Methods for making olefinic materials utilizing catalysts that include non-redox-active elemental additives

Abstract

Olefinic materials may be made by dehydrogenation utilizing a catalyst. The catalyst may include from 0.0005 wt.% to 0.1 wt% of platinum, palladium, rhodium, iridium, ruthenium, osmium, or combinations thereof; from 0.1 wt.% to 10 wt.% of gallium, indium, thallium, or combinations thereof; from 0.1 wt.% to 5 wt.% of one or more non-redox-active elemental additives; and at least 85 wt.% of support.

Description

METHODS FOR MAKING OLEFINIC MATERIALS UTILIZING CATALYSTS THAT INCLUDE NON-REDOX-ACTIVE ELEMENTAL ADDITIVESCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application Serial No. 63 / 656,704 filed June 6, 2024, the contents of which are incorporated in their entirety herein.TECHNICAL FIELD

[0002] Embodiments described herein generally relate to chemical processing and, more specifically, to methods and systems for the production of olefinic materials.BACKGROUND

[0003] Olefinic materials, such as ethylene, butene, and propylene, may be used as base materials to produce many different products, such as polypropylene, isopropanol, and acrylic acid, which may be used in, for example, packaging, construction, and textiles. As a result of this utility, there is a worldwide demand for olefinic materials. Suitable processes for producing olefinic materials generally depend on the given chemical feed and include those that utilize fluidized catalysts. For example, olefinic materials may be formed by the catalytic dehydrogenation of alkanes in a fluidized bed reactor. There is a need for improvements in the methods and associated catalysts used to make olefinic materials.SUMMARY

[0004] As described herein, according to one or more embodiments, hydrocarbons may be dehydrogenated to form olefinic materials, such as forming propylene from propane by catalytic dehydrogenation. Surprisingly, it has been presently discovered that utilizing catalysts that include non-redox-active elemental additives may provide for enhanced catalytic activity as compared with catalysts that do not include the non-redox active elemental additives (as well as catalysts that include redox-active elemental additives). Examples of non-redox-active elemental additives include, without limitation lanthanum, yttrium, zirconium, scandium, titanium, niobium, and tantalum.

[0005] According to one or more embodiments of the present disclosure, a method for making olefinic materials may comprise contacting a hydrocarbon-containing feed with a catalyst in a reactor to form an olefin-containing effluent, wherein the catalyst may have a residence time within the reactor of less than or equal to 3 minutes. The method may further comprise passing the catalyst to a combustor and heating the catalyst by combusting a supplemental fuel, passing the catalyst from the combustor to an oxygen treatment zone and exposing the catalyst to an oxygen-containing gas for from 2 minutes to 20 minutes in the oxygen treatment zone, wherein the oxy gen-containing gas comprise at least 10 mol.% oxygen, and passing the catalyst from the oxygen treatment zone to the reactor, such that all or a portion of the catalyst continuously cycles between the reactor, the combustor, and the oxygen treatment zone. The catalyst may comprise from 0.0005 wt.% to 0.1 wt% of platinum, palladium, rhodium, iridium, ruthenium, osmium, or combinations thereof, from 0.1 wt.% to 10 wt.% of gallium, indium, thallium, or combinations thereof, from 0.1 wt.% to 5 wt.% of one or more non-redox-active elemental additives, and at least 85 wt.% of support.

[0006] It is to be understood that both the preceding general description and the following detailed description describe various embodiments and are intended to provide an overview or framework for understanding the nature and character of the claimed subject matter. Additional features and advantages of the embodiments will be set forth in the detailed description and, in part, will be readily apparent to persons of ordinary skill in the art from that description, which includes the accompanying drawing and claims, or recognized by practicing the described embodiments. The drawing is included to provide a further understanding of the embodiments and, together with the detailed description, serves to explain the principles and operations of the claimed subject matter. However, the embodiment depicted in the drawing is illustrative and exemplary in nature, and not intended to limit the claimed subject matter.BRIEF DESCRIPTION OF THE DRAWINGS

[0007] The following detailed description may be better understood when read in conjunction with the following drawing, in which:

[0008] FIG. 1 schematically depicts a reactor system, according to one or more embodiments of the present disclosure.

[0009] When describing the simplified schematic illustration of FIG. 1, the numerous valves, temperature sensors, electronic controllers, and the like, which may be used and are well known to a person of ordinary skill in the art, are not included. Further, accompanying components that are often included in such reactor systems, such as air supplies, heat exchangers, surge tanks, and the like are also not included. However, it should be understood that these components are within the scope of the present disclosure.

[0010] Reference will now be made in greater detail to various embodiments, some of which are illustrated in the accompanying drawing.DETAILED DESCRIPTION

[0011] The present disclosure is directed to methods for making olefinic materials by dehydrogenation where particular catalyst compositions are utilized, as well as particular reaction temperatures and times, as are described herein. For example, catalysts useful for dehydrogenation may include a catalyst comprising: from 0.0005 wt.% to 0.1 wt.% of platinum, palladium, rhodium, iridium, ruthenium, osmium, or combinations thereof; from 0.1 wt.% to 10 wt.% of gallium, indium, thallium, or combinations thereof; from 0.1 wt.% to 5 wt.% of one or more non-redox- active elemental additives; and at least 85 wt.% of support. In one or more embodiments, such catalysts provide dual catalytic functionality for dehydrogenation of alkanes as well as combustion of supplemental fuels. Such catalysts including one or more non-redox-active elemental additives may be particularly well suited for fluidized dehydrogenation of alkanes to olefinic materials, such as propane to propylene, where methane is utilized as a supplemental fuel to heat the catalyst.

[0012] Some methods and associated systems used to make olefinic materials may utilize supplemental fuels that are combusted to heat the catalyst during the production process. For example, the catalyst may be cycled between a reactor, where olefinic materials are produced in an endothermic reaction, and a combustor, where the catalyst is heated by exothermic combustion of at least a supplemental fuel (sometimes along with combustion of coke). Such catalysts may desirably have catalytic activity not only for the dehydrogenation of alkanes to form olefins, but also for the combustion of supplemental fuels. Some embodiments of such suitable catalysts include, for example, gallium and platinum on a support. In some embodiments, methane may be used in the supplemental fuel. In such embodiments, conventional catalysts used for dehydrogenation may suffer from relatively low methane combustion activity, meaning that usingmethane as a supplemental fuel may not provide heat sufficient to raise the temperature of the catalyst to the desired temperatures utilized in the dehydrogenation reaction. Further, using conventional catalysts that may suffer from low methane combustion activity may negatively impact the safety of the dehydrogenation process, as un-combusted methane may exceed the low flammability level required to safely operate the regenerator.

[0013] Additionally, in order to improve the methane combustion activity, redox-active elemental additives such as iron, manganese, and cerium may be incorporated into the catalyst. Even though these additives may enhance methane combustion activity, their redox-active activity may lead to increased levels of COXand H2O formation in the reactor, resulting in the loss of selectivity of the desired olefinic material products or inhibition of precious metal catalytic components, such as platinum. In particular, for processes that utilize fluidized beds, such impact may be more significant than for processes that do not utilize fluidized beds. In addition, COXspecies generated in the product stream may add to separation challenges downstream of the reactor.

[0014] According to one or more embodiments and, as is described herein, it has been discovered that catalysts that additionally include one or more non-redox-active elemental additives may enhance combustion of methane as compared with conventional catalysts that, for example, do not include non-redox-active elemental additives, while maintaining desired dehydrogenation activity. Additionally, the inclusion of non-redox-active elemental additives may enhance catalytic stability for dehydrogenation, as described herein.

[0015] Embodiments of the methods presently disclosed are described in detail herein in the context of the reactor system of FIG. 1 operating as a fluidized dehydrogenation reactor system to produce olefinic materials. As described herein, “olefinic materials” may refer to a class of chemicals made up of hydrogen and carbon with one or more pairs of carbon atoms linked by a double bond. In some embodiments, olefinic materials may include light olefins, such as ethylene, butene, propylene, and styrene. However, it should be understood that the principles disclosed and taught herein may be applicable to other systems which utilize different system components oriented in different ways. For example, the concepts described herein may be equally applied to other systems with alternate reactor units and regeneration units, such as those that operate under non-fluidized conditions or include downers rather than risers. It should be further understood thatnot all portions of FIG. 1 should be construed as essential to the claimed subject matter. Moreover, while the recited method steps in the appended claims are described herein in the context of FIG. 1, such recited method steps should be understood as adaptable to other systems, as would be understood by those skilled in the art.

[0016] Now referring to FIG. 1, an example reactor system 102 that may be suitable for use with the methods and / or apparatuses described herein is schematically depicted. The reactor system 102 generally comprises multiple system components, such as a reactor portion 200 and a catalyst processing portion 300. As described herein, “system components” refer to portions of the reactor system 102, such as reactors, separators, transfer lines, combinations thereof, and the like. As used herein in the context of FIG. 1, the reactor portion 200 generally refers to the portion of the reactor system 102 in which the major process reaction takes place (e.g., dehydrogenation) to form the olefin-containing effluent. A hydrocarbon-containing feed enters the reactor portion 200, is contacted with a catalyst, converted to an olefin-containing effluent (containing product and unreacted feed), and exits the reactor portion 200. The reactor portion 200 comprises a reactor 202 which may include an upstream reactor section 250 and a downstream reactor section 230. According to one or more embodiments, as depicted in FIG. 1, the reactor portion 200 may additionally include a catalyst separation section 210, which serves to separate the catalyst from the olefin-containing effluent formed in the reactor 202. Also, as used herein, the catalyst processing portion 300 generally refers to the portion of the reactor system 102 where the catalyst is in some way processed, such as by combustion, to, e.g., improve catalytic activity by decoking and / or heating the catalyst. The catalyst processing portion 300 may comprise a combustor 350 and a riser 330, and may additionally comprise a catalyst separation section 310. In one or more embodiments, the catalyst separation section 210 may be in fluid communication with the combustor 350 (e.g, via standpipe 426) and the catalyst separation section 310 may be in fluid communication with the upstream reactor section 250 (e.g., via standpipe 424 and transport riser 430).

[0017] Generally, as is described herein, in embodiments illustrated in FIG. 1, catalyst is cycled between the reactor portion 200 and the catalyst processing portion 300. It should be understood that when “catalysts” are referred to herein, they may refer to solid materials that are catalytically active for a desired reaction. The terms “catalytic activity” and “catalyst activity” refer to the degree to which the catalyst is able to catalyze the reactions conducted in the reactorsystem 102. The catalyst that exits the reactor portion 200 may be deactivated catalyst. As used herein, “deactivated” may refer to a catalyst that has reduced catalytic activity or is cooler as compared to catalyst entering the reactor portion 200. However, deactivated catalyst may maintain some catalytic activity. Reduced catalytic activity may result from contamination with a substance such as coke. Coke may form on the catalyst within the reactor portion 200. Reactivation (sometimes called “regeneration” herein) may remove the contaminant such as coke, raise the temperature of the catalyst, or both. In embodiments, deactivated catalyst may be reactivated by catalyst reactivation in the catalyst processing portion 300. The deactivated catalyst may be reactivated by, but not limited to, removing coke by combustion, oxidizing the catalyst, other reactivation process, or combinations thereof. In some embodiments, the catalyst may be heated during reactivation by combustion of a supplemental fuel, such as methane, ethane, propane, natural gas, hydrogen, or combinations thereof. The reactivated catalyst from the catalyst processing portion 300 is then passed back to the reactor portion 200.

[0018] As is disclosed herein, in one or more embodiments the supplemental fuel may comprise methane. For example the supplemental fuel may comprise an amount of methane greater than or equal to 1 mol.%, such as greater than or equal to 2 mol.%, greater than or equal to 3 mol.%, greater than or equal to 4 mol.%, or even greater than or equal to 5 mol.%. In some embodiments the supplemental fuel comprises methane in an amount no more than 10 mol.%. In some embodiments, the supplemental fuel may comprise methane in an amount greater than 10 mol.%, such as greater than 20 mol.%, greater than 30 mol.%, greater than 40 mol.%, greater than 50 mol.%, greater than 60 mol.%, greater than 70 mol.%, greater than 80 mol.%, greater than 90 mol.%, or even 100 mol.%. Catalysts with improved methane combustion activity, such as those described herein that include one or more non-redox-active elemental additives, can better utilize methane as a supplemental fuel to facilitate re-heating of the catalyst. The catalyst is heated during regeneration to aid with regeneration and also because heated catalyst serves as a heat carrier to carry heat from the combustor 350 to the reactor portion 200 to facilitate the dehydrogenation reaction.

[0019] In non-limiting examples, the reactor system 102 described herein may be utilized to produce olefinic materials from a hydrocarbon-containing feed. According to one or more embodiments, the reaction may be a dehydrogenation reaction. According to such embodiments, the hydrocarbon-containing feed may comprise one or more of ethane, propane, n-butane, i-butane, or ethylbenzene. In one or more embodiments, the hydrocarbon-containing feed may comprise at least 50 wt.%, at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, at least 95 wt.% or even at least 99 wt.% of ethane. In additional embodiments, the hydrocarbon- containing feed may comprise at least 50 wt.%, at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, at least 95 wt.% or even at least 99 wt.% of propane. In additional embodiments, the hydrocarbon-containing feed may comprise at least 50 wt.%, at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, at least 95 wt.% or even at least 99 wt.% of n-butane. In additional embodiments, the hydrocarbon-containing feed may comprise at least 50 wt.%, at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, at least 95 wt.% or even at least 99 wt.% of i-butane. In additional embodiments, the hydrocarbon-containing feed may comprise at least 50 wt.%, at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, at least 95 wt.% or even at least 99 wt.% of the sum of ethane, propane, n-butane, and i-butane.

[0020] In one or more embodiments, the catalyst may comprise, consist essentially of, or consist of gallium, indium, thallium, or combinations thereof; platinum, palladium, rhodium, iridium, ruthenium, osmium, or combinations thereof; one or more non-redox-active elemental additives; and a support. As described herein, “consisting essentially of’ refers to materials with less than 1 wt.% of the non-recited materials (i.e., consisting essentially of A and B means A and B combined are at least 99 wt.% of the composition). In additional embodiments, the catalyst may comprise, consist essentially of, or consist of gallium, indium, thallium, or combinations thereof; platinum, palladium, rhodium, iridium, ruthenium, osmium, or combinations thereof; one or more non-redox-active elemental additives; a support; and one or both of alkali or alkaline earth metals. As is described herein, the catalyst may be solid particles suitable for fluidization.

[0021] In one or more embodiments, the catalyst may comprise gallium, indium, thallium, or combinations thereof in an amount of from 0.1 wt.% to 10 wt.% based on the total mass of the catalyst. Such materials may catalyze the dehydrogenation of alkanes to alkenes, particularly when used in combination with platinum, palladium, rhodium, iridium, ruthenium, osmium, or combinations thereof. Such materials may additionally catalyze the combustion of coke and supplemental fuels. For example, the catalyst may comprise gallium, indium, thallium, or combinations thereof in an amount from 0.1 wt.% to 0.25 wt.%, from 0.25 wt.% to 0.5 wt.%, from 0.5 wt.% to 0.75 wt.%, from 0.75 wt.% to 1 wt.%, from 1 wt.% to 2 wt.%, from 2 wt.% to 3 wt.%, from 3 wt.% to 4 wt.%, from 4 wt.% to 5 wt.%, from 5 wt.% to 6 wt.%, from 6 wt.% to 7 wt.%,from 7 wt.% to 8 wt.%, from 8 wt.% to 9 wt.%, from 9 wt.% to 10 wt.%, or any combination of these ranges. In some embodiments, the catalyst may comprise gallium, indium, thallium, or combinations thereof in an amount from 0.1 wt.% to 9 wt.%, from 0.1 wt.% to 8 wt.%, from 0.1 wt.% to 7 wt.%, from 0.1 wt.% to 6 wt.%, or from 0.1 wt.% to 5 wt.%. In some embodiments, the catalyst comprises only gallium but not indium or thallium, only indium but not gallium or thallium, or only thallium but not gallium or indium. It should be understood that the compositional ranges describing the amount of gallium, indium, and thallium represent ranges for any one of these materials, or for the combination of these materials. Without being bound by any particular theory, it is believed that compositions having gallium, indium, thallium, or combinations thereof in an amount less than 0.1 wt.% negatively impacts the catalyst’s ability to catalyze the alkane dehydrogenation process by lowering both the percentage of total alkane dehydrogenated and the percentage of dehydrogenated alkane that is the intended product. However, it is believed that compositions having gallium, indium, thallium, or combinations thereof in an amount exceeding 10 wt.% may negatively impact the catalyst’s ability to catalyze the alkane dehydrogenation process, negatively impact the catalyst’s selectivity towards the intended product, or both.

[0022] In one or more embodiments, the catalyst may comprise platinum, palladium, rhodium, iridium, ruthenium, osmium, or combinations thereof in an amount from 0.0005 wt.% to 0.1 wt.% based on the total mass of the catalyst. Such materials may catalyze the dehydrogenation of alkanes to alkenes, particularly when used in combination with gallium, indium, thallium, or combinations thereof. Such materials may additionally catalyze the combustion of coke and supplemental fuels. For example, the catalyst may comprise platinum, palladium, rhodium, iridium, ruthenium, osmium, or combinations thereof in an amount from 0.0005 wt.% to 0.005 wt.%, from 0.005 wt.% to 0.01 wt.%, from 0.01 wt.% to 0.02 wt.%, from 0.02 wt.% to 0.03 wt.%, from 0.03 wt.% to 0.04 wt.%, from 0.04 wt.% to 0.05 wt.%, from 0.05 wt.% to 0.06 wt.%, from 0.06 wt.% to 0.07 wt.%, from 0.07 wt.% to 0.08 wt.%, from 0.09 wt.% to 0.1 wt.%, or any combination of these ranges. In some embodiments, the catalyst may comprise platinum, palladium, rhodium, iridium, ruthenium, osmium, or combinations thereof in an amount from 0.0005 wt.% to 0.08 wt.%, from 0.0005 wt.% to 0.06 wt.%, from 0.0005 wt.% to 0.04 wt.%, from 0.0005 wt.% to 0.02 wt.%, from 0.0005 wt.% to 0.01 wt.%, from 0.001 wt.% to 0.005 wt.%, or any combinations of these ranges. In some embodiments, the catalyst comprises only platinumbut not palladium, rhodium, iridium, ruthenium, or osmium, only palladium but not platinum, rhodium, iridium, ruthenium, or osmium, only rhodium, but not platinum, palladium, iridium, ruthenium, or osmium, only iridium, but not platinum, palladium, rhodium, ruthenium, or osmium, only ruthenium but not platinum, palladium, rhodium, iridium, or osmium, or only osmium but not platinum, palladium, rhodium, iridium, or ruthenium. It should be understood that the compositional ranges describing the amount of platinum, palladium, rhodium, iridium, ruthenium, and osmium represent ranges for any one of these materials, or for the combination of these materials. Without being bound by any particular theory, it is believed that compositions having platinum, palladium, rhodium, iridium, ruthenium, osmium, or combinations thereof in an amount less than 0.0005 wt.% negatively impacts the catalyst’s ability to catalyze the alkane dehydrogenation process by lowering both the percentage of total alkane dehydrogenated and the percentage of dehydrogenated alkane that is the intended product. However, it is believed that compositions having one or more of platinum, palladium, rhodium, iridium, ruthenium, or osmium in an amount exceeding 0.1 wt.% may significantly increase the cost of the catalyst.

[0023] In one or more embodiments, the catalyst may comprise one or more non-redox- active elemental additives in an amount from 0.1 wt.% to 5 wt.% based on the total weight of the catalyst. As described herein, “non-redox-active elemental additives” may refer to an elemental additive that has poor redox capacity as compared to redox-active elemental additives. As described herein, “redox-active elemental additives” refer to elemental additives capable of undergoing reduction in the presence of a reducing agent (e.g., hydrogen) and oxidation in the presence of an oxidizing agent (e.g., oxygen or air). In some embodiments, the one or more non- redox-active elemental additives may be chosen from lanthanum, yttrium, zirconium, scandium, titanium, niobium, and tantalum. In some embodiments, the one or more non-redox-active elemental additives may be chosen from lanthanum, yttrium, and zirconium. In some embodiments, the one or more non-redox-active elemental additives may be lanthanum. In some embodiments, the one or more non-redox-active elemental additives may be yttrium. In some embodiments, the one or more non-redox-active elemental additives may be zirconium. The incorporation of one or more non-redox-active elemental additives may promote combustion of methane while not having significant impact on the dehydrogenation of alkanes, according to some embodiments. Additionally, the inclusion of one or more non-redox-active elemental additives may enhance catalytic stability for dehydrogenation, such that over repeated cycling ofdehydrogenation and heating, the catalytic activity may not be significantly diminished. The inclusion of one or more non-redox-active elemental additives also may limit the formation of COXspecies that can form in the reactor, as compared to catalysts that utilize redox-active elemental additives. As described herein, the formation of COXspecies in the reactor may be poisonous to the platinum, palladium, rhodium, iridium, ruthenium, osmium, or combinations thereof.

[0024] In one or more embodiments, the catalyst may comprise the one or more non- redox-active elemental additives in an amount from 0.1 wt.% to 5 wt.% based on the total weight of the catalyst. For example, the catalyst may comprise one or more non-redox-active elemental additives in an amount from 0.25 wt.% to 5 wt.%, from 0.5 wt.% to 5 wt.%, from 0.75 wt.% to 5 wt.%, from 1 wt.% to 5 wt.%, from 1.25 wt.% to 5 wt.%, from 1.5 wt.% to 5 wt.%, from 1.75 wt.% to 5 wt.%, from 2 wt.% to 5 wt.%, from 2.5 wt.% to 5 wt.%, from 3 wt.% to 5 wt.%, from 3.5 wt.% to 5 wt.%, from 4 wt.% to 5 wt.%, from 4.5 wt.% to 5 wt.%, from 0.1 wt.% to 4.5 wt.%, from 0.1 wt.% to 4 wt.%, from 0.1 wt.% to 3.5 wt.%, from 0.1 wt.% to 3 wt.%, from 0.1 wt.% to 2.5 wt.%, from 0.1 wt.% to 2 wt.%, from 0.1 wt.% to 1.75 wt.%, from 0.1 wt.% to 1.5 wt.%, from 0.1 wt.% to 1.25 wt.%, from 0.1 wt.% to 1 wt.%, from 0.1 wt.% to 0.75 wt.%, from 0.1 wt.% to 0.5 wt.%, from 0.1 wt.% to 0.25 wt.%, or any combinations of these ranges, based on the total weight of the catalyst. Without being bound by any particular theory, it is believed that compositions having non-redox-active elemental additives in an amount less than 0.1 wt.% may not sufficiently improve the methane combustion performance of the catalyst. It is believed that compositions having non-redox-active elemental additives in an amount exceeding 5 wt.% may negatively impact the catalyst’s dehydrogenation performance by lowering the percentage of total alkane that is dehydrogenated and / or the percentage of dehydrogenated alkane that is the intended product.

[0025] It should be understood that any combination of one or more of lanthanum, yttrium, zirconium, scandium, titanium, niobium, and tantalum may be present in the catalyst in amounts from 0.1 wt.% to 5 wt.%, or any of the subranges above. For example, in some embodiments, the catalyst may comprise lanthanum in an amount from 0.1 wt.% to 5 wt.%, or any of the subranges above, based on the total weight of the catalyst. In other embodiments, the catalyst may comprise yttrium in an amount from 0.1 wt.% to 5 wt.%, or any of the subranges above, based on the total weight of the catalyst. In other embodiments, the catalyst may comprise zirconium in an amount from 0.1 wt.% to 5 wt.%, or any of the subranges above, based on the total weight of the catalyst.

[0026] As is described herein, in one or more embodiments, the catalyst may comprise a support. The support may comprise one or more of alumina, silica, or combinations thereof. For example, in some embodiments the support may comprise one or more of alumina, silica, titania, or combinations thereof. For example, contemplated supports include alumina, silica-containing alumina, and titania-containing alumina. In some embodiments, the support does not include zirconium. The support may be present in an amount of at least 85 wt.% relative to the total weight of the catalyst, such as at least 85 wt.%, at least 90 wt.%, or at least 95 wt.%. In some embodiments, the support comprises less than or equal to 99.5 wt.% of the catalyst. Generally, the wt.% of the support may fdl the remainder of the total catalyst not specified by other materials described herein.

[0027] In one or more embodiments, the catalyst may optionally comprise one or more alkali metals, one or more alkaline earth metals, or both, in an amount from 0.01 wt.% to 5 wt.% based on the total weight of the catalyst. For example, the catalyst may comprise one or more alkali metals, one or more alkaline earth metals, or both in an amount from 0.01 wt.% to 0.05 wt.%, from 0.05 wt.% to 0.1 wt.%, from 0.1 wt.% to 0.2 wt.%, from 0.2 wt.% to 0.3 wt.%, from 0.3 wt.% to 0.4 wt.%, from 0.4 wt.% to 0.5 wt.%, from 0.5 wt.% to 0.6 wt.%, from 0.6 wt.% to 0.7 wt.%, from 0.7 wt.% to 0.8 wt.%, from 0.8 wt.% to 0.9 wt.%, from 0.9 wt.% to 1 wt.%, from 1 wt.% to 2 wt.%, from 2 wt.% to 3 wt.%, from 3 wt.% to 4 wt.%, from 4 wt.% to 5 wt.%, or any combination of these ranges. In some embodiments, the catalyst may comprise one or more alkali metals, one or more alkaline earth metals, or both from 0.01 wt.% to 1 wt.%, from 0.02 wt.% to 0.75 wt.%, from 0.03 wt.% to 0.5 wt.%, from 0.04 wt.% to 0.4 wt.%, or from 0.05 wt.% to 0.3 wt.%. In some embodiments, the one or more alkali metals or one or more alkaline earth metals may be potassium. However, it is believed that compositions having alkali metals or alkaline earth metals in an amount exceeding 5 wt.% may reduce the catalyst’s dehydrogenation activity.

[0028] In one or more embodiments, the catalyst does not include cerium, iron, manganese, copper, chromium, cobalt, nickel, vanadium, molybdenum, tungsten, or praseodymium in amounts greater than 0.001 wt.% based on the total weight of the catalyst. The group of cerium, iron, manganese, copper, chromium, cobalt, nickel, vanadium, molybdenum, tungsten, and praseodymium may be referred to herein as “redox-active elemental additives”. As described herein, “redox-active elemental additives” refer to elemental additives capable of undergoing reduction in the presence of a reducing agent (e.g., hydrogen) and oxidation in the presence of an oxidizing agent (e.g, oxygen or air). In some embodiments, the catalyst does not include cerium,iron, manganese, copper, chromium, cobalt, nickel, vanadium, molybdenum, tungsten, or praseodymium in amounts greater than 0.0005 wt.%, 0.0001 wt.%, or 0 wt.%. In other words, in some embodiments, the catalyst may be free of cerium, iron, manganese, copper, chromium, cobalt, nickel, vanadium, molybdenum, tungsten, or praseodymium. Without being bound to any particular theory, the presence of these redox-active elemental additives in the catalyst may lead to increased levels of COXand H2O formation in the reactor, resulting in the loss of selectivity of the desired olefinic material products or inhibition of precious metal catalytic components (i.e., “poisoning”), such as platinum.

[0029] In one or more embodiments, the catalyst may comprise, consist essentially of, or consist of gallium, platinum, one or more non-redox-active elemental additives, and a support. For example, the catalyst may comprise, consist essentially of, or consist of from 0.0005 wt.% to 0.1 wt.% of platinum; from 0.1 wt.% to 10 wt.% of gallium; from 0.1 wt.% to 5 wt.% of one or more non-redox-active elemental additives; and at least 85 wt.% of a support. In one or more embodiments, the catalyst may comprise, consist essentially of, or consist of gallium; platinum; and lanthanum, yttrium, zirconium, or combinations thereof. For example, the catalyst may comprise, consist essentially of, or consist of from 0.0005 wt.% to 0.1 wt.% of platinum; from 0.1 wt.% to 10 wt.% of gallium; and from 0.1 wt.% to 5 wt.% of lanthanum, yttrium, zirconium, or combinations thereof. In one exemplary embodiment, the catalyst may comprise, consist essentially of, or consist of from 0.0005 wt.% to 0.05 wt.% of platinum; from 0.1 wt.% to 5 wt.% of gallium; and from 0.1 wt.% to 2 wt.% of lanthanum, yttrium, zirconium, or combinations thereof.

[0030] In one or more embodiments, the catalyst may include solid particulates that are capable of fluidization. In some embodiments, the catalyst may exhibit properties known in the industry as “Geldart A” or “Geldart B” properties. Catalyst type may be classified as “Group A” or “Group B” according to D. Geldart, Gas Fluidization Technology, John Wiley & Sons (New York, 1986), 34-37; and D. Geldart, “Types of Gas Fluidization,” Powder Technol. 7 (1973) 285- 292, the disclosures of which are incorporated herein by reference in their entireties.

[0031] Geldart Group A is understood by those skilled in the art as representing an aeratable powder, having a bubble-free range of fluidization; a high bed expansion; a slow and linear deaeration rate; bubble properties that may include a predominance of splitting / recoalescingbubbles, with a maximum bubble size and large wake; high levels of solids mixing and gas backmixing, assuming equal U-Umf (U is the velocity of the carrier gas, and Umf is the minimum fluidization velocity, typically though not necessarily measured in meters per second, m / s, i.e., there is excess gas velocity); axisymmetric slug properties; and no spouting, except in very shallow beds. The properties listed tend to improve as the mean particle size decreases, assuming equal dp; or as the < 45 micrometers (pm) proportion is increased; or as pressure, temperature, viscosity, and density of the gas increase. In general, the particles may exhibit a small mean particle size and / or low particle density (< 1.4 grams per cubic centimeter, g / cm3), fluidize easily, with smooth fluidization at low gas velocities, and may exhibit controlled bubbling with small bubbles at higher gas velocities.

[0032] Geldart Group B is understood by those skilled in the art as representing a “sandlike” powder that starts bubbling at Umf; that exhibits moderate bed expansion; a fast deaeration; no limits on bubble size; moderate levels of solids mixing and gas backmixing, assuming equal U-Umf; both axisymmetric and asymmetric slugs; and spouting in only shallow beds. These properties tend to improve as mean particle size decreases, but particle size distribution and, with some uncertainty, pressure, temperature, viscosity, or density of gas seem to do little to improve them. In general, most of the particles having a particle size (dp) of 40 pm < dp < 500 pm when the density (pp) is 1.4 < pp < 4 g / cm3.

[0033] In one or more embodiments, the catalyst may be prepared via incipient wetness impregnation also known as dry impregnation or capillary impregnation. For example, such a process is described in Marceau et al., Impregnation and Drying, Synthesis of Solid Catalysts 59 (2008), which is incorporated herein by reference in its entirety. For example, the support may be impregnated using metal precursors, then dried at temperatures less than 200 °C, and then calcined at temperatures less than 800 °C to produce the catalyst. For example, suitable metal precursors may include nitrate or amine nitrate metal precursors. Additionally, other suitable metal precursors are contemplated herein, as would be known by those skilled in the art. In some embodiments, the method of making the catalyst may comprise impregnating the support with gallium, platinum, and one or more non-redox-active elemental additives; drying the support; and calcining the support, wherein the catalyst comprises from 0.0005 wt.% to 0.1 wt.% of platinum, from 0.1 wt.% to 10 wt.% of gallium, from 0.1 wt.% to 5 wt.% of one or more non-redox-active elemental additives, and at least 85 wt.% support.

[0034] In one or more embodiments, the catalyst may be prepared by incipient wetness sequential impregnation, where materials are impregnated in a specific order, either before or after drying and calcining. In incipient wetness sequential impregnation, the catalyst is first impregnated with one or more metal precursors, dried at temperatures less than 200 °C, and then calcined at temperatures less than 800 °C. The catalyst then undergoes a least one additional cycle of impregnation, drying, and calcining with an additional metal precursor to create a finished catalyst. In incipient wetness sequential impregnation, the metals added to the catalyst can be added in sequential order in successive impregnation cycles. In one or more embodiments, the support is sequentially impregnated with gallium and platinum and then with the one or more non- redox-active elemental additives. For some embodiments, the method of making a catalyst may comprise impregnating the support with gallium and platinum, drying the support, calcining the support, impregnating the support with one or more non-redox-active elemental additives following the drying and calcining, and drying and calcining the support following the impregnation with one or more non-redox-active elemental additives, wherein the catalyst comprises from 0.0005 wt.% to 0.1 wt.% of platinum, from 0.1 wt.% to 10 wt.% of gallium, from 0.1 wt.% to 5 wt.% of one or more non-redox-active elemental additives, and at least 85 wt.% support. In additional embodiments, the method of making a catalyst may comprise impregnating the support with one or more non-redox-active elemental additives to create a non-redox-active elemental additive impregnated support, drying the non-redox-active elemental additive impregnated support, calcining the non-redox-active elemental additive impregnated support, impregnating the non-redox-active elemental additive impregnated support with gallium and platinum following the drying and calcining, and drying and calcining the non-redox-active elemental additive impregnated support following the impregnation with gallium and platinum, wherein the catalyst comprises from 0.0005 wt.% to 0.1 wt.% of platinum, from 0.1 wt.% to 10 wt.% of gallium, from 0.1 wt.% to 5 wt.% of one or more non-redox-active elemental additives, and at least 85 wt.% support.

[0035] Incipient wetness sequential impregnation allows the support to be impregnated with metals in a sequential order where some metals may be impregnated onto the support before others. The order of impregnation can be therefore be altered as desired. Additionally, other suitable methods for making the catalysts described herein are contemplated, as would be known by those skilled in the art.

[0036] Now referring again to FIG. 1, the hydrocarbon-containing feed may enter feed inlet 434 into the reactor 202, and the olefin-containing effluent may exit the reactor system 102 via pipe 420. According to one or more embodiments, the reactor system 102 may be operated by feeding a hydrocarbon-containing feed (e.g., in a feed stream) and a fluidized catalyst into the upstream reactor section 250. The hydrocarbon-containing feed contacts the catalyst in the upstream reactor section 250, and each flow upwardly into and through the downstream reactor section 230 to produce an olefin-containing effluent. The reactor 202 may operate at relatively high temperatures, such as from 500 °C to 800 °C (e.g., from 500 °C to 550 °C, from 550 °C to 600 °C, from 600 °C to 650 °C, from 650 °C to 700 °C, from 700 °C to 750 °C, from 750 °C to 800 °C, or any combination of one or more of these ranges.

[0037] Now referring to FIG. 1 in detail, the reactor portion 200 may comprise an upstream reactor section 250, a transition section 258, and a downstream reactor section 230, such as a riser. The transition section 258 may connect the upstream reactor section 250 with the downstream reactor section 230. As depicted in FIG. 1, the upstream reactor section 250 may be positioned below the downstream reactor section 230. Such a configuration may be referred to as an upflow configuration in the reactor 202. The upstream reactor section 250 may include a vessel, drum, barrel, vat, or other container suitable for a given chemical reaction. As depicted in FIG. 1, the upstream reactor section 250 may be connected to the downstream reactor section 230 via the transition section 258. The upstream reactor section 250 may generally comprise a greater cross- sectional area than the downstream reactor section 230. The transition section 258 may be tapered from the size of the cross-section of the upstream reactor section 250 to the size of the crosssection of the downstream reactor section 230 such that the transition section 258 projects inwardly from the upstream reactor section 250 to the downstream reactor section 230. For example, the transition section 258 may be a frustum.

[0038] The upstream reactor section 250 may be connected to a transport riser 430, which, in operation may provide reactivated catalyst in a feed stream to the reactor portion 200. The reactivated catalyst and / or reactant chemicals may be mixed with a distributor 260 housed in the upstream reactor section 250. The catalyst entering the upstream reactor section 250 via transport riser 430 may be passed through standpipe 424 to a transport riser 430, thus arriving from the catalyst processing portion 300. In some embodiments, catalyst may come directly from the catalyst separation section 210 via standpipe 422 and into a transport riser 430, where it enters theupstream reactor section 250, where in such embodiments some of the catalyst is not passed through the catalyst processing portion 300. The catalyst can also be fed via standpipe 422 directly to the upstream reactor section 250 (not depicted in FIG. 1). This catalyst may be somewhat deactivated, but may still, in some embodiments, be suitable for reaction in the upstream reactor section 250, particularly when used in combination with reactivated catalyst.

[0039] In one or more embodiments, the catalyst may have a residence time within the reactor portion 200 of less than or equal to 5 minutes. As the term is used herein, “residence time” refers to the average amount of time the catalyst or other specified material spends within the reactor portion 200. As it is an average, the amount of time the catalyst may spend within the reactor portion 200 during any given cycle may not be equal to the average, but over time will average out to be equal to about the residence time. In some embodiments, the catalyst may have a residence time within the reactor portion 200 of less than or equal to 4.5 min., less than or equal to 4 min., less than or equal to 3.5 min., less than or equal to 3 min., less than or equal to 2.5 min., less than or equal to 2 min., less than or equal to 1.5 min., less than or equal to 1 min., less than or equal to 0.5, or less than or equal to 0.1 min. Without being bound by any particular theory, it is believed that catalyst residence time greater than 3 minutes may increase equipment costs without a matching increase in catalyst dehydrogenation performance. However, it is believed that catalyst residence time less than 0.1 minutes may not allow the catalyst to sufficiently catalyze the dehydrogenation reaction.

[0040] Still referring to FIG. 1, in one or more embodiments, based on the shape, size, and other processing conditions (such as temperature and pressure) in the upstream reactor section 250 and the downstream reactor section 230, the upstream reactor section 250 may operate as a fluidized bed, such as in a fast fluidized, turbulent, or bubbling bed upflow reactor, while the downstream reactor section 230 may operate in more of a plug flow manner, such as in a riser reactor. For example, the reactor 202 of FIG. 1 may comprise an upstream reactor section 250 operating as a fast fluidized, turbulent, or bubbling bed reactor and a downstream reactor section 230 operating as a dilute phase riser reactor, with the result that the average catalyst and gas flow moves concurrently upward. As the term is used herein, “average flow” refers to the net flow, i.e., the total upward flow minus the retrograde or reverse flow, as is typical of the behavior of fluidized particles in general. As described herein, a “fast fluidized” reactor may refer to a reactor utilizing a fluidization regime wherein the superficial velocity of the gas phase isgreater than the choking velocity and may be semi-dense in operation. As described herein, a “turbulent” reactor may refer to a fluidization regime where the superficial velocity of less than the choking velocity and is more dense than the fast fluidized regime. As described herein, a “bubbling bed” reactor may refer to a fluidization regime wherein well defined bubbles in a highly dense bed are present in two distinct phases. The “choking velocity” refers to the minimum velocity required to maintain solids in the dilute-phase mode in a vertical conveying line. As described herein, a “dilute phase riser” may refer to a riser reactor operating at above choking velocity.

[0041] According to one or more embodiments, the olefin-containing effluent and the catalyst may be passed out of the downstream reactor section 230 to a separation device 220 in the catalyst separation section 210, where the catalyst is at least partially separated from the olefin- containing effluent, which is transported out of the catalyst separation section 210. According to one or more embodiments, following separation from vapors in the separation device 220, the catalyst may generally move through the stripper 224 to the catalyst outlet port 222 where the catalyst is transferred out of the reactor portion 200 via standpipe 426 and into the catalyst processing portion 300.

[0042] According to one or more embodiments, the separation device 220 may be a cyclonic separation system, which may include two or more stages of cyclonic separation. In embodiments where the separation device 220 comprises more than one cyclonic separation stages, the first separation device into which the fluidized stream enters is referred to a primary cyclonic separation device. The fluidized effluent from the primary cyclonic separation device may enter into a secondary cyclonic separation device for further separation. Primary cyclonic separation devices may include, for example, primary cyclones, and systems commercially available under the names VSS (commercially available from UOP), TD2 (commercially available from Stone and Webster), and RS2 (commercially available from Stone and Webster). Primary cyclones are described, for example, in U.S. Patent Nos. 4,579,716; 5,190,650; and 5,275,641, which are each incorporated by reference in their entirety herein. In some separation systems utilizing primary cyclones as the primary cyclonic separation device, one or more set of additional cyclones, e.g. secondary cyclones and tertiary cyclones, are employed for further separation of the catalyst from the product gas. ft should be understood that any primary cyclonic separation device may be used in embodiments of the present disclosure.

[0043] Still referring to FIG. 1 , the separated catalyst is passed from the catalyst separation section 210 to the combustor 350. In some embodiments, the catalyst may be exposed to another oxy gen-containing gas, such as air, downstream of the reactor 202 and upstream of the combustor 350, such as in a standpipe leading to the combustor 350. Such oxygen exposure may serve to oxidize the catalyst prior to combustion, which may improve combustion catalytic functionality.

[0044] In the combustor 350, the catalyst may be processed by, for example, combustion of coke with oxygen. For example, and without limitation, the catalyst may be de-coked and / or supplemental fuel may be combusted to heat the catalyst. The catalyst is then passed out of the combustor 350 and through the riser 330 to a riser termination separator 378, where the gas and solid components from the riser 330 are at least partially separated. The vapor and remaining solids are transported to a secondary separation device 320 in the catalyst separation section 310 where the remaining catalyst is separated from the gases from the catalyst processing (e.g., gases emitted by combustion of spent catalyst or supplemental fuel, referred to herein as flue gas). The flue gas may pass out of the catalyst processing portion 300 via outlet pipe 432. The separated catalyst is then passed through the oxygen treatment zone 370 within the catalyst separation section 310 to the upstream reactor section 250 via standpipe 424 and transport riser 430, where it is further utilized in a catalytic reaction. Thus, the catalyst, in operation, may cycle between the reactor portion 200 and the catalyst processing portion 300. In general, the processed chemical streams, including the hydrocarbon-containing feed and olefin-containing effluent may be gaseous, and the catalyst may be fluidized particulate solid.

[0045] Referring now to the catalyst processing portion 300, as depicted in FIG. 1, the combustor 350 of the catalyst processing portion 300 may include one or more lower reactor portion inlet ports 352 and may be in fluid communication with the riser 330. Oxygen-containing gas, such as air, may be passed through pipe 428 into the combustor 350. In general, the oxygencontaining gas may comprise at least 10 mol.% oxygen. In some embodiments, the oxy gencontaining gas may comprise at least 12 mol.% oxygen, at least 14 mol.% oxygen, at least 16 mol.% oxygen, at least 18 wt.% oxygen, or even at least 20 wt.% oxygen. The combustor 350 may be in fluid communication with the catalyst separation section 210 via standpipe 426, which may supply spent catalyst from the reactor portion 200 to the catalyst processing portion 300 for regeneration. The combustor 350 and riser 330, collectively referred to as the catalyst combustion reactor 302, may operate with similar or identical fluidization regimes as to what was disclosed with respectto the upstream reactor section 250 and downstream reactor section 230 of the reactor portion 200. That is, the combustor 350 may operate as a fluidized bed, such as in a fast fluidized, turbulent, or bubbling bed upflow reactor, while the riser 330 may operate in more of a plug flow manner, such as in a riser reactor. Geometries as described with respect to the upstream reactor section 250 and downstream reactor section 230 may equally apply to the combustor 350 and riser 330. Additionally, the combustor 350 may also include a fuel inlet 354, which may supply a fuel, such as a hydrocarbon stream, to the combustor 350.

[0046] As described herein, the catalyst may be heated in the catalyst processing portion 300 by combustion of supplemental fuels. Supplemental fuels may combust with oxygen to heat the catalyst, and supplemental fuels such as a supplemental fuel, such as hydrogen, methane, ethane, propane, natural gas, or combinations thereof. Without being bound by any particular theory, when methane is utilized in the supplemental fuel, catalysts as described herein that include one or more non-redox-active elemental additives may better catalyze the combustion of methane to heat the catalyst. Catalysts that do not contain non-redox-active elemental additives, when methane is utilized in the supplemental fuel, may be deficient by not promoting heating of the catalyst to a temperature needed for dehydrogenation.

[0047] As described in one or more embodiments, following separation of flue gas from catalyst in the riser termination separator 378 and secondary separation device 320, treatment of the processed catalyst with an oxygen-containing gas, such as air, is conducted in the oxygen treatment zone 370. In general, the oxy gen-containing gas in the oxygen treatment zone 370 may comprise at least 10 mol.% oxygen, and is substantially void of combustible gaseous hydrocarbons that are present in the combustor 350. In some embodiments, the oxygen treatment zone 370 includes a fluid solids contacting device. The fluid solids contacting device may include baffles or grid structures to facilitate contact of the processed catalyst with the oxygen-containing gas. Examples of fluid solid contacting devices are described in further detail in U.S. Patent Nos. 9,827,543 and 9,815,040. The fluidization regime within the oxygen treatment zone may be bubbling bed type fluidization. The oxygen treatment zone 370 may include an oxy gen-containing gas inlet 372, which may supply an oxygen-containing gas to the oxygen treatment zone 370 for oxygen treatment of the catalyst.

[0048] As is disclosed herein, in one or more embodiments, all or a portion of the catalyst may be exposed to an oxy gen-containing gas in oxygen treatment zone 370. For example, all or a portion of the catalyst may be exposed to an oxygen-containing gas for 2 min. to 60 min., such as from 2 min. to 5 min., from 5 min. to 10 min., from 10 min. to 15 min., from 15 min. to 20 min., from 20 min. to 25 min., from 25 min. to 30 min., from 35 min. to 40 min., from 45 min. to 50 min., from 50 min. to 55 min., from 55 min. to 60 min. or any combination of these ranges. In some embodiments, the catalyst may be exposed to an oxygen containing gas from 4 min. to 18 min., from 6 min. to 17 min., from 8 min. to 16 min., or from 10 min. to 15 min. In some embodiments, the catalyst may be exposed to an oxygen containing gas from 2 min. to 50 min., from 2 min. to 40 min., from 2 min. to 30 min., from 2 min. to 20 min., from 2 min. to 10 min., from 10 min. to 60 min., from 20 min. to 60 min., from 30 min. to 60 min., from 40 min. to 60 min., or from 50 min. to 60 min. Without being bound by any particular theory, it is believed that exposure of the catalyst to an oxygen-containing gas for more than 20 minutes may increase equipment costs without a matching increase in catalyst regeneration efficiency. However, it is believed that oxygen-containing gas exposure for less than 2 minutes may lead to less efficient regeneration of the catalyst, which may reduce the catalyst’s dehydrogenation activity.

[0049] In one or more embodiments, the catalyst may be exposed to the oxygen-containing gas at a temperature of at least 650 °C, such as from 650 °C to 800 °C. Without being bound by any particular theory, it is believed that the regeneration may be most effective at temperatures of at least 650 °C when the catalyst is loaded with one or more non-redox-active elemental additives, according to embodiments described herein.

[0050] In one or more embodiments, the olefinic materials may be present in a “product stream” sometimes called an “olefin-containing effluent” and include olefinic materials, which may include light olefins. Such a stream exits the reactor system of FIG. 1 and may be subsequently processed. As used herein, “light olefins” may refer to one or more of ethylene, propylene, and butene. The term butene includes any isomers of butene, such as a-butylene, cis- P-butylene, trans-P-butylene, and isobutylene. In some embodiments, the olefin-containing effluent includes at least 25 wt.% olefinic materials based on the total weight of the olefin- containing effluent. For example, the olefin-containing effluent may include at least 35 wt.% olefinic materials, at least 45 wt.% olefinic materials, at least 55 wt.% olefinic materials, at least 65 wt.% olefinic materials, or at least 75 wt.% olefinic materials based on the total weight of theolefin-containing effluent. The olefin-containing effluent may further comprise unreacted components of the hydrocarbon-containing effluent, as well as other reaction products that are not considered olefinic materials. The olefinic materials may be separated from unreacted components in subsequent separation steps.EXAMPLES

[0051] The various embodiments of the present disclosure will be further clarified by the following examples. The examples are illustrative in nature and should not be understood to limit the subject matter of the present disclosure.

[0052] Example I - Sample Preparation

[0053] In Example I, samples of catalytically active particles (z. e. , catalysts) were prepared and the effect of non-redox-active elemental additive loading on the catalysts was observed for reactivation times of 2 minutes. The non-redox-active elemental additives used were lanthanum, yttrium, and zirconium.

[0054] Comparative Example X was a micro-spheroidal alumina support. The support was prepared by spray drying a mixture of hydrated alumina and EUDOX® Silica and then heating the resulting spray dried particles at a temperature of above 1000 °C, sufficient to achieve particles with a particle size ranging from 5 pm to 300 pm, a pore volume of 0.20 ± 0.10 mL / g, a surface area of 70 ± 20 m2 / g, and a silica content of 2.5 ± 2.5 wt.%.

[0055] Comparative Example A, Al, A2, and B were prepared by conventional incipient wetness impregnation. A desired amount of platinum, gallium, and potassium was loaded onto the support (z. e. , Comparative Example X) using nitrate or amine nitrate metal precursors, including tetramine platinum nitrate, gallium nitrate, and potassium nitrate. The samples were then dried at a temperature of less than 200 °C for less than 4 hours. The samples were then calcined at a temperature of less than 800 °C for less than 4 hours.

[0056] Comparative Examples C, D, E, F, and G were prepared similarly to Comparative Example A by co-impregnation of iron (Comparative Examples C and D), manganese (Comparative Example E), and cerium (Comparative Examples F and G) with platinum, gallium, and potassium using their respective nitrate precursors.

[0057] Examples 1-11 were prepared similarly to Comparative Example A by coimpregnation of lanthanum with platinum, gallium, and potassium using their respective nitrate precursors.

[0058] Examples 12 and 13 were prepared by impregnating Comparative Example A with a lanthanum nitrate precursor, followed by drying at a temperature of less than 200 °C for less than 4 hours, and then calcining at a temperature of less than 800 °C for less than 4 hours.

[0059] Examples 14 and 15 were prepared similarly to Comparative Example A by coimpregnation of yttrium with platinum, gallium, and potassium using their respective nitrate precursors.

[0060] Example 16 was prepared similarly to Comparative Example A by coimpregnation of zirconium with platinum, gallium, and potassium using their respective nitrate precursors.

[0061] Example II: Catalyst Testing Method

[0062] The samples were prepared by mixing 0.5 grams (g) of the catalyst with 1.0 g of inert silicon carbide and the samples were loaded into a quartz reactor. The samples were conditioned by first undergoing 10 break-in cycles, which were performed by two steps: a reaction step where a dehydrogenation process was performed at 625 °C with a weight hourly space velocity (WHSV) of propane of 10 hr'1and a feed composition of 90 mol.% propane / 10 mol.% nitrogen for 60 seconds; and a reactivation step where the catalyst was heated at 730 °C under 100% dry air with a flow rate of 50 standard cubic centimeters per minute (seem) for 5 minutes.

[0063] After the samples had run through 10 break-in cycles, they were tested in the dehydrogenation and regeneration testing cycles. The dehydrogenation and regeneration testing cycles were run by performing three steps: reaction / dehydrogenation, combustion, and reactivation. The reaction / dehydrogenation step was performed using the same conditions as the reaction step of the break in cycles, and dehydrogenation performance data was collected at 30 seconds time on stream. The combustion step was performed at 730 °C under 2.5 mol.% methane with balance of air with a total flow of 50 seem and a WHSV of methane of 0.1 hr'1for 3 minutes. Combustion data was collected at 60 seconds time on stream. The reactivation step was performed by heating the samples at 730 °C under 100% dry air with a flow rate of 50 seem for 2 minutes. The dehydrogenation and combustion performances of the samples were reported in Tables 1-5.Table 1: Propane dehydrogenation and methane combustion performance of La-doped catalysts from co-impregnation at cycle 10

[0064] Tables 1-3 show performance of catalyst samples with lanthanum as a non-redox- active elemental additive. As shown in Table 1, the presence of lanthanum in otherwise identical samples increases the methane conversion of the catalyst. For example, Comparative Example A has a methane conversion of 88.7% and Examples 1-4 have methane conversions ranging from 91.6% to 97.0%. Thus, the presence of lanthanum improves the fuel combustion of the catalyst.

[0065] Additionally, the presence of platinum aids in improving propane conversion of the catalyst. For example, Comparative Example Al has no platinum but is otherwise identical to Example 5. The propane conversion of Comparative Example Al is 11.9% which is much less than the propane conversion of Example 5 at 33%. Likewise, the presence of gallium aids in improving propane conversion of the catalyst. For example, Comparative Example A2 has nogallium but is otherwise identical to Example 6. The propane conversion of Comparative Example A2 is 8.8% which is much less than the propane conversion of Example 6 at 40.1%.Table 2: Propane dehydrogenation and methane combustion performance of alkali-free La- doped catalysts from co-impregnation at cycle 10

[0066] As shown in Table 2, the presence of lanthanum in otherwise identical samples increases the methane conversion of the catalyst. For example, Comparative Example B has no lanthanum and a methane conversion of 79.8%. Examples 8-10 have lanthanum present in amounts of 0.3 wt.%, 0.6 wt.%, and 1.279 wt.%, based on the total weight of the catalyst. Each of Examples 8-10 have improved methane conversions than Comparative Example B, ranging from 85.1% to 94.5%. The methane conversion generally increases as the amount of lanthanum increases.

[0067] Further, the propane conversion of the catalysts also were improved. ComparativeExample B has a propane conversion of 42.9% and Examples 8-10 have propane conversions ranging from 43.9% to 45.1%. Thus, the propane conversion of the catalyst were generally improved along with an improvement in fuel combustion.Table 3: Propane dehydrogenation and methane combustion performance of La-doped catalysts from post impregnation at cycle 10

[0068] As shown in Table 3, and as stated herein, the presence of lanthanum improves methane conversion. Comparative Example A has a methane conversion of 88.7% and Examples 11 and 12 have methane conversions of 91.5% and 97.4%, respectively.Table 4: Propane dehydrogenation and methane combustion performance of Y-doped catalysts from co-impregnation at cycle 10.

[0069] Table 4 shows the performance of catalyst samples with yttrium as a non-redox- active elemental additive. As shown, he presence of yttrium improves methane conversion. For example, Comparative Example A has a methane conversion of 88.7% and Examples 14 and 15 have methane conversions of 91.7% and 94.3%, respectively. Thus, the presence of yttrium improves fuel combustion while maintaining the dehydrogenation performance of the catalyst.Table 5: Propane dehydrogenation and methane combustion performance of Zr-doped catalysts from co-impregnation at cycle 10.

[0070] Table 5 shows the performance of catalyst samples with zirconium as a non-redox- active elemental additive. As shown, the presence of zirconium improves methane conversion. For example, Comparative Example A has a methane conversion of 88.7% and Example 16 has a methane conversion of 95.9%. Thus, the presence of zirconium improves fuel combustion while maintaining the dehydrogenation performance of the catalyst.

[0071] Example HI - Redox Capacity Measurement

[0072] In Example III, the redox capacity of selected catalyst samples was measured by thermogravimetric analysis on a TA Discovery 5500 thermogravimetric analyzer. Typically, 70 mg to 80 mg of a catalyst sample was loaded in a ceramic crucible and supported on a ceramic sample pan. Under a constant gas flow of 30 mE / min, the sample was first pretreated at 800 °C in air for 30 minutes, then cooled to 730 °C where it was subjected to three isothermal redox cycles. Each cycle had four steps: nitrogen purge for 10 minutes; reduction in 1 mol.% hydrogen / nitrogen for 60 minutes; nitrogen purge for 10 minutes; and oxidation in air for 30 minutes. The redox capacity of the catalyst was evaluated based on the weight change from the end of the first step (z. e. , the first nitrogen purge) to the end of the second step (z. e. , the reduction step) in each redox cycle. The redox capacity of the catalyst samples are shown in Table 6, with “M” indicating the elemental additive used in the sample.Table 6. Redox active oxygen capacity of the catalyst measured by thermogravimetric analysis.

[0073] As shown in Table 6, the redox capacity of samples with lanthanum (z. e. , Examples 3 and 4) is similar or even less than Comparative Example A which has no elemental additive. For example, Comparative Example A has a redox capacity of 0.009 ± 0.002 wt.% and Example 3 has a redox capacity of 0.009 ± 0.001 wt.%. As described herein, the redox capacity of the elemental additives is generally desired to be low. A greater redox capacity generally means that the catalyst will react with reducing agents (e.g., hydrogen) and oxidizing agents (e.g., oxygen and air) which can produce COXspecies. As stated, the presence of COXspecies may cause loss of selectivity of the desired olefinic material products or inhibition of precious metal catalytic components

[0074] Example IV - CO Concentration Analysis

[0075] The extent of CO formation was evaluated in a circulating fluidized bed unit at a WHSV of propane of 10-20 hr'1at 620 °C at a catalyst-to-oil ratio of 25:60. The results are shown in Table 7 above, with “M” indicating the elemental additive used in the sample.Table 7: CO concentration in the product gas from propane dehydrogenation in circulating fluidized bed

[0076] As shown in Table 7, the presence of redox-active elemental additives (z.e., iron and cerium) in the catalyst samples have a much greater CO presence in the product gas than samples without redox-active elemental additives. For example, Example 11 with lanthanum as a non-redox-active elemental additive resulted in a CO concentration of 383 ppmv. Comparative Examples D with iron and Comparative Example G with cerium resulted in CO concentrations of 1060 ppmv and 3168 ppmv, respectively, which is much higher than that of Example 11. As described herein, the formation of COXspecies in the reactor is generally undesirable because COXmay poison the platinum in the catalyst resulting in a decrease in catalytic activity. Further, Comparative Example A, with no elemental additive, resulted in a CO concentration of 321 ppmv, which is around 60 ppmv less than Example 11. However, as stated with respect to Table 3, Example 11 has improved methane conversion and propane conversion over Comparative Example A. Thus, utilizing catalysts with non-redox-active elemental additives, such as lanthanum, does not produce as high amounts of COXspecies than catalysts with a redox-active elemental additive, such as iron and cerium.

[0077] The present disclosure includes numerous aspects, including aspects 1-15 described herein.

[0078] Aspect 1. A method for making olefinic materials, the method comprising: contacting a hydrocarbon-containing feed with a catalyst in a reactor to form an olefin-containing effluent, wherein the catalyst has a residence time within the reactor of less than or equal to 3 minutes; passing the catalyst to a combustor and heating the catalyst by combusting a supplemental fuel; passing the catalyst from the combustor to an oxygen treatment zone andexposing the catalyst to an oxygen-containing gas for from 2 minutes to 20 minutes in the oxygen treatment zone, wherein the oxygen-containing gas comprise at least 10 mol.% oxygen; and passing the catalyst from the oxygen treatment zone to the reactor, such that all or a portion of the catalyst continuously cycles between the reactor, the combustor, and the oxygen treatment zone; wherein the catalyst comprises: from 0.0005 wt.% to 0.1 wt% of platinum, palladium, rhodium, iridium, ruthenium, osmium, or combinations thereof; from 0.1 wt.% to 10 wt.% of gallium, indium, thallium, or combinations thereof; from 0.1 wt.% to 5 wt.% of one or more non-redox- active elemental additives; and at least 85 wt.% of support.

[0079] Aspect 2. The method of aspect 1, wherein the one or more non-redox-active elemental additives are chosen from lanthanum, yttrium, zirconium, scandium, titanium, niobium, and tantalum.

[0080] Aspect s. The method of aspect 1, wherein the one or more non-redox-active elemental additives are chosen from lanthanum, yttrium, and zirconium.

[0081] Aspect 4. The method of aspect 1, wherein the one or more non-redox-active elemental additives comprises lanthanum.

[0082] Aspect s. The method of aspect 1, wherein the one or more non-redox-active elemental additives comprises yttrium.

[0083] Aspect 6. The method of aspect 1, wherein the one or more non-redox-active elemental additives comprises zirconium.

[0084] Aspect 7. The method of any of the previous aspects, wherein the catalyst does not include cerium, iron, manganese, copper, chromium, cobalt, nickel, vanadium, molybdenum, tungsten, and praseodymium in amounts greater than 0.001 wt.%.

[0085] Aspect 8. The method of any of the previous aspects, wherein the catalyst comprises from 0.1 wt.% to 1.5 wt.% of the one or more non-redox-active elemental additives.

[0086] Aspect 9. The method of any of the previous aspects, wherein the catalyst further comprises from 0.01 wt.% to 5 wt.% of one or more alkali or alkaline earth metals.

[0087] Aspect 10. The method of any of the previous aspects, wherein the contacting the hydrocarbon-containing feed with the catalyst occurs at a temperature of from 500 °C to 700 °C.

[0088] Aspect 11. The method of any of the previous aspects, wherein the supplemental fuel comprises methane, ethane, propane, hydrogen, or combinations thereof.

[0089] Aspect 12. The method of any of the previous aspects, wherein the supplemental fuel comprises methane in an amount of at least 1 mol.%.

[0090] Aspect 13. The method of any of the previous aspects, wherein the support comprises alumina, silica-containing alumina, titanium-containing alumina, or combinations thereof.

[0091] Aspect 14. The method of any of the previous aspects, wherein the support does not include zirconium.

[0092] Aspect 15. The method of aspect 1, wherein: the catalyst comprises: from0.0005 wt.% to 0.1 wt.% of platinum; from 0.1 wt.% to 10 wt.% of gallium; and from 0.1 wt.% to 5 wt.% of lanthanum, yttrium, zirconium, or combinations thereof; the hydrocarbon-containing feed comprises propane; and the olefin-containing effluent comprise propylene.

[0093] It will be apparent to those skilled in the art that various modifications and variations can be made to the presently disclosed technology without departing from the spirit and scope of the technology. Since modifications combinations, sub-combinations and variations of the disclosed embodiments incorporating the spirit and substance of the presently disclosed technology may occur to persons skilled in the art, the technology should be construed to include everything within the scope of the appended claims and their equivalents. Additionally, although some aspects of the present disclosure may be identified herein as favored or particularly advantageous, it is contemplated that the present disclosure is not limited to these aspects.

[0094] It is noted that the various details described in this disclosure should not be taken to imply that these details relate to elements that are essential components of the various embodiments described in this disclosure, even in cases where a particular element is illustrated in each of the drawings that accompany the present description. Unless specifically identified assuch, no feature disclosed and described herein should be construed as “essential”. Contemplated embodiments of the present technology include those that include some or all of the features of the appended claims.

[0095] For the purposes of describing and defining the present disclosure it is noted that the term “about” are utilized in this disclosure to represent the inherent degree of uncertainty that may be attributed to any quantitative comparison, value, measurement, or other representation. The term “about” are also utilized in this disclosure to represent the degree by which a quantitative representation may vary from a stated reference without resulting in a change in the basic function of the subject matter at issue.

[0096] In relevant cases, where a composition is described as “comprising” one or more elements, embodiments of that composition “consisting of’ or “consisting essentially of’ those one or more elements is contemplated herein.

[0097] It should be appreciated that compositional ranges of a chemical constituent in a stream or in a reactor should be appreciated as containing, in some embodiments, a mixture of isomers of that constituent. For example, a compositional range specifying butene may include a mixture of various isomers of butene. It should be appreciated that the examples supply compositional ranges for various streams, and that the total amount of isomers of a particular chemical composition can constitute a range.

[0098] It is noted that one or more of the following claims and the detailed description utilize the terms “where” or “wherein” as a transitional phrase. For the purposes of defining the present technology, it is noted that this term is introduced in the claims as an open-ended transitional phrase that is used to introduce a recitation of a series of characteristics of the structure and should be interpreted in like manner as the more commonly used open-ended preamble term “comprising.”

[0099] It should be understood that any two quantitative values assigned to a property may constitute a range of that property, and all combinations of ranges formed from all stated quantitative values of a given property are contemplated in this disclosure. Where multiple ranges for a quantitative value are provided, these ranges may be combined to form a broader range, which is contemplated in the embodiments described herein.

Claims

CLAIMS1. A method for making olefinic materials, the method comprising: contacting a hydrocarbon-containing feed with a catalyst in a reactor to form an olefin- containing effluent, wherein the catalyst has a residence time within the reactor of less than or equal to 3 minutes; passing the catalyst to a combustor and heating the catalyst by combusting a supplemental fuel; passing the catalyst from the combustor to an oxygen treatment zone and exposing the catalyst to an oxygen-containing gas for from 2 minutes to 20 minutes in the oxygen treatment zone, wherein the oxygen-containing gas comprise at least 10 mol.% oxygen; and passing the catalyst from the oxygen treatment zone to the reactor, such that all or a portion of the catalyst continuously cycles between the reactor, the combustor, and the oxygen treatment zone; wherein the catalyst comprises: from 0.0005 wt.% to 0.1 wt% of platinum, palladium, rhodium, iridium, ruthenium, osmium, or combinations thereof; from 0.1 wt.% to 10 wt.% of gallium, indium, thallium, or combinations thereof; from 0.1 wt.% to 5 wt.% of one or more non-redox-active elemental additives; and at least 85 wt.% of support.

2. The method of claim 1, wherein the one or more non-redox-active elemental additives are chosen from lanthanum, yttrium, zirconium, scandium, titanium, niobium, and tantalum.

3. The method of claim 1, wherein the one or more non-redox-active elemental additives are chosen from lanthanum, yttrium, and zirconium.

4. The method of claim 1, wherein the one or more non-redox-active elemental additives comprises lanthanum.

5. The method of claim 1, wherein the one or more non-redox-active elemental additives comprises yttrium.

6. The method of claim 1, wherein the one or more non-redox-active elemental additives comprises zirconium.

7. The method of any of the previous claims, wherein the catalyst does not include cerium, iron, manganese, copper, chromium, cobalt, nickel, vanadium, molybdenum, tungsten, and praseodymium in amounts greater than 0.001 wt.%.

8. The method of any of the previous claims, wherein the catalyst comprises from 0.1 wt.% to 1.5 wt.% of the one or more non-redox-active elemental additives.

9. The method of any of the previous claims, wherein the catalyst further comprises from 0.01 wt.% to 5 wt.% of one or more alkali or alkaline earth metals.

10. The method of any of the previous claims, wherein the contacting the hydrocarbon- containing feed with the catalyst occurs at a temperature of from 500 °C to 700 °C.

11. The method of any of the previous claims, wherein the supplemental fuel comprises methane, ethane, propane, hydrogen, or combinations thereof.

12. The method of any of the previous claims, wherein the supplemental fuel comprises methane in an amount of at least 1 mol.%.

13. The method of any of the previous claims, wherein the support comprises alumina, silica-containing alumina, titanium-containing alumina, or combinations thereof.

14. The method of any of the previous claims, wherein the support does not include zirconium.

15. The method of claim 1, wherein: the catalyst comprises: from 0.0005 wt.% to 0.1 wt.% of platinum;from 0.1 wt.% to 10 wt.% of gallium; and from 0.1 wt.% to 5 wt.% of lanthanum, yttrium, zirconium, or combinations thereof; the hydrocarbon-containing feed comprises propane; and the olefin-containing effluent comprise propylene.

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