Method for reforming alkanes and alkylaromatic hydrocarbons

Abstract

The present invention discloses a method for reforming hydrocarbons. The method may include (I) contacting a hydrocarbon-containing feed with a catalyst to effect one or more of dehydrogenation, dehydrogenation aromatization, and dehydrogenation cyclization of at least a portion of the hydrocarbon-containing feed, thereby producing a coked catalyst and an effluent, where the catalyst may include a Group 8-10 element or a compound thereof disposed on a support. The method may further include (II) contacting at least a portion of the coked catalyst with an oxidant to effect combustion of at least a portion of the coke, thereby producing a regenerated catalyst. The method may further include (III) contacting an additional amount of the hydrocarbon-containing feed with at least a portion of the regenerated catalyst. The cycle time from contacting the hydrocarbon-containing feed with the catalyst in step (I) to contacting the additional amount of the hydrocarbon-containing feed with the regenerated catalyst in step (III) may be <5 hours.

Description

[0001] Cross - reference to related applications

[0002] This application claims priority and the benefit of U.S. Provisional Application No. 62 / 986,229, filed on March 6, 2020, and European Application No. 20179508.5, filed on June 11, 2020, the disclosures of both of which are incorporated herein by reference in their entireties. Technical field

[0003] The present disclosure relates to methods for reforming alkanes and / or alkylaromatic hydrocarbons. More specifically, the present disclosure relates to methods for dehydrogenating, dehydroaromatizing, and / or dehydrogenocyclizing one or more alkanes and / or one or more alkylaromatic hydrocarbons in the presence of a catalyst to produce an effluent comprising one or more reformed hydrocarbons. Background art

[0004] The catalytic dehydrogenation, dehydroaromatization, and dehydrogenocyclization of alkanes and / or alkylaromatic hydrocarbons are endothermic and equilibrium - limited, industrially important chemical conversion processes. Alkanes such as C 2 -C 12 The dehydrogenation of alkanes and / or alkylaromatic hydrocarbons such as ethylbenzene can be accomplished by a variety of different supported catalyst systems such as Pt - based systems, Cr - based systems, Ga - based systems, V - based systems, Zr - based systems, In - based systems, W - based systems, Mo - based systems, Zn - based systems, and Fe - based systems. In existing propane dehydrogenation methods, some methods use an alumina - supported chromium oxide catalyst, which provides a maximum propylene yield of about 50% (55% propane conversion at 90% propylene selectivity), which is obtained at a temperature of about 560 °C to 650 °C and a low pressure of 20 kPa absolute to 50 kPa absolute. It is desirable to increase the propylene yield without having to operate at such a low pressure to improve the efficiency of the dehydrogenation process.

[0005] Increasing the temperature of the dehydrogenation process is one way to increase the conversion of the process according to the thermodynamics of the process. For example, at 670 °C and 100 kPa absolute pressure in the absence of any inert / diluent, the equilibrium propylene yield is estimated by simulation to be about 74%. However, at such high temperatures, the catalyst deactivates very rapidly and / or the propylene selectivity becomes uneconomically low. The rapid catalyst deactivation is believed to be caused by coke deposition on the catalyst and / or agglomeration of the active phase. The coke can be removed by combustion with an oxygen - containing gas, however, it is believed that the agglomeration of the active phase is exacerbated during the combustion process, which rapidly reduces the activity and stability of the catalyst.

[0006] Accordingly, there is a need for improved methods and catalysts for dehydrogenating, dehydroaromatizing, and / or dehydrogenocyclizing alkanes and / or alkylaromatic hydrocarbons. The present disclosure meets this need and other needs.

[0007] Overview

[0008] The present disclosure provides methods for reforming alkanes and / or alkylaromatic hydrocarbons. In some embodiments, the method for reforming hydrocarbons may include (I) contacting a hydrocarbon-containing feed with a catalyst to effect one or more of dehydrogenation, dehydrogenation aromatization, and dehydrogenation cyclization of at least a portion of the hydrocarbon-containing feed, thereby producing a coked catalyst and an effluent that may include one or more reformed hydrocarbons and molecular hydrogen. The catalyst may include Pt disposed on a support. The hydrocarbon-containing feed may include one or more C 2 -C 16 straight-chain or branched alkanes, or one or more C 4 -C 16 cyclic alkanes, or one or more C 8 -C 16 alkylaromatic hydrocarbons, or mixtures thereof. The hydrocarbon-containing feed and the catalyst may be contacted at a hydrocarbon partial pressure of at least 20 kPa absolute and a temperature in the range of 300 °C to 900 °C for a time of ≤ 3 hours, wherein the hydrocarbon partial pressure is the total partial pressure of any C 2 -C 16 alkanes and any C 8 -C 16 alkylaromatic hydrocarbons in the hydrocarbon-containing feed. The catalyst may include 0.05 wt% to 6 wt% of Pt, based on the weight of the support. The one or more reformed hydrocarbons may include at least one of dehydrogenated hydrocarbons, dehydrogenation aromatized hydrocarbons, and dehydrogenation cyclized hydrocarbons. The method may further include (II) contacting at least a portion of the coked catalyst with an oxidant to effect combustion of at least a portion of the coke, thereby producing a coke-depleted regenerated catalyst and combustion gases. The method may further include (III) contacting an additional amount of the hydrocarbon-containing feed with at least a portion of the regenerated catalyst to produce a recoked catalyst and an additional effluent. The cycle time from contacting the hydrocarbon-containing feed with the catalyst in step (I) to contacting the additional amount of the hydrocarbon-containing feed with the regenerated catalyst in step (III) may be ≤ 5 hours.

[0009] In other embodiments, the method for reforming hydrocarbons may include (I) contacting a hydrocarbon-containing feed with a catalyst to effect one or more of dehydrogenation, dehydrogenation aromatization, and dehydrogenation cyclization of at least a portion of the hydrocarbon-containing feed, thereby producing a coked catalyst and an effluent that may include one or more reformed hydrocarbons and molecular hydrogen. The catalyst may include Group 8-10 elements disposed on a support. The hydrocarbon-containing feed may include one or more C 2 -C 16 straight-chain or branched alkanes, or one or more C 4 -C 16Cycloalkanes, or one or more C 8 -C 16 alkylaromatic hydrocarbons, or mixtures thereof. The hydrocarbon feed and the catalyst can be contacted at a hydrocarbon partial pressure of at least 20 kPa absolute pressure at a temperature in the range of 300 °C to 900 °C for a time of ≤ 3 hours, where the hydrocarbon partial pressure is any C in the hydrocarbon feed 2 -C 16 alkanes and any C 8 -C 16 The total partial pressure of alkylaromatic hydrocarbons. The one or more reformed hydrocarbons can include dehydrogenated hydrocarbons, dehydroaromatized hydrocarbons, dehydrocyclized hydrocarbons, or mixtures thereof. The catalyst can include 0.05 wt% to 6 wt% of the Group 8-10 elements, based on the weight of the support. The support can include at least one of the following: w wt% of a Group 2 element, x wt% of a Group 4 element, y wt% of a Group 12 element, and z wt% of an element having an atomic number of 21, 39, or 57-71, based on the weight of the support, where w, x, y, and z are independently in the range of 0 to 100, where any Group 2 element is associated with a weight % m based on the weight of the support, any Group 4 element is associated with a weight % n based on the weight of the support, any Group 12 element is associated with a weight % p based on the weight of the support, and any element having an atomic number of 21, 39, or 57-71 is associated with a weight % q based on the weight of the support, and m, n, p, and q are independently numbers in the range of 1 to 100. The sum of w / m + x / n + y / p + z / p can be ≥ 1, based on the weight of the support. The method can further include (II) contacting at least a portion of the coked catalyst with an oxidant to effect combustion of at least a portion of the coke, thereby producing a coke-depleted regenerated catalyst and combustion gases. The method can further include (III) contacting an additional amount of the hydrocarbon feed with at least a portion of the regenerated catalyst to produce a recoked catalyst and additional effluent. The cycle time from contacting the hydrocarbon feed with the catalyst in step (I) to contacting the additional amount of the hydrocarbon feed with the regenerated catalyst in step (III) can be ≤ 5 hours.

[0010] In other embodiments, the method for reforming hydrocarbons can include (I) contacting a hydrocarbon feed with a catalyst to effect one or more of dehydrogenation, dehydroaromatization, and dehydrocyclization of at least a portion of the hydrocarbon feed, thereby producing a coked catalyst and an effluent comprising one or more reformed hydrocarbons and molecular hydrogen, the catalyst can include a Group 8-10 element or a compound thereof disposed on a support. The hydrocarbon feed can include one or more C 2 -C 16 linear or branched alkanes, or one or more C4 -C 16 Cycloalkanes, or one or more C 8 -C 16 alkylaromatic hydrocarbons, or mixtures thereof, and based on any C in the hydrocarbon-containing feed 2 -C 16 alkanes and any C 8 -C 16 alkylaromatic hydrocarbons, 0.1 vol% to 50 vol% of steam based on the total volume of the alkanes and any C 2 -C 16 alkanes and any C 8 -C 16 alkylaromatic hydrocarbons. The hydrocarbon-containing feed and the catalyst can be contacted at a hydrocarbon partial pressure of at least 20 kPa absolute for a time of ≤ 3 hours at a temperature in the range of 300 °C to 900 °C, where the hydrocarbon partial pressure is the total partial pressure of any C

[0011] Brief Description of the Drawings

[0012] Figure 1 Shows the catalyst stability results of the catalysts used in Examples 1-3 after 35 cycles (regeneration, reduction, and dehydrogenation) carried out under the same conditions used in Example 1.

[0013] Figure 2 Shows the catalyst stability results of the catalyst used in Example 23 after 49 cycles (regeneration, reduction, and dehydrogenation) in the presence of steam.

[0014] Detailed Description

[0015] Various specific embodiments, variations, and examples of the present invention will now be described, including the preferred embodiments and definitions used herein for understanding the claimed invention. Although the following detailed description gives specific, preferred embodiments, those skilled in the art will appreciate that these embodiments are merely exemplary and that the present invention may be practiced otherwise. For purposes of determining infringement, the scope of the present invention will refer to any one or more of the appended claims, including their equivalents and elements or limitations 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.

[0016] In the present disclosure, a method is described as including at least one "step". It should be understood that each step is an act or operation that may be performed one or more times in the method in a continuous or discontinuous manner. Unless otherwise specified or the context clearly indicates otherwise, multiple steps in a method may be performed successively in the order in which they are listed, with or without overlapping one or more other steps, or may be performed in any other order, if circumstances permit. Additionally, one or more or even all steps may be performed simultaneously on the same or different batches of material. For example, in a continuous method, the second step may be performed simultaneously on intermediate material obtained by processing material fed into the method at an earlier time in the first step while the first step is being performed on the raw material just fed into the starting stage of the method. Preferably, the steps are performed in the described order.

[0017] Unless otherwise indicated, all numerical values specified in the present disclosure should be understood to be modified in all instances by the term "about". It should also be understood that the exact numerical values used in this specification and the claims constitute specific embodiments. Efforts have been made to ensure the accuracy of the data in the examples. However, it should be understood that due to limitations in the techniques and / or equipment used for making measurements, any measured data inherently contains a certain level of error.

[0018] In certain embodiments and features herein, a set of numerical upper limits and a set of numerical lower limits are used to describe. It should be understood that ranges including any combination of two values (e.g., any combination of a lower limit value and an upper limit value, any combination of two lower limit values, and / or any combination of two upper limit values) have been contemplated, unless otherwise indicated.

[0019] As used herein, the indefinite article "a" or "an" means "at least one", unless otherwise specified or the context clearly indicates otherwise. Thus, embodiments using "a reactor" or "a conversion zone" include embodiments in which one, two, or more reactors or conversion zones are used, unless otherwise specified or the context clearly indicates that only one reactor or conversion zone is used.

[0020] The term "hydrocarbon" means (i) any compound consisting of hydrogen and carbon atoms or (ii) any mixture of two or more such compounds of (i). The term "Cn hydrocarbon" (where n is a positive integer) means (i) any hydrocarbon compound containing a total of n carbon atoms in its molecule or (ii) any mixture of two or more such hydrocarbon compounds of (i). Thus, C2 hydrocarbons can be ethane, ethylene, acetylene, or any mixture of at least two of these compounds in any proportion. "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 of them. Thus, "C2 to C3 hydrocarbons" or "C2-C3 hydrocarbons" can be any one of ethane, ethylene, acetylene, propane, propylene, propyne, allene, cyclopropane, and any mixture of two or more of them in any proportion between the components. "Saturated C2-C3 hydrocarbons" can be any mixture of ethane, propane, cyclopropane, or two or more of them in any proportion. "Cn+ hydrocarbons" means (i) any hydrocarbon compound containing a total of at least n carbon atoms in its molecule or (ii) any mixture of two or more such hydrocarbon compounds of (i). "Cn- hydrocarbons" means (i) any hydrocarbon compound containing a total of at most n carbon atoms in its molecule or (ii) any mixture of two or more such hydrocarbon compounds of (i). "Cm hydrocarbon stream" means a hydrocarbon stream consisting essentially of Cm hydrocarbons. "Cm-Cn hydrocarbon stream" means a hydrocarbon stream consisting essentially of Cm-Cn hydrocarbons.

[0021] For the purposes of the present disclosure, the naming of elements is based on the version of the periodic table of the elements provided in Appendix V of Hawley's Condensed Chemical Dictionary, 16th Edition, John Wiley & Sons, Inc. (2016) (in the new notation). For example, Group 8 elements include Fe, Group 9 elements include Co, and Group 10 elements include Ni. The term "metalloid" as used herein means 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 form or in the form of any of its compounds, unless otherwise stated or the context clearly indicates otherwise.

[0022] The term "alkane" refers to a saturated hydrocarbon. The term "cycloalkane" refers to a saturated hydrocarbon that contains a cyclic carbon ring in its molecular structure. Alkanes can be straight-chain, branched, or cyclic.

[0023] The term "aromatic hydrocarbon" should be understood within its generally recognized scope in the art, which includes alkyl-substituted and unsubstituted mono- and polynuclear compounds.

[0024] When used in phrases such as "rich in X" or "X-rich", the term "rich" means that, with respect to an effluent stream obtained from a unit such as a conversion zone, the stream contains the material X at a concentration higher than that in the feed material fed to the same unit from which the stream is derived. When used in a phrase such as "poor in X", the term "poor" means that, with respect to an effluent stream obtained from a unit such as a conversion zone, the stream contains the material X at a concentration lower than that in the feed material fed to the same unit from which the stream is derived.

[0025] The term "selectivity" refers to the production of a specified compound (on a carbon mole basis) in a catalytic reaction. As an example, the phrase "the alkane conversion reaction has 100% olefin selectivity" means that 100% (on a carbon mole basis) of the alkanes converted in the reaction are converted to olefins. When used in combination with a specified reactant, the term "conversion rate" refers to the amount of the reactant consumed in the reaction. For example, when the specified reactant is propane, a 100% conversion rate means that 100% of the propane is consumed in the reaction. The yield (on a carbon mole basis) is the conversion rate multiplied by the selectivity.

[0026] Overview

[0027] The hydrocarbon-containing feed may be or may include, but is not limited to, one or more alkanes, such as C 2 -C 16 straight-chain or branched alkanes and / or C 4 -C 16 cycloalkanes, and / or one or more alkyl aromatic hydrocarbons, such as C 8 -C 16 alkyl aromatic hydrocarbons. In some embodiments, the hydrocarbon-containing feed may optionally include 0.1 vol% to 50 vol% steam, based on the total volume of any C 2 -C 16 alkanes and any C 8 -C 16 alkyl aromatic hydrocarbons in the hydrocarbon-containing feed. In other embodiments, the hydrocarbon-containing feed may include <0.1 vol% steam or may be steam-free, based on the total volume of any C 2 -C 16 alkanes and any C 8 -C16 Based on the total volume of the alkylaromatic hydrocarbons. The hydrocarbon-containing feed can be contacted with a catalyst comprising a Group 8-10 element such as Pt disposed on a support to effect one or more of dehydrogenation, dehydroaromatization, and dehydrogenation cyclization of at least a portion of the hydrocarbon-containing feed, thereby producing a coked catalyst and an effluent that can comprise one or more reformed hydrocarbons and molecular hydrogen. The one or more reformed hydrocarbons can be or can comprise one or more dehydrogenated hydrocarbons, one or more dehydroaromatized hydrocarbons, one or more dehydrogenated cyclized hydrocarbons, or a mixture thereof. The hydrocarbon-containing feed and the catalyst can be contacted at a hydrocarbon partial pressure of at least 20 kPa absolute at a temperature in the range of 300 °C to 900 °C for a first time of ≤ 3 hours, wherein 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 the alkylaromatic hydrocarbons. The catalyst can comprise 0.05 wt% to 6 wt% of a Group 8-10 element such as Pt, based on the weight of the support. The support can be or can comprise, but is not limited to, a Group 2 element, a Group 4 element, a Group 12 element, an element having an atomic number of 21, 39, or 57-71, or a compound thereof.

[0028] At least a portion of the coked catalyst can be contacted with one or more oxidizing agents to effect combustion of at least a portion of the coke, thereby producing a coke-lean regenerated catalyst and combustion gases. In some embodiments, the method can optionally include contacting at least a portion of the regenerated catalyst with a reducing gas to produce a regenerated and reduced catalyst. An additional amount of the hydrocarbon-containing feed can be contacted with at least a portion of the regenerated catalyst and / or at least a portion of any regenerated and reduced catalyst to produce a recoked catalyst and an additional effluent. The cycle time from contacting the hydrocarbon-containing feed with the catalyst to contacting the additional amount of the hydrocarbon-containing feed with the regenerated catalyst can be ≤ 5 hours.

[0029] Surprisingly and unexpectedly, it has been found that a catalyst comprising a Group 8-10 element such as Pt disposed on a support can remain sufficiently active and stable after many cycles (e.g., at least 15 cycles, at least 20 cycles, at least 30 cycles, at least 40 cycles, at least 50 cycles, at least 60 cycles, at least 70 cycles, at least 100 cycles, at least 125 cycles, at least 150 cycles, at least 175 cycles, or at least 200 cycles), with each cycle having a duration of ≤ 5 hours, ≤ 4 hours, ≤ 3 hours, ≤ 2 hours, ≤ 1 hour, ≤ 50 minutes, ≤ 45 minutes, ≤ 30 minutes, ≤ 15 minutes, ≤ 10 minutes, ≤ 5 minutes, ≤ 1 minute, ≤ 30 seconds, or ≤ 10 seconds. In some embodiments, the cycle time can 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 the catalyst performance stabilizes (sometimes the first few cycles may have relatively poor or relatively good performance, but the performance can eventually stabilize), the method can produce a first reformed hydrocarbon product (e.g., propylene when the hydrocarbon feed comprises propane) in a yield of ≥ 75%, ≥ 80%, ≥ 85%, ≥ 90%, or > 95% reformed hydrocarbon such as propylene selectivity upon initial contact with the hydrocarbon feed, and can have a second reformed hydrocarbon product yield in a reformed hydrocarbon such as propylene selectivity of ≥ 75%, ≥ 80%, ≥ 85%, ≥ 90%, or > 95% after completion of the last cycle (a total of at least 15 cycles), and the second reformed hydrocarbon product yield can be at least 90%, at least 93%, at least 95%, at least 97%, at least 98%, at least 99%, at least 99.5%, or at least 100% of the first reformed hydrocarbon product yield. Prior to this discovery, it was believed that a catalyst having a Group 8-10 element such as Pt as the active component would not maintain sufficient activity and stability when subjected to so many short cycles with simple oxidative regeneration that do not require the addition of halogens.

[0030] The first cycle begins when the catalyst is contacted with the hydrocarbon feed, followed by contacting the catalyst with at least an oxidizing agent to produce a regenerated catalyst or contacting the catalyst with at least an oxidizing agent and an optional reducing gas to produce a regenerated and reduced catalyst, and the first cycle ends when the regenerated catalyst or the regenerated and reduced catalyst is contacted with an additional amount of the hydrocarbon feed. The second cycle and each subsequent cycle begin when the regenerated catalyst or the regenerated and reduced catalyst is contacted with the additional amount of the hydrocarbon feed, and the second cycle and each subsequent cycle end when an additional or subsequently regenerated catalyst or regenerated and reduced catalyst is contacted with an additional amount of the hydrocarbon feed.

[0031] In addition, unprecedented propylene yields have been obtained using the methods and catalysts described herein. In some embodiments, when the hydrocarbon feed comprises propane and the reformed hydrocarbon comprises propylene, for at least 15 cycles, at least 20 cycles, at least 30 cycles, at least 40 cycles, at least 50 cycles, at least 60 cycles, at least 70 cycles, at least 100 cycles, at least 125 cycles, at least 150 cycles, at least 175 cycles, or at least 200 cycles, contacting the hydrocarbon feed with the catalyst can produce a propylene yield of at least 52%, at least 53%, at least 55%, at least 57%, at least 60%, at least 62%, or at least 63% at a propylene selectivity of at least 75%, at least 80%, at least 85%, at least 90%, or at least 95%. In other embodiments, when the hydrocarbon feed comprises at least 70 vol% propane based on the total volume of the hydrocarbon feed and is contacted at a propane partial pressure of at least 20 kPa absolute pressure, for at least 15 cycles, at least 20 cycles, at least 30 cycles, at least 40 cycles, at least 50 cycles, at least 60 cycles, at least 70 cycles, at least 100 cycles, at least 125 cycles, at least 150 cycles, at least 175 cycles, or at least 200 cycles, a propylene yield of at least 52%, at least 53%, at least 55%, at least 57%, at least 60%, at least 62%, or at least 63% can be obtained at a propylene selectivity of at least 75%, at least 80%, at least 85%, at least 90%, or at least 95%. It is believed that for at least 15 cycles, at least 20 cycles, at least 30 cycles, at least 40 cycles, at least 50 cycles, at least 60 cycles, at least 70 cycles, at least 100 cycles, at least 125 cycles, at least 150 cycles, at least 175 cycles, or at least 200 cycles, by further optimizing the composition of the support and / or adjusting one or more process conditions, the propylene yield can be further increased to at least 65%, 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% at a propylene selectivity of at least 75%, at least 80%, at least 85%, at least 90%, or at least 95%. In some embodiments, for at least 15 cycles, at least 20 cycles, at least 30 cycles, at least 40 cycles, at least 50 cycles, at least 60 cycles, at least 70 cycles, at least 100 cycles, at least 125 cycles, at least 150 cycles, at least 175 cycles, or at least 200 cycles, the propylene yield can be obtained when the catalyst is contacted with the hydrocarbon feed at a temperature of at least 620 °C, at least 630 °C, at least 640 °C, at least 650 °C, at least 655 °C, at least 660 °C, at least 670 °C, at least 680 °C, at least 690 °C, at least 700 °C, or at least 750 °C.Such a high propylene yield under such processing conditions is not considered possible.

[0032] Hydrocarbon reforming process

[0033] The hydrocarbon-containing feed and the catalyst can be contacted with each other in any suitable environment (such as one or more reaction or conversion zones provided in one or more reactors) to produce an effluent and a coked catalyst. In some embodiments, the reaction or conversion zone can be provided in or 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.

[0034] The hydrocarbon-containing feed and the catalyst can be contacted at a temperature in the range from 300 °C, 350 °C, 400 °C, 450 °C, 500 °C, 550 °C, 600 °C, 620 °C, 650 °C, 660 °C, 670 °C, 680 °C, 690 °C, or 700 °C to 725 °C, 750 °C, 760 °C, 780 °C, 800 °C, 825 °C, 850 °C, 875 °C, or 900 °C. In some embodiments, the hydrocarbon-containing feed and the catalyst can be contacted at a temperature of at least 620 °C, at least 650 °C, at least 660 °C, at least 670 °C, at least 680 °C, at least 690 °C, or at least 700 °C to 725 °C, 750 °C, 760 °C, 780 °C, 800 °C, 825 °C, 850 °C, 875 °C, or 900 °C. The hydrocarbon-containing feed can be introduced into the reaction or conversion zone and contacted with the catalyst therein for a time of ≤ 3 hours, ≤ 2.5 hours, ≤ 2 hours, ≤ 1.5 hours, ≤ 1 hour, ≤ 45 minutes, ≤ 30 minutes, ≤ 20 minutes, ≤ 10 minutes, ≤ 5 minutes, ≤ 1 minute, ≤ 30 seconds, ≤ 10 seconds, ≤ 5 seconds, or ≤ 1 second or ≤ 0.5 second. In some embodiments, the hydrocarbon-containing feed can be contacted with the catalyst for a time in the range from 0.1 second, 0.5 second, 0.7 second, 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.

[0035] The hydrocarbon-containing feed and the catalyst can be contacted at a hydrocarbon partial pressure of at least 20 kPa absolute pressure, wherein the hydrocarbon partial pressure is any C in the hydrocarbon-containing feed 2 -C 16 alkanes and any C 8 -C 16Total partial pressure of alkylaromatic hydrocarbons. In some embodiments, during the contact of the hydrocarbon feed and the catalyst, the hydrocarbon partial pressure can range from 20 kPa absolute, 50 kPa absolute, 100 kPa absolute, at least 150 kPa, at least 200 kPa, 300 kPa absolute, 500 kPa absolute, 750 kPa absolute, or 1,000 kPa absolute to 1,500 kPa absolute, 2,500 kPa absolute, 4,000 kPa absolute, 5,000 kPa absolute, 7,000 kPa absolute, 8,500 kPa absolute, or 10,000 kPa absolute, wherein the hydrocarbon partial pressure is any C in the hydrocarbon feed 2 -C 16 alkane and any C 8 -C 16 Total partial pressure of alkylaromatic hydrocarbons. In other embodiments, during the contact of the hydrocarbon feed and the catalyst, the hydrocarbon partial pressure can 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, wherein the hydrocarbon partial pressure is any C in the hydrocarbon feed 2 -C 16 alkane and any C 8 -C 16 Total partial pressure of alkylaromatic hydrocarbons.

[0036] In some embodiments, the hydrocarbon feed can include at least 60 vol%, at least 65 vol%, at least 70 vol%, at least 75 vol%, at least 80 vol%, at least 85 vol%, at least 90 vol%, at least 95 vol%, or at least 99 vol% of a single C 2 -C 16 alkane, such as propane, based on the total volume of the hydrocarbon feed. The hydrocarbon feed and the catalyst can be contacted at a pressure of at least 20 kPa absolute, at least 50 kPa absolute, at least 100 kPa absolute, at least 150 kPa absolute, at least 250 kPa absolute, at least 300 kPa absolute, at least 400 kPa absolute, at least 500 kPa absolute, or at least 1,000 kPa absolute of a single C 2 -C 16 alkane such as propane.

[0037] The hydrocarbon feed can be contacted with the catalyst in a reaction or conversion zone at any weight hourly space velocity (WHSV) effective for carrying out the reforming process. In some embodiments, the WHSV can range from 0.01 hr-1 ,0.1 hr -1 ,1 hr -1 ,2 hr -1 ,5 hr -1 ,10 hr -1 ,20 hr -1 ,30 hr -1 ,or 50 hr -1 to 100 hr -1 ,250 hr -1 ,500 hr -1 ,or 1,000 hr -1 within the range of. In some embodiments, when the hydrocarbon reforming method includes sulfiding or moving the catalyst, the ratio of the catalyst to the total amount of any C 2 -C 16 alkanes and any C 8 -C 16 alkyl aromatic hydrocarbons can 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, by weight ratio.

[0038] When the activity of the coked catalyst drops below the required minimum amount, the coked catalyst or at least a portion thereof can be contacted with an oxidant in the reaction or conversion zone or in a combustion zone separate from the reaction or conversion zone (depending on the specific reactor configuration) to produce a regenerated catalyst. For example, regeneration of the catalyst can occur in the reaction or conversion zone when a fixed bed or countercurrent reactor is used, or regeneration of the catalyst can occur in a separate combustion zone separate 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 can also occur in the reaction or conversion zone, in the combustion zone, and / or in a separate reduction zone. Accordingly, the hydrocarbon feed can be contacted with the catalyst in a periodic method such as those commonly used for fixed bed and countercurrent reactors and / or in a continuous method commonly used for fluidized bed reactors to effect one or more of dehydrogenation, dehydroaromatization, and dehydrogenation cyclization of at least a portion of the hydrocarbon feed, thereby producing a coked catalyst and a first effluent comprising one or more reformed hydrocarbons and molecular hydrogen. If desired, separation of the effluent comprising the reformed hydrocarbons and molecular hydrogen and the coked catalyst can be achieved by one or more separators such as a cyclone separator.

[0039] The oxidant can be or can include but is not limited to O 2 ,O 3 ,CO 2 ,H 2O, or mixtures thereof. In some embodiments, an oxidizing agent in an amount greater than that required to combust the coke on the catalyst can be used to increase the rate of coke removal from the catalyst, such that the time required for coke removal can be reduced and an increased yield of the reformed product produced over a given period of time can result.

[0040] The coked catalyst and the oxidizing agent can be contacted with each other at a temperature in the range from 300 °C, 350 °C, 400 °C, 450 °C, 500 °C, 550 °C, 600 °C, 650 °C, 700 °C, 750 °C, or 800 °C to 900 °C, 950 °C, 1,000 °C, 1,050 °C, or 1,100 °C to produce a regenerated catalyst. In some embodiments, the coked catalyst and the oxidizing agent can be contacted with each other at a temperature in the range from 500 °C to 1,100 °C, 600 °C to 1,000 °C, 650 °C to 950 °C, 700 °C to 900 °C, or 750 °C to 850 °C to produce a regenerated catalyst.

[0041] The coked catalyst and the oxidizing agent can be contacted with each other for a time of ≤ 2 hours, ≤ 1 hour, ≤ 30 minutes, ≤ 10 minutes, ≤ 5 minutes, ≤ 1 minute, ≤ 30 seconds, ≤ 10 seconds, ≤ 5 seconds, or ≤ 1 second. For example, the coked catalyst and the oxidizing agent can be contacted with each other for a time in the range from 2 seconds to 2 hours. In some embodiments, the coked catalyst and the oxidizing agent can be contacted for a time sufficient to remove ≥ 50 wt%, ≥ 75 wt%, ≥ 90 wt% or > 99% of any coke deposited on the catalyst.

[0042] In some embodiments, the time during which the coked catalyst and the oxidant contact each other can be less than the time during which the catalyst contacts the hydrocarbon feed to produce the effluent and the coked catalyst. For example, the time during which the coked catalyst and the oxidant contact each other can be at least 90%, at least 60%, at least 30%, or at least 10% less than the time during which the catalyst contacts the hydrocarbon feed to produce the effluent. In other embodiments, the time during which the coked catalyst and the oxidant contact each other can be greater than the time during which the catalyst contacts the hydrocarbon feed to produce the effluent and the coked catalyst. For example, the time during which the coked catalyst and the oxidant contact each other can be at least 50%, at least 100%, at least 300%, at least 500%, at least 1,000%, at least 10,000%, at least 30,000%, at least 50,000%, at least 75,000%, at least 100,000%, at least 250,000%, at least 500,000%, at least 750,000%, at least 1,000,000%, at least 1,250,000%, at least 1,500,000%, or at least 1,800,000% greater than the time during which the catalyst contacts the hydrocarbon feed to produce the effluent.

[0043] The coked catalyst and the oxidant can contact each other at an oxidant partial pressure in the range from 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. In other embodiments, during the contact with the coked catalyst, the oxidant partial pressure can 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 to produce the regenerated catalyst.

[0044] Without wishing to be bound by theory, it is believed that at least a portion of Group 8-10 elements such as Pt disposed on the coked catalyst may be agglomerated compared to the catalyst prior to contact with the hydrocarbon feed. It is believed that during the combustion of at least a portion of the coke on the coked catalyst, at least a portion of the Group 8-10 elements may be redispersed on the support. Redispersing at least a portion of any agglomerated Group 8-10 elements can increase activity and improve the stability of the catalyst over multiple cycles.

[0045] In some embodiments, at least a portion of the Group 8-10 elements such as Pt in the regenerated catalyst may be in a higher oxidation state compared to the Group 8-10 elements in the catalyst in contact with the hydrocarbon feed and compared to the Group 8-10 elements in the coked catalyst. Thus, as noted above, in some embodiments the method may optionally include contacting at least a portion of the regenerated catalyst with a reducing gas to produce a regenerated and reduced catalyst. Suitable reducing gases (reductants) can be or can include but are not limited to H 2 , CO, CH 4 , C 2 H 6 , C 3 H 8 , C 2 H 4 , C 3 H 6 , steam, or mixtures thereof. In some embodiments, the reductant may be mixed with an inert gas such as Ar, Ne, He, N 2 , CO 2 , H 2 O or mixtures thereof. In such embodiments, at least a portion of the Group 8-10 elements in the regenerated and reduced catalyst may be reduced to a lower oxidation state such as the elemental state, compared to the Group 8-10 elements in the regenerated catalyst. In this embodiment, an additional amount of hydrocarbon feed may be contacted with at least a portion of the regenerated catalyst and / or at least a portion of the regenerated and reduced catalyst.

[0046] In some embodiments, the regenerated catalyst and the reducing gas can be contacted at a temperature in the range from 300 °C, 350 °C, 400 °C, 450 °C, 500 °C, 550 °C, 600 °C, 620 °C, 650 °C, or 670 °C to 720 °C, 750 °C, 800 °C, or 900 °C. The regenerated catalyst and the reducing gas can be contacted for a time in the range from 1 second, 5 seconds, 10 seconds, 20 seconds, 30 seconds, or 1 minute to 10 minutes, 30 minutes, or 60 minutes. The regenerated catalyst and the reducing gas can be contacted at a reducing agent partial pressure in the range from 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. In other embodiments, the reducing agent partial pressure can 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 during contact with the regenerated catalyst to produce the regenerated catalyst.

[0047] At least a portion of the regenerated catalyst, the regenerated and reduced catalyst, the new or fresh catalyst, or a mixture thereof can be contacted with an additional amount of the hydrocarbonaceous feed in a reaction or conversion zone to produce additional effluent and additional coked catalyst. As noted above, the cycle time from contacting the hydrocarbonaceous feed with the catalyst to contacting an additional amount of the hydrocarbonaceous feed with at least a portion of the regenerated catalyst and / or the regenerated and reduced catalyst and optionally with the new or fresh catalyst can be ≤ 5 hours.

[0048] In some embodiments, one or more additional feeds, such as one or more purge fluids, can be used between the hydrocarbonaceous feed stream and the oxidant stream, between the oxidant and an optional reducing gas (if used), between the oxidant and an additional hydrocarbonaceous feed, and / or between the reducing gas and an additional hydrocarbonaceous feed. The purge fluid can in particular purge or expel unwanted materials such as non-combustible particles including soot from the reactor. In some embodiments, the one or more additional feeds can be inert under the dehydrogenation, dehydroaromatization and dehydrogenation cyclization, combustion, and / or reduction conditions. Suitable purge fluids can be or can include N 2 , He, Ar, CO 2, H 2 O, CO 2 , CH 4 , or mixtures thereof. In some embodiments, if the method uses a purge fluid, the duration or period of use of the purge fluid can range from 1 second, 5 seconds, 10 seconds, 20 seconds, 30 seconds, or 1 minute to 10 minutes, 30 minutes, or 60 minutes.

[0049] As noted above, the first cycle begins when the catalyst contacts the hydrocarbon-containing feed, followed by contacting the catalyst with at least an oxidant to produce a regenerated catalyst or with at least an oxidant and an optional reducing gas to produce a regenerated and reduced catalyst, and the first cycle ends when the regenerated catalyst or the regenerated and reduced catalyst contacts an additional amount of the hydrocarbon-containing feed. If any purge fluid is used between the hydrocarbon-containing feed stream and the oxidant stream, between the oxidant and the reducing gas (if used), between the oxidant and the additional amount of the hydrocarbon-containing feed, and / or between the reducing gas (if used) and the additional amount of the hydrocarbon-containing feed, the time of use of such purge fluid will be included in the time period included in the cycle time. Thus, the cycle time from contacting the hydrocarbon-containing feed with the catalyst in step (I) to contacting an additional amount of the hydrocarbon-containing feed with the regenerated catalyst in step (III) can be ≤ 5 hours.

[0050] Systems suitable for practicing the methods disclosed herein can include systems known in the art, such as the fixed bed reactor disclosed in WO publication number WO2017078894; the fluidized riser reactor and / or downflow reactor disclosed in U.S. Patent Nos. 3,888,762, 7,102,050, 7,195,741, 7,122,160, and 8,653,317 and U.S. Patent Application Publication Nos. 2004 / 0082824, 2008 / 0194891; and the countercurrent reactor disclosed in U.S. Patent No. 8,754,276, U.S. Patent Application Publication No. 2015 / 0065767, and WO publication number WO2013169461.

[0051] Catalyst

[0052] The catalyst may comprise 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.5 wt%, or from 1 wt% to 2 wt%, 3 wt%, 4 wt%, 5 wt%, or 6 wt% of Group 8-10 elements, based on the total weight of the support. In some embodiments, the catalyst may comprise >0.025 wt%, >0.05 wt%, >0.1 wt%, >0.13 wt%, >0.15 wt%, >0.17 wt%, >0.2 wt%, >0.2 wt%, >0.23 wt%, >0.25 wt%, >0.27 wt%, or >0.3 wt% and <0.5 wt%, <1 wt%, <2 wt%, <3 wt%, <4 wt%, <5 wt%, or <6 wt% of Group 8-10 elements, based on the total weight of the support. In some embodiments, the Group 8-10 elements may be or may include, but are not limited to, Fe, Co, Ni, Ru, Pd, Os, Ir, Pt, combinations thereof, or mixtures thereof. In at least one embodiment, the Group 8-10 element may be or may include Pt.

[0053] The support may be or may include, but is not limited to, one or more elements having an atomic number of 4, 12, 20-22, 30, 38-40, 48, or 56-71. Alternatively, the support may be or may include one or more Group 2 elements, one or more Group 4 elements, one or more Group 12 elements, one or more elements having an atomic number of 21, 39, or 57-71, combinations thereof, or mixtures thereof. In some embodiments, the Group 2 elements, Group 4 elements, Group 12 elements, and / or elements having an atomic number of 21, 39, or 57-71 may be present in their elemental form. In other embodiments, the Group 2 elements, Group 4 elements, Group 12 elements, and / or elements having an atomic number of 21, 39, or 57-71 may be present in the form of a compound. For example, the Group 2 elements, Group 4 elements, Group 12 elements, and / or elements having an atomic number of 21, 39, or 57-71 may be oxides, phosphates, halides, halates, sulfates, sulfides,

[0054] in the form of borates, nitrides, carbides, aluminates, aluminosilicates, silicates, carbonates, metaphosphates, selenides, tungstates, molybdates, chromites, chromates, dichromates or silicides. In some embodiments, a mixture of any two or more compounds including Group 2 elements, Group 4 elements, Group 12 elements and / or elements having atomic numbers 21, 39 or 57-71 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, Group 4 elements, Group 12 elements and / or elements having atomic numbers 21, 39 or 57-71 from each other.

[0055] In some embodiments, the carrier may be or may include at least one of the following: w wt% of a Group 2 element, x wt% of a Group 4 element, y wt% of a Group 12 element, and z wt% of an element having an atomic number of 21, 39 or 57-71, based on the weight of the carrier, wherein w, x, y and z are independently in the range of 0 to 100. Any Group 2 element present in the carrier may be associated with a wt% m based on the weight of the carrier, any Group 4 element present in the carrier may be associated with a wt% n based on the weight of the carrier, any Group 12 element present in the carrier may be associated with a wt% p based on the weight of the carrier, and any element having an atomic number of 21, 39 or 57-71 present in the carrier may be associated with a wt% q based on the weight of the carrier, wherein m, n, p and q may independently be numbers in the range of 1 to 100. In some embodiments, the sum of w / m + x / n + y / p + z / p may be at least 1, based on the weight of the carrier. In other embodiments, the sum of w / m + x / n + y / p + z / p may be at least 1, at least 2, at least 4, at least 6, at least 8, at least 12, at least 24, at least 48, or at least 60, based on the weight of the carrier. In other embodiments, the sum of w / m + x / n + y / p + z / p may be in the range from 1, 2, 3, 4, 5, 6, 7, or 8 to 10, 12, 16, 24, 30, 48, or 60. In other embodiments, the sum of w / m + x / n + y / p + z / p may be in the range from 1 to 2, from 2 to 4, from 4 to 6, from 6 to 8, from 8 to 12, from 12 to 24, from 24 to 48, or from 48 to 60.

[0056] In some embodiments, m can be one of ten values selected from 2, 4, 6, 8, 10, 12, 14, 16, 18, and 20; n can be one of twelve values selected from 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, and 24; p can be one of twelve values selected from 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, and 24; and q can be one of twelve values selected from 2, 4, 6, 10, 14, 18, 22, 26, 30, 34, 38, and 40, where m, n, p, and q can be any combination such that there are 17,280 (10 x 12 x 12 x 12) different combinations. In other embodiments, m can be equal to 2, 7, 10, or 20, n can be 2, 10, 20, or 25, p can be 2, 10, 20, or 25, and q can be 2, 10, 30, or 40, where m, n, p, and q can be any combination such that there are 256 (4 x 4 x 4 x 4) different combinations. In some embodiments, m, n, p, and q can each be equal to 2, 10, 15, or 30. In other embodiments, m can be equal to 7, n can be equal to 10, p can be equal to 10, and q can be equal to 10. In other embodiments, m can be equal to 7, n can be equal to 20, p can be equal to 20, and q can be equal to 10. In other embodiments, m can be equal to 10, n can be equal to 20, p can be equal to 20, and q can be equal to 30. In other embodiments, m can be equal to 7, n can be equal to 10, p can be equal to 10, and q can be equal to 30.

[0057] In some embodiments, w, x, y, and z can independently be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or 100, where the sum of w, x, y, z ≤ 100.

[0058] In some embodiments, when the support comprises a Group 2 element, the molar ratio of the Group 2 element to the Group 8-10 element can 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, or 9,500. In some embodiments, when the support comprises a Group 4 element, the molar ratio of the Group 4 element to the Group 8-10 element can range from 0.18, 0.3, 0.5, 1, 10, 50, 100, or 200 to 300, 400, 500, 600, 700, or 810. In some embodiments, when the support comprises a Group 12 element, the molar ratio of the Group 12 element to the Group 8-10 element can range from 0.29, 0.5, 1, 10, 50, or 100 to 200, 300, 400, 500, or 590. In some embodiments, when the support comprises an element with atomic number 21, 39, or 57-71, the molar ratio of the element with atomic number 21, 39, or 57-71 to the Group 8-10 element can range from 0.19, 0.5, 1, 10, 50, 100, or 150 to 200, 250, 300, 350, 400, or 438. In some embodiments, when the support comprises two or more of a Group 2, 4, or 12 element and an element with atomic number 21, 39, or 57-71, the total molar ratio of any Group 2 element, any Group 4 element, any Group 12 element, and any element with atomic number 21, 39, or 57-71 to the Group 8-10 element can range from 0.18, 0.5, 1, 10, 50, 100, 300, 450, 600, 800, 1,000, 1,200, 1,500, 1,700, or 2,000 to 3,000, 3,500, 4,000, 4,500, 5,000, 5,500, 6,000, 6,500, 7,000, 7,500, 8,000, 8,500, 9,000, or 9,500.

[0059] In some embodiments, the support can be or can include, but is not limited to, one or more of the following compounds: Mg u Zn 1-u O, where u is a positive number; Zn v Al 2 O 3+v where v is a positive number; Mg w Al2 O 3+w , where w is a positive number; Ca x Al 2 O 3+x , where x is a positive number; Sr y Al 2 O 3+y , where y is a positive number; 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 ; ZrO 2 ; ZrC; ZrN; ZrSiO 4 ; CaZrO 3 ; Ca 7 ZrAl 6 O 18 ; TiO 2 ; TiC; TiN; TiSiO 4 ; CaTiO 3 ; Ca 7 Al 6 O 18 ; HfO 2 ; HfC; HfN; HfSiO 4 ; HfZrO 3 ; Ca 7 HfAl 6 O 18 ; ZnO; Zn 3 (PO 4 ) 2 ; Zn(ClO 3 ) 2 ; ZnSO 4 ; B 2 O 6 Zn 3 ; Zn 3 N 2 ; ZnCO 3 ; CeO 2 ; Y 2 O 3 ; La 2 O 3 ; Sc 2 O 3 ; Pr 6 O 11 ; CePO 4 ; CeZrO 4 ; CeAlO3 ; BaCeO 3 ; CePO 4 ; yttria-stabilized ZrO 2 ; one or more magnesium chromates, one or more magnesium tungstates, one or more magnesium molybdates, combinations thereof, and mixtures thereof.

[0060] If present as the carrier or as a component of the carrier, the Mg where u is a positive number u Zn 1-u O may have a molar ratio of Mg to Zn in the range from 1, 2, 3 or 6 to 12, 25, 50 or 100. If present as the carrier or as a component of the carrier, the Zn where v is a positive number v Al 2 O 3+v may have a molar ratio of Zn to Al in the range from 0.05, 0.3 or 0.6 to 0.9, 1.5 or 3. If present as the carrier or as a component of the carrier, the Mg where w is a positive number w Al 2 O 3+w may have a molar ratio of Mg to Al in the range from 1, 2, 3, 4 or 5 to 6, 7, 8, 9 or 10. If present as the carrier or as a component of the carrier, the Ca where x is a positive number x Al 2 O 3+x may have a molar ratio of Ca to Al in the range of 1:12, 1:4, 1:2, 2:3, 5:6, 1:1, 12:14, or 1.5:1. In some embodiments, the Ca x Al 2 O 3+x may include tricalcium aluminate, dodecacalcium heptaaluminate, monocalcium aluminate, monocalcium dialuminate, monocalcium hexaaluminate, dicalcium aluminate, pentacalcium trialuminate, tetracalcium trialuminate, or any mixture thereof. If present as the carrier or as a component of the carrier, the Sr where y is a positive number y Al 2 O 3+y may have a molar ratio of Sr to Al in the range from 0.05, 0.3 or 0.6 to 0.9, 1.5 or 3. If present as the carrier or as a component of the carrier, the Ba where z is a positive number z Al 2 O 3+z may have a molar ratio of Ba to Al in the range from 0.05, 0.3 or 0.6 to 0.9, 1.5 or 3.

[0061] In some embodiments, the support may further include, but is not limited to, at least one metal element selected from Groups 5, 6, 7, 11, 13, 14, 15, and 16 and / or at least one metalloid element and / or at least one compound thereof. If the support further includes a compound containing the metal element and / or metalloid element selected from Groups 5, 6, 7, 11, 13, 14, 15, and 16, the compound may be present in the support in the form of an oxide, phosphate, halide, halate, sulfate, sulfide, borate, nitride, carbide, aluminate, aluminosilicate, silicate, carbonate, metaphosphate, selenide, tungstate, molybdate, chromite, chromate, dichromate, or silicide. In some embodiments, suitable compounds containing the metal element and / or metalloid element selected from Groups 5, 6, 7, 11, 13, 14, 15, and 16 may be or may include, but are not limited to, one or more of the following: B 2 O 3 ,AlBO 3 ,Al 2 O 3 ,SiO 2 ,SiC,Si 3 N 4 ,aluminosilicate, VO, V 2 O 3 ,VO 2 ,V 2 O 5 ,Ga 2 O 3 ,In 2 O 3 ,Mn 2 O 3 ,Mn 3 O 4 ,MnO, one or more molybdenum oxides, one or more tungsten oxides, one or more zeolites, and mixtures and combinations thereof.

[0062] In some embodiments, the support may further include one or more promoters disposed thereon. The promoter may be or may include, but is not limited to, Sn, Ga, Zn, Ge, In, Re, Ag, Au, Cu, combinations thereof, or mixtures thereof. Thus, if present as a component of the catalyst, Zn, Ga, and / or In may be present as a component of the support, as a promoter disposed on the support, or both as a component of the support and as a promoter disposed on the support. In some embodiments, the promoter may be associated with Group 8-10 elements such as Pt. For example, the promoter and the Group 8-10 elements disposed on the support may form a Group 8-10 element-promoter cluster, which may be dispersed on the support. If present, the promoter may improve the selectivity / activity / lifetime of the catalyst for a given reformed hydrocarbon. In some embodiments, when the hydrocarbon feed includes propane, adding a promoter may improve the propylene selectivity of the catalyst. The catalyst may include the promoter 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 3 wt%, 5 wt%, 7 wt%, or 10 wt%, based on the weight of the support.

[0063] In some embodiments, the support may further include one or more alkali metal elements disposed on the support. If present, the alkali metal element may be or may 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. If present, the alkali metal element may improve the selectivity of the catalyst for a given reformed hydrocarbon. The catalyst may include the 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 support.

[0064] The preparation of the support can be accomplished by any known method. For simplicity and ease of description, the preparation of a suitable support including a mixed oxide of magnesium and aluminum (Mg(Al)O or MgO / Al 2 O 3 ) will be described in more detail. Catalyst synthesis techniques are well known, and the following description is for illustrative purposes and should not be considered limiting of the synthesis of the support or catalyst. In some embodiments, to prepare MgO / Al2 O 3 A mixed oxide support can be prepared by mixing Mg and Al precursors such as Mg(NO 3 ) 2 and Al(NO 3 ) 3 together, for example by ball milling, followed by calcination. In another embodiment, the two precursors can be dissolved in H 2 O, stirred to dryness (optionally with the application of heat), and then calcined. In another embodiment, the two precursors can be dissolved in H 2 O, and then a base and a carbonate such as NaOH / Na 2 CO 3 are added to produce a hydrotalcite, which is then calcined. In another embodiment, commercially available MgO and Al 2 O 3 can be mixed and ball milled. In another embodiment, the Mg(NO 3 ) 2 precursor can be dissolved in water, and the solution can be impregnated onto an existing support such as Al 2 O 3 support, which can then be dried and calcined. In another embodiment, Mg from Mg(NO 3 ) 2 can be loaded onto an existing Al 2 O 3 support by ion adsorption, followed by liquid-solid separation, drying, and calcination.

[0065] Group 8-10 metals, any cocatalyst, and / or any alkali metal element can be loaded onto the mixed oxide support by any known technique. For example, one or more Group 8-10 element precursors such as chloroplatinic acid, tetraammineplatinum nitrate, and / or tetraammineplatinum hydroxide, one or more cocatalyst precursors (if used) such as salts like 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 can be impregnated onto a support and then dried and calcined. In some embodiments, the Group 8-10 element precursor and optionally the promoter precursor and / or the alkali metal element precursor can be loaded onto the support simultaneously or separately in sequence (with drying and / or calcination steps in between). In other embodiments, the Group 8-10 elements and optionally the promoter and / or alkali metal elements can be loaded onto the support by chemical vapor deposition, where the precursors are volatilized and deposited onto the support, followed by calcination. In other embodiments, the Group 8-10 element precursor and optionally the promoter precursor and / or alkali metal precursor can be loaded onto the support by ion adsorption, followed by liquid-solid separation, drying, and calcination. Optionally, the catalyst can also be synthesized using a one-pot synthesis method, where the support, the Group 8-10 metal active phase, and the precursors of the promoter are all dry or wet mixed together with or without any other additives that assist in the synthesis, followed by drying and calcination.

[0066] Suitable methods for preparing the catalysts disclosed herein can include those described in U.S. Patent Nos. 4,788,371; 4,962,265; 5,922,925; 8,653,317; European Patent No. EP0098622; Journal of Catalysis 94 (1985), pp. 547-557; and / or Applied Catalysis 54 (1989), pp. 79-90.

[0067] When examined under a scanning electron microscope or a transmission electron microscope, the as-synthesized catalyst can appear as primary particles, aggregates of primary particles, aggregated primary particles, or combinations thereof. When examined under a scanning electron microscope or a transmission electron microscope, the primary particles in the as-synthesized catalyst can have an average particle size in the range from 0.2 nm, 0.5 nm, 1 nm, 5 nm, 10 nm, 25 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, 450 nm, or 500 nm to 1 μm, 10 μm, 25 μm, 50 μm, 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 400 μm, or 500 μm, such as the diameter when spherical. In some embodiments, the discrete particles of the catalyst can have an average cross-sectional length in the range of 0.2 nm - 500 μm, 0.5 nm - 300 μm, 1 nm - 200 μm, 2 nm - 100 μm, or 2 nm - 500 nm, measured by transmission electron microscopy.

[0068] The catalyst can have a surface area in the range from 0.1 m 2 / g, 1 m 2 / g, 10 m 2 / g, or 100 m 2 / g to 500 m 2 / g, 800 m 2 / g, 1,000 m 2 / g, or 1,500 m 2 / g. The surface area of the catalyst can be measured by adsorption - desorption of nitrogen (liquid nitrogen temperature 77K) using a Micromeritics 3Flex instrument according to the Brunauer - Emmett - Teller (BET) method after degassing the powder at 350 °C for 4 hours. More information about this method can be found, for example, in "Characterization of Porous Solids and Powders: Surface Area, Pore Size and Density," S. Lowell et al., Springer, 2004.

[0069] In some embodiments, the support can be extruded or otherwise formed into any desired monolithic structure, and the Group 8-10 element and any optional promoter and / or alkali metal element can be disposed thereon. Suitable monolithic structures can be or can include, but are not limited to, structures having a plurality of substantially parallel internal channels, such as those in the form of a ceramic honeycomb. In some embodiments, the support can be in the form of beads, spheres, rings, annuli, irregularly shaped objects, rods, cylinders, flakes, films, cubes, objects of polygonal geometry, sheets, fibers, coils, helices, meshes, sintered porous materials, granules, pellets, platelets, powders, particulate matter, extrudates, cloth or web-forming materials, honeycomb matrix monoliths (including their comminuted or crushed forms), and the Group 8-10 element and any optional promoter and / or alkali metal element can be disposed thereon.

[0070] The as-synthesized catalyst can be formulated into one or more suitable forms for different short-cycle (≤5 hours) hydrocarbon reforming processes. Alternatively, the support can be formulated into a suitable form for different short-cycle hydrocarbon reforming processes before adding the Group 8-10 element and any optional promoter and / or alkali metal element. During the formulation process, one or more binders and / or additives can 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 area in the range of 40 μm to 80 μm are typically used in FCC-type fluidized bed reactors. To prepare spray-dried catalyst, the support / catalyst needs to be made into a slurry having a binder / additive in the slurry, and then spray-dried and calcined.

[0071] Hydrocarbon feed

[0072] The C 2 -C 16The alkane can be or can include but not be limited to ethane, propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, n-heptane, 2-methylhexane, 2,2,3-trimethylbutane, cyclopentane, cyclohexane, methylcyclopentane, ethylcyclopentane, n-propylcyclopentane, 1,3-dimethylcyclohexane, or a mixture thereof. For example, the hydrocarbon-containing feed can include propane and / or isobutane, and propane can be dehydrogenated to produce propylene, and isobutane can be dehydrogenated to produce isobutene. In another example, the hydrocarbon-containing feed can include liquefied petroleum gas (LP gas), which can be in the gas phase when contacted with the catalyst. In some embodiments, the hydrocarbon in the hydrocarbon-containing feed can consist essentially of a single alkane such as propane. In some embodiments, the hydrocarbon-containing feed can include ≥50 mol%, ≥75 mol%, ≥95 mol%, ≥98 mol%, or ≥99 mol% of a single C 2 -C 16 alkane, such as propane, based on the total weight of all hydrocarbons in the hydrocarbon-containing feed. In some embodiments, the hydrocarbon-containing feed can include at least 50 vol%, at least 55 vol%, at least 60 vol%, at least 65 vol%, at least 70 vol%, at least 75 vol%, at least 80 vol%, at least 85 vol%, at least 90 vol%, at least 95 vol%, at least 97 vol%, or at least 99 vol% of a single C 2 -C 16 alkane, such as propane, based on the total volume of the hydrocarbon-containing feed.

[0073] The C 8 -C 16 alkyl aromatic hydrocarbon can be or can include but not be limited to ethylbenzene, propylbenzene, butylbenzene, one or more ethyltoluenes, or a mixture thereof. In some embodiments, the hydrocarbon-containing feed can include ≥50 mol%, ≥75 mol%, ≥95 mol%, ≥98 mol%, or ≥99 mol% of a single C 8 -C 16 alkyl aromatic hydrocarbon, such as ethylbenzene, based on the total weight of all hydrocarbons in the hydrocarbon-containing feed. In some embodiments, ethylbenzene can be dehydrogenated to produce styrene. Thus, in some embodiments, the methods disclosed herein can include propane dehydrogenation, butane dehydrogenation, isobutane dehydrogenation, pentane dehydrogenation, cyclization of pentane to cyclopentadiene, naphtha reforming, ethylbenzene dehydrogenation, ethyltoluene dehydrogenation, etc.

[0074] In some embodiments, the hydrocarbon-containing feed can be diluted, for example, with one or more diluents such as one or more inert gases. Suitable inert gases can be or can include but not be limited to Ar, Ne, He, N 2, CO 2 , CH 4 , or a mixture thereof. If the hydrocarbon-containing feedstock includes a diluent, the hydrocarbon-containing feedstock may include a diluent in the range from 0.1 vol%, 0.5 vol%, 1 vol% or 2 vol% to 3 vol%, 8 vol%, 16 vol% or 32 vol%, based on the total volume of any C 2 -C 16 alkanes and any C 8 -C 16 alkyl aromatic hydrocarbons.

[0075] In some embodiments, the hydrocarbon-containing feedstock may further include hydrogen. In some embodiments, when the hydrocarbon-containing feedstock includes hydrogen, the molar ratio of the hydrogen to the total amount of any C 2 -C 16 alkanes and any C 8 -C 16 alkyl aromatic 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.

[0076] In some embodiments, the hydrocarbon-containing feedstock may be substantially free of any vapor, such as <0.1 vol% vapor, based on the total volume of any C 2 -C 16 alkanes and any C 8 -C 16 alkyl aromatic hydrocarbons. In other embodiments, the hydrocarbon-containing feedstock may include vapor. For example, the hydrocarbon-containing feedstock may include 0.1 vol%, 0.3 vol%, 0.5 vol%, 0.7 vol%, 1 vol%, 3 vol%, or 5 vol% to 10 vol%, 15 vol%, 20 vol%, 25 vol%, 30 vol%, 35 vol%, 40 vol%, 45 vol%, or 50 vol% vapor, based on the total volume of any C 2 -C 16 alkanes and any C 8 -C 16 alkyl aromatic hydrocarbons. In other embodiments, the hydrocarbon-containing feedstock may include ≤50 vol%, ≤45 vol%, ≤40 vol%, ≤35 vol%, ≤30 vol%, ≤25 vol%, ≤20 vol%, or ≤15 vol% vapor, based on the total volume of any C 2 -C 16 alkanes and any C 8 -C 16Based on the total volume of the alkylaromatic hydrocarbons. In other embodiments, the hydrocarbon-containing feed may comprise at least 1 vol%, at least 3 vol%, at least 5 vol%, at least 10 vol%, at least 15 vol%, at least 20 vol%, at least 25 vol%, or at least 30 vol% of vapor, based on any C in the hydrocarbon-containing feed 2 -C 16 alkanes and any C 8 -C 16 Based on the total volume of the alkylaromatic hydrocarbons.

[0077] In some embodiments, the hydrocarbon-containing feed may comprise sulfur. For example, the hydrocarbon-containing feed may comprise sulfur in the range from 0.5 ppm, 1 ppm, 5 ppm, 10 ppm, 20 ppm 30 ppm, 40 ppm, 50 ppm, 60 ppm, 70 ppm, or 80 ppm to 100 ppm, 150 ppm, 200 ppm, 300 ppm, 400 ppm, or 500 ppm. In other embodiments, the hydrocarbon-containing feed may comprise sulfur in the range of 1 ppm - 10 ppm, 10 ppm - 20 ppm, 20 ppm - 50 ppm, 50 ppm - 100 ppm, or 100 ppm - 500 ppm. If present in the hydrocarbon-containing feed, the sulfur may be or may include, but is not limited to, H 2 2S, dimethyldisulfide, one or more thiols, or any mixture thereof.

[0078] The hydrocarbon feed may be substantially free or free of molecular oxygen. In some embodiments, the hydrocarbon feed may comprise ≤5 mol%, ≤3 mol%, or ≤1 mol% of molecular oxygen (O 2 2). It is believed that providing a hydrocarbon feed substantially free of molecular oxygen substantially prevents oxidative coupling reactions that would otherwise consume at least a portion of the alkanes and / or alkylaromatic hydrocarbons in the hydrocarbon feed.

[0079] Recovery and use of the reformed hydrocarbons

[0080] The reformed hydrocarbons may comprise at least one reformed hydrocarbon such as olefins, water, unreacted hydrocarbons, unreacted molecular hydrogen, etc. The reformed hydrocarbons may be recovered or otherwise obtained by any convenient process (e.g., by one or more conventional processes). One such process may include cooling the effluent to condense any water and at least a portion of any heavy hydrocarbons that may be present, leaving the olefins and any unreacted alkanes or alkylaromatic hydrocarbons primarily in the gas phase. The olefins and unreacted alkanes or alkylaromatic hydrocarbons may then be removed from the reaction product in one or more separation drums. For example, one or more splitters may be used to separate the dehydrogenation product from the unreacted hydrocarbon feed.

[0081] In some embodiments, recycled olefins such as propylene can be used to produce polymers. For example, the recycled propylene can be polymerized to produce polymers having segments or units derived from the recycled propylene, such as polypropylene, ethylene-propylene copolymers, and the like. Recycled isobutene can be used, for example, to produce one or more of the following: oxygenates such as methyl tert-butyl ether, fuel additives such as dimeric isobutene, synthetic elastomeric polymers such as butyl rubber, and the like. Examples

[0082] The foregoing discussion can be further described with reference to the following non-limiting examples.

[0083] The following process steps are carried out on the catalyst used in most of the examples below. All experiments were carried out at ambient pressure, with a few exceptions noted in the examples below.

[0084] 1. Pass a gas containing 10 vol% O in He or air at the regeneration temperature (T 2 ) over the catalyst for a certain time (t 再生 ) to regenerate the catalyst. 再生

[0085] 2. Without changing the gas flow rate, change the temperature in the reactor from T 再生 to the reduction temperature (T 还原 ).

[0086] 3. Flush the system with He gas.

[0087] 4. Pass a gas containing 10 vol% hydrogen in Ar over the catalyst at the T 还原 for a period of time (t 还原 ).

[0088] 5. Flush the system with He gas.

[0089] 6. In the presence of an inert gas, change the temperature in the reactor from T 还原 to the reaction temperature (T 反应 ).

[0090] 7. Pass a hydrocarbon feed having a certain flow rate (F 反应 ) and containing 90 vol% C in Ar or Kr or He 3 H 8 over the catalyst at T 反应 for a period of time (t 反应 ). In some embodiments, the hydrocarbon feed is passed through a distributor immersed in deionized water maintained at a temperature T 1 and then through a carefully controlled temperature T 2The reflux device, and then introduce it into the reactor and reach the catalyst. When using the distributor, the hydrocarbon feed in the reactor includes a certain amount of steam, which is shown in the following relevant table.

[0091] 8. Flush the system with He gas.

[0092] 9. Pass a gas containing 10 vol% O in He 2 or air through the catalyst again at T 反应 and change the temperature in the reactor from T 反应 to T 再生 .

[0093] In some embodiments, the catalyst reduction step is not performed, and the following steps are carried out.

[0094] 1. Pass a gas containing 10 vol% O in He 2 or air through the catalyst at T 再生 . 再生 .

[0095] 2. Without changing the gas flow rate, change the temperature in the reactor from T 再生 to T 反应 .

[0096] 3. Flush the system with an inert gas such as He.

[0097] 4. Pass a hydrocarbon feed with a flow rate of F 反应 containing 90 vol% C in Ar or Kr or He 3 H 8 through the catalyst at T 反应 . In some embodiments, pass the hydrocarbon feed through a distributor immersed in deionized water maintained at a temperature of T 反应 , then through a reflux device with a carefully controlled temperature of T 1 , and then introduce it into the reactor and reach the catalyst. 2

[0098] 5. Flush the system with an inert gas such as He.

[0099] 6. Pass a gas containing 10 vol% O in He 2 or air through the catalyst again at T 反应 and change the temperature in the reactor from T 反应 to T 再生 .

[0100] Use every 1 minute to 1.5 minutes The microGC 490 measures the composition of the reactor effluent. Then the concentration of each component in the reactor effluent is used to calculate the C 3 H 6 yield and selectivity. At t 反应 start and t 反应 end, the C 3 H 6 yields and selectivities are denoted as Y 开始 、Y 结束 、S 开始 and S 结束 ,and are reported as percentages in the following data table. For some experiments, repeated cycles are carried out to understand the catalyst stability. The C 3 H 6 yields reported in these examples are based only on carbon.

[0101] In each example, a certain amount (M 催化剂 ) of catalyst is mixed with an appropriate amount of quartz / SiC diluent and loaded into a quartz reactor. The amount of diluent is determined such that the catalyst bed (catalyst + diluent) is mostly isothermal during operation. The dead volume of the reactor is filled with quartz chips / quartz rods.

[0102] When the reaction temperature (T 反应 ) is greater than 620 °C, the thermal cracking of propane / propylene becomes significant. Since the thermal cracking of propane / propylene has a much higher selectivity to C 1 and C 2 hydrocarbons, the total selectivity to C 3 H 6 decreases. The amount of thermal cracking in the reactor is related to how much quartz / SiC diluent is added to the reactor and how well the dead volume in the reactor is reduced by the packing material. Therefore, depending on how the reactor is filled in different experiments, the performance can vary. Thus, the experimental results shown in different tables are not necessarily comparable to each other.

[0103] Examples 1 - 23, Catalyst 1

[0104] Catalyst 1: The catalyst used in Examples 1 - 23 is a Pt-based Sn-containing catalyst supported on a Mg / Al mixed oxide support, which is crushed and sieved to a particle size of 20 - 40 mesh. Elemental analysis shows that, based on the total weight of the metal elements, the catalyst contains 0.48 wt% Pt, 1.25 wt% Sn, 67.93 wt% Mg, and 29.23 wt% Al, where the molar ratio of Mg to Al is about 2.58.

[0105] Table 1 shows the experimental results of Examples 1 - 3.

[0106]

[0107] Comparison between Example 1 and Example 3 shows that the reduction of the catalyst in the presence of molecular hydrogen after oxidative regeneration improves the propylene yield. Examples 1 and 3 also show that under the experimental conditions used for these examples, the catalyst is not very sensitive to the duration of the reduction step (1 minute vs. 5 minutes). However, under other conditions, there may be an optimal duration for carrying out the reduction step. Figure 1 The catalyst stability results of the catalysts used in Examples 1 - 3 are shown after having undergone 35 cycles (regeneration, reduction, and dehydrogenation) carried out under the same conditions used in Example 1.

[0108] Table 2 shows the experimental results of Examples 4 and 5. The results in Table 2 show that the reduction step can be carried out at different temperatures (670 °C vs. 750 °C).

[0109]

[0110] Table 3 shows the experimental results of Examples 6 - 10. Examples 6 - 10 were carried out by introducing a partial plug at the exhaust of the reactor such that when the hydrocarbon feed passed through the reactor at room temperature (e.g., 25 °C), the pressure indicator reading upstream of the reactor was 1.43 bara. During the experiment, the gas volume flow rate in the reactor was expected to increase due to steam addition, higher temperature, and the volumetric expansion of the gas stream due to propane dehydrogenation. Therefore, the pressure inside the reactor should be significantly higher than 1.43 bara. Unfortunately, due to equipment limitations, the pressure inside the reactor could not be monitored. Experiments 8 - 10 show the effect of regeneration carried out at different temperatures and durations.

[0111]

[0112] Table 4 shows the experimental results of Examples 11 - 14. The results in Table 4 show the effect of the space velocity on the catalyst performance.

[0113]

[0114]

[0115] Table 5 shows the experimental results of Examples 15 and 16. Table 5 shows the effect of reduction in the presence of steam, respectively.

[0116]

[0117] Table 6 shows the results of Examples 17 and 18. Table 6 shows the effect of the regeneration duration.

[0118]

[0119] Table 7 shows the results of Examples 19 - 22. Table 7 shows the effect of the amount of steam in the hydrocarbon feed on the yield and selectivity.

[0120]

[0121]

[0122] In Example 23, the catalyst underwent a total of 49 cycles in the presence of approximately 11 vol% steam. The results of Example 23 are shown in Table 8.

[0123]

[0124] Figure 2 The catalyst stability results of the catalyst used in Example 23 are shown after having undergone 49 cycles (regeneration, reduction, and dehydrogenation) in the presence of steam.

[0125] Example 24, Catalyst 2

[0126] The catalyst comprises 1 wt% Pt and 3 wt% Sn supported on CeO 2 , based on the weight of the CeO 2 . The CeO 2 support is prepared by calcining cerium(III) nitrate hexahydrate (Sigma - Aldrich 202991). The catalyst is prepared by incipient wetness impregnation of 3 g of CeO 2 with 0.788 g of an 8 wt% aqueous solution of chloroplatinic acid (Sigma Aldrich, 262587) and 0.266 g of tin(IV) chloride pentahydrate (Acros Organics 22369) and then drying and calcining at 800 °C for 12 h.

[0127]

[0128] The data in Table 9 indicate that the catalyst is stable within 42 cycles.

[0129] Examples 25 and 26, Catalyst 3

[0130] The catalyst comprises 1 wt% of Pt and 2.7 wt% of Sn supported on cerium-zirconium oxide, based on the weight of the cerium-zirconium oxide. The catalyst was prepared by isovolumetric impregnation of 16.5 g of cerium-zirconium oxide (Sigma Aldrich 634174) with 0.44 g of chloroplatinic acid hexahydrate (BioXtra, P7082) and 1.33 g of tin(IV) chloride pentahydrate (Acros Organics 22369) dissolved in an appropriate amount of deionized water, followed by drying and calcination at 800 °C for 12 h.

[0131]

[0132] Examples 27 - 29, Catalyst 4

[0133] The catalyst comprises 1 wt% of Pt and 2.7 wt% of Sn supported on Y 2 O 3 , based on the weight of the Y 2 O 3 The catalyst was prepared by isovolumetric impregnation of 4 g of Y 2 O 3 (US nano3553) with 0.106 g of chloroplatinic acid hexahydrate (BioXtra, P7082) and 0.322 g of tin(IV) chloride pentahydrate (Acros Organics 22369) dissolved in an appropriate amount of deionized water, followed by drying and calcination at 800 °C for 12 h.

[0134]

[0135] The data in Table 11 show that the performance of the catalyst is stable within 20 cycles.

[0136] Examples 30 - 34, Catalyst 5

[0137] The catalyst comprises 1 wt% of Pt and 2.7 wt% of Sn supported on CeO 2 and Al 2 O 3 support. The CeO 2 and Al 2 O 3The support was prepared by isovolumetric impregnation of 8.25 g of alumina (Sigma Aldrich 199443) with 5.67 g of cerium(III) nitrate hexahydrate (Sigma Aldrich 202991) dissolved in a suitable amount of deionized water and then drying and calcining at 800 °C for 12 h. The catalyst was prepared by isovolumetric impregnation of the CeO 2 and Al 2 O 3 support with 0.22 g of chloroplatinic acid hexahydrate (BioXtra, P7082) and 0.67 g of tin(IV) chloride pentahydrate (Acros Organics 22369) dissolved in a suitable amount of deionized water and then drying and calcining at 800 °C for 12 h.

[0138]

[0139] The data in Table 12 show that the introduction of both steam and catalyst pre-reduction helps to increase the yield and selectivity.

[0140] Examples 35 - 38, Catalyst 6

[0141] The catalyst is a catalyst obtained from Alfa Aesar and contains 0.2 wt% Pt, 0.2 wt% Sn and 0.67 wt% K supported on high surface area ZrO 2 .

[0142]

[0143] The data in Table 13 show that the catalyst is stable within 24 cycles and the addition of steam significantly increases the yield.

[0144] The present disclosure may further include the following embodiments / aspects:

[0145] E1. A method for reforming hydrocarbons, the method comprising:

[0146] (I) contacting a hydrocarbon-containing feed with a catalyst comprising Pt disposed on a support to effect one or more of dehydrogenation, dehydrogenation aromatization, and dehydrogenation cyclization of at least a portion of the hydrocarbon-containing feed, thereby producing a coked catalyst and an effluent comprising one or more reformed hydrocarbons and molecular hydrogen:

[0147] The hydrocarbon-containing feed comprises one or more C 2 -C 16 linear or branched alkanes, or one or more C 4 -C 16 cycloalkanes, or one or more C 8 -C 16An alkyl aromatic hydrocarbon, or a mixture thereof; wherein

[0148] The hydrocarbon-containing feedstock and the catalyst are contacted at a hydrocarbon partial pressure of at least 20 kPa absolute pressure at a temperature in the range of 300 °C to 900 °C for a time of ≤ 3 hours, wherein the hydrocarbon partial pressure is any C in the hydrocarbon-containing feedstock 2 -C 16 alkane and any C 8 -C 16 The total partial pressure of alkyl aromatic hydrocarbons; the catalyst contains 0.05 wt% to 6 wt% of Pt, based on the weight of the support; and the one or more reformed hydrocarbons include at least one of dehydrogenated hydrocarbons, dehydroaromatized hydrocarbons, and dehydrocyclized hydrocarbons;

[0149] (II) Contacting at least a portion of the coked catalyst with an oxidant to effect combustion of at least a portion of the coke, thereby producing a coke-depleted regenerated catalyst and combustion gas; and

[0150] (III) Contacting an additional amount of the hydrocarbon-containing feedstock with at least a portion of the regenerated catalyst to produce a recoked catalyst and additional effluent, wherein the cycle time from contacting the hydrocarbon-containing feedstock with the catalyst in step (I) to contacting the additional amount of the hydrocarbon-containing feedstock with the regenerated catalyst in step (III) is ≤ 5 hours.

[0151] The method of E2.E1, wherein in step (I) the hydrocarbon-containing feedstock and the catalyst are contacted in the presence of steam, the amount of the steam being 0.1 vol% to 30 vol%, based on any C in the hydrocarbon-containing feedstock 2 -C 16 alkane, any C 4 -C 16 cycloalkane and any C 8 -C 16 The total volume of alkyl aromatic hydrocarbons.

[0152] The method of E3.E1 or E2, wherein in step (I) the hydrocarbon-containing feedstock and the catalyst are contacted in the presence of steam, the amount of the steam being 1 vol% to 15 vol%, based on any C in the hydrocarbon-containing feedstock 2 -C 16 alkane, any C 4 -C 16 cycloalkane and any C 8 -C 16 The total volume of alkyl aromatic hydrocarbons.

[0153] A method according to any one of E4.E1 to E3, wherein the coked catalyst comprises agglomerated Pt disposed on the support, and wherein at least a portion of the agglomerated Pt on the support is redispersed on the support during the coke combustion process in step (II).

[0154] A method according to any one of E5.E1 to E4, wherein the hydrocarbon-containing feed comprises propane, wherein the reformed hydrocarbon comprises propylene, and wherein the contact of the hydrocarbon-containing feed with the catalyst in step (I) has a propylene yield of at least 52% or at least 62% or at least 72% at a propylene selectivity of ≥75%, ≥80%, ≥85%, ≥90%, or ≥95%.

[0155] A method according to any one of E6.E1 to E5, wherein the hydrocarbon-containing feed comprises ≥70 vol% propane based on the total volume of the hydrocarbon-containing feed, wherein the hydrocarbon-containing feed and the catalyst are contacted at a propane partial pressure of at least 40 kPa absolute pressure, and wherein the contact of the hydrocarbon-containing feed with the catalyst in step (I) has a propylene yield of at least 52% or at least 62% or at least 72% at a propylene selectivity of ≥75%, ≥80%, ≥85%, ≥90%, or ≥95%.

[0156] A method according to any one of E7.E1 to E6, wherein steps (I) to (III) are repeated at least 15 cycles, wherein the catalyst has a first yield when initially contacted with the hydrocarbon-containing feed, and wherein the catalyst has a second activity at the completion of the 15th cycle, and the second activity is at least 98% of the first yield.

[0157] A method according to any one of E8.E1 to E7, wherein at least a portion of the Pt in the regenerated catalyst is in a higher oxidation state compared to the Pt in the catalyst in contact with the hydrocarbon-containing feed; the method further comprises the following step after step (II) and before step (III):

[0158] (IIa) contacting at least a portion of the regenerated catalyst with a reducing gas to produce a regenerated and reduced catalyst, wherein at least a portion of the Pt in the regenerated and reduced catalyst is reduced to a lower oxidation state compared to the Pt in the regenerated catalyst, and wherein the additional amount of the hydrocarbon-containing feed is contacted with at least a portion of the regenerated and reduced catalyst.

[0159] A method according to E9.E8, wherein in step (IIa), the regenerated catalyst and the reducing gas are contacted at a temperature in the range of 450 °C to 900 °C, preferably 600 °C to 900 °C, more preferably 620 °C to 800 °C, more preferably 650 °C to 750 °C, more preferably 670 °C to 720 °C.

[0160] A method according to E10, E8 or E9, wherein in step (IIa), the regenerated catalyst and the reducing gas are contacted at a reducing agent partial pressure of from 20 kPa absolute pressure to 10,000 kPa absolute pressure, or from 50 kPa absolute pressure to 5,000 kPa absolute pressure, or from 100 kPa absolute pressure to 1,000 kPa absolute pressure.

[0161] A method according to any one of E11 - E10, wherein at least a part of the Pt in the regenerated and reduced catalyst is in the elemental state.

[0162] A method according to any one of E1 - E11, wherein the hydrocarbon - containing feed further comprises an inert gas, such as Ar, Ne, He, N 2 , CH 4 , or a mixture thereof.

[0163] A method according to any one of E1 - E12, wherein in step (I), the hydrocarbon - containing feed and the catalyst are contacted at a temperature in the range of 600 °C to 900 °C, preferably 600 °C to 800 °C, more preferably 650 °C to 750 °C, even more preferably 670 °C to 720 °C.

[0164] A method according to any one of E1 - E13, wherein in step (I), the hydrocarbon - containing feed and the catalyst are contacted at a hydrocarbon partial pressure in the range of from 20 kPa absolute pressure to 10,000 kPa absolute pressure, or from 50 kPa absolute pressure to 5,000 kPa absolute pressure, or from 100 kPa absolute pressure to 1,000 kPa absolute pressure.

[0165] A method according to any one of E1 - E14, wherein in step (II), the coked catalyst and the oxidant are contacted at a temperature in the range of 600 °C to 1,100 °C, preferably 650 °C to 1,000 °C, more preferably 700 °C to 900 °C, even more preferably 750 °C to 850 °C.

[0166] A method according to any one of E1 - E15, wherein in step (II), the coked catalyst and the oxidant are contacted at an oxidant partial pressure of from 20 kPa absolute pressure to 10,000 kPa absolute pressure, or from 50 kPa absolute pressure to 5,000 kPa absolute pressure, or from 100 kPa absolute pressure to 1,000 kPa absolute pressure.

[0167] A method according to any one of E1 - E16, wherein the catalyst further comprises a promoter.

[0168] A method according to E18 of E17, wherein the promoter comprises one or more of the following elements: Sn, Ga, Zn, Ge, In, Re, Ag, Au, Cu, combinations thereof, or mixtures thereof.

[0169] A method according to E19, E17 or 18, wherein the promoter is arranged on the support.

[0170] A method according to any one of E20, E17 to E19, wherein the promoter is associated with the Pt.

[0171] A method according to any one of E21, E17 to E20, wherein the promoter and the Pt form Pt-promoter clusters, which are dispersed on the support.

[0172] A method according to any one of E22, E17 to E21, wherein the catalyst comprises at most 10% by weight of the promoter, based on the total weight of the support.

[0173] A method according to any one of E23, E1 to E22, wherein the catalyst further comprises an alkali metal element arranged on the support.

[0174] A method according to E24, E17, wherein the alkali metal element comprises one or more of the following: Li, Na, K, Rb, Cs, combinations thereof, or mixtures thereof.

[0175] A method according to E25, E23 or 24, wherein the catalyst comprises at most 5% by weight of the alkali metal element, based on the total weight of the support.

[0176] A method according to any one of E26, E1 to E25, wherein the support comprises at least one of the following: w% by weight of a Group 2 element, x% by weight of a Group 4 element, y% by weight of a Group 12 element, and z% by weight of an element having an atomic number of 21, 39 or 57 - 71, based on the weight of the support, where w, x, y and z are independently in the range from 0 to 100, wherein:

[0177] Any Group 2 element is associated with a weight % m based on the weight of the support,

[0178] Any Group 4 element is associated with a weight % n based on the weight of the support,

[0179] Any Group 12 element is associated with a weight % p based on the weight of the support, and

[0180] Any element having an atomic number of 21, 39 or 57 - 71 is associated with a weight % q based on the weight of the support,

[0181] m, n, p and q are independently numbers in the range from 1 to 100, and

[0182] where the sum of w / m + x / n + y / p + z / p ≥ 1, based on the weight of the carrier.

[0183] The method of E27.E26, where m, n, p, and q are each equal to 1, 15, or 30, or where m = 1, n = 15, p = 15, and q = 1.

[0184] The method of E28.E26 or 27, where the total molar ratio of any Group 2 element, any Group 4 element, any Group 12 element, and any element with atomic number 21, 39, or 57 - 71 to Pt is at least 0.18, at least 0.19, at least 0.24, or at least 0.29.

[0185] The method of any one of E29.E26 to E28, where the carrier further comprises at least one compound that contains at least one metal element or metalloid element selected from Groups 5, 6, 7, 11, 13, 14, 15, and 16.

[0186] The method of any one of E30.E26 to E29, where at least a portion of any Group 2 element, any Group 4 element, any Group 12 element, and any element with atomic number 21, 39, or 57 - 71 present in the carrier is an oxide, phosphate, halide, halate, sulfate, sulfide, borate, nitride, carbide, aluminate, aluminosilicate, silicate, carbonate, metaphosphate, selenide, tungstate, molybdate, chromite, chromate, dichromate, or silicide.

[0187] The method of any one of E31.E26 to E30, where the carrier comprises one or more of the following: Mg u Zn 1- u O, where u is a positive number; Zn v Al 2 O 3+v where v is a positive number; Mg w Al 2 O 3+w where w is a positive number; Ca x Al 2 O 3+x where x is a positive number; Sr y Al 2 O 3+y where y is a positive number; Ba z Al 2 O 3+z where z is a positive number; BeO; MgO; CaO; BaO; SrO; BeCO 3 ; MgCO 3 ; CaCO3 ; SrCO 3 ; BaCO 3 ; ZrO 2 ; ZrC; ZrN; ZrSiO 4 ; CaZrO 3 ; Ca 7 ZrAl 6 O 18 ; TiO 2 ; TiC; TiN; TiSiO 4 ; CaTiO 3 ; Ca 7 Al 6 O 18 ; HfO 2 ; HfC; HfN; HfSiO 4 ; HfZrO 3 ; Ca 7 HfAl 6 O 18 ; ZnO; Zn 3 (PO 4 ) 2 ; Zn(ClO 3 ) 2 ; ZnSO 4 ; B 2 O 6 Zn 3 ; Zn 3 N 2 ; ZnCO 3 ; CeO 2 ; Y 2 O 3 ; La 2 O 3 ; Sc 2 O 3 ; Pr 6 O 11 ; CePO 4 ; CeZrO 4 ; CeAlO 3 ; BaCeO 3 ; CePO 4 ; Yttria-stabilized ZrO 2 ; Combinations thereof, and mixtures thereof.

[0188] The method according to any one of E32.E26 to E31, wherein the support further comprises one or more of the following: B 2 O 3 , Al 2 O 3 , SiO 2 , SiC, Si 3 N4 , aluminosilicate, VO, V 2 O 3 , VO 2 , V 2 O 5 , Ga 2 O 3 , In 2 O 3 , Mn 2 O 3 , Mn 3 O 4 , MnO, one or more zeolites, and mixtures and combinations thereof.

[0189] The method according to any one of E33.E1 to E32, wherein the cycle time is from 1 minute to 70 minutes, such as from 5 minutes to 45 minutes.

[0190] The method according to any one of E34.E1 to E32, wherein the cycle time is from 5 minutes to 300 minutes, such as from 10 minutes to 50 minutes.

[0191] The method according to any one of E35.E1 to E32, wherein the cycle time is from 0.1 second to 30 minutes, such as from 5 seconds to 10 minutes.

[0192] The method according to any one of E36.E1 to E35, wherein the support is in the form of a plurality of primary particles, the primary particles comprising Pt disposed thereon.

[0193] The method according to any one of E37.E1 to E36, wherein the catalyst comprises primary particles having an average cross-sectional length of from 0.2 nm to 500 μm, preferably from 0.5 nm to 300 μm, more preferably from 1 nm to 200 μm, more preferably from 5 nm to 100 μm, still more preferably from 2 nm to 100 nm, measured by transmission electron microscopy.

[0194] The method according to any one of E38.E1 to E37, wherein the catalyst is in the form of a plurality of fluidized particles when contacted with the hydrocarbon-containing feed.

[0195] The method according to any one of E39.E1 to E36, wherein the support is a monolithic structure comprising Pt disposed thereon.

[0196] The method according to any one of E40.E1 to E39, wherein Pt is disposed on the support such that Pt is the active component of the catalyst that effects one or more of dehydrogenation, dehydrogenation aromatization and dehydrogenation cyclization in step (I).

[0197] The method according to any one of E41.E1 to E40, which is a fluidized bed method, a fixed bed method or a countercurrent reactor method.

[0198] A method according to any one of E42.E1 to E39, wherein the catalyst is in a fixed bed when contacted with the hydrocarbon-containing feedstock.

[0199] A method according to any one of E43.E1 to E42, wherein the support has a surface area of 0.1 m 2 / g to 1,500 m 2 / g, preferably 1 m 2 / g to 1,000 m 2 / g, more preferably 10 m 2 / g to 800 m 2 / g, more preferably 100 m 2 / g to 500 m 2 / g.

[0200] A method according to E44.E1 or any one of E4 to E43, wherein the hydrocarbon-containing feedstock is contacted with the catalyst in the absence of any steam or in the presence of steam in an amount of less than 0.1 vol% based on the total volume of any C 2 -C 16 alkanes, any C 4 -C 16 cycloalkanes and any C 8 -C 16 alkylaromatic hydrocarbons in the hydrocarbon-containing feedstock.

[0201] A method according to any one of E45.E26 to E44, wherein the catalyst comprises a Group 3 element and wherein the hydrocarbon-containing feedstock comprises 0.1 vol% to 50 vol% of steam, based on the total volume of any C 2 -C 16 alkanes, any C 4 -C 16 cycloalkanes and any C 8 -C 16 alkylaromatic hydrocarbons in the hydrocarbon-containing feedstock.

[0202] E46. A method for reforming hydrocarbons, the method comprising:

[0203] (I) contacting a hydrocarbon-containing feedstock with a catalyst comprising a Group 8-10 element disposed on a support to effect one or more of dehydrogenation, dehydrogenation aromatization, and dehydrogenation cyclization of at least a portion of the hydrocarbon-containing feedstock, thereby producing a coked catalyst and an effluent comprising one or more reformed hydrocarbons and molecular hydrogen, wherein:

[0204] the hydrocarbon-containing feedstock comprises one or more C 2 -C 16 linear or branched alkanes, or one or more C 4 -C 16Cycloalkanes, or one or more C 8 -C 16 alkylaromatic hydrocarbons, or mixtures thereof;

[0205] The hydrocarbon feed and the catalyst are contacted at a hydrocarbon partial pressure of at least 20 kPa absolute for a time of ≤ 3 hours at a temperature in the range of 300 °C to 900 °C, where the hydrocarbon partial pressure is any C in the hydrocarbon feed 2 -C 16 alkane and any C 8 -C 16 total partial pressure of alkylaromatic hydrocarbons;

[0206] The one or more reformed hydrocarbons comprise dehydrogenated hydrocarbons, dehydroaromatized hydrocarbons, dehydrocyclized hydrocarbons, or mixtures thereof;

[0207] The catalyst comprises 0.05 wt% to 6 wt% of the Group 8-10 element, based on the weight of the support, and wherein the support comprises at least one of the following: w wt% of a Group 2 element, x wt% of a Group 4 element, y wt% of a Group 12 element, and z wt% of an element having an atomic number of 21, 39, or 57-71, based on the weight of the support, where w, x, y, and z are independently in the range of 0 to 100, where:

[0208] Any Group 2 element is associated with a weight % m based on the weight of the support,

[0209] Any Group 4 element is associated with a weight % n based on the weight of the support,

[0210] Any Group 12 element is associated with a weight % p based on the weight of the support, and

[0211] Any element having an atomic number of 21, 39, or 57-71 is associated with a weight % q based on the weight of the support, and

[0212] m, n, p, and q are independently numbers in the range of 1 to 100, and

[0213] where the sum of w / m + x / n + y / p + z / p ≥ 1, based on the weight of the support;

[0214] (II) contacting at least a portion of the coked catalyst with an oxidant to effect combustion of at least a portion of the coke, thereby producing a coke-lean regenerated catalyst and combustion gases; and

[0215] (III) Contact an additional amount of the hydrocarbon feed with at least a portion of the regenerated catalyst to produce a recoked catalyst and an additional effluent, wherein the cycle time from contacting the hydrocarbon feed with the catalyst in step (I) to contacting the additional amount of the hydrocarbon feed with the regenerated catalyst in step (III) ≤ 5 hours.

[0216] E47. A process for reforming hydrocarbons, the process comprising:

[0217] (I) Contact a hydrocarbon feed with a catalyst comprising a Group 8-10 element or a compound thereof disposed on a support to effect one or more of dehydrogenation, dehydroaromatization, and dehydrogenation cyclization of at least a portion of the hydrocarbon feed, thereby producing a coked catalyst and an effluent comprising one or more reformed hydrocarbons and molecular hydrogen, wherein:

[0218] The hydrocarbon feed comprises one or more C 2 -C 16 linear or branched alkanes, or one or more C 4 -C 16 cycloalkanes, or one or more C 8 -C 16 alkylaromatic hydrocarbons, or mixtures thereof, and 0.1 vol% to 50 vol% steam based on the total volume of any C 2 -C 16 alkanes and any C 8 -C 16 alkylaromatic hydrocarbons in the hydrocarbon feed;

[0219] The hydrocarbon feed and the catalyst are contacted for a time ≤ 3 hours at a temperature in the range of 300 °C to 900 °C at a hydrocarbon partial pressure of at least 20 kPa absolute, wherein the hydrocarbon partial pressure is the total partial pressure of any C 2 -C 16 alkanes and any C 8 -C 16 alkylaromatic hydrocarbons in the hydrocarbon feed;

[0220] The catalyst comprises 0.05 wt% to 6 wt% of the Group 8-10 element or a compound thereof, based on the weight of the support, and wherein the reformed hydrocarbons comprise dehydrogenated hydrocarbons, dehydroaromatized hydrocarbons, dehydrogenation cyclized hydrocarbons, or mixtures thereof;

[0221] (II) Contact at least a portion of the coked catalyst with an oxidant to effect combustion of at least a portion of the coke, thereby producing a coke-lean regenerated catalyst and combustion gases; and

[0222] (III) Contact an additional amount of the hydrocarbon-containing feed with at least a portion of the regenerated catalyst to produce a re-coked catalyst and additional effluent, wherein the cycle time from contacting the hydrocarbon-containing feed with the catalyst in step (I) to contacting the additional amount of the hydrocarbon-containing feed with the regenerated catalyst in step (III) ≤ 5 hours.

[0223] The method of E48.E47, wherein the hydrocarbon-containing feed comprises 1 vol% to 15 vol% steam.

[0224] The method of E49.E47 or 48, wherein the support comprises at least one of the following: w wt% of a Group 2 element, x wt% of a Group 4 element, y wt% of a Group 12 element, and z wt% of an element having an atomic number of 21, 39, or 57-71, based on the weight of the support, wherein w, x, y, and z are independently in the range of 0 to 100, wherein:

[0225] Any Group 2 element is associated with a weight % m based on the weight of the support,

[0226] Any Group 4 element is associated with a weight % n based on the weight of the support,

[0227] Any Group 12 element is associated with a weight % p based on the weight of the support, and

[0228] Any element having an atomic number of 21, 39, or 57-71 is associated with a weight % q based on the weight of the support,

[0229] m, n, p, and q are independently numbers in the range of 1 to 100, and

[0230] wherein the sum of w / m + x / n + y / p + z / p ≥ 1, based on the weight of the support.

[0231] The method of E50.E46 or E49, wherein m, n, p, and q each equal 1 or 15 or 30, or wherein m = 1, n = 15, p = 15, and q = 1.

[0232] The method of any one of E51.E46 to E50, wherein the hydrocarbon-containing feed comprises propane, wherein the reformed hydrocarbon comprises propylene, and wherein the contact of the hydrocarbon-containing feed with the catalyst in step (I) has an at least 52% or at least 62% or at least 72% propylene yield at an at least 75%, ≥ 80%, ≥ 85%, ≥ 90%, or > 95% propylene selectivity.

[0233] A method according to any one of E46 to E51, wherein the hydrocarbon-containing feed comprises ≥51 vol% propane based on the total volume of the hydrocarbon-containing feed, wherein the hydrocarbon-containing feed and the catalyst are contacted at a propane partial pressure of at least 20 kPa absolute pressure, and wherein in step (I) the contact of the hydrocarbon-containing feed with the catalyst has an ethylene yield of >52% or >62% or >72% at an ethylene selectivity of ≥75%, ≥80%, ≥85%, ≥90%, or >95%.

[0234] A method according to any one of E46 to E52, wherein steps (I) to (III) are repeated at least 15 cycles, wherein the catalyst has a first yield of the reformed hydrocarbon when initially contacted with the hydrocarbon-containing feed, and wherein at the completion of the 15th cycle the catalyst has a second yield of the reformed hydrocarbon, which second yield is at least 95%, at least 97%, at least 98%, or at least 99% of the first yield.

[0235] A method according to any one of E46 to E53, further comprising the following step after step (II) and before step (III):

[0236] (IIa) contacting at least a portion of the regenerated catalyst with a reducing gas to produce a regenerated and reduced catalyst, wherein the additional amount of the hydrocarbon-containing feed is contacted with at least a portion of the regenerated and reduced catalyst.

[0237] A method according to E55, wherein at least a portion of the Group 8-10 elements in the regenerated catalyst are in a higher oxidation state compared to the Group 8-10 elements in the catalyst contacted with the hydrocarbon-containing feed, and wherein at least a portion of the Group 8-10 elements in the regenerated and reduced catalyst are reduced to a lower oxidation state compared to the Group 8-10 elements in the regenerated catalyst.

[0238] A method according to E56, wherein at least a portion of the Group 8-10 elements in the regenerated and reduced catalyst are in the elemental state.

[0239] A method according to any one of E54 to E56, wherein in step (IIa), the regenerated catalyst and the reducing gas are contacted at a temperature in the range of 450 °C to 900 °C, preferably 600 °C to 900 °C, more preferably 620 °C to 800 °C, more preferably 650 °C to 750 °C, more preferably 670 °C to 720 °C.

[0240] A method according to any one of E58 to E57, wherein in step (IIa), the regenerated catalyst and the reducing gas are contacted at a reducing agent partial pressure of from 20 kPa absolute pressure to 10,000 kPa absolute pressure, or from 50 kPa absolute pressure to 5,000 kPa absolute pressure, or from 100 kPa absolute pressure to 1,000 kPa absolute pressure.

[0241] A method according to any one of E59 to E46, wherein the Group 8-10 element comprises Pt.

[0242] A method according to any one of E60 to E46, wherein the hydrocarbon-containing feed further comprises an inert gas such as Ar, Ne, He, N 2 , CH 4 , and mixtures thereof.

[0243] A method according to any one of E61 to E46, wherein in step (I), the hydrocarbon-containing feed and the catalyst are contacted at a temperature in the range of from 650 °C to 900 °C, more preferably from 650 °C to 800 °C, preferably from 660 °C to 780 °C, more preferably from 670 °C to 760 °C.

[0244] A method according to any one of E62 to E46, wherein in step (I), the hydrocarbon-containing feed and the catalyst are contacted at a hydrocarbon partial pressure in the range of from 20 kPa absolute pressure to 10,000 kPa absolute pressure, or from 50 kPa absolute pressure to 5,000 kPa absolute pressure, or from 100 kPa absolute pressure to 1,000 kPa absolute pressure.

[0245] A method according to any one of E63 to E46, wherein the catalyst further comprises a promoter disposed on the support.

[0246] A method according to E64, wherein the promoter comprises Sn, Ga, Zn, Ge, In, Re, Ag, Au, Cu, compounds thereof, or mixtures thereof.

[0247] A method according to E63 or 64, wherein the promoter is associated with the Group 8-10 element.

[0248] A method according to any one of E65 to E63, wherein the promoter and the Group 8-10 element form a Group 8-10 element / promoter cluster dispersed on the support.

[0249] A method according to any one of E66 to E63, wherein the catalyst comprises up to 10% by weight of the promoter, based on the total weight of the support.

[0250] A method according to any one of E68.E46 to E67, wherein the catalyst further comprises an alkali metal disposed on the support.

[0251] A method according to E69.E68, wherein the alkali metal comprises Li, Na, K, Rb, Cs, a combination thereof, or a mixture thereof.

[0252] A method according to E70.E68 or 69, wherein the catalyst comprises up to 5 wt% of an alkali metal, based on the total weight of the support.

[0253] A method according to E71.E46 or E49 to E70, wherein at least a portion of any Group 2 element, any Group 4 element, any Group 12 element, and any element having an atomic number of 21, 39, or 57 - 71 present in the support is an oxide, phosphate, halide, halate, sulfate, sulfide, borate, nitride, carbide, aluminate, aluminosilicate, silicate, carbonate, metaphosphate, selenide, tungstate, molybdate, chromite, chromate, dichromate, or silicide.

[0254] A method according to E72.E46 or E49 to E71, wherein the total molar ratio of any Group 2 element, any Group 4 element, any Group 12 element, and any element having an atomic number of 21, 39, or 57 - 71 to Pt is at least 0.18.

[0255] A method according to E73.E46 or E49 to E72, wherein the support comprises one or more of the following: Mg u Zn 1-u O, where u is a positive number; Zn v Al 2 O 3+v , where v is a positive number; Mg w Al 2 O 3+w , where w is a positive number; Ca x Al 2 O 3+x , where x is a positive number; Sr y Al 2 O 3+y , where y is a positive number; 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 ; ZrO 2; ZrC; ZrN; ZrSiO 4 ; CaZrO 3 ; Ca 7 ZrAl 6 O 18 ; TiO 2 ; TiC; TiN; TiSiO 4 ; CaTiO 3 ; Ca 7 Al 6 O 18 ; HfO 2 ; HfC; HfN; HfSiO 4 ; HfZrO 3 ; Ca 7 HfAl 6 O 18 ; ZnO; Zn 3 (PO 4 ) 2 ; Zn(ClO 3 ) 2 ; ZnSO 4 ; B 2 O 6 Zn 3 ; Zn 3 N 2 ; ZnCO 3 ; CeO 2 ; Y 2 O 3 ; La 2 O 3 ; Sc 2 O 3 ; Pr 6 O 11 ; CePO 4 ; CeZrO 4 ; CeAlO 3 ; BaCeO 3 ; CePO 4 ; Yttria-stabilized ZrO 2 ; Combinations thereof, and mixtures thereof.

[0256] A method according to any one of E74.E46 or E49 to E73, wherein the support further comprises one or more of the following: B 2 O 3 , Al 2 O 3 , SiO 2 , SiC, Si 3 N 4 , Aluminosilicate, VO, V 2 O 3 , VO2 , V 2 O 5 , Ga 2 O 3 , In 2 O 3 , Mn 2 O 3 , Mn 3 O 4 , MnO, one or more zeolites, and mixtures and combinations thereof.

[0257] The method according to any one of E75.E46 to E74, wherein the cycle time is from 1 minute to 70 minutes, such as from 5 minutes to 45 minutes.

[0258] The method according to any one of E76.E46 to E75, wherein the cycle time is from 5 minutes to 300 minutes, such as from 10 minutes to 50 minutes.

[0259] The method according to any one of E77.E46 to E75, wherein the cycle time is from 0.1 second to 30 minutes, such as from 5 seconds to 10 minutes.

[0260] The method according to any one of E78.E46 to E77, wherein the carrier comprises a plurality of primary particles, and the primary particles comprise Group 8-10 elements disposed thereon.

[0261] The method according to any one of E79.E46 to E77, wherein the catalyst comprises primary particles, and wherein the primary particles have an average cross-sectional length of from 0.2 nm to 500 μm, preferably from 1 nm to 300 μm, more preferably from 2 nm to 200 μm, more preferably from 2 nm to 100 μm, still more preferably from 2 nm to 500 nm, still more preferably from 2 nm to 100 nm, as measured by transmission electron microscopy.

[0262] The method according to any one of E80.E46 to E79, wherein the catalyst is in the form of a plurality of fluidized particles when contacted with the hydrocarbon-containing feed.

[0263] The method according to any one of E81.E46 to E77, wherein the carrier is a monolithic structure comprising Group 8-10 elements disposed thereon.

[0264] The method according to any one of E82.E46 to E81, wherein the Group 8-10 element comprises Pt, and wherein the Pt is disposed on the carrier such that the Pt is an active component of the catalyst that effects one or more of dehydrogenation, dehydrogenation aromatization, and dehydrogenation cyclization in step (I).

[0265] A method according to any one of E83.E46 to E82, which is a fluidized bed method, a fixed bed method or a countercurrent reactor method.

[0266] A method according to any one of E84.E46 to E83, wherein the catalyst is in a fixed bed when contacted with the hydrocarbon feed.

[0267] A method according to any one of E85.E46 to E84, wherein the support has a surface area of 0.1 m 2 / g to 1,500 m 2 / g, preferably 1 m 2 / g to 1,000 m 2 / g, more preferably 10 m 2 / g to 800 m 2 / g, more preferably 100 m 2 / g to 500 m 2 / g.

[0268] A method according to E86.E46 or any one of E49 to E85, wherein the catalyst comprises a Group 3 element and wherein the hydrocarbon feed comprises 0.1 vol% to 50 vol% steam, based on the total volume of any C 2 -C 16 alkanes, any C 4 -C 16 cycloalkanes and any C 8 -C 16 alkyl aromatic hydrocarbons.

[0269] Various terms have been defined above. If a term used in a claim is not defined above, the term shall have the broadest definition given to that term by a person skilled in the relevant art, as reflected in at least one printed publication or an issued patent. In addition, all patents, test procedures and other documents cited in this application are incorporated herein by reference in their entirety, provided that such disclosure is not inconsistent with this application and is applicable in all jurisdictions permitting such incorporation.

[0270] Although the foregoing is directed to embodiments of the invention, other and further embodiments of the invention may be devised without departing from the basic scope of the invention, and the scope of the invention is determined by the appended claims.

Claims

1. A method for reforming hydrocarbons, the method comprises: (I) contacting a hydrocarbon-containing feedstock with a catalyst comprising Pt disposed on a support to effect one or more of dehydrogenation, dehydrogenation aromatization, and dehydrogenation cyclization of at least a portion of the hydrocarbon-containing feedstock, thereby producing a coked catalyst and an effluent comprising one or more reformed hydrocarbons and molecular hydrogen: The hydrocarbon-containing feed comprises one or more C 2 -C 16 linear or branched alkanes, or one or more C 4 -C 16 cyclic alkanes, or one or more C 8 -C 16 alkyl aromatic hydrocarbons, or mixtures thereof, and 0.1 vol% to 50 vol% steam, based on the total volume of any C 2 -C 16 alkanes and any C 8 -C 16 alkyl aromatic hydrocarbons; wherein The hydrocarbon-containing feed and the catalyst are contacted for a time of ≤ 3 hours at a temperature in the range of 300 °C to 900 °C at a hydrocarbon partial pressure of at least 20 kPa absolute pressure, where the hydrocarbon partial pressure is the total partial pressure of any C 2 -C 16 alkanes and any C 8 -C 16 alkyl aromatic hydrocarbons; the catalyst comprises 0.05 wt% to 6 wt% of Pt, based on the weight of the support; and the one or more reformed hydrocarbons comprise at least one of dehydrogenated hydrocarbons, dehydrogenation aromatized hydrocarbons, and dehydrogenation cyclized hydrocarbons; (II) contacting at least a portion of the coked catalyst with an oxidant to effect combustion of at least a portion of the coke, thereby producing a coke-lean regenerated catalyst and combustion gases; and (III) contacting an additional amount of the hydrocarbon-containing feedstock with at least a portion of the regenerated catalyst to produce a recoked catalyst and an additional effluent, wherein the cycle time from contacting the hydrocarbon-containing feedstock with the catalyst in step (I) to contacting the additional amount of the hydrocarbon-containing feedstock with the regenerated catalyst in step (III) ≤ 5 hours.

2. The method according to claim 1, wherein in step (I), the hydrocarbon-containing feedstock and the catalyst are contacted in the presence of steam, and the amount of the steam is 0.1 vol% to 30 vol%, based on the total volume of any C 2 -C 16 -alkanes, any C 4 -C 16 -cycloalkanes and any C 8 -C 16 -alkyl aromatic hydrocarbons.

3. The method according to claim 1 or claim 2, wherein in step (I), the hydrocarbon-containing feed and the catalyst are contacted in the presence of steam, the amount of the steam being 1 vol% to 15 vol%, based on the total volume of any C 2 -C 16 alkanes, any C 4 -C 16 cycloalkanes and any C 8 -C 16 alkyl aromatic hydrocarbons.

4. The method according to claim 1, wherein the hydrocarbon-containing feedstock comprises propane, the reformed hydrocarbon comprises propylene, and the contacting of the hydrocarbon-containing feedstock with the catalyst in step (I) has an at least 52% propylene yield at a propylene selectivity of ≥ 75%.

5. The method according to claim 1, wherein the hydrocarbon-containing feedstock comprises ≥ 70 vol% propane based on the total volume of the hydrocarbon-containing feedstock, the hydrocarbon-containing feedstock and the catalyst are contacted at a propane partial pressure of at least 40 kPa absolute pressure, and the contacting of the hydrocarbon-containing feedstock with the catalyst in step (I) has an at least 52% propylene yield at a propylene selectivity of ≥ 75%.

6. The method according to claim 1, wherein at least a portion of the Pt in the regenerated catalyst is in a higher oxidation state compared to the Pt in the catalyst in contact with the hydrocarbon-containing feedstock; the method further comprises the following step after step (II) and before step (III): (IIa) contacting at least a portion of the regenerated catalyst with a reducing gas to produce a regenerated and reduced catalyst, wherein at least a portion of the Pt in the regenerated and reduced catalyst is reduced to a lower oxidation state compared to the Pt in the regenerated catalyst, and the additional amount of the hydrocarbon-containing feedstock is contacted with at least a portion of the regenerated and reduced catalyst.

7. The method according to claim 6, wherein in step (IIa), at least one of the following conditions is satisfied: (i) the regenerated catalyst and the reducing gas are contacted at a temperature in the range of 450 °C to 900 °C; and (ii) the regenerated catalyst and the reducing gas are contacted at a reducing agent partial pressure in the range of 20 kPa absolute pressure to 10,000 kPa absolute pressure.

8. The method according to claim 1, wherein the hydrocarbon-containing feedstock further comprises an inert gas.

9. The method according to claim 1, wherein in step (I), at least one of the following conditions is satisfied: (i) The hydrocarbon-containing feedstock and the catalyst are contacted at a temperature in the range of 600 °C to 900 °C; and (ii) The hydrocarbon-containing feedstock and the catalyst are contacted at a hydrocarbon partial pressure in the range of 20 kPa absolute pressure to 10,000 kPa absolute pressure.

10. The method according to claim 1, wherein in step (II), at least one of the following conditions is satisfied: (i) The coked catalyst and the oxidant are contacted at a temperature in the range of 600 °C to 1,100 °C; and (ii) The coked catalyst and the oxidant are contacted at an oxidant partial pressure in the range of 20 kPa absolute pressure to 10,000 kPa absolute pressure.

11. The method according to claim 1, wherein the catalyst further comprises a promoter.

12. The method according to claim 11, wherein the promoter comprises one or more of the following elements: Sn, Ga, Zn, Ge, In, Re, Ag, Au, Cu, combinations thereof, or mixtures thereof.

13. The method according to claim 11 or claim 12, wherein the catalyst comprises up to 10% by weight of the promoter, based on the total weight of the support.

14. The method according to claim 1, wherein the catalyst further comprises an alkali metal element disposed on the support.

15. The method according to claim 14, wherein the alkali metal element comprises one or more of the following: Li, Na, K, Rb, Cs, combinations thereof, or mixtures thereof.

16. The method according to claim 14 or claim 15, wherein the catalyst comprises up to 5% by weight of the alkali metal element, based on the total weight of the support.

17. The method according to claim 1, wherein the support comprises at least one of the following: w% by weight of a Group 2 element, x% by weight of a Group 4 element, y% by weight of a Group 12 element, and z% by weight of an element having an atomic number of 21, 39, or 57 - 71, based on the weight of the support, where w, x, y, and z are independently in the range of 0 to 100, wherein: any Group 2 element is associated with a weight % m based on the weight of the support, any Group 4 element is associated with a weight % n based on the weight of the support, any Group 12 element is associated with a weight % p based on the weight of the support, and any element having an atomic number of 21, 39, or 57 - 71 is associated with a weight % q based on the weight of the support, m, n, p, and q are independently numbers in the range of 1 to 100, and where the sum of w / m + x / n + y / p + z / p ≥ 1, based on the weight of the support.

18. The method according to claim 17, wherein m, n, p, and q each equal 1, 15, or 30, or wherein m = 1, n = 15, p = 15, and q = 1.

19. The method according to claim 17 or claim 18, wherein the total amount of any Group 2 element, any Group 4 element, any Group 12 element, and any element having an atomic number of 21, 39, or 57 - 71 and the molar ratio of Pt is at least 0.

18.

20. The method according to claim 17, wherein the support further comprises at least one compound comprising at least one metallic element or metalloid element selected from Groups 5, 6, 7, 11, 13, 14, 15, and 16.

21. The method according to claim 1, wherein the cycle time is from 0.1 second to 30 minutes.

22. The method according to claim 1, wherein the Pt is disposed on the support such that the Pt is an active component of the catalyst that effects one or more of dehydrogenation, dehydrogenation aromatization, and dehydrogenation cyclization in step (I).

23. The method according to claim 1, wherein the catalyst is in a fixed bed when contacted with the hydrocarbon-containing feed.

24. The method according to claim 17, wherein the catalyst comprises a Group 3 element and wherein the hydrocarbon feed comprises from 0.1 vol% to 50 vol% steam, based on the total volume of any C 2 -C 16 -alkanes, any C 4 -C 16 -cycloalkanes and any C 8 -C 16 -alkylaromatic hydrocarbons.

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