promoters M2 are present in the catalyst material in a total amount in the range of 0.05-3 wt%, e.g., in the range of 0.05-2.5 wt%, or in the range of 0.05-2 wt%, or in the range of 0.05-1.5 wt%, or in the range of 0.05-1 wt%, calculated as M2O on a calcined basis.Embodiment 41. The catalyst material of any of embodiments 31-40, having a total amount of M1 and M2 promoters in the catalyst material of up to 2.5 wt%, e.g., up to 2 wt%, or up to 1 .5 wt%, or up to 1 wt%, calculated as M12O and M2O on a calcined basis.Embodiment 42. The catalyst material of any of embodiments 31-3840 having a total amount of M1 and M2 promoters in the catalyst material in the range of 0.01-3 wt%, e.g., in the range of 0.01 -2.5 wt%, or in the range of 0.01 -2 wt%, or in the range of 0.01 -1.5 wt%, or in the range of 0.01-1 wt%, calculated as M12O and M2O on a calcined basis.Embodiment 43. The catalyst material of any of embodiments 31-40, having a total amount of M1 and M2 promoters in the catalyst material in the range of 0.05-3 wt%, e.g., in the range of 0.05-2.5 wt%, or in the range of 0.05-2 wt%, or in the range of 0.05-1.5 wt%, or in the range of 0.05-1 wt%, calculated as M12O and M2O on a calcined basis.Embodiment 44. The catalyst material of any of embodiments 1 -43, wherein a total amount of gallium, zirconium, aluminum, M1 promoter(s) and M2 promoter(s), platinum and cerium, each calculated as oxide on a calcined basis, is at least 90 wt% of the catalyst material, e.g. at least 95 wt%, or at least 98 wt%, or at least 99 wt%.Embodiment 45. The catalyst material of any of embodiments 1-44, wherein a chromium content of the catalyst material is less than 0.1 wt% chromium, e.g., less than 0.05 wt%, or less than 0.01 wt%, based on the total weight of the catalyst.DEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT Embodiment 46. The catalyst material of any of embodiments 1-45, wherein a copper content of the catalyst material is less than 0.1 wt% copper, e.g., less than 0.05 wt%, or less than 0.01 wt%, based on the total weight of the catalyst.Embodiment 47. The catalyst material of any of embodiments 1-46, wherein a cobalt content of the catalyst material is less than 0.1 wt% cobalt, e.g., less than 0.05 wt%, or less than 0.01 wt%, based on the total weight of the catalyst.Embodiment 48. The catalyst material of any of embodiments 1-47, wherein the catalyst material does not include chromium.Embodiment 49. The catalyst material of any of embodiments 1-48, wherein the catalyst material does not include copper.Embodiment 50. The catalyst material of any of embodiments 1-49, wherein the catalyst material does not include cobalt.Embodiment 51. The catalyst material of any of embodiments 1 -50, exhibiting, in a calcined form, a ratio of a peak height of an infrared absorbance peak at 1595 ± 5 cm'1to a peak height of an infrared absorbance peak at 1615 ± 5 cm'1in the range of 0.1 -0.7, e.g., 0.2-0.7, or 0.3-0.7 in a pyridine FTIR experiment.Embodiment 52. The catalyst material of any of embodiments 1-50, exhibiting, in a calcined form, a ratio of a peak height of an infrared absorbance peak at 1595 ± 5 cm'1to a peak height of an infrared absorbance peak at 1615 ± 5 cm'1of no more than 0.6, e.g., in the range of 0.1 -0.6, e.g., 0.2-0.6, or 0.3-0.6, in a pyridine FTIR experiment.Embodiment 53. The catalyst material of any of embodiments 1-50, exhibiting, in a calcined form, a ratio of a peak height of an infrared absorbance peak at 1595 ± 5 cm'1to a peak height of an infrared absorbance peak at 1615 ± 5 cm'1of no more than 0.5, e.g., in the range of 0.1 -0.5, e.g., 0.2-0.5, or 0.3-0.5, in a pyridine FTIR experiment.Embodiment 54. The catalyst material of any of embodiments 1 -53, wherein at least 50 wt%, e.g., at least 75 wt%, or at least 90 wt%, of the zirconium present in the catalyst material has crystalline Zr©2 domain size of no more than 4 nm (e.g., in the range of 0.5-4 nm, or in the range of 1-4 nm) as determined by Rietveld refinement of x-ray diffraction spectra as described in the specification.DEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCTEmbodiment 55. The catalyst material of any of embodiments 1 -54, wherein at least 50 wt%, e.g., at least 75 wt%, or at least 90 wt%, of the zirconium present in the catalyst material has crystalline Zr©2 domain size of no more than 3 nm (e.g., in the range of 0.5-3 nm, e.g., in the range of 1-3 nm), as determined by Rietveld refinement of x-ray diffraction spectra as described in the specification.Embodiment 56. The catalyst material of any of embodiments 1 -54, wherein at least 50 wt%, e.g., at least 75 wt%, or at least 90 wt%, of the zirconium present in the catalyst material has crystalline Zr©2 domain size of no more than 2.5 nm (e.g., in the range of 0.5-2.5 nm, or in the range of 1-2.5 nm), as determined by Rietveld refinement of x-ray diffraction spectra as described in the specificationEmbodiment 57. The catalyst material of any of embodiments 1 -54, wherein at least 50 wt%, e.g., at least 75 wt%, or at least 90 wt%, of the zirconium present in the catalyst material has crystalline Zr©2 domain size of no more than 2 nm (e.g., in the range of 0.5-2 nm, or in the range of 1-2 nm), as determined by Rietveld refinement of x-ray diffraction spectra as described in the specification.Embodiment 58. A method for preparing the catalyst material of any of embodiments 1 -57, the method comprisingproviding an aqueous mixture comprising:a gallium source;a zirconium source; andan aluminum source;forming a solid from the aqueous mixture; andcalcining the solid so formed.Embodiment 59. The method of embodiment 58, wherein the gallium source is substantially dissolved in the aqueous mixture.Embodiment 60. The method of embodiment 58 or embodiment 59, wherein the zirconium source is substantially dissolved in the aqueous mixture.Embodiment 61. The method of any of embodiments 58-60, wherein the aqueous mixture further comprises a platinum source, a cerium source, a promoter M1 source, a promoter M2 source, and / or a silicon source.DEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCTEmbodiment 62, The method of embodiment 61 , wherein the platinum source, the cerium source, the promoter M1 source, and / or the M2 source are substantially dissolved in the aqueous mixture.Embodiment 63. The method of embodiment any of embodiments 58-62, wherein the aqueous mixture has a pH of no more than 3, e.g., no more than 2, or no more than 1.Embodiment 64. The method any of embodiments 58-63, wherein at least one of the gallium source, the zirconium source, the platinum source, the cerium source, the promoter M1 source, and / or the promotor M2 source comprises one or more nitrate counterions.Embodiment 65. The method of any of embodiments 58-64, wherein nitric acid is used to adjust the pH of the aqueous mixture.Embodiment 66. The method of embodiment 65, wherein the nitric acid is concentrated nitric acid (i.e., nitric acid having a molarity of around 15.7 M)Embodiment 67. The method of any of embodiments 58-66, wherein at least 70%, e.g., at least 80%, or at least 90% of the zirconium of the catalyst material is provided from the zirconium source.Embodiment 68. The method of any of embodiments 58-67, wherein forming the solid comprises extruding the solid.Embodiment 69. The method of any of embodiments 58-68, wherein calcining the solid is performed at a calcination temperature in the range of 500-1200 °C, e.g., in the range of 500-1000 °C, or in the range of 500-800 °C, or in the range of 700-1200 °C, or in the range of 700-1000 °C, or in the range of 900-1200 °C.Embodiment 70. A catalyst bed comprising:the catalyst material of any of embodiments 1 -69 or prepared from the methods of any of embodiments 56-65.Embodiment 71. The catalyst bed of embodiment 70, wherein catalyst material is present in the catalyst bed in an amount in the range of 40-70 vol%, e.g., in the range of 40-DEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT 65 vol%, or 40-60 vol%, or 40-55 vol%, or 40-50 vol%, based on a total fill volume of the catalyst bed.Embodiment 72. The catalyst bed of embodiment 70, wherein catalyst material is present in the catalyst bed in an amount in the range of 45-70 vol%, e.g., in the range of 45-65 vol%, or 45-60 vol%, or 45-55 vol%, or 45-50 vol%, based on a total catalyst volume of the catalyst bed.Embodiment 73. The catalyst bed of embodiment 70, wherein catalyst material is present in the catalyst bed in an amount in the range of 50-70 vol%, e.g., in the range of SO-65 vol%, or 50-60 vol%, or 50-55 vol%, based on a total catalyst volume of the catalyst bed.Embodiment 74. The catalyst bed of any of embodiments 70-73, further comprising an inert material.Embodiment 75. The catalyst bed of embodiment 74, wherein the inert material includes (or is) silica, alumina, aluminate, or a mixture thereof.Embodiment 76. The catalyst bed of embodiment 75, wherein the inert material includes (or is) alumina in the form of a-, y-, q-, 0-, x-, K-, and / or b-alumina.Embodiment 77. The catalyst bed of embodiment 75, wherein the inert material includes (or is) aluminate in the form of Ca-aluminate, Zn-aluminate, and / or Mg-aluminate.Embodiment 78. The catalyst bed of any of embodiments 75-77, wherein silica, alumina, and aluminate are present in the inert material in an amount of at least 80 wt%, e.g., at least 90 wt%, or at least 95 wt%, based a total weight of the inert material.Embodiment 79. The catalyst bed of any of embodiments 75-78, wherein the inert material is present in the catalyst bed in an amount in the range of 20-45 vol%, e.g., 20-40 vol%, or 20-35 vol%, or 20-30 vol%, based on a total fill volume of the catalyst bed.Embodiment 80. The catalyst bed of any of embodiments 75-78, wherein the inert material is present in the catalyst bed in an amount in the range of 25-50 vol%, e.g., in the range of 25-45 vol%, or 25-40 vol%, or 25-35 vol%, or 25-30 vol%, based on a total fill volume of the catalyst bed.DEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT Embodiment 81. The catalyst bed of any of embodiments 75-78, wherein the inert material is present in the catalyst bed in an amount in the range of 30-50 vol%, e.g., in the range of 30-45 vol%, or 30-40 vol%, or 30-35 vol%, based on a total fill volume of the catalyst bed.Embodiment 82. The catalyst bed of any of embodiments 74-81 , wherein the catalyst material and the inert material are present in the catalyst bed in a volume ratio of catalyst material to inert material in the range of 3:1 to 1 :3, e.g., in the range of 2:1 to 1 :2.Embodiment 83. The catalyst bed of any of embodiments 70-82, further comprising a heat generating material.Embodiment 84. The catalyst bed of embodiment 83, wherein the heat-generating material comprises:a heat-generating metal, present in the heat-generating material in an amount in the range of 1-40 wt%, based on the total weight of the heat generating material; and a carrier, present in the heat-generating material in an amount in the range of 40-90 wt%, based on the total weight of the heat generating material.Embodiment 85. The catalyst bed of embodiment 84, wherein the heat-generating metal includes (or is) copper, chromium, molybdenum, vanadium, cerium, yttrium, scandium, tungsten, manganese, iron, cobalt, nickel, silver, bismuth, and a mixture thereof.Embodiment 86. The catalyst bed of embodiment 84, wherein the heat-generating metal includes (or is) copper oxide, copper aluminate, calcium sulfate, copper sulfate, zinc oxide, nickel oxide, iron oxide, tin oxide, cobalt oxide, vanadium oxide, lanthanum oxide, cerium oxide, manganese oxide, and a mixture thereof.Embodiment 87. The catalyst bed of any of embodiments 84-86, wherein the heatgenerating metal is present in the heat-generating material in an amount in the range of 0.5-50 wt%, e.g., in the range of 0.5-45 wt%, or 0.5-40 wt%, or 0.5-35 wt%, or 0.5-30 wt%, or 0.5-25 wt%.Embodiment 88. The catalyst bed of any of embodiments 84-86, wherein the heatgenerating metal is present in the heat-generating material in an amount in the range of 1-60 wt%, e.g., in the range of 5-60 wt%, or 10-60 wt%, or 15-60 wt%, or 20-60 wt%, or 25-60 wt%, or 30-60 wt%.DEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCTEmbodiment 89. The catalyst bed of any of embodiments 84-86, wherein the carrier includes (or is) silica, alumina, aluminate, and a mixture thereof.Embodiment 90. The catalyst bed of embodiment 89, wherein the carrier includes (or is) alumina in the form of a-, y-, q-, 0-, x-, K-, and / or b-alumina.Embodiment 91. The catalyst bed of embodiment 89, wherein the carrier includes (or is) aluminate in the form of Ca-aluminate, Zn-aluminate, and / or Mg-aluminate.Embodiment 92. The catalyst bed of any of embodiments 84-91 , wherein the carrier is present in the heat-generating material in an amount in the range of 40-95 wt%, e.g., in the range of 40-90 wt%, or 40-80 wt%, or 40-70 wt%, or 40-60 wt%, based on the total weight of the heat-generating material.Embodiment 93. The catalyst bed of any of embodiments 84-91 , wherein the carrier is present in the heat-generating material in an amount in the range of 45-99 wt%, e.g., in the range of 50-99 wt%, or 55-99 wt%, or 60-99 wt%, based on a total weight of the heatgenerating material.Embodiment 94. The catalyst bed of any of embodiments 84-93, wherein the heatgenerating metal and the carrier are present in the heat-generating material in a total amount of at least 80 wt%, e.g., at least 85%, or at least 90 wt%, or at least 95 wt%, based on the total weight of the heat-generating material.Embodiment 95. The catalyst bed of any of embodiments 70-94, wherein a total volume of the catalyst bed comprises and upstream volume and a downstream volume.Embodiment 96. The catalyst bed of embodiment 95, wherein the upstream volume is in the range of 15-50%, e.g., in the range of 15-40%, or in the range of 15-30%, or in the range of 20-50%, or in the range of 20-40%, or in the range of 20-30%, of the total fill volume of the catalyst bed.Embodiment 97. The catalyst bed of embodiment 95 or embodiment 96, wherein the downstream volume is in the range of 25-75% of the total fill volume of the catalyst bed, e.g., in the range of 25-65%, or in the range of 25-55%, or in the range of 35-75%, or in the rangeDEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT of 35-65%, or in the range of 35-55%, or in the range of 45-75%, or in the range of 45-65%, or in the range of 45-55%, of the total fill volume of the catalyst bed.Embodiment 98. The catalyst bed of any of embodiments 95-97, wherein at least 80 wt% of the total amount of the heat-generating material in the catalyst bed, e.g., at least 85 wt%, or at least 90 wt%, or at least 95 wt%, or at least 99 wt%, is located in the upstream volume.Embodiment 99. The catalyst bed of embodiment 98, wherein the heat-generating material comprises at least 85 vol%, e.g., at least 90 wt%, or at least 95 wt%, of a total volume of the upstream volume.Embodiment 100. The catalyst bed of embodiments 98 or 99, wherein no more than 10 wt% of the total amount of the catalyst material in the catalyst bed, e.g., no more than 5 wt%, or no more than 1 vol%, is located in the upstream volume.Embodiment 101. The catalyst bed of any of embodiments 98-100, wherein the catalyst material comprises no more than 10 vol%, e.g., no more than 5 vol%, or no more than 1 vol%, of the total fill volume of the upstream volume.Embodiment 102. The catalyst bed of any of embodiments 95-97, wherein at least 80 vol% of the total amount of the heat-generating material in the catalyst bed, e.g., at least 85 vol%, or at least 90 vol%, or at least 95 vol%, or at least 99 vol% is located in the downstream volume.Embodiment 103. The catalyst bed of embodiment 102, wherein the heat-generating material comprises at least 85 vol%, e.g., at least 90 vol%, or at least 95 vol%, of a total volume of the downstream volume.Embodiment 104. The catalyst bed of embodiment 102 or embodiment 103, wherein no more than 10 vol% of the total amount of the catalyst material in the catalyst bed, e.g., no more than 5 vol%, or no more than 1 vol%, is located in the downstream volume.Embodiment 105. The catalyst bed of any of embodiments 102-104, wherein the catalyst material comprises no more than 10 vol%, e.g., no more than 5 vol%, or no more than 1 vol%, of the total volume of the downstream volume.DEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT Embodiment 106. The catalyst bed of embodiment 95 or embodiment 97, wherein the total volume of the catalyst bed further comprises a middle volume, disposed in between the upstream volume and the downstream volume.Embodiment 107. The catalyst bed of embodiment 105, wherein the middle volume is in the range of 15-40%, e.g., in the range of 15-35%, or in the range of 15-30%, or in the range of 20-50%, or in the range of 20-40%, or in the range of 20-30%, of the total volume of the catalyst bed.Embodiment 108. The catalyst bed of embodiment 106 or embodiment 107, wherein the upstream volume is in the range of 1-30%, e.g., in the range of 1-25%, or in the range of 1-20%, or in the range of 5-30%, or in the range of 5-25%, or in the range of 5-20%, or in the range of 10-30%, or in the range of 10-25%, or in the range of 10-20%, of the total volume of the catalyst bed.Embodiment 109. The catalyst bed of any of embodiments 106-108, wherein at least 80 vol% of the total amount of the heat-generating material in the catalyst bed, e.g., at least 85 vol%, or at least 90 vol%, or at least 95 vol%, or at least 99 vol%, is located in the middle volume.Embodiment 110. The catalyst bed of embodiment 109, wherein the heat-generating material comprises at least 85 vol%, e.g., at least 90 vol%, or at least 95 vol% of a total volume of the middle volume.Embodiment 111. The catalyst bed of embodiment 109 or embodiment 111, wherein no more than 10 vol% of the total amount of the catalyst material in the catalyst bed, e.g., no more than 5 vol%, or no more than 1 vol%, is located in the middle volume.Embodiment 112. The catalyst bed of any of embodiments 109-111 , wherein the catalyst material comprises no more than 10 vol%, e.g., no more than 5 vol%, or no more than 1 vol%, of the total volume of the middle volume.Embodiment 113. A method for dehydrogenating hydrocarbons, the method comprising:providing a catalyst bed of any of embodiments 70-112 in a dehydrogenation reaction zone; andperforming a plurality of reaction cycles, each reaction cycle comprising: reducing the catalyst material under a reducing atmosphere comprising H2;DEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT contacting a feed stream comprising hydrocarbons with the catalyst bed to provide a product stream comprising dehydrogenated hydrocarbons and a deactivated catalyst, wherein a reaction by-product comprising coke is formed in the catalyst bed;purging the dehydrogenation reaction zone with a purge stream (e.g., a steam purge stream) to substantially remove the product stream thereof; regenerating the deactivated catalyst bed under an oxidizing atmosphere comprising O2 to provide the catalyst material;removing the oxidizing atmosphere from the dehydrogenation reaction zone.Embodiment 114. The method of embodiment 113, wherein the plurality of reaction cycles are performed at a reaction temperature in the range of 450-700 °C, e.g., in the range of 500-700 °C, or in the range of 550-700 °C, or in the range of 600-700 °C.Embodiment 115. The method of embodiment 113 or embodiment 114, wherein the reducing atmosphere comprises hydrogen in an amount of at least 10 vol%, e.g., at least 20 vol% or at least 30 vol%.Embodiment 116. The method of any of embodiments 113-115, wherein the reducing atmosphere further comprises inert gases, e.g., N2or Ar.Embodiment 117. The method of any of embodiments 113-116, wherein the reducing atmosphere further comprises hydrocarbons.Embodiment 118. The method of any of embodiments 113-117, wherein reducing the catalyst material is performed for a reduction time in the range of 0.5-250 seconds, e.g., in the range of 0.5-200 seconds, or in the range of 0.5-150 seconds, or in the range of 0.5-100 seconds, or in the range of 0.5-80 seconds.Embodiment 119. The method of any of embodiments 113-117, wherein reducing the catalyst material is performed for a reduction time in the range of 0.1-60 seconds, e.g., in the range of 0.1-50 seconds, or in the range of 0.1-40 seconds, or in the range of 0.1-30 seconds, or in the range of 0.1-20 seconds, or in the range of 0.1-10 seconds.Embodiment 120. The method of any one of embodiments 113-119, wherein the feed stream comprises C3-C5 hydrocarbons.DEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT Embodiment 121. The method of embodiment 113-120 wherein the feed stream comprises one or more of propane, n-butane, isobutene, and n-butylene; and the product stream comprises one or more of propylene, n-butylene, isobutylene, and butadiene.Embodiment 122. The method of embodiment 121, wherein the feed stream comprises propane and the product stream comprises propylene.Embodiment 123. The method of any of embodiments 113-122, wherein contacting the feed stream with the catalyst bed is performed with a feed stream temperature in the range of 500-700 °C, e.g., in the range of 550-700 °C, or in the range of 500-650 °C, or in the range of 550-650 °C.Embodiment 124. The method of any of embodiments 113-123, wherein contacting the feed stream with the catalyst bed is performed with a feed stream liquid hourly space velocity in the range of 0.5-3.0 h-1, e.g., in the range of 0.5-2.5 h-1, or in the range of 0.5-2.0 h’1, in the range of 0.5-1.5 h’1, or in the range of 0.8-3.0 h’1, or in the range of 0.8-2.5 h’1, or in the range of 0.8-2.0 h-1, or in the range of 0.8-1.5 h-1.Embodiment 125. The method of any of embodiments 113-124, wherein contacting the feed stream with the catalyst bed is performed with a dehydrogenation pressure in the range of 0.1 -2.0 atm.Embodiment 126. The method of any of embodiments 113-125, wherein contacting the feed stream with the catalyst bed is performed for a dehydrogenation time in the range of 200-900 seconds,Embodiment 127. The method of embodiment 126, wherein the dehydrogenation time is in the range of 200-500 seconds, e.g., in the range of 200-400 seconds, or in the range of 200-300 seconds, or in the range of 250-500 seconds, or in the range of 250-400 seconds, or in the range of 250-300 seconds.Embodiment 128. The method of embodiment 126, wherein the dehydrogenation time is in the range of 400-900 seconds, e.g., in the range of 400-800 seconds, or in the range of 400-700 seconds, or in the range of 400-600 seconds, or in the range of 500-900 seconds, or in the range of 500-800 seconds, or in the range of 500-700 seconds, or in the range of 500-600 seconds.DEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT Embodiment 129. The method of any of embodiments 113-128, wherein the purge stream comprises steam.Embodiment 130. The method of any of embodiments 113-128, wherein the purge stream comprises nitrogen.Embodiment 131. The method of any of embodiments 113-130, wherein purging the dehydrogenation reaction zone is performed for a purge time in the range of 30-120 seconds, e.g., in the range of 40-120 seconds, or in the range of 50-120 seconds, or in the range of 60-120 seconds, or in the range of 70-120 seconds, or in the range of 80-120 seconds.Embodiment 132. The method of any of embodiments 113-131, wherein the oxidizing atmosphere comprising O2 includes (or is) air.Embodiment 133. The method of embodiment 132, wherein the oxidizing atmosphere is provided in an amount such that a weight ratio of air to hydrocarbons is in the range of 1 :1 to 10:1, e.g., in the range of 1 :1 to 8:1 , or in the range of 2:1 to 10:1 , or in the range of 2:1 to 8:1 , or in the range of 4:1 to 10:1 , or in the range of 4:1 to 8:1.Embodiment 134. The method of any of embodiments 113-133, wherein regenerating the deactivated catalyst bed is performed for a regeneration time in the range of 200-900 secondsEmbodiment 135. The method of embodiment 134, wherein the regeneration time is in the range of 200-500 seconds, e.g., in the range of 200-400 seconds, or in the range of 200-300 seconds, or in the range of 250-500 seconds, or in the range of 250-400 seconds, or in the range of 250-300 seconds.Embodiment 136. The method of embodiment 134, wherein the regeneration time is in the range of 400-900 seconds, e.g., in the range of 400-800 seconds, or in the range of 400-700 seconds, or in the range of 400-600 seconds, or in the range of 500-900 seconds, or in the range of 500-800 seconds, or in the range of 500-700 seconds, or in the range of 500-600 seconds.DEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT Embodiment 137. The method of any of embodiments 113-136, wherein removing the oxidizing atmosphere from the dehydrogenation reaction zone is performed using a nitrogen purge.Embodiment 138. The method of any of embodiments 113-137, wherein removing the oxidizing atmosphere from the dehydrogenation reaction zone is performed by evacuation of the dehydrogenation reaction zone.Embodiment 139. The method of any of embodiments 113-138, wherein removing the oxidizing atmosphere from the dehydrogenation reaction zone is performed for an oxidizing atmosphere removal time in the range of 30-120 seconds, e.g., in the range of 40-120 seconds, or in the range of 50-120 seconds, or in the range of 60-120 seconds, or in the range of 30-100 seconds, or in the range of 40-100 seconds, or in the range of 50-100 seconds, or in the range of 60-100 seconds.Embodiment 140. The method of any of embodiments 113-139, wherein the dehydrogenation is performed with an alkene selectivity in the range of 75-95%, e.g., in the range of 75-90%, or in the range of 80-95%, or in the range of 80-90%, on a weight basis.Embodiment 141. The method of any of embodiments 113-140, wherein the plurality of reaction cycles comprises:a first reaction cycle having a first conversion, a first alkene selectivity, and a first alkene yield; anda subsequent reaction cycle occurring “n” cycles after the first reaction cycle, having a second conversion, a second alkene selectivity, a second alkene yield.Embodiment 142. The method of embodiment 141, wherein “n” is an integer of at least 100, e.g., at least 120, or at least 140, or at least 160.Embodiment 143. The method of embodiment 142, wherein the second conversion is at least 60%, e.g., at least 70%, or at least 80% of the first conversion.Embodiment 144. The method of embodiment 142 or embodiment 143, wherein the second alkene selectivity is at least 60%, e.g., at least 70%, or at least 80% of the first selectivity.DEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT Embodiment 145. The method of any of embodiments 142-144, wherein the second alkene yield is at least 60%, e.g., at least 70%, or at least 80% of the first alkene yield.

[0136] The particulars shown herein are by way of example and for purposes of illustrative discussion of the preferred embodiments of the present invention only and are presented in the cause of providing what is believed to be the most useful and readily understood description of the principles and conceptual aspects of various embodiments of the invention. In this regard, no attempt is made to show structural details of the invention in more detail than is necessary for the fundamental understanding of the invention, the description taken with the drawings and / or examples making apparent to those skilled in the art how the several forms of the invention may be embodied in practice. Thus, before the disclosed processes and devices are described, it is to be understood that the aspects described herein are not limited to specific embodiments, apparatuses, or configurations, and as such can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and, unless specifically defined herein, is not intended to be limiting.

[0137] The terms “a,” “an,” “the” and similar referents used in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Recitation of ranges of values herein is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range. Unless otherwise indicated herein, each individual value is incorporated into the specification as if it were individually recited herein. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.

[0138] All processes described herein can be performed in any suitable order of steps unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention otherwise claimed. No language in the specification should be construed as indicating any non-claimed element essential to the practice of the invention.

[0139] Unless the context clearly requires otherwise, throughout the description and the claims, the words ‘comprise’, ‘comprising’, and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is to say, in the sense of “including, but not limited to”. Words using the singular or plural number also include the plural and singular number, respectively. Additionally, the words “herein,” “above,” andDEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT “below” and words of similar import, when used in this application, shall refer to this application as a whole and not to any particular portions of the application.

[0140] As will be understood by one of ordinary skill in the art, each embodiment disclosed herein can comprise, consist essentially of or consist of its particular stated element, step, ingredient or component. As used herein, the transition term “comprise” or “comprises” means includes, but is not limited to, and allows for the inclusion of unspecified elements, steps, ingredients, or components, even in major amounts. The transitional phrase “consisting of” excludes any element, step, ingredient or component not specified. The transition phrase “consisting essentially of” limits the scope of the embodiment to the specified elements, steps, ingredients or components and to those that do not materially affect the embodiment.

[0141] Unless indicated to the contrary, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0142] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

[0143] Groupings of alternative elements or embodiments of the invention disclosed herein are not to be construed as limitations. Each group member may be referred to and claimed individually or in any combination with other members of the group or other elements found herein. It is anticipated that one or more members of a group may be included in, or deleted from, a group for reasons of convenience and / or patentability. When any such inclusion or deletion occurs, the specification is deemed to contain the group as modified thus fulfilling the written description of all Markush groups used in the appended claims.

[0144] Some embodiments of this invention are described herein, including the best mode known to the inventors for carrying out the invention. Of course, variations on these described embodiments will become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventor expects skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted byDEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.

[0145] Furthermore, it is to be understood that the embodiments of the invention disclosed herein are illustrative of the principles of the present invention. Other modifications that may be employed are within the scope of the invention. Thus, by way of example, but not of limitation, alternative configurations of the present invention may be utilized in accordance with the teachings herein. Accordingly, the present invention is not limited to that precisely as shown and described.

Claims

DEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT What is claimed is1 . A catalyst material for the dehydrogenation of hydrocarbons, the catalyst material comprising:an alumina or silica-alumina carrier, the catalyst material having in the range of 39- 98.75 wt% aluminum, calculated as AI2O3 on a calcined basis, and a ratio of an amount of silicon to a combined amount of silicon and aluminum of up to 20 wt%, in which silicon and aluminum are respectively calculated as SiC>2 and AI2O3 on a calcined basis;gallium, present in the catalyst material in an amount in the range of 0.5-8 wt%, calculated as Ga2Os on a calcined basis;zirconium, present in the catalyst material in an amount in the range of 0.5-30 wt%, calculated as ZrC>2 on a calcined basis,the catalyst material exhibiting, in a calcined form, a ratio of a peak height of an infrared absorbance peak at 1595 ± 5 cm-1to a peak height of an infrared absorbance peak at 1615 ± 5 cm'1of no more than 0.7 in a pyridine FTIR experiment.

2. The catalyst material of claim 1 , wherein gallium is present in the catalyst material in an amount in the range of 0.5-6 wt%, calculated as Ga2Os on a calcined basis.

3. The catalyst material of claim 1 , wherein zirconium is present in the catalyst material in an amount in the range of 2-30 wt%, calculated as ZrC>2 on a calcined basis.

4. The catalyst material of claim 1 , wherein aluminum is present in the catalyst material in an amount in the range of 75-98.75 wt%, calculated as AI2O3 on a calcined basis.

5. The catalyst material of claim 1 , wherein the catalyst material further comprises silicon, wherein aluminum and silicon are present in the catalyst material in a weight ratio of aluminum to silicon, calculated as AI2O3 and SiC>2 on a calcined basis, in the range of 9:1 to 50:1.

6. The catalyst material of claim 1 , further comprising platinum, present in the catalyst material in an amount in the range of 1-250 ppm, calculated as PtO2 on a calcined basis.

7. The catalyst material of claim 1 , further comprising cerium, present in the catalyst material in an amount in the range of 0.02-1 wt%, calculated as CeO2 on a calcined basis.DEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT8. The catalyst material of claim 1 , wherein one or more promoters M1 selected from lithium, sodium, potassium, and a combination thereof are present in the catalyst material a total amount in the range of 0.01-3 wt%, calculated as M12O on a calcined basis.

9. The catalyst material of claim 1 , wherein a total amount of gallium, zirconium, aluminum, M1 promoter(s) and M2 promoter(s), platinum and cerium, each calculated as oxide on a calcined basis, is at least 95 wt% of the catalyst material.

10. The catalyst material of claim 1 , wherein a chromium content of the catalyst material is less than 0.05 wt% chromium, based on the total weight of the catalyst.

11. The catalyst material of claim 1 , exhibiting, in a calcined form, a ratio of a peak height of an infrared absorbance peak at 1595 ± 5 cm-1to a peak height of an infrared absorbance peak at 1615 ± 5 cm'1of no more than 0.5 in a pyridine FTIR experiment.

12. The catalyst material of claim 1 , wherein at least 75 wt% of the zirconium present in the catalyst material has crystalline ZrO2domain size of no more than 4 nm as determined by Rietveld refinement of x-ray diffraction spectra as described in the specification.

13. The catalyst material of claim 1 , whereingallium is present in the catalyst material in an amount in the range of 0.5-6 wt%, calculated as Ga2Os on a calcined basis;zirconium is present in the catalyst material in an amount in the range of 3.5-30 wt%, calculated as ZrO2on a calcined basis;aluminum is present in the catalyst material in an amount in the range of 75-98.75 wt%, calculated as AI2Os on a calcined basis;the catalyst material further comprises silicon, wherein aluminum and silicon are present in the catalyst material in a weight ratio of aluminum to silicon, calculated as AI2C>3 and SiO2on a calcined basis, in the range of 9:1 to 50:1 ;the catalyst material further comprises platinum, present in the catalyst material in an amount in the range of 1-250 ppm, calculated as PtO2on a calcined basis. a total amount of gallium, zirconium, aluminum, M1 promoter(s) and M2 promoter(s), platinum and cerium, each calculated as oxide on a calcined basis, is at least 95 wt% of the catalyst material;a chromium content of the catalyst material is less than 0.05 wt% chromium, based on the total weight of the catalyst; andDEHYDROGENATION CATALYST MATERIALS AND SYSTEMS AND METHODS FOR USING SAME Matthew GREANEY 202300426- 2025US702-WO-PCT at least 75 wt% of the zirconium present in the catalyst material has crystalline ZrO2domain size of no more than 4 nm as determined by Rietveld refinement of x-ray diffraction spectra as described in the specification.

14. A method for preparing the catalyst material of claim 1 , the method comprising providing an aqueous mixture comprising:a gallium source;a zirconium source; andan aluminum source;forming a solid from the aqueous mixture; andcalcining the solid so formed.

15. A method for dehydrogenating hydrocarbons, the method comprising:providing a catalyst bed of claim 1 in a dehydrogenation reaction zone; and performing a plurality of reaction cycles, each reaction cycle comprising: reducing the catalyst material under a reducing atmosphere comprising H2; contacting a feed stream comprising hydrocarbons with the catalyst bed to provide a product stream comprising dehydrogenated hydrocarbons and a deactivated catalyst, wherein a reaction by-product comprising coke is formed in the catalyst bed;purging the dehydrogenation reaction zone with a purge stream (e.g., a steam purge stream) to substantially remove the product stream thereof; regenerating the deactivated catalyst bed under an oxidizing atmosphere comprising O2to provide the catalyst material;removing the oxidizing atmosphere from the dehydrogenation reaction zone.

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