Process for upgrading alkanes and alkyl aromatic hydrocarbons

Abstract

A method for upgrading hydrocarbons. The method may include contacting a hydrocarbon-containing feed with fluidized catalyst particles that may include an 8-10 group element or a compound thereof disposed on a carrier, so that at least a portion of the hydrocarbon-containing feed is subjected to one or more of dehydrogenation, dehydrogenation aromatization, and dehydrogenation cyclization to produce a coked catalyst and an effluent. The method may also include contacting at least a portion of the coked catalyst particles with an oxidant so that at least a portion of the coke is burned to produce regenerated catalyst particles. The method may also include contacting an additional amount of hydrocarbon-containing feed with at least a portion of the regenerated catalyst particles to produce additional effluent and re-coked catalyst particles.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and benefits of U.S. Provisional Application No. 62 / 993,985, filed on March 24, 2020, and EP Application No. 20179409.6, filed on June 11, 2020, the disclosures of which are incorporated herein by reference in their entirety. Technical Field

[0003] The present disclosure relates to a process for upgrading alkanes and / or alkyl aromatic hydrocarbons. More specifically, the present disclosure relates to a process for dehydrogenating, dehydroaromatizing and / or dehydrocyclizing one or more alkanes and / or one or more alkyl aromatic hydrocarbons in the presence of fluidized catalyst particles to produce an effluent comprising one or more upgraded hydrocarbons. Background Art

[0004] Catalytic dehydrogenation, dehydroaromatization and dehydrocyclization of alkanes and / or alkylaromatics are endothermic and equilibrium-limited industrially important chemical conversion processes. 16 The dehydrogenation of propane (such as alkylene) and / or alkyl aromatic hydrocarbons (such as ethylbenzene) can be carried out via a variety of supported catalyst particle systems, such as Pt-based, Cr-based, Ga-based, V-based, Zr-based, In-based, W-based, Mo-based, Zn-based, and Fe-based systems. Among the existing propane dehydrogenation processes, a certain process uses an alumina-supported chromium oxide catalyst, which provides one of the highest propylene yields of about 50% (55% propane conversion at 90% propylene selectivity), which is achieved 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 increase the efficiency of the dehydrogenation process.

[0005] Increasing the temperature of the dehydrogenation process is one way to increase the conversion of the process, based on the thermodynamics of the process. For example, at 670°C, 100 kPa absolute pressure, in the absence of any inert / diluent, the equilibrium propylene yield was estimated to be about 74% via simulation. However, at such high temperatures, the catalyst particles deactivate very quickly and / or the propylene selectivity becomes uneconomically low. The rapid deactivation of the catalyst particles is believed to be caused by the deposition of coke on the catalyst particles and / or agglomeration of the active phase. The coke can be removed by combustion using 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 particles.

[0006]

[0006] Therefore, there remains a need for improved processes and catalyst particles for dehydrogenating, dehydroaromatizing, and / or dehydrocyclizing alkanes and / or alkylaromatic hydrocarbons. The present disclosure satisfies this need and other needs. Summary of the invention

[0007] A method for upgrading alkanes and / or alkyl aromatic hydrocarbons is provided. In some embodiments, the method for upgrading hydrocarbons may include (I) contacting a hydrocarbon-containing feed with fluidized catalyst particles disposed on a support and comprising elements of Groups 8-10 in a conversion zone to subject at least a portion of the hydrocarbon-containing feed to one or more of dehydrogenation, dehydroaromatization, and dehydrocyclization to produce a conversion effluent that may include coked catalyst particles, one or more upgraded hydrocarbons, and molecular hydrogen. The hydrocarbon-containing feed may include C2-C 16 One or more linear or branched alkanes, C4-C 16 One or more cycloalkanes, C8-C 16 The hydrocarbon feed and the catalyst particles may be contacted at a temperature of 300° C. to 900° C. for a period of 0.1 second to 2 minutes at a hydrocarbon partial pressure of at least 20 kPa absolute pressure, wherein the hydrocarbon partial pressure is the hydrocarbon of any C2-C 16 Alkanes and any C8-C 16The total partial pressure of alkyl aromatic hydrocarbons. The catalyst particles may include 0.05 wt % to 6 wt % of Group 8-10 elements, based on the weight of the support. The carrier may include at least one of: w weight % of Group 2 elements, x weight % of Group 4 elements, y weight % of Group 12 elements, and z weight % of elements with atomic numbers 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, wherein any Group 2 element can be associated with a weight % m, based on the weight of the carrier, any Group 4 element can be associated with a weight % n, based on the weight of the carrier, any Group 12 element can be associated with a weight % p, based on the weight of the carrier, and any element with atomic numbers 21, 39 or 57-71 can be associated with a weight % q, based on the weight of the carrier, wherein m, n, p and q are independently numbers in the range of 1 to 100, and wherein the sum of w / m+x / n+y / p+z / p is ≥ 1, based on the weight of the carrier. The one or more upgraded hydrocarbons may include dehydrogenated hydrocarbons, dehydrogenated aromatic hydrocarbons, dehydrogenated cyclized hydrocarbons, or mixtures thereof; the method may further include (II) obtaining a first gaseous stream rich in the one or more upgraded hydrocarbons and the molecular hydrogen and a first particle stream rich in the coked catalyst particles from the conversion effluent. The method may further include (III) contacting at least a portion of the coked catalyst particles in the first particle stream with an oxidant in a combustion zone to burn at least a portion of the coke to produce a combustion effluent that may include regenerated catalyst particles depleted in coke and combustion gases. The method may further include (IV) obtaining a second gaseous stream rich in the combustion gases and a second particle stream rich in the regenerated catalyst particles from the combustion effluent. The method may further include (V) contacting an additional amount of hydrocarbon-containing feed with the fluidized regenerated catalyst particles to produce an additional conversion effluent comprising re-coked catalyst particles, additional one or more upgraded hydrocarbons, and additional molecular hydrogen. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] Figure 1 A system for upgrading a hydrocarbonaceous feed according to one or more embodiments described is depicted and includes a reactor and a regenerator.

[0009] Figure 2 Another system for upgrading a hydrocarbonaceous feed according to one or more embodiments described is depicted and includes a reactor, a regenerator, and a reduction reactor.

[0010] Figure 3 Another system for upgrading a hydrocarbonaceous feed according to one or more embodiments described is depicted and includes a reactor, a regenerator, a reduction reactor, and a recycle line for recycling at least a portion of the coked catalyst particles to the reactor.

[0011] Figure 4 Another system for upgrading a hydrocarbonaceous feed according to one or more embodiments described is depicted and includes a reactor, a regenerator, a reduction reactor, and a heat input device for heating catalyst particles.

[0012] Figure 5 Another system for upgrading a hydrocarbonaceous feed according to one or more embodiments described is depicted and includes a reactor, a regenerator, a reduction reactor, and a transfer line for supplying at least a portion of coked catalyst particles to the reduction reactor.

[0013] Figure 6 Another system for upgrading a hydrocarbon-containing feed according to one or more embodiments described is depicted and includes a reactor, a regenerator, a reduction reactor, and a side reactor.

[0014] Figure 7 Another system for upgrading a hydrocarbon-containing feed according to one or more embodiments described is depicted and includes a reactor, a regenerator, a reduction reactor, and a side reactor.

[0015] Figure 8 The catalyst stability results for the catalysts used in Examples 1-3 after 35 cycles (regeneration, reduction and dehydrogenation) under the same conditions as used in Example 1 are shown.

[0016] Fig. 9 The catalyst stability results are shown for the catalyst used in Example 23 after 49 cycles (regeneration, reduction and dehydrogenation) in the presence of steam.

[0017] Detailed Description

[0018] Various specific embodiments, versions and examples of the present invention are now described, including preferred embodiments and definitions adopted for understanding the present invention claimed as rights. Although the following detailed description gives specific preferred embodiments, it should be appreciated by those skilled in the art that these embodiments are exemplary only, and the present invention may be practiced in other ways. For the purpose of determining infringement, the scope of the present invention refers to any one or more of the appended claims, including their equivalents, and elements or limitations equivalent to those listed. Any reference to this "invention" may refer to one or more of the present inventions defined by the claims, but not necessarily all.

[0019] In the present disclosure, a method is described as comprising at least one "step". It should be understood that each step is an action or operation that can be performed one or more times in a method in a continuous or discontinuous manner. Unless otherwise specified or the context clearly indicates otherwise, the multiple steps in the method can be performed in the order in which they are listed, with or without overlapping with one or more other steps, or in any other order, as the case may be. In addition, one or more, or even all steps can be performed simultaneously in terms of the same or different batches of materials. For example, in a continuous method, although the first step in the method is being performed on the raw material that has just been fed into the starting point of the method, the second step can be performed simultaneously on the intermediate product produced by processing the raw material that was fed into the method at an early stage in the first step. Preferably, these steps are performed in the described order.

[0020] Unless otherwise stated, all numerical values ​​indicating quantities in the present disclosure are to be understood as being modified by the term "approximately" in all cases. It should also be understood that the precise numerical values ​​used in the specification and claims constitute specific embodiments. Efforts have been made to ensure the accuracy of the data in the examples. However, it should be understood that any measurement data inherently contains a certain level of error due to the limitations of the technology and / or equipment used to make the measurements.

[0021] Certain embodiments and features are described herein using a set of numerical upper limits and a set of numerical lower limits. It is self-evident that the range including the combination of any two values, such as the combination of any lower limit value with any upper limit value, the combination of any two lower limits, and / or the range of the combination of any two upper limits is considered, unless otherwise stated.

[0022] As used herein, the indefinite article "a" or "an" shall mean "at least one," unless specified to the contrary or the context clearly indicates otherwise. Thus, embodiments using a "reactor" or "conversion zone" include embodiments in which one, two, or more reactors or conversion zones are used, unless specified to the contrary or the context clearly indicates that only one reactor or conversion zone is used.

[0023] The terms "up" and "down"; "upwardly" and "downwardly"; "upper" and "lower"; "upwardly" and "downwardly"; "above" and "below"; and other similar terms used herein refer to relative positions to each other and are not intended to indicate a particular spatial orientation, as the devices and methods of using the devices can be equally effective at a variety of angles or orientations.

[0024] The term "hydrocarbon" refers to (i) any compound consisting of hydrogen and carbon atoms or (ii) any mixture of two or more such compounds in (i). The term "Cn hydrocarbon", where n is a positive integer, refers to (i) any hydrocarbon compound containing a total of n carbon atoms (one or more) in its molecule or (ii) any mixture of two or more such hydrocarbon compounds in (i). Thus, C2 hydrocarbons can be ethane, ethylene, acetylene, or a 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, refers to any one of Cm, Cm+1, Cm+2, …, Cn-1, Cn hydrocarbons, or any mixture of two or more thereof. 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 thereof in any proportion between and among the components. "Saturated C2-C3 hydrocarbons" can be ethane, propane, cyclopropane, or any mixture of two or more thereof in any proportion. "Cn+ hydrocarbons" refers to (i) any hydrocarbon compound containing a total of at least n carbon atoms (one or more) in its molecule or (ii) any mixture of two or more such hydrocarbon compounds in (i). "Cn- hydrocarbons" refers to (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 in (i). "Cm hydrocarbon stream" refers to a hydrocarbon stream consisting essentially of Cm hydrocarbon(s). "Cm-Cn hydrocarbon stream" refers to a hydrocarbon stream consisting essentially of Cm-Cn hydrocarbon(s).

[0025] For the purposes of this disclosure, the naming of elements is based on the version of the periodic table (under the new symbols) provided in Appendix V of Hawley's Condensed Chemical Dictionary, 16th Edition, John Wiley & Sons, Inc., (2016). For example, Group 8 elements can include one or more of Fe, Ru, and Os, Group 9 elements can include one or more of Co, Rh, and Ir, and Group 10 elements can include one or more of Ni, Pd, and Pt. The term "metalloid" as used herein refers to the following elements: B, Si, Ge, As, Sb, Te, and At. In this disclosure, when a given element is indicated as being present, it can be in elemental form or present as any of its compounds, unless the context otherwise indicates or is otherwise expressly stated.

[0026] The term "alkane" refers to a saturated hydrocarbon. The term "cycloalkane" refers to a saturated hydrocarbon containing a cyclic carbon ring in its molecular structure. Alkanes can be linear, branched, or cyclic.

[0027] The term "aromatic" is understood in accordance with the art-recognized scope to include alkyl-substituted and unsubstituted mono- and polynuclear compounds.

[0028] When used in phrases such as "rich in X" or "enriched in X", the term "enriched" means that, relative to an output stream obtained from a device, such as a conversion zone, the stream comprises a concentration of material X that is higher than the concentration of material X in the feed material fed to the same device from which the stream originates. When used in phrases such as "depleted in X" or "depleted in X", the term "depleted in X" means that, relative to an output stream obtained from a device, such as a conversion zone, the stream comprises a concentration of material X that is lower than the concentration of material X in the feed material fed to the same device from which the stream originates.

[0029] The term "selectivity" refers to the amount of a particular compound produced (on a carbon mole basis) in a catalytic reaction. For example, the phrase "an alkane conversion reaction has a selectivity of 100% over olefins" means that 100% of the alkanes converted in the reaction (on a carbon mole basis) are converted to olefins. When used in conjunction with a specified reactant, the term "conversion" refers to the amount of the reactant consumed in the reaction. For example, when the specified reactant is propane, 100% conversion means that 100% of the propane is consumed in the reaction. Yield (on a carbon mole basis) is the conversion multiplied by the selectivity.

[0030] Overview

[0031] The hydrocarbon-containing feedstock may be or may include, but is not limited to, one or more alkanes, such as C2-C 16 Linear or branched alkanes and / or C4-C 16 Cycloalkanes, and / or one or more alkyl aromatic hydrocarbons, such as C8-C 16 In some embodiments, the hydrocarbon-containing feedstock may optionally include 0.1 vol% to 50 vol% steam, based on any C2-C 16 Alkanes and any C8-C 16 In other embodiments, based on any C2-C 16 Alkanes and any C8-C 16The total volume of alkyl aromatic hydrocarbons, the hydrocarbon feed may include <0.1 volume % steam or may be free of steam. The hydrocarbon feed may be contacted with fluidized catalyst particles in a conversion zone, the fluidized catalyst particles including one or more Group 8-10 elements, such as Pt, arranged on a carrier, so that at least a portion of the hydrocarbon feed undergoes one or more of dehydrogenation, dehydroaromatization and dehydrocyclization to produce a conversion effluent that may include coked catalyst particles and an effluent that may include one or more upgraded hydrocarbons and molecular hydrogen. The one or more upgraded hydrocarbons may be or may include one or more dehydrogenated hydrocarbons, one or more dehydroaromatized hydrocarbons, one or more dehydrocyclized hydrocarbons or mixtures thereof. The hydrocarbon feed and catalyst particles may be contacted at a temperature in the range of 300°C to 900°C at a hydrocarbon partial pressure of at least 20 kPa absolute for a period of 0.1 seconds to 2 or even 3 minutes, wherein the hydrocarbon partial pressure is any C2-C 16 Alkanes and any C8-C 16 The total partial pressure of alkyl aromatic hydrocarbons. The catalyst particles may include 0.05 wt % to 6 wt % of a Group 8-10 element, such as Pt, based on the weight of the carrier. The carrier may be or may include, but is not limited to, a Group 2 element, a Group 4 element, a Group 12 element, an element with an atomic number of 21, 39, or 57-71, or a compound thereof.

[0032] A first gaseous stream rich in one or more upgraded hydrocarbons and molecular hydrogen and a first particle stream rich in coked catalyst particles can be separated or otherwise obtained from the conversion effluent. At least a portion of the coked catalyst particles in the first particle stream can be contacted with one or more oxidants in the conversion zone to burn at least a portion of the coke, thereby producing a combustion effluent, which can include regenerated catalyst particles and combustion gases that are lean in coke. A second gaseous stream rich in combustion gases and a second particle stream rich in the regenerated catalyst particles can be separated or otherwise obtained from the combustion effluent. An additional amount of hydrocarbon-containing feed can be contacted with fluidized regenerated catalyst particles to produce re-coked catalyst particles and additional conversion effluent, and the additional conversion effluent includes re-coked catalyst particles, additional one or more upgraded hydrocarbons and additional molecular hydrogen. In some embodiments, the cycle time from contacting the hydrocarbon-containing feed with the catalyst particles to contacting the additional amount of hydrocarbon-containing feed with the regenerated catalyst particles may be ≤ 70 minutes, e.g., from 1, 5, 10, or 20 minutes to 30, 45, 60, or 70 minutes.

[0033] The catalyst particles disclosed herein may show improved activity and selectivity after undergoing an additional reduction step before re-contacting with a hydrocarbon-containing feed. In addition, the post-reduced catalyst particles can maintain improved activity and selectivity for 10 minutes or more in the presence of a hydrocarbon-containing feed. Therefore, in some embodiments, the method may optionally include contacting at least a portion of the regenerated catalyst particles in the second particle stream with a reducing gas to produce regenerated and reduced catalyst particles. In this embodiment, an additional amount of hydrocarbon-containing feed may contact at least a portion of the regenerated and reduced catalyst particles to produce additional conversion effluent. In other embodiments, the method may include contacting at least a portion of the regenerated catalyst particles and at least a portion of the regenerated and reduced catalyst particles with an additional amount of hydrocarbon-containing feed to produce additional conversion effluent. In other embodiments, the method may include contacting at least a portion of the regenerated catalyst particles, at least a portion of the regenerated and reduced catalyst particles, and / or new or supplemented catalyst particles to produce additional conversion effluent. If the process includes an optional reduction step, the cycle time from contacting the hydrocarbon-containing feed with the catalyst particles to contacting the additional amount of hydrocarbon-containing feed with the regenerated and reduced catalyst particles can also be ≤ 70 minutes, e.g., from 1 minute, 5 minutes, 10 minutes or 20 minutes to 30 minutes, 45 minutes, 60 minutes or 70 minutes.

[0034] It has been surprisingly and unexpectedly discovered that catalyst particles comprising a Group 8-10 element (e.g., Pt) disposed on a support can remain sufficiently active and stable after many cycles, e.g., at least 15, at least 20, at least 30, at least 40, at least 50, at least 60, at least 70, at least 100 cycles, at least 125 cycles, at least 150 cycles, at least 175 cycles, or at least 200 cycles, wherein each cycle time lasts ≤ 70 minutes. In some embodiments, after the performance of the catalyst particles stabilizes (sometimes several first cycles may have poorer or better performance, but the performance may eventually stabilize), when the hydrocarbon-containing feed comprises propane, the process may produce a first upgraded hydrocarbon product yield (e.g., propylene) at an upgraded hydrocarbon selectivity (e.g., propylene) of ≥75%, ≥80%, ≥85%, or ≥90%, or >95% upon initial contact with the hydrocarbon-containing feed, and may have a second upgraded hydrocarbon product yield after completion of the last cycle (at least 15 cycles total), which may be at least 90%, at least 93%, at least 95%, at least 97%, at least 98%, at least 99%, at least 99.5%, or at least 100% of the first upgraded hydrocarbon product yield at an upgraded hydrocarbon selectivity (e.g., propylene) of ≥75%, ≥80%, ≥85%, or ≥90%, or >95%. Prior to this discovery, it was believed that catalyst particles having a Group 8-10 element (eg, Pt) as the active component would not maintain adequate activity and stability when subjected to so many short cycles of simple oxidative regeneration without the need for added halogen.

[0035] The first cycle begins when the catalyst particles are contacted with a hydrocarbon-containing feed, and then contacted with at least an oxidant to produce regenerated catalyst particles or contacted with at least an oxidant and optionally a reducing gas to produce regenerated and reduced catalyst particles, and the first cycle ends when the regenerated catalyst particles or regenerated and reduced catalyst particles are contacted with an additional amount of hydrocarbon-containing feed. The second and each subsequent cycle begins when the regenerated catalyst particles or regenerated and reduced catalyst particles are contacted with an additional amount of hydrocarbon-containing feed, and the second and each subsequent cycle ends when additional or subsequent regenerated catalyst particles or regenerated and reduced catalyst particles are contacted with an additional amount of hydrocarbon-containing feed.

[0036] In addition, unprecedented propylene yields have been achieved via the methods and catalyst particles described herein. In some embodiments, when the hydrocarbonaceous feed comprises propane and the upgraded hydrocarbon comprises propylene, contacting the hydrocarbonaceous feed with the catalyst particles can produce a propylene yield of at least 52%, at least 53%, at least 55%, at least 57%, at least 60%, at least 62%, at least 63%, at least 65%, at least 67%, or at least 69% at a propylene selectivity of at least 75%, at least 80%, at least 85%, at least 90%, or at least 95%, for at least 15, at least 20, at least 30, at least 40, at least 50, at least 60, at least 70, at least 100 cycles, at least 125 cycles, at least 150 cycles, at least 175 cycles, or at least 200 cycles. In other embodiments, when a hydrocarbon-containing feed comprising at least 70 volume percent propane, based on the total volume of the hydrocarbon-containing feed, is contacted at a propane partial pressure of at least 20 kPa absolute, a propylene yield of at least 52%, at least 53%, at least 55%, at least 57%, at least 60%, at least 62%, at least 63%, at least 65%, at least 67%, or at least 69% can be achieved at a propylene selectivity of at least 75%, at least 80%, at least 85%, at least 90%, or at least 95% for at least 15, at least 20, at least 30, at least 40, at least 50, at least 60, at least 70, at least 100 cycles, at least 125 cycles, at least 150 cycles, at least 175 cycles, or at least 200 cycles. It is believed that 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 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% for at least 15 cycles, at least 20, at least 30, at least 40, at least 50, at least 60, at least 70, at least 100 cycles, at least 125 cycles, at least 150 cycles, at least 175 cycles, or at least 200 cycles. In some embodiments, the propylene yields may be achieved when the catalyst particles are contacted with a hydrocarbonaceous feed at a temperature of at least 620° C., at least 630° C., at least 640° C., at least 650° C., at least 655° C., at least 660° C., at least 670° C., at least 680° C., at least 690° C., at least 700° C., or at least 750° C. for at least 15, at least 20, at least 30, at least 40, at least 50, at least 60, at least 70, at least 100 cycles, at least 125 cycles, at least 150 cycles, at least 175 cycles, or at least 200 cycles. It is not believed possible to achieve such high propylene yields under such processing conditions.

[0037] Hydrocarbon Upgrading Methods

[0038] The hydrocarbon-containing feed can be contacted with the catalyst particles in any suitable conversion zone so that at least a portion of the hydrocarbon-containing feed is subjected to one or more of dehydrogenation, dehydroaromatization and dehydrocyclization to produce a conversion effluent, which can include coked catalyst particles, one or more upgraded hydrocarbons and molecular hydrogen. In some embodiments, the hydrocarbon-containing feed and the catalyst particles can be contacted in a conversion zone arranged in a continuous process commonly used in a fluidized bed reactor. In some embodiments, the conversion zone can be arranged in a riser reactor. In other embodiments, the conversion zone can be arranged in a downer reactor. In other embodiments, the conversion zone can be arranged in a vortex reactor. In other embodiments, the conversion zone can be arranged in a reactor and can allow the fluidized particles to form a denser turbulent fluidized bed therein during contact with the hydrocarbon-containing feed. A denser turbulent fluidized bed is one in which the superficial gas velocity is above the transition velocity known as the critical velocity between the transition between a bubbling bed and a turbulent bed, but below the transport velocity delimiting the fast fluidization regime in which the catalyst particles are transported, for example, in a riser reactor.

[0039] Any number of reactors can be operated in series and / or in parallel. Any two or more types of reactors can be used in combination with each other. If two or more reactors are used, the reactors can be operated under the same conditions and / or different conditions, and can receive the same hydrocarbon feed or different hydrocarbon feeds. If two or more reactors are used, the reactors can be arranged in series, in parallel or in combination relative to each other. In some embodiments, suitable reactors can be or can include, but are not limited to, high gas velocity riser reactors, high gas velocity down-type reactors, vortex reactors, reactors with denser fluidized catalyst beds at the first or bottom end and with less dense fluidized catalyst in the riser located at the second or top end, multiple riser reactors and / or down-type reactors operated in parallel and / or in series under the same or different conditions relative to each other, or combinations thereof.

[0040] In some examples, the catalyst particles can be pneumatically moved through the reaction system via a carrier fluid or a transport fluid, such as being fed into a reforming zone, fed into a combustion zone, transported via a pipeline connecting two or more locations, etc. The transport fluid can be or can include, but is not limited to, a diluent, one or more reactants in gaseous form, i.e., one or more C2-C 16 Alkanes, one or more C8-C 16Alkyl aromatic hydrocarbons or their mixtures.Suitable conveying fluid can be or can include but is not limited to molecular nitrogen, volatile hydrocarbons such as methane, ethane and / or propane, argon, carbon monoxide, carbon dioxide, steam etc.The amount of conveying fluid can be enough to keep catalyst particles in fluidized state and transport catalyst particles from one position (such as combustion zone or regeneration zone) to a second position (such as conversion zone).In some embodiments, the weight ratio of catalyst particles to conveying fluid can be in the range of 5,10,15 or 20 to 50,60,80,90 or 100.The injection point of conveying fluid can be arranged at multiple points of any one or more conveying pipelines along connecting any two zones or other positions (such as combustion zone and conversion zone or regeneration zone and conversion zone).

[0041] The hydrocarbonaceous feed and catalyst particles may be contacted at a temperature in the range of 300°C, 350°C, 400°C, 450°C, 500°C, 550°C, 600°C, 620°C, 630°C, 640°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 hydrocarbonaceous feed and catalyst particles may be contacted at a temperature of at least 620° C., at least 630° C., at least 640° 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 hydrocarbonaceous feed may be introduced into the conversion zone and contacted with the catalyst particles therein for a period of from 0.1 seconds, 1 second, 1.5 seconds, 2 seconds, or 3 seconds to 5 seconds, 10 seconds, 20 seconds, 30 seconds, 45 seconds, 1 minute, 1.5 minutes, 2 minutes, 2.5 minutes, or 3 minutes.

[0042] The average residence time of the catalyst particles in the conversion zone may be ≤7 minutes, ≤6 minutes, ≤5 minutes, ≤4 minutes, ≤3 minutes, ≤2 minutes, ≤1.5 minutes, ≤1 minute, ≤45 seconds, ≤30 seconds, ≤20 seconds, ≤15 seconds, ≤10 seconds, ≤7 seconds, ≤5 seconds, ≤3 seconds, ≤2 seconds, or ≤1 second. In some embodiments, the average residence time of the catalyst particles in the conversion zone may be greater than the average residence time of the gaseous components, such as the hydrocarbonaceous feed and the conversion effluent obtained therefrom, in the conversion zone.

[0043] The hydrocarbonaceous feed and the catalyst particles may be contacted at a hydrocarbon partial pressure of at least 20 kPa absolute, wherein the hydrocarbon partial pressure is the hydrocarbon partial pressure of any C2-C 16 Alkanes and any C8-C 16In some embodiments, the hydrocarbon partial pressure during contact of the hydrocarbon-containing feed with the catalyst particles can be in the range of 20 kPa-absolute pressure, 50 kPa-absolute pressure, 70 kPa-absolute pressure, 100 kPa-absolute pressure, 150 kPa-absolute pressure, or 200 kPa-absolute pressure to 300 kPa-absolute pressure, 500 kPa-absolute pressure, 750 kPa-absolute pressure, or 1,000 kPa-absolute pressure, wherein the hydrocarbon partial pressure is the total partial pressure of the alkyl aromatic hydrocarbons in the hydrocarbon-containing feed. 16 Alkanes and any C8-C 16 Total partial pressure of alkyl aromatic hydrocarbons.

[0044] In some embodiments, the hydrocarbon-containing feed may 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 C2-C 16 The hydrocarbon-containing feed and catalyst particles may be at a pressure of at least 20 kPa absolute, at least 50 kPa absolute, at least 70 kPa absolute, at least 100 kPa absolute, at least 150 kPa absolute, or at least 250 kPa absolute to 300 kPa absolute, 400 kPa absolute, 500 kPa absolute, or 1,000 kPa absolute for a single C2-C4 hydrocarbon. 16 Alkane (such as propane) is contacted under pressure.

[0045] The hydrocarbonaceous feed can be contacted with the catalyst particles in the conversion zone at any weight hourly space velocity (WHSV) effective to carry out the upgrading process. In some embodiments, the WHSV can be 0.1 hr -1 、0.2hr -1 、0.4hr -1 、0.8hr -1 , 2hr -1 , 4hr -1 or 8 hours -1 Up to 16 hours -1 、32hr -1 、64hr -1 or 100hr -1 In some embodiments, the catalyst particles are combined with any C2-C 16 Alkanes and any C8-C 16 The ratio of the total amount of alkyl aromatic hydrocarbons may range from 1, 3, 5, 10, 15, 20, 25, 30 or 40 to 50, 60, 70, 80, 90, 100, 110, 125 or 150 on a weight:weight basis.

[0046] In some embodiments, at least a portion of the fluidized catalyst particles in the conversion zone can be removed and fed into a heat input device, where the catalyst particles can be heated, and the heated catalyst particles can be fed back into the conversion zone. In the case where the reaction occurring in the conversion zone is heat absorbing, it may be advantageous to remove a portion of the fluidized catalyst particles therefrom, to further increase the temperature after some contacts with the hydrocarbon-containing feed. Heat can be indirectly transferred from any suitable heat transfer medium, provided via an electric heater or any other suitable heater that is generally used for indirect heating of catalyst particles. In another embodiment, heat can be directly applied in the conversion zone.

[0047] A first particle stream rich in coked catalyst particles and a first gaseous stream rich in one or more upgraded hydrocarbons and molecular hydrogen can be separated from the conversion effluent or otherwise obtained via any suitable device. In some embodiments, the first particle stream and the first gaseous stream can be obtained from the conversion effluent via one or more solid-gas impact separators, such as one or more cyclone separators. In some examples, the cyclone separator can be or can include a two-stage or "coupled" structure, including a positive pressure structure and a negative pressure structure. In some embodiments, suitable cyclone separators may include those disclosed in U.S. Patent Nos. 4,502,947; 4,985,136; and 5,248,411. In other embodiments, the first particle stream and the first gaseous stream can be obtained from the conversion effluent via a "T" shaped conduit, which can allow the catalyst particles to flow in one direction via gravity and the gaseous components to flow in another direction.

[0048] At least a portion of the coked catalyst particles in the first particle stream may be contacted with an oxidant in a regeneration or combustion zone to produce regenerated catalyst particles. The oxidant may be or may include, but is not limited to, molecular oxygen, ozone, carbon dioxide, steam, or a mixture thereof. In some embodiments, an oxidant in excess of the amount required to burn 100% of the coke on the coked catalyst particles may be used to increase the rate of removal of coke from the catalyst particles, so that the time required to remove the coke can be reduced and the yield of the upgraded product produced in a given period may be increased. In some embodiments, in addition to the coked catalyst particles, one or more supplementary fuels may be contacted with an oxidant in a combustion zone to burn at least a portion of the supplementary fuel, thereby generating heat and additional combustion gases. The optional supplementary fuel may be or may include, but is not limited to, molecular hydrogen, methane, ethane, propane, or a mixture thereof. The optional supplementary fuel may be mixed with an inert gas such as argon, neon, helium, molecular nitrogen, methane, or a mixture thereof.

[0049] The coked catalyst particles and the oxidant may be contacted with each other at a temperature ranging from 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 regenerated catalyst particles. In some embodiments, the coked catalyst particles and the oxidant may be contacted at a temperature ranging from 500°C to 1,100°C, 600°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 regenerated catalyst particles. The coked catalyst particles and the oxidant may contact one another at an oxidant partial pressure of 20 kPa-absolute, 50 kPa-absolute, 70 kPa-absolute, 100 kPa-absolute, 150 kPa-absolute, or 200 kPa-absolute to 300 kPa-absolute, 500 kPa-absolute, 750 kPa-absolute, or 1,000 kPa-absolute.

[0050] The coked catalyst particles and the oxidant may be in contact with each other for a period of 15 seconds, 30 seconds, 1 minute, 2 minutes, or 5 minutes to 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, or 60 minutes. For example, the coked catalyst particles and the oxidant may be in contact with each other for a period of 2 seconds to 50 minutes, 55 minutes, or 60 minutes. In some embodiments, the coked catalyst particles and the oxidant may be in contact with each other for a period sufficient to remove ≥50 wt%, ≥75 wt%, or ≥90 wt%, or >99% of any coke disposed on the catalyst particles.

[0051] In some embodiments, the coked catalyst particles and the oxidant may be in contact with each other for a period of time that is greater than the period of time that the catalyst particles are in contact with the hydrocarbonaceous feed to produce the conversion effluent. For example, the period of time that the coked catalyst particles and the oxidant are in contact with each other may 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%, at least 1,800,000%, at least 2,500,000%, at least 3,500,000%, or 4,140,000% longer than the period of time that the catalyst particles are in contact with the hydrocarbon-containing feed to produce the conversion effluent.

[0052] Without wishing to be bound by theory, it is believed that at least a portion of the Group 8-10 elements (e.g., Pt) disposed on the coked catalyst particles may be agglomerated compared to the catalyst particles prior to contact with the hydrocarbon-containing feed. It is believed that during combustion of at least a portion of the coke on the coked catalyst particles, at least a portion of the Group 8-10 elements may be redispersed around the support. Redispersing at least a portion of any agglomerated Group 8-10 elements may increase activity and improve stability of the catalyst particles over many cycles.

[0053] In some embodiments, compared with the 8-10 group elements in the catalyst particles contacting the hydrocarbon-containing feed and compared with the 8-10 group elements in the coked catalyst particles, at least a portion of the 8-10 group elements (e.g., Pt) in the regenerated catalyst particles can be in a higher oxidation state. Thus, as described above, in some embodiments, the method may optionally include contacting at least a portion of the regenerated catalyst particles with a reducing gas to produce regenerated and reduced catalyst particles. Suitable reducing gas (reducing agent) may be or may include, but is not limited to, molecular hydrogen, carbon monoxide, methane, ethane, ethylene, propane, propylene, steam, or a mixture thereof. In some embodiments, the reducing agent may be mixed with an inert gas such as argon, neon, helium, molecular nitrogen, or a mixture thereof. In such an embodiment, compared with the 8-10 group elements in the regenerated catalyst particles, at least a portion of the 8-10 group elements in the regenerated and reduced catalyst particles may be reduced to a lower oxidation state, such as an elemental state. In this embodiment, an additional amount of hydrocarbon-containing feed may contact at least a portion of the regenerated catalyst particles and / or at least a portion of the regenerated and reduced catalyst particles.

[0054] In some embodiments, the regenerated catalyst particles and the reducing gas may be contacted at a temperature ranging from 400°C, 450°C, 500°C, 550°C, 600°C, 620°C, 650°C, or 670°C to 720°C, 750°C, 800°C, or 900°C. The regenerated catalyst particles and the reducing gas may be contacted for a period of 1 second, 5 seconds, 10 seconds, 20 seconds, 30 seconds, or 1 minute to 10 minutes, 30 minutes, or 60 minutes. The regenerated catalyst particles and the reducing gas may be contacted at a reducing agent partial pressure of 20 kPa absolute pressure, 50 kPa absolute pressure, 70 kPa absolute pressure, 100 kPa absolute pressure, 150 kPa absolute pressure, or 200 kPa absolute pressure to 300 kPa absolute pressure, 500 kPa absolute pressure, 750 kPa absolute pressure, or 1,000 kPa absolute pressure.

[0055] In some embodiments, a first portion of the coked catalyst particles in the first particle stream rich in coked catalyst particles can be fed into the combustion zone to regenerate the catalyst particles, and a second portion of the coked catalyst particles can be directly circulated back to the conversion zone. In some embodiments, if the method includes both regeneration and reduction, a first portion of the coked catalyst particles in the first particle stream rich in coked catalyst particles can be fed into the combustion zone to regenerate the catalyst particles, and a second portion of the coked catalyst particles can be fed into the reduction zone. In other embodiments, if the method includes both regeneration and reduction, a first portion of the coked catalyst particles in the first particle stream rich in coked catalyst particles can be fed into the combustion zone to regenerate the catalyst particles, a second portion of the coked catalyst particles can be directly circulated back to the conversion zone, and a third portion of the coked catalyst particles can be fed into the reduction zone. In any of these embodiments, a portion of the coked catalyst particles, a portion of the regenerated catalyst particles, and / or a portion of the regenerated and reduced catalyst particles can be removed from the method on a continuous or intermittent basis, and new or supplementary catalyst particles can be introduced into the method. Removal of catalyst particles may occur when the catalyst particles degrade in size, become deactivated, or begin to convert the hydrocarbonaceous feed at an undesirable conversion rate.

[0056] At least a portion of the coked catalyst particles, at least a portion of the regenerated catalyst particles, at least a portion of the regenerated and reduced catalyst particles, new or supplemental catalyst particles, or a mixture thereof can be contacted with an additional amount of hydrocarbonaceous feed in the conversion zone to produce additional conversion effluent. As described above, the cycle time from contacting the hydrocarbonaceous feed with the catalyst particles to contacting the additional amount of hydrocarbonaceous feed with at least a portion of the regenerated catalyst particles and / or the regenerated and reduced catalyst particles and optionally with new or supplemental catalyst particles can be ≤ 70 minutes, e.g., from 1 minute to 70 minutes or from 5 minutes to 45 minutes.

[0057] In some embodiments, one or more additional feeds, such as one or more stripping fluids, can be used to remove at least a portion of any entrained gaseous components from the catalyst particles. In some examples, the coked catalyst particles can be contacted with a stripping fluid before contacting with an oxidant to remove at least a portion of any entrained upgraded hydrocarbons and / or molecular hydrogen and / or other gaseous components. Similarly, regenerated catalyst particles and / or regenerated and reduced catalyst particles can be contacted with a stripping gas to remove at least a portion of any entrained combustion gas or reducing gas therefrom. In some embodiments, the stripping gas can be inert under dehydrogenation, dehydrogenation aromatization and dehydrogenation cyclization, combustion and / or reduction conditions. Suitable stripping fluids can be or can include, but are not limited to, molecular nitrogen, helium, argon, carbon dioxide, steam, methane, or mixtures thereof. The stripping gas can be mixed with the coked catalyst particles, the regenerated catalyst particles, and / or the regenerated and reduced catalyst particles at a rate of about 0.1 m3 / cm3 of catalyst particles. 3 Up to 10m 3 The volume ratio of the stripping gas is contact.

[0058] As described above, the first cycle begins when the catalyst particles are contacted with a hydrocarbon-containing feed, followed by contact with at least an oxidant to produce regenerated catalyst particles or at least an oxidant and, optionally, a reducing gas to produce regenerated and reduced catalyst particles, and the first cycle ends when the regenerated catalyst particles or the regenerated and reduced catalyst particles are contacted with an additional amount of hydrocarbon-containing feed. If any purge fluid is used, for example, to strip residual hydrocarbons from coked catalyst particles, the period during which such purge fluid is used will be included in the cycle time. Thus, the cycle time from contacting the hydrocarbon-containing feed with the catalyst particles in step (I) to contacting the additional amount of hydrocarbon-containing feed with the regenerated catalyst particles and / or the regenerated and reduced catalyst particles in step (III) may be ≤70 minutes, for example, from 1 minute to 70 minutes or from 5 minutes to 45 minutes.

[0059] In one embodiment, a riser configuration can be implemented, wherein the hydrocarbon-containing feed can be mixed with a diluent gas and contacted with the heated and fluidized catalyst particles in the riser. The diluent gas can be or can include, but is not limited to, molecular nitrogen, methane, steam, molecular hydrogen or a mixture thereof. The combined gas can cause the fluidized catalyst particles to be convected or otherwise transported through the riser, while contacting and reacting when the mixture flows through the riser to produce a conversion effluent comprising upgraded hydrocarbons, molecular hydrogen and coking catalyst particles. The residence time of the hydrocarbon-containing feed and the fluidized catalyst particles can be sufficient to achieve the desired conversion of the hydrocarbon-containing feed to one or more upgraded hydrocarbons, and the mixture can be separated by using a gas-solid separation device, wherein the gas can be sent for recovery and the catalyst particles can be recovered. The specific design (including manufacture and size) of the riser can depend at least in part on the expected chemical process, but it may generally be necessary to exceed a speed of 4.5 m / s at an average gas composition. In order to reduce the thermal cracking of hydrocarbons, after achieving the desired conversion of the hydrocarbon-containing feed but before solid-gas separation, the conversion effluent can be quenched via one or more of many different methods. Such methods include injecting a cooling medium such as steam directly into the reformed effluent, passing the reformed effluent through a heat exchanger, etc. The gaseous product after the gas-solid separation device can also be quenched using similar methods to avoid or reduce thermal cracking.

[0060] Systems suitable for carrying out the methods disclosed herein may include systems known in the art, such as fluidized bed reactors disclosed in U.S. Patent Nos. 3,888,762; 7,102,050; 7,195,741; 7,122,160; and 8,653,317; U.S. Patent Application Publication Nos. 2004 / 0082824; 2008 / 0194891; and WO Publication Nos. WO2001 / 85872; WO2004 / 029178; and WO2005 / 077867.

[0061] Catalyst particles

[0062] The catalyst particles may include 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.5 wt%, or 1 wt% to 2 wt%, 3 wt%, 4 wt%, 5 wt%, or 6 wt% of the Group 8-10 elements, based on the total weight of the support. In some embodiments, the catalyst particles may include >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, >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 the Group 8-10 elements, based on the total weight of the support. In some embodiments, the Group 8-10 element may be or may include, but is 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.

[0063] The carrier can be or can include but is not limited to, atomic number is 4,12,20-22,30,38-40,48 or 56-71 one or more elements. In other words, the carrier can be or can include one or more 2nd group elements, one or more 4th group elements, one or more 12th group elements, one or more atomic numbers are 21,39 or 57-71 elements, its combination or its mixture. In some embodiments, the 2nd group element, the 4th group element, the 12th group element and / or the atomic number are 21,39 or 57-71 elements can exist in its elemental form. In other embodiments, the 2nd group element, the 4th group element, the 12th group element and / or the atomic number are 21,39 or 57-71 elements can exist in the form of compounds. For example, the 2nd group element, the 4th group element, the 12th group element and / or the element with atomic number 21,39 or 57-71 can be present as oxide, phosphate, halide, halogenate (a halate), sulfate, sulfide, borate, nitride, carbide, aluminate, aluminosilicate, silicate, carbonate, metaphosphate, selenide, tungstate, molybdate, chromite, chromate, dichromate or silicide. In some embodiments, the mixture of any two or more compounds including the 2nd group element, the 4th group element, the 12th group element and / or the element with atomic number 21,39 or 57-71 can exist in different forms. For example, the first compound can be an oxide, and the second compound can be an aluminate, wherein the first compound and the second compound contain the same or different 2nd group element, the 4th group element, the 12th group element and / or the element with atomic number 21,39 or 57-71.

[0064] In some embodiments, the carrier can be or can include at least one of: w weight % of Group 2 elements, x weight % of Group 4 elements, y weight % of Group 12 elements, and z weight % of elements with atomic numbers 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 can be associated with a weight % m, based on the weight of the carrier, any Group 4 element present in the carrier can be associated with a weight % n, based on the weight of the carrier, any Group 12 element present in the carrier can be associated with a weight % p, based on the weight of the carrier, and any element with atomic numbers of 21, 39, or 57-71 present in the carrier can be associated with a weight % q, based on the weight of the carrier, wherein m, n, p, and q can independently be numbers in the range of 1 to 100. In some embodiments, the sum of w / m+x / n+y / p+z / p can 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 of 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 of 1 to 2, 2 to 4, 4 to 6, 6 to 8, 8 to 12, 12 to 24, 24 to 48, or 48 to 60.

[0065] In some embodiments, m can be one of ten values ​​selected from the following: 2, 4, 6, 8, 10, 12, 14, 16, 18 and 20; n can be one of twelve values ​​selected from the following: 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22 and 24; p can be one of twelve values ​​selected from the following: 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22 and 24; q can be one of twelve values ​​selected from the following: 2, 4, 6, 10, 14, 18, 22, 26, 30, 34, 38 and 40, where m, n, p and q can be any combination, so that there are 17,280 (10×12×12×12) different combinations. In other embodiments, m may be equal to 2, 7, 10, or 20, n may be 2, 10, 20, or 25, p may be 2, 10, 20, or 25, and q may be 2, 10, 30, or 40, wherein m, n, p, and q may be any combination such that there are 256 (4×4×4×4) different combinations. In some embodiments, m, n, p, and q may each be equal to 2, 10, 15, or 30. In other embodiments, m may be equal to 7, n may be equal to 10, p may be equal to 10, and q may be equal to 10. In other embodiments, m may be equal to 7, n may be equal to 20, p may be equal to 20, and q may be equal to 10. In other embodiments, m may be equal to 10, n may be equal to 20, p may be equal to 20, and q may be equal to 30. In other embodiments, m may be equal to 7, n may be equal to 10, p may be equal to 10, and q may be equal to 30.

[0066] 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 1, 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, and z is ≤ 100.

[0067] 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 be in the range of 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 may be in the range of 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 may be in the range of 0.29, 0.5, 1, 10, 50, or 100 to 200, 300, 400, 500, or 590. In some embodiments, when the carrier comprises an element with an atomic number of 21, 39 or 57-71, the molar ratio of the element with an atomic number of 21, 39 or 57-71 to the element of Groups 8-10 may be in the range of 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 an atomic number of 21, 39 or 57-71, the molar ratio of the total amount of any Group 2 element, any Group 4 element, any Group 12 element and any element with an atomic number of 21, 39 or 57-71 to the Group 8-10 element may be in the range of 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.

[0068] In some embodiments, the carrier may be or may 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 Al2O 3+v , where v is a positive number; Mg w Al2O 3+w , where w is a positive number; Ca x Al2O 3+x, where x is a positive number; Sr y Al2O 3+y , where y is a positive number; Ba z Al2O 3+z , where z is a positive number; BeO; MgO; CaO; BaO; SrO; BeCO3; MgCO3; CaCO3; SrCO3, BaCO3; ZrO2; ZrC; ZrN; ZrSiO4; CaZrO3; Ca7ZrAl6O 18 ;TiO2; TiC; TiN; TiSiO4; CaTiO3; Ca7Al6O 18 ;HfO2; HfC; HfN; HfSiO4; HfZrO3; Ca7HfAl6O 18 ;ZnO; Zn3(PO4)2; Zn(ClO3)2; ZnSO4; B2O6Zn3; Zn3N2; ZnCO3; CeO2; Y2O3; La2O3; Sc2O3; Pr6O 11 ; CePO4; CeZrO4; CeAlO3; BaCeO3; CePO4; yttria-stabilized ZrO2; one or more magnesium chromates, one or more magnesium tungstates, one or more magnesium molybdates, combinations thereof, and mixtures thereof.

[0069] If present as a carrier or as a component of a carrier, Mg u Zn 1-u O (where u is a positive number) may have a molar ratio of Mg to Zn of 1, 2, 3, or 6 to 12, 25, 50, or 100. Zn v Al2O 3+v (where v is a positive number) if present as a support or as a component of a support, may have a molar ratio of Zn to Al of from 0.05, 0.3 or 0.6 to 0.9, 1.5 or 3. Mg w Al2O 3+w (where w is a positive number) if present as a support or as a component of a support, may have a molar ratio of Mg to Al of 1, 2, 3, 4 or 5 to 6, 7, 8, 9 or 10. Ca x Al2O 3+x (where x is a positive number) if present as a support or as a component of a support, 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, Ca x Al2O 3+x It may include tricalcium aluminate, dodecacalcium heptaaluminate, monocalcium aluminate, monocalcium dialuminate, monocalcium hexaaluminate, dicalcium aluminate, pentacalcium trialuminate, tetracalcium trialuminate, or any mixture thereof. y Al2O 3+y(where y is a positive number) if present as a support or as a component of a support, may have a molar ratio of Sr to Al in the range of 0.05, 0.3 or 0.6 to 0.9, 1.5 or 3. z Al2O 3+z (where z is a positive number) if present as a support or as a component of a support, may have a molar ratio of Ba to Al in the range of 0.05, 0.3 or 0.6 to 0.9, 1.5 or 3.

[0070] In some embodiments, the support may also include, but is not limited to, at least one metal element and / or at least one metalloid element and / or at least one compound thereof selected from Groups 5, 6, 7, 11, 13, 14, 15, and 16. If the support further includes a compound containing a metal element and / or a metalloid element selected from Groups 5, 6, 7, 11, 13, 14, 15, and 16, the compound may be present in the support as an oxide, phosphate, halide, halide, sulfate, sulfide, borate, nitride, carbide, aluminate, aluminosilicate, silicate, carbonate, metaphosphate, selenide, tungstate, molybdate, chromite, chromate, dichromate, or silicide. In some embodiments, suitable compounds comprising metal elements and / or metalloid elements 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 substances: B2O3, AlBO3, Al2O3, SiO2, SiC, Si3N4, aluminosilicates, VO, V2O3, VO2, V2O5, Ga2O3, In2O3, Mn2O3, Mn3O4, MnO, one or more molybdenum oxides, one or more tungsten oxides, one or more zeolites, and mixtures and combinations thereof.

[0071] In some embodiments, the carrier may also include one or more promoters arranged thereon. Promoters may be or may include but are not limited to Sn, Ga, Zn, Ge, In, Re, Ag, Au, Cu, combinations thereof, or mixtures thereof. Therefore, if promoters exist as components of catalyst particles, they may exist as components of the carrier, as promoters arranged on the carrier, or as components of the carrier and as promoters arranged on the carrier. In some embodiments, promoters may be associated with Group 8-10 elements (e.g., Pt). For example, promoters and Group 8-10 elements arranged on the carrier may form Group 8-10 element-promoter clusters that may be dispersed on the carrier. If present, promoters may improve the selectivity / activity / lifespan of the catalyst to a given upgraded hydrocarbon. In some embodiments, when the hydrocarbon-containing feed includes propane, adding promoters may improve the propylene selectivity of the catalyst particles. The catalyst particles may include a promoter in an amount from 0.01 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt% or 1 wt% to 3 wt%, 5 wt%, 7 wt% or 10 wt%, based on the weight of the support.

[0072] In some embodiments, the carrier may further include one or more alkali metal elements arranged on the carrier. The alkali metal element (if present) may be or may include but is not limited to Li, Na, K, Rb, Cs, a combination thereof or a mixture thereof. In at least some embodiments, the alkali metal element may be or may include K and / or Cs. The alkali metal element (if present) may improve the selectivity of the catalyst particles to a given upgraded hydrocarbon. The catalyst particles may be 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 % including the alkali metal element, based on the weight of the carrier.

[0073] The preparation of the carrier can be completed via any known method. For simplicity and ease of description, the preparation of a suitable carrier including a mixed oxide of magnesium and aluminum (Mg (Al) O or MgO / Al2O3) carrier will be described in more detail. Catalyst synthesis technology is well known, and the following description is for illustrative purposes, and should not be considered to limit the synthesis of carriers or catalyst particles. In some embodiments, in order to prepare MgO / Al2O3 mixed oxide carriers, Mg and Al precursors such as Mg (NO3) 2 and Al (NO3) 3 can be mixed together, such as ball milling, and then calcined. In another embodiment, the two precursors can be dissolved in H2O, stirred until dry (optionally applying heat), and then calcined. In another embodiment, the two precursors can be dissolved in H2O, then alkali and carbonate are added, such as NaOH / Na2CO3 to produce hydrotalcite, and then calcined. In another embodiment, commercial ready-made MgO and Al2O3 can be mixed and ball milled. In another embodiment, the Mg(NO3)2 precursor can be dissolved in H2O and the solution can be impregnated onto an existing support such as an Al2O3 support which can be dried and calcined. In another embodiment, the Mg from Mg(NO3)2 can be loaded onto an existing Al2O3 support via ion adsorption followed by liquid-solid separation, drying and calcination.

[0074] The 8-10 group metal and any promoter and / or any alkali metal element can be loaded on the mixed oxide support by any known technology.For example, one or more 8-10 group element precursors, such as chloroplatinic acid, tetraamine platinum nitrate and / or tetraamine platinum hydroxide, one or more promoter precursors (if used), such as salts such as SnCl4 and / or AgNO3, and one or more alkali metal element precursors (if used), such as KNO3, KCl and / or NaCl, are dissolved in water.The solution can be impregnated on the support, then dried and calcined.In some embodiments, the 8-10 group element precursor and optionally, promoter precursor and / or alkali metal element precursor can be loaded on the support simultaneously, or separately loaded on the support in the order separated by drying and / or calcining steps.In other embodiments, the 8-10 group element and optionally, promoter and / or alkali metal element can be loaded on the support by chemical vapor deposition, wherein the precursor is volatilized and deposited on the support, then calcined. In other embodiments, the Group 8-10 element precursor and optionally, the promoter precursor and / or the alkali metal precursor can be loaded onto the support via ion adsorption, followed by liquid-solid separation, drying and calcination. Optionally, the catalyst particles can also be synthesized using a one-pot synthesis method, in which the precursors of the support, the Group 8-10 metal active phase and the promoter are all mixed together, dried or wetted, with or without any other additives to aid the synthesis, and then dried and calcined.

[0075] Suitable methods for preparing the catalyst particles disclosed herein may include those described in U.S. Patent Nos. 4,788,371; 4,962,265; 5,922,925; 8,653,317; EP Patent No. EP0098622; Journal of Catalysis 94 (1985), pp. 547-557; and / or Applied Catalysis 54 (1989), pp. 79-90.

[0076] When examined under a scanning electron microscope or a transmission electron microscope, the catalyst particles as synthesized may appear as primary particles, agglomerates of primary particles, aggregates of primary particles, or a combination thereof. Primary particles, agglomerates of primary particles, and aggregates of primary particles are described in Powder Technology 181 (2008) 292-300. The primary particles in the as-synthesized catalyst particles may have an average cross-sectional length or average particle size (e.g., diameter when spherical) in the range of 0.2 nm, 0.5 nm, 1 nm, 5 nm, 10 nm, 25 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, 450 nm, or 500 nm to 1 μm, 10 μm, 25 μm, 50 μm, 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 400 μm, or 500 μm when examined under a scanning electron microscope or a transmission electron microscope. In some embodiments, the primary particles in the as-synthesized catalyst particles may have an average particle size of 0.2 nm to 500 μm, 0.5 nm to 300 μm, 1 nm to 200 μm, 2 nm to 100 μm, 2 nm to 500 nm, or 2 nm to 100 nm as measured by transmission electron microscopy.

[0077] The catalyst particles as synthesized may have a particle size of 0.1 μm. 2 / g, 1m 2 / g, 10m 2 / g or 100m 2 / g to 500m 2 / g、800m 2 / g、1,000m 2 / g or 1,500m 2The surface area of ​​the catalyst particles can be measured according to the Brunauer-Emmett-Teller (Bet) method using a Micromeritics 3Flex instrument at 350°C for 4 hours after degassing the powder using nitrogen adsorption-desorption (temperature of liquid nitrogen, 77K). For more information about the method, see, for example, "Characterization of Porous Solids and Powders: Surface Area, Pore Size and Density", S. Lowell et al., Springer, 2004.

[0078] The catalyst particles as synthesized can be formulated into one or more suitable forms for use in different short-cycle (≤70 minutes) hydrocarbon upgrading processes. Alternatively, the support can be formulated into a suitable form for use in different short-cycle hydrocarbon upgrading processes before adding the Group 8-10 elements and any optional promoters and / or alkali metal elements. During formulation, one or more binders and / or additives can be added to the catalyst particles and / or support to improve the chemical / physical properties of the catalyst particles ultimately produced and used in the process. The binder / additive may be or may include, but is not limited to, silica, silica sol, silica-alumina, alumina, aluminum chlorohydrate, peptized alumina, aluminosilicates, smectites, kaolins, acid-treated metakaolins, illites, chlorites, attapulgites, pillared interlayered clays and mixed layer clays, silanes, alkoxysilanes, aryloxysilanes, acyloxysilanes, oximinosilanes, halosilanes, aminooxysilanes, aminosilanes, amidosilanes, silazanes, silicones, or mixtures thereof.

[0079] In some embodiments, the catalyst particles can be prepared via a known spray drying method. The spray-dried catalyst particles with an average cross-sectional area in the range of 20 μm, 40 μm or 50 μm to 80 μm, 90 μm or 100 μm are generally used in FCC type fluidized bed reactors. In order to prepare the spray-dried catalyst particles, the carrier, the 8-10 group elements and any additional components (such as promoters and / or alkali metals) can be made into a slurry before spray drying and calcination, wherein the binder / additive is in the slurry. Alternatively, the 8-10 group elements and any additional components, such as promoters and / or alkali metals can be added to the prepared carrier to produce a prepared catalyst.

[0080] The formulated catalyst particles may have a3 , 0.7g / cm 3 , 0.9g / cm 3 , 1g / cm 3 , 1.2g / cm 3 or 1.3 g / cm 3 Up to 1.5g / cm 3 , 1.8g / cm 3 , 2g / cm 3 , 2.3g / cm 3 , 2.5g / cm 3 , 2.7g / cm 3 or 3g / cm 3 The particle density is within the range of g / cm 3 The pore volume in units of pore volume can be measured by mercury porosimetry. The particle density of the catalyst particles can be measured according to UOP578-11. In some embodiments, the catalyst particles can have an average particle size and particle density consistent with the Geldart A definition.

[0081] Hydrocarbon-containing feed

[0082] C2-C 16 The alkane may be or may include, but is not limited to, ethane, propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, n-heptane, 2-methylhexane, 2,2,3-trimethylbutane, cyclopentane, cyclohexane, methylcyclopentane, ethylcyclopentane, n-propylcyclopentane, 1,3-dimethylcyclohexane or a mixture thereof. For example, the hydrocarbon-containing feed may include propane, which may be dehydrogenated to produce propylene, and / or isobutane, which may be dehydrogenated to produce isobutylene. In another example, the hydrocarbon-containing feed may include liquefied petroleum gas (LP gas), which may be in a gas phase when in contact with the catalyst particles. In some embodiments, the hydrocarbons in the hydrocarbon-containing feed may be substantially composed of a single alkane such as propane. In some embodiments, the hydrocarbon-containing feed may contain ≥50 mol%, ≥75 mol%, ≥95 mol%, ≥98 mol% or ≥99 mol% of a single C2-C 16 The alkane, such as propane, is based on the total weight of all hydrocarbons in the hydrocarbon-containing feed. In some embodiments, the hydrocarbon-containing feed may include at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 97%, or at least 99% by volume of a single C2-C 16 The alkane, such as propane, is based on the total volume of the hydrocarbon-containing feed.

[0083] C8-C16 The alkyl aromatic hydrocarbon may be or may include, but is not limited to, ethylbenzene, propylbenzene, butylbenzene, one or more ethyltoluenes, or mixtures thereof. In some embodiments, the hydrocarbon-containing feed may include ≥50 mol%, ≥75 mol%, ≥95 mol%, ≥98 mol%, or ≥99 mol% of a single C8-C 16 Alkyl aromatic compounds, such as ethylbenzene, are based on the total weight of all hydrocarbons in the hydrocarbon-containing feed. In some embodiments, ethylbenzene can be dehydrogenated to produce styrene. Therefore, in some embodiments, the methods disclosed herein can include propane dehydrogenation, butane dehydrogenation, isobutane dehydrogenation, pentane dehydrogenation, pentane dehydrogenation cyclization to cyclopentadiene, naphtha reforming, ethylbenzene dehydrogenation, ethyltoluene dehydrogenation, etc.

[0084] In some embodiments, the hydrocarbon-containing feed can be diluted with one or more diluent gases. Suitable diluents can be or can include, but are not limited to, argon, neon, helium, molecular nitrogen, carbon dioxide, methane, molecular hydrogen, or mixtures thereof. If the hydrocarbon-containing feed includes a diluent, then based on any C2-C 16 Alkanes and any C8-C 16 The hydrocarbon-containing feed can include 0.1 volume %, 0.5 volume %, 1 volume % or 2 volume % to 3 volume %, 8 volume %, 16 volume % or 32 volume % of diluent, based on the total volume of alkyl aromatic hydrocarbons. When the diluent includes molecular hydrogen, the molecular hydrogen and any C2-C 16 Alkanes and any C8-C 16 The molar ratio of the total amount of alkyl aromatic hydrocarbons may be in the range of 0.1, 0.3, 0.5, 0.7 or 1 to 2, 3, 4, 5, 6, 7, 8, 9 or 10. In some embodiments, if a diluent is used, the diluent may be mixed with the hydrocarbonaceous feed and / or introduced as a separate feed into the conversion zone via one or more inlets dedicated to feeding diluent into the conversion zone or otherwise fed into the conversion zone. Similarly, the hydrocarbonaceous feed may also be introduced into the conversion zone via one or more inlets dedicated to feeding hydrocarbonaceous feed into the conversion zone.

[0085] In some embodiments, based on any C2-C 16 Alkanes and any C 8- C 16 The hydrocarbon-containing feed may be substantially free of any steam, e.g., <0.1 volume % steam, based on the total volume of the alkyl aromatic hydrocarbons. In other embodiments, the hydrocarbon-containing feed may contain steam. For example, based on any C2-C 16 Alkanes and any C8-C 16The hydrocarbonaceous feed may contain 0.1%, 0.3%, 0.5%, 0.7%, 1%, 3%, or 5% to 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50% steam by volume, based on the total volume of the alkylaromatic hydrocarbons. In other embodiments, the hydrocarbonaceous feed may contain 0.1%, 0.3%, 0.5%, 0.7%, 1%, 3%, or 5% to 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50% steam by volume, based on the total volume of the alkylaromatic hydrocarbons. 16 Alkanes and any C8-C 16 The hydrocarbon-containing feed may contain ≤50 vol%, ≤45 vol%, ≤40 vol%, ≤35 vol%, ≤30 vol%, ≤25 vol%, ≤20 vol%, or ≤15 vol% steam, based on the total volume of the alkylaromatic hydrocarbons. 16 Alkanes and any C8-C 16 The hydrocarbonaceous feed may contain at least 1 volume %, at least 3 volume %, at least 5 volume %, at least 10 volume %, at least 15 volume %, at least 20 volume %, at least 25 volume %, or at least 30 volume % steam, based on the total volume of alkyl aromatic hydrocarbons. Similar to the diluent, if steam is fed to the reforming zone, the steam may be fed to the reforming zone as a component of the hydrocarbonaceous feed or via one or more separate inlets dedicated to introducing steam into the reforming zone.

[0086] In some embodiments, hydrocarbon feed can include sulfur. For example, hydrocarbon feed can include 0.5ppm, 1ppm, 5ppm, 10ppm, 20ppm, 30ppm, 40ppm, 50ppm, 60ppm, 70ppm or 80ppm to 100ppm, 150ppm, 200ppm, 300ppm, 400ppm or 500ppm of sulfur. In other embodiments, hydrocarbon feed can include 1ppm to 10ppm, 10ppm to 20ppm, 20ppm to 50ppm, 50ppm to 100ppm or 100ppm to 500ppm of sulfur. If present in hydrocarbon feed, sulfur can be or can include but is not limited to, H2S, dimethyl disulfide (as one or more mercaptans) or any mixture thereof. In some embodiments, sulfur can be introduced into conversion zone as a single feed, as a component (if used) of a diluent and / or as a component (if used) of steam.

[0087] The hydrocarbon-containing feed may be substantially free of or free of molecular oxygen. In some embodiments, the hydrocarbon-containing feed may contain ≤5 mol%, ≤3 mol%, or ≤1 mol% of molecular oxygen (O2). It is believed that providing a hydrocarbon-containing feed substantially free of molecular oxygen significantly prevents oxidative coupling reactions, which would otherwise consume at least a portion of the alkanes and / or alkyl aromatic hydrocarbons in the hydrocarbon-containing feed.

[0088] Recovery and application of upgraded hydrocarbons

[0089] The upgraded hydrocarbon can include at least one upgraded hydrocarbon, such as olefin, water, unreacted hydrocarbon, unreacted molecular hydrogen, etc. The upgraded hydrocarbon can be recovered or otherwise obtained via any convenient method, such as by one or more conventional methods. Such a method can include cooling the effluent to condense at least a portion of any water and any heavy hydrocarbon that may be present, so that olefin and any unreacted alkane or alkyl aromatic hydrocarbon are mainly left in the gas phase. Olefin and unreacted alkane or alkyl aromatic hydrocarbon can then be removed from the reaction product in one or more separator drums. For example, one or more splitters can be used to separate the dehydrogenated product from the unreacted hydrocarbon-containing feed.

[0090] In some embodiments, the recovered olefins, such as propylene, can be used to produce polymers, for example, the recovered propylene can be polymerized to produce polymers having segments or units derived from the recovered propylene, such as polypropylene, ethylene-propylene copolymers, etc. The recovered isobutylene can be used, for example, to produce one or more of the following: oxygenates such as methyl tert-butyl ether, fuel additives such as diisobutylene, synthetic elastomeric polymers such as butyl rubber, etc.

[0091] Exemplary embodiments

[0092] Figure 1 A system for upgrading a hydrocarbonaceous feed in line 20 is depicted, according to one or more embodiments, comprising a reactor or conversion zone 1 and a regenerator or combustion zone 2. The hydrocarbonaceous feed via line 20 may be introduced into the reactor 1, for example, at the bottom end of a riser reactor or the top end of a downcomer reactor. In some embodiments, a dilution gas via line 21 may be mixed with the hydrocarbonaceous feed in line 20. The hydrocarbonaceous feed and, optionally, the dilution gas may be mixed or otherwise contacted with regenerated catalyst particles introduced into the reactor 1 via line 50. The regenerated catalyst particles in line 50 may be moved or otherwise transported through line 50 via a transport gas introduced through line 31. As the hydrocarbonaceous feed reacts and passes through the reactor 1 in the presence of the catalyst particles, additional hydrocarbonaceous feed via line 22 and / or additional dilution gas via line 23 may optionally be introduced into the reactor 1. The gaseous components and the coked catalyst particles may be separated via one or more gas-solid separation devices, as previously described, wherein a first gaseous stream rich in one or more upgraded hydrocarbons, unreacted hydrocarbons, molecular hydrogen, and any other gaseous components is recovered via line 24, and a first particle stream rich in coked catalyst particles is recovered via line 51. Although the separation of the gaseous components and the coked catalyst particles is shown as occurring within the reactor 1, such separation may also occur outside the reactor 1.

[0093] The first gaseous stream via line 24 may be sent to product recovery and additional processing steps. The first particle stream rich in coked catalyst particles may be introduced into the regenerator 2 via line 51. The regenerator 2 may be a reactor in which the coked catalyst particles may be contacted with an oxidant (e.g., air) introduced via line 25 to burn at least a portion of the coke deposited on the surface of the catalyst particles. In some embodiments, an optional supplemental fuel may also be introduced into the regenerator 2 via line 26. The supplemental fuel may be used to generate additional heat, which may further heat the regenerated catalyst particles within the regenerator 2 to a desired temperature to support the endothermic reaction occurring within the reactor 1.

[0094] Within the regenerator 2, a gas-solid separation device may be used to separate the regenerated catalyst particles from the combustion gases with a second gaseous stream rich in combustion gases recovered via line 27 and a second particle stream rich in regenerated catalyst particles recovered via line 50. In some embodiments, the combustion gases in line 27 (which may contain fine catalyst particles) may be directed to a secondary separation device to recover the fine catalyst particles, heat recovery, or disposal. The regenerated catalyst particles may be introduced into the reactor 1 via line 50, wherein a transport gas is used to transport the catalyst particles into the reactor 1 via line 31.

[0095] Figure 2 Another system for upgrading a hydrocarbonaceous feed in line 20 is depicted, according to one or more embodiments, comprising a reactor or conversion zone 1, a regenerator or combustion zone 2, and a reduction reactor or reduction zone 3. The hydrocarbonaceous feed via line 20 may be introduced into the reactor 1, for example, at the bottom end of a riser reactor or the top end of a downcomer reactor. In some embodiments, a dilution gas via line 21 may be mixed with the hydrocarbonaceous feed in line 20. The hydrocarbonaceous feed and, optionally, the dilution gas may be mixed or otherwise contacted with the regenerated and reduced catalyst particles introduced into the reactor 1 via line 50. The regenerated and reduced catalyst particles in line 50 may be moved or otherwise transported through line 50 via a transport gas introduced through line 31. As the hydrocarbonaceous feed reacts and passes through the reactor 1 in the presence of the catalyst particles, additional hydrocarbonaceous feed via line 22 and / or additional dilution gas via line 23 may be optionally introduced into the reactor 1. The gaseous components and coked catalyst particles can be separated via one or more gas-solid separation devices, as previously described, wherein a first gaseous stream rich in one or more upgraded hydrocarbons, unreacted hydrocarbons, molecular hydrogen and any other gaseous components is recovered via pipeline 24, and a first particle stream rich in coked catalyst particles is recovered via pipeline 51.

[0096] The first gaseous stream via line 24 may be sent to product recovery and additional processing steps. The first particle stream rich in coked catalyst particles may be introduced into the regenerator 2 via line 51. The regenerator 2 may be a reactor in which the coked catalyst particles may be contacted with an oxidant (e.g., air) introduced via line 25 to burn at least a portion of the coke deposited on the surface of the catalyst particles. Supplemental fuel may also be introduced into the regenerator 2 via line 26 as desired. The supplemental fuel may be used to further heat the regenerated catalyst particles within the regenerator 2 to a desired temperature to support the endothermic reaction occurring within the reactor 1.

[0097] Within regenerator 2, a gas-solid separation device may be used to separate the regenerated catalyst particles from the combustion gases with a second gaseous stream rich in combustion gases recovered via line 27 and a second particle stream rich in regenerated catalyst particles recovered via line 52. In some embodiments, the combustion gases in line 27, which may contain fine catalyst particles, may be directed to a secondary separation device for recovery of the fine catalyst particles, heat recovery, or disposal.

[0098] Regenerated catalyst particles via line 52 and reducing gas via line 28 may be introduced into the reduction reactor 3. The regenerated catalyst particles may be contacted with the reducing gas within the reduction reactor 3 to produce regenerated and reduced catalyst particles. Within the reduction reactor 3, a gas-solid separation device may be used to separate the regenerated and reduced catalyst particles from the reducing gas, wherein a third gaseous stream rich in reducing gas recovered via line 30 and / or line 29 and a third particle stream rich in regenerated and reduced catalyst particles via line 50 are employed. Depending at least in part on the composition of the reducing gas, the reducing gas may be introduced into the regenerator 2 in whole or in part via line 30 to provide at least a portion of the optional supplemental fuel that may be fed into the regenerator 2. In some embodiments, the reducing gas may be removed from the system via line 29. In some embodiments, the residual reducing gas and gaseous products from the catalyst reduction may be carried directly into the reactor 1 without separation from the catalyst. The regenerated and reduced catalyst particles can be introduced into the reactor 1 via the line 50 , wherein a transport gas is used via the line 31 to transport the catalyst particles into the reactor 1 .

[0099] Figure 3Another system for upgrading a hydrocarbon-containing feed in line 20 according to one or more embodiments is depicted, comprising a reactor or conversion zone 1, a regenerator or combustion zone 2, a reduction reactor or reduction zone 3, and a recycle line 53 for recycling at least a portion of the coked catalyst particles in line 51 to the reactor 1. In some embodiments, the extent of catalyst deactivation within the reactor 1 may not be sufficient to require the introduction of all of the coked catalyst particles into the regenerator 2. Thus, at least a portion of the coked catalyst particles may be recycled to the reactor 1 to reduce or minimize the amount of catalyst particles introduced into the regenerator.

[0100] Figure 4 Another system for upgrading a hydrocarbonaceous feed according to one or more embodiments is depicted, comprising a reactor or conversion zone 1, a regenerator or combustion zone 2, a reduction reactor or reduction zone 3, and a heat input device 4 for heating catalyst particles. Depending at least in part on the specific hydrocarbonaceous feed, the weight ratio of catalyst particles to hydrocarbonaceous feed, the temperature of the regenerated and reduced catalyst particles, and other process parameters, it may be necessary to heat at least a portion of the catalyst particles once introduced into the reactor 1. Therefore, in some embodiments, at least a portion of the catalyst particles in the reactor 1 can be directed to the heat input device 4 via pipeline 54, where the catalyst particles can be heated. Any suitable heat source can be used to heat the catalyst particles. In some embodiments, heat can be indirectly transferred from a heated medium to increase the temperature of the catalyst particles to a desired temperature. Suitable heat media can be or can include, but are not limited to, steam, flue gas, hot oil, molten salt, etc. In some embodiments, heat can be generated by one or more electric heating elements. The heated catalyst particles can be recovered from the heat input device 4 via pipeline 55 and reintroduced into the reactor 1. In an alternative embodiment, the heat input device may be arranged within the reactor 1 so that the catalyst particles do not need to be removed from the reactor 1 via line 54 and returned to the reactor 1 via line 55 .

[0101] Figure 5Another system for upgrading a hydrocarbon-containing feed in line 20 according to one or more embodiments is depicted, comprising a reactor or conversion zone 1, a regenerator or combustion zone 2, a reduction reactor or reduction zone 3, and a transfer line 56 for feeding at least a portion of the coked catalyst particles in line 51 to the reduction zone 3. In some embodiments, the extent of catalyst deactivation within reactor 1 may not be sufficient to require the introduction of all of the coked catalyst particles into the regenerator 2. Therefore, at least a portion of the coked catalyst particles may be fed into the reduction zone 3 to reduce or minimize the amount of catalyst particles introduced into the regenerator. Feeding at least a portion of the coked catalyst particles into the reduction zone 3 may also be used to adjust or otherwise control the temperature of the regenerated catalyst particles fed into the reduction zone 3 via line 52. In some embodiments, at least a portion of the coked catalyst particles via line 56 may be introduced into the reduction zone 3, and the coked catalyst particles via line 53 ( Figure 3 ) is recycled to reactor 1, and at least a portion of the coked catalyst particles via pipeline 51 can be fed into regeneration zone 2.

[0102] Figure 6 Another system for upgrading the hydrocarbonaceous feed in line 20 according to one or more embodiments is depicted, which includes a reactor or conversion zone 1, a regenerator or combustion zone 2, a reduction reactor or reduction zone 3, and a secondary reactor 5. The hydrocarbonaceous feed via line 20 can be introduced into the reactor 1, for example, at the bottom end of a riser reactor or the top end of a down-type reactor. In some embodiments, a dilution gas via line 21 can be mixed with the hydrocarbonaceous feed in line 20. The hydrocarbonaceous feed and optional dilution gas can be mixed or otherwise contacted with the regenerated and reduced catalyst particles introduced into the reactor 1 via line 50. The regenerated and reduced catalyst particles in line 50 can be moved or otherwise transported through line 50 via a transport gas introduced through line 31. When the hydrocarbonaceous feed reacts in the presence of the catalyst particles and passes through the reactor 1, additional hydrocarbonaceous feed via line 22 and / or additional dilution gas via line 23 can be optionally introduced into the reactor 1. The gaseous components and coked catalyst particles can be separated via one or more gas-solid separation devices, as previously described, wherein a first gaseous stream rich in one or more upgraded hydrocarbons, unreacted hydrocarbons, molecular hydrogen and any other gaseous components is recovered via pipeline 24, and a first particle stream rich in coked catalyst particles is recovered via pipeline 51.

[0103] The first gaseous stream via line 24 can be sent to product recovery and additional processing steps. The first particle stream rich in coked catalyst particles can be introduced into the secondary reactor 5 via line 51. The reactant stream (e.g., additional hydrocarbon-containing feed) via line 32 and the optional diluent stream via line 33 can also be introduced into the secondary reactor 5. In some embodiments, the hydrocarbon-containing feed in line 20 may include hydrocarbons different from the reactant stream in line 32. In some embodiments, the hydrocarbon-containing feed in line 20 may require the fluidized catalyst particles to be heated to a higher temperature than the reactant feed in line 32 to produce the desired conversion effluent. Therefore, the upgraded hydrocarbons in line 24 and the upgraded hydrocarbons in line 34 can be the same or different relative to each other. In another embodiment, at least a portion of the gaseous stream in line 24 can be introduced into the secondary reactor 5 via line 32.

[0104] Gas-solid separation equipment, such as a cyclone separator, can be used to separate the byproducts in line 34 from the coked catalyst. The byproducts via line 34 can be sent to product recovery and additional processing steps. In another embodiment, at least a portion of the byproducts in line 34 can be introduced into reactor 1 via line 20 and / or line 22. Coked catalyst particles can be fed into regenerator 2 via line 57. Regenerator 2 can be a reactor in which coked catalyst particles can be contacted with an oxidant (e.g., air) introduced via line 25 to burn at least a portion of the coke deposited on the surface of the catalyst particles. Supplemental fuel can also be introduced into regenerator 2 via line 26 as needed. Supplemental fuel can be used to further heat the regenerated catalyst particles in regenerator 2 to a desired temperature to support the endothermic reaction occurring in reactor 1.

[0105] Within regenerator 2, a gas-solid separation device may be used to separate the regenerated catalyst particles from the combustion gases with a second gaseous stream rich in combustion gases recovered via line 27 and a second particle stream rich in regenerated catalyst particles recovered via line 52. In some embodiments, the combustion gases in line 27, which may contain fine catalyst particles, may be directed to a secondary separation device for recovery of the fine catalyst particles, heat recovery, or disposal.

[0106] Regenerated catalyst particles via line 52 and reducing gas via line 28 may be introduced into the reduction reactor 3. The regenerated catalyst particles may be contacted with the reducing gas within the reduction reactor 3 to produce regenerated and reduced catalyst particles. Within the reduction reactor 3, a gas-solid separation device may be used to separate the regenerated and reduced catalyst particles from the reducing gas, wherein a third gaseous stream rich in reducing gas recovered via line 30 and / or line 29 and a third particle stream rich in regenerated and reduced catalyst particles via line 50 are employed. Depending at least in part on the composition of the reducing gas, the reducing gas may be introduced into the regenerator 2 in whole or in part via line 30 to provide at least a portion of the optional supplemental fuel that may be fed into the regenerator 2. In some embodiments, the reducing gas may be removed from the system via line 29. The regenerated and reduced catalyst particles may be introduced into the reactor 1 via line 50, wherein a transport gas is used to transport the catalyst particles into the reactor 1 via line 31.

[0107] Figure 7 Another system for upgrading the hydrocarbonaceous feed in line 20 according to one or more embodiments is depicted, which includes a reactor or conversion zone 1, a regenerator or combustion zone 2, a reduction reactor or reduction zone 3, and a secondary reactor 6. The hydrocarbonaceous feed via line 20 can be introduced into the reactor 1, for example, at the bottom end of a riser reactor or the top end of a down-type reactor. In some embodiments, a dilution gas via line 21 can be mixed with the hydrocarbonaceous feed in line 20. The hydrocarbonaceous feed and optional dilution gas can be mixed or otherwise contacted with the regenerated and reduced catalyst particles introduced into the reactor 1 via line 50. The regenerated and reduced catalyst particles in line 50 can be moved or otherwise transported through line 50 via a transport gas introduced through line 31. When the hydrocarbonaceous feed reacts in the presence of the catalyst particles and passes through the reactor 1, additional hydrocarbonaceous feed via line 22 and / or additional dilution gas via line 23 can be optionally introduced into the reactor 1. The gaseous components and coked catalyst particles can be separated via one or more gas-solid separation devices, as previously described, wherein a first gaseous stream rich in one or more upgraded hydrocarbons, unreacted hydrocarbons, molecular hydrogen and any other gaseous components is recovered via pipeline 24, and a first particle stream rich in coked catalyst particles is recovered via pipeline 58.

[0108] The first gaseous stream via line 24 may be sent to product recovery and additional processing steps. The first particle stream rich in coked catalyst particles may be introduced into the regenerator 2 via line 58. The regenerator 2 may be a reactor in which the coked catalyst particles may be contacted with an oxidant (e.g., air) introduced via line 25 to burn at least a portion of the coke deposited on the surface of the catalyst particles. Supplemental fuel may also be introduced into the regenerator 2 via line 26 as desired. The supplemental fuel may be used to further heat the regenerated catalyst particles within the regenerator 2 to a desired temperature to support the endothermic reaction occurring within the reactor 1.

[0109] Within regenerator 2, a gas-solid separation device may be used to separate the regenerated catalyst particles from the combustion gases with a second gaseous stream rich in combustion gases recovered via line 27 and a second particle stream rich in regenerated catalyst particles recovered via line 52. In some embodiments, the combustion gases in line 27, which may contain fine catalyst particles, may be directed to a secondary separation device for recovery of the fine catalyst particles, heat recovery, or disposal.

[0110] Regenerated catalyst particles via line 52 and reducing gas via line 28 may be introduced into the reduction reactor 3. The regenerated catalyst particles may be contacted with the reducing gas within the reduction reactor 3 to produce regenerated and reduced catalyst particles. Within the reduction reactor 3, a gas-solid separation device may be used to separate the regenerated and reduced catalyst particles from the reducing gas, wherein a third gaseous stream rich in reducing gas recovered via line 30 and / or line 29, a third particle stream rich in regenerated and reduced catalyst particles via line 50, and a fourth particle stream rich in regenerated and reduced catalyst particles via line 60 are employed. Depending at least in part on the composition of the reducing gas, the reducing gas may be introduced into the regenerator 2 in whole or in part via line 30 to provide at least a portion of the optional supplemental fuel that may be fed into the regenerator 2. In some embodiments, the reducing gas may be removed from the system via line 29.

[0111] A first portion of the regenerated and reduced catalyst particles may be introduced into the reactor 1 via line 50, wherein a transport gas is used to transport the catalyst particles into the reactor 1 via line 31. A second portion of the regenerated and reduced catalyst particles may be introduced into the secondary reactor 6 via line 60, wherein a transport gas in line 35 is used to transport the catalyst particles into the secondary reactor 6. A hydrocarbonaceous feed via line 32 and an optional diluent stream via line 33 may also be fed into the secondary reactor. The hydrocarbonaceous feed may contact the reduced and regenerated catalyst particles within the secondary reactor 6 to produce another conversion effluent.

[0112] The gaseous components and the coked catalyst particles can be separated via one or more gas-solid separation devices, as previously described, wherein a second gaseous stream rich in one or more upgraded hydrocarbons, unreacted hydrocarbons, molecular hydrogen, and any other gaseous components is recovered via line 34, and a particle stream rich in coked catalyst particles is recovered via line 59. In another embodiment, at least a portion of the first gaseous stream in line 24 can be introduced into the secondary reactor 6 via line 32. In another embodiment, at least a portion of the second gaseous stream in line 34 can be introduced into the reactor 1 via line 20 and / or line 22.

[0113] Although the separation of various gaseous products (e.g., upgraded hydrocarbons and molecular hydrogen) from coked catalyst particles, combustion gases from regenerated catalyst particles, and reducing gases from regenerated and reduced catalyst particles is Figure 1-7 As occurring within reactor 1, regenerator 2, reduction reactor 3, secondary reactor 5, and secondary reactor 6, this separation may also occur external to any one or more of those reactors. Example

[0114] The foregoing discussion can be further described with reference to the following non-limiting examples.

[0115] The following process steps were performed on the catalysts used in most of the following examples. All experiments were performed at ambient pressure with a few exceptions described in the following examples.

[0116] 1. A gas containing 10% by volume of O2 in He, or air at the regeneration temperature (T 再生 ) passes through the catalyst for a period of time (t 再生 ) to regenerate the catalyst.

[0117] 2. Without changing the gas flow rate, the temperature in the reactor changes from T 再生 Change to the reduction temperature (T 还原 ).

[0118] 3. Purge the system with He gas.

[0119] 4. A gas containing 10 vol% H2 in Ar is heated to T 还原 Pass through the catalyst for a period of time (t 还原 ).

[0120] 5. Purge the system with He gas.

[0121] 6. In the presence of inert gas, the temperature in the reactor is lowered from T 还原 Change to reaction temperature (T 反应 ).

[0122] 7. A hydrocarbon feed containing 90% by volume of C3H8 in Ar or Kr or He is fed at a certain flow rate (F 反应 ) in the T 反应 Pass through the catalyst for a period of time (t 反应 ). In some examples, the hydrocarbon-containing feed is passed through a distributor immersed in deionized water maintained at a temperature of T1, and then through a reflux having a carefully controlled temperature T2 before being introduced into the reactor and reaching the catalyst. When a distributor is used, the hydrocarbon-containing feed contains a certain amount of steam in the reactor, which is shown in the relevant table below.

[0123] 8. Purge the system with He gas.

[0124] 9. A gas containing 10 vol% O2 in He, or air at T 反应 The catalyst is passed through again, and the temperature in the reactor is increased from T 反应 Change to T 再生 .

[0125] In certain embodiments, the catalyst reduction step is not performed and the following steps are performed.

[0126] 1. A gas or air containing 10 vol% O2 in He is heated to T 再生 Keep t through the catalyst 再生 .

[0127] 2. Without changing the gas flow rate, the temperature in the reactor is increased from T 再生 Change to T 反应 .

[0128] 3. Purge the system with an inert gas (eg He).

[0129] 4. A hydrocarbon feed containing 90% by volume of C3H8 in Ar or Kr or He is reacted with F 反应 The flow rate at T 反应 Keep t through the catalyst 反应 In some examples, the hydrocarbonaceous feed is passed through a sparger immersed in deionized water maintained at temperature T1 and then through a reflux having a carefully controlled temperature T2 before being introduced into the reactor and reaching the catalyst.

[0130] 5. Purge the system with an inert gas (eg He).

[0131] 6. A gas containing 10 vol% O2 in He, or air at T 反应 The catalyst is passed through again, and the temperature in the reactor is increased from T 反应 Change to T 再生 .

[0132] The microGC 490 was used to measure the composition of the reactor effluent every 1 to 1.5 minutes. The concentration of each component in the reactor effluent was then used to calculate the C3H6 yield and selectivity. 反应 At the beginning and t 反应 The C3H6 yield and selectivity at the end are denoted as Y 初始 , Y 结束 , S 初始 and S 结束 , and reported as a percentage in the data tables below. For some experiments, repeated cycles were performed to understand catalyst stability. The C3H6 yields reported in these examples are based on carbon only.

[0133] In each example, a certain amount of catalyst M 催化剂 Mix with the appropriate amount of quartz / SiC diluent and load into a quartz reactor. The amount of diluent is determined so that the catalyst bed (catalyst + diluent) is essentially isothermal during operation. The dead volume of the reactor is filled with quartz chips / rods.

[0134] When the reaction temperature (T 反应 )>620°C, thermal cracking of propane / propylene becomes significant. Since thermal cracking of propane / propylene has much higher selectivity to C1 and C2 hydrocarbons, the overall selectivity to C3H6 is reduced. The amount of thermal cracking in the reactor is related to the amount of quartz / SiC diluent added to the reactor and the degree to which the packing material reduces the dead volume in the reactor. Therefore, depending on how the reactor is filled in different experiments, the performance changes. Therefore, the experimental results shown in different tables are not necessarily equivalent to each other.

[0135] Example 1-23, Catalyst 1

[0136] Catalyst 1: The catalyst used in Examples 1-23 (Exs. 1-23) was a Pt-based Sn-containing catalyst supported on a Mg / Al mixed oxide support, crushed and sieved to a particle size of 20-40 mesh. Elemental analysis showed that the catalyst contained 0.48 wt. % Pt, 1.25 wt. % Sn, 67.93 wt. % Mg and 29.23 wt. % Al, based on the total weight of the metal elements, with a molar ratio of Mg to Al of about 2.58.

[0137] Table 1 shows the experimental results of Examples 1-3. Comparison between Example 1 and Example 3 shows that reduction of the catalyst in the presence of molecular hydrogen after oxidative regeneration improves propylene yield. Examples 1 and Example 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 performing the reduction step. Figure 8The catalyst stability results are shown for the catalysts used in Examples 1-3 after 35 cycles (regeneration, reduction and dehydrogenation) under the same conditions as used in Example 1. Table 2 shows the experimental results for Examples 4 and 5. The results in Table 2 show that the reduction step can be performed at different temperatures (670°C vs. 750°C).

[0138]

[0139] Table 3 shows the experimental results of embodiment 6-10. Embodiment 6-10 is carried out by introducing partial blockage at the exhaust of reactor, so that when hydrocarbon-containing feed passes through reactor at room temperature (e.g., 25°C), the pressure indicator reading of reactor upstream is 1.43 bara. During the experiment, the gas volume flow rate in the expected reactor increases due to steam addition, higher T and the volume expansion of the fluid caused by propane dehydrogenation. Therefore, the pressure in the reactor should be significantly higher than 1.43 bara. Unfortunately, due to equipment limitations, the pressure during the reactor can not be monitored. Experiments 8-10 show the effect of regeneration under different temperatures and durations.

[0140]

[0141]

[0142] Table 4 shows the experimental results of Examples 11-14. The results in Table 4 show the effect of space velocity on catalyst performance. Table 5 shows the experimental results of Examples 15 and 16. Table 5 shows the effect of reduction in the presence of steam, respectively. Table 6 shows the results of Examples 17 and 18. Table 6 shows the effect of regeneration duration.

[0143]

[0144]

[0145] Table 7 shows the results of Examples 19-22. Table 7 shows the effect of the amount of steam in the hydrocarbon-containing feed on the yield and selectivity. In Example 23, the catalyst was cycled a total of 49 times in the presence of about 11 volume % steam. The results of Example 23 are shown in Table 8. Fig. 9 The catalyst stability results are shown for the catalyst used in Example 23 after 49 cycles (regeneration, reduction and dehydrogenation) in the presence of steam.

[0146]

[0147] Example 24, Catalyst 2

[0148] The catalyst includes 1 wt % Pt and 3 wt % Sn supported on CeO2, based on the weight of CeO2. The CeO2 support was prepared by calcining cerium (III) nitrate hexahydrate (Sigma-Aldrich 202991). The catalyst was prepared as follows: 3 g of CeO2 was incipiently impregnated with 0.788 g of 8 wt % chloroplatinic acid in water (Sigma Aldrich, 262587) and 0.266 g of tin (IV) chloride pentahydrate (Acros Organics 22369), then dried and calcined at 800°C for 12 hours. The data in Table 9 show that the catalyst is stable over 42 cycles.

[0149] Examples 25 and 26, Catalyst 3

[0150] The catalyst comprises 1 wt% Pt and 2.7 wt% Sn supported on ceria-zirconia, based on the weight of ceria-zirconia. The catalyst was prepared by incipient wetness impregnation of 16.5 g ceria-zirconia (Sigma Aldrich 634174) with 0.44 g chloroplatinic acid hexahydrate (Bioxtra, P7082) and 1.33 g 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 hours.

[0151] The results are shown in Table 10.

[0152]

[0153] Examples 27-29, Catalyst 4

[0154] The catalyst includes 1 wt % Pt and 2.7 wt % Sn supported on Y2O3, based on the weight of Y2O3. The catalyst was prepared as follows: 4 g Y2O3 (US nano 3553) was incipiently impregnated with 0.106 g chloroplatinic acid hexahydrate (Bioxtra, P7082) and 0.322 g tin (IV) chloride pentahydrate (Acros Organics 22369) dissolved in an appropriate amount of deionized water, then dried and calcined at 800°C for 12 hours. The data in Table 11 show that the performance of the catalyst is stable within 20 cycles.

[0155] Examples 30-34, Catalyst 5

[0156] The catalyst included 1 wt% Pt, 2.7 wt% Sn supported on CeO2 and Al2O3 supports. The CeO2 and Al2O3 supports were prepared by incipient wetness impregnation of 8.25 g alumina (Sigma Aldrich 199443) with 5.67 g cerium (III) nitrate hexahydrate (SigmaAldrich 202991) dissolved in appropriate amount of deionized water, followed by drying and calcination at 800°C for 12 hours. The catalyst was prepared by incipient wetness impregnation of CeO2 and Al2O3 supports with 0.22 g chloroplatinic acid hexahydrate (Bioxtra, P7082) and 0.67 g tin (IV) chloride pentahydrate (Acros Organics 22369) dissolved in appropriate amount of deionized water, followed by drying and calcination at 800°C for 12 hours. The data in Table 12 show that both the co-addition of steam and pre-reduction of the catalyst helped to improve the yield and selectivity.

[0157]

[0158] Examples 35-38, Catalyst 6

[0159] The catalyst was 0.2 wt% Pt, 0.2 wt% Sn, and 0.67 wt% K on high surface area ZrO2 obtained from Alfa Aesar. The data in Table 13 show that the catalyst was stable over 24 cycles and that the addition of steam significantly increased the yield.

[0160]

[0161] The present disclosure may also include the following non-limiting embodiments / aspects:

[0162] E1. A method for upgrading hydrocarbons, comprising:

[0163] (I) contacting a hydrocarbonaceous feed with fluidized catalyst particles comprising a Group 8-10 element disposed on a support in a conversion zone to subject at least a portion of the hydrocarbonaceous feed to one or more of dehydrogenation, dehydroaromatization, and dehydrocyclization to produce a conversion effluent comprising coked catalyst particles, one or more upgraded hydrocarbons, and molecular hydrogen, wherein:

[0164] The hydrocarbon feed comprises C2-C 16 One or more linear or branched alkanes, C4-C 16 One or more cycloalkanes, C8-C 16 One or more of alkyl aromatic hydrocarbons or mixtures thereof;

[0165] The hydrocarbonaceous feed and the catalyst particles are contacted at a temperature of 300° C. to 900° C. for a period of 0.1 second to 2 minutes at a hydrocarbon partial pressure of at least 20 kPa absolute, wherein the hydrocarbon partial pressure is the pressure of any C2-C4 hydrocarbons in the hydrocarbonaceous feed. 16 Alkanes and any C8-C 16 Total partial pressure of alkyl aromatic hydrocarbons;

[0166] The catalyst particles contain 0.05 wt % to 6 wt % of a Group 8-10 element, based on the weight of the support; and

[0167] The vector comprises:

[0168] 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 with 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, wherein:

[0169] Any Group 2 element is associated with wt % m, based on the weight of the carrier,

[0170] Any Group 4 element is associated with wt % n, based on the weight of the carrier,

[0171] Any Group 12 element is associated with weight % p, based on the weight of the carrier, and

[0172] Any element having an atomic number of 21, 39 or 57-71 is associated with a weight %q, based on the weight of the carrier,

[0173] m, n, p and q are independently numbers ranging from 1 to 100, and

[0174] The sum of w / m+x / n+y / p+z / p is ≥ 1, based on the weight of the carrier;

[0175] The one or more upgraded hydrocarbons comprise dehydrogenated hydrocarbons, dehydroaromatized hydrocarbons, dehydrocyclized hydrocarbons, or mixtures thereof;

[0176] (II) obtaining from the conversion effluent a first gaseous stream rich in the one or more upgraded hydrocarbons and the molecular hydrogen and a first particle stream rich in the coked catalyst particles;

[0177] (III) contacting at least a portion of the coked catalyst particles in the first particle stream with an oxidant in a combustion zone to combust at least a portion of the coke to produce a combustion effluent comprising coke-depleted regenerated catalyst particles and combustion gases;

[0178] (IV) obtaining from said combustion effluent a second gaseous stream enriched in said combustion gases and a second particulate stream enriched in said regenerated catalyst particles; and

[0179] (V) contacting an additional amount of the hydrocarbon-containing feed with the fluidized regenerated catalyst particles to produce an additional conversion effluent comprising recoked catalyst particles, additional one or more upgraded hydrocarbons, and additional molecular hydrogen.

[0180] E2. The method of E1 further comprises the following steps after step (IV) and before step (V):

[0181] (IVa) contacting at least a portion of the regenerated catalyst particles with a reducing gas to produce regenerated and reduced catalyst particles, wherein in step (V) the additional amount of hydrocarbon-containing feed is contacted with the fluidized regenerated and reduced catalyst particles.

[0182] E3. The method of E2, wherein at least a portion of the Group 8-10 elements in the regenerated catalyst particles are in a higher oxidation state than the Group 8-10 elements in the catalyst particles contacting the hydrocarbon feed, and wherein at least a portion of the Group 8-10 elements in the regenerated and reduced catalyst particles are reduced to a lower oxidation state than the Group 8-10 elements in the regenerated catalyst particles.

[0183] E4. The method of E2 or E3, wherein in step (IVa), the regenerated catalyst particles and the reducing gas are contacted at a temperature of 450°C to 900°C, preferably 600°C to 900°C, more preferably 620°C to 900°C, more preferably 650°C to 850°C, or more preferably 670°C to 800°C.

[0184] E5. The method of any one of E2 to 4, wherein in step (IVa), the regenerated catalyst particles and the reducing gas are contacted under a reducing gas partial pressure in the range of 20 kPa absolute pressure to 1,000 kPa absolute pressure, preferably 50 kPa absolute pressure to 500 kPa absolute pressure, or more preferably 70 kPa absolute pressure to 300 kPa absolute pressure.

[0185] E6. The method of any one of E2 to E5, wherein at least a portion of the Group 8-10 elements in the regenerated and reduced catalyst particles are in an elemental state.

[0186] E7. The method of any one of E2 to E6, wherein the reducing gas comprises molecular hydrogen, carbon monoxide, methane, ethane, ethylene, propane, propylene, steam, molecular nitrogen, argon, carbon dioxide or a mixture thereof.

[0187] E8. The method of any one of E2 to E7, wherein the cycle time from contacting the hydrocarbon-containing feed with the catalyst particles in step (I) to contacting the additional amount of the hydrocarbon-containing feed with the fluidized regenerated and reduced catalyst particles in step (V) is ≤ 70 minutes, preferably 1 minute to 70 minutes, or more preferably 5 minutes to 45 minutes.

[0188] E9. The method of E1, wherein the cycle time from contacting the hydrocarbon-containing feed with the catalyst particles in step (I) to contacting the additional amount of the hydrocarbon-containing feed with the regenerated catalyst particles in step (V) is ≤ 70 minutes, preferably 1 minute to 70 minutes, or more preferably 5 minutes to 45 minutes.

[0189] E10. The method of any one of E1 to E9, wherein in step (I), the hydrocarbon-containing feed and the catalyst particles are contacted with each other in the presence of steam, the amount of the steam being based on any C2-C 16 Alkanes and any C8-C 16 The total volume of the alkyl aromatic hydrocarbons is 0.1 vol% to 50 vol%, preferably 0.5 vol% to 30 vol%, or more preferably 1 vol% to 15 vol%.

[0190] E11. The method of any one of E1 to E9, wherein the support comprises a Group 2 element, and wherein in step (I), the hydrocarbon-containing feed and the catalyst particles are contacted with each other in the presence of steam, the amount of which is based on any C2-C 16 Alkanes and any C8-C 16 The total volume of the alkyl aromatic hydrocarbons is 0.1 vol% to 50 vol%, preferably 0.5 vol% to 30 vol%, or more preferably 1 vol% to 15 vol%.

[0191] E12. The method of any one of E1 to E9, wherein the support comprises a Group 4 element, and wherein in step (I), the hydrocarbon-containing feed and the catalyst particles are contacted with each other in the presence of steam, the amount of which is based on any C2-C 16 Alkanes and any C8-C 16 The total volume of the alkyl aromatic hydrocarbons is 0.1 vol% to 50 vol%, preferably 0.5 vol% to 30 vol%, or more preferably 1 vol% to 15 vol%.

[0192] E13. The method of any one of E1 to E9, wherein the support comprises a Group 12 element, and wherein in step (I), the hydrocarbon-containing feed and the catalyst particles are contacted with each other in the presence of steam, the amount of which is based on any C2-C 16 Alkanes and any C8-C 16The total volume of the alkyl aromatic hydrocarbons is 0.1 vol% to 50 vol%, preferably 0.5 vol% to 30 vol%, or more preferably 1 vol% to 15 vol%.

[0193] E14. The process of any one of E1 to E9, wherein the support comprises an element having an atomic number of 21, 39 or 57-71, and wherein in step (I), the hydrocarbon-containing feed and the catalyst particles are contacted with each other in the presence of steam, the amount of which is based on any C2-C 16 Alkanes and any C8-C 16 The total volume of the alkyl aromatic hydrocarbons is 0.1 vol% to 50 vol%, preferably 0.5 vol% to 30 vol%, or more preferably 1 vol% to 15 vol%.

[0194] E15. The method of any one of E1 to E9, wherein the hydrocarbon-containing feed and the catalyst particles are in the absence of any steam or based on any C2-C 16 Alkanes and any C8-C 16 The alkyl aromatic hydrocarbons are contacted with each other in the presence of less than 0.1 volume percent steam, based on the total volume of the alkyl aromatic hydrocarbons.

[0195] E16. The method of any one of E1 to E15, wherein the coked catalyst particles comprise agglomerates of Group 8-10 elements arranged on a carrier, and wherein at least a portion of the agglomerated Group 8-10 elements arranged on the carrier are redispersed around the carrier during the combustion of the coke in step (III).

[0196] E17. The method of any one of E1 to E16, wherein the hydrocarbon-containing feed comprises propane, wherein the upgraded hydrocarbon comprises propylene, and wherein in step (I), contacting the hydrocarbon-containing feed with the catalyst particles 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%.

[0197] E18. The method of any one of E1 to E17, wherein the hydrocarbon-containing feed comprises ≥70 volume % propane based on the total volume of the hydrocarbon-containing feed, wherein the hydrocarbon-containing feed and catalyst particles are contacted at a propane partial pressure of at least 40 kPa absolute pressure, and wherein in step (I), the hydrocarbon-containing feed is contacted with the catalyst particles to have 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%.

[0198] E19. The method of any one of E1 or E9 to E18, wherein steps (I) to (V) are repeated for at least 15 cycles, wherein the catalyst particles produce a first yield when initially contacted with a hydrocarbon-containing feed, and wherein the regenerated catalyst particles produce a second yield upon completion of the fifteenth cycle, the second yield being at least 98% of the first yield.

[0199] E20. The method of any one of E2 to E18, wherein steps (I) to (V) are repeated for at least 15 cycles, wherein the catalyst particles produce a first yield when initially contacted with a hydrocarbon-containing feed, and wherein the regenerated and reduced catalyst particles produce a second yield upon completion of the fifteenth cycle, the second yield being at least 98% of the first yield.

[0200] E21. The method of any one of E1 to E20, wherein the hydrocarbon-containing feed further comprises an inert gas comprising argon, neon, helium, molecular nitrogen, methane or a mixture thereof.

[0201] E22. The method of any one of E1 to E21, wherein in step (I), the hydrocarbon-containing feed and the catalyst particles are contacted at a temperature of 600°C to 900°C, preferably 600°C to 800°C, more preferably 650°C to 750°C, and more preferably 670°C to 720°C.

[0202] E23. The method of any one of E1 to E22, wherein in step (I), the hydrocarbon-containing feed and the catalyst particles are contacted under a hydrocarbon partial pressure in the range of 20 kPa absolute pressure to 1,000 kPa absolute pressure, preferably 50 kPa absolute pressure to 500 kPa absolute pressure, or more preferably 70 kPa absolute pressure to 300 kPa absolute pressure.

[0203] E24. The method of any one of E1 to E23, wherein in step (III), the coked catalyst particles and the oxidant are contacted at a temperature of 600°C to 1,100°C, preferably 650°C to 1,000°C, more preferably 700°C to 900°C, and more preferably 750°C to 850°C.

[0204] E25. The method of any one of E1 to E24, wherein in step (III), the coked catalyst particles and the oxidant are contacted at an oxidant partial pressure in the range of 20 kPa absolute pressure to 1,000 kPa absolute pressure, preferably 50 kPa absolute pressure to 500 kPa absolute pressure, or more preferably 100 kPa absolute pressure to 300 kPa absolute pressure.

[0205] E26. The method of any one of E1 to E25, wherein the catalyst particles further comprise a promoter.

[0206] E27. The method of E26, wherein the promoter comprises Sn, Ga, Zn, Ge, In, Re, Ag, Au, Cu, combinations thereof, or mixtures thereof.

[0207] E28. The method of E26 or E27, wherein the promoter is disposed on the carrier.

[0208] E29. The method of any one of E26 to E28, wherein the promoter is associated with the Group 8-10 element.

[0209] E30. The method of any one of E26 to E29, wherein the promoter and the Group 8-10 element form Group 8-10 element-promoter clusters dispersed on the support.

[0210] E31. The method of any one of E26 to E30, wherein the catalyst particles comprise up to 10 weight percent of a promoter, based on the total weight of the support.

[0211] E32. The method of any one of E1 to E31, wherein the catalyst particles further comprise an alkali metal element disposed on a support.

[0212] E33. The method of E32, wherein the alkali metal element comprises Li, Na, K, Rb, Cs, a combination thereof, or a mixture thereof.

[0213] E34. The method of E32 or E33, wherein the catalyst particles contain up to 5 weight percent alkali metal elements based on the total weight of the support.

[0214] E35. The method of any one of E1 to E34, wherein m, n, p and q are each equal to 1, 15 or 30, or wherein m=1, n=15, p=15 and q=1.

[0215] E36. The method of any one of E1 to E35, wherein the molar ratio of the total amount of any Group 2 element, any Group 4 element, any Group 12 element and any element with an atomic number of 21, 39 or 57-71 to the Group 8-10 element is at least 0.18, at least 0.19, at least 0.24 or at least 0.29.

[0216] E37. The method of any one of E1 to E36, wherein the support further comprises at least one compound comprising at least one metal element or metalloid element selected from Groups 5, 6, 7, 11, 13, 14, 15 and 16.

[0217] E38. The method of any one of E1 to E37, wherein at least a portion of any Group 2 element, at least a portion of any Group 4 element, at least a portion of any Group 12 element, and at least a portion of any element with an atomic number of 21, 39, or 57-71 present in the carrier is an oxide, phosphate, halide, halide, sulfate, sulfide, borate, nitride, carbide, aluminate, aluminosilicate, silicate, carbonate, metaphosphate, selenide, tungstate, molybdate, chromite, chromate, dichromate, or silicide.

[0218] E39. The method of any one of E1 to E38, wherein the carrier comprises one or more of the following substances: Mg u Zn 1-u O, where u is a positive number; Zn v Al2O 3+v , where v is a positive number; Mg w Al2O 3+w , where w is a positive number; Ca x Al2O 3+x , where x is a positive number; Sr y Al2O 3+y , where y is a positive number; Ba z Al2O 3+z , where z is a positive number; BeO; MgO; CaO; BaO; SrO; BeCO3; MgCO3; CaCO3; SrCO3, BaCO3; ZrO2; ZrC; ZrN; ZrSiO4; CaZrO3; Ca7ZrAl6O 18 ;TiO2; TiC; TiN; TiSiO4; CaTiO3; Ca7Al6O 18 ;HfO2; HfC; HfN; HfSiO4; HfZrO3; Ca7HfAl6O 18 ;ZnO; Zn3(PO4)2; Zn(ClO3)2; ZnSO4; B2O6Zn3; Zn3N2; ZnCO3; CeO2; Y2O3; La2O3; Sc2O3; Pr6O 11 ; CePO4; CeZrO4; CeAlO3; BaCeO3; CePO4; yttria-stabilized ZrO2; combinations thereof and mixtures thereof.

[0219] E40. A method as described in any one of E1 to E39, wherein the carrier further comprises one or more of the following substances: B2O3; Al2O3; SiO2; SiC; Si3N4; aluminosilicates; VO; V2O3; VO2; V2O5; Ga2O3; In2O3; Mn2O3; Mn3O4; MnO; zeolites; combinations thereof and mixtures thereof.

[0220] E41. The method of any one of E1 to E40, wherein the support is in the form of a plurality of primary particles comprising the Group 8-10 element disposed thereon.

[0221] E42. The method of any one of E1 to E41, wherein the catalyst particles comprise primary particles having an average cross-sectional length of 0.2 nm-500 μm, preferably 0.5 nm-300 μm, more preferably 1 nm-200 μm, more preferably 5 nm-100 μm, and even more preferably 2 nm-100 nm, as measured by transmission electron microscopy.

[0222] E43. The method of any one of E1 to E42, wherein the Group 8-10 element is arranged on a carrier so that the Group 8-10 element is an active component of the catalyst particles, which enables one or more of the dehydrogenation, dehydrogenation aromatization and dehydrogenation cyclization in step (I) to proceed.

[0223] E44. The method of any one of E1 to E43, wherein the carrier has 0.1 m 2 / g-1,500m 2 / g, preferably 1m 2 / g-1,000m 2 / g, more preferably 10m 2 / g-800m 2 / g, or more preferably 100m 2 / g-500m 2 / g of surface area.

[0224] E45. The method of any one of E1 to E44, wherein in step (I) the hydrocarbon-containing feed and the catalyst particles are contacted for a period of 0.1 seconds to 1.5 minutes, preferably 0.5 seconds to 1 minute, or more preferably 1 second to 30 seconds.

[0225] E46. The method of any one of E1 to E45, wherein the catalyst particles are 16 Alkanes and any C8-C 16 The weight ratio of the total amount of aromatic hydrocarbons is in the range of 1 to 150, preferably 5 to 100, or more preferably 10 to 80.

[0226] E47. The method of any one of E1 to E46, wherein based on any C2-C 16 Alkanes and any C8-C 16 The weight of aromatic hydrocarbons, the hydrocarbon feed at 0.1hr -1 Up to 100hr -1 , preferably 0.2 hr -1 Up to 64 hours -1 , or more preferably 0.4 hr -1Up to 32 hours -1 The catalyst is contacted in step (I) at a weight hourly space velocity of

[0227] E48. The method of any one of E1 to E47, wherein the hydrocarbon-containing feed comprises ethane, propane, isobutane, butane, ethylbenzene, propylbenzene, methylethylbenzene or a mixture thereof.

[0228] E49. The method of any one of E1 to E48, further comprising contacting the supplemental fuel with an oxidant in the combustion zone in step (III) to burn at least a portion of the supplemental fuel to generate heat and an additional amount of combustion gas.

[0229] E50. The method of E49, wherein the supplemental fuel comprises molecular hydrogen, methane, ethane, propane, or a mixture thereof.

[0230] E51. The method of any one of E1 to E50, wherein the catalyst particles are in the form of a dense turbulent fluidized bed when contacted with the hydrocarbon-containing feed.

[0231] E52. The method of any one of E1 to E50, wherein the conversion zone is arranged in the riser reactor.

[0232] E53. The method of any one of E1 to E50, wherein the conversion zone is arranged in a downflow reactor.

[0233] E54. The method of any one of E1 to E53, wherein the hydrocarbon-containing feed and the catalyst particles are in co-current flow, counter-current flow, or a combination thereof when contacting each other.

[0234] E55. A method according to any one of E1 to E54, wherein a first portion of the coked catalyst particles in a first particle stream rich in the coked catalyst particles is contacted with the oxidant in the combustion zone in step (II), and wherein a second portion of the coked catalyst particles in the first particle stream rich in the coked catalyst particles is contacted with the additional amount of hydrocarbon-containing feed in step (V).

[0235] E56. A method according to any one of E2 to E54, wherein a first portion of the coked catalyst particles in a first particle stream rich in the coked catalyst particles is contacted with the oxidant in the combustion zone in step (II), and wherein a second portion of the coked catalyst particles in the first particle stream rich in the coked catalyst particles is contacted with the reducing gas in step (IVa).

[0236] E57. A method according to any one of E2 to E54, wherein a first portion of the coked catalyst particles in a first particle stream rich in the coked catalyst particles is contacted with the oxidant in the combustion zone in step (II), wherein a second portion of the coked catalyst particles in the first particle stream rich in the coked catalyst particles is contacted with the reducing gas in step (IVa), and wherein a third portion of the coked catalyst particles in the first particle stream rich in the coked catalyst particles is contacted with the additional amount of hydrocarbon-containing feed in step (V).

[0237] E58. The method of any one of E1 to E57, further comprising:

[0238] During step (I), during contacting of the hydrocarbon-containing feed with the fluidized catalyst particles, removing a portion of the catalyst particles from the conversion zone;

[0239] heating the portion of catalyst particles removed from the conversion zone to produce heated catalyst particles; and

[0240] The heated catalyst particles are fed into the conversion zone to contact the hydrocarbon-containing feed.

[0241] E59. The method of any one of E1 to E58, further comprising supplying heat to the catalyst particles in the conversion zone during contact between the catalyst particles and the hydrocarbon-containing feed.

[0242] E60. The method of any one of E1 to E59, wherein the catalyst particles have a thickness of 0.5 g / cm 3 Up to 3g / cm 3 , 0.7g / cm 3 Up to 2g / cm 3 or 0.8g / cm 3 Up to 1.4g / cm 3 Particle density within the range.

[0243] E61. The method of any of E1 to E60, wherein the catalyst particles have a size and particle density consistent with the Geldart A definition.

[0244] Various terms have been defined above. If a term used in a claim is not defined above, it should be given the broadest definition persons in the relevant art have given that term as reflected in at least one printed publication or issued patent. In addition, all patents, test procedures, and other documents cited in this application are fully incorporated by reference to the extent this disclosure is not inconsistent with the present invention and for all jurisdictions in which such incorporation is permitted.

[0245] While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope of the invention is determined by the claims that follow.

Claims

1. A method for upgrading hydrocarbons, comprising: (I) contacting a hydrocarbonaceous feed with fluidized catalyst particles comprising Ni, Pd or Pt elements disposed on a support in a conversion zone to subject at least a portion of the hydrocarbonaceous feed to one or more of dehydrogenation, dehydroaromatization and dehydrocyclization to produce a conversion effluent comprising coked catalyst particles, one or more upgraded hydrocarbons and molecular hydrogen, wherein: The hydrocarbon feed comprises C2-C 16 One or more linear or branched alkanes, C4-C 16 One or more cycloalkanes, C8-C 16 One or more of the alkyl aromatic hydrocarbons or a mixture thereof, and 0.1% to 50% by volume of steam, based on any C2-C 16 Alkanes and any C8-C 16 The total volume of alkyl aromatic hydrocarbons; The hydrocarbonaceous feed and the catalyst particles are contacted at a temperature of 300° C. to 900° C. for a period of 0.1 second to 2 minutes at a hydrocarbon partial pressure of at least 20 kPa absolute, wherein the hydrocarbon partial pressure is the pressure of any C2-C4 hydrocarbons in the hydrocarbonaceous feed. 16 Alkanes and any C8-C 16 Total partial pressure of alkyl aromatic hydrocarbons; The catalyst particles contain 0.05 wt % to 6 wt % of Ni, Pd or Pt element based on the weight of the support; and The vector 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 with 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, wherein: Any Group 2 element is associated with wt % m, based on the weight of the carrier, Any Group 4 element is associated with wt % n, based on the weight of the carrier, Any Group 12 element is associated with weight % p, based on the weight of the carrier, 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 carrier, m, n, p and q are independently numbers ranging from 1 to 100, and The sum of w / m+x / n+y / p+z / p is ≥ 1, based on the weight of the carrier; The one or more upgraded hydrocarbons comprise dehydrogenated hydrocarbons, dehydroaromatized hydrocarbons, dehydrocyclized hydrocarbons, or mixtures thereof; (II) obtaining from the conversion effluent a first gaseous stream rich in the one or more upgraded hydrocarbons and the molecular hydrogen and a first particle stream rich in the coked catalyst particles; (III) contacting at least a portion of the coked catalyst particles in the first particle stream with an oxidant in a combustion zone to combust at least a portion of the coke to produce a combustion effluent comprising coke-depleted regenerated catalyst particles and combustion gases; (IV) obtaining from said combustion effluent a second gaseous stream enriched in said combustion gases and a second particulate stream enriched in said regenerated catalyst particles; and (V) contacting an additional amount of hydrocarbon-containing feed with the fluidized regenerated catalyst particles to produce an additional conversion effluent comprising recoked catalyst particles, additional one or more upgraded hydrocarbons, and additional molecular hydrogen; and wherein the catalyst particles remain active and stable after at least 15 cycles, wherein each cycle time lasts ≤ 70 minutes, wherein the cycle time is from contacting the hydrocarbon-containing feed with the catalyst particles in step (I) to contacting the additional amount of the hydrocarbon-containing feed with the regenerated and reduced catalyst particles in step (V).

2. The method according to claim 1, further comprising, after step (IV) and before step (V), the following steps: (IVa) contacting at least a portion of the regenerated catalyst particles with a reducing gas to produce regenerated and reduced catalyst particles, wherein in step (V) the additional amount of hydrocarbon-containing feed is contacted with the fluidized regenerated and reduced catalyst particles.

3. The method according to claim 2, wherein in step (IVa), at least one of the following conditions is met: (i) contacting the regenerated catalyst particles with a reducing gas at a temperature of 450° C. to 900° C.; and (ii) contacting the regenerated catalyst particles and the reducing gas at a reducing gas partial pressure in the range of 20 kPa absolute pressure to 1,000 kPa absolute pressure.

4. The method of claim 2 or claim 3, wherein at least a portion of the Ni, Pd or Pt elements in the regenerated and reduced catalyst particles are in an elemental state.

5. The process according to claim 1, wherein the support comprises a Group 2 element, and wherein in step (I), the hydrocarbon-containing feed and the catalyst particles are contacted with each other in the presence of steam, the amount of which is based on any C2-C 16 Alkanes and any C8-C 16 The total volume of the alkyl aromatic hydrocarbons is calculated to be 0.1 volume % to 50 volume %.

6. The process of claim 1, wherein the hydrocarbonaceous feed comprises propane, wherein the upgraded hydrocarbon comprises propylene, and wherein contacting the hydrocarbonaceous feed with the catalyst particles in step (I) has a propylene yield of at least 52% at a propylene selectivity of ≥ 75%.

7. The process of claim 1, 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 particles are contacted at a propane partial pressure of at least 40 kPa absolute, and wherein contacting the hydrocarbon-containing feed with the catalyst particles in step (I) has a propylene yield of at least 52% at a propylene selectivity of ≥ 75%.

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

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

10. The method of claim 1, wherein the catalyst particles further comprise a promoter, and wherein the promoter comprises Sn, Ga, Zn, Ge, In, Re, Ag, Au, Cu, combinations thereof, or mixtures thereof.

11. The method of claim 1, wherein the catalyst particles further comprise an alkali metal element selected from the group consisting of Li, Na, K, Rb, Cs, and combinations and mixtures thereof disposed on the support, the catalyst particles comprising up to 5 wt% of the alkali metal element based on the total weight of the support.

12. The method of claim 1, wherein m, n, p and q are each equal to 1, 15 or 30, or wherein m=1, n=15, p=15 and q=1.

13. The method of claim 1, wherein the molar ratio of the total amount of any Group 2 element, any Group 4 element, any Group 12 element and any element with an atomic number of 21, 39 or 57-71 to the Ni, Pd or Pt element is at least 0.

18.

14. The method of claim 1, wherein the support further comprises at least one compound comprising at least one metal element or metalloid element selected from Groups 5, 6, 7, 11, 13, 14, 15, and 16.

15. The method according to claim 1, wherein at least one of the following items is satisfied: (i) contacting the hydrocarbon-containing feed and the catalyst particles in step (I) for a period of 0.1 seconds to 1.5 minutes; (ii) the catalyst particles are 16 Alkanes and any C8-C 16 The weight ratio of the total amount of aromatic hydrocarbons is in the range of 1 to 150; and (iii) based on any C2-C 16 Alkanes and any C8-C 16 The weight of aromatic hydrocarbons, the hydrocarbon feed at 0.1hr -1 Up to 100hr -1 The catalyst is contacted in step (I) at a weight hourly space velocity of 16. The process of claim 1 wherein the catalyst particles are in the form of a dense turbulent fluidized bed when contacted with the hydrocarbonaceous feed.

17. The process of claim 1, wherein the conversion zone is arranged in a riser reactor or a downcomer reactor.

18. A process according to claim 1, wherein a first portion of the coked catalyst particles in a first particle stream rich in the coked catalyst particles is contacted with the oxidant in the combustion zone in step (II), and wherein a second portion of the coked catalyst particles in the first particle stream rich in the coked catalyst particles is contacted with the additional amount of hydrocarbon-containing feed in step (V).

19. The method of claim 1, further comprising: During step (I), during contacting of the hydrocarbon-containing feed with the fluidized catalyst particles, removing a portion of the catalyst particles from the conversion zone; heating the portion of catalyst particles removed from the conversion zone to produce heated catalyst particles; and The heated catalyst particles are fed into the conversion zone to contact the hydrocarbon-containing feed.

20. The method of claim 1 further comprising supplying heat to the catalyst particles within the conversion zone during contacting of the catalyst particles with the hydrocarbon-containing feed.

21. The method of claim 1, wherein the catalyst particles have a particle size of 0.5 g / cm 3 Up to 3g / cm 3 Particle density within the range.

22. The method of claim 1 wherein the catalyst particles have a size and particle density consistent with the Geldar t A definition.

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