CN117561118A

CN117561118A - Method for regenerating catalyst and upgrading alkane and/or alkylaromatic hydrocarbons

Info

Publication number: CN117561118A
Application number: CN202280045378.6A
Authority: CN
Inventors: 鲍筱颖; C·A·迪亚兹乌鲁蒂亚; 柏传盛; J·S·克尔曼; K·H·库克莱尔
Original assignee: ExxonMobil Chemical Patents Inc
Current assignee: ExxonMobil Chemical Patents Inc
Priority date: 2021-06-02
Filing date: 2022-05-06
Publication date: 2024-02-13

Abstract

A method of regenerating an at least partially deactivated catalyst that may include a group 10 element, an inorganic support, and a contaminant. The group 10 element may have a concentration of 0.001 wt% to 6 wt% based on the weight of the inorganic support. The method may include (I) using a concentration based on the total moles in the mixture>5mol% of H ₂ The heated gas mixture of O heats the deactivated catalyst to produce a precursor catalyst. The method may further include (II) providing a catalyst comprising ∈5mol% H based on the total moles in the oxidizing gas ₂ An oxidizing gas of O, and (III) reacting the procatalyst with an oxidizing agent at an oxidizing temperatureThe gas is contacted for a duration of at least 30 seconds to produce an oxidized precursor catalyst. The method may further comprise (IV) obtaining a regenerated catalyst from the oxidized precursor catalyst.

Description

Method for regenerating catalyst and upgrading alkane and/or alkylaromatic hydrocarbons

Cross Reference to Related Applications

The present application claims priority and benefit from U.S. provisional application number 63/195,966, having a filing date of 2021, month 6, and 2, and U.S. provisional application number 63/328,923, having a filing date of 2022, month 4, 8, the disclosures of which are incorporated herein by reference in their entireties.

Technical Field

The present disclosure relates to methods of regenerating catalysts and upgrading alkanes and/or alkylaromatic hydrocarbons.

Background

Catalytic dehydrogenation, dehydroaromatization and dehydrocyclization of alkanes and/or alkylaromatic hydrocarbons are industrially important chemical conversion processes that are endothermic and equilibrium limited. Alkanes such as C can be made by a variety of different supported catalyst systems such as Pt-based, cr-based, ga-based, V-based, zr-based, in-based, W-based, mo-based, zn-based and Fe-based systems ₂ -C ₁₂ Dehydrogenation of alkanes and/or alkylaromatics such as ethylbenzene. Among existing propane dehydrogenation processes, a process uses an alumina-supported chromia catalyst that provides one of the highest propylene yields (55% propane conversion at 90% propane selectivity) of about 50% obtained at a temperature of about 560 ℃ to 650 ℃ and at a low pressure of 20 kPa-absolute to 50 kPa-absolute. It is desirable to increase propylene yield without having to operate at such low pressures to increase the efficiency of the dehydrogenation process.

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, the equilibrium yield propylene yield was estimated to be about 74% by simulation at 670 ℃, 100 kPa-absolute, in the absence of any inert/diluent. At such high temperatures, however, the catalyst deactivates very rapidly and/or the propylene selectivity becomes uneconomically low. Rapid catalyst deactivation is believed to be caused by coke deposition onto the catalyst and/or aggregation of the active phase. Coke can be removed by combustion using an oxygen-containing gas, however, aggregation of the active phase is believed to be exacerbated during the combustion process, which rapidly reduces the activity and stability of the catalyst.

Thus, there is a need for improved processes for regenerating at least partially deactivated catalysts and for dehydrogenating, dehydroaromatizing and/or dehydrocyclizing alkanes and/or alkylaromatic hydrocarbons. The present disclosure meets this and other needs.

Disclosure of Invention

Methods of regenerating an at least partially deactivated catalyst and methods of upgrading hydrocarbons are provided. In some embodiments, the method may be used to regenerate an at least partially deactivated catalyst that may include group 10 elements, inorganic carriers, and contaminants. The group 10 element may have a concentration in the range of 0.001 wt% to 6 wt% based on the weight of the inorganic support. The method may include (I) using a catalyst that may include H at a concentration greater than 5 mole percent based on the total moles in the heated gas mixture ₂ The heated gas mixture of O heats the at least partially deactivated catalyst to produce a precursor catalyst. The method may further include (II) providing that the catalyst may include not more than 5mol% H based on the total moles in the oxidizing gas ₂ Oxidizing gas of O. The method may further comprise (III) contacting the procatalyst with an oxidizing gas at an oxidizing temperature in the range of 620 ℃ to 1,000 ℃ for a duration of at least 30 seconds, preferably at least 1 minute, preferably at least 5 minutes, thereby producing an oxidized procatalyst. The method may further comprise (IV) obtaining a regenerated catalyst from the oxidized precursor catalyst.

In other embodiments, a process for upgrading hydrocarbons may include (I) contacting a hydrocarbon-containing feed with a catalyst that may include a group 10 element and an inorganic support to effect dehydrogenation of at least a portion of the hydrocarbon-containing feedOne or more of dehydroaromatization and dehydrocyclization, thereby producing an at least partially deactivated catalyst that may comprise group 10 elements, inorganic supports and contaminants and an effluent that may comprise one or more upgraded hydrocarbons and molecular hydrogen. The hydrocarbon-containing feed may include C ₂ -C ₁₆ One or more of linear or branched alkanes, or C ₄ -C ₁₆ One or more of the cyclic alkanes, C ₈ -C ₁₆ One or more of alkyl aromatic hydrocarbons, or mixtures thereof. The group 10 element may have a concentration in the range of 0.001 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 ℃ to 900 ℃. The one or more upgraded hydrocarbons may include at least one of dehydrogenated hydrocarbons, dehydroaromatized hydrocarbons, and dehydrocyclized hydrocarbons. The method may further comprise (II) using a catalyst comprising H in a concentration of greater than 5 mole percent based on the total moles of the heated gas mixture ₂ The heated gas mixture of O heats the at least partially deactivated catalyst to produce a precursor catalyst. The method may further include (III) providing that the catalyst may include not more than 5mol% H based on the total moles in the oxidizing gas ₂ Oxidizing gas of O. The method may further comprise (IV) contacting the precursor catalyst with an oxidizing gas at an oxidation temperature in the range of 620 ℃ to 1,000 ℃ for a duration of at least 30 seconds to produce an oxidized precursor catalyst. The method may further comprise (V) obtaining a regenerated catalyst from the oxidized precursor catalyst. The process may further comprise (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 additional effluent.

Brief description of the drawings

Figure 1 shows that the catalyst used in example 6 can be effectively regenerated using some two-step regeneration scheme for 80+ cycles.

Figure 2 shows that isobutane dehydrogenation using the catalyst was stable over 30+ cycles, although the catalyst was subjected to a regeneration temperature of 800 ℃.

Fig. 3 shows that the performance of the catalyst used in example 19 was stable over 30+ cycles, although the catalyst was subjected to a regeneration temperature of 800 ℃.

Fig. 4 shows that the performance of the first catalyst used in example 20 was stable over 20+ cycles, although the catalyst was subjected to a regeneration temperature of 800 ℃.

Fig. 5 shows that the performance of the second catalyst used in example 20 was stable over 30+ cycles, although the catalyst was subjected to a regeneration temperature of 800 ℃.

Fig. 6 shows that the performance of the catalyst used in example 26 was stable over 20+ cycles, although the catalyst was subjected to a regeneration temperature of 800 ℃.

Figure 7 shows that the performance of comparative catalyst 1 is continuously deactivated even though the regeneration temperature (620 ℃) is much lower than in the other examples.

Figure 8 shows that the catalyst composition (catalyst 33) maintains its performance for 204 cycles.

Detailed description of the preferred embodiments

Various specific embodiments, variations and examples of the invention will now be described, including preferred embodiments and definitions employed for the purpose of understanding the claimed invention. While the following detailed description presents specific preferred embodiments, those skilled in the art will appreciate that these embodiments are exemplary only, and that the invention may be practiced in other ways. For purposes of determining infringement, the scope of the invention will refer to any one or more of the appended claims, including equivalents thereof 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 inventions defined by the claims.

In this disclosure, a method is described as comprising at least one "step". It should be understood that each step is an action or operation that may be performed one or more times in a continuous or discontinuous manner in the method. The steps in a method may be performed sequentially as their listed order, with or without overlapping one or more other steps, or in any other order, as appropriate, unless specified to the contrary or the context clearly indicates otherwise. In addition, one or more or even all steps may be performed simultaneously for the same or different batches of material. For example, in a continuous process, while the first step in the process may be performed with respect to the feedstock just fed to the beginning of the process, the second step may be performed simultaneously with respect to intermediate material resulting from the treatment of the feedstock fed to the process at an earlier time in the first step. Preferably, the steps are performed in the order described.

Unless otherwise indicated, all numbers expressing quantities in this disclosure are to be understood as being modified in all instances by the term "about". It should also be understood that the precise numerical values used in the specification and claims constitute specific embodiments. Efforts have been made to ensure accuracy in the data in the examples. However, it should be appreciated that any measured data inherently contains certain levels of error due to limitations of the techniques and/or equipment used to obtain the measurement results.

Certain embodiments and features are described herein using a set of upper numerical limits and a set of lower numerical limits. It will be appreciated that ranges including any two values, such as any lower value in combination with any upper value, any combination of two lower values, and/or any combination of two upper values, are contemplated unless otherwise indicated.

As used herein, the indefinite article "a" or "an" means "at least one" unless specified to the contrary or the context clearly indicates otherwise. Thus, unless specified to the contrary or the context clearly indicates that only one reactor or conversion zone is used, embodiments using "reactors" or "conversion zones" include embodiments using one, two, or more reactors or conversion zones.

The term "hydrocarbon" means (i) any compound consisting of hydrogen and carbon atoms or (ii) any mixture of two or more such compounds in (i). The term "Cn hydrocarbon", where n is a positive integer, means (i) any hydrocarbon compound that contains carbon atom(s) in its molecule in total n, or (ii) any mixture of two or more such hydrocarbon compounds in (i). Thus, the C2 hydrocarbon may be ethane, ethylene, acetylene, or a mixture of at least two of these compounds in any ratio. "Cm to Cn hydrocarbons" or "Cm-Cn hydrocarbons", 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 thereof. Thus, a "C2 to C3 hydrocarbon" or "C2-C3 hydrocarbon" may be any of ethane, ethylene, acetylene, propane, propylene, propyne, propadiene, cyclopropane, and any mixture of two or more thereof in any ratio between the components. The "saturated C2-C3 hydrocarbon" may be ethane, propane, cyclopropane, or any mixture of two or more thereof in any ratio. "Cn+ hydrocarbons" means (i) any hydrocarbon compound containing carbon atom(s) in its molecule in a total of at least n, or (ii) any mixture of two or more such hydrocarbon compounds in (i). "Cn-hydrocarbon" means (i) any hydrocarbon compound containing carbon atoms in its molecule in a total number of up to n, or (ii) any mixture of two or more such hydrocarbon compounds in (i). By "Cm hydrocarbon stream" is meant a hydrocarbon stream consisting essentially of Cm hydrocarbon(s). By "Cm-Cn hydrocarbon stream" is meant a hydrocarbon stream consisting essentially of Cm-Cn hydrocarbon(s).

For the purposes of this disclosure, the nomenclature of the elements is according to the version of the periodic table of the elements (according to the new notation) as described in Hawley's Condensed Chemical Dictionary, 16 th edition, john Wiley & Sons, inc., (2016), appendix V. For example, group 2 elements include Mg, group 8 elements include Fe, group 9 elements include Co, group 10 elements include Ni, and group 13 elements include Al. The term "metalloid" as used herein refers to the following elements: B. si, ge, as, sb, te and At. In the present disclosure, when a given element is indicated as being present, it may be present in elemental state or as any compound thereof, unless otherwise specified or clear from context.

The term "alkane" means a saturated hydrocarbon. The term "cyclic alkane" means a saturated hydrocarbon containing a cyclic carbocyclic ring in the molecular structure. The alkane may be linear, 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.

The term "enriched" when used in a phrase such as "enriched in X" or "enriched in X" means that the stream comprises a higher concentration of material X than in the feed material fed to the same device from which the stream originates, in terms of the output stream obtained from the device such as the conversion zone. The term "lean" when used in a phrase such as "lean X" or "lean X" means that, in terms of an output stream obtained from a plant such as a conversion zone, the stream comprises a lower concentration of material X than in feed material fed to the same plant from which the stream originates.

The term "mixed metal oxide" refers to a composition comprising oxygen atoms and at least two different metal atoms mixed on an atomic scale. For example, "mixed Mg/Al metal oxide" has O, mg and Al atoms mixed on an atomic scale and having the general formulaIs substantially the same or identical, wherein A is a counter anion having a negative charge n and x is a radical derived from the calcination of Mg/Al hydrotalcite>0 to 0<Within the range of 1, and m is ≡0. From nm-sized MgO particles and nm-sized Al mixed together ₂ O ₃ The material of the particle composition is not a mixed metal oxide, as Mg and Al atoms are not mixed on an atomic scale but instead on a nm scale.

The term "selectivity" refers to the productivity (based on moles of carbon) of a given compound in a catalytic reaction. By way of example, the phrase "alkane conversion reaction has 100% selectivity to alkene" means that 100% of the alkane (on a carbon mole basis) converted in the reaction is converted to alkene. The term "conversion" when used in connection with a given reactant means the amount of reactant consumed in the reaction. For example, when the reactant is specified to be propane, 100% conversion means 100% of the propane is consumed in the reaction. In another example, when the reactant is specified to be propane, if one mole of propane is converted to one mole of methane and one mole of ethylene, then the methane selectivity is 33.3% and the ethylene selectivity is 66.7%. Yield (on a carbon mole basis) is conversion times selectivity.

Hydrocarbon upgrading and catalyst regeneration process

The hydrocarbon-containing feed may be or include, but is not limited to, one or more alkanes, such as C ₂ -C ₁₆ Linear or branched alkanes and/or C ₄ -C ₁₆ Cyclic alkanes, and/or one or more alkylaromatic hydrocarbons, e.g. C ₈ -C ₁₆ Alkyl aromatic hydrocarbons. In some embodiments, the hydrocarbon-containing feed may optionally include 0.1 to 50% by volume steam, based on any C in the hydrocarbon-containing feed ₂ -C ₁₆ Alkanes and any C ₈ -C ₁₆ Total volume of alkyl aromatic hydrocarbon. In other embodiments, the hydrocarbon-containing feed may comprise<0.1% by volume of steam or may be free of steam, based on any C in the hydrocarbon-containing feed ₂ -C ₁₆ Alkanes and any C ₈ -C ₁₆ Total volume of alkyl aromatic hydrocarbon. The hydrocarbon-containing feed can be contacted with a catalyst comprising a group 10 element, such as Pt, 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 the group 10 element, the inorganic support, and contaminants, such as coke, and an effluent that can comprise one or more upgraded hydrocarbons and molecular hydrogen.

The one or more upgraded hydrocarbons may be or may include, but are not limited to, one or more dehydrogenated hydrocarbons, one or more dehydroaromatized hydrocarbons, one or more dehydrocyclized hydrocarbons, or mixtures thereof. The hydrocarbon-containing feed and the catalyst may be contacted at a temperature in the range of 300 ℃ to 900 ℃. In some embodiments, the hydrocarbon-containing feed and catalyst may be contacted for a period of time 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 the catalyst may be contacted at a hydrocarbon partial pressure of at least 20 kPa-absolute, where the hydrocarbon partial pressure is any C in the hydrocarbon-containing feed ₂ -C ₁₆ Alkanes and any C ₈ -C ₁₆ Total partial pressure of alkyl aromatic hydrocarbon. The catalyst may include 0.001 wt% to 6 wt% of a group 10 element such as Pt, based on the weight of the inorganic support.

The procatalyst may beObtained from an at least partially deactivated catalyst. In some embodiments, the at least partially deactivated catalyst may be provided directly as a procatalyst. In other embodiments, the procatalyst may be obtained by: using H in a concentration of more than 5mol%, based on the total moles in the heated gas mixture ₂ The heated gas mixture of O heats the at least partially deactivated catalyst to produce a precursor catalyst. In some embodiments, the heated gas mixture may be produced by combusting at least a portion of contaminants disposed on the at least partially deactivated catalyst, such as coke, and/or the remaining hydrocarbon-containing feed with an oxidizing gas. In some embodiments, the heated gas mixture may be produced by combusting a fuel with an oxidizing gas. In other embodiments, the heated gas mixture may be produced by combusting at least a portion of the contaminants and fuel disposed on the at least partially deactivated catalyst with an oxidizing gas. In other embodiments, H may be included at a concentration greater than 5mol% ₂ H of O ₂ The heated gas mixture of O may be H ₂ O, e.g. having more than 5mol% H ₂ O is provided by heated air. The fuel may be or include, but is not limited to, H ₂ At least one of CO and hydrocarbon. The oxidizing gas may be or include, but is not limited to O ₂ 、O ₃ CO, or any mixture thereof. In some embodiments, the heated gas mixture may contact a partially deactivated catalyst<5min、<2min、<1min、<30s、<10s、<5s、<1s、<0.5s、<Duration of 0.1 s.

An oxidizing gas may be provided. The oxidizing gas may include not more than 5mol% H ₂ O, not more than 4.5mol% H ₂ O, not more than 4mol% of H ₂ O, not more than 3.5mol% of H ₂ O, not more than 3mol% of H ₂ O, not more than 2.5mol% H ₂ O, not more than 2mol% of H ₂ O, not more than 1.7mol% H ₂ O, not more than 1.5mol% H ₂ O, not more than 1.3mol% H ₂ O, not more than 1mol% of H ₂ O, not more than 0.7mol% H ₂ O, not more than 0.5mol% H ₂ O, not more than 0.3mol% H ₂ O, or not greater than0.1mol% of H ₂ O, based on the total moles in the oxidizing gas. Whether the at least partially deactivated catalyst is provided directly as a precursor catalyst or the at least partially deactivated catalyst is heated using a heated gas mixture, the precursor catalyst may be contacted with an oxidizing gas.

It has been surprisingly and unexpectedly found that whether an at least partially deactivated catalyst is provided directly as a precursor catalyst or heated using a heated gas mixture to heat the at least partially deactivated catalyst to produce a precursor catalyst, the precursor catalyst is reacted with a catalyst comprising no more than 5 mole percent H ₂ The contact of the oxidizing gas with O can significantly improve the activity and/or selectivity of the regenerated catalyst. Without wishing to be bound by theory, it is believed that H present in the oxidizing gas ₂ O can significantly reduce the effectiveness of Pt redispersion and thus the effectiveness of the regenerated catalyst.

The procatalyst may be contacted with an oxidizing gas at an oxidizing temperature in the range of from 620 ℃, 650 ℃, 675 ℃, 700 ℃, or 750 ℃ to 775 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃, or 1,000 ℃ to produce an oxidized procatalyst. The procatalyst may be contacted with the 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, or at least 30 minutes to produce an oxidized procatalyst. In some embodiments, the procatalyst may be contacted with the oxidizing gas for a duration in the range of from 30 seconds, 1 minute, 5 minutes, or 10 minutes to 30 minutes, 60 minutes, or 120 minutes to produce an oxidized procatalyst. In some embodiments, the precursor catalyst and the oxidizing gas can 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 an oxidized precursor catalyst. For example, the procatalyst and the oxidizing gas may be contacted with each other for a duration in the range of 2 seconds to 2 hours to produce an oxidized procatalyst. In some embodiments, the precursor catalyst and oxidizing gas may be contacted for a duration sufficient to remove ≡50 wt%, ≡75 wt%, or ≡90 wt% or >99 wt% of contaminants such as coke disposed on the precursor catalyst.

The precursor catalyst and the oxidizing gas may be contacted with each other at an oxidizing gas partial pressure in the range 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 precursor catalyst. In some embodiments, the partial pressure of the oxidizing gas during contact with the precursor catalyst may be in the 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 to produce an oxidized precursor catalyst.

Without wishing to be bound by theory, it is believed that at least a portion of the group 10 elements, such as Pt, disposed on the precursor catalyst may aggregate as compared to the catalyst prior to contact with the hydrocarbon-containing feed. It is believed that at least a portion of the group 10 element may redisperse around the inorganic support as at least a portion of the contaminants on the procatalyst may burn during contact of the procatalyst with the oxidizing gas. Redispersing at least a portion of the aggregated group 10 element may increase activity and improve the stability of the catalyst over many cycles.

In some embodiments, the oxidizing gas may be provided at a temperature below the oxidation temperature, and the oxidizing gas may be preheated to a temperature above the temperature of the precursor catalyst prior to contacting the precursor catalyst with the oxidizing gas at the oxidation temperature. In some embodiments, the oxidizing gas may be preheated by using a radiant/conductive heat source, a heat exchanger, or a combination thereof. In other embodiments, the oxidizing gas, the precursor catalyst, or both the oxidizing gas and the precursor catalyst may be heated by using a radiant/conductive heat source, a heat exchanger, or a combination thereof. In other words, the precursor catalyst and/or oxidizing gas may be heated separately and then brought into contact 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 may include one or more electrical heating elements.

Regenerated catalyst may be obtained from oxidized precursor catalyst. In some embodiments, the oxidized precursor catalyst may be provided directly as a regenerated catalyst. In some embodiments, the oxidized procatalyst may optionally be free of O ₂ Is contacted with a first stripping gas to produce a stripped oxidized precursor catalyst, and the regenerated catalyst is obtainable from the stripped oxidized precursor catalyst. The first stripping gas may be or include, but is not limited to, CO ₂ 、N ₂ 、C ₁ -C ₄ Hydrocarbons, H ₂ O, he, ne, ar, or any mixtures thereof. In some embodiments, the stripped oxidized precursor catalyst may be provided directly as a regenerated catalyst.

In some embodiments, at least a portion of the group 10 elements, e.g., pt, in the oxidized precursor catalyst 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 the stripped oxidized procatalyst may be mixed with a catalyst containing H ₂ The atmosphere contacts to produce a reduced catalyst. In other embodiments, the oxidized procatalyst or the stripped oxidized procatalyst may be combined with a catalyst containing H ₂ 、CO、CH ₄ 、C ₂ H ₆ 、C ₃ H ₈ 、C ₂ H ₄ 、C ₃ H ₆ The atmosphere of steam or a mixture thereof to produce a reduced catalyst. In some embodiments, the atmosphere in contact with the oxidized precursor catalyst may also include an inert gas such as Ar, ne, he, N ₂ 、CO ₂ 、H ₂ O or mixtures thereof. In such embodiments, the reduced catalyst is one in which, in comparison to the group 10 element of the oxidized precursor catalystMay be reduced to a lower oxidation state, such as an elemental state.

In some embodiments, the oxidized procatalyst or the stripped oxidized procatalyst may be reacted with the H-containing catalyst at a temperature in the range of from 400 ℃, 450 ℃,500 ℃, 550 ℃, 600 ℃, 620 ℃, 650 ℃, or 670 ℃ to 720 ℃, 750 ℃, 800 ℃, or 900 DEG C ₂ Atmosphere or contain H ₂ 、CO、CH ₄ 、C ₂ H ₆ 、C ₃ H ₈ 、C ₂ H ₄ 、C ₃ H ₆ An atmosphere contact of steam or a mixture thereof. Oxidized or stripped oxidized precursor catalyst and H-containing catalyst ₂ Atmosphere or contain H ₂ 、CO、CH ₄ 、C ₂ H ₆ 、C ₃ H ₈ 、C ₂ H ₄ 、C ₃ H ₆ The atmosphere of steam or mixtures thereof may be contacted for a duration in the range 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. Oxidized or stripped oxidized precursor catalyst and H-containing catalyst ₂ Atmosphere or contain H ₂ 、CO、CH ₄ 、C ₂ H ₆ 、C ₃ H ₈ 、C ₂ H ₄ 、C ₃ H ₆ The atmosphere of steam or mixtures thereof may be contacted under a partial pressure of the reducing agent of 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, wherein the reducing agent includes any H ₂ 、CO、CH ₄ 、C ₂ H ₆ 、C ₃ H ₈ 、C ₂ H ₄ 、C ₃ H ₆ And steam. In other embodiments, the partial pressure of the reducing agent may be in the range of from 0.1 kPa-absolute, 1 kPa-absolute, 5 kPa-absolute, 10 kPa-absolute, 20 kPa-absolute, 50 kPa-absolute, 100 kPa-absoluteA pair value, 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, wherein the reducing agent includes any H ₂ 、CO、CH ₄ 、C ₂ H ₆ 、C ₃ H ₈ 、C ₂ H ₄ 、C ₃ H ₆ And steam.

In some embodiments, the oxidized procatalyst or the stripped oxidized procatalyst may be mixed with a catalyst containing H ₂ The atmosphere is contacted at a temperature above the use temperature of the regenerated catalyst. In such embodiments, the reduced catalyst may be cooled to a use temperature. In some embodiments, the reduced catalyst may be cooled to the use temperature for a duration of no greater than 20 minutes, no greater than 15 minutes, no greater than 10 minutes, no greater than 7 minutes, no greater than 5 minutes, no greater than 2 minutes, no greater than 1 minute, no greater than 30 seconds, no greater than 10 seconds, no greater than 5 seconds, no greater than 2 seconds, no greater than 1 second, no greater than 0.1 seconds, no greater than 0.01 seconds, or no greater than 0.001 seconds. The temperature at which the catalyst is used is the temperature at which the hydrocarbon-containing feed or an additional amount of hydrocarbon-containing feed is contacted with the catalyst or 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 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 directly as a regenerated catalyst. In other embodiments, the reduced catalyst may be contacted with a second stripping gas to produce a regenerated catalyst. The second stripping gas may be or include, but is not limited to, CO ₂ 、N ₂ 、C ₁ -C ₄ Hydrocarbons, H ₂ O, he, ne, ar, or any mixtures thereof.

At least a portion of the regenerated catalyst, fresh or fresh catalyst, or a mixture thereof may be contacted with an additional amount of hydrocarbon-containing feed in the reaction 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 with fresh or fresh 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 contacts at least an oxidizing gas to produce an oxidized precursor catalyst, which may be provided directly as a regenerated catalyst, or contacts at least an oxidizing gas and optionally a reducing gas to produce a regenerated catalyst, and the first cycle ends when the regenerated catalyst is contacted with an additional amount of hydrocarbon-containing feed. If the first stripping gas and/or the second stripping gas or any other stripping gas(s) are used between the flow of hydrocarbon-containing feed and oxidizing gas, between oxidizing gas and reducing gas (if used), between oxidizing gas and additional amount of hydrocarbon-containing feed, and/or between reducing gas (if used) and additional amount of hydrocarbon-containing feed, the period of time during which such stripping gas(s) are used will be included in the period of time included in the cycle time. As such, the cycle time from contacting the hydrocarbonaceous feed with the catalyst in the step to contacting an additional amount of hydrocarbonaceous feed with regenerated catalyst can be 5 hours or less.

The catalyst comprising a group 10 element, such as Pt, and an inorganic support, can retain sufficient activity and stability after a number of cycles, such as at least 15, at least 20, at least 30, at least 40, at least 50, at least 60, at least 70, at least 100, at least 125, at least 150, at least 175, or at least 200 cycles, wherein each cycle lasts for less than 5 hours, less than 4 hours, less than 3 hours, less than 2 hours, less than 1 hour, less than 50 minutes, less than 45 minutes, less than 30 minutes, less than 15 minutes, less than 10 minutes, less than 5 minutes, less than 1 minute, less than 30 seconds, or less than 10 seconds. In some embodiments, the cycle time may be from 5 seconds, 30 seconds, 1 minute, or 5 minutes to 10 minutes, 20 minutes, 30 minutes, 45 minutes, 50 minutes, 70 minutes, 2 hours, 3 hours, 4 hours, or 5 hours. In some embodiments, after catalyst performance is stable (sometimes the first few cycles may have relatively poor or relatively good performance, but performance may eventually stabilize), the process may produce a first upgraded hydrocarbon product yield when initially contacted with the hydrocarbonaceous feed, such as propylene when the hydrocarbonaceous feed comprises propane, at an upgraded hydrocarbon selectivity, such as propylene of ∈75% >, > 80% >, > 85% >, or ∈90%, or >95%, and may have a second upgraded hydrocarbon product yield when the last cycle (total of at least 15 cycles) is completed, which is 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%, at an upgraded hydrocarbon selectivity, such as propylene of ∈75% >, > 80% >, > 85%, or ∈90%, or >95%.

In some embodiments, when the hydrocarbonaceous feed comprises propane and the upgraded hydrocarbon comprises propylene, contacting the hydrocarbonaceous feed with the catalyst composition can produce a propylene yield of ≡75%,. Gtoreq.80%,. Gtoreq.85%,. Gtoreq.90%,. Gtoreq.93%, or ≡95%, of ≡48%,. Gtoreq.49%,. Gtoreq.50%,. Gtoreq.51%,. Gtoreq.52%,. Gtoreq.53%,. Gtoreq.54%,. Gtoreq.55%,. Gtoreq.56%,. Gtoreq.57%,. Gtoreq.58%,. Gtoreq.59%,. Gtoreq.60%,. Gtoreq.61%,. Gtoreq.62%,. Gtoreq.63%,. Gtoreq.64%,. Gtoreq.65%, or ≡66%. In some embodiments, when the hydrocarbon-containing feed comprises propane and the upgraded hydrocarbon comprises propylene, contacting the hydrocarbon-containing feed with the catalyst may selectively produce at least 48%, at least 49%, at least 50%, at least 51%, 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% propylene yield 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, at least 125, at least 150, at least 175, or at least 200 cycles of propylene. In other embodiments, when contacting a hydrocarbonaceous feed comprising at least 70 vol.%, at least 75 vol.%, at least 80 vol.%, at least 85 vol.%, at least 90 vol.%, or at least 95 vol.% propane based on the total volume of the hydrocarbonaceous feed at a partial pressure of propane of at least 20 kPa-absolute, a propylene yield of at least 48%, at least 49%, at least 50%, at least 51%, 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% 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, at least 125, at least 150, at least 175, or at least 200 cycles is obtained 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 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%, 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, at least 125, at least 150, at least 175, or at least 200 cycles, propylene selectivities of at least 75%, at least 80%, at least 85%, at least 90%, or at least 95% by further optimizing the composition of the support and/or adjusting one or more process conditions. In some embodiments, the propylene yield is obtained when the catalyst is contacted with the hydrocarbon feed at a temperature of at least 620 ℃, at least 630 ℃, at least 640 ℃, at least 650 ℃, at least 655 ℃, at least 660 ℃, at least 670 ℃, at least 680 ℃, at least 690 ℃, at least 700 ℃, or at least 750 ℃ for at least 15 times, at least 20 times, at least 30 times, at least 40 times, at least 50 times, at least 60 times, at least 70 times, at least 100 times, at least 125 times, at least 150 times, at least 175 times, or at least 200 times.

Systems suitable for carrying out the methods disclosed herein may include systems known in the art, such as the fixed bed reactors disclosed in WO publication No. WO 2017078894; 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 No. 2004/0082824;2008/0194891 a fluidized riser reactor and/or a downer reactor; and U.S. patent No. 8,754,276; countercurrent reactors as disclosed in U.S. patent application publication No. 2015/0065767 and WO 2013169461.

Catalyst

The catalyst may include 0.001 wt%, 0.002 wt%, 0.003 wt%, 0.004 wt%, 0.005 wt%, 0.006 wt%, 0.007 wt%, 0.008 wt%, 0.009 wt%, 0.01 wt%, 0.015 wt%, 0.02 wt%, 0.025 wt%, 0.03 wt%, 0.035 wt%, 0.04 wt%, 0.045 wt%, 0.05 wt%, 0.055 wt%, 0.06 wt%, 0.065 wt%, 0.07 wt%, 0.075 wt%, 0.08 wt%, 0.085 wt%, 0.09 wt%, 0.095 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%, 5 wt%, or 6 wt% of a group 10 element disposed on an inorganic support, based on the inorganic support. In some embodiments, the catalyst composition may include +.5.5 wt%, +.4.5 wt%, +.3.5 wt%, +.2.5 wt%, +.1 wt%, +.0.9 wt%, +.0.8 wt%, +.0.7 wt%, +.0.6 wt%, +.0.5 wt%, +.0.4 wt%, +.0.3 wt%, +.0.2 wt%, +.0.15 wt%, +.0.1 wt%, +.0.09 wt%, +.0.08 wt%, +.0.07 wt%, +.0.06 wt%, +.0.05 wt%, +.0.04 wt%,.0.03 wt%,.02 wt%, +.0.009 wt%,.008 wt%,.006 wt%,.0.003 wt%,.0.002 wt%,.0.0.004 wt%,.10 wt%,.0.10 wt% based on the inorganic carrier. In some embodiments, the catalyst may comprise >0.001、>0.003 wt%,>0.005 wt%,>0.007、>0.009 wt.%,>0.01 wt%、>0.02 wt%,>0.04 wt%,>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% by weight of a group 10 element disposed on the inorganic support, based on the weight of the inorganic support. In some embodiments, the group 10 element may be or may include Ni, pd, pt, combinations thereof, or mixtures thereof. In at least one embodiment, the group 10 element may be or may include Pt. If two or more group 10 elements are provided on the inorganic support, the catalyst may include 0.001 wt%, 0.002 wt%, 0.003 wt%, 0.004 wt%, 0.005 wt%, 0.006 wt%, 0.007 wt%, 0.008 wt%, 0.009 wt%, 0.01 wt%, 0.015 wt%, 0.02 wt%, 0.025 wt%, 0.03 wt%, 0.035 wt%, 0.04 wt%, 0.045 wt%, 0.05 wt%, 0.055 wt%, 0.06 wt%, 0.065 wt%, 0.07 wt%, 0.075 wt%, 0.08 wt%, 0.085 wt%, 0.09 wt%, 0.095 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%, 5 wt%, or 6 wt%, based on the total amount of two or more inorganic supports. In some embodiments, the active component of the catalyst that may enable regeneration of one or more of dehydrogenation, dehydroaromatization, and dehydrocyclization of a hydrocarbon-containing feed comprising C may comprise a group 10 element ₂ -C ₁₆ One or more of linear or branched alkanes, or C ₄ -C ₁₆ One or more of the cyclic alkanes, C ₈ -C ₁₆ One or more of alkyl aromatic hydrocarbons, or mixtures thereof.

The inorganic support may be or include, but is not limited to, one or more group 2 elements, combinations thereof, or mixtures thereof. In some embodiments, the group 2 element may be present in its elemental form. In other embodiments, the group 2 element may be present in the form of a compound. For example, the group 2 element may be present as an oxide, phosphate, halide, halite, sulfate, sulfide, borate, nitride, carbide, aluminate, aluminosilicate, silicate, carbonate, metaphosphate, selenide, tungstate, molybdate, chromite, chromate, dichromate, or silicide. In some embodiments, a mixture of any two or more compounds comprising a group 2 element may exist in different forms. For example, the first compound may be an oxide and the second compound may be an aluminate, wherein the first compound and the second compound include the same or different group 2 elements relative to each other.

The inorganic carrier may include 0.5 wt% or more, 1 wt% or more, 2 wt% or more, 3 wt% or more, 4 wt% or more, 5 wt% or more, 6 wt% or more, 7 wt% or more, 8 wt% or more, 9 wt% or more, 10 wt% or more, 11 wt% or more, 12 wt% or more, 13 wt% or more, 14 wt% or more, 15 wt% or more, 16 wt% or more, 17 wt% or more, 18 wt% or more, 19 wt% or more, 20 wt% or more, 21 wt% or more, 22 wt% or more, 23 wt% or more, 24 wt% or more, 25 wt% or more, 26 wt% or more, 27 wt% or more, 28 wt% or more, 29 wt% or more, 30 wt% or more, 35 wt% or more, 40 wt% or more, 45 wt% or more, 50 wt% or more, 55 wt% or more, 60 wt% or more, or less, 85 wt% or less, or more, and 75 wt% or more of the carrier elements. In some embodiments, the inorganic support may include a group 2 element in a range from 0.5 wt%, 1 wt%, 2 wt%, 2.5 wt%, 3 wt%, 5 wt%, 7 wt%, 10 wt%, 11 wt%, 13 wt%, 15 wt%, 17 wt%, 19 wt%, 21 wt%, 23 wt%, or 25 wt% to 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, or 92.34 wt%, based on the weight of the inorganic support. In some embodiments, the molar ratio of the group 2 element to the group 10 element may range from 0.24, 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, 9,500, 10,000, 15,000, 20,000, 25,000, 30,000, 35,000, 40,000, 45,000, 50,000, 55,000, 60,000, 65,000, 70,000, 75,000, 80,000, 85,000, 90,000, 95,000, 100,000, 200,000, 300,000, 400,000, 500,000, 600,000, 700,000, 800,000, or 900,000.

In some embodiments, the inorganic support may include a group 2 element and Al and may be in the form of a mixed group 2 element/Al metal oxide having O, mg and Al atoms mixed on an atomic scale. In some embodiments, the inorganic support may be or may include a group 2 element and Al in an oxide or one or more oxides of a group 2 element and Al that may be mixed on a nm scale ₂ O ₃ Form of the invention. In some embodiments, the inorganic support may be or may include oxides of group 2 elements such as MgO and Al mixed on the nm scale ₂ O ₃ 。

In some embodiments, the inorganic support may be or may include a first amount of a group 2 element and Al in the form of a mixed group 2 element/Al metal oxide and a second amount of a group 2 element in the form of an oxide of the group 2 element. In such embodiments, the mixed group 2 element/Al metal oxide and the oxide of the group 2 element may be mixed on the nm scale and the group 2 element and Al in the mixed group 2 element/Al metal oxide may be mixed on the atomic scale.

In other embodiments, the inorganic support may be or may include a first amount of a group 2 element and a first amount of Al in the form of a mixed group 2 element/Al metal oxide, a second amount of a group 2 element in the form of an oxide of a group 2 element, and an amount of Al in the form of an oxide of a group 2 element ₂ O ₃ A second amount of Al in form. In such a wayIn an embodiment, a mixed group 2 element/Al metal oxide, group 2 element oxide and Al ₂ O ₃ The group 2 elements and Al in the group 2 element/Al metal oxide that can be mixed on the nm scale and mixed can be mixed on the atomic scale.

In some embodiments, when the inorganic support includes a group 2 element and Al, the weight ratio of the group 2 element to Al in the inorganic support can be in the range from 0.001, 0.005, 0.01, 0.05, 0.1, 0.15, 0.2, 0.3, 0.5, 0.7, or 1 to 3, 6, 12.5, 25, 50, 75, 100, 200, 300, 400, 500, 600, 700, 800, 900, or 1,000. In some embodiments, when the inorganic support comprises Al, the inorganic support may comprise Al in a range from 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.1 wt%, 2.3 wt%, 2.5 wt%, 2.7 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, or 11 wt% to 15 wt%, 20 wt%, 25 wt%, 30 wt%, 40 wt%, 45 wt%, or 50 wt%, based on the weight of the inorganic support.

In some embodiments, the inorganic support may be or may include, but is not limited to, one or more of the following compounds: mg of _w Al ₂ O _3+w Wherein w is a positive number; ca (Ca) _x Al ₂ O _3+x Wherein x is a positive number; sr (Sr) _y Al ₂ O _3+y Wherein y is a positive number; ba (Ba) _z Al ₂ O _3+z Where z is a positive number. BeO; mgO; caO; baO; srO; beCO ₃ ；MgCO ₃ ；CaCO ₃ ；SrCO ₃ 、BaCO ₃ ；CaZrO ₃ ；Ca ₇ ZrAl ₆ O ₁₈ ；CaTiO ₃ ；Ca ₇ Al ₆ O ₁₈ ；Ca ₇ HfAl ₆ O ₁₈ ；BaCeO ₃ The method comprises the steps of carrying out a first treatment on the surface of the One or more magnesium chromates, one or more magnesium tungstates, one or more magnesium molybdates, combinations thereof, and mixtures thereof. In some embodiments, the group 2 element may include Mg and at least a portion of the group 2 element may be in the form of MgO or a mixed oxide including MgO. In some casesIn embodiments, the inorganic support may be or may include, but is not limited to, mgO-Al ₂ O ₃ Mixed metal oxides. In some embodiments, when the inorganic support is MgO-Al ₂ O ₃ When mixed metal oxides, the inorganic support may have a Mg to Al molar ratio equal to 20, 10, 5, 2, 1 to 0.5, 0.1 or 0.01.

Mg _w Al ₂ O _3+w Where w is a positive number, may have a molar ratio of Mg to Al in the range from 0.5, 1, 2, 3, 4 or 5 to 6, 7, 8, 9 or 10 if present as inorganic support or as a component of an inorganic support. In some embodiments, mg _w Al ₂ O _3+w May include MgAl ₂ O ₄ 、Mg ₂ Al ₂ O ₅ Or mixtures thereof. Ca (Ca) _x Al ₂ O _3+x Where x is a positive number, if present as an inorganic support or as a component of an inorganic support, can have a molar ratio of Ca to Al in the range from 1:12, 1:4, 1:2, 2:3, 5:6, 1:1, 12:14, or 1.5:1. In some embodiments, ca _x Al ₂ O _3+x May include tricalcium aluminate, dodecacalcium heptaluminate, monocalcium aluminate, monocalcium dialuminate, monocalcium hexaaluminate, dicalcium aluminate, pentacalcium trialuminate, tetracalcium trialuminate, or any mixtures thereof. Sr (Sr) _y Al ₂ O _3+y Where y is a positive number, and if present as an inorganic support or as a component of an inorganic support, may have a mole ratio of Sr to Al in the range from 0.05, 0.3 or 0.6 to 0.9, 1.5 or 3. Ba (Ba) _z Al ₂ O _3+z Where z is a positive number, it may have a molar ratio of Ba to Al of 0.05, 0.3 or 0.6 to 0.9, 1.5 or 3 if present as inorganic support or as a component of an inorganic support.

In some embodiments, the inorganic support may further include one or more promoters disposed thereon. The promoter may be or include, but is not limited to, sn, ag, 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 the group 10 element disposed on the inorganic support may form a group 10 element-promoter cluster that is dispersible on the inorganic support. The promoters, if present, may improve the selectivity/activity/lifetime of the catalyst for a given upgraded hydrocarbon. In some embodiments, when the hydrocarbon-containing feed comprises propane, the addition of the promoter may improve the propylene selectivity of the catalyst. The catalyst may include an amount of promoter 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 3 wt%, 5 wt%, 7 wt%, or 10 wt%, based on the weight of the inorganic support.

In some embodiments, the inorganic support may further include one or more alkali metal elements disposed thereon. The alkali metal element, if present, may be or include, but is not limited to Li, na, K, rb, cs, combinations thereof, or mixtures thereof. In at least some embodiments, the alkali metal element may be or may include K and/or Cs. The alkali metal element, 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 may include U.S. patent nos. 5,073,662 and 6,313,063; U.S. patent application publication Nos. 2011/0301392 and 2005/0003960; and those described in European patent application publication Nos. EP0486993A1 and EP1073516A 1.

In some embodiments, the inorganic support may further include, but is not limited to, at least one metal element and/or at least one metalloid element selected from groups other than group 2 and group 10 and/or at least one compound thereof, wherein the at least one metal element and/or the at least one metalloid element is not Li, na, K, rb, cs, sn, ag, cu. If the carrier further comprises a compound comprising a metal element and/or a metalloid element selected from the group other than group 2 and group 10, wherein at least one metal element and/or at least one metalloid element is not Li, na, K, rb, cs, sn, ag, cu, then The compounds may be present in the support as oxides, phosphates, halides, haloates, sulphates, sulphides, borates, nitrides, carbides, aluminates, aluminosilicates, silicates, carbonates, metaphosphates, selenides, tungstates, molybdates, chromites, chromates, bichromates or silicides. In some embodiments, suitable compounds comprising a metal element and/or metalloid element selected from groups other than groups 2 and 10 (wherein at least one metal element and/or at least one metalloid element is not Li, na, K, rb, cs, sn, ag, cu) may be or include, but are not limited to, one or more of the following: b (B) ₂ O ₃ 、AlBO ₃ 、Al ₂ O ₃ 、SiO ₂ 、SiC、Si ₃ N ₄ Aluminum silicate, zinc aluminate, znO, VO, V ₂ O ₃ 、VO ₂ 、V ₂ O ₅ 、Ga _s O _t 、In _u O _v 、Mn ₂ O ₃ 、Mn ₃ O ₄ 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.

The preparation of the inorganic support may be accomplished by any known method. For brevity and convenience of description, preparation of mixed oxide (Mg (Al) O or MgO/Al including magnesium and aluminum will be described in more detail ₂ O ₃ ) Inorganic support suitable inorganic supports are those which are suitable for use in inorganic supports. Catalyst synthesis techniques are well known and the following description is for illustrative purposes and is not to be taken as limiting the synthesis of inorganic supports or catalysts. In some embodiments, to make MgO/Al ₂ O ₃ Mixed oxide inorganic supports, mg and Al precursors such as Mg (NO) ₃ ) ₂ And Al (NO) ₃ ) ₃ Mixed together, e.g., ball milled, followed by calcination. In another embodiment, both precursors may be dissolved in H ₂ In O, stirring until dry (wherein heat is optionally applied), followed by calcination to produce the inorganic support. In another embodiment, both precursors may be dissolved in H ₂ In O, alkali and carbonate such as NaOH/Na are added later ₂ CO ₃ To produce hydrotalcite, followed by calcination to produce an inorganic support. In another embodiment, commercially available MgO and Al may be mixed and ball milled ₂ O ₃ Thereby producing an inorganic support. In another embodiment, mg (NO ₃ ) ₂ The precursor is dissolved in H ₂ O, and impregnating the solution into an existing inorganic support such as Al ₂ O ₃ On the inorganic support, it may be dried and calcined to produce the inorganic support. In another embodiment, the ion adsorption may be used to adsorb ions from Mg (NO ₃ ) ₂ Mg loading to existing Al ₂ O ₃ On the inorganic support, followed by liquid-solid separation, drying and calcination to produce the inorganic support. Without wishing to be bound by theory, it is believed that the inorganic support produced via any of the above methods and/or other methods may include (i) Mg and Al mixed together on the nm scale, (ii) Mg and Al in the form of mixed Mg/Al metal oxides, or (iii) a combination of (i) and (ii).

The group 10 metal and any promoter and/or any alkali metal element may 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, tetraamineplatinum nitrate and/or tetraamineplatinum hydroxide, and one or more promoter precursors (if used) such as salts such as SnCl ₄ And/or AgNO ₃ And one or more alkali metal element precursors (if used) such as KNO ₃ KCl and/or NaCl are dissolved in water. The solution may be impregnated onto an inorganic support, followed by drying and calcination. In some embodiments, the group 10 element precursor and optional promoter precursor and/or alkali metal element precursor may be loaded onto the inorganic support simultaneously, or separately, in a sequence separated by a drying and/or calcining step. In other embodiments, the group 10 element and optional promoters and/or alkali metal elements may be loaded onto the inorganic support by chemical vapor deposition, wherein the precursor is volatilized and deposited onto the inorganic support, followed by calcination. In other embodiments, the group 10 element precursor and optional promoter precursor and/or alkali metal precursor may be loaded onto the inorganic support by ion adsorption followed by liquid-solid separation, drying And calcining. Optionally, the catalyst may also be synthesized using a one-pot synthesis process wherein the precursor of the inorganic support, the group 10 metal active phase and the promoter are all wet or dry mixed together, with or without any other additives to aid synthesis, followed by drying and calcination.

Suitable methods that can be used to prepare the catalysts disclosed herein can include those described in U.S. patent No. 4,788,371;4,962,265;5,922,925;8,653,317; EP patent No. EP0098622; journal of Catalysis 94 (1985), pages 547-557; and/or Applied Catalysis 54 (1989), pages 79-90.

The catalyst in the synthesized state may appear as primary particles, agglomerates of primary particles, aggregated primary particles, or a combination thereof when examined under a scanning electron microscope or transmission electron microscope. The primary particles in the as-synthesized catalyst may have an average particle size in the range from 0.2nm, 0.5nm, 1nm, 5nm, 10nm, 25nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 150nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm or 500nm 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, such as a diameter when spherical. In some embodiments, the catalyst particles may have an average cross-sectional length of 0.2nm to 500 μm, 0.5nm to 300 μm, 1nm to 200 μm, 2nm to 100 μm, or 2nm to 500nm, as measured by transmission electron microscopy.

The catalyst may have a molecular weight of from 0.1m 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 Surface area in the range of/g. The surface area of the catalyst was measured after degassing the powder at 350℃for 4 hours using a Micromeritics 3flex instrument according to the Brunauer-Emmett-Teller (BET) method using nitrogen adsorption-desorption (temperature of liquid nitrogen, 77K). Further information about this approach can be found, for example, in "Characterization of Porous Solids and Powders:surface Area, pore Size and Density", S.Lowell et al Springer,2004.

In some embodiments, the inorganic support may be extruded or otherwise formed into any desired overall structure, and may have disposed thereon a group 10 element and any optional promoters and/or alkali metal elements. Suitable monolithic structures may be or include, but are not limited to, structures having a plurality of substantially parallel internal channels, such as those in the form of ceramic honeycomb. In some embodiments, the support may be in the form of beads, spheres, rings, curved shapes, irregular shapes, rods, columns, flakes, films, cubes, polygonal geometries, sheets, fibers, coils, spirals, nets, sintered porous substances, pellets, granules, tablets, powders, microparticles, extrudates, cloth or web-form materials, honeycomb matrix monoliths, including crushed or crushed forms, and may have disposed thereon a group 10 element and any optional promoters and/or alkali metal elements.

The catalyst in the synthesized state may be formulated in one or more suitable forms for use in various short-cycle (.ltoreq.5 hours) hydrocarbon upgrading processes. Alternatively, the support may be configured in an appropriate form for use in a different short cycle hydrocarbon upgrading process 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 and/or support to improve the chemical/physical properties of the catalyst. For example, spray dried catalyst particles having an average cross-sectional diameter in the range of 40 μm to 100 μm are typically used in FCC fluid bed reactors. To prepare a spray dried catalyst, the support/catalyst needs to be slurried with the binder/additive in the slurry prior to spray drying and calcination.

Hydrocarbon upgrading process

Returning to the hydrocarbon upgrading process, the hydrocarbon-containing feed and catalyst and/or at least a portion of the regenerated catalyst may be contacted with one another in any suitable environment, such as in one or more reaction or conversion zones disposed in one or more reactors, thereby producing an effluent and at least partially deactivated catalyst. In some embodiments, the reaction 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 countercurrent reactors, or any combination thereof.

The hydrocarbon-containing feed and the catalyst and/or at least a portion of the regenerated catalyst may be contacted at a temperature in the range of from 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 620 ℃, 650 ℃, 660 ℃, 670 ℃, 680 ℃, 690 ℃, or 700 ℃ to 725 ℃, 750 ℃, 760 ℃, 780 ℃, 800 ℃, 825 ℃, 850 ℃, 875 ℃, or 900 ℃. In some embodiments, the hydrocarbon-containing feed and the catalyst and/or at least a portion of the regenerated catalyst may be contacted at a temperature of at least 620 ℃, at least 650 ℃, at least 660 ℃, at least 670 ℃, at least 680 ℃, at least 690 ℃, or at least 700 ℃ to 725 ℃, 750 ℃, 760 ℃, 780 ℃, 800 ℃, 825 ℃, 850 ℃, 875 ℃, or 900 ℃. The hydrocarbon-containing feed may be introduced into the reaction or conversion zone and contacted with the catalyst and/or at least a portion of the regenerated catalyst therein for a period of time of less than or equal to 3 hours, less than or equal to 2.5 hours, less than or equal to 2 hours, less than or equal to 1.5 hours, less than or equal to 1 hour, less than or equal to 45 minutes, less than or equal to 30 minutes, less than or equal to 20 minutes, less than or equal to 10 minutes, less than or equal to 5 minutes, less than or equal to 1 minute, less than or equal to 30 seconds, less than or equal to 10 seconds, less than or equal to 5 seconds, or less than or equal to 0.5 seconds. In some embodiments, the hydrocarbon-containing feed may be contacted with the catalyst and/or at least a portion of the regenerated catalyst for a period of 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.

The hydrocarbon-containing feed and the catalyst and/or at least a portion of the regenerated catalyst may be contacted at a hydrocarbon partial pressure of at least 20 kPa-absolute, where the hydrocarbon partial pressure is any C in the hydrocarbon-containing feed ₂ -C ₁₆ Alkanes and any C ₈ -C ₁₆ Total partial pressure of alkyl aromatic hydrocarbon. In some embodiments, the hydrocarbon partial pressure during the contacting of the hydrocarbon-containing feed and the catalyst and/or at least a portion of the regenerated catalyst may be in the range of from 20 kPa-absolute, 50 kPa-absolute, 100 kPa-absolute, at least 150kPa, at least 200kPa 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, 5,000kPa-Absolute, 7,000 kPa-absolute, 8,500 kPa-absolute, or 10,000 kPa-absolute, where the hydrocarbon partial pressure is any C in the hydrocarbon-containing feed ₂ -C ₁₆ Alkanes and any C ₈ -C ₁₆ Total partial pressure of alkyl aromatic hydrocarbon. In other embodiments, the hydrocarbon partial pressure during the contacting of the hydrocarbon-containing feed with the catalyst and/or at least a portion of the regenerated catalyst may be in the 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, where the hydrocarbon partial pressure is any C in the hydrocarbon-containing feed ₂ -C ₁₆ Alkanes and any C ₈ -C ₁₆ Total partial pressure of alkyl aromatic hydrocarbon.

In some embodiments, the hydrocarbon-containing feed may include at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, or at least 99% by volume of a single C ₂ -C ₁₆ Alkanes, such as propane, are based on the total volume of the hydrocarbon-containing feed. The hydrocarbon-containing feed and the catalyst and/or at least a portion of the regenerated catalyst may be at a single C 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 ₂ -C ₁₆ Alkane such as propane is contacted under pressure.

The hydrocarbon-containing feed may be contacted with the catalyst and/or at least a portion of the regenerated catalyst in the reaction or conversion zone at any Weight Hourly Space Velocity (WHSV) effective for conducting the upgrading process. In some embodiments, the WHSV may be 0.01hr ^-1 、0.1hr ^-1 、1hr ^-1 、2hr ^-1 、5hr ^-1 、10hr ^-1 、20hr ^-1 、30hr ^-1 Or 50hr ^-1 For 100hr ^-1 、250hr ^-1 、500hr ^-1 Or 1,000hr ^-1 . In some embodiments, when the hydrocarbon upgrading process comprises fluidization orCatalyst circulation mass flow rate with any C when otherwise moving catalyst and/or moving regenerated catalyst ₂ -C ₁₆ Alkanes and any C ₈ -C ₁₆ The ratio of the total amount of alkylaromatic mass flow rate may be in the 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 weight to weight basis.

When the activity of the at least partially deactivated catalyst decreases below a desired minimum amount, the at least partially deactivated catalyst or at least a portion thereof may be subjected to the regeneration process described above to produce a regenerated catalyst. Regeneration of the at least partially deactivated catalyst may occur within the reaction or conversion zone or within a combustion zone separate and apart from the reaction or conversion zone (depending on the particular reactor configuration) to produce a regenerated catalyst. For example, regeneration of the catalyst may occur in the reaction or conversion zone when a fixed bed or counter-current reactor is used, or in a separate combustion zone, which may be separate and apart from the reaction or conversion zone when a fluidized bed reactor or other circulating or fluidized type reactor is used. Similarly, the optional reduction step may also occur in the reaction or conversion zone, in the combustion zone, and/or in a separate reduction zone. Thus, in cyclic type processes such as those commonly used in fixed bed and countercurrent reactors and/or continuous type processes commonly used in fluidized bed reactors, the hydrocarbon-containing feed may be contacted with a catalyst to effect one or more of dehydrogenation, dehydroaromatization, and dehydrocyclization of at least a portion of the hydrocarbon-containing feed to produce coked catalyst and a first effluent comprising one or more upgraded hydrocarbons and molecular hydrogen. Separation of the effluent including upgraded hydrocarbons and molecular hydrogen from the coked catalyst may be accomplished via one or more separators, such as cyclones, if desired. As noted above, the oxidizing gas may be or include, but is not limited to, O ₂ 、O ₃ 、CO ₂ Or mixtures thereof, and may include not greater than 5 mole% H ₂ O. In some embodiments, an amount of oxidizing gas may be used that exceeds the amount required to combust 100% of the contaminants, such as coke, disposed on the catalystIncreasing the rate of contaminant removal from the catalyst allows for a reduction in the time required to remove the contaminant and results in an increase in the yield of upgraded product produced over a given period of time.

Hydrocarbon-containing feed

C ₂ -C ₁₆ The 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-dimethylbutane, n-heptane, 2-methylhexane, 2, 3-trimethylbutane, cyclopentane, cyclohexane, methylcyclopentane, ethylcyclopentane, n-propylcyclopentane, 1, 3-dimethylcyclohexane, or mixtures thereof. For example, the hydrocarbon-containing feed may include propane that may be dehydrogenated to produce propylene, and/or isobutane that may be dehydrogenated to produce isobutylene. In another example, the hydrocarbon-containing feed may include liquid petroleum gas (LP gas), which may be in a gaseous phase when contacted with the catalyst. In some embodiments, the hydrocarbons in the hydrocarbon-containing feed may consist essentially of a single alkane, such as propane. In some embodiments, the hydrocarbonaceous feed can include greater than or equal to 50 mole percent, greater than or equal to 75 mole percent, greater than or equal to 95 mole percent, greater than or equal to 98 mole percent, or greater than or equal to 99 mole percent of a single C ₂ -C ₁₆ Alkanes, such as propane, are based on the total weight of all hydrocarbons in the hydrocarbon-containing feed. In some embodiments, the hydrocarbon-containing feed may include at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 97%, or at least 99% by volume of a single C ₂ -C ₁₆ Alkanes, such as propane, are based on the total volume of the hydrocarbon-containing feed.

C ₈ -C ₁₆ The alkylaromatic hydrocarbon may be or include, but is not limited to, ethylbenzene, propylbenzene, butylbenzene, one or more ethyltoluene, or mixtures thereof. In some embodiments, the hydrocarbonaceous feed can include greater than or equal to 50 mole percent, greater than or equal to 75 mole percent, greater than or equal to 95 mole percent, greater than or equal to 98 mole percent, or greater than or equal to 99 mole percent of a single C ₈ -C ₁₆ Alkylaromatic hydrocarbons such as ethylbenzene are based on the total weight of all hydrocarbons in the hydrocarbon-containing feed. In some embodiments, ethylbenzene may be dehydrogenatedStyrene is produced. As such, in some embodiments, the methods disclosed herein can include propane dehydrogenation, butane dehydrogenation, isobutane dehydrogenation, pentane dehydrocyclization to cyclopentadiene, naphtha reforming, ethylbenzene dehydrogenation, ethyltoluene dehydrogenation, and the like.

In some embodiments, the hydrocarbon-containing feed may be diluted, for example, with 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, N ₂ 、CO ₂ 、CH ₄ Or mixtures thereof. If the hydrocarbonaceous feed includes a diluent, the hydrocarbonaceous feed can include 0.1, 0.5, 1, or 2 to 3, 8, 16, or 32% by volume of diluent, based on any C in the hydrocarbonaceous feed ₂ -C ₁₆ Alkanes and any C ₈ -C ₁₆ Total volume of alkyl aromatic hydrocarbon.

In some embodiments, the hydrocarbon-containing feed may also include H ₂ . In some embodiments, when the hydrocarbon-containing feed comprises H ₂ When H is ₂ With any C ₂ -C ₁₆ Alkanes and any C ₈ -C ₁₆ The molar ratio of the total amount of alkylaromatic hydrocarbons may be in the range from 0.1, 0.3, 0.5, 0.7 or 1 to 2, 3, 4, 5, 6, 7, 8, 9 or 10.

In some embodiments, the hydrocarbon-containing feed may be substantially free of any vapors, e.g<0.1% by volume of steam, based on any C in the hydrocarbon-containing feed ₂ -C ₁₆ Alkanes and any C ₈ -C ₁₆ Total volume of alkyl aromatic hydrocarbon. In other embodiments, the hydrocarbon-containing feed may include steam. For example, the hydrocarbon-containing feed may include 0.1, 0.3, 0.5, 0.7, 1, 3, or 5 to 10, 15, 20, 25, 30, 35, 40, 45, or 50 percent steam by volume, based on any C in the hydrocarbon-containing feed ₂ -C ₁₆ Alkanes and any C ₈ -C ₁₆ Total volume of alkyl aromatic hydrocarbon. In other embodiments, the hydrocarbonaceous feed can include ∈50 vol% +.ltoreq.45 vol%, +.ltoreq.40 vol%, +.35 vol.%, 30 vol.%, 25 vol.%, 20 vol.%, or 15 vol.% steam based on any C in the hydrocarbon-containing feed ₂ -C ₁₆ Alkanes and any C ₈ -C ₁₆ Total volume of alkyl aromatic hydrocarbon. In other embodiments, the hydrocarbon-containing feed may include at least 1 volume%, at least 3 volume%, at least 5 volume%, at least 10 volume%, at least 15 volume%, at least 20 volume%, at least 25 volume%, or at least 30 volume% steam, based on any C in the hydrocarbon-containing feed ₂ -C ₁₆ Alkanes and any C ₈ -C ₁₆ Total volume of alkyl aromatic hydrocarbon.

In some embodiments, the hydrocarbon-containing feed may include sulfur. For example, the hydrocarbon-containing feed may include sulfur in the range from 0.5ppm, 1ppm, 5ppm, 10ppm, 20ppm 30ppm, 40ppm, 50ppm, 60ppm, 70ppm, or 80ppm to 100ppm, 150ppm, 200ppm, 300ppm, 400ppm, or 500 ppm. In other embodiments, the hydrocarbon-containing feed may include sulfur in the range of 1ppm to 10ppm, 10ppm to 20ppm, 20ppm to 50ppm, 50ppm to 100ppm, or 100ppm to 500 ppm. Sulfur, if present in the hydrocarbon-containing feed, may be or include, but is not limited to, H ₂ S, dimethyl disulfide, as one or more thiols, or any mixture thereof.

The hydrocarbon feed may be substantially free of molecular oxygen. In some embodiments, the hydrocarbon feed may include 5mol% or less, 3mol% or less, or 1mol% or less of molecular oxygen (O) ₂ ). It is believed that providing a hydrocarbon feed that is substantially free of molecular oxygen substantially prevents oxidative coupling reactions of alkanes and/or alkylaromatics that would otherwise consume at least a portion of the hydrocarbon feed.

Recovery and use of upgraded hydrocarbons

The upgraded hydrocarbon may include at least one upgraded hydrocarbon such as olefins, water, unreacted hydrocarbons, molecular hydrogen, and the like. The upgraded hydrocarbon may be recovered or otherwise obtained by any convenient method, such as by one or more conventional methods. One such process may include cooling and/or compressing 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 alkanes or alkylaromatics predominantly in the gas phase. Olefins and unreacted alkane or alkylaromatic hydrocarbons may then be recovered from the reaction product in one or more separator drums. For example, one or more separators or distillation columns may be used to separate the dehydrogenation product from the unreacted hydrocarbon feed.

In some embodiments, the recovered olefin, such as propylene, may be used to produce a polymer, e.g., the recovered propylene may be polymerized to produce a polymer having segments or units derived from the recovered propylene, e.g., polypropylene, ethylene-propylene copolymers, and the like. Recovered isobutene may be used, for example, for the production of one or more of the following: oxygenates such as methyl tertiary butyl ether, fuel additives such as diisobutylene, synthetic elastomeric polymers such as butyl rubber, and the like.

Examples:

the foregoing discussion may be further described with reference to the following non-limiting examples. Catalysts 1-27 and comparative catalysts were prepared according to the following procedure.

Catalyst 1 catalyst was prepared according to the following procedure: leave 2.3gMG 70/170 (Sasol), which is MgO-Al obtained by calcining hydrotalcite ₂ O ₃ And (3) mixing metal oxides. The mixed metal oxide contains 70 wt% MgO and 30 wt% Al ₂ O ₃ . BET surface area of 170m according to Sasol ² And/g. Tin (IV) chloride pentahydrate (0.103 g) (Acros Organics), chloroplatinic acid hexahydrate (0.0184 g) (BioXtra) and deionized water (2.2 mL) were mixed in a vial to prepare a solution. Soaking->MG 70/170 vector. The impregnated material was dried at 110 ℃ for 6 hours and calcined at 800 ℃ for 12 hours, all in air. The final product nominally contains 0.3 wt% Pt and 1.5 wt% Sn.

Catalyst 2 catalyst was prepared according to the following procedure: leave 3gMG 80/150(Sasol), which is MgO-Al obtained by calcining hydrotalcite ₂ O ₃ And (3) mixing metal oxides. The mixed metal oxide contains 80 wt% MgO and 20 wt% Al ₂ O ₃ . BET surface area of 150m according to Sasol ² And/g. Tin (IV) chloride pentahydrate (0.134 g) (Acros Organics), chloroplatinic acid hexahydrate (0.024 g) (BioXtra) and deionized water (2.25 mL) were mixed in a vial to prepare a solution. Soaking->MG 80/150 vector. The impregnated material was allowed to stand in a closed vessel at room temperature for 24 hours, then dried at 110℃for 6 hours, and calcined at 800℃for 12 hours, all in air. The final product nominally contains 0.3 wt% Pt and 1.5 wt% Sn.

Catalyst 3. Catalyst is a Pt-based Sn-containing catalyst supported on a Mg/Al mixed oxide support. Elemental analysis showed that the catalyst contained 0.48 wt% Pt, 1.25 wt% Sn, 67.93 wt% Mg, and 29.23 wt% Al, based on the total weight of the metallic elements, with a Mg to Al molar ratio of about 2.58.

Catalyst 4 a catalyst was prepared according to the following procedure: leave 3gMG 30/260 (Sasol) which is MgO-Al obtained by calcining hydrotalcite ₂ O ₃ And (3) mixing metal oxides. The mixed metal oxide contains 30 wt% MgO and 70 wt% Al ₂ O ₃ . BET surface area according to Sasol of 260m ² And/g. Tin (IV) chloride pentahydrate (0.134 g) (Acros Organics), chloroplatinic acid hexahydrate (0.024 g) (BioXtra) and deionized water (3.15 mL) were mixed in a vial to prepare a solution. Soaking->MG30/260 vector. The impregnated material was stored in a closed container at room temperature for 120 hours, then dried at 110 ℃ for 6 hours and calcined at 800 ℃ for 12 hours, all in air. The final product nominally contains 0.3 weight percent% Pt and 1.5 wt% Sn.

Catalyst 5 a catalyst was prepared according to the following procedure: leave 3gMG30/70 (Sasol), which is MgO-Al obtained by calcining hydrotalcite ₂ O ₃ And (3) mixing metal oxides. The mixed metal oxide contains 30 wt% MgO and 70 wt% Al ₂ O ₃ . BET surface area according to Sasol of 70m ² And/g. Puralox MG30/70 contains more MgAl than Puralox MG30/260 ₂ O ₄ Spinel phase. Tin (IV) chloride pentahydrate (0.134 g) (Acros Organics), chloroplatinic acid hexahydrate (0.024 g) (BioXtra) and deionized water (2.4 mL) were mixed in a vial to prepare a solution. Impregnating with the solutionMG30/70 vector. The impregnated material was stored in a closed container at room temperature for 120 hours, then dried at 110 ℃ for 6 hours and calcined at 800 ℃ for 12 hours, all in air. The final product nominally contains 0.3 wt% Pt and 1.5 wt% Sn.

Catalyst 6 catalyst was prepared according to the following procedure: leave 2.3gMG 28/100 (Sasol), essentially MgAl ₂ O ₄ Spinel. BET surface area of 100m according to Sasol ² And/g. Tin (IV) chloride pentahydrate (0.103 g) (Acros Organics), chloroplatinic acid hexahydrate (0.0184 g) (BioXtra) and deionized water (2.4 mL) were mixed in a vial to prepare a solution. Soaking->MG 28/100 vector. The impregnated material was dried at 110 ℃ for 6 hours and calcined at 800 ℃ for 12 hours, all in air. The final product nominally contains 0.3 wt% Pt and 1.5 wt% Sn.

Catalyst 7 catalyst was prepared according to the following procedure: 3.5g is leftMG 70 (Sasol), which is a Mg/Al based hydrotalcite, is activated for 3 hours at 550 ℃ to form a catalyst containing 70% MgO by weight and 30% Al by weight ₂ O ₃ MgO-Al of (C) ₂ O ₃ And (3) mixing metal oxides. Tin (IV) chloride pentahydrate (0.103 g) (Acros Organics), chloroplatinic acid hexahydrate (0.0184 g) (BioXtra) and deionized water (2.6 mL) were mixed in a vial to prepare a solution. The PURAL 70 support was impregnated with this solution. The impregnated material was stored in a closed container at room temperature for 24 hours, then dried at 110 ℃ for 6 hours and calcined at 800 ℃ for 12 hours, all in air. The final product nominally contains 0.3 wt% Pt and 1.5 wt% Sn.

Catalyst 8. Catalyst was prepared according to the following procedure: 2.5g MgO (50nm,Sigma Aldrich) was left. Tin (IV) chloride pentahydrate (0.0158 g) (Acros Organics), chloroplatinic acid hexahydrate (0.0314 g) (BioXtra) and deionized water (1 mL) were mixed in a vial to prepare a solution. The MgO support is impregnated with the solution. The impregnated material was dried at 110 ℃ for 6 hours and calcined at 800 ℃ for 12 hours, all in air. The final product nominally contains 0.5 wt% Pt and 0.25 wt% Sn.

Catalyst 93g of alumina (Sigma Aldrich), 1.93g of magnesium nitrate hexahydrate (Sigma Aldrich) and 2.06g of deionized water were mixed and stirred on a hotplate set at 60℃until the mixture was dry. The mixture was further heated to 110 ℃ for 6 hours and calcined at 800 ℃ for 12 hours, all in air. The solid support obtained contains 91% by weight of Al ₂ O ₃ And 9 wt% MgO. Tin (IV) chloride pentahydrate (0.134 g) (Acros Organics), chloroplatinic acid hexahydrate (0.0244 g) (BioXtra) and deionized water (1 mL) were mixed in a vial to prepare a solution. The solution is impregnated onto the solid support mentioned above. The impregnated material was dried at 110 ℃ for 6 hours and calcined at 800 ℃ for 12 hours, all in air. The final product nominally contains 0.3 wt% Pt and 1.5 wt% Sn.

Catalyst 10 a catalyst was prepared according to the following procedure: leave 20gMG 70/170 (Sasol), which is MgO-Al obtained by calcining hydrotalcite ₂ O ₃ And (3) mixing metal oxides. The mixed metal oxide contains 70 wt% MgO and 30 wt% Al ₂ O ₃ . BET surface area of 170m according to Sasol ² And/g. Silver nitrate, tetraamineplatinum (II) nitrate, deionized water were mixed in appropriate equivalents to form a solution. Soaking->MG 70/170 vector. The impregnated material was stored in a closed vessel at room temperature for 1h, then dried overnight at 120 ℃ and calcined at 800 ℃ for 12 h, all in air. The final product nominally contained 0.3 wt% Pt and 1.5 wt% Ag.

Catalyst 11. Catalyst was prepared according to the following procedure: leave 20gMG 70/170 (Sasol), which is MgO-Al obtained by calcining hydrotalcite ₂ O ₃ And (3) mixing metal oxides. The mixed metal oxide contains 70 wt% MgO and 30 wt% Al ₂ O ₃ . BET surface area of 170m according to Sasol ² And/g. The appropriate equivalent of copper nitrate trihydrate, platinum (II) tetramine nitrate, and deionized water are mixed to form a solution. Soaking->MG 70/170 vector. The impregnated material was stored in a closed vessel at room temperature for 1h, then dried overnight at 120 ℃ and calcined at 800 ℃ for 12 h, all in air. The final product nominally contained 0.3 wt% Pt and 1.5 wt% Cu.

Catalyst 12. Catalyst was prepared according to the following procedure: leave 20gMG 70/170 (Sasol), which is MgO-Al obtained by calcining hydrotalcite ₂ O ₃ And (3) mixing metal oxides. The mixed metal oxide contains 70 wt% MgO and 30 wt% Al ₂ O ₃ . BET surface area of 170m according to Sasol ² And/g. Appropriate equivalents of gallium (III) nitrate, platinum (II) tetramine nitrate, and deionized water were mixed to form a solution. Soaking->MG 70/170 vector. The impregnated material was stored in a closed vessel at room temperature for 1h, then dried overnight at 120 ℃ and calcined at 800 ℃ for 12 h, all in air. The final product nominally contains 0.3 wt% Pt and 1.5 wt% Ga.

Catalyst 13 catalyst was prepared according to the following procedure: leave 2.3gMG 80/150 (Sasol), which is MgO-Al obtained by calcining hydrotalcite ₂ O ₃ And (3) mixing metal oxides. The mixed metal oxide contains 80 wt% MgO and 20 wt% Al ₂ O ₃ . BET surface area of 150m according to Sasol ² And/g. Tin (IV) chloride pentahydrate (0.054 g) (Acros Organics), chloroplatinic acid hexahydrate (0.0184 g) (BioXtra) and deionized water (1.725 mL) were mixed in a vial to prepare a solution. Soaking->MG 80/150 vector. The impregnated material was dried at 110 ℃ for 6 hours and calcined at 800 ℃ for 12 hours, all in air. The final product nominally contains 0.3 wt% Pt and 0.75 wt% Sn.

Catalyst 14. Catalyst was prepared according to the following procedure: leave 2.3gMG 80/150 (Sasol), which is MgO-Al obtained by calcining hydrotalcite ₂ O ₃ And (3) mixing metal oxides. The mixed metal oxide contains 80 wt% MgO and 20 wt% Al ₂ O ₃ . BET surface area of 150m according to Sasol ² /g. Tin (IV) chloride pentahydrate (0.103 g) (Acros Organics), chloroplatinic acid hexahydrate (0.0184 g) (BioXtra) and deionized water (1.725 mL) were mixed in a vial to prepare a solution. Soaking->MG 80/150 vector. The impregnated material was dried at 110 ℃ for 6 hours and calcined at 800 ℃ for 12 hours, all in air. The final product nominally contains 0.3 wt% Pt and 1.5 wt% Sn.

Catalyst 15 preparation of catalyst according to the following procedure: leave 2.3gMG 80/150 (Sasol), which is MgO-Al obtained by calcining hydrotalcite ₂ O ₃ And (3) mixing metal oxides. The mixed metal oxide contains 80 wt% MgO and 20 wt% Al ₂ O ₃ . BET surface area of 150m according to Sasol ² And/g. Tin (IV) chloride pentahydrate (0.214 g) (Acros Organics), chloroplatinic acid hexahydrate (0.0184 g) (BioXtra) and deionized water (1.725 mL) were mixed in a vial to prepare a solution. Soaking->MG 80/150 vector. The impregnated material was dried at 110 ℃ for 6 hours and calcined at 800 ℃ for 12 hours, all in air. The final product nominally contains 0.3 wt% Pt and 3.0 wt% Sn.

Catalyst 16. Catalyst was prepared according to the following procedure: leave 5gMG 80/150 (Sasol), which is MgO-Al obtained by calcining hydrotalcite ₂ O ₃ And (3) mixing metal oxides. The mixed metal oxide contains 80 wt% MgO and 20 wt% Al ₂ O ₃ . BET surface area of 150m according to Sasol ² And/g. Tin (IV) chloride pentahydrate (0.100 g) (Acros Organics), chloroplatinic acid hexahydrate (0.04 g) (BioXtra) and deionized water (3.75 mL) were mixed in a vial to prepare a solution.Soaking->MG 80/150 vector. The impregnated material was dried at 110 ℃ for 6 hours and calcined at 800 ℃ for 12 hours, all in air. The final product nominally contains 0.3 wt% Pt and 0.67 wt% Sn.

Catalyst 17 KNO in a glass vial ₃ (0.00812 g) was mixed with deionized water (0.7 mL) to prepare a solution. Catalyst 16 (1.5 g) was impregnated with this solution. The impregnated material was dried at 110 ℃ for 6 hours and calcined at 800 ℃ for 12 hours, all in air. The final product nominally contains 0.3 wt% Pt, 0.67 wt% Sn, and 0.21 wt% K.

Catalyst 18 a catalyst was prepared according to the following procedure: leave 2.3gMG 80/150 (Sasol), which is MgO-Al obtained by calcining hydrotalcite ₂ O ₃ And (3) mixing metal oxides. The mixed metal oxide contains 80 wt% MgO and 20 wt% Al ₂ O ₃ . BET surface area of 150m according to Sasol ² And/g. Tin (IV) chloride pentahydrate (0.103 g) (Acros Organics), chloroplatinic acid hexahydrate (0.0307 g) (BioXtra) and deionized water (1.725 mL) were mixed in a vial to prepare a solution. Soaking->MG 80/150 vector. The impregnated material was dried at 100 ℃ for 10 hours and calcined at 800 ℃ for 15 hours, all in air. The final product nominally contains 0.5 wt% Pt and 1.5 wt% Sn.

Catalyst 19 preparation of catalyst according to the following procedure: leave 2.3gMG 80/150 (Sasol), which is MgO-Al obtained by calcining hydrotalcite ₂ O ₃ And (3) mixing metal oxides. The mixed metal oxide contains 80 wt% MgO and 20 wt% Al ₂ O ₃ . BET surface area of 150m according to Sasol ² And/g. Tin (IV) chloride pentahydrate (0.103 g) (Acros Organics), chloroplatinic acid hexahydrate (0.0187 g) (BioXtra) and deionized water (1.725 mL) were mixed in a vial to prepare a solution. Soaking->MG 80/150 vector. The impregnated material was dried at 100 ℃ for 10 hours and calcined at 800 ℃ for 15 hours, all in air. The final product nominally contains 0.3 wt% Pt and 1.5 wt% Sn.

Catalyst 20. Catalyst was prepared according to the following procedure: leave 2.3g MG 80/150 (Sasol), which is MgO-Al obtained by calcining hydrotalcite ₂ O ₃ And (3) mixing metal oxides. The mixed metal oxide contains 80 wt% MgO and 20 wt% Al ₂ O ₃ . BET surface area of 150m according to Sasol ² And/g. Will->MG 80/150 carrier was transferred to a 200mL beaker filled with 80mL of deionized water. The mixture was stirred to form slurry a. Tin (II) chloride dihydrate (0.0663 g) (Sigma Aldrich) and fuming HCl (2 mL) were mixed to form solution A. Chloroplatinic acid hexahydrate (0.0307 g) (BioXtra) was mixed with deionized water (10 mL) to form solution B. The solution a and the solution B were mixed to form a solution C having an amber color. Solution C was added drop wise to slurry a and stirred for 45 minutes. The resulting mixture was filtered to form a filter cake, which was washed three times with sufficient deionized water. Both the supernatant and the wastewater from washing the filter cake were colorless. The filter cake was dried at 100 ℃ for 10 hours and calcined at 800 ℃ for 15 hours, all in air. The final product nominally contains 0.5 wt% Pt and 1.5 wt% Sn.

Catalyst 21 is prepared by reacting Mg (NO ₃ ) ₂ ·6H ₂ O (44.58 g) (Sigma-Aldrich) and Al (NO) ₃ ) ₃ ·9H ₂ O (51.55 g) (Sigma-Aldrich) was dissolved in deionized water (100 g)1/1 (weight/weight) of the Mg/Al mixed metal oxide support was prepared. The solution was stirred at 70 ℃ to evaporate the water until a solid began to form. The material was then calcined at 200 ℃ for 4 hours and then 800 ℃ for 4 hours, all in air. The material was finally ball milled in an agate cup at 500rpm for 2 hours to obtain a carrier.

In a glass bottle, chloroplatinic acid hexahydrate (0.1280 g) (Sigma Aldrich) and tin (II) chloride dihydrate (0.0998 g) (Fluka) were dissolved in deionized water (10.4960 g) to obtain a dark orange clear solution. The Mg/Al mixed metal oxide support (13.3279 g) was transferred to a 50mL plastic bottle to which was added a Pt/Sn solution (9.8957 g). The materials were mixed using a small laboratory shaker until a uniform light orange powder was obtained. The metal impregnated material was calcined at 120 ℃ for 4 hours and then 800 ℃ for 12 hours, all in air. The final product nominally contains 0.33 wt% Pt and 0.33 wt% Sn.

Catalyst 22 by reacting Mg (NO ₃ ) ₂ ·6H ₂ O (31.89 g) (Sigma-Aldrich) and Al (NO) ₃ ) ₃ ·9H ₂ O (73.64 g) (Sigma-Aldrich) was dissolved in deionized water (25.47 g) to prepare a 0.5/1 (weight/weight) Mg/Al mixed metal oxide support. The solution was stirred at 70 ℃ to evaporate the water until a solid began to form. The material was placed in an oven at 120 ℃ for 1h to further evaporate the water. The dried material was calcined at 200 ℃ for 4 hours and then 800 ℃ for 4 hours, all in air. The calcined material was finally ball-milled in an agate cup at 500rpm for 2 hours to obtain a carrier.

In a glass bottle, chloroplatinic acid hexahydrate (0.1727 g) (Sigma Aldrich) and tin (II) chloride dihydrate (0.1313 g) (Fluka) were added to deionized water (10.7014 g) to obtain a dark orange clear solution. The Mg/Al mixed metal oxide support (14.2533 g) was transferred to a 50mL plastic bottle to which was added a Pt/Sn solution (8.0550 g). The materials were mixed using a small laboratory shaker until a uniform light orange powder was obtained. The metal impregnated material was calcined at 120 ℃ for 4 hours and then 800 ℃ for 12 hours, all in air. The final product nominally contains 0.33 wt% Pt and 0.33 wt% Sn.

Catalyst 23 by hydrating zirconyl (IV) nitrate at 50℃The material (3.69 g) (Sigma-Aldrich) was dissolved in deionized water (40 g) to prepare a 2/1 (weight/weight) Mg/Zr mixed metal oxide support. Mg (NO) was added to the solution ₃ ) ₂ ·6H ₂ O (12.55 g) (Sigma-Aldrich). The mixture was stirred at 70 ℃ to evaporate the water until a solid began to form. The material was then calcined at 200 ℃ for 4 hours and then at 800 ℃ for 4 hours, all in air, to obtain a support.

In a glass bottle, chloroplatinic acid hexahydrate (0.0212 g) (Sigma Aldrich) and tin (IV) chloride pentahydrate (0.0318 g) (Sigma Aldrich) were dissolved in deionized water (0.6647 g) to obtain a dark orange clear solution. The Mg/Zr mixed metal oxide support (2.0412 g) was transferred to a 50mL plastic bottle, to which was added a Pt/Sn solution (0.6007 g). The materials were mixed using a small laboratory shaker until a uniform light orange powder was obtained. The metal impregnated catalyst was dried at 120 ℃ for 4 hours and then calcined at 800 ℃ for 12 hours, all in air. The final product nominally contains 0.33 wt% Pt and 0.33 wt% Sn.

Catalyst 24: to prepare a 2/1 (weight/weight) Mg/Ti mixed metal oxide support, 8.04g MgO (Acros), 4.02g TiO in an agate ball milling cup ₂ (Anatase, sigma Aldrich) and 10g H ₂ O was added with 3 agate balls. Ball milling the material at 500rpm for 70h. The cover is sealed to reduce water evaporation during ball milling. After ball milling, a thick slurry was obtained. The slurry was calcined at 200 ℃ for 4 hours and then at 800 ℃ for 4 hours to obtain a support.

In a glass bottle, 0.0288g of chloroplatinic acid hexahydrate (Sigma Aldrich) and 0.0336g tin (IV) chloride pentahydrate (Sigma Aldrich) were dissolved in 1.6007g H ₂ O to give a dark orange clear solution. 2.7321g of the Mg/Ti mixed metal oxide support was transferred to a 50mL plastic bottle, after which 1.4080g of the Pt/Sn solution prepared above was added dropwise. The materials were mixed using a small laboratory shaker until a uniform light orange powder was obtained. The metal impregnated catalyst was dried at 120 ℃ for 4 hours and then calcined at 800 ℃ for 12 hours. The final product nominally contains 0.33 wt% Pt and 0.33 wt% Sn.

Catalyst 25 by adding MgO (8.04 g) (Acros), siO ₂ (4.03g)(Sigma-Aldrich)、Deionized water (10 g) and 3 agate balls 2/1 (weight/weight) Mg/Si mixed metal oxide was prepared in an agate ball milling cup. Ball milling the material at 500rpm for 70h. The lid was sealed to reduce water evaporation during ball milling. After ball milling, a thick slurry was obtained. The slurry was calcined at 200 ℃ for 4 hours and then at 800 ℃ for 4 hours, all in air, to obtain a carrier.

In a glass bottle, chloroplatinic acid hexahydrate (0.0296 g) (Sigma Aldrich) and tin (IV) chloride pentahydrate (0.0365 g) (Sigma Aldrich) were dissolved in deionized water (1.4319 g) to obtain a dark orange clear solution. A2/1 Mg/Si mixed metal oxide support (2.8178 g) was added to a 50mL plastic bottle followed by dropwise addition of a Pt/Sn solution (1.2704 g). The materials were mixed using a small laboratory shaker until a uniform light orange powder was obtained. The metal impregnated catalyst was dried at 120 ℃ for 4 hours and then calcined at 800 ℃ for 12 hours, all in air. The final product nominally contains 0.33 wt% Pt and 0.33 wt% Sn.

Catalyst 26 MgO (23.4 g) (Aldrich), snO were combined and thoroughly mixed ₂ (1.56 g) (Aldrich), calcium aluminate cement (12.8 g) (Almatis) and Al ₂ O ₃ (60.5 g) (Versal 300) to prepare a Mg/Ca/Sn/Al mixed metal oxide support. An aqueous acetic acid solution was prepared by adding 10.24mL of acetic acid to 100mL of deionized water. A60.4 mL sample was taken from the solution and an additional 0.5mL of acetic acid was added to the sample. The sample was added to the powder in 5mL increments with stirring for two minutes between additions until the sample was exhausted. Deionized water is then added to the mixture until a slurry is formed. The slurry was then calcined at 300 ℃ for 20 hours and then 843 ℃ for 5 hours, all in air, to obtain a carrier. 0.3 wt% Pt and additional 0.3 wt% Sn were impregnated onto the support prepared above, thereby producing a final catalyst.

Catalyst 27. Catalyst was prepared according to the following procedure: leave 20gMG 70/170 (Sasol), which is MgO-Al obtained by calcining hydrotalcite ₂ O ₃ And (3) mixing metal oxides. The mixed metal oxide contains 70 wt% MgO and 30 wt%％Al ₂ O ₃ . BET surface area of 170m according to Sasol ² And/g. The appropriate equivalent of tin (II) chloride dihydrate and deionized water are mixed to form a solution. Soaking->MG 70/170 vector. The impregnated material was stored in a closed vessel at room temperature for 1h and then dried overnight at 120 ℃. The appropriate equivalent of tetraamineplatinum (II) nitrate and deionized water are mixed to form a solution. The Sn-impregnated support was further impregnated with a Pt solution. The impregnated material was allowed to stand in a closed vessel at room temperature for 1h, then dried overnight at 120 ℃ and calcined at 800 ℃ for 12 h, all in air. The final product nominally contains 0.3 wt% Pt and 1.5 wt% Sn.

Catalyst compositions 28-41 were prepared according to the following procedure. Calcination in air at 550℃for each catalyst compositionMG 80/150 (3 g) (Sasol) for 3 hours, which is a catalyst containing 80% by weight MgO and 20% by weight Al ₂ O ₃ And has 150m ² Mixed Mg/Al metal oxide of surface area per gram to form a support. A solution containing the appropriate amount of tin (IV) chloride pentahydrate (when used to prepare the catalyst composition (Acros Organics)) and/or chloroplatinic acid (when used to prepare the catalyst composition (Sigma Aldrich)) and 1.8ml of deionized water was prepared in a vial. For each catalyst composition, calcined with the corresponding solution +. >MG 80/150 support (2.3 g) was impregnated. The impregnated material was equilibrated in a closed vessel at Room Temperature (RT) for 24 hours, dried at 110 ℃ for 6 hours and calcined at 800 ℃ for 12 hours. Table 1 shows nominal Pt and Sn content of each catalyst composition based on the weight of the support.

Comparative catalyst 1: in a graduated flask, snCl is combined ₂ (0.048 g) (Aldrich), chloroplatinic acid, 8% solution (0.79 g) (Aldrich) and the balance HCl (1.2M) (Acculute) to prepare 5.6mL of dark solution. The solution was added to θ -alumina (10 g) and stirred for 15 minutes. The catalyst was allowed to stand for 1 hour. The catalyst was placed in a muffle furnace and warmed to 120 ℃ at 3 ℃/min, held at 120 ℃ for 2 hours, and then the catalyst was warmed to 550 ℃ at 3 ℃/min, held for 2 hours, all in air. The catalyst was then cooled to room temperature.

In a graduated flask, KNO ₃ (0.258 g) (Aldrich) was dissolved in deionized water to yield 5.6mL of solution. The solution was added to the Pt-Sn catalyst and stirred for 15 minutes. The catalyst was allowed to stand for 1 hour. The catalyst was placed in a muffle furnace and warmed to 120 ℃ at 3 ℃/min, held at 120 ℃ for 2 hours, and then the catalyst was warmed to 550 ℃ at 3 ℃/min, held for 2 hours, all in air. The catalyst was then cooled to room temperature. The final product nominally contains 0.3 wt% Pt, 0.3 wt% Sn, and 1.0 wt% K.

Examples of catalysts are described above.

The fixed bed experiments were carried out at about 100kPa absolute. Gas Chromatography (GC) was used to measure the composition of the reactor effluent. The concentration of each component in the reactor effluent was then used to calculate C ₃ H ₆ Yield and selectivity. Calculation of C based on carbon moles as reported in these examples ₃ H ₆ Yield and selectivity.

In each example, a quantity of catalyst "M _cat "mixed with an appropriate amount of quartz diluent and loaded into a quartz reactor. The amount of diluent is determined such that the catalyst bed (catalyst + diluent) overlaps the isothermal zone of the quartz reactor and such that the catalyst bed is largely isothermal during operation. The dead volume of the reactor was filled with quartz chips/rods.

Calculation of C using the concentration of each component in the reactor effluent ₃ H ₆ Yield and selectivity。t _rxn At the beginning and t _rxn C at the end ₃ H ₆ Yield and selectivity are respectively expressed as Y _ini 、Y _end 、S _ini And S is _end And reported as a percentage in the data table below.

Example 1-effect of exposing spent catalyst to steam at 800 ℃ prior to oxidation. Two options (option a and option B) were used in step 1 to evaluate the effect of exposing the spent catalyst to steam, referred to as case 1A and case 1B, respectively. The method comprises the following steps: 1. (option A/case 1A) -simultaneously heating the reaction zone to the oxidation temperature T with an inert gas purging system _oxi . After this, 46.6sccm of He and 5.1sccm of vapor were passed through the reaction zone for 5 minutes. 1. (option B/case 1B) -simultaneously heating the reaction zone to the oxidation temperature T with an inert gas purging system _oxi . After this, 46.6sccm of He was passed through the reaction zone for 5min.2. Oxygen-containing gas (O gas) at a flow rate (F _oxi ) Through the branches of the reaction zone, while an inert gas (insert) is passed through the reaction zone. 3. The oxygen-containing gas is then passed through the reaction zone for a period of time (t _oxi ) To oxidize the catalyst. 4. At t _oxi Thereafter, an inert gas is passed through the reaction zone and the temperature in the reaction zone is adjusted from T _oxi Change to reduction temperature (T) _red ). 5. Containing H ₂ The gas (H gas) is at a flow rate (F _red ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. This is then followed by T _red The following is H-containing ₂ The gas flows through the reaction zone for a certain period of time (t _red ). 6. The system was purged with inert gas. During this process, the temperature of the reaction zone is varied from T _red The reaction temperature was changed to 670 ℃.7. Comprises 81% by volume of C ₃ H ₈ Hydrocarbon (HC) containing feed of 9 vol% inert gas (Ar or Kr) and 10 vol% steam at flow rate (F _rxn ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. The hydrocarbonaceous feed was then passed through the reaction zone at 670 ℃ for 10min. GC sampling of the reaction effluent was started as soon as the feed was switched from branch to reaction zone. The above method steps are cyclically repeated until stable performance is obtained. As shown in table 2 below, comparing case 1A using option a with case 1B using option B shows that the performance of the catalyst was not affected when the spent catalyst was exposed to steam at 800 ℃ prior to oxidation.

Example 2-effect of exposing spent catalyst to steam at 670 ℃ prior to oxidation. Two options (option a and option B) were used in step 8 to evaluate the effect of exposing the spent catalyst to steam, referred to as case 2A and case 2B, respectively. The method comprises the following steps: 1. simultaneously heating the reaction zone to the oxidation temperature T by means of an inert gas flushing system _oxi .2. Oxygen-containing gas (O gas) at a flow rate (F _oxi ) Through the branches of the reaction zone, while inert gas is passed through the reaction zone. 3. The oxygen-containing gas is then passed through the reaction zone for a period of time (t _oxi ) To oxidize the catalyst. 4. At t _oxi Thereafter, an inert gas is passed through the reaction zone and the temperature in the reaction zone is adjusted from T _oxi Change to reduction temperature (T) _red ). 5. Containing H ₂ The gas (H gas) is at a flow rate (F _red ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. This is then followed by T _red The following is H-containing ₂ The gas flows through the reaction zone for a certain period of time (t _red ). 6. The system was purged with inert gas. During this process, the temperature of the reaction zone is varied from T _red The reaction temperature was changed to 670 ℃.7. Comprises 81% by volume of C ₃ H ₈ Hydrocarbon (HC) containing feed of 9 vol% inert gas (Ar or Kr) and 10 vol% steam at flow rate (F _rxn ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. The hydrocarbonaceous feed was then passed through the reaction zone at 670 ℃ for 10min. GC sampling of the reaction effluent was started as soon as the feed was switched from branch to reaction zone. 8. (option a) 46.6 seem of He was passed with 5.1 seem of steam through the reaction zone for 5min.8. (option B) 46.6sccm of He was passed through the reaction zone for 5min. Repeating the above steps circularly until stable performance is obtained. As shown in table 3 below, comparing case 2A using option a with case 2B using option B shows that the performance of the catalyst is not affected when the spent catalyst is exposed to steam at 670 ℃ prior to oxidation.

Example 3A-preferred oxidation temperature/duration. The method comprises the following steps: 1. simultaneously heating the reaction zone to the oxidation temperature T by means of an inert gas flushing system _oxi .2. Oxygen-containing gas (O gas) at a flow rate (F _oxi ) Through the branches of the reaction zone, while inert gas is passed through the reaction zone. 3. The oxygen-containing gas is then passed through the reaction zone for a period of time (t _oxi ) To oxidize the catalyst. 4. At t _oxi Thereafter, an inert gas is passed through the reaction zone and the temperature in the reaction zone is adjusted from T _oxi Change to reduction temperature (T) _red ). 5. Containing H ₂ The gas (H gas) is at a flow rate (F _red ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. This is then followed by T _red The following is H-containing ₂ The gas flows through the reaction zone for a certain period of time (t _red ). 6. The system was purged with inert gas. During this process, the temperature of the reaction zone is varied from T _red The reaction temperature was changed to 670 ℃.7. Comprises 81% by volume of C ₃ H ₈ Hydrocarbon (HC) containing feed of 9 vol% inert gas (Ar or Kr) and 10 vol% steam at flow rate (F _rxn ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. The hydrocarbonaceous feed was then passed through the reaction zone at 670 ℃ for 10min. GC sampling of the reaction effluent was started as soon as the feed was switched from branch to reaction zone. The above method steps are cyclically repeated until stable performance is obtained.

Example 3B-preferred oxidation temperature/duration. SquareThe method comprises the following steps: 1. simultaneously heating the reaction zone to the oxidation temperature T by means of an inert gas flushing system _oxi .2. Oxygen-containing gas (O gas) at a flow rate (F _oxi ) Through the branches of the reaction zone, while inert gas is passed through the reaction zone. 3. The oxygen-containing gas is then passed through the reaction zone for a period of time (t _oxi ) To oxidize the catalyst. 4. At t _oxi Thereafter, an inert gas is passed through the reaction zone and the temperature in the reaction zone is adjusted from T _oxi Change to reduction temperature (T) _red ). 5. Containing H ₂ The gas (H gas) is at a flow rate (F _red ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. This is then followed by T _red The following is H-containing ₂ The gas flows through the reaction zone for a certain period of time (t _red ). 6. The system was purged with inert gas. During this process, the temperature of the reaction zone is varied from T _red The reaction temperature was changed to 670 ℃.7. Comprises 81% by volume of C ₃ H ₈ Hydrocarbon (HC) containing feed of 9 vol% inert gas (Ar or Kr) and 10 vol% steam at flow rate (F _rxn ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. The hydrocarbonaceous feed was then passed through the reaction zone at 670 ℃ for 10min. GC sampling of the reaction effluent was started as soon as the feed was switched from branch to reaction zone. Tables 4A, 4B-1 and 4B-2 show that longer oxidation durations result in more efficient regeneration of the catalyst. Table 4B-3 shows that higher oxidation temperatures of 800℃or 850℃are more effective oxidation temperatures than 750 ℃. For example, using an oxidation temperature of 750 ℃ would require three (3) times the time required at 800 ℃ to achieve similar yields/selectivities.

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Example 4-O ₂ Partial pressure and CO ₂ Is effective in the presence of (a). The method comprises the following steps: 1. simultaneously heating the reaction zone to the oxidation temperature T by means of an inert gas flushing system _oxi .2. Oxygen-containing gas (O gas) at a flow rate (F _oxi ) Through the branches of the reaction zone, while inert gas is passed through the reaction zone. 3. The oxygen-containing gas is then passed through the reaction zone for a period of time (t _oxi ) To oxidize the catalyst. 4. The system was purged with inert gas. During this process, the temperature of the reaction zone changes to T _red .5. Containing H ₂ The gas (H gas) is at a flow rate (F _red ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. This is then followed by T _red The following is H-containing ₂ The gas flows through the reaction zone for a certain period of time (t _red ). 6. The system was purged with inert gas. During this process, the temperature of the reaction zone is varied from T _red The reaction temperature was changed to 670 ℃.7. Comprises 81% by volume of C ₃ H ₈ Hydrocarbon (HC) containing feed of 9 vol% inert gas (Ar or Kr) and 10 vol% steam at flow rate (F _rxn ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. The hydrocarbonaceous feed was then passed through the reaction zone at 670 ℃ for 10min. GC sampling of the reaction effluent was started as soon as the feed was switched from branch to reaction zone. The above method steps are cyclically repeated until stable performance is obtained. Table 5 shows O ₂ Partial pressure of (2) vs. oxidation and CO ₂ Is present on oxidation.

Example 5-effect of steam during oxidation. The method comprises the following steps: 1. simultaneous heating with inert gas purging systemThe reaction area reaches the oxidation temperature T _oxi .2. Oxygen-containing gas (O gas) at a flow rate (F _oxi ) Through the branches of the reaction zone, while inert gas is passed through the reaction zone. 3. The oxygen-containing gas is then passed through the reaction zone for a period of time (t _oxi ) To oxidize the catalyst. 4. At t _oxi Thereafter, an inert gas is passed through the reaction zone and the temperature in the reaction zone is adjusted from T _oxi Change to reduction temperature (T) _red ). 5. The system was purged with inert gas. 6. Containing H ₂ The gas (H gas) is at a flow rate (F _red ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. This is then followed by T _red The following is H-containing ₂ The gas flows through the reaction zone for a certain period of time (t _red ). 7. The system was purged with inert gas. During this process, the temperature of the reaction zone is varied from T _red The reaction temperature was changed to 670 ℃.8. Comprises 81% by volume of C ₃ H ₈ Hydrocarbon (HC) containing feed of 9 vol% inert gas (Ar or Kr) and 10 vol% steam at flow rate (F _rxn ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. The hydrocarbonaceous feed was then passed through the reaction zone at 670 ℃ for 10min. GC sampling of the reaction effluent was started as soon as the feed was switched from branch to reaction zone. The above method steps are cyclically repeated until stable performance is obtained. Table 6 shows that the presence of more than 10% by volume of steam in the air during oxidation produces even more deactivated catalyst after regeneration. The more steam is present in the air during oxidation, the lower the activity. On the other hand, if the humid air is switched to the dry air after 2min of oxidation, the catalyst is effectively regenerated.

Example 6A-effect of steam during oxidation. 1. The system was purged with inert gas. 2. Oxygen-containing gas (O gas) at a flow rate (F _oxi ) Through the branches of the reaction zone, while inert gas is passed through the reaction zone. Heating the reaction zone to an oxidation temperature T _oxi .3. Containing oxygenThe body is then passed through the reaction zone for a period of time (t _oxi ) To oxidize the catalyst. At t _oxi Thereafter, the temperature in the reaction zone is from T _oxi Change to reduction temperature (T) _red ) While maintaining the flow of oxygen-containing gas. 4. The system was purged with inert gas. 5. Containing H ₂ The gas (H gas) is at a flow rate (F _red ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. This is then followed by T _red The following is H-containing ₂ The gas flows through the reaction zone for a certain period of time (t _red ). 6. The system was purged with inert gas. During this process, the temperature of the reaction zone is varied from T _red The reaction temperature was changed to 670 ℃.7. Comprises 81% by volume of C ₃ H ₈ Hydrocarbon (HC) containing feed of 9 vol% inert gas (Ar or Kr) and 10 vol% steam at flow rate (F _rxn ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. The hydrocarbonaceous feed was then passed through the reaction zone at 670 ℃ for 10min. GC sampling of the reaction effluent was started as soon as the feed was switched from branch to reaction zone. The above method steps are cyclically repeated until stable performance is obtained. Table 7A shows the effect of the presence of steam during oxidation. The shorter the duration of contact between catalyst and steam during oxidation (1 vs. 3 min), the easier it is to restore the catalyst's performance by subsequent oxidation by dry air.

Example 6B effect of steam during oxidation. 1. The system was purged with inert gas. 2. Oxygen-containing gas (O gas) at a flow rate (F _oxi ) Through the branches of the reaction zone, while inert gas is passed through the reaction zone. Heating the reaction zone to an oxidation temperature T _oxi .3. The oxygen-containing gas is then passed through the reaction zone for a period of time (t _oxi ) To oxidize the catalyst. At t _oxi Thereafter, the temperature in the reaction zone is from T _oxi Change to reduction temperature (T) _red ) While maintaining the flow of oxygen-containing gas. 4. The system was purged with inert gas. 5. Containing H ₂ The gas (H gas) is at a flow rate (F _red ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. This is then followed by T _red The following is H-containing ₂ The gas flows through the reaction zone for a certain period of time (t _red ). 6. The system was purged with inert gas. During this process, the temperature of the reaction zone is varied from T _red The reaction temperature was changed to 655 ℃.7. Comprises 81% by volume of C ₃ H ₈ Hydrocarbon (HC) containing feed of 9 vol% inert gas (Ar or Kr) and 10 vol% steam at flow rate (F _rxn ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. The hydrocarbonaceous feed was then passed through the reaction zone at 655 ℃ for 10min. GC sampling of the reaction effluent was started as soon as the feed was switched from branch to reaction zone. The above method steps are cyclically repeated until stable performance is obtained. Table 7B shows that if a two-step oxidation scheme is employed in which a 1min humid air oxidation is followed by a 10min dry air oxidation, then the negative effects of humid air on oxidation are negligible. Figure 1 shows that the catalyst can be effectively regenerated for 80+ cycles by using such a two-step oxidation scheme.

Example 7-effect of reduction temperature. 1. The system was purged with inert gas. 2. Oxygen-containing gas (O gas) at a flow rate (F _oxi ) Through the branches of the reaction zone, while inert gas is passed through the reaction zone. 3. The oxygen-containing gas then passes through the reaction zone. During this process, the temperature of the reaction zone changes to the oxidation temperature (T _oxi ) And it is kept at T _oxi For a certain period of time (t _oxi ) To oxidize the catalyst. At t _oxi Thereafter, the temperature in the reaction zone is from T _oxi Change to reduction temperature (T) _red ). 4. The system was purged with inert gas. 5. Containing H ₂ The gas (H gas) is at a flow rate (F _red ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. This is then followed by T _red The following is H-containing ₂ The gas flows through the reaction zone for a certain period of time (t _red ). 6. The system was purged with inert gas. During this process, the temperature of the reaction zone is varied from T _red The reaction temperature was changed to 670 ℃.7. Comprises 81% by volume of C ₃ H ₈ Hydrocarbon (HC) containing feed of 9 vol% inert gas (Ar or Kr) and 10 vol% steam at flow rate (F _rxn ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. The hydrocarbonaceous feed was then passed through the reaction zone at 670 ℃ for 10min. GC sampling of the reaction effluent was started as soon as the feed was switched from branch to reaction zone. The above method steps are cyclically repeated until stable performance is obtained. Table 8 shows that the reduction can be performed at various temperatures. Reduction durations as short as 0.05min may be used.

Example 8-effect of steam during reduction. 1. Simultaneously heating the reaction zone to the oxidation temperature T by means of an inert gas flushing system _oxi .2. Oxygen-containing gas (O gas) at a flow rate (F _oxi ) Through the branches of the reaction zone, while inert gas is passed through the reaction zone. 3. The oxygen-containing gas is then passed through the reaction zone for a period of time (t _oxi ) To oxidize the catalyst. 4. At t _oxi Thereafter, an inert gas is passed through the reaction zone and the temperature in the reaction zone is adjusted from T _oxi Change to reduction temperature (T) _red ). 5. Containing H ₂ The gas (H gas) is at a flow rate (F _red ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. This is then followed by T _red The following is H-containing ₂ The gas flows through the reaction zone for a certain period of time (t _red ). 6. The system was purged with inert gas. During this process, the temperature of the reaction zone is varied from T _red The reaction temperature was changed to 670 ℃.7. Comprises 81% by volume of C ₃ H ₈ Hydrocarbon (HC) containing feed of 9 vol% inert gas (Ar or Kr) and 10 vol% steam at flow rate (F _rxn ) The branch through the reaction zone lasts for a certain period of timeA stage, while inert gas is passed through the reaction zone. The hydrocarbonaceous feed was then passed through the reaction zone at 670 ℃ for 10min. GC sampling of the reaction effluent was started as soon as the feed was switched from branch to reaction zone. The above method steps are cyclically repeated until stable performance is obtained. Table 9 shows that the negative effect of steam on the effectiveness of the reduction increases with the amount of steam in the reducing gas.

Example 9-effect of hydrocarbons during reduction. 1. Simultaneously heating the reaction zone to the oxidation temperature T by means of an inert gas flushing system _oxi .2. Oxygen-containing gas (O gas) at a flow rate (F _oxi ) Through the branches of the reaction zone, while inert gas is passed through the reaction zone. 3. The oxygen-containing gas is then passed through the reaction zone for a period of time (t _oxi ) To oxidize the catalyst. 4. At t _oxi Thereafter, an inert gas is passed through the reaction zone and the temperature in the reaction zone is adjusted from T _oxi Change to reduction temperature (T) _red ). 5. Containing H ₂ The gas (H gas) is at a flow rate (F _red ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. This is then followed by T _red The following is H-containing ₂ The gas flows through the reaction zone for a certain period of time (t _red ). 6. The system was purged with inert gas. During this process, the temperature of the reaction zone is varied from T _red The reaction temperature was changed to 670 ℃.7. Comprises 81% by volume of C ₃ H ₈ Hydrocarbon (HC) containing feed of 9 vol% inert gas (Ar or Kr) and 10 vol% steam at flow rate (F _rxn ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. The hydrocarbonaceous feed was then passed through the reaction zone at 670 ℃ for 10min. GC sampling of the reaction effluent was started as soon as the feed was switched from branch to reaction zone. The above method steps are cyclically repeated until stable performance is obtained. Table 10 shows the negative effect of trace hydrocarbons on reduction effectiveness.

Example 10-reduction of wet solids. 1. Simultaneously heating the reaction zone to the oxidation temperature T by means of an inert gas flushing system _oxi .2. Oxygen-containing gas (O gas) at a flow rate (F _oxi ) Through the branches of the reaction zone, while inert gas is passed through the reaction zone. 3. The oxygen-containing gas is then passed through the reaction zone for a period of time (t _oxi ) To oxidize the catalyst. 4. At t _oxi Thereafter, an inert gas is passed through the reaction zone and the temperature in the reaction zone is adjusted from T _oxi Change to reduction temperature (T) _red ). Step 5 is performed in one of three options below to evaluate the effectiveness of reducing wet solids. 5. (option 1/case 5A) -H-containing ₂ The gas (H gas) is at a flow rate (F _red ) The branch through the reaction zone was 1.5min, while 83.9sccm of He was passed through the reaction zone. This is then followed by T _red The following is H-containing ₂ The gas flows through the reaction zone for a certain period of time (t _red ). 5. (option 2/case 5B) -H-containing ₂ The gas (H gas) is at a flow rate (F _red ) The branch through the reaction zone was 1.5min, while 83.9sccm of He and 9.2sccm of steam were passed through the reaction zone. This is then followed by T _red The following is H-containing ₂ The gas flows through the reaction zone for a certain period of time (t _red ). 5. (option 3/case 5C) -H-containing ₂ The gas (H gas) is at a flow rate (F _red ) The branch through the reaction zone was 3.0min. At the same time, 83.9sccm of He and 9.2sccm of vapor were passed through the reaction zone during the first 1.5min, and 89.3sccm of He was passed through the reaction zone during the subsequent 1.5 min. This is then followed by T _red The following is H-containing ₂ The gas flows through the reaction zone for a certain period of time (t _red ). 6. The system was purged with inert gas. During this process, the temperature of the reaction zone is varied from T _red The reaction temperature was changed to 670 ℃.7. Comprises 81% by volume of C ₃ H ₈ Hydrocarbon (HC) containing feed of 9 vol% inert gas (Ar or Kr) and 10 vol% steam at flow rate (F _rxn ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. The hydrocarbonaceous feed is then passed through the reaction zone at 670 DEG CDomain 10min. GC sampling of the reaction effluent was started as soon as the feed was switched from branch to reaction zone. The above method steps are cyclically repeated until stable performance is obtained. Table 11 shows the results for cases 5A-5C. Comparison of cases 5A and 5B shows adsorbed H for oxidized catalysts ₂ O reduction is ineffective. Comparison of cases 5B and 5C shows that adsorbed H can be removed by dry gas purging ₂ O。

The re-dried catalyst may then be passed through H ₂ And (3) effective reduction.

Example 11-effect of steam on reduction catalyst. 1. Simultaneously heating the reaction zone to the oxidation temperature T by means of an inert gas flushing system _oxi .2. Oxygen-containing gas (O gas) at a flow rate (F _oxi ) Through the branches of the reaction zone, while inert gas is passed through the reaction zone. 3. The oxygen-containing gas is then passed through the reaction zone for a period of time (t _oxi ) To oxidize the catalyst. 4. The system was purged with inert gas. During this process, the temperature of the reaction zone changes to T _red .5. Containing H ₂ The gas (H gas) is at a flow rate (F _red ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. This is then followed by T _red The following is H-containing ₂ The gas flows through the reaction zone for a certain period of time (t _red ). 6. At t _red Thereafter, 111.8sccm of He, with or without additional vapor at 12.3sccm, is passed through the reaction zone while the temperature of the reaction zone is changed from T _red The reaction temperature was changed to 670 ℃.7. Comprises 81% by volume of C ₃ H ₈ Hydrocarbon (HC) containing feed of 9 vol% inert gas (Ar or Kr) and 10 vol% steam at flow rate (F _rxn ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. The hydrocarbonaceous feed was then passed through the reaction zone at 670 ℃ for 10min. GC sampling of the reaction effluent was started as soon as the feed was switched from branch to reaction zone. Repeating the above steps circularly until stable is obtainedPerformance. Table 12 shows the effect of the presence of steam on the reduction catalyst.

Example 12-effect of cooling after reduction. 1. The reaction zone was simultaneously heated to an oxidation temperature of 800 c with an inert gas purge system. 2. Oxygen-containing gas (O gas) at a flow rate (F _oxi ) Through the branches of the reaction zone, while inert gas is passed through the reaction zone. 3. The oxygen-containing gas is then passed through the reaction zone for a period of time (t _oxi ) To oxidize the catalyst. 4. The system was purged with inert gas. During this process, the temperature of the reaction zone was maintained at 800 ℃.5. Containing H ₂ The gas (H gas) is at a flow rate (F _red ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. This is then followed by bringing the H-containing phase to 800 ℃ ₂ The gas flows through the reaction zone for a certain period of time (t _red ). 6. The reaction zone is subjected to various flow rates (F _he ) He of (c). During this process, the temperature of the reaction zone was reduced from 800 ℃ to a reaction temperature of 670 ℃. Higher F _he Resulting in a faster cooling rate (R _c ) Defined as the decrease in temperature during cooling for the 1 st minute. 7. Comprises 81% by volume of C ₃ H ₈ Hydrocarbon (HC) containing feed of 9 vol% inert gas (Ar or Kr) and 10 vol% steam at flow rate (F _rxn ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. The hydrocarbonaceous feed was then passed through the reaction zone at 670 ℃ for 10min. GC sampling of the reaction effluent was started as soon as the feed was switched from branch to reaction zone. The above method steps are cyclically repeated until stable performance is obtained. Table 13 shows that after reduction, it is desirable to cool the reduction catalyst in a short period of time to maintain high activity.

EXAMPLE 13 reduction period H ₂ Partial pressure effect. 1. The reaction zone was simultaneously heated to an oxidation temperature of 800 c with an inert gas purge system. 2. Oxygen-containing gas (O gas) at a flow rate (F _oxi ) Through the branches of the reaction zone, while inert gas is passed through the reaction zone. 3. The oxygen-containing gas is then passed through the reaction zone for a period of time (t _oxi ) To oxidize the catalyst. 4. The system was purged with inert gas. During this process, the temperature of the reaction zone was maintained at 800 ℃.5. Containing H ₂ The gas (H gas) is at a flow rate (F _red ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. This is then followed by bringing the H-containing phase to 800 ℃ ₂ The gas flows through the reaction zone for a certain period of time (t _red ). 6. The reaction zone is vented with He. During this process, the temperature of the reaction zone was reduced from 800 ℃ to a reaction temperature of 670 ℃.7. Comprises 81% by volume of C ₃ H ₈ Hydrocarbon (HC) containing feed of 9 vol% inert gas (Ar or Kr) and 10 vol% steam at flow rate (F _rxn ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. The hydrocarbonaceous feed was then passed through the reaction zone at 670 ℃ for 10min. GC sampling of the reaction effluent was started as soon as the feed was switched from branch to reaction zone. The above method steps are cyclically repeated until stable performance is obtained. Table 14 shows the values at 10% and 40% H ₂ There is little difference between them.

Examples 14A to H ₂ Effect of duration of reduction. 1. The reaction zone was simultaneously heated to an oxidation temperature of 800 c with an inert gas purge system. 2. Oxygen-containing gas (O gas) at a flow rate (F _oxi ) Through the branches of the reaction zone, while inert gas is passed through the reaction zone. 3. The oxygen-containing gas is then passed through the reaction zone for a period of time (t _oxi ) To oxidize the catalyst. 4. The system was purged with inert gas. During this process, the temperature of the reaction zone was maintained at 800 ℃.5. Containing H ₂ The gas (H gas) is at a flow rate (F _red ) Through the reaction zoneThe branching off of the domain continues for a period of time while inert gas passes through the reaction zone. This is then followed by bringing the H-containing phase to 800 ℃ ₂ The gas flows through the reaction zone for a certain period of time (t _red ). 6. The reaction zone is vented with He. During this process, the temperature of the reaction zone was reduced from 800 ℃ to a reaction temperature of 670 ℃.7. Comprises 81% by volume of C ₃ H ₈ Hydrocarbon (HC) containing feed of 9 vol% inert gas (Ar or Kr) and 10 vol% steam at flow rate (F _rxn ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. The hydrocarbonaceous feed was then passed through the reaction zone at 670 ℃ for 10min. GC sampling of the reaction effluent was started as soon as the feed was switched from branch to reaction zone. The above method steps are cyclically repeated until stable performance is obtained. Table 15A shows little difference between reduction durations in terms of catalyst performance.

Examples 14B to H ₂ Effect of duration of reduction. 1. The reaction zone was simultaneously heated to an oxidation temperature of 800 c with an inert gas purge system. 2. Oxygen-containing gas (O gas) at a flow rate (F _oxi ) Through the branches of the reaction zone, while inert gas is passed through the reaction zone. 3. The oxygen-containing gas is then passed through the reaction zone for a period of time (t _oxi ) To oxidize the catalyst. 4. The system was purged with inert gas. During this process, the temperature of the reaction zone was maintained at 800 ℃.5. Containing H ₂ The gas (H gas) is at a flow rate (F _red ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. This is then followed by bringing the H-containing phase to 800 ℃ ₂ The gas flows through the reaction zone for a certain period of time (t _red ). 6. The reaction zone is vented with He. During this process, the temperature of the reaction zone was reduced from 800 ℃ to a reaction temperature of 655 ℃.7. Comprises 81% by volume of C ₃ H ₈ Hydrocarbon (HC) containing feed of 9 vol% inert gas (Ar or Kr) and 10 vol% steam at flow rate (F _rxn ) By-pass of the reaction zoneFor a period of time while inert gas is passed through the reaction zone. The hydrocarbonaceous feed was then passed through the reaction zone at 655 ℃ for 10min. GC sampling of the reaction effluent was started as soon as the feed was switched from branch to reaction zone. The above method steps are cyclically repeated until stable performance is obtained. Table 15B shows that without catalyst reduction, the propylene yield of the oxidation catalyst (53.7%) was even lower than that of the deactivated catalyst (61.3%).

Example 15-effect of exposing spent catalyst to inert gas at 800 ℃.1. The reaction zone was simultaneously heated to an oxidation temperature of 800 c with an inert gas purge system. Step 2 was performed in one of the following two options to evaluate the exposure of the spent catalyst to inert gas at 800 ℃.2. (option 1/case 15A) oxygen-containing gas (O gas) at a flow rate (F _oxi ) The branch through the reaction zone is 1min, while He passes through the reaction zone for 1min.2. (option 2/case 15B) oxygen-containing gas (O gas) at a flow rate (F _oxi ) The branch through the reaction zone is 3min, while He passes through the reaction zone for 7min.3. The oxygen-containing gas is then passed through the reaction zone for a period of time (t _oxi ) To oxidize the catalyst. 4. At t _oxi Thereafter, an inert gas is passed through the reaction zone and the temperature in the reaction zone is adjusted from T _oxi Change to reduction temperature (T) _red ). 5. Containing H ₂ The gas (H gas) is at a flow rate (F _red ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. This is then followed by T _red The following is H-containing ₂ The gas flows through the reaction zone for a certain period of time (t _red ). 6. The system was purged with inert gas. During this process, the temperature of the reaction zone is varied from T _red The reaction temperature was changed to 670 ℃.7. Comprises 81% by volume of C ₃ H ₈ Hydrocarbon (HC) containing feed of 9 vol% inert gas (Ar or Kr) and 10 vol% steam at flow rate (F _rxn ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. Hydrocarbon-containing feedThen passed through the reaction zone at 670℃for 10min. GC sampling of the reaction effluent was started as soon as the feed was switched from branch to reaction zone. The above method steps are cyclically repeated until stable performance is obtained. Table 16 shows that there is little difference in catalyst performance for the two cases.

Example 16-dehydrogenation of n-butane. 1. The reaction zone was simultaneously heated to an oxidation temperature of 800 c with an inert gas purge system. 2. Oxygen-containing gas (O gas) at a flow rate (F _oxi ) Through the branches of the reaction zone, while inert gas is passed through the reaction zone. 3. The oxygen-containing gas is then passed through the reaction zone for a period of time (t _oxi ) To oxidize the catalyst. 4. At t _oxi Thereafter, an inert gas is passed through the reaction zone and the temperature in the reaction zone is adjusted from T _oxi Change to reduction temperature (T) _red ). 5. Containing H ₂ The gas (H gas) is at a flow rate (F _red ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. This is then followed by T _red The following is H-containing ₂ The gas flows through the reaction zone for a certain period of time (t _red ). 6. The system was purged with inert gas. During this process, the temperature of the reaction zone is varied from T _red The reaction temperature was changed to 635 ℃.7. A hydrocarbon (HC gas) containing feed comprising 89% by volume n-butane and 11% by volume steam at a flow rate (F _rxn ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. The hydrocarbonaceous feed was then passed through the reaction zone at 635 ℃ for 10min. GC sampling of the reaction effluent was started as soon as the feed was switched from branch to reaction zone. The above method steps are cyclically repeated until stable performance is obtained. The catalyst showed no deactivation after 30+ cycles. Thus, no internal standard was used during this experiment to calculate selectivity and yield, material not analyzed by GC (C ₅ And C ₅₊ Coke) is considered negligible. By small amounts of CO/CO generated during oxidation ₂ To confirm the absence of production during the reactionA large amount of coke is produced. Preparation of all predominantly linear C during the reaction ₄ The yield/selectivity is defined based on the molar flow rate of the material (including 1-butene, cis-2-butene, trans-2-butene, 1, 3-butadiene). Table 17 shows that the catalyst was effective in butane dehydrogenation.

Example 17-isobutane dehydrogenation. 1. The reaction zone was simultaneously heated to an oxidation temperature of 800 c with an inert gas purge system. 2. Oxygen-containing gas (O gas) at a flow rate (F _oxi ) Through the branches of the reaction zone, while inert gas is passed through the reaction zone. 3. The oxygen-containing gas is then passed through the reaction zone for a period of time (t _oxi ) To oxidize the catalyst. 4. At t _oxi Thereafter, an inert gas is passed through the reaction zone and the temperature in the reaction zone is adjusted from T _oxi Change to reduction temperature (T) _red ). 5. Containing H ₂ The gas (H gas) is at a flow rate (F _red ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. This is then followed by T _red The following is H-containing ₂ The gas flows through the reaction zone for a certain period of time (t _red ). 6. The system was purged with inert gas. During this process, the temperature of the reaction zone is varied from T _red The reaction temperature was changed to 670 ℃.7. A hydrocarbon (HC gas) containing feed comprising 89% by volume isobutane and 11% by volume steam at a flow rate (F _rxn ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. The hydrocarbonaceous feed was then passed through the reaction zone at 670 ℃ for 10min. GC sampling of the reaction effluent was started as soon as the feed was switched from branch to reaction zone. The above method steps are cyclically repeated until stable performance is obtained. The catalyst showed no deactivation after 30+ cycles. Thus, no internal standard was used during this experiment to calculate selectivity and yield, material not analyzed by GC (C ₅ And C ₅₊ Coke) is considered negligible. By small amounts of CO/CO generated during oxidation ₂ To confirm that there is no significant amount generated during the reactionAnd (3) coke. The yield/selectivity is defined on the basis of the molar flow rate of the isobutene prepared during the reaction. Table 18 shows that the catalyst was effective in the dehydrogenation of isobutane. Figure 2 shows that isobutane dehydrogenation was stable over this catalyst for more than 30+ cycles despite the high temperatures used during the reaction, reduction and oxidation.

Example 18-ethane dehydrogenation. 1. The reaction zone was simultaneously heated to an oxidation temperature of 800 c with an inert gas purge system. 2. Oxygen-containing gas (O gas) at a flow rate (F _oxi ) Through the branches of the reaction zone, while inert gas is passed through the reaction zone. 3. The oxygen-containing gas is then passed through the reaction zone for a period of time (t _oxi ) To oxidize the catalyst. 4. At t _oxi Thereafter, an inert gas is passed through the reaction zone and the temperature in the reaction zone is adjusted from T _oxi Change to reduction temperature (T) _red ). 5. Containing H ₂ The gas (H gas) is at a flow rate (F _red ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. This is then followed by T _red The following is H-containing ₂ The gas flows through the reaction zone for a certain period of time (t _red ). 6. The system was purged with inert gas. During this process, the temperature of the reaction zone is varied from T _red The reaction temperature was changed to 670 ℃.7. Comprises 81% by volume of C ₂ H ₆ Hydrocarbon (HC) containing feed with 9 vol% Ar and 10 vol% steam at flow rate (F _rxn ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. The hydrocarbonaceous feed was then passed through the reaction zone at 670 ℃ for 10min. GC sampling of the reaction effluent was started as soon as the feed was switched from branch to reaction zone. The above method steps are cyclically repeated until stable performance is obtained. The catalyst showed no deactivation after 30+ cycles. Table 19 shows that the catalyst was effective in ethane dehydrogenation. C measured when the catalyst in the reaction zone was replaced by quartz ₂ H ₄ The yield was less than 1Cmol, indicating that the homogeneous reaction was not evident under the test conditions.

Example 19-effect of the vector. 1. The reaction zone was simultaneously heated to an oxidation temperature of 800 c with an inert gas purge system. 2. Oxygen-containing gas (O gas) at a flow rate (F _oxi ) Through the branches of the reaction zone, while inert gas is passed through the reaction zone. 3. The oxygen-containing gas is then passed through the reaction zone for a period of time (t _oxi ) To oxidize the catalyst. 4. The system was purged with inert gas. During this process, the temperature of the reaction zone was maintained at 800 ℃.5. Containing H ₂ The gas (H gas) is at a flow rate (F _red ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. This is then followed by bringing the H-containing phase to 800 ℃ ₂ The gas flows through the reaction zone for a certain period of time (t _red ). 6. The reaction zone is vented with He. During this process, the temperature of the reaction zone was reduced from 800 ℃ to a reaction temperature of 670 ℃.7. Comprises 81% by volume of C ₃ H ₈ Hydrocarbon (HC) containing feed of 9 vol% inert gas (Ar or Kr) and 10 vol% steam at flow rate (F _rxn ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. The hydrocarbonaceous feed was then passed through the reaction zone at 670 ℃ for 10min. GC sampling of the reaction effluent was started as soon as the feed was switched from branch to reaction zone. The above method steps are cyclically repeated until stable performance is obtained. Table 20 shows that highly active/selective/stable catalysts can be prepared from various Mg-containing catalyst supports.

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Figure 3 shows that the performance of catalyst 6 was stable over 30+ cycles despite the use of high temperatures during the reaction, reduction and oxidation.

Example 20-effect of the carrier. 1. The reaction zone was simultaneously heated to an oxidation temperature of 800 c with an inert gas purge system. 2. Oxygen-containing gas (O gas) At a flow rate (F) _oxi ) Through the branches of the reaction zone, while inert gas is passed through the reaction zone. 3. The oxygen-containing gas is then passed through the reaction zone for a period of time (t _oxi ) To oxidize the catalyst. 4. The system was purged with inert gas. During this process, the temperature of the reaction zone was cooled to 620 ℃.5. Containing H ₂ The gas (H gas) is at a flow rate (F _red ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. This is then followed by bringing the H-containing phase to 620 DEG C ₂ The gas flows through the reaction zone for a certain period of time (t _red ). 6. Inert gas is introduced into the reaction area. During this process, the temperature of the reaction zone was maintained at 620 ℃.7. Comprises 81% by volume of C ₃ H ₈ Hydrocarbon (HC) containing feed of 9 vol% inert gas (Ar or Kr) and 10 vol% steam at flow rate (F _rxn ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. The hydrocarbonaceous feed was then passed through the reaction zone at 620 ℃ for 10min. GC sampling of the reaction effluent was started as soon as the feed was switched from branch to reaction zone. The above method steps are cyclically repeated until stable performance is obtained. Table 21 shows that highly active/selective/stable catalysts can be prepared from various Mg-containing catalyst supports.

Figure 4 shows that the performance of catalyst 8 was stable over 20+ cycles despite the use of high temperatures during the reaction, reduction and oxidation. Figure 5 shows that the performance of catalyst 9 was stable over this catalyst over 30+ cycles despite the use of high temperatures during the reaction, reduction and oxidation.

Example 21-effect of metal promoters. 1. The reaction zone was simultaneously heated to an oxidation temperature of 800 c with an inert gas purge system. 2. Oxygen-containing gas (O gas) at a flow rate (F _oxi ) By reversingThe branches of the reaction zone, while inert gas is passed through the reaction zone. 3. The oxygen-containing gas is then passed through the reaction zone for a period of time (t _oxi ) To oxidize the catalyst. 4. At t _oxi Thereafter, an inert gas is passed through the reaction zone and the temperature in the reaction zone is adjusted from T _oxi Change to reduction temperature (T) _red ). 5. Containing H ₂ The gas (H gas) is at a flow rate (F _red ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. This is then followed by T _red The following is H-containing ₂ The gas flows through the reaction zone for a certain period of time (t _red ). 6. The system was purged with inert gas. During this process, the temperature of the reaction zone is varied from T _red The reaction temperature was changed to 670 ℃.7. Comprises 81% by volume of C ₃ H ₈ Hydrocarbon (HC) containing feed of 9 vol% inert gas (Ar or Kr) and 10 vol% steam at flow rate (F _rxn ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. The hydrocarbonaceous feed was then passed through the reaction zone at 670 ℃ for 10min. GC sampling of the reaction effluent was started as soon as the feed was switched from branch to reaction zone. The above method steps are cyclically repeated until stable performance is obtained. Table 22 shows that metals other than Sn can be used with Pt for dehydrogenation.

Example 22-effect of Sn level. 1. Oxygen-containing gas (O gas) at a flow rate (F _oxi ) Through the branches of the reaction zone maintained at 670 c while inert gas is passed through the reaction zone. 2. The oxygen-containing gas is then passed through the reaction zone while the temperature of the reaction zone is raised up to 800 ℃. The oxygen-containing gas remains flowing through the reaction zone for a period of time (t _oxi ) To oxidize the catalyst. Thereafter, the reaction zone was cooled to 670 ℃ in an oxygen-containing gas. 3. By inert actionA gas flushing system. During this process, the temperature of the reaction zone was maintained at 670 ℃.4. Containing H ₂ The gas (H gas) is at a flow rate (F _red ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. This is then followed by bringing the H-containing phase to 670 DEG C ₂ The gas flows through the reaction zone for a certain period of time (t _red ). 5. Inert gas is introduced into the reaction area. During this process, the temperature of the reaction zone was maintained at 670 ℃.6. Comprises 81% by volume of C ₃ H ₈ Hydrocarbon (HC) containing feed of 9 vol% inert gas (Ar or Kr) and 10 vol% steam at flow rate (F _rxn ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. The hydrocarbonaceous feed was then passed through the reaction zone at 670 ℃ for 10min. GC sampling of the reaction effluent was started as soon as the feed was switched from branch to reaction zone. The above method steps are cyclically repeated until stable performance is obtained. Table 23 shows the Sn loading on the variable catalysts.

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Example 23-effect of alkali metal additive. 1. Oxygen-containing gas (O gas) at a flow rate (F _oxi ) Through the branches of the reaction zone maintained at 670 c while inert gas is passed through the reaction zone. 2. The oxygen-containing gas is then passed through the reaction zone and the temperature of the reaction zone is raised up to 800 ℃.2. The oxygen-containing gas remains flowing through the reaction zone for a period of time (t _oxi ) To oxidize the catalyst. Thereafter, the reaction zone was cooled to 670 ℃ in an oxygen-containing gas. 3. The system was purged with inert gas. During this process, the temperature of the reaction zone was maintained at 670 ℃.4. Containing H ₂ The gas (H gas) is at a flow rate (F _red ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. This is then followed by a subsequent step of bringing the mixture to 670 DEG CContaining H ₂ The gas flows through the reaction zone for a certain period of time (t _red ). 5. Inert gas is introduced into the reaction area. During this process, the temperature of the reaction zone was maintained at 670 ℃.6. Comprises 81% by volume of C ₃ H ₈ Hydrocarbon (HC) containing feed of 9 vol% inert gas (Ar or Kr) and 10 vol% steam at flow rate (F _rxn ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. The hydrocarbonaceous feed was then passed through the reaction zone at 670 ℃ for 10min. GC sampling of the reaction effluent was started as soon as the feed was switched from branch to reaction zone. The above method steps are cyclically repeated until stable performance is obtained. Table 24 shows that alkali metals such as K can be added to the catalyst.

Example 24-effect of Pt level and synthesis method. 1. The reaction zone was simultaneously heated to an oxidation temperature of 800 c with an inert gas purge system. 2. Oxygen-containing gas (O gas) at a flow rate (F _oxi ) Through the branches of the reaction zone, while inert gas is passed through the reaction zone. 3. The oxygen-containing gas is then passed through the reaction zone for a period of time (t _oxi ) To oxidize the catalyst. 4. At t _oxi Thereafter, an inert gas is passed through the reaction zone and the temperature in the reaction zone is adjusted from T _oxi Change to reduction temperature (T) _red ). 5. Containing H ₂ The gas (H gas) is at a flow rate (F _red ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. This is then followed by T _red The following is H-containing ₂ The gas flows through the reaction zone for a certain period of time (t _red ). 6. The system was purged with inert gas. During this process, the temperature of the reaction zone is varied from T _red The reaction temperature was changed to 670 ℃.7. Comprises 81% by volume of C ₃ H ₈ 9% by volume of inert gasHydrocarbon (HC) containing feed (Ar or Kr) and 10% by volume steam at a flow rate (F) _rxn ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. The hydrocarbonaceous feed was then passed through the reaction zone at 670 ℃ for 10min. GC sampling of the reaction effluent was started as soon as the feed was switched from branch to reaction zone. The above method steps are cyclically repeated until stable performance is obtained. Table 25 shows the Pt loading on the variable catalyst and the method of synthesis.

Example 25-effect of the vector. 1. Oxygen-containing gas (O gas) at a flow rate (F _oxi ) Through the branches of the reaction zone maintained at 620 c while inert gas is passed through the reaction zone. 2. The oxygen-containing gas is then passed through the reaction zone and the temperature of the reaction zone is raised up to 800 ℃. The oxygen-containing gas remains flowing through the reaction zone for a period of time (t _oxi ) To oxidize the catalyst. Thereafter, the reaction zone was cooled to 620 ℃ in an oxygen-containing gas. 3. The system was purged with inert gas. During this process, the temperature of the reaction zone was maintained at 620 ℃.4. Containing H ₂ The gas (H gas) is at a flow rate (F _red ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. This is then followed by bringing the H-containing phase to 620 DEG C ₂ The gas flows through the reaction zone for a certain period of time (t _red ). 5. Inert gas is introduced into the reaction area. During this process, the temperature of the reaction zone was maintained at 620 ℃.6. Comprises 81% by volume of C ₃ H ₈ Hydrocarbon (HC) containing feed of 9 vol% inert gas (Ar or Kr) and 10 vol% steam at flow rate (F _rxn ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. The hydrocarbonaceous feed was then passed through the reaction zone at 620 ℃ for 10min. GC sampling of the reaction effluent was started as soon as the feed was switched from branch to reaction zone. The above method steps are cyclically repeated until stable performance is obtained. Table 26 shows that various Mg-containing catalyst supports can be used to prepare catalyst supports having good activity, selectionCatalysts of nature and high temperature stability.

Example 26-effect of the carrier. 1. Simultaneous modification of the reaction zone to T with an inert gas purging system _oxi Is used for the oxidation temperature of the catalyst. 2. Oxygen-containing gas (O gas) at a flow rate (F _oxi ) Through the branches of the reaction zone, while inert gas is passed through the reaction zone. 3. The oxygen-containing gas is then passed through the reaction zone for a period of time (t _oxi ) To oxidize the catalyst. 4. The system was purged with inert gas. During this process, the temperature of the reaction zone changes to T _red .5. Containing H ₂ The gas (H gas) is at a flow rate (F _red ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. This is then followed by T _red The following is H-containing ₂ The gas flows through the reaction zone for a certain period of time (t _red ). 6. Inert gas is introduced into the reaction area. During this process, the temperature of the reaction zone changes to T _rxn .7. Comprises 81% by volume of C ₃ H ₈ Hydrocarbon (HC) containing feed of 9 vol% inert gas (Ar or Kr) and 10 vol% steam at flow rate (F _rxn ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. The hydrocarbonaceous feed is then at T _rxn Pass through the reaction zone for 10min. GC sampling of the reaction effluent was started as soon as the feed was switched from branch to reaction zone. The above method steps are cyclically repeated until stable performance is obtained.

Table 27 above shows that catalysts with good activity, selectivity and high temperature stability can be prepared using various Mg-containing catalyst supports. Fig. 6 shows that the performance of the catalyst 24 is stable over 20+ cycles despite the use of high temperatures during the reaction, reduction and oxidation.

Comparative example 1:1. by inert gasThe flushing system heats the reaction zone to T at the same time _oxi Is used for the oxidation temperature of the catalyst. 2. Oxygen-containing gas (O gas) at a flow rate (F _oxi ) Through the branches of the reaction zone, while inert gas is passed through the reaction zone. 3. The oxygen-containing gas is then passed through the reaction zone for a period of time (t _oxi ) To oxidize the catalyst. 4. The system was purged with inert gas. During this process, the temperature of the reaction zone was cooled to 620 ℃.5. Containing H ₂ The gas (H gas) is at a flow rate (F _red ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. This is then followed by bringing the H-containing phase to 620 DEG C ₂ The gas flows through the reaction zone for a certain period of time (t _red ). 6. Inert gas is introduced into the reaction area. During this process, the temperature of the reaction zone was maintained at 620 ℃.7. Comprises 90% by volume of C ₃ H ₈ Hydrocarbon (HC) containing feed of 10% by volume inert gas (Ar or Kr) at flow rate (F _rxn ) The bypass through the reaction zone continues for a period of time while inert gas passes through the reaction zone. The hydrocarbonaceous feed was then passed through the reaction zone at 620 ℃ for 10min. GC sampling of the reaction effluent was started as soon as the feed was switched from branch to reaction zone. Table 28 shows further details of the test conditions of the comparative examples. Fig. 7 shows that the performance of comparative catalyst 1 remains deactivated even though the oxidation temperature (620 ℃) is much lower than in the other examples.

Example 27-fixed bed experiments using catalysts 28-41 were conducted at about 100 kPa-absolute. Gas Chromatography (GC) was used to measure the composition of the reactor effluent. The concentration of each component in the reactor effluent was then used to calculate C ₃ H ₆ Yield and selectivity. Calculation of C based on carbon moles as reported in these examples ₃ H ₆ Yield and selectivity.

In each example, 0.3g of the catalyst composition was mixed with an appropriate amount of quartz diluent and loaded into a quartz reactor. The amount of diluent is determined such that the catalyst bed (catalyst + diluent) overlaps the isothermal zone of the quartz reactor and such that the catalyst bed is largely isothermal during operation. The dead volume of the reactor was filled with quartz chips/rods.

t _rxn At the beginning and t _rxn C at the end ₃ H ₆ Yield and selectivity are respectively expressed as Y _ini 、Y _end 、S _ini And S is _end And are reported as a percentage for catalysts 28-35 in tables 29 and 30 below.

The method steps of the catalysts 28-35 are as follows: 1. the system was purged with inert gas. 2. Drying air was passed through the branches of the reaction zone at a flow rate of 83.9sccm while inert gas was passed through the reaction zone. The reaction zone was heated to a regeneration temperature of 800 ℃.3. The catalyst regenerated by drying air at a flow rate of 83.9sccm and then passing through the reaction zone for 10 min. 4. The system was purged with inert gas. 5. With 10% H by volume ₂ And 90% by volume Ar of H-containing ₂ The gas was passed through the branch of the reaction zone at a flow rate of 46.6sccm for a period of time while the inert gas was passed through the reaction zone. This is then followed by bringing the H-containing phase to 800 ℃ ₂ The gas flowed through the reaction zone for 3 seconds. 6. The system was purged with inert gas. During this process, the temperature of the reaction zone was changed from 800 ℃ to a reaction temperature of 670 ℃.7. Comprises 81% by volume of C ₃ H ₈ A Hydrocarbon (HC) containing feed of 9% by volume inert gas (Ar or Kr) and 10% by volume steam was passed through the branch of the reaction zone at a flow rate of 35.2sccm for a period of time while inert gas was passed through the reaction zone. The hydrocarbonaceous feed was then passed through the reaction zone at 670 ℃ for 10min. GC sampling of the reaction effluent was started as soon as the feed was switched from branch to reaction zone.

The above method steps are cyclically repeated until stable performance is obtained. Tables 29 and 30 show that catalyst 33 containing only 0.025 wt% Pt and 1 wt% Sn has similar yields and similar selectivities as compared to catalyst 28 containing 0.4 wt% Pt and 1 wt% Sn, which is surprising and unexpected. The catalyst 35, which did not include any Pt, did not show significant propylene yield.

Catalysts 36-41 were also tested using the same method steps 1-7 described above with respect to catalysts 28-35. Table 31 shows that for optimal propylene yields for catalyst compositions comprising 0.1 wt% Pt based on the weight of the support, the Sn level should not be too low or too high.

Table 32 shows that for optimal propylene yields for catalyst compositions comprising 0.0125 wt% Pt based on the weight of the support, the Sn level should not be too high or too low.

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Catalyst 33 containing only 0.025 wt% Pt and 1 wt% Sn was also subjected to life testing using the same method steps 1-7 described above with respect to catalysts 28-35 except that a flow rate of 17.6sccm was used instead of 35.2sccm in step 7. FIG. 8 shows that the catalyst 33 maintains performance for 204 cycles (x-axis is time, y-axis is C ₃ H ₆ Yield and C ₃ H ₆ Selectivity, all in mole% carbon).

List of embodiments

The present disclosure also includes the following non-limiting embodiments.

A1. To contain a group 10 element and an inorganic carrierAnd a method of at least partially deactivated catalyst regeneration of contaminants, wherein the group 10 element has a concentration in the range of 0.001 wt% to 6 wt%, based on the weight of the inorganic support, and the method comprises: (I) Obtaining a precursor catalyst from the at least partially deactivated catalyst; (II) providing a catalyst comprising not more than 5mol% H based on the total moles in the oxidizing gas ₂ Oxidizing gas of O; (III) contacting the precursor catalyst with an oxidizing gas at an oxidation temperature in the range of 620 ℃ to 1,000 ℃ for a duration of at least 30 seconds, preferably at least 1 minute, preferably at least 5 minutes, thereby producing an oxidized precursor catalyst; and (IV) obtaining regenerated catalyst from the oxidized precursor catalyst.

A method of a2 a1, wherein the group 10 element comprises Pt, and wherein the inorganic support comprises at least 0.5 wt% of the group 2 element, based on the weight of the inorganic support.

A method of a3.a2, wherein: the group 2 element contains Mg, and at least a part of the group 2 element is in the form of MgO or a mixed oxide containing MgO.

The process of any one of a4 a1 to A3, wherein the at least partially deactivated catalyst further comprises up to 10 wt% of a promoter, based on the weight of the inorganic support, and wherein the promoter comprises one or more of the following elements: sn, ag, cu, combinations thereof, or mixtures thereof.

The process of any one of a5 a1 to A4, wherein the at least partially deactivated catalyst further comprises up to 5 wt% of an alkali metal element disposed on an inorganic support, and wherein the alkali metal element comprises at least one of: li, na, K, rb and Cs.

The process of any one of a6.a1 to A5, wherein the active component of the regenerated catalyst capable of effecting one or more of dehydrogenation, dehydroaromatization and dehydrocyclization of a hydrocarbon-containing feed comprising C comprises a group 10 element ₂ -C ₁₆ One or more of linear or branched alkanes, or C ₄ -C ₁₆ One or more of the cyclic alkanes, C ₈ -C ₁₆ One or more of alkyl aromatic hydrocarbons, or mixtures thereof.

A7.The method of any one of A1 to A6, wherein step (I) comprises: using H in a concentration of more than 5mol%, based on the total moles in the heated gas mixture ₂ The heated gas mixture of O heats the at least partially deactivated catalyst to produce a precursor catalyst.

A8.a7 method wherein the heated gas mixture is produced by combusting a fuel with an oxidizing gas, and wherein the fuel comprises H ₂ At least one of CO and hydrocarbon, and the oxidizing gas comprises O ₂ 。

The process according to any one of a9 a1 to A6, wherein in step (I) an at least partially deactivated catalyst is directly provided as a procatalyst.

The method of any one of a10 a1 to A9, wherein step (II) comprises: (IIa) providing an oxidizing gas at a temperature below the oxidation temperature; and (IIb) preheating the oxidizing gas to a temperature above the temperature of the precursor catalyst prior to contacting in step (III).

The method of any one of a11 A1 to a10, further comprising: (V) heating the oxidizing gas or the precursor catalyst during step (III) by using a radiant heat source, a heat exchanger, or a combination thereof.

The method of any one of a12 A1 to a11, wherein step (IV) comprises: (IVa) reacting an oxidized procatalyst with an oxygen free catalyst ₂ Is contacted with a first stripping gas to produce a stripped oxidized precursor catalyst; and (IVb) obtaining regenerated catalyst from the stripped oxidized precursor catalyst.

The method of any one of a13 A1 to a12, wherein step (IV) comprises: (IVc) reacting an oxidized or stripped oxidized procatalyst with an H-containing catalyst ₂ Contacting the atmosphere to produce a reduced catalyst; and (IVd) obtaining regenerated catalyst from the reduced catalyst.

A method of a14.a13, wherein step (IVd) comprises: (IVd-1) contacting the reduced catalyst with a second stripping gas to produce a regenerated catalyst.

A process of a15, a13 or a14, wherein step (IVc) is performed 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 or regenerated catalyst to a service temperature for a duration of no more than 10 minutes, no more than 5 minutes, no more than 1 minute, no more than 30 seconds, no more than 10 seconds, no more than 5 seconds, no more than 1 second, no more than 0.5 seconds, no more than 0.1 seconds, no more than 0.01 seconds, or no more than 0.001 seconds.

A16. A dehydrogenation process using a regenerated catalyst produced by the process of any one of A1 to a15, the dehydrogenation process comprising: (VI) contacting the 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 group 10 elements, inorganic supports, and contaminants and an effluent comprising one or more upgraded hydrocarbons and molecular hydrogen, wherein the hydrocarbon feed comprises C ₂ -C ₁₆ One or more of linear or branched alkanes, C ₄ -C ₁₆ One or more of cyclic alkanes, C ₈ -C ₁₆ One or more of the alkylaromatic hydrocarbons, or mixtures thereof; and (VII) repeating steps (I) through (IV), wherein in step (III) additional oxidized procatalyst is produced, and wherein in step (IV) additional regenerated catalyst is obtained from the additional oxidized procatalyst; and (VIII) contacting an additional amount of a hydrocarbon-containing feed with at least a portion of the additional regenerated catalyst to produce additional at least partially deactivated catalyst and additional effluent.

A17.a16 dehydrogenation process wherein the cycle time from contacting the hydrocarbonaceous feed with regenerated catalyst in step (VI) to contacting an additional amount of hydrocarbonaceous feed with additional regenerated catalyst in step (VIII) is less than or equal to 5 hours.

B1. A method of upgrading hydrocarbons comprising: (I) Contacting the 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 comprises C ₂ -C ₁₆ One or more of the linear or branched alkanes, or C ₄ -C ₁₆ One or more of cyclic alkanes, C ₈ -C ₁₆ One or more of alkyl aromatic hydrocarbons, or mixtures thereof; and the group 10 element has a concentration in the range of 0.001 wt% to 6 wt%, based on the weight of the inorganic support; contacting a hydrocarbon-containing feed with a catalyst at a temperature in the range of 300 ℃ to 900 ℃; and the one or more upgraded hydrocarbons comprise at least one of dehydrogenated hydrocarbons, dehydroaromatized hydrocarbons, and dehydrocyclized hydrocarbons; (II) obtaining a precursor catalyst from the at least partially deactivated catalyst; (III) providing a catalyst comprising not more than 2mol% H based on the total moles in the oxidizing gas ₂ Oxidizing gas of O; (IV) contacting the precursor catalyst with an oxidizing gas at an oxidation temperature in the range of 620 ℃ to 1,000 ℃ for a duration of at least 30 seconds, preferably at least 1 minute, preferably at least 5 minutes, thereby producing an oxidized precursor catalyst; (V) obtaining a regenerated catalyst from the oxidized precursor catalyst; 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 additional effluent.

B2. method of b1, wherein: the group 10 element comprises Pt, the inorganic support comprises at least 0.5 wt% of a group 2 element, the catalyst optionally further comprises up to 10 wt% of a promoter, based on the weight of the inorganic support, wherein the promoter (if present) comprises one or more of the following elements: sn, ag, cu, combinations thereof, or mixtures thereof, the catalyst optionally further comprising up to 5 wt% of an alkali metal element, and the alkali metal element (if present) comprises at least one of: li, na, K, rb and Cs.

A method of B3, B2, wherein step (II) comprises: using H in a concentration of more than 5mol%, based on the total moles in the heated gas mixture ₂ The heated gas mixture of O heats the at least partially deactivated catalyst to produce a precursor catalyst.

B4.b3 method, wherein the heated gas mixture is produced by combusting a fuel with an oxidizing gas, and wherein the fuel comprises H ₂ At least one of CO and hydrocarbon, and the oxidizing gas comprises O ₂ 。

The process according to any one of B5 to B4, wherein in step (II) an at least partially deactivated catalyst is directly provided as a procatalyst.

The method of any one of B6 to B5, wherein step (III) comprises: (IIIa) providing an oxidizing gas at a temperature below the oxidation temperature; and (IIIb) preheating the oxidizing gas to a temperature above the temperature of the procatalyst prior to contacting in step (IV).

The method of any one of B7 to B6, further comprising: (VI) heating the oxidizing gas or the precursor catalyst during step (IV) by using a radiant heat source, a heat exchanger, or a combination thereof.

The process of any of B8.b1 to B7, wherein the cycle time from contacting the hydrocarbonaceous feed with the catalyst in step (I) to contacting an additional amount of hydrocarbonaceous feed with regenerated catalyst in step (VI) is less than or equal to 5 hours.

Various terms are defined above. Where a term is used in a claim without the above definition, the person skilled in the relevant art should be given the broadest definition persons have given that term as reflected in at least one printed publication or issued patent. Furthermore, all patents, test procedures, and other documents cited in this application are fully incorporated by reference for all jurisdictions in which such incorporation is permitted, so long as such disclosure is not inconsistent with this application.

While the foregoing 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, and the scope thereof is determined by the claims that follow.

Claims

1. A method of regenerating an at least partially deactivated catalyst comprising a group 10 element, an inorganic support, and a contaminant, wherein the group 10 element has a concentration in the range of 0.001 wt% to 6 wt%, based on the weight of the inorganic support, and the method comprises:

(I) Using addition-basedThe total moles of H in the hot gas mixture comprise a concentration of greater than 5 mole percent ₂ Heating the gas mixture of O to heat the at least partially deactivated catalyst to produce a precursor catalyst;

(II) providing a catalyst comprising not more than 5mol% H based on the total moles in the oxidizing gas ₂ Oxidizing gas of O;

(III) contacting the precursor catalyst with an oxidizing gas at an oxidation temperature in the range of 620 ℃ to 1,000 ℃ for a duration of at least 30 seconds, preferably at least 1 minute, preferably at least 5 minutes, thereby producing an oxidized precursor catalyst; and

(IV) obtaining regenerated catalyst from the oxidized precursor catalyst.

2. The method of claim 1, wherein the heated gas mixture is produced by combusting a fuel with an oxidizing gas.

3. The method of claim 2, wherein the fuel comprises H ₂ At least one of CO and hydrocarbon, and the oxidizing gas comprises O ₂ 。

4. A method according to any one of claims 1 to 3, wherein the group 10 element comprises Pt, and wherein the inorganic support comprises at least 0.5 wt% of the group 2 element, based on the weight of the inorganic support.

5. The method according to claim 4, wherein:

group 2 element contains Mg, and

at least a portion of the group 2 element is in the form of MgO or a mixed oxide containing MgO.

6. The process of any of the preceding claims, wherein the at least partially deactivated catalyst further comprises up to 10 wt% of a promoter, based on the weight of the inorganic support, and wherein the promoter comprises one or more of the following elements: sn, ag, cu, combinations thereof, or mixtures thereof.

7. The method of any of the preceding claims, wherein the at least partially deactivated catalyst further comprises up to 5 wt% of an alkali metal element disposed on an inorganic support, and wherein the alkali metal element comprises at least one of: li, na, K, rb and Cs.

8. The process of any of the preceding claims, wherein the active component of the regenerated catalyst capable of effecting one or more of dehydrogenation, dehydroaromatization, and dehydrocyclization of a hydrocarbon-containing feed comprising C comprises a group 10 element ₂ -C ₁₆ One or more of linear or branched alkanes, or C ₄ -C ₁₆ One or more of the cyclic alkanes, C ₈ -C ₁₆ One or more of alkyl aromatic hydrocarbons, or mixtures thereof.

9. The method of any one of the preceding claims, wherein step (II) comprises:

(IIa) providing an oxidizing gas at a temperature below the oxidation temperature; and

(IIb) preheating the oxidizing gas to a temperature above the temperature of the precursor catalyst prior to contacting in step (III).

10. The method of any of the preceding claims, further comprising:

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

11. The method of any one of the preceding claims, wherein step (IV) comprises:

(IVa) reacting an oxidized procatalyst with an oxygen free catalyst ₂ Is contacted with a first stripping gas to produce a stripped oxidized precursor catalyst; and

(IVb) obtaining regenerated catalyst from the stripped oxidized precursor catalyst.

12. The method of any one of the preceding claims, wherein step (IV) comprises:

(IVc) reacting an oxidized or stripped oxidized procatalyst with an H-containing catalyst ₂ Contacting the atmosphere to produce a reduced catalyst; and

(IVd) obtaining regenerated catalyst from the reduced catalyst.

13. The method of claim 12, wherein step (IVd) comprises:

(IVd-1) contacting the reduced catalyst with a second stripping gas to produce a regenerated catalyst.

14. The method of claim 12 or claim 13, wherein step (IVc) is performed 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 or regenerated catalyst to a service temperature for a duration of no more than 10 minutes, no more than 5 minutes, no more than 1 minute, no more than 30 seconds, no more than 10 seconds, no more than 5 seconds, no more than 1 second, no more than 0.5 seconds, no more than 0.1 seconds, no more than 0.01 seconds, or no more than 0.001 seconds.

15. A dehydrogenation process using a regenerated catalyst produced by the process of any one of the preceding claims, the dehydrogenation process comprising:

(VI) contacting the 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 group 10 elements, inorganic supports, and contaminants and an effluent comprising one or more upgraded hydrocarbons and molecular hydrogen, wherein the hydrocarbon feed comprises C ₂ -C ₁₆ One or more of linear or branched alkanes, C ₄ -C ₁₆ One or more of cyclic alkanes, C ₈ -C ₁₆ One or more of the alkylaromatic hydrocarbons, or a mixture thereofA compound; and

(VII) repeating steps (I) to (IV), wherein in step (III) additional oxidized procatalyst is produced, and wherein in step (IV) additional regenerated catalyst is obtained from the additional oxidized procatalyst; and

(VIII) contacting an additional amount of a hydrocarbon-containing feed with at least a portion of the additional regenerated catalyst to produce additional at least partially deactivated catalyst and additional effluent.

16. The dehydrogenation process of claim 15 wherein the cycle time from contacting the hydrocarbonaceous feed with regenerated catalyst in step (VI) to contacting an additional amount of hydrocarbonaceous feed with additional regenerated catalyst in step (VIII) is less than or equal to 5 hours.

17. A method of upgrading hydrocarbons comprising:

(I) Contacting the 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 comprises C ₂ -C ₁₆ One or more of linear or branched alkanes, or C ₄ -C ₁₆ One or more of the cyclic alkanes, C ₈ -C ₁₆ One or more of alkyl aromatic hydrocarbons, or mixtures thereof;

the group 10 element has a concentration in the range of 0.001 wt% to 6 wt%, based on the weight of the inorganic support;

Contacting a hydrocarbon-containing feed with a catalyst at a temperature in the range of 300 ℃ to 900 ℃; and

the one or more upgraded hydrocarbons comprise at least one of dehydrogenated hydrocarbons, dehydroaromatized hydrocarbons, and dehydrocyclized hydrocarbons;

(II) use of a catalyst comprising a concentration of greater than 5 mole%, based on the total moles of heated gas mixtureH of (2) ₂ Heating the gas mixture of O to heat the at least partially deactivated catalyst to produce a precursor catalyst;

(III) providing a catalyst comprising not more than 2mol% H based on the total moles in the oxidizing gas ₂ Oxidizing gas of O;

(IV) contacting the precursor catalyst with an oxidizing gas at an oxidation temperature in the range of 620 ℃ to 1,000 ℃ for a duration of at least 30 seconds, preferably at least 1 minute, preferably at least 5 minutes, thereby producing an oxidized precursor catalyst;

(V) obtaining a regenerated catalyst from the oxidized precursor catalyst; 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 additional effluent.

18. The method of claim 17, wherein the heated gas mixture is produced by combusting a fuel with an oxidizing gas.

19. The method of claim 18, wherein the fuel comprises H ₂ At least one of CO and hydrocarbon, and the oxidizing gas comprises O ₂ 。

20. The method of any one of claims 17 to 19, wherein:

the group 10 element contains Pt, and

the inorganic support comprises at least 0.5 wt% of a group 2 element, based on the weight of the inorganic support.

21. The method of any one of claims 17 to 20, wherein the catalyst further comprises up to 10 wt% of a promoter, based on the weight of the inorganic support, and wherein the promoter comprises one or more of the following elements: sn, ag, cu, combinations thereof, or mixtures thereof.

22. The method of any one of claims 17 to 21, wherein the catalyst further comprises up to 5 wt% alkali metal element, and wherein the alkali metal element comprises at least one of: li, na, K, rb and Cs.

23. The method of any one of claims 17 to 22, wherein step (III) comprises:

(IIIa) providing an oxidizing gas at a temperature below the oxidation temperature; and

(IIIb) preheating the oxidizing gas to a temperature above the temperature of the precursor catalyst prior to contacting in step (IV).

24. The method of any of claims 17 to 23, further comprising:

(VII) heating the oxidizing gas, the precursor catalyst, or both during step (IV) by using a radiant/conductive heat source, a heat exchanger, or a combination thereof.

25. The process of any one of claims 17 to 24, wherein the cycle time from contacting the hydrocarbonaceous feed with the catalyst in step (I) to contacting an additional amount of hydrocarbonaceous feed with regenerated catalyst in step (VI) is less than or equal to 5 hours.