Process for regenerating catalysts and upgrading alkanes and / or alkylaromatic hydrocarbons - Patent Application 2007023333

Abstract

A process for regenerating an at least partially deactivated catalyst that may include a Group 10 element, an inorganic support, and contaminants. The Group 10 element may have a concentration of 0.06 wt% to 6 wt% based on the weight of the inorganic support. The process may include (I) heating the deactivated catalyst with a heated gas mixture that includes H2O at a concentration of >5 mole% based on its total moles to produce a procatalyst. The process may also include (II) providing an oxidizing gas that includes ≦5 mole% H2O based on its total moles, and (III) contacting the procatalyst with the oxidizing gas at an oxidation temperature for a duration of at least 30 seconds to produce an oxidized procatalyst. The process may also include (IV) obtaining a regenerated catalyst from the oxidized procatalyst.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to and the benefit of U.S. Provisional Application No. 63 / 231,946, filed August 11, 2021, the disclosure of which is incorporated herein by reference in its entirety.

[0002] Field The present disclosure relates to a process for regenerating catalysts and upgrading alkanes and / or alkylaromatic hydrocarbons. [Background technology]

[0003] background Catalytic dehydrogenation, dehydroaromatization, and dehydrocyclization of alkanes and / or alkylaromatic hydrocarbons are endothermic, equilibrium-limited, industrially important chemical conversion processes. Alkanes, e.g., C-C 12 Dehydrogenation of alkanes and / or alkyl aromatic hydrocarbons, such as ethylbenzene, can be carried out over a variety of different supported catalyst systems, such as Pt-, Cr-, Ga-, V-, Zr-, In-, W-, Mo-, Zn-, and Fe-based systems. Among the existing propane dehydrogenation processes, certain processes use an alumina-supported chromia catalyst, which provides one of the highest propylene yields of about 50% (55% propane conversion with 90% propylene selectivity), which is obtained at temperatures of about 560° C. to 650° C. and low pressures of 20 kPa absolute to 50 kPa absolute. It is desirable to increase the propylene yield to increase the efficiency of the dehydrogenation process without having to operate at such low pressures. Increasing the temperature of the dehydrogenation process is one way to increase the conversion of the process according to the thermodynamics of the process. For example, at 670° C. and 100 kPa absolute pressure, in the absence of any inert / diluent, the equilibrium propylene yield was estimated by simulation to be about 74%. However, at such high temperatures, the catalyst deactivates very quickly and / or the propylene selectivity becomes uneconomically low. The rapid catalyst deactivation is believed to be due to coke deposition and / or agglomeration of the active phase on the catalyst. Although the coke can be removed by combustion with oxygen-containing gas, the agglomeration of the active phase is believed to worsen during the combustion process, which rapidly reduces the activity and stability of the catalyst. Thus, there is a need for an improved process for regenerating at least partially deactivated catalysts and an improved process for dehydrogenating, dehydroaromatizing, and / or dehydrocyclizing alkanes and / or alkylaromatic hydrocarbons. The present disclosure meets this and other needs. Summary of the Invention

[0004] summary A process for regenerating at least partially deactivated catalysts and upgrading hydrocarbons is provided. In some embodiments, the process can be used to regenerate at least partially deactivated catalysts that may include a group 10 element, an inorganic support, and contaminants. The group 10 element may have a concentration in the range of 0.06 wt% to 6 wt% based on the weight of the inorganic support. The process may include (I) heating the at least partially deactivated catalyst with a heated gas mixture that may include H2O at a concentration greater than 5 mole % based on the total moles of the heated gas mixture to produce a procatalyst. The process may also include (II) providing an oxidizing gas that may include 5 mole % or less H2O based on the total moles of the heated gas mixture. The process may also include (III) contacting the procatalyst with the oxidizing gas at an oxidation temperature in the range of 620°C to 1,000°C for a duration of at least 30 seconds, preferably at least 1 minute, preferably at least 5 minutes to produce an oxidized procatalyst. The process may also include the step of (IV) obtaining a regenerated catalyst from the oxidized precatalyst.

[0005] In another embodiment, a hydrocarbon upgrading process may include the steps of: (I) contacting a hydrocarbon-containing feed with a catalyst, which may include a Group 10 element and an inorganic support, to effect one or more of dehydrogenation, dehydroaromatization, and dehydrocyclization of at least a portion of the hydrocarbon-containing feed to produce an at least partially deactivated catalyst, which may include a Group 10 element, an inorganic support, and contaminants, and an effluent, which may include one or more upgraded hydrocarbons and molecular hydrogen. The hydrocarbon-containing feed may include one or more C2-C 16 Linear or branched alkanes, or one or more C4-C 16 Cyclic alkanes, one or more of C8-C 16 The catalyst may include an alkyl aromatic hydrocarbon, an alkyl aromatic hydrocarbon, or a mixture thereof. The Group 10 element may have a concentration in the range of 0.06 wt% to 6 wt%, based on the weight of the inorganic support. The hydrocarbon-containing feed and the catalyst may be contacted at a temperature in the range of 300° C. to 900° C. The one or more upgraded hydrocarbons may include at least one of dehydrogenated hydrocarbons, dehydroaromatized hydrocarbons, and dehydrocyclized hydrocarbons. The process may also include (II) heating the at least partially deactivated catalyst with a heated gas mixture, the heated gas mixture may include H2O at a concentration of greater than 5 mole % based on the total moles of the heated gas mixture to produce a procatalyst. The process may also include (III) providing an oxidizing gas, the oxidizing gas may include 5 mole % or less H2O based on the total moles of the heated gas mixture. The process may also include (IV) contacting the procatalyst with the oxidizing gas at an oxidation temperature in the range of 620° C. to 1,000° C. for a duration of at least 30 seconds to produce an oxidized procatalyst. The process may also include (V) obtaining a regenerated catalyst from the oxidized precatalyst. The process may also include (VI) contacting an additional amount of a hydrocarbon-containing feed with at least a portion of the regenerated catalyst to produce additional at least partially deactivated catalyst and an additional effluent. [Brief description of the drawings]

[0006] [Figure 1]1 shows that the performance of the catalyst used in Example 5 for PDH was stable after 75+ cycles. [Diagram 2] The performance of Comparative Catalyst 1 shows that it continued to deactivate even though the regeneration temperature (620° C.) was much lower than the other examples. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] Detailed Description Below, various specific embodiments, versions and examples of the present invention are described, including preferred embodiments and definitions adopted herein for the purpose of understanding the claimed invention. The detailed description below provides certain preferred embodiments, but those skilled in the art will recognize that these embodiments are merely exemplary and that the present invention may be practiced in other ways. For purposes of determining infringement, the scope of the present invention refers to any one or more of the appended claims, including their equivalents and elements or limitations that are equivalent to those recited. Any reference to the "invention" may refer to one or more, but not necessarily all, of the invention defined by the claims. In this disclosure, a process is described as including at least one "step." Each step should be understood to be an act or operation that may be performed once in the process or multiple times in a continuous or discontinuous manner. Unless otherwise specified or the context clearly indicates otherwise, the steps of the process may be performed consecutively in the order as described, with or without overlap with one or more other steps, or, in some cases, in any other order. Furthermore, one or more or even all steps may be performed simultaneously on the same or different batches of material. For example, in a continuous process, a first step of the process may be performed on raw material just fed at the beginning of the process while a second step may be performed simultaneously on intermediate material resulting from processing of raw material fed to the process at an earlier point in the first step. Preferably, the steps are performed in the order as described.

[0008] Unless otherwise indicated, all numbers indicating quantities in this disclosure should be understood to be modified in all cases by the term "about". It should also be understood that the exact numerical values ​​used in the specification and claims constitute specific embodiments. Efforts have been made to ensure the accuracy of the data in the examples. However, it should be understood that any measured data inherently contains a certain level of error due to the limitations of the techniques and / or instruments utilized to make the measurements. Certain embodiments and features are described herein with a series of upper numerical limits and a series of lower numerical limits, and unless otherwise indicated, it should be understood that ranges including any combination of two values ​​are contemplated, for example, any combination of a lower limit with any upper limit, any combination of two lower limits, and / or any combination of two upper limits. As used herein, the indefinite article "a" or "an" means "at least one" unless otherwise specified or the context clearly dictates otherwise. Thus, embodiments using "a reactor" or "a conversion zone" include embodiments using one, two, or more than two reactors or conversion zones, unless otherwise specified or the context clearly dictates that only one reactor or conversion zone is used.

[0009] The term "hydrocarbon" means (i) any compound consisting of hydrogen atoms and carbon atoms or (ii) any mixture of two or more of such compounds of (i). The term "Cn hydrocarbon" (where n is a positive integer) means (i) any hydrocarbon compound containing a total of n carbon atoms in its molecule or (ii) any mixture of two or more of such hydrocarbon compounds of (i). Thus, C2 hydrocarbons can be ethane, ethylene, acetylene, or any mixture of at least two of these compounds in any ratio. "Cm~Cn hydrocarbon" or "Cm-Cn hydrocarbon" (where m and n are positive integers and m < n) means any one of Cm, Cm+1, Cm+2,..., Cn-1, Cn hydrocarbons or any mixture of two or more of these. Thus, "C2~C3 hydrocarbon" or "C2-C3 hydrocarbon" can be any one of ethane, ethylene, acetylene, propane, propene, propyne, propadiene, cyclopropane, and any mixture of two or more of these components in any ratio. "Saturated C2-C3 hydrocarbon" can be ethane, propane, cyclopropane, or any mixture of two or more of these in any ratio. "Cn+ hydrocarbon" means (i) any hydrocarbon compound containing at least n carbon atoms in total in its molecule or (ii) any mixture of two or more of such hydrocarbon compounds of (i). "Cn- hydrocarbon" means (i) any hydrocarbon compound containing at most n carbon atoms in total in its molecule or (ii) any mixture of two or more of such hydrocarbon compounds of (i). "Cm hydrocarbon stream" means a hydrocarbon stream consisting essentially of Cm hydrocarbons. "Cm-Cn hydrocarbon stream" means a hydrocarbon stream consisting essentially of Cm-Cn hydrocarbons.

[0010] For the purposes of this disclosure, the nomenclature of the elements is that of Hawley's Condensed Chemical Dictionary, 16 thThe periodic table is based on the version of the periodic table (under the new notation) provided in Ed., John Wiley & Sons, Inc., (2016), Appendix V. For example, Group 2 elements include Mg, Group 4 elements include Zr, Group 8 elements include Fe, Group 9 elements include Co, Group 10 elements include Ni, and Group 13 elements include Al. As used herein, the term "metalloid" refers to the following elements: B, Si, Ge, As, Sb, Te, and At. In this disclosure, when a given element is indicated as present, it may be present in the elemental state or as any compound thereof, unless otherwise stated or the context clearly indicates otherwise. The term "alkane" means a saturated hydrocarbon. The term "cyclic alkane" means a saturated hydrocarbon that contains a cyclic carbon ring in its molecular structure. Alkanes can be straight-chained, branched, or cyclic. The term "aromatic" is to be understood in accordance with its art-recognized scope and includes alkyl substituted and unsubstituted mononuclear and polynuclear compounds.

[0011] When used in expressions such as "X-rich" or "rich in X" with respect to an exit stream obtained from an apparatus, e.g., a conversion zone, the term "rich" means that the stream contains material X at a higher concentration than in the feed material supplied to the same apparatus from which the stream is drawn. When used in expressions such as "X-lean" or "lean in X" with respect to an exit stream obtained from an apparatus, e.g., a conversion zone, the term "lean" means that the stream contains material X at a lower concentration than in the feed material supplied to the same apparatus from which the stream is drawn. The term "selectivity" refers to the production rate (based on moles of carbon) of a particular compound in a catalytic reaction. For example, the phrase "alkane hydrocarbon conversion reaction has 100% selectivity to olefinic hydrocarbons" means that 100% (based on moles of carbon) of the alkane hydrocarbons converted in the reaction are converted to olefinic hydrocarbons. When used with respect to a particular reactant, the term "conversion" refers to the amount of reactant consumed in the reaction. For example, when the particular reactant is propane, 100% conversion means that 100% of the propane is consumed in the reaction. In another example, when the particular reactant is propane, if 1 mole of propane is converted to 1 mole of methane and 1 mole of ethylene, the selectivity to methane is 33.3% and the selectivity to ethylene is 66.7%. The yield (based on moles of carbon) is the conversion rate times the selectivity.

[0012] Hydrocarbon Upgrading and Catalyst Regeneration Processes The hydrocarbon-containing feed may include, but is not limited to, one or more alkane hydrocarbons, such as C2-C 16 Linear or branched alkanes and / or C4-C 16 Cyclic alkanes, and / or one or more alkyl aromatic hydrocarbons, e.g., C8-C 16 In some embodiments, the hydrocarbon-containing feed may be or may include alkyl aromatic hydrocarbons. In some embodiments, the hydrocarbon-containing feed may optionally include any C-C alkyl aromatic hydrocarbons in the hydrocarbon-containing feed. 16 Alkanes and any C8-C 16 The hydrocarbon-containing feed may contain 0.1 vol.% to 50 vol.% water vapor based on the total volume of the alkylaromatic hydrocarbon. In another embodiment, the hydrocarbon-containing feed may contain any C2-C 16 Alkanes and any C8-C 16The feed may contain <0.1 vol.% water vapor based on the total volume of the alkylaromatic hydrocarbons, or may contain no water vapor. The feed may be contacted with a catalyst comprising a Group 10 element, e.g., Pt, and an inorganic support to effect one or more of dehydrogenation, dehydroaromatization, and dehydrocyclization of at least a portion of the feed to produce an at least partially deactivated catalyst comprising the Group 10 element, the inorganic support, and contaminants, e.g., coke, and an effluent that may include one or more upgraded hydrocarbons and molecular hydrogen.

[0013] The one or more upgraded hydrocarbons may be or include, but are not limited to, one or more dehydrogenated hydrocarbons, one or more dehydrogenated aromatized hydrocarbons, one or more dehydrogenated cyclized hydrocarbons, or mixtures thereof. The hydrocarbon-containing feed and catalyst may be contacted at a temperature ranging from 300° C. to 900° C. In some embodiments, the hydrocarbon-containing feed and catalyst may be contacted for a time period of ≦5 hours, ≦4 hours, or ≦3 hours, ≦1 hour, ≦0.5 hours, ≦0.1 hours, ≦3 minutes, ≦1 minute, ≦30 seconds, or ≦0.1 seconds. In some embodiments, the hydrocarbon-containing feed and catalyst may be contacted under a hydrocarbon partial pressure of at least 20 kPa absolute, where the hydrocarbon partial pressure is the total amount of any C2-C4 hydrocarbons in the hydrocarbon-containing feed. 16 Alkanes and any C8-C 16 is the total partial pressure of the alkylaromatic hydrocarbons. The catalyst may contain 0.06 wt% to 6 wt% of a Group 10 element, such as Pt, based on the weight of the inorganic support.

[0014] A precursor catalyst can be obtained from the at least partially deactivated catalyst. In some embodiments, the at least partially deactivated catalyst can be provided as a precursor catalyst as is. In other embodiments, the precursor catalyst can be provided by heating the at least partially deactivated catalyst with a heated gas mixture, the heated gas mixture including HO at a concentration of more than 5 mole % based on the total moles of the heated gas mixture to produce a precursor catalyst. In some embodiments, the heated gas mixture can be generated by combusting at least a portion of the contaminant disposed on the at least partially deactivated catalyst, e.g., coke and / or residual hydrocarbon-containing feed, with an oxidizing gas. In some embodiments, the heated gas mixture can be generated by combusting a fuel with an oxidizing gas. In other embodiments, the heated gas mixture can be generated by combusting at least a portion of the contaminant disposed on the at least partially deactivated catalyst and a fuel with an oxidizing gas. In other embodiments, the heated gas mixture can include HO at a concentration of more than 5 mole % HO can be provided with the HO, e.g., heated air having HO, e.g., more than 5 mole % HO. The fuel may be or include, but is not limited to, at least one of H2, CO, and hydrocarbons. The oxidizing gas may be or include, but is not limited to, O2, O3, CO, or any mixture thereof. In some embodiments, the heated gas mixture may contact the partially deactivated catalyst for a duration of <5 minutes, <2 minutes, <1 minute, <30 seconds, <10 seconds, <5 seconds, <1 second, <0.5 seconds, <0.1 seconds.

[0015] An oxidizing gas may be provided. The oxidizing gas may contain, based on its total moles, 5 mol% or less of H2O, 4.5 mol% or less of H2O, 4 mol% or less of H2O, 3.5 mol% or less of H2O, 3 mol% or less of H2O, 2.5 mol% or less of H2O, 2 mol% or less of H2O, 1.7 mol% or less of H2O, 1.5 mol% or less of H2O, 1.3 mol% or less of H2O, 1 mol% or less of H2O, 0.7 mol% or less of H2O, 0.5 mol% or less of H2O, 0.3 mol% or less of H2O, or 0.1 mol% or less of H2O. The precursor catalyst may be contacted with the oxidizing gas whether the at least partially deactivated catalyst is provided as a precursor catalyst as is or the at least partially deactivated catalyst is heated using a heated gas mixture. Surprisingly and unexpectedly, it has been found that whether the at least partially deactivated catalyst is provided as a precatalyst as such or the at least partially deactivated catalyst is heated with a heated gas mixture to produce a precatalyst, contacting the precatalyst with an oxidizing gas containing 5 mole % or less of HO can significantly improve the activity and / or selectivity of the regenerated catalyst. Without wishing to be bound by theory, it is believed that the HO present in the oxidizing gas can significantly reduce the effectiveness of Pt redispersion and therefore the effectiveness of the regenerated catalyst.

[0016] The precursor catalyst may be contacted with an oxidizing gas at an oxidation temperature ranging from 620° C., 650° C., 675° C., 700° C., or 750° C. to 775° C., 800° C., 850° C., 900° C., 950° C., or 1,000° C. to produce an oxidized precursor catalyst. The precursor catalyst may be contacted with an oxidizing gas for a duration of at least 30 seconds, at least 1 minute, at least 5 minutes, at least 7 minutes, at least 10 minutes, at least 15 minutes, at least 20 minutes, at least 25 minutes, at least 30 minutes, at least 45 minutes, at least 60 minutes, or at least 120 minutes to produce an oxidized precursor catalyst. In some embodiments, the precursor catalyst may be contacted with an oxidizing gas for a duration ranging from 30 seconds, 1 minute, 5 minutes, or 10 minutes to 30 minutes, 60 minutes, or 120 minutes to produce an oxidized precursor catalyst. In some embodiments, the procatalyst and the oxidizing gas may be contacted with each other for a duration of ≦2 hours, ≦1 hour, ≦30 minutes, ≦10 minutes, ≦5 minutes, ≦1 minute, ≦30 seconds, ≦10 seconds, ≦5 seconds, or ≦1 second to produce the oxidized procatalyst. For example, the procatalyst and the oxidizing gas may be contacted with each other for a duration of 2 seconds to 2 hours to produce the oxidized procatalyst. In some embodiments, the procatalyst and the oxidizing gas may be contacted with each other for a duration sufficient to remove ≧50 wt%, ≧75 wt%, or ≧90 wt% or >99 wt% of the contaminants, e.g., coke, disposed on the procatalyst.

[0017] The procatalyst and oxidizing gas may be contacted with each other under an oxidizing gas partial pressure ranging from 5 kPa absolute, 10 kPa absolute, 20 kPa absolute, 50 kPa absolute, 100 kPa absolute, 300 kPa absolute, 500 kPa absolute, 750 kPa absolute, or 1,000 kPa absolute to 1,500 kPa absolute, 2,500 kPa absolute, 4,000 kPa absolute, 5,000 kPa absolute, 7,000 kPa absolute, 8,500 kPa absolute, or 10,000 kPa absolute to produce an oxidized procatalyst. In some embodiments, the oxidative gas partial pressure during contact with the precursor catalyst to produce the oxidized precursor catalyst can range from 5 kPa absolute, 10 kPa absolute, 20 kPa absolute, 50 kPa absolute, 100 kPa absolute, 150 kPa absolute, 200 kPa absolute, 250 kPa absolute, or 300 kPa absolute to 500 kPa absolute, 600 kPa absolute, 700 kPa absolute, 800 kPa absolute, 900 kPa absolute, or 1,000 kPa absolute.

[0018] Without wishing to be bound by theory, it is believed that at least a portion of the Group 10 element, e.g., Pt, disposed on the precursor catalyst may be agglomerated compared to the catalyst prior to contact with the hydrocarbon-containing feed. It is believed that when at least a portion of the contaminants on the precursor catalyst may be combusted during contact of the precursor catalyst with the oxidizing gas, at least a portion of the Group 10 element may be redispersed around the inorganic support. Redispersing at least a portion of the agglomerated Group 10 element may increase the activity of the catalyst and improve the stability of the catalyst over multiple cycles. In some embodiments, the oxidative gas is provided at a temperature below the oxidation temperature, and the oxidative gas may be preheated to a temperature above the temperature of the precursor catalyst before contacting the precursor catalyst with the oxidative gas at the oxidation temperature. In some embodiments, the oxidative gas may be preheated by using a radiant / conductive heat source, a heat exchanger, or a combination thereof. In other embodiments, the oxidative gas, the precursor catalyst, or both may be preheated by using a radiant / conductive heat source, a heat exchanger, or a combination thereof. In other words, the precursor catalyst and / or the oxidative gas may be heated separately and then contacted with each other at the oxidation temperature or heated to the oxidation temperature in the presence of each other. In some embodiments, the radiant / conductive heat source may be or include one or more electrical heating bodies.

[0019] The regenerated catalyst is obtained from the oxidized precursor catalyst. In some embodiments, the oxidized precursor catalyst may be provided as the regenerated catalyst as is. In some embodiments, the oxidized precursor catalyst is contacted with a first stripping gas, which may be free of O2, to produce a stripped oxidized precursor catalyst from which the regenerated catalyst is obtained. The first stripping gas may be or include, but is not limited to, CO, CO2, N2, C1-C4 hydrocarbons, HO, He, Ne, Ar, or any mixture thereof. In some embodiments, the stripped oxidized precursor catalyst may be provided as the regenerated catalyst as is. In some embodiments, at least a portion of the Group 10 elements, e.g., Pt, in the oxidized procatalyst may be in a higher oxidation state than the Group 10 elements in the catalyst contacted with the hydrocarbon-containing feed and than the Group 10 elements in the at least partially deactivated catalyst. In some embodiments, the oxidized procatalyst or stripped oxidized procatalyst may be contacted with an atmosphere containing H2 to produce a reduced catalyst. In other embodiments, the oxidized procatalyst or stripped oxidized procatalyst may be contacted with an atmosphere containing H2, CO, CH4, C2H6, C3H8, C2H4, C3H6, water vapor, or mixtures thereof to produce a reduced catalyst. In some embodiments, the atmosphere contacted with the oxidized procatalyst may also include an inert gas, e.g., Ar, Ne, He, N2, CO2, H2O, or mixtures thereof. In such embodiments, at least a portion of the Group 10 elements in the reduced catalyst may be reduced to a lower oxidation state, e.g., elemental state, than the Group 10 elements in the oxidized procatalyst.

[0020] In some embodiments, the oxidized or stripped oxidized procatalyst may be contacted with an H2-containing atmosphere or an atmosphere containing H2, CO, CH4, C2H6, C3H8, C2H4, C3H6, water vapor, or mixtures thereof at a temperature ranging from 400° C., 450° C., 500° C., 550° C., 600° C., 620° C., 650° C., or 670° C. to 720° C., 750° C., 800° C., or 900° C. The oxidized or stripped oxidized procatalyst may be contacted with an H2-containing atmosphere or an atmosphere containing H2, CO, CH4, C2H6, C3H8, C2H4, C3H6, water vapor, or mixtures thereof for a duration ranging from 0.01 seconds, 0.1 seconds, 1 second, 5 seconds, 10 seconds, 20 seconds, 30 seconds, or 1 minute to 10 minutes, 30 minutes, or 60 minutes. The oxidized procatalyst or stripped oxidized procatalyst may be contacted with an H2-containing atmosphere or an atmosphere containing H2, CO, CH4, C2H6, C3H8, C2H4, C3H6, water vapor, or mixtures thereof at a reducing agent partial pressure ranging from 0.1 kPa absolute, 1 kPa absolute, 5 kPa absolute, 10 kPa absolute, 20 kPa absolute, 50 kPa absolute, or 100 kPa absolute, 300 kPa absolute, 500 kPa absolute, 750 kPa absolute, or 1,000 kPa absolute to 1,500 kPa absolute, 2,500 kPa absolute, 4,000 kPa absolute, 5,000 kPa absolute, 7,000 kPa absolute, 8,500 kPa absolute, or 10,000 kPa absolute. The reducing agent includes any of H2, CO, CH4, C2H6, C3H8, C2H4, C3H6, and water vapor. In other embodiments, the reducing agent partial pressure can range from 0.1 kPa absolute, 1 kPa absolute, 5 kPa absolute, 10 kPa absolute, 20 kPa absolute, 50 kPa absolute, 100 kPa absolute, 150 kPa absolute, 200 kPa absolute, 250 kPa absolute, or 300 kPa absolute to 500 kPa absolute, 600 kPa absolute, 700 kPa absolute, 800 kPa absolute, 900 kPa absolute, or 1,000 kPa absolute to generate regenerated catalyst. The reducing agent includes any of H2, CO, CH4, C2H6, C3H8, C2H4, C3H6, and water vapor.

[0021] In some embodiments, the oxidized precursor catalyst or the stripped oxidized precursor catalyst can be contacted with the H2-containing atmosphere at a temperature higher than the use temperature of the regenerated catalyst. In such embodiments, the reduced catalyst can be cooled to the use temperature. In some embodiments, the reduced catalyst can be cooled to the use temperature in a duration of 20 minutes or less, 15 minutes or less, 10 minutes or less, 7 minutes or less, 5 minutes or less, 2 minutes or less, 1 minute or less, 30 seconds or less, 10 seconds or less, 5 seconds or less, 2 seconds or less, 1 second or less, 0.1 seconds or less, 0.01 seconds or less, or 0.001 seconds or less. The use temperature of the catalyst is the temperature at which the hydrocarbon-containing feed or an additional amount of the hydrocarbon-containing feed is contacted with the catalyst or the regenerated catalyst to cause one or more of dehydrogenation, dehydroaromatization, and dehydrocyclization of at least a portion of the hydrocarbon-containing feed to produce an at least partially deactivated catalyst that may include Group 10 elements, inorganic supports, and contaminants, and an effluent that may include one or more upgraded hydrocarbons and molecular hydrogen. The regenerated catalyst may be obtained from a reduced catalyst. In some embodiments, the reduced catalyst may be provided as the regenerated catalyst as is. In other embodiments, the reduced catalyst may be contacted with a second stripping gas to produce the regenerated catalyst. The second stripping gas may be or include, but is not limited to, CO, CO2, N2, C1-C4 hydrocarbons, HO, He, Ne, Ar, or any mixture thereof.

[0022] At least a portion of the regenerated catalyst, fresh or unused catalyst, or mixtures thereof may be contacted with an additional amount of hydrocarbon-containing feed in the reaction zone or conversion zone to produce additional effluent and additional at least partially deactivated catalyst. The cycle time from contacting the hydrocarbon-containing feed with the catalyst to contacting the additional amount of hydrocarbon-containing feed with at least a portion of the regenerated catalyst and optionally fresh or unused catalyst may be ≦5 hours, ≦4.5 hours, ≦4 hours, ≦3.5 hours, ≦3 hours, ≦2.5 hours, ≦2 hours, ≦1 hour, ≦0.5 hours, ≦0.2 hours, ≦0.1 hours, ≦0.05 hours, or ≦0.01 hours. The first cycle begins when the catalyst is contacted with a hydrocarbon-containing feed, and then the catalyst is contacted with at least an oxidizing gas to produce an oxidized precatalyst that can be directly used as a regenerated catalyst, or at least an oxidizing gas and an optional reducing gas to produce a regenerated catalyst, and the first cycle ends when the regenerated catalyst is contacted with an additional amount of a hydrocarbon-containing feed. If a first stripping gas and / or a second stripping gas or any other stripping gas(es) is used between the flow of the hydrocarbon-containing feed and the oxidizing gas, between the oxidizing gas and the reducing gas (if used), between the oxidizing gas and the additional amount of the hydrocarbon-containing feed, and / or between the reducing gas (if used) and the additional amount of the hydrocarbon-containing feed, the period during which the stripping gas(es) is used will be included in the period included in the cycle time. As a result, the cycle time from the contact step of the hydrocarbon-containing feed with the catalyst to the contact step of the additional amount of the hydrocarbon-containing feed with the regenerated catalyst can be ≦5 hours.

[0023] A catalyst, which may include a Group 10 element, e.g., Pt, and an inorganic support, may remain fully active and stable after multiple cycles, e.g., at least 15, at least 20, at least 30, at least 40, at least 50, at least 60, at least 70, at least 100 cycles, at least 125 cycles, at least 150 cycles, at least 175 cycles, or at least 200 cycles, with each cycle time lasting <5 hrs, <4 hrs, <3 hrs, <2 hrs, <1 hr, <50 min, <45 min, <30 min, <15 min, <10 min, <5 min, <1 min, <30 s, or <10 s. In some embodiments, the cycle time may be from 5 s, 30 s, 1 min, or 5 min to 10 min, 20 min, 30 min, 45 min, 50 min, 70 min, 2 hr, 3 hr, 4 hr, or 5 hr. In some embodiments, after the catalyst performance has stabilized (the first few cycles may have relatively poor or relatively good performance, but the performance may eventually stabilize), the process may provide a first upgraded hydrocarbon product yield, e.g., a propylene yield when the hydrocarbon-containing feed comprises propane, when first contacted with the hydrocarbon-containing feed, with an upgraded hydrocarbon selectivity, e.g., a propylene selectivity, of ≧75%, ≧80%, ≧85%, or ≧90%, or >95%, and upon completion of the last cycle (at least 15 cycles in total), a second upgraded hydrocarbon product yield may be at least 90%, at least 93%, at least 95%, at least 97%, at least 98%, at least 99%, at least 99.5%, or at least 100% of the first upgraded hydrocarbon product yield with an upgraded hydrocarbon selectivity, e.g., a propylene selectivity, of ≧75%, ≧80%, ≧85%, or ≧90%, or >95%.

[0024] In some embodiments, when the hydrocarbon-containing feed comprises propane and the upgraded hydrocarbons comprise propylene, contacting the hydrocarbon-containing feed with the catalyst may result in a propylene yield of at least 45%, at least 50%, at least 52%, at least 53%, at least 55%, at least 57%, at least 60%, at least 62%, at least 63%, at least 64%, at least 65%, or at least 66% with a propylene selectivity of at least 75%, at least 80%, at least 85%, at least 90%, or at least 95% for at least 15, at least 20, at least 30, at least 40, at least 50, at least 60, at least 70, at least 100 cycles, at least 125 cycles, at least 150 cycles, at least 175 cycles, or at least 200 cycles. In other embodiments, when the hydrocarbon-containing feed comprises at least 70 vol.% propane, based on the total volume of the hydrocarbon-containing feed, and is contacted at a propane partial pressure of at least 20 kPa absolute pressure, a propylene yield of at least 45%, at least 50%, at least 52%, at least 53%, at least 55%, at least 57%, at least 60%, at least 62%, at least 63%, at least 64%, at least 65%, or at least 66% can be obtained over at least 15, at least 20, at least 30, at least 40, at least 50, at least 60, at least 70, at least 100 cycles, at least 125 cycles, at least 150 cycles, at least 175 cycles, or at least 200 cycles with a propylene selectivity of at least 75%, at least 80%, at least 85%, at least 90%, or at least 95%.It is believed that by further optimizing the composition of the support and / or adjusting one or more process conditions, the propylene yield may be further increased to at least 67%, at least 68%, at least 70%, at least 72%, at least 75%, at least 77%, at least 80%, or at least 82% over at least 15 cycles, at least 20, at least 30, at least 40, at least 50, at least 60, at least 70, at least 100 cycles, at least 125 cycles, at least 150 cycles, at least 175 cycles, or at least 200 cycles with a propylene selectivity of at least 75%, at least 80%, at least 85%, at least 90%, or at least 95%. In some embodiments, this propylene yield can be obtained when the catalyst is contacted with the hydrocarbon feed at a temperature of at least 620°C, at least 630°C, at least 640°C, at least 650°C, at least 655°C, at least 660°C, at least 670°C, at least 680°C, at least 690°C, at least 700°C, or at least 750°C for at least 15, at least 20, at least 30, at least 40, at least 50, at least 60, at least 70, at least 100 cycles, at least 125 cycles, at least 150 cycles, at least 175 cycles, or at least 200 cycles.

[0025] Systems suitable for carrying out the processes disclosed herein include systems known in the art such as fixed bed reactors as disclosed in International Publication No. WO2017078894; fluidized riser and / or downer reactors as disclosed in U.S. Pat. Nos. 3,888,762; 7,102,050; 7,195,741; 7,122,160; and 8,653,317; and U.S. Patent Application Publication Nos. 2004 / 0082824; 2008 / 0194891; and countercurrent reactors as disclosed in U.S. Pat. No. 8,754,276; U.S. Patent Application Publication No. 2015 / 0065767; and International Publication No. WO2013169461.

[0026] catalyst The catalyst may comprise from 0.06 wt%, 0.07 wt%, 0.08 wt%, 0.09 wt%, 0.1 wt%, 0.2 wt%, 0.5 wt%, or 1 wt% to 2 wt%, 3 wt%, 4 wt%, 5 wt%, or 6 wt% of a Group 10 element based on the weight of the inorganic support. In some embodiments, the catalyst may include >0.06 wt%, >0.08 wt%, >0.1 wt%, >0.13 wt%, >0.15 wt%, >0.17 wt%, >0.2 wt%, >0.2 wt%, >0.23, >0.25 wt%, >0.27 wt%, or >0.3 wt% and <0.5 wt%, <1 wt%, <2 wt%, <3 wt%, <4 wt%, <5 wt%, or <6 wt% of a Group 10 element based on the weight of the inorganic support. In some embodiments, the Group 10 element may be or include Ni, Pd, Pt, combinations thereof, or mixtures thereof. In at least one embodiment, the Group 10 element may be or include Pt. In some embodiments, one or more C2-C 16 Linear or branched alkanes, or one or more C4-C 16 Cyclic alkanes, one or more of C8-C 16 The active component of the regenerating catalyst, which may be capable of effecting one or more of the dehydrogenation, dehydroaromatization, and dehydrocyclization of a hydrocarbon-containing feed, including alkylaromatic hydrocarbons, or mixtures thereof, may comprise a Group 10 element.

[0027] The inorganic support may be or include, but is not limited to, one or more group 4 elements, combinations thereof, or mixtures thereof. In some embodiments, the group 4 element may be present in its elemental form. In other embodiments, the group 4 element may be present in the form of a compound. For example, the group 4 element may be present as an oxide, phosphate, halide, halate, sulfate, sulfide, borate, nitride, carbide, aluminate, aluminosilicate, silicate, carbonate, metaphosphate, selenide, tungstate, molybdate, chromate, chromate, dichromate, or silicide. In some embodiments, a mixture of any two or more compounds containing a group 4 element may be present in different forms. For example, a first compound may be an oxide and a second compound may be an aluminate, and the first compound and the second compound may contain the same or different group 4 elements from each other. In some embodiments, at least a portion of the group 4 element may be in the form of ZrO2. In some embodiments, at least a portion of the group 4 element may be in the form of ZrO2 or in the form of a mixed oxide including ZrO2. In some embodiments, when the group 4 element is in the form of a mixed oxide including ZrO2, the other oxide may be or include, but is not limited to, Al2O3, SiO2, TiO2, MgO, CeO2, or any mixture thereof. In some embodiments, the group 4 element may be or include, but is not limited to, one or more of the following compounds: ZrO2, ZrC, ZrN, ZrSiO4, CaZrO3, Ca7ZrAl6O 18 , CaTiO3, TiO2, TiC, TiN, TiSiO4, CaTiO3, HfO2, HfC, HfN, HfSiO4, HfZrO3, Ca7HfAl6O 18 , CeZrO4, sulfated zirconia, tungsten oxide zirconia, zirconia alumina, magnesia stabilized zirconia, magnesium zirconium oxide, cerium zirconium oxide, combinations thereof, and mixtures thereof.

[0028] The inorganic support may comprise ≧0.5 wt%, ≧1 wt%, ≧2 wt%, ≧3 wt%, ≧4 wt%, ≧5 wt%, ≧10 wt%, or ≧20 wt%, ≧40 wt%, ≧80 wt%, or ≧90 wt% of a Group 4 element based on the weight of the inorganic support. In some embodiments, the inorganic support may comprise a Group 4 element ranging from 0.5 wt%, 3 wt%, 5 wt%, or 10 wt% to 30 wt%, 50 wt%, 70 wt%, or 90 wt% based on the weight of the inorganic support. In some embodiments, the molar ratio of Group 4 element to Group 10 element may range from 0.18, 0.3, 0.5, 1, 10, 50, 100, or 200 to 300, 400, 500, 600, 700, or 810. In some embodiments, the inorganic support may also include at least one metal element and / or at least one metalloid element and / or at least one compound thereof selected from a group other than, but not limited to, Groups 4 and 10, where the at least one metal element and / or at least one metalloid element is not Li, Na, K, Rb, Cs, Sn, Ga, Zn, Ge, In, Re, Ag, Au, or Cu. When the support also comprises at least one metal and / or metalloid element selected from a group other than groups 4 and 10 (wherein the at least one metal and / or at least one metalloid element is not Li, Na, K, Rb, Cs, Sn, Ga, Zn, Ge, In, Re, Ag, Au, or Cu), the compound may be present in the support as an oxide, phosphate, halide, halate, sulfate, sulfide, borate, nitride, carbide, aluminate, aluminosilicate, silicate, carbonate, metaphosphate, selenide, tungstate, molybdate, chromate, chromate, dichromate, or silicide. In some embodiments, suitable compounds comprising metal elements and / or metalloid elements selected from groups other than Groups 4 and 10 (wherein the at least one metal element and / or the at least one metalloid element is not Li, Na, K, Rb, Cs, Sn, Ga, Zn, Ge, In, Re, Ag, Au, or Cu) may be or include, but are not limited to, one or more of the following compounds: B2O3, AlBO3, Al2O3, SiO2, SiC, Si3N4, aluminosilicates, zinc aluminate, ZnO, VO, VO2, VO2, VO5, Ga s O t , In u O v , Mn2O3, Mn3O4, MnO, one or more molybdenum oxides, one or more tungsten oxides, one or more zeolites (where s, t, u, and v are positive numbers) and mixtures and combinations thereof.

[0029] In some embodiments, the at least one metallic element and / or at least one metalloid element selected from a group other than Group 4 and Group 10 and / or at least one compound thereof (wherein the at least one metallic element and / or at least one metalloid element is not Li, Na, K, Rb, Cs, Sn, Ga, Zn, Ge, In, Re, Ag, Au, or Cu) can be or include, without limitation, one or more elements having an atomic number of 57 to 71. In such embodiments, the catalyst may comprise a total amount of one or more elements having an atomic number of 57-71 of from 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.3 wt%, 0.5 wt%, 0.7 wt%, or 0.9 wt%, up to 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, or 10 wt%, based on the weight of the inorganic support. In some embodiments, when the catalyst comprises an element having an atomic number of 57-71, the molar ratio of the element having an atomic number of 57-71 to the Group 10 element may range from 0.19, 0.5, 1, 10, 50, 100, or 150 to 200, 250, 300, 350, 400, or 438. In some embodiments, when the catalyst comprises two or more Group 4 elements and / or elements having an atomic number of 57 to 71, the molar ratio of the total amount of all Group 4 elements and all elements having an atomic number of 57 to 71 to the Group 10 element can be in the range of from 0.18, 0.5, 1, 10, 50, 100, 300, 450, 600, 800, 1,000, 1,200, 1,500, 1,700, or 2,000 to 3,000, 3,500, 4,000, 4,500, 5,000, 5,500, 6,000, 6,500, 7,000, 7,500, 8,000, 8,500, 9,000, or 9,500.

[0030] In some embodiments, the one or more elements having an atomic number of 57-71 may be or include, but are not limited to, La, Ce, Pr, combinations thereof, or mixtures thereof. In some embodiments, the one or more elements having an atomic number of 57-71 may be present as an oxide, phosphate, halide, halate, sulfate, sulfide, borate, nitride, carbide, aluminate, aluminosilicate, silicate, carbonate, metaphosphate, selenide, tungstate, molybdate, chromate, chromate, dichromate, or silicide. In some embodiments, the inorganic support may also include one or more promoters disposed thereon. The promoter may be or include, but is not limited to, Sn, Ga, Zn, Ge, In, Re, Ag, Au, Cu, combinations thereof, or mixtures thereof. In some embodiments, the promoter may be associated with a group 10 element, such as Pt. For example, the promoter and group 10 element disposed on the inorganic support may form a group 10 element-promoter cluster, which may be dispersed on the inorganic support. The promoter, when present, may improve the selectivity / activity / life of the catalyst for a given upgraded hydrocarbon. In some embodiments, the addition of a promoter may improve the propylene selectivity of the catalyst when the hydrocarbon-containing feed includes propane. The catalyst may comprise the promoter in an amount of from 0.01 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, or 1 wt% to 3 wt%, 5 wt%, 7 wt%, or 10 wt%, based on the weight of the inorganic support.

[0031] In some embodiments, the inorganic support may also include one or more alkali metal elements disposed thereon. The alkali metal elements, if present, may be or include, but are not limited to, Li, Na, K, Rb, Cs, combinations thereof, or mixtures thereof. In at least some embodiments, the alkali metal elements may be or include K and / or Cs. The alkali metal elements, if present, may improve the selectivity of the catalyst for a given upgraded hydrocarbon. The catalyst may include an alkali metal element in an amount of 0.01 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, or 1 wt% to 2 wt%, 3 wt%, 4 wt%, or 5 wt%, based on the weight of the inorganic support. In some embodiments, suitable catalysts include those described in U.S. Patent Nos. 6,989,346; 7,087,802; and 8,680,005 and U.S. Patent Application Publication No. 2007 / 009929.

[0032] The preparation of the inorganic support can be accomplished by any known process. For simplicity and ease of explanation, the preparation of suitable inorganic supports, including ZrO2 and SiO2 mixed oxide inorganic supports, will be described in more detail. Catalyst synthesis techniques are well known, and the following description is for illustrative purposes and should not be considered as limiting the synthesis of inorganic supports or catalysts. In some embodiments, ZrO2 and SiO2 can be mixed together, e.g., ball milled, and then calcined to prepare a ZrO2 / SiO2 mixed oxide inorganic support. In some embodiments, ZrO2 and SiO2 can be mixed together, e.g., ball milled, slurried, spray dried, and calcined to prepare a ZrO2 / SiO2 mixed oxide inorganic support. In another embodiment, the Zr-containing precursor and the Si-containing precursor can be dissolved in H2O, stirred (optionally with the addition of heat or a precipitating agent) to dryness, and then calcined. In another embodiment, the Si-containing precursor can be dissolved in H2O, and the solution can be impregnated onto an existing inorganic support, e.g., a ZrO2 inorganic support, which can be dried and calcined. In another embodiment, Si from a Si-containing precursor can be loaded onto a pre-existing ZrO2 inorganic support via liquid-phase adsorption, followed by liquid-solid separation, drying, and calcination. In another embodiment, Si from a Si-containing precursor can be loaded onto a pre-existing ZrO2 inorganic support by gas-phase adsorption, e.g., chemical vapor deposition, followed by calcination.

[0033] The group 10 metal(s) and any promoter and / or any alkali metal element and / or any at least one metal element and / or at least one metalloid element selected from groups other than group 4 and group 10 and / or at least one compound thereof (wherein the at least one metal element and / or at least one metalloid element is not Li, Na, K, Rb, Cs, Sn, Ga, Zn, Ge, In, Re, Ag, Au, or Cu) can be loaded onto the mixed oxide inorganic support by any known technique. For example, one or more group 10 element precursors, such as chloroplatinic acid, tetraammineplatinum nitrate, and / or tetraammineplatinum hydroxide, one or more promoter precursors (if used), such as salts such as SnCl2, SnCl4, and / or AgNO3, and one or more alkali metal element precursors (if used), such as KNO3, KCl, and / or NaCl, can be dissolved in water. The solution may be impregnated onto the inorganic support followed by drying and calcination. In some embodiments, the group 10 element precursor and optionally the promoter precursor and / or optionally the alkali metal element precursor and / or optionally at least one metal element and / or at least one metalloid element (not Li, Na, K, Rb, Cs, Sn, Ga, Zn, Ge, In, Re, Ag, Au, or Cu) may be loaded onto the inorganic support simultaneously or separately in a sequence separated by one or more drying and / or calcination steps. In another embodiment, the group 10 element and, optionally, the promoter and / or the alkali metal element and / or at least one metal element and / or at least one metalloid element selected from groups other than group 4 and group 10 and / or at least one compound thereof (wherein the at least one metal element and / or at least one metalloid element is not Li, Na, K, Rb, Cs, Sn, Ga, Zn, Ge, In, Re, Ag, Au, or Cu) are loaded onto the inorganic support by chemical vapor deposition, in which case the precursor may be calcined after being vaporized and deposited on the inorganic support.In another embodiment, the group 10 element precursor and, optionally, the promoter precursor and / or the alkali metal precursor and / or at least one metal element and / or at least one metalloid element selected from groups other than group 4 and group 10 and / or at least one compound thereof (wherein the at least one metal element and / or at least one metalloid element is not Li, Na, K, Rb, Cs, Sn, Ga, Zn, Ge, In, Re, Ag, Au, or Cu) are loaded onto the inorganic support by ion adsorption, followed by liquid-solid separation, drying and calcination. In some cases, the catalyst may be synthesized using a one-pot synthesis method, in which the precursor of the inorganic support, the Group 10 metal(s) and any promoter and / or any alkali metal element and / or any at least one metal element and / or at least one metalloid element selected from groups other than Groups 4 and 10 and / or at least one compound thereof (wherein the at least one metal element and / or at least one metalloid element is not Li, Na, K, Rb, Cs, Sn, Ga, Zn, Ge, In, Re, Ag, Au, or Cu) may all be dry or wet mixed together with or without any other additives to aid in the synthesis, followed by drying and calcination. Suitable processes that can be used to prepare the catalysts disclosed herein include those described in US Pat. Nos. 6,989,346; 7,087,802; and 8,680,005 and US Patent Application Publication No. 2007 / 009929.

[0034] The as-synthesized catalyst may appear as primary particles, agglomerates of primary particles, aggregated primary particles, or combinations thereof when examined under a scanning electron microscope or a transmission electron microscope. The primary particles in the as-synthesized catalyst may have an average particle size, e.g., diameter when spherical, ranging from 0.2 nm, 0.5 nm, 1 nm, 5 nm, 10 nm, 25 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, 450 nm, or 500 nm to 1 μm, 10 μm, 25 μm, 50 μm, 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 400 μm, or 500 μm when examined under a scanning electron microscope or a transmission electron microscope. In some embodiments, the catalyst particles may have an average cross-sectional length of 0.2 nm to 500 μm, 0.5 nm to 300 μm, 1 nm to 200 μm, 2 nm to 100 μm, or 2 nm to 500 nm, as measured by transmission electron microscopy. The catalyst is 0.1 m 2 / g, 1m 2 / g, 10m 2 / g, or 100m 2 / g to 500m 2 / g, 800m 2 / g, 1,000m 2 / g, or 1,500m 2 The catalyst may have a surface area ranging from 0.1 to 1.0 μm / g. The surface area of ​​the catalyst can be measured according to the Brunauer-Emmett-Teller (BET) method using nitrogen adsorption-desorption (liquid nitrogen temperature, 77 K) on a Micromeritics 3flex instrument after degassing the powder at 350° C. for 4 hours. Further information regarding the method can be found, for example, in “Characterization of Porous Solids and Powders: Surface Area, Pore Size and Density,” S. Lowell et al., Springer, 2004.

[0035] In some embodiments, the inorganic support is extruded or otherwise formed into any desired monolithic structure onto which the Group 10 element and any optional promoter and / or alkali metal element and / or other components may be disposed. Suitable monolithic structures may be or include, but are not limited to, structures having a plurality of substantially parallel internal passages, such as structures in the form of ceramic honeycombs. In some embodiments, the support is in the form of beads, spheres, rings, donuts, irregular shapes, rods, cylinders, flakes, films, cubes, polygonal geometries, sheets, fibers, coils, spirals, meshes, sintered porous masses, granules, pellets, tablets, powders, particulates, extrudates, fabric or web-type materials, honeycomb matrix monoliths (including crushed or shattered forms) onto which the Group 10 element and any optional promoter and / or alkali metal element may be disposed.

[0036] The as-synthesized catalyst may be formulated into one or more forms suitable for various short cycle (≦5 hours) hydrocarbon upgrading processes. Alternatively, the support may be formulated into a form suitable for various short cycle hydrocarbon upgrading processes prior to the addition of the Group 10 element and any optional promoters and / or alkali metal elements. During formulation, one or more binders and / or additives may be added to the catalyst / support or catalyst / support precursor to improve the chemical / physical properties of the catalyst. Spray-dried catalyst particles having an average cross-sectional diameter in the range of 40 μm to 100 μm are typically used in FCC type fluidized bed reactors. To make a spray-dried catalyst, it is preferred to slurry the support / catalyst or support / catalyst precursor with the binder / additive in the slurry prior to spray drying and calcination. In some embodiments, the spray-dried catalyst is in the form of particles, and the morphology of the particles may be predominantly spherical such that the particles are suitable for moving in a fluidized bed reactor. In some embodiments, the catalyst particles may have a size and density consistent with the Geldart A or Geldart B definition of a flowable solid.

[0037] Hydrocarbon Upgrading Process Returning to the hydrocarbon upgrading process, the hydrocarbon-containing feed and at least a portion of the catalyst and / or regenerated catalyst may be contacted with each other in any suitable environment, such as in one or more reaction zones or conversion zones disposed within one or more reactors, to produce an effluent and at least partially deactivated catalyst. In some embodiments, the reaction zone or conversion zone may be disposed or otherwise located within one or more fixed bed reactors, one or more fluidized or moving bed reactors, one or more counter-current reactors, or any combination thereof. The hydrocarbon-containing feed and at least a portion of the catalyst and / or regenerated catalyst may be contacted at a temperature ranging from 300°C, 350°C, 400°C, 450°C, 500°C, 550°C, 600°C, 620°C, 650°C, 660°C, 670°C, 680°C, 690°C, or 700°C to 725°C, 750°C, 760°C, 780°C, 800°C, 825°C, 850°C, 875°C, or 900°C. In some embodiments, the hydrocarbon-containing feed and at least a portion of the catalyst and / or regenerated catalyst may be contacted at a temperature of at least 620° C., at least 650° C., at least 660° C., at least 670° C., at least 680° C., at least 690° C., or at least 700° C. up to 725° C., 750° C., 760° C., 780° C., 800° C., 825° C., 850° C., 875° C., or 900° C. The hydrocarbon-containing feed may be introduced into a reaction zone or conversion zone and contacted therein with at least a portion of the catalyst and / or regenerated catalyst for a time of ≦3 hours, ≦2.5 hours, ≦2 hours, ≦1.5 hours, ≦1 hour, ≦45 minutes, ≦30 minutes, ≦20 minutes, ≦10 minutes, ≦5 minutes, ≦1 minute, ≦30 seconds, ≦10 seconds, ≦5 seconds, or ≦1 second or ≦0.5 seconds. In some embodiments, the hydrocarbon-containing feed may be contacted with at least a portion of the catalyst and / or regenerated catalyst for a time ranging from 0.1 seconds, 0.5 seconds, 0.7 seconds, 1 second, 30 seconds, 1 minute, 5 minutes, or 10 minutes to 30 minutes, 50 minutes, 70 minutes, 1.5 hours, 2 hours, or 3 hours.

[0038] The hydrocarbon-containing feed and at least a portion of the catalyst and / or regenerated catalyst may be contacted under a hydrocarbon partial pressure of at least 20 kPa absolute, where the hydrocarbon partial pressure is at least 20 kPa absolute, and is less than or equal to any C2-C4 in the hydrocarbon-containing feed.16 Alkanes and any C8-C 16 The total partial pressure of alkyl aromatic hydrocarbons. In some embodiments, the hydrocarbon partial pressure during contacting of the hydrocarbon-containing feed with at least a portion of the catalyst and / or regenerated catalyst may range from 20 kPa absolute, 50 kPa absolute, 100 kPa absolute, at least 150 kPa, at least 200 kPa, 300 kPa absolute, 500 kPa absolute, 750 kPa absolute, or 1,000 kPa absolute to 1,500 kPa absolute, 2,500 kPa absolute, 4,000 kPa absolute, 5,000 kPa absolute, 7,000 kPa absolute, 8,500 kPa absolute, or 10,000 kPa absolute. Here, the hydrocarbon partial pressure is the total partial pressure of any C2-C4 alkyl aromatic hydrocarbons in the hydrocarbon-containing feed. 16 Alkanes and any C8-C 16 is the total partial pressure of alkyl aromatic hydrocarbons. In other embodiments, the hydrocarbon partial pressure during contacting of the hydrocarbon-containing feed with at least a portion of the catalyst and / or regenerated catalyst may range from 20 kPa absolute, 50 kPa absolute, 100 kPa absolute, 150 kPa absolute, 200 kPa absolute, 250 kPa absolute, or 300 kPa absolute to 500 kPa absolute, 600 kPa absolute, 700 kPa absolute, 800 kPa absolute, 900 kPa absolute, or 1,000 kPa absolute. Here, the hydrocarbon partial pressure is the total partial pressure of any C2-C4 alkyl aromatic hydrocarbons in the hydrocarbon-containing feed. 16 Alkanes and any C8-C 16 is the total partial pressure of alkyl aromatic hydrocarbons.

[0039] In some embodiments, the hydrocarbon-containing feed is at least 60 vol.%, at least 65 vol.%, at least 70 vol.%, at least 75 vol.%, at least 80 vol.%, at least 85 vol.%, at least 90 vol.%, at least 95 vol.%, or at least 99 vol.% of a single C2-C 16At least a portion of the hydrocarbon-containing feed and the catalyst and / or regenerated catalyst may comprise a single C2-C alkane having a pressure of at least 20 kPa absolute, at least 50 kPa absolute, at least 100 kPa absolute, at least 150 kPa absolute, at least 250 kPa absolute, at least 300 kPa absolute, at least 400 kPa absolute, at least 500 kPa absolute, or at least 1,000 kPa absolute. 16 The contact may be under pressure of an alkane, such as propane. The hydrocarbon-containing feed may be contacted with at least a portion of the catalyst and / or regenerated catalyst in the reaction zone or conversion zone at any mass hourly space velocity (WHSV) effective for carrying out the upgrading process. In some embodiments, the WHSV is less than 0.01 h -1 , 0.1 hours -1 , 1 hour -1 , 2 hours -1 , 5 hours -1 , 10 hours -1 , 20 hours -1 , 30 hours -1 or 50 hours -1 From 100 hours -1 , 250 hours -1 , 500 hours -1 or 1,000 hours -1 In some embodiments, when the hydrocarbon upgrading process includes a fluidized or otherwise moving catalyst and / or a moving regenerated catalyst, the catalyst circulation mass flow rate and any C2-C 16 Alkanes and any C8-C 16 The ratio of the total amount of mass flow of alkyl aromatic hydrocarbons can range from 1, 3, 5, 10, 15, 20, 25, 30, or 40 to 50, 60, 70, 80, 90, 100, 110, 125, or 150 on a mass to mass basis.

[0040] When the activity of the at least partially deactivated catalyst falls below a desired minimum amount, the at least partially deactivated catalyst, or at least a portion thereof, may undergo a regeneration process as described above to produce a regenerated catalyst. Regeneration of the at least partially deactivated catalyst may occur within the reaction zone or conversion zone or in a separate combustion zone separate from the reaction zone or conversion zone, depending on the particular reactor configuration, to produce a regenerated catalyst. For example, catalyst regeneration may occur within the reaction zone or conversion zone when using a fixed bed or counter-flow reactor, or in a separate combustion zone separate from the reaction zone or conversion zone when using a fluidized bed reactor or other circulating or fluidized type reactor. Similarly, the optional reduction step may also occur within the reaction zone or conversion zone, within the combustion zone, and / or in a separate reduction zone. Thus, the hydrocarbon-containing feed may be contacted with the catalyst in a cyclic process, such as those commonly used in fixed-bed and countercurrent reactors, and / or in a continuous process, such as those commonly used in fluidized-bed reactors, to cause at least one of dehydrogenation, dehydroaromatization, and dehydrocyclization of at least a portion of the hydrocarbon-containing feed to produce a coking catalyst and a first effluent containing one or more upgraded hydrocarbons and molecular hydrogen. Optionally, separation of the effluent containing the upgraded hydrocarbons and molecular hydrogen from the coking catalyst may be accomplished by one or more separators, such as a cyclone separator. As described above, the oxidizing gas may be or include, but is not limited to, O2, O3, CO2, or mixtures thereof, and may contain 5 mol% or less of H2O. In some embodiments, an amount of oxidizing gas in excess of the amount required to combust 100% of the contaminants, such as coke, located on the catalyst may be used to increase the contaminant removal rate from the catalyst, resulting in a shorter time required to remove the contaminants, which may lead to an increased yield of upgraded products produced within a given time.

[0041] Hydrocarbon-containing feed C2-C 16The alkane may be or include, but is not limited to, ethane, propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, n-heptane, 2-methylhexane, 2,2,3-trimethylbutane, cyclopentane, cyclohexane, methylcyclopentane, ethylcyclopentane, n-propylcyclopentane, 1,3-dimethylcyclohexane, or mixtures thereof. For example, the hydrocarbon-containing feed may include propane, which may be dehydrogenated to produce propylene, and / or isobutane, which may be dehydrogenated to produce isobutylene. In another example, the hydrocarbon-containing feed may include liquefied petroleum gas (LP gas), which may be in the gas phase when contacted with the catalyst. In some embodiments, the hydrocarbons in the hydrocarbon-containing feed may be substantially composed of a single alkane, such as propane. In some embodiments, the hydrocarbon-containing feed comprises ≥ 50 mol%, ≥ 75 mol%, ≥ 95 mol%, ≥ 98 mol%, or ≥ 99 mol% of a single C-C 16 In some embodiments, the hydrocarbon-containing feed may comprise at least 50 vol%, at least 55 vol%, at least 60 vol%, at least 65 vol%, at least 70 vol%, at least 75 vol%, at least 80 vol%, at least 85 vol%, at least 90 vol%, at least 95 vol%, at least 97 vol%, or at least 99 vol% of a single C2-C 16 It may include alkanes such as propane.

[0042] C8-C 16 The alkyl aromatic hydrocarbon may be or include, but is not limited to, ethylbenzene, propylbenzene, butylbenzene, one or more ethyltoluenes, or mixtures thereof. In some embodiments, the hydrocarbon-containing feed contains ≥ 50 mol%, ≥ 75 mol%, ≥ 95 mol%, ≥ 98 mol%, or ≥ 99 mol% of a single C8-C8 hydrocarbon, based on the total mass of all hydrocarbons in the hydrocarbon-containing feed.16 It may include alkyl aromatic hydrocarbons, such as ethylbenzene. In some embodiments, ethylbenzene may be dehydrogenated to produce styrene. Thus, in some embodiments, the processes disclosed herein may include propane dehydrogenation, butane dehydrogenation, isobutane dehydrogenation, pentane dehydrogenation cyclization to cyclopentadiene, naphtha reforming, ethylbenzene dehydrogenation, ethyltoluene dehydrogenation, and the like. In some embodiments, the hydrocarbon-containing feed may be diluted with, for example, one or more diluents, such as one or more inert gases. Suitable inert gases may be or include, but are not limited to, Ar, Ne, He, N2, CO2, CH4, or mixtures thereof. When the hydrocarbon-containing feed includes a diluent, the hydrocarbon-containing feed may be diluted with, for example, one or more diluents, such as one or more inert gases. When the hydrocarbon-containing feed includes a diluent, the hydrocarbon-containing feed may be diluted with, for example, one or more inert gases, such as ... 16 Alkanes and any C8-C 16 It may contain from 0.1 vol%, 0.5 vol%, 1 vol%, or 2 vol% to 3 vol%, 8 vol%, 16 vol%, or 32 vol% of the diluent based on the total volume of the alkyl aromatic hydrocarbon. In some embodiments, the hydrocarbon-containing feed may also include H2. In some embodiments, when the hydrocarbon-containing feed includes H2, H2 and any C2-C 16 Alkanes and any C8-C 16 The molar ratio of the total amount of alkyl aromatic hydrocarbons can range from 0.1, 0.3, 0.5, 0.7, or 1 to 2, 3, 4, 5, 6, 7, 8, 9, or 10.

[0043] In some embodiments, the hydrocarbon-containing feed is substantially free of water vapor, e.g., any C-C 16 Alkanes and any C8-C 16 The amount of water vapor may be <0.1 vol.% based on the total volume of alkylaromatic hydrocarbons. In other embodiments, the hydrocarbon-containing feed may contain water vapor. For example, the hydrocarbon-containing feed may contain <0.1 vol.% water vapor based on the total volume of alkylaromatic hydrocarbons. 16 Alkanes and any C8-C 16Based on the total volume of alkylaromatic hydrocarbons, the feed may contain from 0.1 vol%, 0.3 vol%, 0.5 vol%, 0.7 vol%, 1 vol%, 3 vol%, or 5 vol% to 10 vol%, 15 vol%, 20 vol%, 25 vol%, 30 vol%, 35 vol%, 40 vol%, 45 vol%, or 50 vol% water vapor. In other embodiments, the feed may contain any C2-C 16 Alkanes and any C8-C 16 Based on the total volume of alkylaromatic hydrocarbons, the hydrocarbon-containing feed may contain ≦50 vol%, ≦45 vol%, ≦40 vol%, ≦35 vol%, ≦30 vol%, ≦25 vol%, ≦20 vol%, or ≦15 vol% water vapor. In other embodiments, the hydrocarbon-containing feed may contain ≦50 vol%, ≦45 vol%, ≦40 vol%, ≦35 vol%, ≦30 vol%, ≦25 vol%, ≦20 vol%, or ≦15 vol% water vapor. 16 Alkanes and any C8-C 16 Based on the total volume of the alkylaromatic hydrocarbon, it may contain at least 1 vol.%, at least 3 vol.%, at least 5 vol.%, at least 10 vol.%, at least 15 vol.%, at least 20 vol.%, at least 25 vol.%, or at least 30 vol.% water vapor.

[0044] In some embodiments, the hydrocarbon-containing feed may contain sulfur. For example, the hydrocarbon-containing feed may contain sulfur in the range of 0.5 ppm, 1 ppm, 5 ppm, 10 ppm, 20 ppm, 30 ppm, 40 ppm, 50 ppm, 60 ppm, 70 ppm, or 80 ppm to 100 ppm, 150 ppm, 200 ppm, 300 ppm, 400 ppm, or 500 ppm. In other embodiments, the hydrocarbon-containing feed may contain sulfur in the range of 1 ppm to 10 ppm, 10 ppm to 20 ppm, 20 ppm to 50 ppm, 50 ppm to 100 ppm, or 100 ppm to 500 ppm. Sulfur, when present in the hydrocarbon-containing feed, may be or include, but is not limited to, H2S, dimethyl disulfide, one or more mercaptans, or any mixture thereof. The hydrocarbon feed may be substantially free of or completely free of molecular oxygen. In some embodiments, the hydrocarbon feed may contain ≦5 mol%, ≦3 mol%, or ≦1 mol% molecular oxygen (O2). Providing a hydrocarbon feed substantially free of molecular oxygen is believed to substantially prevent oxidation reactions that would otherwise consume at least a portion of the alkanes and / or alkyl aromatic hydrocarbons in the hydrocarbon feed.

[0045] Recovery and use of upgraded hydrocarbons The upgraded hydrocarbons may include at least one upgraded hydrocarbon, such as olefins, water, unreacted hydrocarbons, molecular hydrogen, and the like. The upgraded hydrocarbons may be recovered or otherwise obtained by any conventional process, for example, by one or more conventional processes. One such process may cool and / or compress the effluent to condense at least a portion of any water and any heavy hydrocarbons that may be present, leaving the olefins and any unreacted alkane or alkylaromatic hydrocarbons primarily in the gas phase. The olefins and unreacted alkane or alkylaromatic hydrocarbons may then be removed from the reaction product in one or more separation units, such as distillation columns, adsorptive separators, membrane separators, cryogenic separators, and the like. For example, one or more splitters or distillation columns may be used to separate the dehydrogenation product from the unreacted hydrocarbon feed. In some embodiments, the recovered olefins, e.g., recovered propylene, can be used to make polymers, e.g., recovered propylene can be polymerized to produce polymers having segments or units derived from the recovered propylene, e.g., polypropylene, ethylene-propylene copolymers, etc. The recovered isobutene can be used, for example, to make one or more of oxygenates, e.g., methyl tert-butyl ether, fuel additives, e.g., diisobutene, synthetic elastomeric polymers, e.g., butyl rubber, etc. EXAMPLES

[0046] Working Example: The foregoing discussion can be further illustrated with reference to the following non-limiting examples: Catalyst 1 and Comparative Catalyst 1 were prepared according to the following procedure. Catalyst 1: A catalyst was prepared according to the following procedure. A solution of 0.036 g SnCl2·2H2O and 0.0236 g H2PtCl6·6H2O in 18.375 ml (14.5 g) of ethanol was poured onto 3 g of ZrO2 (Saint-Gobain) doped with 5% SiO2 while stirring the mixture with a magnetic stir bar. The excess solution was allowed to evaporate overnight. The composition was dried at 100 °C for 15 h and calcined at 560 °C for 3 h to produce calcined solid particles. A solution of 0.0232 g CsNO3, 0.0408 g KNO3 and 0.295 g La(NO)3·6H2O in 11.25 ml of H2O was then poured onto the calcined solid particles while stirring the mixture with a magnetic stir bar. The supernatant was allowed to evaporate over several days at temperatures between 60 °C and 90 °C. The final solid was dried at 110° C. for 6 hours and calcined at 800° C. for 12 hours to produce recalcined catalyst particles.

[0047] Comparative Catalyst 1: In a graduated cylinder, SnCl2 (0.048 g) (Aldrich), 8% solution of chloroplatinic acid (0.79 g) (Aldrich), and the remaining HCl (1.2 M) (Acculute) were combined to make 5.6 mL of a dark solution. This solution was added to theta alumina (10 g) and stirred for 15 minutes. The catalyst was allowed to sit for 1 hour. The catalyst was placed in a muffle furnace and the temperature was ramped to 120°C at 3°C / min and held at 120°C for 2 hours, then the catalyst temperature was ramped to 550°C at 3°C / min and held for 2 hours, all in air. The catalyst was then allowed to cool to room temperature. In a graduated cylinder, KNO3 (0.258 g) (Aldrich) was dissolved in deionized water to give 5.6 mL of solution. This solution was added to the Pt-Sn catalyst and stirred for 15 minutes. The catalyst was allowed to sit for 1 hour. The catalyst was placed in a muffle furnace and the temperature was ramped to 120°C at 3°C / min and held at 120°C for 2 hours, then the catalyst temperature was ramped to 550°C at 3°C / min and held for 2 hours, all in air. The catalyst was then cooled to room temperature. The final product contained nominally 0.3 wt% Pt, 0.3 wt% Sn, and 1.0 wt% K.

[0048] Examples using the above catalysts Fixed bed experiments were carried out at approximately 100 kPa absolute pressure. The composition of the reactor effluent was measured using a gas chromatograph (GC). The concentrations of each component in the reactor effluent were then used to calculate the C3H6 yield and selectivity. The C3H6 yields and selectivities reported in these examples were calculated on a moles of carbon basis. For each example, a specific amount of catalyst "Mcat" was mixed with an appropriate amount of quartz diluent and loaded into a quartz reactor. The amount of diluent was determined so that the catalyst bed (catalyst + diluent) overlapped with the isothermal zone of the quartz reactor and the catalyst bed was mostly isothermal during operation. Quartz chips / rods filled the dead volume of the reactor. The concentration of each component in the reactor effluent was used to calculate the yield and selectivity of C3H6. rxn At the start of t rxn The yield and selectivity of C3H6 at the end of ini , Y end , S ini , and S end and are reported as percentages in the data tables below.

[0049] Example 1 - Regeneration temperature / duration for catalyst 1. 1. The reaction zone is heated to a regeneration temperature T regen 1. While the inert gas was flowing into the reaction zone, oxygen-containing gas (Ogas) was introduced at a flow rate (F regen 3. An oxygen-containing gas is then introduced into the reaction zone for a specific time (t regen 4. The catalyst was regenerated by passing it through a 2000 ml cyclohexane. regen Then, an inert gas is passed through the reaction zone to raise the temperature in the reaction zone to T regen to the reduction temperature (T red 5. While passing the inert gas through the reaction zone, the flow rate of H2-containing gas (Hgas) was changed to F red ) was passed through the reaction zone bypass for a specific time. After this, H2-containing gas was passed through the reaction zone bypass at T red In the reaction zone for a specific time (t red 6. The system was flushed with inert gas. During this process, the temperature of the reaction zone was increased to T red From Trxn 7. While passing the inert gas through the reaction zone, a hydrocarbon-containing (HCgas) feed containing 81 vol.% C3H8, 9 vol.% inert (Ar or Kr) and 10 vol.% water vapor was added at a flow rate (F rxn ) through the bypass of the reaction zone for a specified time. The hydrocarbon-containing feed was then passed through the bypass at T rxn °C reaction zone for 10 min. GC sampling of the reaction effluent was started immediately after the feed was switched from the reaction zone bypass to the reaction zone. Tables 1-3 show the effect of regeneration duration / temperature on the PDH performance of the catalyst.

[0050] [Table 1]

[0051] [Table 2]

[0052] [Table 3]

[0053] Example 2 - Effect of catalyst reduction and simultaneous steam supply on catalyst 1. 1. The reaction zone is heated to a regeneration temperature T regen 2. While passing the inert gas through the reaction zone, oxygen-containing gas (Ogas) was introduced at a flow rate (F regen 3. An oxygen-containing gas is then introduced into the reaction zone for a specific time (t regen 4. The catalyst was regenerated by passing it through a 2000 ml cyclohexane. regen Then, an inert gas is passed through the reaction zone to raise the temperature in the reaction zone to T regen to the reduction temperature (T red 5. While passing the inert gas through the reaction zone, the flow rate of H2-containing gas (Hgas) was changed to F red ) was passed through the reaction zone bypass for a specific time. After this, H2-containing gas was passed through the reaction zone bypass at T red In the reaction zone for a specific time (tred 6. The system was flushed with inert gas. During this process, the temperature of the reaction zone was increased to T red From T rxn 7. While passing the inert gas through the reaction zone, the hydrocarbon-containing (HCgas) was added at a flow rate (F rxn ) through the bypass of the reaction zone for a specified time. The hydrocarbon-containing feed was then passed through the bypass at T rxn The mixture was passed through the reaction zone at 10 °C for 10 minutes. GC sampling of the reaction effluent was started immediately after the feed was switched from the reaction zone bypass to the reaction zone. Table 4 shows that both catalysts are most active for PDH when there is catalyst reduction and steam co-feed.

[0054] [Table 4]

[0055] Example 3 - Effect of water vapor during regeneration of catalyst 1. 1. The reaction zone is heated to the regeneration temperature T regen 2. While passing the inert gas through the reaction zone, oxygen-containing gas (Ogas) was introduced at a flow rate (F regen 3. An oxygen-containing gas is then introduced into the reaction zone for a specific time (t regen 4. The catalyst was regenerated by passing it through a 2000 ml cyclohexane. regen Then, an inert gas is passed through the reaction zone to raise the temperature in the reaction zone to T regen to the reduction temperature (T red 5. The system was flushed with inert gas. 6. While the inert gas was being passed through the reaction zone, the H2-containing gas (Hgas) was introduced at a flow rate (F red ) was passed through the reaction zone bypass for a specific time. After this, H2-containing gas was passed through the reaction zone bypass at T red In the reaction zone for a specific time (t red 7. The system was flushed with inert gas. During this process, the temperature of the reaction zone was increased to T red8. The reaction temperature was changed from 0 to 650°C. 9. A hydrocarbon-containing (HCgas) feed containing 81 vol% C3H8, 9 vol% inert (Ar or Kr) and 10 vol% water vapor was added at a flow rate (F rxn ) through the bypass of the reaction zone for a specified time. The hydrocarbon-containing feed was then passed through the reaction zone at 650°C for 10 minutes. GC sampling of the reaction effluent was started as soon as the feed was switched from the reaction zone bypass to the reaction zone. The above process steps were repeated periodically until stable performance was obtained. Table 5 shows that the presence of more than 10 vol% water vapor in the air during regeneration led to even more deactivated catalyst after regeneration. On the other hand, switching the wet air to dry air after 1 minute of regeneration efficiently regenerated the catalyst.

[0056] [Table 5]

[0057] Example 4 - Effect of duration of H2 reduction on catalyst 1. 1. Inert gas was flowed through the system while the reaction zone was heated to the regeneration temperature of 700°C. 2. While the inert gas was passed through the reaction zone, oxygen-containing gas (Ogas) was passed at a flow rate (F regen 3. An oxygen-containing gas is then introduced into the reaction zone for a specific time (t regen ) to regenerate the catalyst. 4. Inert gas was flowed through the system. During this process, the temperature of the reaction zone was maintained at 700. 5. While the inert gas was flowing through the reaction zone, H2-containing gas (Hgas) was flowed through the reaction zone at a flow rate (F red ) into the bypass of the reaction zone for a specific time. After this, H2-containing gas was passed into the reaction zone at 700 °C for a specific time (t red ) over a flow rate (F ). 6. He gas was passed through the reaction zone. During this process, the temperature of the reaction zone was reduced from 700°C to the reaction temperature of 650°C. 7. While the inert gas was passed through the reaction zone, a hydrocarbon-containing (HCgas) feed containing 81 vol% C3H8, 9 vol% inert (Ar or Kr) and 10 vol% water vapor was passed through the reaction zone at a flow rate (F rxn) through the bypass of the reaction zone for a specific time. The hydrocarbon-containing feed was then passed through the reaction zone at 650°C for 10 minutes. GC sampling of the reaction effluent was started as soon as the feed was switched from the reaction zone bypass to the reaction zone. The above process steps were repeated periodically until stable performance was obtained. Table 6 shows the effect of reduction duration on the performance of the catalyst.

[0058] [Table 6]

[0059] Example 5 - Catalyst Life of Catalyst 1. 1. To study the catalyst life of catalyst 1, 0.3g of catalyst 1 was mixed with an appropriate amount of quartz diluent and loaded into a quartz reactor. The amount of diluent was determined so that the catalyst bed (catalyst + diluent) overlapped with the isothermal zone of the quartz reactor and the catalyst bed was mostly isothermal during operation. Quartz chips / rods filled the dead volume of the reactor. 1. The system was flushed with inert gas while the reaction zone was heated to a regeneration temperature of 670°C. 2. While the reaction zone was being flushed with inert gas, a gas containing 90% air and 10% H2O was passed through the reaction zone bypass at a flow rate of 93.2 sccm. 3. The gas containing air and H2O was then flowed into the reaction zone for 1 minute to regenerate the catalyst. 4. The water vapor was discontinued and 83.9 sccm of dry air was flowed into the reaction zone for 30 minutes to further regenerate the catalyst. 5. An inert gas was flowed into the reaction zone to maintain the temperature in the reaction zone at 670°C. 6. While the inert gas was being passed through the reaction zone, a gas containing 10% H2 and 90% Ar was passed through the bypass of the reaction zone at a flow rate of 46.6 sccm for a specified time. This was followed by a flow of H2-containing gas into the reaction zone at 670°C for 1 minute. 7. The inert gas was flowed through the system. During this process, the temperature of the reaction zone was changed from 670°C to the reaction temperature of 650°C. 8. While the inert gas was being passed through the reaction zone, a hydrocarbon-containing feed containing 81 vol% C3H8, 9 vol% inert (Ar or Kr) and 10 vol% water vapor was passed through the bypass of the reaction zone at a flow rate of 9.4 sccm for a specified time. The hydrocarbon-containing feed was then passed through the reaction zone at 650°C for 10 minutes. GC sampling of the reaction effluent was started as soon as the feed was switched from the bypass of the reaction zone to the reaction zone. The above process steps were repeated periodically until stable performance was obtained. FIG. 1 shows that the catalytic performance was stable after 75+ cycles towards PDH.

[0060] Comparative Example 1: 1. The reaction zone is oxi 2. While the inert gas was passing through the reaction zone, an oxygen-containing gas (Ogas) was passed at a flow rate (F oxi 3. An oxygen-containing gas is then introduced into the reaction zone for a specific time (toxi ) to oxidize the catalyst. 4. An inert gas was passed through the system. During this process, the temperature of the reaction zone was cooled to 620°C. 5. While the inert gas was passed through the reaction zone, H2-containing gas (Hgas) was passed through the reaction zone at a flow rate (F red ) into the bypass of the reaction zone for a specific time. After this, H2-containing gas was passed into the reaction zone at 620°C for a specific time (t red ) over a flow rate (F ). 6. An inert gas was passed through the reaction zone. During this process, the temperature of the reaction zone was maintained at 620°C. 7. While the inert gas was being passed through the reaction zone, a hydrocarbon-containing (HCgas) feed containing 90 vol% C3H8, 10 vol% inert (Ar or Kr) was added at a flow rate (F rxn ) through the bypass of the reaction zone for a specified time. The hydrocarbon-containing feed was then passed through the reaction zone at 620°C for 10 minutes. GC sampling of the reaction effluent was started immediately after the feed was switched from the reaction zone bypass to the reaction zone. Table 7 provides further details of the test conditions for the comparative examples. Figure 2 shows that the performance of Comparative Catalyst 1 continued to deactivate even though the oxidation temperature (620°C) was much lower than the other examples.

[0061] [Table 7]

[0062] LIST OF EMBODIMENTS The present disclosure further includes the following non-limiting embodiments. A1. A process for regenerating an at least partially deactivated catalyst comprising a Group 10 element, an inorganic support, and contaminants, wherein the Group 10 element has a concentration in the range of 0.06 wt% to 6 wt% based on the weight of the inorganic support, and the process comprises the steps of: (I) obtaining a precursor catalyst from the at least partially deactivated catalyst; (II) providing an oxidizing gas, the oxidizing gas comprising 5 mole % or less HO based on the total moles of the precursor catalyst; (III) contacting the precursor catalyst with the oxidizing gas at an oxidation temperature in the range of 620°C to 1,000°C for a duration of at least 30 seconds, preferably at least 1 minute, preferably at least 5 minutes to produce an oxidized precursor catalyst; and (IV) obtaining a regenerated catalyst from the oxidized precursor catalyst. A2. The process of A1, wherein the Group 10 element comprises Pt and the inorganic support comprises at least 0.5 wt% of a Group 4 element, based on the weight of the inorganic support. A3. The process of A2, wherein the inorganic support comprises at least 0.5 wt% Zr. A4. The process of A2 or A3, wherein at least a portion of the Group 4 element is in the form of ZrO2.

[0063] A5. Any one of the processes of A1-A4, wherein the at least partially deactivated catalyst further comprises up to 10 wt. % of a promoter, based on the weight of the inorganic support, the promoter comprising one or more of the following elements: Sn, Ga, Zn, Ge, In, Re, Ag, Au, Cu, combinations thereof, or mixtures thereof. A6. Any one of the processes of A1-A5, wherein the at least partially deactivated catalyst further comprises up to 5 wt.% of an alkali metal element disposed on an inorganic support, the alkali metal element comprising at least one of the following: Li, Na, K, Rb, and Cs. A7. One or more types of C2-C 16 Linear or branched alkanes, or one or more C4-C 16 Cyclic alkanes, one or more of C8-C 16The process of any one of A1-A6, wherein the active component of the regenerated catalyst capable of causing one or more of dehydrogenation, dehydroaromatization, and dehydrocyclization of a hydrocarbon-containing feed comprising alkylaromatic hydrocarbons, or mixtures thereof, comprises a Group 10 element. A8. Any one of the processes of A1-A7, wherein step (I) comprises heating the at least partially deactivated catalyst with a heated gas mixture comprising HO at a concentration greater than 5 mole % based on the total moles of the heated gas mixture to produce a precursor catalyst. A9. The process of A8, wherein the heated gas mixture is generated by burning a fuel with an oxidizing gas, the fuel comprising at least one of H2, CO, and a hydrocarbon, and the oxidizing gas comprises O2.

[0064] A10. Any one of the processes of A1 to A7, wherein in step (I), the at least partially deactivated catalyst is provided as a precatalyst. A11. Any one of the processes of A1-A10, wherein step (II) comprises the steps of (IIa) providing an oxidative gas at a temperature equal to or lower than the oxidation temperature, and (IIb) preheating the oxidative gas to a temperature higher than the temperature of the precursor catalyst prior to the contacting of step (III). A12. Any one of the processes of A1-A11, further comprising (V) during step (III), heating the oxidative gas or the procatalyst by using a radiant heat source, a heat exchanger, or a combination thereof. A13. Any one of the processes of A1-A12, wherein step (IV) comprises: (IVa) contacting the oxidized precatalyst with a first stripping gas not containing O2 to produce a stripped oxidized precatalyst; and (IVb) obtaining a regenerated catalyst from the stripped oxidized precatalyst. A14. Any one of the processes of A1-A13, wherein step (IV) comprises: (IVc) contacting the oxidized precatalyst or the stripped oxidized precatalyst with an H2-containing atmosphere to produce a reduced catalyst; and (IVd) obtaining a regenerated catalyst from the reduced catalyst. A15. The process of A14, wherein step (IVd) comprises (IVd-1) contacting the reduced catalyst with a second stripping gas to produce a regenerated catalyst. A16. The process of A14 or A15, wherein step (IVc) is carried out at a temperature of the oxidized precursor catalyst that is higher than the use temperature of the regenerated catalyst, and step (IVd) further comprises (IVd-2) cooling the reduced catalyst or regenerated catalyst to the use temperature in a time duration of 10 minutes or less, 5 minutes or less, 1 minute or less, 30 seconds or less, 10 seconds or less, 5 seconds or less, 1 second or less, 0.5 seconds or less, 0.1 seconds or less, 0.01 seconds or less, or 0.001 seconds or less.

[0065] A17. A dehydrogenation process using a regenerated catalyst produced by any one of the processes of A1-A16, comprising the steps of: (VI) contacting a hydrocarbon-containing feed with the regenerated catalyst to effect one or more of dehydrogenation, dehydroaromatization, and dehydrocyclization of at least a portion of the hydrocarbon-containing feed to produce an at least partially deactivated catalyst comprising a Group 10 element, an inorganic support, and contaminants, and an effluent comprising one or more upgraded hydrocarbons and molecular hydrogen, wherein the hydrocarbon feed is one or more C2-C 16 Linear or branched alkanes, one or more of C4-C 16 Cyclic alkanes, one or more of C8-C 16 (VII) repeating steps (I)-(IV), wherein in step (III) an additional oxidized precatalyst is produced, and in step (IV) an additional regenerated catalyst is obtained from the additional oxidized precatalyst; and (VIII) contacting an additional amount of the hydrocarbon-containing feed with at least a portion of the additional regenerated catalyst to produce additional at least partially deactivated catalyst and an additional effluent. A18. The dehydrogenation process of A17, wherein the cycle time from contacting the hydrocarbon-containing feed with the regenerated catalyst in step (VI) to contacting an additional amount of the hydrocarbon-containing feed with additional regenerated catalyst in step (VIII) is ≦5 hours.

[0066] B1. A process for upgrading a hydrocarbon comprising: (I) contacting a hydrocarbon-containing feed with a catalyst comprising a Group 10 element and an inorganic support to effect one or more of dehydrogenation, dehydroaromatization, and dehydrocyclization of at least a portion of the hydrocarbon-containing feed to produce an at least partially deactivated catalyst comprising a Group 10 element, an inorganic support, and contaminants, and an effluent comprising one or more upgraded hydrocarbons and molecular hydrogen; wherein the hydrocarbon-containing feed is contacted with one or more C2-C 16 Linear or branched alkanes, or one or more C4-C 16 Cyclic alkanes, one or more of C8-C 16 % to 6 wt %, based on the weight of the inorganic support, the hydrocarbon-containing feed and the catalyst are contacted at a temperature in the range of 300° C. to 900° C., and the one or more upgraded hydrocarbons include at least one of dehydrogenated hydrocarbons, dehydrogenated aromatized hydrocarbons, and dehydrogenated cyclized hydrocarbons; (II) obtaining a procatalyst from the at least partially deactivated catalyst; (III) providing an oxidizing gas, the oxidizing gas comprising 2 mole % or less HO based on the total moles of the procatalyst; (IV) contacting the procatalyst with the oxidizing gas at an oxidation temperature in the range of 620° C. to 1,000° C. for a duration of at least 30 seconds, preferably at least 1 minute, preferably at least 5 minutes to produce an oxidized procatalyst; (V) obtaining a regenerated catalyst from the oxidized procatalyst; and (VI) contacting an additional amount of the hydrocarbon-containing feed with at least a portion of the regenerated catalyst to produce additional at least partially deactivated catalyst and an additional effluent.

[0067] B2. The process of B1, wherein the Group 10 element comprises Pt; the inorganic support comprises at least 0.5 wt.% of a Group 4 element based on the weight of the inorganic support; and the catalyst optionally further comprises up to 10 wt.% of a promoter based on the weight of the inorganic support, the promoter comprising one or more of the following elements, if present: Sn, Ga, Zn, Ge, In, Re, Ag, Au, Cu, combinations or mixtures thereof; and the catalyst optionally further comprises up to 5 wt.% of an alkali metal element, which, if present, comprises at least one of the following: Li, Na, K, Rb, and Cs. B3. The process of B1 or B2, wherein step (II) comprises heating the at least partially deactivated catalyst with a heated gas mixture comprising HO at a concentration greater than 5 mole % based on the total moles of the heated gas mixture to produce a pre-catalyst. B4. The process of B3, wherein the heated gas mixture is generated by burning a fuel with an oxidizing gas, the fuel comprising at least one of H2, CO, and a hydrocarbon, and the oxidizing gas comprising O2. B5. The process of any one of B1 to B4, wherein in step (II), the at least partially deactivated catalyst is provided as a precatalyst. B6. Any one of the processes of B1-B5, wherein step (III) comprises the steps of (IIIa) providing an oxidative gas at a temperature equal to or lower than the oxidation temperature, and (IIIb) preheating the oxidative gas to a temperature higher than the temperature of the precursor catalyst prior to the contacting of step (IV). B7. Any one of the processes of B1-B6, further comprising (VI) heating the oxidative gas or the procatalyst during step (IV) by using a radiant heat source, a heat exchanger, or a combination thereof. B8. Any one of the processes of B1-B7, wherein the cycle time from contacting the hydrocarbon-containing feed with the catalyst in step (I) to contacting the additional amount of the hydrocarbon-containing feed with the regenerated catalyst in step (VI) is ≦5 hours. B9. Any one of the processes B2 to B8, in which the Group 4 element includes Zr. B10.The process of B9, wherein the Zr is in the form of ZrO2.

[0068] Various terms have been defined above. Unless a term used in the claims is defined above, it should be given the broadest definition that one skilled in the art would give that term as reflected in at least one publication or issued patent. Furthermore, all patents, test procedures, and other documents cited in this application are incorporated by reference in their entirety to the extent that their disclosures are not inconsistent with this application, and for all authorities to which such incorporation is permitted. While the forgoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, the scope of which is determined by the claims that follow.

Claims

1. 1. A dehydrogenation process using a regenerated catalyst produced by a process for regenerating an at least partially deactivated catalyst comprising a Group 10 element, an inorganic support, and contaminants, wherein the Group 10 element has a concentration in the range of 0.06 wt % to 6 wt %, based on the weight of the inorganic support, and the regeneration process comprises: (I) A heated gas mixture containing H at a concentration of more than 5 mole percent based on the total moles of the gas mixture. 2 heating the at least partially deactivated catalyst with the heated gas mixture containing O to form a procatalyst; (II) An oxidative gas containing not more than 5 mole percent H, based on the total moles of the gas. 2 providing the oxidizing gas comprising O; (III) contacting the procatalyst with the oxidizing gas at an oxidation temperature in the range of 620°C to 1,000°C for a duration of at least 30 seconds to form an oxidized procatalyst; (IV) obtaining the regenerated catalyst from the oxidized precursor catalyst; Including, Step (IV) (IVc-1) contacting the oxidized precursor catalyst with an H 2 -containing atmosphere to produce a reduced catalyst; (IVd) obtaining the regenerated catalyst from the reduced catalyst; Including, The dehydrogenation process (VI) contacting a hydrocarbon-containing feed with the regenerated catalyst to effect one or more of dehydrogenation, dehydroaromatization, and dehydrocyclization of at least a portion of the hydrocarbon-containing feed to produce the at least partially deactivated catalyst comprising the Group 10 element, the inorganic support, and the contaminants, and an effluent comprising one or more upgraded hydrocarbons and molecular hydrogen, wherein the hydrocarbon feed comprises one or more C2-C16 linear or branched alkanes, one or more C4-C16 cyclic alkanes, one or more C8-C16 alkyl aromatic hydrocarbons, or a mixture thereof; (VII) repeating steps (I) through (IV), wherein additional oxidized pre-catalyst is produced in step (III), and additional regenerated catalyst is obtained from the additional oxidized pre-catalyst in step (IV); (VIII) contacting an additional amount of said hydrocarbon-containing feed with at least a portion of said additional regenerated catalyst to produce additional at least partially deactivated catalyst and an additional effluent; Including, The process wherein the cycle time from contacting the hydrocarbon-containing feed with the regenerated catalyst in step (VI) to contacting the additional amount of hydrocarbon-containing feed with the additional regenerated catalyst in step (VIII) is ≦1 hour.

2. 10. The process of claim 1, wherein the heated gas mixture is generated by burning a fuel with an oxidizing gas.

3. The fuel is H 2 , CO, and at least one of hydrocarbons, and the oxidizing gas is O 2 3. The process of claim 2, comprising:

4. 10. The process of claim 1, wherein the Group 10 element comprises Pt.

5. 10. The process of claim 1, wherein the inorganic support comprises at least 0.5 wt. % of a Group 4 element, based on the weight of the inorganic support.

6. 10. The process of claim 1, wherein the at least partially deactivated catalyst further comprises one or more elements having an atomic number of 57 to 71.

7. 10. The process of claim 1, wherein the at least partially deactivated catalyst further comprises up to 10 wt. % of a promoter based on the weight of the inorganic support, the promoter comprising one or more of the following elements: Sn, Ga, Zn, Ge, In, Re, Ag, Au, Cu, combinations thereof, or mixtures thereof.

8. Step (II) (IIa) providing the oxidizing gas at a temperature below the oxidation temperature; (IIb) preheating the oxidizing gas to a temperature greater than the temperature of the procatalyst prior to contacting in step (III); 2. The process of claim 1, comprising:

9. moreover, (V) heating the oxidizing gas, the procatalyst, or both during step (III) by using a radiant / conductive heat source, a heat exchanger, or a combination thereof.

2. The process of claim 1, comprising:

10. Step (IV) (IVa) The oxidation precursor catalyst is 2 with a first stripping gas free of (IVb) obtaining the regenerated catalyst from the stripped oxidized precatalyst; 2. The process of claim 1, comprising:

11. Step (IV) (IVc-2) contacting the stripped oxidized precursor catalyst with an H 2 -containing atmosphere to produce a reduced catalyst; (IVd) obtaining the regenerated catalyst from the reduced catalyst; 11. The process of claim 10, comprising:

12. Step (IVd) 12. The process of claim 1 or 11, comprising the step of (IVd-1) contacting the reduced catalyst with a second stripping gas to produce the regenerated catalyst.

13. Step (IVc-1) or (IVc-2) is carried out at a temperature of the oxidation procatalyst that is higher than the use temperature of the regenerated catalyst, and step (IVd) further comprises: (IVd-2) Cooling the reduced catalyst or the regenerated catalyst to the use temperature for a duration of 10 minutes or less 13. The process of claim 12, comprising:

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