Method for calcining catalyst

Abstract

Disclosed herein are methods for calcining a catalyst. The method may include subjecting a synthetic catalyst including Pt disposed on a support to an initial calcination including exposing the catalyst to a first reducing gas or a first oxidizing gas to produce an initial calcined catalyst. The method may optionally include subjecting the initially calcined catalyst to a cyclical calcination including exposing the initially calcined catalyst to a second reducing gas and a second oxidizing gas to produce a cyclically calcined catalyst. The method may optionally include subjecting the initially or cyclically calcined catalyst to a final calcination including exposing the initially or cyclically calcined catalyst to a third reducing gas or a third oxidizing gas. At least one of the cyclic calcination and the final calcination may be performed. A calcined catalyst can be obtained at the end of the cycle or final calcination.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefit of U.S. Provisional Application No. 63 / 357,729, filed on July 1, 2022, the entire disclosure of which is incorporated herein by reference.

[0003] field

[0004] The present disclosure relates to methods for calcining a synthesized catalyst. More specifically, the present disclosure relates to calcining a synthesized catalyst comprising Pt disposed on a support to produce a calcined catalyst.

[0005] background

[0006] Catalytic reforming or dehydrogenation, dehydroaromatization and / or dehydrocyclization of alkanes and / or alkylaromatics are endothermic and equilibrium-limited industrially important chemical conversion processes. 12 Reforming or dehydrogenation, dehydrogenation aromatization and / or dehydrogenation cyclization of alkanes and / or alkyl aromatics such as ethylbenzene can be carried out via a variety of different catalysts Pt-based, Ni-based, Pd-based, Ru-based, Re-based, Cr-based, Ga-based, V-based, Zr-based, In-based, W-based, Mo-based, Zn-based and Fe-based systems.

[0007] After synthesis, the catalyst usually needs to be pretreated or conditioned before the synthesized catalyst can be used in a commercial reactor. One conditioning process includes equilibration, usually performed at room temperature with flowing or stationary gas to allow any liquid precursors to diffuse into the catalyst. Another conditioning process includes drying, usually performed at a temperature lower than calcination with flowing gas or in a vacuum to allow most volatile components to leave the catalyst. Another conditioning process includes calcination, usually performed at a temperature higher than drying with flowing gas or in a vacuum to allow the precursors in the catalyst to be converted into active materials or materials that are structurally / chemically closer to the active materials. Although these conditioning processes improve the performance of the as-synthesized catalyst, such improvements are lower than the desired improvements.

[0008] Therefore, there is a need for improved methods for regulating synthetic catalysts. The present disclosure satisfies this need and other needs.

[0009] Overview

[0010] The present disclosure provides a method for calcining a synthesized catalyst. In some embodiments, the method for calcining a catalyst may include subjecting a synthesized catalyst including Pt disposed on a support to an initial calcination, the initial calcination comprising exposing the synthesized catalyst to a first reducing gas under reducing conditions or to a first oxidizing gas under oxidizing conditions to produce an initially calcined catalyst. The synthesized catalyst may include <0.05wt% Pt, based on the non-volatile weight of the catalyst. The method may optionally include subjecting the initially calcined catalyst to a cyclic calcination, the cyclic calcination comprising exposing the initially calcined catalyst to a second reducing gas under reducing conditions and to a second oxidizing gas under oxidizing conditions for n cycles to produce a cyclically calcined catalyst. The variable n may be an integer. The cyclic calcination may start with a second oxidizing gas when the initial calcination uses a first reducing gas. The cyclic calcination may start with a second reducing gas when the initial calcination uses a first oxidizing gas. When n≥2, the composition of the second reducing gas used in each cyclic calcination may be the same or different, and the composition of the second oxidizing gas used in each cyclic calcination may be the same or different. The method may optionally include subjecting the initial calcined catalyst or the cyclic calcined catalyst to a final calcination, which may include exposing the initial calcined catalyst or the cyclic calcined catalyst to a third reducing gas under reducing conditions or to a third oxidizing gas under oxidizing conditions. At least one of the cyclic calcination and the final calcination may be performed. When the initial calcination uses a first reducing gas, the final calcination may use a third oxidizing gas if the final calcination is performed, or the cyclic calcination ends with a second reducing gas if the cyclic calcination is performed. When the initial calcination uses a first oxidizing gas, the final calcination may use a third reducing gas if the final calcination is performed, or the cyclic calcination ends with a second oxidizing gas if the cyclic calcination is performed. The reducing conditions used in the initial calcination, the optional cyclic calcination, and the optional final calcination may independently include heating the catalyst at a temperature in the range of 500° C. to 850° C. for a period of time in the range of 30 seconds to 10 hours. The oxidizing conditions used in the initial calcination, the optional cyclic calcination and the optional final calcination may independently include heating the catalyst at a temperature in the range of 350° C. to 850° C. for a period in the range of 30 seconds to 10 hours. A calcined catalyst may be obtained at the end of the cyclic calcination or at the end of the final calcination.

[0011] In some embodiments, the method for calcining a catalyst may include subjecting synthesized catalyst particles that may include Pt disposed on a support to an initial calcination, which may include exposing the catalyst particles to a first reducing gas under reducing conditions or to a first oxidizing gas under oxidizing conditions to produce initially calcined catalyst particles. The synthesized catalyst particles may have a size and particle density that conforms to the Geldart A definition of a fluidizable solid. The method may optionally include subjecting the initially calcined catalyst particles to a cyclic calcination, which may include exposing the initially calcined catalyst particles to a second reducing gas under reducing conditions and to a second oxidizing gas under oxidizing conditions for n cycles to produce cyclically calcined catalyst particles. The variable n may be an integer. The cyclic calcination may start with a second oxidizing gas when the initial calcination uses a first reducing gas. The cyclic calcination may start with a second reducing gas when the initial calcination uses a first oxidizing gas. When n≥2, the composition of the second reducing gas used in each cyclic calcination may be the same or different, and the composition of the second oxidizing gas used in each cyclic calcination may be the same or different. The method may optionally include subjecting the initial calcined catalyst particles or the cyclic calcined catalyst particles to a final calcination, which may include exposing the initial calcined catalyst particles or the cyclic calcined catalyst particles to a third reducing gas under reducing conditions or to a third oxidizing gas under oxidizing conditions. At least one of the cyclic calcination and the final calcination may be performed. When the initial calcination uses a first reducing gas, the final calcination may use a third oxidizing gas if the final calcination is performed, or the cyclic calcination ends with a second reducing gas if the cyclic calcination is performed. When the initial calcination uses a first oxidizing gas, the final calcination may use a third reducing gas if the final calcination is performed, or the cyclic calcination ends with a second oxidizing gas if the cyclic calcination is performed. The reducing conditions used in the initial calcination, the optional cyclic calcination, and the optional final calcination may independently include heating the catalyst particles at a temperature in the range of 500° C. to 850° C. for a period of time in the range of 30 seconds to 10 hours. The oxidizing conditions used in the initial calcination, the optional cyclic calcination, and the optional final calcination may independently include heating the catalyst particles at a temperature in the range of 350° C. to 850° C. for a period in the range of 30 seconds to 10 hours. Calcinated catalyst particles may be obtained at the end of the cyclic calcination or at the end of the final calcination.

[0012] Detailed Description

[0013] Various specific embodiments, variations and examples of the present invention will now be described, including preferred embodiments and definitions adopted herein for understanding the claimed invention. Although the following detailed description gives specific, preferred embodiments, those skilled in the art will appreciate that these embodiments are exemplary only and that the present invention may be practiced in other ways. For the purpose of determining infringement, the scope of the present invention will refer to any one or more of the appended claims, including their equivalents and elements or limitations equivalent to those mentioned. Any reference to the "invention" may refer to one or more but not necessarily all of the inventions defined in the claims.

[0014] In the present disclosure, methods are described as comprising at least one "step". It should be understood that each step is an act or operation that can be performed one or more times in the method in a continuous or discontinuous manner. Unless otherwise specified or the context clearly indicates otherwise, multiple steps in a method can be performed successively in the order in which they are listed, with or without overlapping with one or more other steps, or can be performed in any other order, if the situation permits. In addition, one or more or even all steps can be performed simultaneously with respect to the same or different batches of materials. For example, in a continuous method, while the first step of the method is performed with respect to the raw materials just fed into the initial stage of the method, the second step can be performed simultaneously with respect to the intermediate materials obtained by processing the raw materials fed into the method at an earlier time in the first step. Preferably, the steps are performed in the order described.

[0015] Unless otherwise indicated, all numerical values ​​indicating quantities in this disclosure are to be understood in all cases as being modified by the term "about". It should also be understood that the precise numerical values ​​used in this specification and claims constitute specific embodiments. Efforts have been made to ensure the accuracy of the data in the examples. However, it should be understood that any measured data inherently contain a certain level of error due to the limitations of the techniques and / or equipment used to make the measurements.

[0016] Certain embodiments and features are described herein using a set of numerical upper limits and a set of numerical lower limits. It should be understood that the range including the combination of any two values ​​(e.g., the combination of any lower limit value with any upper limit value, the combination of any two lower limits, and / or the combination of any two upper limits) is contemplated unless otherwise specified.

[0017] As used herein, the indefinite article "a" or "an" means "at least one", unless otherwise specified or the context clearly indicates otherwise. Thus, embodiments using "a reactor" or "a conversion zone" include embodiments in which one, two, or more reactors or conversion zones are used, unless otherwise specified or the context clearly indicates that only one reactor or conversion zone is used.

[0018] The term "hydrocarbon" means (i) any compound consisting of hydrogen and carbon atoms or (ii) any mixture of two or more such compounds of (i). The term "Cn hydrocarbon" (where n is a positive integer) means (i) any hydrocarbon compound containing a total of n carbon atoms in its molecule or (ii) any mixture of two or more such hydrocarbon compounds of (i). Thus, C2 hydrocarbons can be ethane, ethylene, acetylene, or any mixture of at least two of these compounds in any proportion. "Cm to Cn hydrocarbons" or "Cm-Cn hydrocarbons" (where m and n are positive integers and m < n) means any one of Cm, Cm+1, Cm+2, …, Cn-1, Cn hydrocarbons or any mixture of two or more of them. Thus, "C2 to C3 hydrocarbons" or "C2-C3 hydrocarbons" can be any one of ethane, ethylene, acetylene, propane, propylene, propyne, allene, cyclopropane and any mixture of two or more of them in any proportion between the components. "Saturated C2-C3 hydrocarbons" can be any mixture of ethane, propane, cyclopropane, or two or more of them in any proportion. "Cn+ hydrocarbons" means (i) any hydrocarbon compound containing a total of at least n carbon atoms in its molecule or (ii) any mixture of two or more such hydrocarbon compounds of (i). "Cn- hydrocarbons" means (i) any hydrocarbon compound containing a total of at most n carbon atoms in its molecule or (ii) any mixture of two or more such hydrocarbon compounds of (i). "Cm hydrocarbon stream" means a hydrocarbon stream consisting essentially of Cm hydrocarbons. "Cm-Cn hydrocarbon stream" means a hydrocarbon stream consisting essentially of Cm-Cn hydrocarbons.

[0019] For purposes of this disclosure, the nomenclature of elements follows the version of the periodic table provided in Hawley's Condensed Chemical Dictionary, 16th edition, John Wiley & Sons, Inc., (2016), Appendix V (according to the new notation). For example, Group 2 elements include Mg, Group 8 elements include Fe, Group 9 elements include Co, Group 10 elements include Ni, and Group 13 elements include Al. The term "metalloid" as used herein refers to the following elements: B, Si, Ge, As, Sb, Te, and At. In this disclosure, when a given element is indicated as being present, it may be present in the elemental state or as any compound thereof, unless the context otherwise dictates or otherwise explicitly stated.

[0020] The term "alkane" refers to a saturated hydrocarbon. The term "cycloalkane" refers to a saturated hydrocarbon that contains a cyclic carbon ring in its molecular structure. Alkanes can be linear, branched or cyclic.

[0021] The term "aromatic hydrocarbon" is to be understood in accordance with its art-recognized scope, which includes alkyl-substituted and unsubstituted monocyclic and polycyclic compounds.

[0022] The term "rich" when used in phrases such as "rich in X" or "enriched in X" refers to an output stream obtained from a device, such as a conversion zone, which stream contains a higher concentration of material X than the concentration in the feedstock fed to the same device from which the stream is obtained. The term "lean" when used in phrases such as "depleted in X" or "depleted in X" refers to an output stream obtained from a device, such as a conversion zone, which stream contains a lower concentration of material X than the concentration in the feedstock fed to the same device from which the stream is obtained.

[0023] The term "mixed metal oxide" refers to a composition comprising oxygen atoms and at least two different metal atoms mixed at the atomic scale. For example, a "mixed Mg / Al metal oxide" has O, Mg, and Al atoms mixed at the atomic scale and has a chemical formula of The compositions obtained are substantially the same or equivalent to those obtained with Mg / Al hydrotalcites of the invention, wherein A is a counter anion of negative charge n, x is in the range of >0 to <1, and m ≥ 0. Materials consisting of nm-sized MgO particles and nm-sized Al2O3 particles mixed together are not mixed metal oxides, since the Mg and Al atoms are not mixed on an atomic scale, but on a nm scale.

[0024] The term "calcining" refers to heating a material such as a synthesized catalyst or support to a temperature of 350°C or higher in any atmosphere, such as an oxidizing atmosphere, an inert atmosphere, or a reducing atmosphere. The term "calcined" refers to a material such as a synthesized catalyst or support that has undergone calcination.

[0025] The term "selectivity" refers to the yield (based on moles of carbon) of a specified compound in a catalytic reaction. For example, the phrase "an alkane conversion reaction has a 100% selectivity to olefins" means that 100% of the alkanes converted in the reaction (based on moles of carbon) 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. In another example, when the specified reactant is propane, if 1 mole of propane is converted to 1 mole of methane and 1 mole of ethylene, the methane selectivity is 33.3% and the ethylene selectivity is 66.7%. The yield (based on moles of carbon) is the conversion multiplied by the selectivity.

[0026] As used herein, "sccm" means standard cubic centimeters per minute, which is a term used to indicate the volume of a gas passing through a given point in one minute at standard temperature and pressure. 3 ) flow measurement value. Standard temperature and pressure (STP) refers to a temperature of 273.15K (0°C) and 10 5 Pa (100 kPa, 1 bar) absolute pressure.

[0027] In the present disclosure, “A, B, ... or a combination thereof” means “A, B, ... or any combination of any two or more of A, B, ...”. “A, B, ... or a mixture thereof” means “A, B, ... or any mixture of any two or more of A, B, ...”.

[0028] Method for calcining catalyst

[0029] It has been surprisingly and unexpectedly discovered that when a synthesized catalyst for upgrading one or more hydrocarbons (e.g., dehydrogenating alkanes to produce olefins) is first subjected to a calcination process to produce a calcined catalyst, it can exhibit significantly improved performance when contacted with one or more alkanes under dehydrogenation conditions, compared to a synthesized catalyst that has not undergone the calcination process. In some embodiments, the synthesized catalyst may include Pt disposed on a support. In some embodiments, the synthesized catalyst may include <0.05 wt%, <0.045 wt%, <0.04 wt%, <0.035 wt%, or <0.03 wt% Pt based on the non-volatile weight of the catalyst. In other embodiments, the synthesized catalyst may be in the form of catalyst particles having a size and particle density that meets the Geldart A definition of a fluidizable solid and may include 0.001 wt%-6 wt% Pt based on the non-volatile weight of the catalyst.

[0030] The term "synthesized catalyst" as used herein refers to a catalyst comprising Pt disposed on a support that has not been subjected to a temperature of 350°C or higher. However, it should be understood that the support may be subjected to a temperature greater than 350°C before the addition of Pt, but once Pt has been disposed on the support, the synthesized catalyst is no longer heated to a temperature of 350°C or higher until the catalyst undergoes the calcination process. It should also be understood that the "synthesized catalyst" may be subjected to equilibration and / or drying treatments, as long as the "synthesized catalyst" is not heated to a temperature of 350°C or higher.

[0031] Since the synthesized catalyst has not been subjected to a temperature of 350°C or higher, the synthesized catalyst may include one or more volatile compounds adsorbed thereon and / or one or more compounds capable of forming volatile compounds and desorbing at a higher temperature (e.g., when the synthesized catalyst is heated to a temperature of 350°C or higher in an oxidizing atmosphere, a reducing atmosphere, or other atmosphere such as an inert atmosphere). As used herein, the term "non-volatile weight of the catalyst" refers to the residual weight of the synthesized catalyst or the synthesized catalyst conditioned in any manner after being heated to a temperature of 900°C under flowing air. The non-volatile weight of the catalyst can be quantified by thermogravimetric analysis. A typical thermogravimetric analysis procedure is as follows: 10-20 mg of the solid to be analyzed is loaded into a platinum pan of a TGA 550 from TA instruments. The weight of the solid is monitored and recorded by a microbalance connected to the platinum pan. The temperature of the platinum pan and the solid can be raised from 25°C to 900°C at a heating rate of 5°C / min under a constant air flow. Once the solids reach a temperature of 900°C, the remaining weight is the "non-volatile weight of the solids".

[0032] Illustrative volatile compounds may be or may include, but are not limited to, CO, H2, CO2, H2O, SO3, SO2, HCl, H2S, CH4, one or more alcohols, acetone, chloroform, dichloromethane, dimethylformamide, dimethylsulfoxide, glycerol, ethyl acetate, or any mixture thereof. In some embodiments, if the synthesized catalyst includes CO2 and / or H2O, such volatile compounds may be adsorbed from the surrounding environment. In some embodiments, if the synthesized catalyst includes CO2, H2O, one or more alcohols, acetone, chloroform, dichloromethane, dimethylformamide, dimethylsulfoxide, glycerol, ethyl acetate, or any mixture thereof, such volatile compounds may be adsorbed thereon during the preparation of the synthesized catalyst. For example, a method of preparing the synthesized catalyst may include forming a slurry of a support and / or one or more compounds from which the support may be derived, one or more Pt-containing compounds, and optionally one or more additional compounds such as a promoter-containing compound, wherein the liquid medium includes water, one or more alcohols, and / or other liquid mediums. In some embodiments, if the metal-containing compound added to the support contains a chloride, such as chloroplatinic acid for platinum, tin (IV) chloride for tin, the chloride can react with H2O molecules to form HCl, which can be desorbed from the synthesized catalyst when the synthesized catalyst is heated to a temperature above 350° C. In some embodiments, if the metal-containing compound added to the support contains a sulfate, such as tin (II) sulfate for tin, the sulfate can decompose to form SO2, which can be desorbed from the synthesized catalyst when the synthesized catalyst is heated to a temperature above 350° C.

[0033] The method for calcining the synthesized catalyst may include subjecting the synthesized catalyst to an initial calcination, which may include exposing the synthesized catalyst to a first reducing gas under reducing conditions or to a first oxidizing gas under oxidizing conditions to produce an initially calcined catalyst. In some embodiments, when the synthesized catalyst undergoes the initial calcination, the synthesized catalyst may include one or more adsorbed volatile compounds. The initially calcined catalyst may have a reduced amount of adsorbed volatile compounds compared to the synthesized catalyst.

[0034] The method for calcining the catalyst may also include at least one of two additional steps, i.e., cyclic calcination and / or final calcination. At least one of the cyclic calcination and the final calcination may be performed. In some embodiments, the catalyst initially calcined may be subjected to cyclic calcination for n cycles, wherein n may be an integer. In some embodiments, n may be equal to 1,2,3,4,5,6,7,8,9,10 or greater. In some other embodiments, the catalyst initially calcined may be subjected to final calcination. In some further embodiments, the catalyst initially calcined may be subjected to cyclic calcination and then to final calcination. A calcined catalyst may be obtained at the end of the cyclic calcination or at the end of the final calcination.

[0035] The optional cyclic calcination may include exposing the initially calcined catalyst to a second reducing gas under reducing conditions and to a second oxidizing gas under oxidizing conditions for n cycles. The variable n is an integer. The cyclic calcination may begin with the second oxidizing gas when the initial calcination uses the first reducing gas, or the cyclic calcination may begin with the second reducing gas when the initial calcination uses the first oxidizing gas. When n≥2, the composition of the second reducing gas used in each cyclic calcination may be the same or different, and the composition of the second oxidizing gas used in each cyclic calcination may be the same or different.

[0036] In some other embodiments, the method for calcining the catalyst may include subjecting the initial calcined catalyst to an optional final calcination, which may include exposing the initial calcined catalyst or the cyclic calcined catalyst to a third reducing gas under reducing conditions or to a third oxidizing gas under oxidizing conditions. When the initial calcination uses the first reducing gas, the final calcination may use the third oxidizing gas if the final calcination is performed, or the cyclic calcination may end with the second reducing gas if the cyclic calcination is performed. When the initial calcination uses the first oxidizing gas, the final calcination may use the third reducing gas if the final calcination is performed, or the cyclic calcination may end with the second oxidizing gas if the cyclic calcination is performed.

[0037] In some embodiments, the temperature in the reducing conditions used in the initial calcination, the optional cyclic calcination, and the optional final calcination may be equal to or greater than the temperature in the oxidizing conditions used in the initial calcination, the optional cyclic calcination, and the optional final calcination. In some embodiments, the sum of the time periods in the reducing conditions used in the initial calcination, the optional cyclic calcination, and the optional final calcination may be greater than the sum of the time periods in the oxidizing conditions used in the initial calcination, the optional cyclic calcination, and the optional final calcination.

[0038] The reducing conditions used in the initial calcination, the optional cyclic calcination, and the optional final calcination may independently include heating the catalyst at a temperature ranging from 500° C., 525° C., 550° C., 575° C., 600° C., 625° C., 650° C., or 675° C. to 700° C., 725° C., 750° C., 775° C., 800° C., 825° C., or 850° C. The reducing conditions used in the initial calcination, the optional cyclic calcination, and the optional final calcination independently include heating the catalyst for a time period ranging from 30 seconds, 1 minute, 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, or 30 minutes to 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, or 10 hours. The reducing conditions used in the initial calcination, the optional cycle calcination, and the optional final calcination can independently include heating the catalyst at an absolute pressure ranging from 30 kPa, 60 kPa, or 90 kPa to 150 kPa, 300 kPa, or 600 kPa. It has been found through microscopic analysis that when a promoter is used to make a synthesized catalyst, incorporating a reducing calcination step in the method described herein for calcining a synthesized catalyst can improve the distribution of the promoter (Sn) on the support.

[0039] It should be understood that the composition, temperature and / or pressure of the reducing gas during any given calcination step (i.e., initial calcination, cyclic calcination, and final calcination) can vary. For example, if the initial calcination begins with a first reducing gas, the composition can start with a reducing gas comprising about 10 vol% H2 and can be switched to a reducing gas comprising 100 vol% H2. Similarly, the initial calcination can begin at a temperature of 550°C in the first duration and can be increased to a temperature of 575°C in the second duration of the initial calcination step. It should be understood that when the optional cyclic calcination is adopted and n≥2, the composition, temperature, time and / or pressure of the second reducing gas used during each reducing condition in the cyclic calcination can be the same or different from each other, and can also be changed during any given cyclic calcination step.

[0040] The oxidizing conditions used in the initial calcination, the optional cyclic calcination, and the optional final calcination may independently include heating the catalyst at a temperature in the range of 350° C., 375° C., 400° C., 425° C., 450° C., 475° C., 500° C., 525° C., 550° C., 575° C., or 600° C. to 625° C., 650° C., 675° C., 700° C., 725° C., 750° C., 775° C., 800° C., 825° C., or 850° C. The oxidizing conditions used in the initial calcination, the optional cyclic calcination, and the optional final calcination may independently include heating the catalyst for a time period in the range of 30 seconds, 1 minute, 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, or 30 minutes to 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, or 10 hours. The oxidizing conditions used in the initial calcination, the optional cycle calcination, and the optional final calcination may independently include heating the catalyst at an absolute pressure in the range of 30 kPa, 60 kPa, or 90 kPa to 150 kPa, 300 kPa, or 600 kPa.

[0041] It should be understood that the composition, temperature and / or pressure of the oxidizing gas during any given calcination step (i.e., initial calcination, cyclic calcination, and final calcination) can vary. For example, if the initial calcination begins with a first oxidizing gas, the composition can start with an oxidizing gas comprising about 10 vol% O2 and can be switched to a reducing gas such as air comprising 21 vol% O2. Similarly, the initial calcination can begin at a temperature of 450°C during a first duration and can be increased to a temperature of 475°C during a second duration of the initial calcination step. It should be understood that when the optional cyclic calcination is employed and n≥2, the composition, temperature, time and / or pressure of the second oxidizing gas used during each oxidizing condition in the cyclic calcination can be the same or different from each other and can also vary during any given cyclic calcination step.

[0042] The first reducing gas, the second reducing gas and the third reducing gas may independently be or include, but are not limited to, H2, CO, CH4, C2H6, C3H8, C2H4, C3H6, steam or any mixture thereof. In some embodiments, the first, second and third reducing gases may be independently mixed with one or more inert gases. Suitable inert gases may be or may include, but are not limited to, He, Ne, Ar, N2, CO2, CH4 or any mixture thereof. In some embodiments, during the initial calcination, during the reducing conditions in the cyclic calcination, and during the reducing conditions in the final calcination, the composition of the first, second and third reducing gases may be changed or varied. For example, the initial calcination may start with a reducing gas comprising 100% H2, and may be switched to a reducing gas comprising 10% H2 or any other amount of H2 during the initial calcination. In some other embodiments, during the initial calcination, during the reducing conditions in the cyclic calcination, and during the reducing conditions in the final calcination, the composition of the first, second and third reducing gases may remain constant.

[0043] The first oxidizing gas, the second oxidizing gas, and the third oxidizing gas may independently be or include, but are not limited to, O2, O3, CO2, steam, or any mixture thereof. In some embodiments, the first, second, and third oxidizing gases may be independently mixed with one or more inert gases. Suitable inert gases may be or may include, but are not limited to, He, Ne, Ar, N2, CO2, CH4, or any mixture thereof. In some embodiments, the composition of the first, second, and third oxidizing gases may be changed during the initial calcination, during the oxidizing conditions in the cyclic calcination, and during the oxidizing conditions in the final calcination. For example, the initial calcination may start with a reducing gas including 100% O2, and may be switched to a reducing gas including about 21% O2 such as air or a reducing gas including any other amount of O2 during the initial calcination. In some other embodiments, the composition of the first, second, and third oxidizing gases may remain constant during the initial calcination, during the oxidizing conditions in the cyclic calcination, and during the oxidizing conditions in the final calcination.

[0044] Industrial-scale calcination usually uses a box kiln, a belt calciner or a rotary calciner. Simultaneous microwave / ultrasonic treatment can also assist calcination.

[0045] Synthesized catalyst

[0046] In some embodiments, the synthesized catalyst may include 0.001 wt%, 0.002 wt%, 0.003 wt%, 0.004 wt%, 0.005 wt%, 0.006 wt%, 0.007 wt%, 0.008 wt%, 0.009 wt%, 0.01 wt%, 0.015 wt%, 0.02 wt%, 0.025 wt%, 0.03 wt%, 0.035 wt%, 0.04 wt%, 0.045 wt%, 0.05 wt%, 0.055 wt%, 0.060 wt%, 0.061 wt%, 0.062 wt%, 0.063 wt%, 0.064 wt%, 0.065 wt%, 0.066 wt%, 0.067 wt%, 0.068 wt%, 0.070 wt%, 0.071 wt%, 0.072 wt%, 0.073 wt%, 0.074 wt%, 0.075 wt%, 0.076 wt%, 0.077 wt%, 0.078 wt%, 0.079 wt%, 0.080 wt%, 0.081 wt%, 0.082 wt%, %. 0.06wt%, 0.065wt%, 0.07wt%, 0.075wt%, 0.08wt%, 0.085wt%, 0.09wt%, 0.095wt%, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt% or 1wt% to 2wt%, 3wt%, 4wt%, 5wt% or 6wt% of Pt disposed on the support, based on the non-volatile weight of the catalyst. In other embodiments, the synthesized catalyst may include ≤5.5wt%, ≤4.5wt%, ≤3.5wt%, ≤2.5wt%, ≤1.5wt%, ≤1wt%, ≤0.9wt%, ≤0.8wt%, ≤0.7wt%, ≤0.6wt%,

[0047] ≤0.5wt%, ≤0.4wt%, ≤0.3wt%, ≤0.2wt%, ≤0.15wt%, ≤0.1wt%, ≤0.09wt%, ≤0.08wt%, ≤0.07wt%, ≤0.06wt%, ≤0.05 wt%, ≤0.045wt%, ≤0.04wt%, ≤0.035wt%, ≤0.03wt%, ≤0.025wt%, ≤0.02wt%, ≤0.015wt%, ≤0.01wt%, ≤0.009wt%,

[0048] % Pt disposed on the support, based on the non-volatile weight of the catalyst. In some embodiments, the synthesized catalyst may include >0.0001 wt%, >0.0005 wt%, >0.001 wt%, >0.003 wt%, >0.005 wt%, >0.007, >0.009 wt%, >0.01 wt%, >0.02 wt%, >0.001 ...

[0049] % Pt disposed on the support based on the non-volatile weight of the catalyst.

[0050] In some embodiments, the synthesized catalyst may optionally further include Ni, Pd, or a combination thereof, or a mixture thereof, disposed on a carrier. If Ni, Pd, or a combination thereof, or a mixture thereof, is also disposed on a carrier, the synthesized catalyst may include a total amount of 0.001 wt%, 0.002 wt%, 0.003 wt%, 0.004 wt%, 0.005 wt%, 0.006 wt%, 0.007 wt%, 0.008 wt%, 0.009 wt%, 0.01 wt%, 0.015 wt%, 0.02 wt%, 0.025 wt%, 0.03 wt%, 0.035 wt%, 0.04 wt%, 0.045 wt%, 0.05 wt%, 0.06 wt%, 0.07 wt%, 0.08 wt%, 0.09 wt%, 0.10 wt%, 0.11 wt%, 0.12 wt%, 0.13 wt%, 0.14 wt%, 0.15 wt%, 0.16 wt%, 0.17 wt%, 0.18 wt%, 0.19 wt%, 0.20 wt%, 0.21 wt%, 0.22 wt%, 0.23 wt%, 0.24 wt%, 0.25 wt%, 0.26 wt%, 0.27 wt%, 0.28 wt%, 0.29 wt%, 0.30 wt%, 0.31 wt%, 0.32 wt%, 0.33 wt%, 0.34 wt%, 0.35 wt%, 0.36 wt%, 0.37 %, 55 wt%, 0.06 wt%, 0.065 wt%, 0.07 wt%, 0.075 wt%, 0.08 wt%, 0.085 wt%, 0.09 wt%, 0.095 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, or 1 wt% to 2 wt%, 3 wt%, 4 wt%, 5 wt%, or 6 wt% of Pt and any Ni and / or any Pd disposed on the support, based on the non-volatile weight of the catalyst. In some embodiments, the active component of the synthesized catalyst capable of reforming or dehydrogenating, dehydroaromatizing, and dehydrocyclizing a hydrocarbon-containing feedstock may include Pt, or Pt and Ni and / or Pd. It will be appreciated that the active components may not be active or may be less active than the calcined catalyst obtained at the end of the cyclic calcinations or at the end of the final calcination. It will also be appreciated that Pt and, if present, Ni and / or Pd may be present in the synthesized catalyst in elemental form and / or in the form of compounds containing Pt and, if present, compounds containing Ni and / or compounds containing Pd.

[0051] In some embodiments, the synthesized catalyst may include a promoter disposed on a support in an amount of up to 10 wt %, based on the non-volatile weight of the catalyst. The promoter may be or may include, but is not limited to, Sn, Cu, Au, Ag, Ga, or a combination thereof or a mixture thereof. In some embodiments, the promoter may be associated with Pt and / or Ni and / or Pd if present. For example, the promoter and Pt disposed on the support may form a Pt-promoter cluster that may be dispersed on the support. The promoter may improve the selectivity / activity / life of the catalyst for a given upgraded hydrocarbon. In some embodiments, when the hydrocarbon-containing feed includes propane, the promoter may improve the propylene selectivity of the catalyst. The synthesized catalyst may include the promoter in an amount of 0.01 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt% or 1 wt% to 3 wt%, 5 wt%, 7 wt% or 10 wt%, based on the non-volatile weight of the catalyst. It should be understood that the promoter may not be associated with Pt and / or Ni and / or Pd, if present, or may be less associated with Pt and / or Ni and / or Pd, if present, than the calcined catalyst obtained at the end of the cyclic calcination or at the end of the final calcination. It should also be understood that the promoter may be present in the synthesized catalyst in elemental form and / or in the form of a compound containing the promoter.

[0052] In some embodiments, the synthesized catalyst may optionally include one or more alkali metal elements disposed on a carrier, in an amount up to 5wt%, based on the non-volatile weight of the catalyst. If present, the alkali metal element may be or may include but is not limited to Li, Na, K, Rb, Cs or 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. In some embodiments, if present, the alkali metal element may improve the selectivity of the catalyst particles for a given upgraded hydrocarbon. The synthesized catalyst may include alkali metal elements in an amount of 0.01wt%, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt% or 1wt% to 2wt%, 3wt%, 4wt% or 5wt%, based on the non-volatile weight of the catalyst. It should be understood that, if present, the one or more alkali metal elements may be in elemental form and / or in the form of one or more compounds containing the alkali metal element.

[0053] The carrier may be or may include but is not limited to one or more Group 2 elements or their combination or their mixture. In some embodiments, the Group 2 element may exist in its elemental form. In some other embodiments, the Group 2 element may exist in the form of a compound. For example, the Group 2 element may exist in the form of an oxide, phosphate, halide, 14alite, sulfate, sulfide, borate, nitride, carbide, aluminate, aluminosilicate, silicate, carbonate, metaphosphate, selenide, tungstate, molybdate, chromite, chromate, dichromate or silicide. In some embodiments, a mixture of any two or more compounds comprising the Group 2 element may exist in different forms. For example, the first compound may be an oxide, and the second compound may be an aluminate, wherein the first compound and the second compound include the Group 2 element that is identical or different from each other.

[0054] The synthesized catalyst may include ≥0.5wt%, ≥1wt%, ≥2wt%, ≥3wt%, ≥4wt%, ≥5wt%, ≥6wt%, ≥7wt%, ≥8wt%, ≥9wt%, ≥10wt%, ≥11wt%, ≥12wt%, ≥13wt%, ≥14wt%, ≥15wt%, ≥16wt%, ≥17wt%, ≥18wt%, ≥19wt%, ≥20wt%, ≥21wt%, ≥22wt% %, ≥23 wt%, ≥24 wt%, ≥25 wt%, ≥26 wt%, ≥27 wt%, ≥28 wt%, ≥29 wt%, ≥30 wt%, ≥35 wt%, ≥40 wt%, ≥45 wt%, ≥50 wt%, ≥55 wt%, ≥60 wt%, ≥65 wt%, ≥70 wt%, ≥75 wt%, ≥80 wt%, ≥85 wt% or ≥90 wt% of the Group 2 element, based on the non-volatile weight of the catalyst. In some embodiments, the synthesized catalyst may include a Group 2 element in an amount ranging from 0.5 wt%, 1 wt%, 2 wt%, 2.5 wt%, 3 wt%, 5 wt%, 7 wt%, 10 wt%, 11 wt%, 13 wt%, 15 wt%, 17 wt%, 19 wt%, 21 wt%, 23 wt%, or 25 wt% to 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, or 92.34 wt%, based on the non-volatile weight of the catalyst. In some embodiments, the molar ratio of Group 2 elements to Pt or Pt and any Ni and / or Pd present can be from 0.24, 0.5, 1, 10, 50, 100, 300, 450, 600, 800, 1,000, 1,200, 1,500, 1,700, or 2,000 to 3,000, 3,500, 4,000, 4,500, 5,000, 5,500, 6,000, 6,500, 7,000, 7,500, 8,000, 8,500, 9,000, 9,500, 10,000, 11,000, 12,000, 15,000, 16,000, 17,000, 18,000, 19,000, 20,000, 21,000, 22,000, 23,000, 24,000, 25,000, 26,000, 27,000, 28,000, 29,000, 30,000, 31,000, 33,000, 34,000, 35,000, 36,000, 37,000, 38,000, 39,000, 40,000, 41,000, 42,000, 43,000 0, 15,000, 20,000, 25,000, 30,000, 35,000, 40,000, 45,000, 50,000, 55,000, 60,000, 65,000, 70,000, 75,000, 80,000, 85,000, 90,000, 95,000, 100,000, 200,000, 300,000, 400,000, 500,000, 600,000, 700,000, 800,000 or 900,000.

[0055] In some embodiments, the support may include Group 2 elements and Al and may be in the form of a mixed Group 2 element / Al metal oxide having O, Mg, and Al atoms mixed at the atomic scale. In some embodiments, the support may be or may include Group 2 elements and Al in the form of oxides or one or more Group 2 element oxides and Al2O3 that may be mixed at the nanoscale. In some embodiments, the support may be or may include oxides of Group 2 elements such as MgO and Al2O3 mixed at the nanoscale.

[0056] In some embodiments, the support may be or may include a first amount of a Group 2 element and Al in the form of a mixed Group 2 element / Al metal oxide and a second amount of a Group 2 element in the form of an oxide of the Group 2 element. In such embodiments, the mixed Group 2 element / Al metal oxide and the Group 2 element oxide may be mixed at the nanoscale, and the Group 2 element and Al in the mixed Group 2 element / Al metal oxide may be mixed at the atomic scale.

[0057] In other embodiments, the support may be or may include a first amount of a Group 2 element and a first amount of Al in the form of a mixed Group 2 element / Al metal oxide, a second amount of a Group 2 element in the form of a Group 2 element oxide, and a second amount of Al in the form of Al2O3. In such embodiments, the mixed Group 2 element / Al metal oxide, the Group 2 element oxide, and Al2O3 may be mixed at the nanoscale, and the Group 2 element and Al in the mixed Group 2 element / Al metal oxide may be mixed at the atomic scale.

[0058] In some embodiments, when the support includes a Group 2 element and Al, the weight ratio of the Group 2 element to Al in the support may be in the range of 0.001, 0.005, 0.01, 0.05, 0.1, 0.15, 0.2, 0.3, 0.5, 0.7, or 1 to 3, 6, 12.5, 25, 50, 75, 100, 200, 300, 400, 500, 600, 700, 800, 900, or 1,000. In some embodiments, when the support includes Al, the synthesized catalyst can include Al in the range of 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.1 wt%, 2.3 wt%, 2.5 wt%, 2.7 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt% or 11 wt% to 15 wt%, 20 wt%, 25 wt%, 30 wt%, 40 wt%, 45 wt% or 50 wt% based on the non-volatile weight of the catalyst.

[0059] In some embodiments, the carrier may be or may include, but is not limited to, one or more of the following compounds: 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; CaZrO3; Ca7ZrAl6O 18 ;CaTiO3;Ca7Al6O 18 ;Ca7HfAl6O 18 ; BaCeO3; one or more magnesium chromates, one or more magnesium tungstates, one or more magnesium molybdates, combinations thereof, and mixtures thereof. In some embodiments, the Group 2 elements may include Mg, and at least a portion of the Group 2 elements may be in the form of MgO or a mixed oxide including MgO. In some embodiments, the support may be or may include, but is not limited to, a MgO-Al2O3 mixed metal oxide. In some embodiments, when the support is a MgO-Al2O3 mixed metal oxide, the support may have a Mg to Al molar ratio equal to 20, 10, 5, 2, 1 to 0.5, 0.1 or 0.01.

[0060] If present as a support or as a component of a support, Mg, where w is a positive number w Al2O 3+w The molar ratio of Mg to Al may be in the range of 0.5, 1, 2, 3, 4, or 5 to 6, 7, 8, 9, or 10. In some embodiments, the Mg w Al2O 3+w It may include MgAl2O4, Mg2Al2O5 or mixtures thereof. If present as a support or as a component of an inorganic support, Ca wherein x is a positive number x Al2O 3+x The molar ratio of Ca to Al may be in the range of 1:12, 1:4, 1:2, 2:3, 5:6, 1:1, 12:14 or 1.5:1. x Al2O 3+xIt may include tricalcium aluminate, dodecaluminate heptaaluminate, monocalcium aluminate, monocalcium 16alite 16nate, monocalcium hexaaluminate, dicalcium aluminate, pentacalcium trialuminate, tetracalcium trialuminate, or any mixture thereof. If present as a carrier or as a component of a carrier, Sr wherein y is a positive number y Al2O 3+y The molar ratio of Sr to Al may be in the range of 0.05, 0.3 or 0.6 to 0.9, 1.5 or 3. If present as a support or as a component of a support, Ba wherein z is a positive number z Al2O 3+z The molar ratio of Ba to Al may be in the range of 0.05, 0.3 or 0.6 to 0.9, 1.5 or 3.

[0061] In some embodiments, the carrier may further 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 a group other than Groups 2 and 10, wherein the at least one metal element and / or at least one metalloid element is not one of the alkali metal elements or one of the promoter elements. If the carrier further includes a compound comprising the metal element and / or metalloid element selected from a group other than Groups 2 and 10, wherein the at least one metal element and / or at least one metalloid element is not one of the alkali metal elements or one of the promoter elements, the compound may be present on the carrier as an oxide, phosphate, halide, 16alite, sulfate, sulfide, borate, nitride, carbide, aluminate, aluminosilicate, silicate, carbonate, metaphosphate, selenide, tungstate, molybdate, chromite, chromate, dichromate or silicide. In some embodiments, the at least one metal element and / or at least one metalloid element and / or at least one compound thereof selected from a group other than Groups 2 and 10 (wherein the at least one metal element and / or at least one metalloid element is not one of the alkali metal elements or one of the promoter elements) may be or may include but is not limited to one or more rare earth elements, i.e., elements with atomic numbers 21, 39 or 57-71.

[0062] If the carrier includes at least one metal element and / or at least one metalloid element and / or at least one compound thereof selected from a group other than Groups 2 and 10 (wherein the at least one metal element and / or at least one metalloid element is not one of the alkali metal elements or one of the promoter elements), the at least one metal element and / or at least one metalloid element may function as a binder in some embodiments and may be referred to as a "binder". Regardless of the at least one metal element and / or at least one metalloid element and / or at least one compound thereof selected from a group other than Groups 2 and 10 (wherein the at least one metal element and / or at least one metalloid element is not one of the alkali metal elements or one of the promoter elements), for clarity and ease of description, the at least one metal element and / or at least one metalloid element selected from a group other than Groups 2 and 10 will be further described herein as a "binder". In some embodiments, when the support includes a binder, the synthesized catalyst can include 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.5 wt%, 1 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt% or 40 wt% to 50 wt%, 60 wt%, 70 wt%, 80 wt% or 90 wt% binder, based on the non-volatile weight of the catalyst.

[0063] In some embodiments, suitable compounds comprising a binder may be or may include, but are not limited to, one or more of the following: B2O3, AlBO3, Al2O3, SiO2, ZrO2, TiO2, SiC, Si3N4, aluminosilicates, zinc aluminate, ZnO, VO, V2O3, VO2, V2O5, Ga s O t 、In u O v , Mn2O3, Mn3O4, MnO, one or more molybdenum oxides, one or more tungsten oxides, one or more zeolites, and mixtures and combinations thereof, wherein s, t, u and v are positive numbers.

[0064] In some embodiments, the synthesized catalyst may be in the form of a monolithic structure. In other embodiments, the synthesized catalyst may be in the form of particles. In some embodiments, the synthesized catalyst particles may have a median particle size in the range of 1 μm, 5 μm, 10 μm, 20 μm, 40 μm or 60 μm to 80 μm, 100 μm, 115 μm, 130 μm, 150 μm, 200 μm, 300 μm or 400 μm or 500 μm. In some embodiments, the synthesized catalyst particles may have a particle size of 0.3 g / cm 3, 0.4g / cm 3 , 0.5g / cm 3 , 0.6g / cm 3 , 0.7g / cm 3 , 0.8g / cm 3 , 0.9g / cm 3 or 1g / cm 3 Up to 1.1g / cm 3 , 1.2g / cm 3 , 1.3g / cm 3 , 1.4g / cm 3 , 1.5g / cm 3 , 1.6g / cm 3 , 1.7g / cm 3 , 1.8g / cm 3 , 1.9g / cm 3 or 2g / cm 3 The apparent loose bulk density in the range of , measured according to a modified ASTM D7481-18 with a 10, 25 or 50 mL measuring cylinder instead of a 100 or 250 mL measuring cylinder. In some embodiments, the synthesized catalyst particles may have a one-hour attrition loss of ≤5 wt%, ≤4 wt%, ≤3 wt%, ≤2 wt%, ≤1 wt%, ≤0.7 wt%, ≤0.5 wt%, ≤0.4 wt%, ≤0.3 wt%, ≤0.2 wt%, ≤0.1 wt%, ≤0.07 wt% or ≤0.05 wt%, measured according to ASTM D5757-11 (2017). The morphology of the synthesized particles is mainly spherical, making them suitable for operation in a fluidized bed reactor. In some embodiments, the synthesized catalyst particles may have a size and density that conforms to the Geldart A or Geldart B definition of a fluidizable solid.

[0065] In some embodiments, the synthesized catalyst particles may have a diameter 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 2 / g range. The surface area of ​​the synthesized 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.

[0066] Method for preparing synthetic catalyst

[0067] The method for preparing the synthesized catalyst may include preparing a slurry or gel, which may include grinding, mixing, blending, combining or otherwise contacting a compound containing a Group 2 element and a liquid medium, but is not limited thereto. In some embodiments, the preparation of the slurry or gel may also include contacting a compound containing at least a Group 2 element, a liquid medium, and one or more additives. In other embodiments, the preparation of the slurry or gel may include contacting a compound containing at least a Group 2 element, a liquid medium, a binder or a binder precursor, and optionally one or more additives.

[0068] The compound containing the Group 2 element may be in the form of an oxide, a hydroxide, a hydrated carbonate, a salt, a clay containing the Group 2 element, a layered double hydroxide, a phosphate, a halide, a halogenate, a sulfate, a sulfide, a borate, a nitride, a carbide, aluminate, aluminosilicate, a silicate, a carbonate, a metaphosphate, a selenide, a tungstate, a molybdate, a chromite, a chromate, a dichromate, a silicide, or a mixture thereof. In some embodiments, the Group 2 element may be or may include Mg, and the compound containing the Group 2 element may be in the form of magnesium oxide, magnesium hydroxide, hydromagnesite (hydrated magnesium carbonate mineral, Mg5(CO3)4(OH)2·4H2O)), a magnesium salt, a magnesium-containing clay, a hydrotalcite (layered double hydroxide), an organic magnesium compound, or a mixture thereof. In some embodiments, the Group 2 element may be or may include Mg, and the Group 2 element-containing compound may be in the form of calcined magnesium oxide, calcined magnesium hydroxide, calcined hydromagnesite (hydrated magnesium carbonate mineral, Mg5(CO3)4(OH)2·4H2O)), calcined magnesium salt, calcined magnesium-containing clay, calcined hydrotalcite (layered double hydroxide), calcined organic magnesium compound, or a mixture thereof.

[0069] The liquid medium may be or may include, but is not limited to, water, alcohol, acetone, chloroform, methylene chloride, dimethylformamide, dimethyl sulfoxide, glycerol, ethyl acetate, or any mixture thereof. Illustrative alcohols may be or may include, but are not limited to, methanol, ethanol, isopropanol, or any mixture thereof. If present, the binder may be or may include the above-mentioned binder. If present, the binder precursor may be or may include, but is not limited to, Al2Si2O5(OH)4(kaolin), hydrated aluminum chloride, boehmite, pseudoboehmite, gibbsite, bayerite, aluminum nitrate, aluminum chloride, sodium aluminate, alumina sol, silica sol, or any mixture thereof. Some compounds known in the literature herein referred to as "binders" may also be referred to as fillers, matrix, additives, etc. If present, the one or more additives may be or may include, but are not limited to: acids such as formic acid, lactic acid, citric acid, acetic acid, HNO3, HCl, oxalic acid, stearic acid, carbonic acid, etc.; bases such as ammonia solution, NaOH, KOH, etc.; inorganic salts such as nitrates, carbonates, bicarbonates, chlorides, etc.; organic salts such as acetates, oxalates, formates, citrates, etc.; polymers such as polyvinyl alcohol, polysaccharides, etc., or any mixture thereof. The additives may help improve the chemical / physical properties of the spray-dried material and / or improve the rheological properties of the slurry / gel to aid spray drying.

[0070] The slurry or gel can be spray dried to produce spray-dried carrier particles containing Group 2 elements. Spray drying refers to a method for producing a dry particulate solid product from a slurry or gel. The method may include spraying or atomizing (e.g., forming small droplets) the slurry or gel into a temperature-controlled gas stream to evaporate the liquid medium from the atomized droplets and produce a particulate solid product. For example, in a spray drying process, the slurry or gel can be atomized into small droplets and mixed with hot air or a hot inert gas such as nitrogen to evaporate the liquid from the droplets. The temperature of the slurry or gel during the spray drying process can generally be close to or higher than the boiling temperature of the liquid. An outlet air temperature of about 60°C to about 120°C can be common.

[0071] The slurry or gel can be atomized with one or more pressure nozzles (e.g., fluid nozzle atomizers), one or more pulse atomizers, one or more high-speed rotating disks (e.g., centrifugal or rotary atomizers), or any other known method. The median particle size, liquid (e.g., water) concentration, apparent loose bulk density, or any combination thereof of the granular solid product prepared via spray drying can be controlled, regulated, or otherwise affected by one or more operating conditions and / or parameters of the spray dryer. Illustrative operating conditions can include, but are not limited to, the feed rate and temperature of the gas stream, the atomizer speed, the feed rate of the slurry or gel via the atomizer, the temperature of the slurry or gel, the size of the droplets, and / or the solid concentration, the spray dryer size, or any combination thereof. It is well known in the art that various operating conditions will vary according to the specific spray drying equipment used, and can be easily determined by those of ordinary skill in the art.

[0072] In some embodiments, the spray-dried support particles can be calcined in an oxidizing atmosphere, such as an air atmosphere, to produce calcined support particles comprising Group 2 elements. In some embodiments, the spray-dried support particles can be calcined at a temperature ranging from 450°C, 500°C, 525°C, 550°C, 575°C, 600°C, 625°C, 650°C, or 675°C to 700°C, 725°C, 750°C, 775°C, 800°C, 850°C, 900°C, 950°C, or more. In some embodiments, the spray-dried support particles can be calcined at a temperature of ≤950°C, ≤900°C, ≤850°C, ≤800°C, ≤750°C, ≤700°C, ≤650°C, ≤600°C, ≤550°C, ≤525°C, ≤500°C, ≤475°C, or ≤460°C. In some embodiments, the spray-dried carrier particles may be calcined for a period of ≤240 minutes, ≤180 minutes, ≤120 minutes, ≤90 minutes, ≤60 minutes, ≤45 minutes, ≤30 minutes, ≤25 minutes, ≤20 minutes, or ≤15 minutes. In some embodiments, the spray-dried carrier particles may be calcined in the presence of oxygen, such as in an air atmosphere. In some embodiments, the spray-dried particles may be calcined at a temperature in the range of 550°C to 900°C or 550°C to 850°C for a period of ≤240 minutes, ≤180 minutes, ≤120 minutes, ≤90 minutes, ≤60 minutes, ≤45 minutes, ≤30 minutes, ≤25 minutes, ≤20 minutes, or ≤15 minutes. In some other embodiments, the spray-dried particles are calcined at a temperature of ≤550°C, ≤540°C, ≤530°C, ≤520°C, ≤510°C or ≤500°C for a period of ≤240 minutes, ≤180 minutes, ≤120 minutes, ≤90 minutes, ≤60 minutes, ≤45 minutes, ≤30 minutes, ≤25 minutes, ≤20 minutes or ≤15 minutes.

[0073] The Pt and, if present, Ni and / or Pd present in the synthesized catalyst may be introduced in one or two ways. For simplicity, Pt will be described below, but Ni-containing and / or Pd-containing compounds may be used in addition to Pt. In some embodiments, the method of preparing the synthesized catalyst may include (i) contacting at least the compound containing the Group 2 element and the liquid medium with a Pt-containing compound so that Pt may be present in the slurry or gel, and the synthesized catalyst may include spray-dried catalyst particles comprising carrier particles having Pt disposed thereon. In such an embodiment, the spray-dried particles may be the synthesized catalyst, or the spray-dried particles may be subjected to an equilibration and / or drying treatment to produce the synthesized catalyst, but the equilibration and / or drying treatment is not performed at a temperature ≥350°C.

[0074] In some other embodiments, the method for preparing the synthesized catalyst may include (ii) depositing Pt on the calcined spray-dried particles by contacting the calcined spray-dried particles with a Pt-containing compound to produce calcined spray-dried particles containing Pt. In some embodiments, the calcined spray-dried particles may be contacted with a Pt-containing compound in the presence of a liquid medium to produce a mixture, and the solid portion may be recovered by filtration. The Pt-containing compound may be or may include, but is not limited to, chloroplatinic acid hexahydrate, tetraammine platinum (II) nitrate, acetylacetonate platinum (II), platinum (II) bromide, platinum (II) iodide, platinum (II) chloride, platinum (IV) chloride, diammine platinum (II) dichloride, ammonium tetrachloroplatinate (II), tetraammine platinum (II) chloride hydrate, tetraammine platinum (II) hydroxide hydrate, or any mixture thereof. Suitable nickel-containing and palladium-containing compounds may be or may include, but are not limited to, nickel chloride (II), palladium acetate (II), palladium nitrate (II), or a mixture thereof.

[0075] The promoter and / or alkali metal element that can be optionally present in the catalyst of the synthesis can be introduced in the same manner as the introduction of Pt. The compound including the promoter element can be or can include but is not limited to tin oxide (II), tin oxide (IV), tin chloride pentahydrate (IV), tin chloride dihydrate (II), tin bromide (II), tin bromide (IV), tin acetylacetonate (II), tin acetate (II), tin acetate (IV), silver nitrate (I), gold nitrate (III), copper nitrate (II), gallium nitrate (III) or any mixture thereof. The compound including the alkali metal element can be or can include but is not limited to lithium nitrate, sodium nitrate, potassium nitrate, rubidium nitrate, cesium nitrate or any mixture thereof.

[0076] In some embodiments, platinum oxalate (II) and tin oxalate (II) can be used as Pt-containing compounds and Sn-containing compounds. Tin oxalate (II) can be dissolved in an aqueous solution containing ammonium oxalate, or in an aqueous solution containing ammonium oxalate and platinum oxalate. The aqueous solution containing tin oxalate (II) and ammonium oxalate or ammonium oxalate and platinum oxalate can be added to a carrier, and then balanced, dried and / or calcined. By using Sn oxalate (including tin oxalate (II) and tin oxalate (IV)) as Sn-containing compounds, Sn distribution on the carrier can be improved. Using platinum oxalate (II) and tin oxalate (II) as Pt-containing compounds and Sn-containing compounds for different applications on different carriers has been described in U.S. Patent No. 8,569,203B2.

[0077] The first method of upgrading hydrocarbons

[0078] The first method of upgrading hydrocarbons can include contacting the first hydrocarbon-containing feed with a calcined catalyst to carry out one or more of the dehydrogenation, dehydrogenation aromatization and dehydrogenation cyclization of at least a portion of the first hydrocarbon-containing feed, to produce a coked catalyst and an effluent that can contain one or more upgraded hydrocarbons and molecular hydrogen. The calcined catalyst and the first hydrocarbon-containing feed can be in any suitable environment, for example, contacted with each other in one or more reactions or conversion zones arranged in one or more reactors, to produce an effluent and a coked catalyst. The reaction or conversion zone can be arranged in or located in one or more fixed-bed reactors, one or more fluidized beds or moving bed reactors, one or more flow conversion reactors or any combination thereof.

[0079] The first hydrocarbon-containing feed and the calcined catalyst 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., 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 first hydrocarbon-containing feed and the calcined catalyst may be contacted at a temperature of at least 620° C., at least 650° C., at least 660° C., at least 670° C., at least 680° C., at least 690° C., or at least 700° C. to 725° C., 750° C., 760° C., 780° C., 800° C., 825° C., 850° C., 875° C., or 900° C. The first hydrocarbon-containing feed may be introduced into the reaction or conversion zone and contacted with the calcined catalyst therein for a period of ≤3 hours, ≤2.5 hours, ≤2 hours, ≤1.5 hours, ≤1 hour, ≤45 minutes, ≤30 minutes, ≤20 minutes, ≤10 minutes, ≤5 minutes, ≤1 minute, ≤30 seconds, ≤10 seconds, ≤5 seconds, or ≤1 second or ≤0.5 seconds. In some embodiments, the first hydrocarbon-containing feed may be contacted with the calcined catalyst for a period of time ranging from 0.1 seconds, 0.5 seconds, 0.7 seconds, 1 second, 30 seconds, 1 minute, 5 minutes, or 10 minutes to 30 minutes, 50 minutes, 70 minutes, 1.5 hours, 2 hours, or 3 hours.

[0080] The first hydrocarbon-containing feed and the calcined catalyst 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-C4 in the first hydrocarbon-containing feed. 16 Alkanes and any C8-C 16 In some embodiments, the hydrocarbon partial pressure during contact of the first hydrocarbon-containing feed and the calcined catalyst can be in the range of 20 kPa absolute, 50 kPa absolute, 100 kPa absolute, at least 150 kPa, at least 200 kPa, 300 kPa absolute, 500 kPa absolute, 750 kPa absolute, or 1,000 kPa absolute to 1,500 kPa absolute, 2,500 kPa absolute, 4,000 kPa absolute, 5,000 kPa absolute, 7,000 kPa absolute, 8,500 kPa absolute, or 10,000 kPa absolute, wherein the hydrocarbon partial pressure is the total partial pressure of the alkyl aromatic hydrocarbons in any C2-C4 hydrocarbons in the first hydrocarbon-containing feed. 16 Alkanes and any C8-C 16In other embodiments, the hydrocarbon partial pressure during contact of the hydrocarbon-containing feed with the calcined catalyst may be in the range of 20 kPa absolute, 50 kPa absolute, 100 kPa absolute, 150 kPa absolute, 200 kPa absolute, 250 kPa absolute, or 300 kPa absolute to 500 kPa absolute, 600 kPa absolute, 700 kPa absolute, 800 kPa absolute, 900 kPa absolute, or 1,000 kPa absolute, wherein the hydrocarbon partial pressure is the total partial pressure of the alkyl aromatic hydrocarbons in any C2-C4 hydrocarbons in the first hydrocarbon-containing feed. 16 Alkanes and any C8-C 16 Total partial pressure of alkyl aromatics.

[0081] In some embodiments, the first 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 first hydrocarbon-containing feed and the calcined catalyst may be a single C2-C4 hydrocarbon at a pressure of at least 20 kPa absolute, at least 50 kPa absolute, at least 100 kPa absolute, at least 150 kPa absolute, at least 250 kPa absolute, at least 300 kPa absolute, at least 400 kPa absolute, at least 500 kPa absolute, or at least 1,000 kPa absolute. 16 Alkanes such as propane are contacted under pressure.

[0082] The first hydrocarbonaceous feed may be contacted with the calcined catalyst in the reaction or conversion zone at any weight hourly space velocity (WHSV) effective to carry out the described upgrading process. In some embodiments, the WHSV may be 0.01 hr -1 、0.1hr -1 , 1hr -1 , 2hr -1 , 5hr -1 、10hr -1 、20hr -1 、30hr -1 or 50hr -1 Up to 100hr -1 、250hr -1 、500hr -1 or 1,000hr -1 In some embodiments, when the hydrocarbon upgrading process includes a fluidized or otherwise moved calcined catalyst, the calcined catalyst circulation mass flow rate is equal to any C2-C 16 Alkanes and any C8-C 16The ratio of the total amount of alkyl aromatic hydrocarbon mass flow rates can range from 1, 3, 5, 10, 15, 20, 25, 30, or 40 to 50, 60, 70, 80, 90, 100, 110, 125, or 150 on a weight to weight basis.

[0083] When the activity of the coked catalyst is reduced to below the required minimum amount, the coked catalyst or at least a portion thereof can undergo a regeneration process to produce a regenerated catalyst. More specifically, the coked catalyst can be contacted with one or more oxidants to carry out the combustion of at least a portion of coke, to produce a regenerated catalyst and combustion gases lean in coke. The regeneration of the coked catalyst can occur in a reaction or conversion zone or in a combustion zone separated from a reaction or conversion zone according to a specific reactor configuration, to produce a regenerated catalyst. For example, when using a fixed bed or flow conversion reactor, the regeneration of the coked catalyst can occur in a reaction or conversion zone, or when using a fluidized bed reactor or other circulation or fluidized reactor, the regeneration of the coked catalyst occurs in a separate combustion zone that can be separated from a reaction or conversion zone. In some embodiments, fuel can be added to the combustion zone to produce heat that can heat the coked catalyst. Illustrative fuels may be or may include, but are not limited to, hydrocarbons such as methane, ethane, propane, butane, pentane, or hydrocarbon-containing streams such as natural gas, molecular hydrogen, fuel oil, heavy fuel oil, gasoline, diesel, kerosene, distillate and / or other combustible compounds. In some embodiments, the regeneration process may include burning fuel in a combustion zone, then passing a relatively dry oxidant through the combustion zone to produce a regenerated catalyst. In some embodiments, the regeneration process may include burning fuel and coked catalyst in a first combustion zone to produce at least partially regenerated catalyst, transporting the at least partially regenerated catalyst to a second combustion zone, and passing a relatively dry oxidant through the second combustion zone to produce a regenerated catalyst. An example of a dry oxidant includes air containing <2 vol% water vapor.

[0084] In some embodiments, the method may optionally include contacting at least a portion of the regenerated catalyst with a reducing gas to produce a regenerated and reduced catalyst. An additional amount of the hydrocarbon-containing feed may contact at least a portion of the regenerated catalyst and / or at least a portion of any regenerated and reduced catalyst to produce a re-coked catalyst and additional effluent.

[0085] In some embodiments, the cycle time from contacting the hydrocarbon-containing feed with the calcined catalyst to contacting the additional amount of hydrocarbon-containing feed with the regenerated catalyst may be ≤ 5 hours. The first cycle begins when the calcined catalyst is contacted with the first hydrocarbon-containing feed, then contacted with at least an oxidizing gas to produce a regenerated catalyst, or at least an oxidizing gas and an optional reducing gas to produce a regenerated and reduced catalyst, and the first cycle ends when the regenerated catalyst is contacted with the additional amount of the first hydrocarbon-containing feed. If one or more additional feeds (described in more detail below) are used between the first hydrocarbon-containing feed and the oxidizing gas flow, between the oxidizing gas and the reducing gas (if used) flow, between the oxidizing gas and the additional amount of the first hydrocarbon-containing feed flow, and / or between the reducing gas (if used) and the additional amount of the first hydrocarbon-containing feed flow, the time period during which such one or more stripping gases are used will be included in the time period included in the cycle time. Thus, in some embodiments, the cycle time from contacting the first hydrocarbon-containing feed with the calcined catalyst to contacting the additional amount of hydrocarbon-containing feed with the regenerated catalyst can be ≤5 hours, ≤4 hours, ≤3 hours, ≤2 hours, ≤1 hour, ≤55 minutes, ≤50 minutes, or ≤45 minutes.

[0086] The oxidant may be or may include, but is not limited to, O2, O3, CO2, H2O, or mixtures thereof. In some embodiments, an oxidant in an amount exceeding that required to burn 100% of the coke on the coked catalyst may be used to increase the rate of removal of coke from the catalyst, such that the time required to remove the coke may be reduced and an increased yield of upgraded products produced in a given time period may be achieved. Using pure O2 as an oxidant may help capture and sequester CO2 produced during combustion in one or more downstream CO2 recovery systems.

[0087] The coked catalyst and oxidant may be contacted with one another at a temperature in the range of 500°C, 550°C, 600°C, 650°C, 700°C, 750°C, or 800°C to 900°C, 950°C, 1,000°C, 1,050°C, or 1,100°C to produce a regenerated catalyst. In some embodiments, the coked catalyst and oxidant may be contacted with one another at a temperature in the range of 500°C to 1,100°C, 600°C to 1,000°C, 650°C to 950°C, 700°C to 900°C, or 750°C to 850°C to produce a regenerated catalyst.

[0088] The coked catalyst and oxidant can contact each other for a time period of ≤2 hours, ≤1 hour, ≤30 minutes, ≤10 minutes, ≤5 minutes, ≤1 minute, ≤30 seconds, ≤10 seconds, ≤5 seconds, or ≤1 second. For example, the coked catalyst and oxidant can contact each other for a time period in the range of 2 seconds to 2 hours. In some embodiments, the coked catalyst and oxidant can contact a time period of ≥50 wt %, ≥75 wt %, or ≥90 wt %, or >99% of any coke deposited on the coked catalyst.

[0089] In some embodiments, the time period during which the coked catalyst and the oxidant contact each other may be less than the time period during which the calcined / regenerated catalyst contacts the hydrocarbon feed to produce an effluent and the coked catalyst. For example, the time period during which the coked catalyst and the oxidant contact each other may be at least 90%, at least 60%, at least 30%, or at least 10% shorter than the time period during which the calcined / regenerated catalyst contacts the hydrocarbon feed to produce an effluent. In other embodiments, the time period during which the coked catalyst and the oxidant contact each other may be greater than the time period during which the calcined / regenerated catalyst contacts the hydrocarbon feed to produce an effluent and the coked catalyst. For example, the period of time that the coked catalyst and the oxidant are in contact with each other can be at least 50%, at least 100%, at least 300%, at least 500%, at least 1,000%, at least 10,000%, at least 30,000%, at least 50,000%, at least 75,000%, at least 100,000%, at least 250,000%, at least 500,000%, at least 750,000%, at least 1,000,000%, at least 1,250,000%, at least 1,500,000%, or at least 1,800,000% longer than the period of time that the calcined / regenerated catalyst is in contact with the hydrocarbon feed to produce the effluent.

[0090] The coked catalyst and oxidant can be heated at 20 kPa absolute pressure, 50 kPa absolute pressure, 100 kPa absolute pressure, 300 kPa absolute pressure, 500 kPa absolute pressure,

[0091] 750kPa absolute pressure or 1,000kPa absolute pressure to 1,500kPa absolute pressure,

[0092] 2,500kPa absolute pressure, 4,000kPa absolute pressure, 5,000kPa absolute pressure,

[0093] In some embodiments, the oxidant partial pressure during contact with the coked catalyst can be in the range of 20 kPa absolute pressure, 50 kPa absolute pressure, 100 kPa absolute pressure, 150 kPa absolute pressure, 200 kPa absolute pressure, 250 kPa absolute pressure or 300 kPa absolute pressure to 500 kPa absolute pressure, 600 kPa absolute pressure, 700 kPa absolute pressure, 800 kPa absolute pressure, 900 kPa absolute pressure or 1,000 kPa absolute pressure to produce a regenerated catalyst.

[0094] Without wishing to be bound by theory, it is believed that the Pt and at least a portion of Ni and / or Pd disposed on the coked catalyst can agglomerate compared to the calcined / regenerated catalyst before contacting the first hydrocarbon-containing feed. It is believed that during at least a portion of the coke combustion on the coked catalyst, Pt and at least a portion of any Ni and / or Pd, if any, can be redispersed on the carrier. Any agglomerated Pt and at least a portion of Ni and / or Pd, if any, can be redispersed to improve the activity of the catalyst and improve the stability of the catalyst in many cycles.

[0095] In some embodiments, compared with the Pt in the catalyst contacted with the first hydrocarbon-containing feed and Ni and / or Pd if present and compared with the Pt in the coked catalyst and Ni and / or Pd if present, at least a portion of the Pt in the catalyst of the regeneration and Ni and / or Pd if present can be in a higher oxidation state. Therefore, as described above, in some embodiments, the method may optionally include contacting at least a portion of the catalyst of the regeneration with a reducing gas to produce a regenerated and reduced catalyst. Suitable reducing gas (reducing agent) may be or may include but is not limited to H2, CO, CH4, C2H6, C3H8, C2H4, C3H6, steam or a mixture thereof. In some embodiments, the reducing agent may be mixed with an inert gas such as Ar, Ne, He, N2, CO2, H2O or a mixture thereof. In such an embodiment, compared with the Pt in the catalyst of the regeneration and Ni and / or Pd if present, at least a portion of the Pt in the catalyst of the regeneration and reduction and Ni and / or Pd if present can be reduced to a lower oxidation state, such as an elemental state. In this embodiment, an additional amount of the hydrocarbon-containing feed may be contacted with at least a portion of the regenerated catalyst and / or at least a portion of the regenerated and reduced catalyst.

[0096] In some embodiments, the regenerated catalyst 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 and the reducing gas may be contacted for a period of time ranging from 1 second, 5 seconds, 10 seconds, 20 seconds, 30 seconds, or 1 minute to 10 minutes, 30 minutes, or 60 minutes. The regenerated catalyst and the reducing gas may be contacted at a reducing agent partial pressure in the range of 20 kPa absolute, 50 kPa absolute, 100 kPa absolute, 300 kPa absolute, 500 kPa absolute, 750 kPa absolute, or 1,000 kPa absolute to 1,500 kPa absolute, 2,500 kPa absolute, 4,000 kPa absolute, 5,000 kPa absolute, 7,000 kPa absolute, 8,500 kPa absolute, or 10,000 kPa absolute. In other embodiments, the partial pressure of the reductant during contact with the regenerated catalyst can be in the range of 20 kPa absolute, 50 kPa absolute, 100 kPa absolute, 150 kPa absolute, 200 kPa absolute, 250 kPa absolute, or 300 kPa absolute to 500 kPa absolute, 600 kPa absolute, 700 kPa absolute, 800 kPa absolute, 900 kPa absolute, or 1,000 kPa absolute to produce a regenerated catalyst.

[0097] At least a portion of the regenerated catalyst, the regenerated and reduced catalyst, the new or fresh catalyst, or a mixture thereof may be contacted with an additional amount of the first hydrocarbonaceous feed in a reaction or conversion zone to produce additional effluent and additional coked catalyst. As described above, in some embodiments, the cycle time from contacting the hydrocarbonaceous feed with the calcined / regenerated catalyst to contacting the additional amount of the hydrocarbonaceous feed with at least a portion of the regenerated catalyst and / or the regenerated and reduced catalyst and optionally with a new or fresh catalyst may be ≤5 hours, ≤4 hours, ≤3 hours, ≤2 hours, ≤1 hour, ≤55 minutes, ≤50 minutes, or ≤45 minutes.

[0098] In some embodiments, as described above, one or more additional feeds, such as one or more purge fluids, can be used between the first hydrocarbon-containing feed and the oxidant stream, between the oxidant and the optional reducing gas (if used) stream, between the oxidant and the additional first hydrocarbon-containing feed stream and / or between the reducing gas and the additional first hydrocarbon-containing feed stream. The purge fluid can especially purge or otherwise expel undesirable materials such as non-combustible particles including soot from the reactor. In some embodiments, the additional one or more feeds can be inert under dehydrogenation, dehydrogenation aromatization and dehydrogenation cyclization, combustion and / or reduction conditions. Suitable purge fluids can be or can include but are not limited to N2, He, Ar, CO2, H2O, CO2, CH4 or mixtures thereof. In some embodiments, if the method utilizes a purge fluid, the duration or time period of using the purge fluid can be in the range of 1 second, 5 seconds, 10 seconds, 20 seconds, 30 seconds or 1 minute to 10 minutes, 30 minutes or 60 minutes.

[0099] In some embodiments, the calcined / regenerated catalyst can remain sufficiently active and stable after many cycles, such as at least 15 cycles, at least 20 cycles, at least 30 cycles, at least 40 cycles, at least 50 cycles, at least 60 cycles, at least 70 cycles, at least 100 cycles, at least 125 cycles, at least 150 cycles, at least 175 cycles, or at least 200 cycles, wherein each cycle time lasts ≤5 hours, ≤4 hours, ≤3 hours, ≤2 hours, ≤1 hour, ≤50 minutes, ≤45 minutes, ≤30 minutes, ≤15 minutes, ≤10 minutes, ≤5 minutes, ≤1 minute, ≤30 seconds, or ≤10 seconds. In some embodiments, the cycle time can be from 5 seconds, 30 seconds, 1 minute, or 5 minutes to 10 minutes, 20 minutes, 30 minutes, 45 minutes, 50 minutes, 70 minutes, 2 hours, 3 hours, 4 hours, or 5 hours. In some embodiments, after the catalyst performance stabilizes (sometimes the first few cycles may have poor or better performance, but the performance may eventually stabilize), the process may produce a first upgraded hydrocarbon product, such as propylene yield, with a selectivity of ≥75%, ≥80%, ≥85%, ≥90% or ≥95% to upgraded hydrocarbons (e.g., propylene when the hydrocarbon-containing feed comprises propane) upon initial contact with the first hydrocarbon-containing feed, and may have a second upgraded hydrocarbon product yield with a selectivity of ≥75%, ≥80%, ≥85%, ≥90% or ≥95% to upgraded hydrocarbons, such as propylene, upon completion of the last cycle (at least 15 cycles in 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.

[0100] In some embodiments, when the first hydrocarbon-containing feed comprises propane and the upgraded hydrocarbon comprises propylene, contacting the hydrocarbon-containing feed with the calcined / regenerated catalyst may produce ≥48%, ≥49%, ≥50%, ≥51%, ≥52%, ≥53%, ≥54%, ≥55%, ≥56%, ≥57%, ≥58%, ≥59%, ≥60%, ≥61%, ≥62%, ≥63%, ≥64%, ≥65%, ≥66%, ≥67%, ≥68%, ≥69%, ≥70%, ≥71%, ≥72%, ≥73%, ≥74%, ≥75%, ≥76%, ≥77%, ≥78%, ≥79%, ≥80%, ≥85%, ≥90%, ≥93%, or ≥95% propylene selectivity.

[0101] ≥56%, ≥57%, ≥58%, ≥59%, ≥60%, ≥61%, ≥62%, ≥63%, ≥64%, ≥65%, ≥66%, ≥67%, ≥68% or ≥69% propylene yield. In some embodiments, when the hydrocarbon-containing feed comprises propane and the upgraded hydrocarbon comprises propylene, contacting the hydrocarbon-containing feed with the calcined / regenerated catalyst can produce a propylene yield of at least 48%, at least 49%, at least 50%, at least 51%, at least 52%, at least 53%, at least 55%, at least 57%, at least 60%, at least 62%, at least 63%, at least 64%, at least 65%, at least 66%, at least 67%, at least 68%, or at least 69% with a propylene selectivity of at least 75%, at least 80%, at least 85%, at least 90%, or at least 95% for at least 15, at least 20, at least 30, at least 40, at least 50, at least 60, at least 70, at least 100 cycles, at least 125 cycles, at least 150 cycles, at least 175 cycles, or at least 200 cycles. In other embodiments, when a hydrocarbon-containing feed comprising at least 70 vol%, at least 75 vol%, at least 80 vol%, at least 85 vol%, at least 90 vol%, or at least 95 vol% propane based on the total volume of the first hydrocarbon-containing feed is contacted at a propane partial pressure of at least 20 kPa absolute, 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 15 In some embodiments, the present invention provides a propylene yield of at least 48%, at least 49%, at least 50%, at least 51%, at least 52%, at least 53%, at least 55%, at least 57%, at least 60%, at least 62%, at least 63%, at least 64%, at least 65%, at least 66%, at least 67%, at least 68% or at least 69% with a propylene selectivity of at least 75%, at least 80%, at least 85%, at least 90% or at least 95% for 10 cycles, at least 175 cycles or at least 200 cycles. It is believed that by further optimizing the support composition 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 obtained 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 when the calcined / regenerated catalyst is contacted with a hydrocarbon-containing 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.

[0102] Systems suitable for carrying out the methods disclosed herein may include systems well known in the art, such as fixed bed reactors disclosed in WO Publication No. WO2017078894; U.S. Patent Nos. 3,888,762; 7,102,050; 7,195,741; 7,122,160; and 8,653,317; and U.S. Patent Application Publication Nos. 2004 / 0082824; fluidized riser reactors and / or downcomer reactors disclosed in 2008 / 0194891; and U.S. Patent No. 8,754,276; U.S. Patent Application Publication No. 2015 / 0065767; and the flow conversion reactor disclosed in WO Publication No. WO2013169461.

[0103] The first hydrocarbon-containing feed 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 aromatics, such as C8-C 16 In some embodiments, the first 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 16 The first hydrocarbon-containing feed may include <0.1 vol% steam, based on the total volume of alkylaromatic hydrocarbons, or may be free of steam.

[0104] The C2-C 16The 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 first hydrocarbon-containing feed may include propane that may be dehydrogenated to produce propylene, and / or isobutane that may be dehydrogenated to produce isobutylene. In another example, the first hydrocarbon-containing feed may include liquefied petroleum gas (LP gas), which may be in a gas phase when in contact with the catalyst. In some embodiments, the first hydrocarbon in the hydrocarbon-containing feed may be substantially composed of a single alkane such as propane. In some embodiments, the hydrocarbon-containing feed may include ≥50 mol%, ≥75 mol%, ≥95 mol%, ≥98 mol%, or ≥99 mol% of a single C2-C 16 The first hydrocarbon-containing feedstock may contain 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 first hydrocarbon-containing feed.

[0105] The C8-C 16 The alkyl aromatic hydrocarbons may be or may include, but are not limited to, ethylbenzene, propylbenzene, butylbenzene, one or more ethyltoluenes, or mixtures thereof. In some embodiments, the hydrocarbon-containing feed may contain ≥50 mol%, ≥75 mol%, ≥95 mol%, ≥98 mol%, or ≥99 mol% of a single C8-C 16 The alkyl aromatics, such as ethylbenzene, are based on the total weight of all hydrocarbons in the first hydrocarbon-containing feed. In some embodiments, ethylbenzene can be dehydrogenated to produce styrene. Therefore, in some embodiments, the first method of upgrading hydrocarbons disclosed herein can include propane dehydrogenation, butane dehydrogenation, isobutane dehydrogenation, pentane dehydrogenation, pentane dehydrogenation cyclization to cyclopentadiene, naphtha reforming, ethylbenzene dehydrogenation, ethyltoluene dehydrogenation, etc.

[0106] In some embodiments, the first hydrocarbon-containing feed may be diluted, for example, with one or more diluents such as one or more inert gases. Suitable inert gases may be or may include, but are not limited to, Ar, Ne, He, N2, CO2, CH4, or mixtures thereof. If the hydrocarbon-containing feed includes a diluent, then based on any C2-C4 in the hydrocarbon-containing feed, the first hydrocarbon-containing feed may be diluted with one or more diluents such as one or more inert gases. Suitable inert gases may be or may include, but are not limited to, Ar, Ne, He, N2, CO2, CH4, or mixtures thereof. 16 Alkanes and any C8-C 16The hydrocarbonaceous feed may contain from 0.1 vol%, 0.5 vol%, 1 vol% or 2 vol% to 3 vol%, 8 vol%, 16 vol% or 32 vol% diluent, based on the total volume of alkyl aromatic hydrocarbons.

[0107] In some embodiments, the first hydrocarbon-containing feed may further comprise H2. In some embodiments, when the first hydrocarbon-containing feed comprises H2, H2 and any C2-C 16 Alkanes and any C8-C 16 The molar ratio of the total amount of alkyl aromatics 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.

[0108] In some embodiments, the first hydrocarbon-containing feed may be substantially free of any steam, e.g., <0.1 vol. % steam, based on any C2-C 16 Alkanes and any C8-C 16 In other embodiments, the first hydrocarbon-containing feed may include steam. For example, the first hydrocarbon-containing feed may include 0.1%, 0.3%, 0.5%, 0.7%, 1%, 3%, or 5% to 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50% steam by volume, based on any C2-C8 hydrocarbons in the first hydrocarbon-containing feed. 16 Alkanes and any C8-C 16 In other embodiments, the first 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 alkyl aromatics in the first hydrocarbon-containing feed. 16 Alkanes and any C8-C 16 In other embodiments, the first hydrocarbon-containing 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 C2-C8 alkyl aromatics in the first hydrocarbon-containing feed. 16 Alkanes and any C8-C 16 The total volume of alkyl aromatics.

[0109] In some embodiments, the first hydrocarbon-containing feed can contain sulfur. For example, the first hydrocarbon-containing feed can contain from 0.5 ppm, 1 ppm, 5 ppm, 10 ppm, 20 ppm, 30 ppm, 40 ppm, 50 ppm, 60 ppm, 70 ppm, or 80 ppm to 100 ppm, 150 ppm,

[0110] In some embodiments, the first hydrocarbon-containing feedstock may contain 1 ppm to 10 ppm, 10 ppm to 20 ppm, 20 ppm to 50 ppm, 50 ppm to 100 ppm, or 100 ppm to 500 ppm of sulfur. If present in the first hydrocarbon-containing feedstock, the sulfur may be or may include, but is not limited to, H2S, dimethyl disulfide, as one or more mercaptans, or any mixture thereof.

[0111] In some embodiments, the first hydrocarbon-containing feed may be substantially free of or free of molecular oxygen. In some embodiments, the first hydrocarbon-containing feed may contain ≤5 mol%, ≤3 mol%, or ≤1 mol% of molecular oxygen (O2). It is believed that providing a first hydrocarbon-containing feed substantially free of molecular oxygen substantially prevents oxidation reactions that would otherwise consume at least a portion of the alkanes and / or alkyl aromatics in the first hydrocarbon-containing feed.

[0112] Recovery and application of the first upgraded hydrocarbons

[0113] In some embodiments, the first upgraded hydrocarbon may include at least one upgraded hydrocarbon such as olefins, water, unreacted hydrocarbons, molecular hydrogen, etc. The first upgraded hydrocarbon may be recovered or obtained via any convenient method, such as by one or more conventional methods. Such a method may include cooling and / or compressing the effluent to condense at least a portion of any water and any heavy hydrocarbons that may be present, leaving olefins and any unreacted alkanes or alkyl aromatics mainly in the gas phase. Olefins and unreacted alkanes or alkyl aromatics may then be removed from the reaction product in one or more separator drums. For example, one or more splitters or distillation towers may be used to separate the dehydrogenated product from the unreacted first hydrocarbon-containing feed.

[0114] In some embodiments, recovered olefins such as propylene can be used to produce polymers, for example, recovered propylene can be polymerized to produce polymers having segments or units derived from recovered propylene, such as polypropylene, ethylene-propylene copolymers, etc. 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 dimerized isobutylene, synthetic elastomeric polymers such as butyl rubber, etc.

[0115] The second method of upgrading hydrocarbons

[0116] The second method of hydrocarbon upgrading can include contacting the second hydrocarbon-containing feed with the described calcined catalyst including catalyst particles, to carry out the reforming of at least a portion of the second hydrocarbon-containing feed, to produce the catalyst of coking and the effluent that can include carbon monoxide and molecular hydrogen, the described catalyst particles include Pt and optional promoters arranged on a carrier. The described calcined catalyst and the second hydrocarbon-containing feed can contact each other in any suitable environment as being arranged in one or more reactions or conversion zones in one or more reactors, to produce the catalyst of effluent and coking. The described reaction or conversion zone can be arranged or be located in one or more fixed-bed reactors, one or more fluidized beds or moving bed reactors, one or more flow conversion reactors or any combination thereof. For the clarity and ease of description, reforming reaction will be discussed under the background of fluidized bed reactor, but it should be understood that fixed-bed reactor, flow conversion or moving bed reactor or any other reactor can be used for carrying out the reforming of the second hydrocarbon-containing feed.

[0117] The reforming reaction can be used to produce reformed hydrocarbons via a continuous reaction process or a discontinuous reaction process. In some embodiments, the reaction process may include a reforming step (e.g., an endothermic reaction) and a regeneration step (e.g., an exothermic reaction), which are operated continuously while the fluidized catalyst is transported between the reforming and regeneration zones of the reactor. The endothermic reaction may include hydrocarbon reforming in the presence of a calcined catalyst. Fresh hydrocarbons and regenerated fluidized catalyst particles may enter the reforming zone. After a period of time in the reforming zone, hydrocarbons may be at least partially converted into reformed products, which may leave the reforming zone together with the spent catalyst. The reformed products and unreacted feed may be separated from the spent catalyst by one or more separation devices. While the reformed products and unreacted feed from the separation device are further purified downstream, the spent catalyst may be sent to the regeneration zone for regeneration. The exothermic regeneration reaction may be a reaction of an oxidant and an optional fuel under combustion conditions to produce a regenerated catalyst and flue gas. After regeneration, the regenerated catalyst may be separated from the flue gas by one or more separation devices, and may be transported back to the reforming zone, adding more hydrocarbon feed to enter the reforming zone to trigger more reforming reactions. The reforming step may convert CO2 and / or H2O and hydrocarbons such as CH4 into a synthesis gas comprising H2 and CO. The regeneration step may burn reactants such as coke and / or optional fuel and oxidant disposed on the spent catalyst to generate heat for heating the regenerated catalyst, which may provide heat that can be used to drive the reforming reaction. In some embodiments, the catalyst may be heated to an average temperature of 600°C, 700°C, or 800°C to 1,000°C, 1,300°C, or 1,600°C during the regeneration step.

[0118] Illustrative fuels may be or may include, but are not limited to, hydrocarbons such as methane, ethane, propane, butane, pentane, or hydrocarbon-containing streams such as natural gas, molecular hydrogen, fuel oil, heavy fuel oil, gasoline, diesel, kerosene, distillates, and / or other combustible compounds. The oxidant may be or may include O2. In some embodiments, the oxidant may be or may include air, O2-enriched air, O2-depleted air, or any other suitable O2-containing stream.

[0119] The regeneration of catalyst can correspond to removing coke from catalyst particles. In some embodiments, during reforming, a portion of the feed introduced into the reforming zone can form coke. This coke may potentially hinder the catalytic site (e.g., metal site) of the catalyst. During regeneration, at least a portion of the coke produced during reforming can be removed as CO or CO2. The regeneration of catalyst can also correspond to the redispersion of any agglomerated active phase of catalyst such as Pt.

[0120] The second hydrocarbon-containing feed may be or may include but is not limited to one or more reformable C1-C 16 In some embodiments, the second hydrocarbon-containing feed can be or can include methane, ethane, propane, butane, pentane or a mixture thereof. In some embodiments, the second hydrocarbon-containing feed can be exposed to a catalyst at a pressure less than 35kPag. For example, the second hydrocarbon-containing feed can be exposed to a catalyst at a pressure of 0.7kPag, 2kPag, 3.5kPag, 5kPag or 10kPag to 15kPag, 20kPag, 25kPag or 30kPag. In other embodiments, the second hydrocarbon-containing feed can be exposed to a catalyst at a pressure of 35kPag to 15MPag. In still other embodiments, the second hydrocarbon-containing feed can be exposed to the catalyst at a pressure of 0.7 kPag, 2 kPag, 5 kPag, 20 kPag, 35 kPag, 50 kPag or 100 kPag to 200 kPag, 1 MPag, 3 MPag, 5 MPag, 10 MPag or 15 MPag. In still other embodiments, the second hydrocarbon-containing feed can be exposed to the catalyst at a pressure of less than 2.8 MPag, less than 2.5 MPag, less than 2.2 MPag or less than 2 MPag.

[0121] The reforming reaction of the second hydrocarbon-containing feed such as CH4 can occur in the presence of H2O (steam reforming), in the presence of CO2 (dry reforming), or in the presence of both H2O and CO2 (double reforming). Examples of the stoichiometry of steam reforming, dry reforming, and double reforming of CH4 are shown in equations (1)-(3).

[0122] (1) Dry reforming: CH4+CO2=2CO+2H2

[0123] (2) Steam reforming: CH4+H2O=CO+3H2

[0124] (3) Double reorganization: 3CH4+2H2O+CO2=4CO+8H2

[0125] As shown in equations (1)-(3), dry reforming can produce a lower H2 to CO ratio than steam reforming. Reforming reactions performed with steam alone can typically produce a syngas having a H2:CO molar ratio of about 3, such as 2.5 to 3.5. In contrast, reforming reactions performed with CO2 alone can typically produce a syngas having a H2:CO molar ratio of about 1 or even lower. By using a combination of CO2 and H2O during reforming, the reforming reaction can be controlled to produce a variety of H2 to CO ratios in the resulting syngas.

[0126] It should be noted that the ratio of H2 to CO in the syngas may also depend on the water-gas shift equilibrium. Although the stoichiometry in equations (1)-(3) shows a ratio of about 1 or about 3 for dry reforming and steam reforming, respectively, the balance of H2 and CO in the syngas may be different from the reaction stoichiometry. The balance may be determined based on the water-gas shift equilibrium, which is based on the concentrations of H2, CO, CO2, and H2O involved in the reaction shown in equation (4).

[0127] (4)H2O+CO←→H2+CO2

[0128] In some embodiments, the calcined catalyst may also be used as a water-gas shift catalyst. Thus, if the reaction environment for producing H2 and CO also includes H2O and / or CO2, the initial stoichiometry from the reforming reaction may change based on the water-gas shift equilibrium. However, this equilibrium is also temperature dependent, with higher temperatures favoring the production of CO and H2O. As a result, the ratio of H2 to CO produced when forming synthesis gas is limited by the water-gas shift equilibrium at the reaction zone temperature when the synthesis gas is produced.

[0129] The ability to adjust the H2:CO molar ratio of the syngas provides a flexible method that can be combined with various syngas upgrading methods. Illustrative syngas upgrading methods may include, but are not limited to, Fischer-Tropsch processes, methanol and / or other alcohol (e.g., one or more C1-C4 alcohols) synthesis, fermentation methods, separation methods that can separate hydrogen to produce H2-rich products, dimethyl ether, and combinations thereof. These syngas upgrading methods are well known to those of ordinary skill in the art. In some embodiments, the upgraded products may include, but are not limited to, methanol, synthetic crude oil, diesel, lubricants, waxes, olefins, dimethyl ether, other chemicals, or any combination thereof.

[0130] Systems suitable for carrying out reforming of the second hydrocarbon-containing feed may include systems well known in the art, such as fixed bed reactors disclosed in WO Publication No. WO2017078894; U.S. Patent Nos. 3,888,762; 7,102,050; 7,195,741; 7,122,160; and 8,653,317 and U.S. Patent Application Publication Nos. 2004 / 0082824; 2008 / 0194891, fluidized riser reactors and / or downcomer reactors disclosed; and U.S. Patent Nos.: 7,740,829; 8,551,444; 8,754,276; 9,687,803 and 10,160,708 and flow conversion reactors disclosed in U.S. Patent Application Publication Nos. 2015 / 0065767 and 2017 / 0137285 and WO Publication No. WO2013169461. Example:

[0131] The foregoing discussion can be further described in conjunction with the following non-limiting examples.

[0132] The synthesized catalyst 1 was prepared according to the following procedure. Calcined hydrotalcite support particles (23.0 g; MgO:Al2O3=71 / 29 weight / weight) having physical properties consistent with those of Geldart A fluidizable particles were mixed with 40 ml of deionized (DI) water to prepare a slurry. An aqueous mixture containing 0.38 g of 8% chloroplatinic acid solution, 2.97 g of 23.65% tin (IV) chloride pentahydrate and 20 ml of DI water was prepared. The aqueous mixture was slowly added to the slurry under stirring. After the addition was complete, the mixture was stirred for an additional 10 minutes and then the solid portion was recovered by filtration. The solid was then dried at 110° C. in air for 6 hours. After drying, the solid still contained a large amount of volatile compounds and / or compounds capable of forming volatile compounds when heat treated at a temperature above 110° C. The non-volatile weight of the catalyst was quantified by thermogravimetric analysis (TGA) in an oxidizing environment (air) by heating the synthesized catalyst to a temperature of 900° C. The synthesized Catalyst 1 had Pt and Sn loadings of about 0.05 wt% and about 1.0 wt%, respectively, based on the non-volatile weight of the catalyst.

[0133] Nine separate samples of the synthesized catalyst 1 were obtained and calcined under nine different calcination processes to obtain calcined catalysts (Examples 1-9). The calcination process was as follows.

[0134] Calcination 1 (Example 1; (O)): 1. Under an air flow of 46.6 sccm, the reaction zone temperature was increased from room temperature to 800°C at a rate of 5°C / min, and the catalyst particles were calcined at 800°C for 12 hours to produce calcined catalyst particles.

[0135] Calcination 2 (Example 2; (O)): 1. Under an air flow of 46.6 sccm, the reaction zone temperature was increased from room temperature to 550°C at a rate of 30°C / min, and the catalyst particles were calcined at 550°C for 0.5 hours to produce calcined catalyst particles.

[0136] Calcination 3 (Example 3; (R)): 1. Under an air flow of 46.6 sccm, the reaction zone temperature was increased from room temperature to 110°C at a rate of 30°C / min, and the catalyst particles were dried at 110°C for 0.5 hour. 2. The reaction zone temperature was then increased from 110°C to 600°C at a rate of 30°C / min under an inert gas flow. 3. Under an argon flow of 46.6 sccm containing 10% H2, the catalyst particles were calcined at 600°C for 2.5 hours to produce calcined catalyst particles.

[0137] Calcination 4 (Example 4; (OR)): 1. Under an air flow of 46.6 sccm, the reaction zone temperature was increased from room temperature to 450°C at a rate of 30°C / min, and the catalyst particles were calcined at 450°C for 0.5 hours. 2. Under an inert gas flow, the reaction zone temperature was increased from 450°C to 600°C at a rate of 30°C / min. 3. Under an argon flow of 46.6 sccm containing 10% H2, the catalyst particles were calcined at 600°C for 2.5 hours to produce calcined catalyst particles.

[0138] Calcination 5 (Example 5; (OR)): 1. Under an air flow of 46.6 sccm, the reaction zone temperature was increased from room temperature to 550°C at a rate of 30°C / min, and the catalyst particles were calcined at 550°C for 0.5 hour. 2. The reaction zone temperature was then increased from 550°C to 600°C at a rate of 30°C / min under an inert gas flow. 3. Under an argon flow of 46.6 sccm containing 10% H2, the catalyst particles were calcined at 600°C for 2.5 hours to produce calcined catalyst particles.

[0139] Calcination 6 (Example 6; (OR)): 1. Under an air flow of 46.6 sccm, the reaction zone temperature was increased from room temperature to 800° C. at a rate of 30° C. / min, and the catalyst particles were calcined at 800° C. for 0.5 hour. 2. The reaction zone temperature was then decreased from 800° C. to 600° C. at a rate of 30° C. / min under an inert gas flow. 3. Under an argon flow of 46.6 sccm containing 10% H2, the catalyst particles were calcined at 600° C. for 2.5 hours to produce calcined catalyst particles.

[0140] Calcination 7 (Example 7; (OR)): 1. Under an air flow of 46.6 sccm, the reaction zone temperature was increased from room temperature to 550°C at a rate of 30°C / min, and the catalyst particles were calcined at 550°C for 0.5 hour. 2. The reaction zone temperature was then increased from 550°C to 600°C at a rate of 30°C / min under an inert gas flow. 3. Under an argon flow of 46.6 sccm containing 10% H2, the catalyst particles were calcined at 600°C for 1.25 hours to produce calcined catalyst particles.

[0141] Calcination 8 (Example 8; (OR)): 1. Under an air flow of 46.6 sccm, the reaction zone temperature was increased from room temperature to 550°C at a rate of 30°C / min, and the catalyst particles were calcined at 550°C for 0.5 hours. 2. The reaction zone temperature was then increased from 550°C to 600°C at a rate of 30°C / min under an inert gas flow. 3. Under an argon flow of 46.6 sccm containing 10% H2, the catalyst particles were calcined at 600°C for 5 hours to produce calcined catalyst particles.

[0142] Calcination 9 (Example 9; (OROR)): 1. Under an air flow of 46.6 sccm, the reaction zone temperature was increased from room temperature to 550°C at a rate of 30°C / min, and the catalyst particles were calcined at 550°C for 0.25 hours. 2. The reaction zone temperature was then increased from 550°C to 600°C at a rate of 30°C / min under an inert gas flow. 3. Under an argon flow of 46.6 sccm containing 10% H2, the catalyst particles were calcined at 600°C for 0.625 hours. 4. The system was then purged with an inert gas. 5. The reaction zone temperature was then decreased from 600°C to 550°C at a rate of 30°C / min under an air flow of 46.6 sccm, and the catalyst particles were calcined at 550°C for 0.25 hours. 6. The reaction zone temperature was increased from 550°C to 600°C at a rate of 30°C / min under an inert gas flow. 7. The catalyst particles were calcined at 600°C for 0.625 hours under a flow of 46.6 seem of argon gas containing 10% H2 to produce calcined catalyst particles.

[0143] Fixed bed experiments were conducted at about 100 kPa absolute pressure using the calcined catalysts of Examples 1-9. The composition of the reactor effluent was measured using a gas chromatograph (GC). The concentration of each component in the reactor effluent was then used to calculate the C3H6 yield and selectivity. The C3H6 yield and selectivity at the start of the reaction are denoted as Y ini and S ini , and are reported as percentages in the table below. The C3H6 yields and selectivities reported in the examples are calculated based on moles of carbon.

[0144] In each example, 0.3 g of catalyst (based on non-volatiles) was mixed with an appropriate amount of silicon carbide and loaded into a quartz reactor. The amount of SiC should be such that the catalyst bed (catalyst + SiC) overlaps the isothermal zone of the quartz reactor and the catalyst bed remains substantially isothermal during operation. The dead volume of the reactor was filled with quartz rods.

[0145] The process steps used in the example are as follows: 1. Purge the system with an inert gas. 2. Pass dry air at a flow rate of 83.9 sccm through a bypass of the reaction zone while passing an inert gas through the reaction zone. 3. Heat the reaction zone to a regeneration temperature of 800°C. 4. Then pass air at a flow rate of 83.9 sccm through the reaction zone for 10 minutes to regenerate the catalyst. 5. Purge the system with an inert gas. 6. Pass a H2-containing gas (10 vol% H2 and 90 vol% Ar) through a bypass of the reaction zone at a flow rate of 46.6 sccm for a period of time while passing an inert gas through the reaction zone. Then flow the H2-containing gas through the reaction zone at 800°C for 3 seconds. Purge the system with an inert gas. During this process, the temperature of the reaction zone is varied from 800°C to a reaction temperature of 670°C. 7. A hydrocarbon-containing (HC gas) feed comprising 81 vol% C3H8, 9 vol% Ar and 10 vol% steam at a flow rate of 17.6 sccm was passed through the bypass of the reaction zone for a period of time while an inert gas was passed through the reaction zone. The hydrocarbon-containing feed was then passed through the reaction zone at 670°C for 10 minutes. GC sampling of the reaction effluent was started as soon as the feed was switched from the bypass of the reaction zone to the reaction zone. 8. The above process steps 1-7 were repeated for 14 cycles. Stable performance was obtained after 8 cycles.

[0146]

[0147] Comparison between calcinations 1 and 2 and calcinations 3-9 shows that reduction calcination may be more effective than oxidation calcination. Comparison between calcinations 1 and 2 and calcinations 4-9 shows that reduction calcination after oxidation calcination may help to significantly increase the yield of C3H6. For example, calcinations 4, 5, 7 and 8 produce catalysts with better performance, while calcination 6 produces a catalyst with slightly worse performance. Comparison between calcinations 4-8 shows that oxidation calcination should not be carried out at too high or too low a temperature. Comparison between calcinations 5, 7 and 8 shows that the reduction calcination time should not be too long or too short. Comparison between calcinations 5 and 9 shows that it may be advantageous to divide oxidation calcination and reduction calcination into two repeated cycles while keeping the total duration unchanged.

[0148] Three additional samples of the synthesized catalyst 1 were obtained and calcined through three additional calcination processes to obtain calcined catalysts (Examples 10-12). The calcination process was as follows.

[0149] Calcination 10 (Example 10, (OROR)): 1. Under an air flow of 46.6 sccm, the reaction zone temperature was increased from room temperature to 600°C at a rate of 30°C / min, and the catalyst particles were calcined at 600°C for 0.25 hours. 2. The system was then purged with an inert gas. 3. Under an argon flow of 10% H2 at 46.6 sccm, the catalyst particles were calcined at 600°C for 0.625 hours. 4. The system was purged with an inert gas. 5. Under an air flow of 46.6 sccm, the catalyst particles were calcined at 600°C for 0.25 hours. 6. The system was then purged with an inert gas. 7. Under an argon flow of 10% H2 at 46.6 sccm, the catalyst particles were calcined at 600°C for 0.625 hours to produce calcined catalyst particles.

[0150] Calcination 11 (Example 11; (OROR)): 1. Under an air flow of 46.6 sccm, the reaction zone temperature was increased from room temperature to 550°C at a rate of 30°C / min, and the catalyst particles were calcined at 550°C for 0.25 hours. 2. The reaction zone temperature was increased from 550°C to 650°C at a rate of 30°C / min under an inert gas flow. 3. Under an argon flow of 46.6 sccm containing 10% H2, the catalyst particles were calcined at 650°C for 0.625 hours. 4. The system was purged with an inert gas. 5. Under an air flow of 46.6 sccm, the reaction zone temperature was reduced from 650°C to 550°C at a rate of 30°C / min, and the catalyst particles were calcined at 550°C for 0.25 hours. 6. The reaction zone temperature was then increased from 550°C to 650°C at a rate of 30°C / min under an inert gas flow. 7. The catalyst particles were calcined at 650°C for 0.625 hours under a flow of 46.6 seem of 10% H2 in argon to produce calcined catalyst particles.

[0151] Calcination 12 (Example 12; (OROROROR)): 1. Raise the reaction zone temperature from room temperature to 600°C at a rate of 30°C / min under an air flow of 46.6 sccm, and calcine the catalyst particles at 600°C for 5 minutes. 2. Purge the system with an inert gas. 3. Calcine the catalyst particles at 600°C for 15 minutes under an argon flow of 10% H2 at 46.6 sccm. 4. Purge the system with an inert gas. 5. Calcine the catalyst particles at 600°C for 5 minutes under an air flow of 46.6 sccm. 6. Purge the system with an inert gas. 7. Calcine the catalyst particles at 600°C for 15 minutes under an argon flow of 10% H2 at 46.6 sccm. 8. Repeat steps 4-7 two (2) times. 9. Purge the system with an inert gas. 10. Calcine the catalyst particles at 600°C for 5 minutes under a flow of 46.6 sccm of air. 11. Purge the system with an inert gas. 12. Calcine the catalyst particles at 600°C for 20 minutes under a flow of 46.6 sccm of argon containing 10% H2 to produce calcined catalyst particles.

[0152] Fixed bed experiments were conducted at approximately 100 kPa absolute pressure using the calcined catalysts of Examples 10-12. The same procedure used for the calcined catalysts of Examples 1-9 was used for the calcined catalysts of Examples 10-12. The results are shown in Table 2 below. It is worth noting that the reactor used to conduct the fixed bed experiments in Examples 10-12 was different from the reactor used in Examples 1-9. Therefore, since the reactors are not the same, the results shown in Tables 1 and 2 should not be compared with each other in terms of catalyst performance.

[0153]

[0154] Comparison between Examples 10 and 12 shows that splitting the oxidation and reduction calcinations into 5 repeated cycles while keeping the total duration constant does not provide an advantage in C3H6 yield. Comparison between Examples 10 and 11 shows that reducing the temperature during the oxidation calcination from 600°C to 550°C and increasing the temperature during the reduction calcination from 600°C to 650°C increases the C3H6 yield.

[0155] The synthesized catalyst 2 was prepared according to the following procedure. Calcined hydrotalcite support particles (46.0 g; MgO:Al2O3=77 / 23 w / w) having physical properties consistent with those of Geldart A fluidizable particles were mixed with 80 ml of DI water to prepare a slurry. An aqueous mixture containing 0.32 g of 8% chloroplatinic acid solution, 5.95 g of 23.65% tin (IV) chloride pentahydrate and 40 ml of DI water was prepared. The aqueous mixture was slowly added to the slurry under stirring. After the addition was complete, the mixture was stirred for an additional 10 minutes and then the solid portion was recovered by filtration. The recovered solid was equilibrated at room temperature for 30 minutes and then dried in air at 300°C for 0.5 hour. After drying, the solid still contained a large amount of volatile compounds or compounds that can form volatile compounds when heat treated at a temperature above 300°C. The non-volatile weight of the synthesized catalyst was quantified by thermogravimetric analysis (TGA) in an oxidizing environment (air) by heating the synthesized catalyst to a temperature of 900° C. The synthesized catalyst 2 had a Pt and Sn loading of approximately 0.025 wt % and approximately 1.0 wt %, respectively, based on the non-volatile weight of the catalyst.

[0156] Four separate samples of the synthesized catalyst 2 were obtained and calcined under four different calcination processes to obtain calcined catalysts (Examples 13-16). The calcination process was as follows.

[0157] Calcination 13 (Example 13; (O)): 1. Under an air flow of 46.6 sccm, the reaction zone temperature was increased from room temperature to 550°C at a rate of 30°C / min, and the catalyst particles were calcined at 550°C for 0.5 hours to produce calcined catalyst particles.

[0158] Calcination 14 (Example 14; (OR)): 1. Under an air flow of 46.6 sccm, the reaction zone temperature was increased from room temperature to 550°C at a rate of 30°C / min, and the catalyst particles were calcined at 550°C for 0.5 hours. 2. The reaction zone temperature was then increased from 550°C to 650°C at a rate of 30°C / min under an inert gas flow. 3. Under a 100% H2 flow of 46.6 sccm, the catalyst particles were calcined at 650°C for 1.25 hours to produce calcined catalyst particles.

[0159] Calcination 15 (Example 16; (OR)): 1. Under an air flow of 46.6 sccm, the reaction zone temperature was increased from room temperature to 550°C at a rate of 30°C / min, and the catalyst particles were calcined at 550°C for 0.5 hours. 2. The reaction zone temperature was then increased from 550°C to 650°C at a rate of 30°C / min under an inert gas flow. 3. Under an argon flow of 46.6 sccm containing 10% H2, the catalyst particles were calcined at 650°C for 1.25 hours to produce calcined catalyst particles.

[0160] Calcination 16 (Example 16; (ORO)): 1. Under an air flow of 46.6 sccm, the reaction zone temperature was increased from room temperature to 550°C at a rate of 30°C / min, and the catalyst particles were calcined at 550°C for 0.5 hour. 2. The reaction zone temperature was then increased from 550°C to 650°C at a rate of 30°C / min under an inert gas flow. 3. Under a 100% H2 flow of 46.6 sccm, the catalyst particles were calcined at 650°C for 1.25 hours. 4. The system was purged with an inert gas. 5. Under an air flow of 46.6 sccm, the reaction zone temperature was reduced from 650°C to 550°C at a rate of 30°C / min, and the catalyst particles were calcined at 550°C for 0.5 hour to produce calcined catalyst particles.

[0161] Fixed bed experiments were conducted at approximately 100 kPa absolute pressure using the calcined catalysts of Examples 13 to 16. The same procedure used for the calcined catalysts of Examples 1 to 9 was used for the calcined catalysts of Examples 13 to 16.

[0162]

[0163] Table 3 shows that the combination of reduction / oxidation calcination can also improve the C3H6 yield of the catalyst containing 0.025 wt% Pt and a slightly different MgO:Al2O3 ratio compared to the synthesized catalyst 1. However, compared to Catalyst 1, the synthesized catalyst 2 required 100% H2 instead of 10% H2 to achieve the highest C3H6 yield, which may be because the MgO:Al2O3 ratio of Catalyst 2 (77 / 23 wt / wt) is higher than that of the synthesized catalyst 1 (71 / 29 wt / wt).

[0164] List of implementation plans

[0165] The present disclosure may further include the following non-limiting embodiments.

[0166] A1. A method for calcining a catalyst, the method comprising: subjecting a synthesized catalyst comprising Pt disposed on a support to a calcination process, the calcination process comprising heating the synthesized catalyst at a first temperature under a first atmosphere for a first period of time and heating the synthesized catalyst at a second temperature under a second atmosphere for a second period of time to produce a calcined catalyst, wherein: the synthesized catalyst comprises <0.05 wt% Pt, based on the non-volatile weight of the catalyst, and (i) the first atmosphere comprises a first oxidizing gas, the first temperature is in the range of 350°C to 850°C, the first period of time is in the range of 30 seconds to 10 hours, the second atmosphere comprises a first reducing gas, the second temperature is in the range of 500°C to 850°C, and the second period of time is in the range of 30 seconds to 10 hours, or (ii) the first atmosphere comprises a first reducing gas, the first temperature is in the range of 500°C to 850°C, the first period of time is in the range of 30 seconds to 10 hours, the second atmosphere comprises a first oxidizing gas, the second temperature is in the range of 350°C to 850°C, and the second period of time is in the range of 30 seconds to 10 hours.

[0167] A2. The method described in A1, wherein the first oxidizing gas comprises O2, O3, CO2, steam or a mixture thereof, and wherein the first reducing gas comprises H2, CO, CH4, C2H6, C3H8, C2H4, C3H6, steam or a mixture thereof.

[0168] A3. The method described in A1 or A2, wherein when the synthesized catalyst initially undergoes the calcination process, the synthesized catalyst contains one or more volatile compounds, and wherein the one or more volatile compounds contain adsorbed CO2, adsorbed H2O, adsorbed ethanol or a mixture thereof.

[0169] A4. The method described in any one of A1-A3, wherein the first atmosphere contains a first oxidizing gas and the second atmosphere contains a first reducing gas, and the method further comprises: heating the synthesized catalyst at a third temperature for a third time period under a third atmosphere to produce the calcined catalyst, wherein the third atmosphere contains the second oxidizing gas, the third temperature is in the range of 350°C to 850°C, and the third time period is in the range of 30 seconds to 10 hours.

[0170] A5. The method described in A4 also includes heating the synthesized catalyst at a fourth temperature under a fourth atmosphere for a fourth time period to produce the calcined catalyst, wherein the fourth atmosphere contains a second reducing gas, the fourth temperature is in the range of 500°C to 850°C, and the fourth time period is in the range of 30 seconds to 10 hours.

[0171] A6. The method described in A5, wherein the second oxidizing gas contains O2, O3, CO2, steam or a mixture thereof, and wherein the second reducing gas contains H2, CO, CH4, C2H6, C3H8, C2H4, C3H6, steam or a mixture thereof.

[0172] A7. The method described in any one of A1-A3, wherein the first atmosphere contains a first reducing gas and the second atmosphere contains a first oxidizing gas, and the method further comprises: heating the synthesized catalyst at a third temperature for a third time period under a third atmosphere to produce the calcined catalyst, wherein the third atmosphere contains a second reducing gas, the third temperature is in the range of 500°C to 850°C, and the third time period is in the range of 30 seconds to 10 hours.

[0173] A8. The method described in A7 also includes heating the synthesized catalyst at a fourth temperature under a fourth atmosphere for a fourth time period to produce the calcined catalyst, wherein the fourth atmosphere contains a second oxidizing gas, the fourth temperature is in the range of 350°C to 850°C, and the fourth time period is in the range of 30 seconds to 10 hours.

[0174] A9. The method described in A8, wherein the second reducing gas contains H2, CO, CH4, C2H6, C3H8, C2H4, C3H6, steam or a mixture thereof, and wherein the second oxidizing gas contains O2, O3, CO2, steam or a mixture thereof.

[0175] A10. The method described in any one of A1-A9, wherein: the synthesized catalyst also contains up to 10 wt% of a promoter disposed on a carrier, the promoter comprising Sn, Cu, Au, Ag, Ga, a combination thereof or a mixture thereof, the carrier containing at least 0.5 wt% of a Group 2 element, and all weight percentage values ​​are based on the non-volatile weight of the catalyst.

[0176] A11. The method described in A10, wherein: the Group 2 element includes Mg, and at least a portion of the Group 2 element is in the form of MgO or a mixed metal oxide including Mg.

[0177] A12. The method described in A10, wherein: the support further comprises a Group 13 element, the promoter comprises Sn, the Group 2 element comprises Mg, the Group 13 element comprises Al, and the support comprises a mixed Mg / Al metal oxide.

[0178] A13. The method of any one of A1-A12, wherein the synthesized catalyst is in the form of particles having a size and particle density that conforms to the Geldart A definition of fluidizable solids.

[0179] A14. The method of any one of A1-A13, wherein when the calcined catalyst is contacted with propane under dehydrogenation conditions, the calcined catalyst produces a propylene yield of ≥48% with a propylene selectivity of ≥90%.

[0180] A15. The method described in any one of A1-A14, wherein the composition of the first atmosphere and the composition of the second atmosphere remain unchanged or change independently during the first time period and during the second time period, respectively.

[0181] B1. A method for calcining a catalyst, the method comprising: subjecting synthesized catalyst particles comprising Pt disposed on a carrier to a calcination process, the calcination process comprising heating the synthesized catalyst particles at a first temperature under a first atmosphere for a first time period and heating the synthesized catalyst particles at a second temperature under a second atmosphere for a second time period to produce calcined catalyst particles, wherein: the synthesized catalyst particles have a size and particle density that meets the Geldart A definition of fluidizable solids, and (i) the first atmosphere comprises a first oxidizing gas, the first temperature is in the range of 350°C to 850°C, the first time period is in the range of 30 seconds to 10 hours, the second atmosphere comprises a first reducing gas, the second temperature is in the range of 500°C to 850°C, and the second time period is in the range of 30 seconds to 10 hours, or (ii) the first atmosphere comprises a first reducing gas, the first temperature is in the range of 500°C to 850°C, the first time period is in the range of 30 seconds to 10 hours, the second atmosphere comprises a first oxidizing gas, the second temperature is in the range of 350°C to 850°C, and the second time period is in the range of 30 seconds to 10 hours.

[0182] B2. The method described in B1, wherein the first oxidizing gas contains O2, O3, CO2, steam or a mixture thereof, and wherein the first reducing gas contains H2, CO, CH4, C2H6, C3H8, C2H4, C3H6, steam or a mixture thereof.

[0183] B3. The method described in B1 or B2, wherein when the catalyst particles initially undergo the calcination process, the catalyst particles contain one or more volatile compounds, and wherein the one or more volatile compounds contain adsorbed CO2, adsorbed H2O, adsorbed ethanol or a mixture thereof.

[0184] B4. The method described in any one of B1-B3, wherein the first atmosphere contains a first oxidizing gas and the second atmosphere contains a first reducing gas, and the method further comprises: heating the synthesized catalyst particles at a third temperature for a third time period under a third atmosphere to produce the calcined catalyst particles, wherein the third atmosphere contains a second oxidizing gas, the third temperature is in the range of 350°C to 850°C, and the third time period is in the range of 30 seconds to 10 hours.

[0185] B5. The method described in claim B4 further includes heating the synthesized catalyst particles at a fourth temperature under a fourth atmosphere for a fourth time period to produce the calcined catalyst particles, wherein the fourth atmosphere contains a second reducing gas, the fourth temperature is in the range of 500°C to 850°C, and the fourth time period is in the range of 30 seconds to 10 hours.

[0186] B6. The method described in B5, wherein the second oxidizing gas contains O2, O3, CO2, steam or a mixture thereof, and wherein the second reducing gas contains H2, CO, CH4, C2H6, C3H8, C2H4, C3H6, steam or a mixture thereof.

[0187] B7. The method described in any one of B4-B6, wherein the first atmosphere contains a first reducing gas and the second atmosphere contains a first oxidizing gas, and the method further comprises: heating the synthesized catalyst particles at a third temperature for a third time period under a third atmosphere to produce the calcined catalyst particles, wherein the third atmosphere contains a second reducing gas, the third temperature is in the range of 500°C to 850°C, and the third time period is in the range of 30 seconds to 10 hours.

[0188] B8. The method described in B7 also includes heating the synthesized catalyst particles at a fourth temperature under a fourth atmosphere for a fourth time period to produce the calcined catalyst particles, wherein the fourth atmosphere contains a second oxidizing gas, the fourth temperature is in the range of 350°C to 850°C, and the fourth time period is in the range of 30 seconds to 10 hours.

[0189] B9. The method described in B8, wherein the second reducing gas contains H2, CO, CH4, C2H6, C3H8, C2H4, C3H6, steam or a mixture thereof, and wherein the second oxidizing gas contains O2, O3, CO2, steam or a mixture thereof.

[0190] B10. The method described in any one of B1-B9, wherein: the synthesized catalyst particles also contain up to 10wt% of a promoter disposed on a carrier, the promoter comprising Sn, Cu, Au, Ag, Ga, a combination thereof or a mixture thereof, the carrier containing at least 0.5wt% of a Group 2 element, and all weight percentage values ​​are based on the non-volatile weight of the catalyst.

[0191] B11. The method described in B10, wherein: the Group 2 element contains Mg, and at least a portion of the Group 2 element is in the form of MgO or a mixed metal oxide containing Mg.

[0192] B12. The method described in B10, wherein: the carrier also contains a Group 13 element, the promoter contains Sn, the Group 2 element contains Mg, the Group 13 element contains Al, and the carrier contains a mixed Mg / Al metal oxide.

[0193] B13. The method described in any one of B1-B12, wherein when the calcined catalyst particles are contacted with propane under dehydrogenation conditions, the calcined catalyst particles produce a propylene yield of ≥48% with a propylene selectivity of ≥90%.

[0194] B14. A method as described in any of B1-B13, wherein the composition of the first atmosphere and the composition of the second atmosphere remain unchanged or change independently during the first time period and during the second time period, respectively.

[0195] C1. A method for upgrading hydrocarbons, the method comprising: subjecting a synthesized catalyst comprising Pt disposed on a carrier to an initial calcination, the initial calcination comprising exposing the synthesized catalyst to a first reducing gas under reducing conditions or to a first oxidizing gas under oxidizing conditions to produce an initially calcined catalyst, wherein the synthesized catalyst comprises <0.05 wt% Pt, based on the weight of the non-volatiles of the catalyst; optionally, subjecting the initially calcined catalyst to a cyclic calcination, the cyclic calcination comprising exposing the initially calcined catalyst to a second reducing gas under reducing conditions and to a second oxidizing gas under oxidizing conditions for n cycles to produce a cyclically calcined catalyst. wherein: n is an integer, when the initial calcination uses the first reducing gas, the cyclic calcination starts with the second oxidizing gas, and when the initial calcination uses the first oxidizing gas, the cyclic calcination starts with the second reducing gas; when n≥2, the composition of the second reducing gas used in each cyclic calcination is the same or different, and the composition of the second oxidizing gas used in each cyclic calcination is the same or different; and optionally, subjecting the initial calcined catalyst or the cyclic calcined catalyst to a final calcination, the final calcination comprising exposing the initial calcined catalyst or the cyclic calcined catalyst to a third reducing gas under reducing conditions or to a third reducing gas under oxidizing conditions. wherein: at least one of the cyclic calcination and the final calcination is performed, when the initial calcination uses the first reducing gas, if the final calcination is performed, the final calcination uses the third oxidizing gas, or if the cyclic calcination is performed, the cyclic calcination is ended with the second reducing gas, when the initial calcination uses the first oxidizing gas, if the final calcination is performed, the final calcination uses the third reducing gas, or if the cyclic calcination is performed, the cyclic calcination is ended with the second oxidizing gas, and the reducing conditions used in the initial calcination, the optional cyclic calcination, and the optional final calcination independently include heating the cyclic calcination at a temperature in the range of 500° C. to 850° C. wherein the oxidizing conditions used in the initial calcination, the optional cyclic calcination and the optional final calcination independently comprise heating the catalyst at a temperature in the range of 350° C. to 850° C. for a period of time in the range of 30 seconds to 10 hours, and obtaining a calcined catalyst at the end of the cyclic calcination or at the end of the final calcination; and contacting a hydrocarbon-containing feed with the calcined catalyst to perform one or more of dehydrogenation, dehydroaromatization and dehydrocyclization of at least a portion of the hydrocarbon-containing feed to produce a coked catalyst composition and an effluent comprising one or more upgraded hydrocarbons and molecular hydrogen, wherein: the hydrocarbon-containing feed comprises C2-C 16 One or more linear or branched alkanes or C4-C 16 One or more cycloalkanes or C8-C16 The hydrocarbon feed and the calcined catalyst are contacted at a temperature in the range of 300°C to 900°C under a hydrocarbon partial pressure of at least 20 kPa absolute for a period of time of ≤ 3 hours, wherein the hydrocarbon partial pressure is any C2-C 16 Alkanes and any C8-C 16 The total partial pressure of the alkyl aromatic hydrocarbons, and the one or more upgraded hydrocarbons comprise at least one of dehydrogenated hydrocarbons, dehydroaromatized hydrocarbons, and dehydrocyclized hydrocarbons.

[0196] C2. The method described in C1 also includes: contacting at least a portion of the coked catalyst with an oxidant to burn at least a portion of the coke to produce a regenerated catalyst lean in coke and combustion gas; and contacting an additional amount of hydrocarbon-containing feed with at least a portion of the regenerated catalyst to produce a re-coked catalyst and additional effluent, wherein the cycle time from contacting the hydrocarbon-containing feed with the calcined catalyst to contacting the additional amount of hydrocarbon-containing feed with the regenerated catalyst is ≤5 hours.

[0197] D1. A method for upgrading hydrocarbons, the method comprising: subjecting synthesized catalyst particles comprising Pt disposed on a carrier to an initial calcination, the initial calcination comprising exposing the catalyst particles to a first reducing gas under reducing conditions or to a first oxidizing gas under oxidizing conditions to produce initial calcined catalyst particles, wherein the synthesized catalyst particles have a size and a particle density that conforms to the Geldart A definition of a fluidizable solid; optionally, subjecting the initial calcined catalyst particles to a cyclic calcination, the cyclic calcination comprising exposing the initial calcined catalyst particles to a second reducing gas under reducing conditions and to a second oxidizing gas under oxidizing conditions for n cycles to produce cyclic calcined catalyst particles, wherein: n is an integer, when the initial calcination uses the first reducing gas, the cyclic calcination starts with the second oxidizing gas, when the initial calcination uses the first oxidizing gas, the cyclic calcination starts with the second reducing gas, and when n≥2, the second reducing gas used in each cyclic calcination is the composition of the catalyst particles is the same or different, and the composition of the second oxidizing gas used in each cyclic calcination is the same or different; and optionally, subjecting the initial calcined catalyst particles or the cyclic calcined catalyst particles to a final calcination, the final calcination comprising exposing the initial calcined catalyst particles or the cyclic calcined catalyst particles to a third reducing gas under reducing conditions or to a third oxidizing gas under oxidizing conditions, wherein: at least one of the cyclic calcination and the final calcination is performed, and when the initial calcination uses the first reducing gas, if the final calcination is performed, the final The calcination uses a third oxidizing gas, or if the cyclic calcination is performed, the cyclic calcination is ended with a second reducing gas, when the initial calcination uses a first oxidizing gas, if the final calcination is performed, the final calcination uses a third reducing gas, or if the cyclic calcination is performed, the cyclic calcination is ended with a second oxidizing gas, the reducing conditions used in the initial calcination, the optional cyclic calcination, and the optional final calcination independently include heating the catalyst particles at a temperature in the range of 500° C. to 850° C. for a time period in the range of 30 seconds to 10 hours, and in the initial calcination, the optional The oxidizing conditions used in the cyclic calcination and the optional final calcination independently include heating the catalyst particles at a temperature in the range of 350° C. to 850° C. for a period of time in the range of 30 seconds to 10 hours, and obtaining calcined catalyst particles at the end of the cyclic calcination or at the end of the final calcination; and contacting a hydrocarbon-containing feed with the calcined catalyst to perform one or more of dehydrogenation, dehydroaromatization and dehydrocyclization of at least a portion of the hydrocarbon-containing feed to produce a coked catalyst composition and an effluent comprising one or more upgraded hydrocarbons and molecular hydrogen, wherein: the hydrocarbon-containing feed comprises C2-C 16 One or more linear or branched alkanes or C4-C16 One or more cycloalkanes or C8-C 16 The hydrocarbon feed and the calcined catalyst are contacted at a temperature in the range of 300°C to 900°C under a hydrocarbon partial pressure of at least 20 kPa absolute for a period of time of ≤ 3 hours, wherein the hydrocarbon partial pressure is any C2-C 16 Alkanes and any C8-C 16 The total partial pressure of the alkyl aromatic hydrocarbons, and the one or more upgraded hydrocarbons comprise at least one of dehydrogenated hydrocarbons, dehydroaromatized hydrocarbons, and dehydrocyclized hydrocarbons.

[0198] D2. The method described in D1 also includes: contacting at least a portion of the coked catalyst with an oxidant to burn at least a portion of the coke to produce a regenerated catalyst lean in coke and combustion gas; and contacting an additional amount of hydrocarbon-containing feed with at least a portion of the regenerated catalyst to produce a re-coked catalyst and additional effluent, wherein the cycle time from contacting the hydrocarbon-containing feed with the calcined catalyst to contacting the additional amount of hydrocarbon-containing feed with the regenerated catalyst is ≤5 hours.

[0199] 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 consistent with this application and for all jurisdictions in which such incorporation is permitted.

[0200] 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 calcining a catalyst, the method comprising: subjecting a synthesized catalyst comprising Pt disposed on a support to an initial calcination comprising exposing the synthesized catalyst to a first reducing gas under reducing conditions or to a first oxidizing gas under oxidizing conditions to produce an initial calcined catalyst, wherein the synthesized catalyst comprises <0.05 wt % Pt based on the non-volatile weight of the catalyst; Optionally, subjecting the initially calcined catalyst to a cyclic calcination comprising exposing the initially calcined catalyst to a second reducing gas under reducing conditions and to a second oxidizing gas under oxidizing conditions for n cycles to produce a cyclic calcined catalyst, wherein: n is an integer, When the initial calcination uses the first reducing gas, the cyclic calcination begins with the second oxidizing gas. When the initial calcination uses the first oxidizing gas, the cyclic calcination begins with the second reducing gas. When n≥2, the composition of the second reducing gas used in each calcination cycle is the same or different, and the composition of the second oxidizing gas used in each calcination cycle is the same or different; and Optionally, the initially calcined catalyst or the cyclically calcined catalyst is subjected to a final calcination comprising exposing the initially calcined catalyst or the cyclically calcined catalyst to a third reducing gas under reducing conditions or to a third oxidizing gas under oxidizing conditions, wherein: At least one of the cyclic calcination and the final calcination is performed, When the initial calcination uses the first reducing gas, if the final calcination is performed, the final calcination uses the third oxidizing gas, or if the cyclic calcination is performed, the cyclic calcination ends with the second reducing gas. When the first oxidizing gas is used in the initial calcination, the third reducing gas is used in the final calcination, or the second oxidizing gas is used in the cyclic calcination. The reducing conditions used in the initial calcination, the optional cycle calcination, and the optional final calcination independently comprise heating the catalyst at a temperature in the range of 500° C. to 850° C. for a time period in the range of 30 seconds to 10 hours, The oxidizing conditions used in the initial calcination, the optional cycle calcination, and the optional final calcination independently comprise heating the catalyst at a temperature in the range of 350° C. to 850° C. for a time period in the range of 30 seconds to 10 hours, and At the end of the calcination cycle or at the end of the final calcination a calcined catalyst is obtained.

2. The method of claim 1, wherein the first oxidizing gas, the second oxidizing gas if used, and the third oxidizing gas if used independently contain O2, O3, CO2, steam or a mixture thereof, and wherein the first reducing gas, the second reducing gas if used, and the third reducing gas if used independently contain H2, CO, CH4, C2H6, C3H8, C2H4, C3H6, steam or a mixture thereof.

3. The method of claim 1 or claim 2, wherein: The reducing conditions used in the initial calcination, the optional cycle calcination, and the optional final calcination independently comprise heating the catalyst at a temperature in the range of 550° C. to 700° C. for a time period in the range of 5 minutes to 1 hour, and The oxidizing conditions used in the initial calcination, the optional cycle calcination, and the optional final calcination independently comprise heating the catalyst at a temperature in the range of 400°C to 600°C for a time period in the range of 5 minutes to 1 hour.

4. The method of any one of claims 1 to 3, wherein the temperature in the reducing conditions used in the initial calcination, the optional circulating calcination, and the optional final calcination is equal to or greater than the temperature in the oxidizing conditions used in the initial calcination, the optional circulating calcination, and the optional final calcination.

5. The process of any one of claims 1 to 4, wherein the sum of the time periods in reducing conditions used in the initial calcination, the optional cyclic calcination, and the optional final calcination is greater than the sum of the time periods in oxidizing conditions used in the initial calcination, the optional cyclic calcination, and the optional final calcination.

6. The method of any one of claims 1-5, wherein when the synthesized catalyst undergoes the initial calcination, the synthesized catalyst comprises one or more volatile compounds, and wherein the one or more volatile compounds comprise adsorbed CO2, adsorbed H2O, adsorbed ethanol, or a mixture thereof.

7. The method of any one of claims 1 to 6, wherein: The synthesized catalyst further comprises up to 10 wt% of a promoter disposed on the carrier, the promoter comprising Sn, Cu, Au, Ag, Ga, a combination thereof or a mixture thereof, The synthesized catalyst comprises at least 0.5 wt% of a Group 2 element, and All weight percent values ​​are based on the non-volatile weight of the catalyst.

8. The method of claim 7, wherein: The Group 2 element includes Mg, and At least a portion of the Group 2 element is in the form of MgO or a mixed metal oxide containing Mg.

9. The method of claim 7, wherein: The carrier further comprises a Group 13 element, The accelerator comprises Sn, The Group 2 element includes Mg, The Group 13 element includes Al, and The support comprises a mixed Mg / Al metal oxide.

10. The process of any one of claims 1 to 9, wherein the synthesized catalyst is in the form of particles having a size and particle density that conforms to the Geldart A definition of fluidizable solids.

11. The process of any one of claims 1 to 10, wherein when the calcined catalyst is contacted with propane under dehydrogenation conditions, the calcined catalyst is heated to ≥ A propylene selectivity of 90% results in a propylene yield of ≥ 48%.

12. The method of any one of claims 1-11, wherein the synthesized catalyst comprises 0.001 wt% to 0.045 wt% Pt based on the non-volatile weight of the catalyst.

13. The method of any one of claims 1 to 12, wherein both the cyclic calcination and the final calcination are performed.

14. The method of any one of claims 1 to 13, wherein the composition of the first oxidizing gas, the composition of the second oxidizing gas if used, and the composition of the third oxidizing gas if used, are independently kept constant or changed during the initial calcination, during the cyclic calcination, and during the final calcination, respectively.

15. The method of any one of claims 1 to 14, wherein the composition of the first reducing gas, the composition of the second reducing gas if used, and the composition of the third reducing gas if used, respectively, remain unchanged or vary independently during the initial calcination process, during the cyclic calcination process, and during the final calcination process.

16. A method for calcining a catalyst, the method comprising: subjecting synthesized catalyst particles comprising Pt disposed on a support to an initial calcination comprising exposing the catalyst particles to a first reducing gas under reducing conditions or to a first oxidizing gas under oxidizing conditions to produce initial calcined catalyst particles, wherein the synthesized catalyst particles have a size and particle density that meets the Geldart A definition of a fluidizable solid; Optionally, the initially calcined catalyst particles are subjected to a cyclic calcination comprising exposing the initially calcined catalyst particles to a second reducing gas under reducing conditions and to a second oxidizing gas under oxidizing conditions for n cycles to produce cyclic calcined catalyst particles, wherein: n is an integer, When the initial calcination uses the first reducing gas, the cyclic calcination begins with the second oxidizing gas. When the initial calcination uses the first oxidizing gas, the cyclic calcination begins with the second reducing gas. When n≥2, the composition of the second reducing gas used in each calcination cycle is the same or different, and the composition of the second oxidizing gas used in each calcination cycle is the same or different; and Optionally, the initially calcined catalyst particles or the cycled calcined catalyst particles are subjected to a final calcination comprising exposing the initially calcined catalyst particles or the cycled calcined catalyst particles to a third reducing gas under reducing conditions or to a third oxidizing gas under oxidizing conditions, wherein: At least one of the cyclic calcination and the final calcination is performed, When the initial calcination uses the first reducing gas, if the final calcination is performed, the final calcination uses the third oxidizing gas, or if the cyclic calcination is performed, the cyclic calcination ends with the second reducing gas. When the first oxidizing gas is used in the initial calcination, the third reducing gas is used in the final calcination, or the second oxidizing gas is used in the cyclic calcination. The reducing conditions used in the initial calcination, the optional cycle calcination, and the optional final calcination independently comprise heating the catalyst particles at a temperature in the range of 500° C. to 850° C. for a time period in the range of 30 seconds to 10 hours, The oxidizing conditions used in the initial calcination, the optional cycle calcination, and the optional final calcination independently comprise heating the catalyst particles at a temperature in the range of 350° C. to 850° C. for a time period in the range of 30 seconds to 10 hours, and At the end of the calcination cycle or at the end of the final calcination, calcined catalyst particles are obtained.

17. The method of claim 16, wherein the first oxidizing gas, the second oxidizing gas if used, and the third oxidizing gas if used independently contain O2, O3, CO2, steam or a mixture thereof, and wherein the first reducing gas, the second reducing gas if used, and the third reducing gas if used independently contain H2, CO, CH4, C2H6, C3H8, C2H4, C3H6, steam or a mixture thereof.

18. The method of claim 16 or claim 17, wherein: The reducing conditions used in the initial calcination, the optional cycle calcination, and the optional final calcination independently comprise heating the catalyst particles at a temperature in the range of 550° C. to 700° C. for a time period in the range of 5 minutes to 1 hour, and The oxidizing conditions used in the initial calcination, the optional cycle calcination, and the optional final calcination independently comprise heating the catalyst particles at a temperature in the range of 400°C to 600°C for a time period in the range of 5 minutes to 1 hour.

19. The method of any one of claims 16 to 18, wherein the temperature in the reducing conditions used in the initial calcination, the optional circulating calcination, and the optional final calcination is equal to or greater than the temperature in the oxidizing conditions used in the initial calcination, the optional circulating calcination, and the optional final calcination.

20. The process of any one of claims 16 to 19, wherein the sum of the time periods in reducing conditions used in the initial calcination, the optional cyclic calcinations, and the optional final calcination is greater than the sum of the time periods in oxidizing conditions used in the initial calcination, the optional cyclic calcinations, and the optional final calcination.

21. The method of any one of claims 16-20, wherein the synthesized catalyst particles comprise one or more volatile compounds when the synthesized catalyst particles undergo the initial calcination, and wherein the one or more volatile compounds comprise adsorbed CO2, adsorbed H2O, adsorbed ethanol, or a mixture thereof.

22. The method of any one of claims 16-21, wherein: The synthesized catalyst particles further comprise up to 10 wt % of a promoter disposed on the support, the promoter comprising Sn, Cu, Au, Ag, Ga, a combination thereof or a mixture thereof, The synthesized catalyst particles contain at least 0.5 wt% of a Group 2 element, and All weight percent values ​​are based on the non-volatile weight of the catalyst.

23. The method of claim 22, wherein: The Group 2 element includes Mg, and At least a portion of the Group 2 element is in the form of MgO or a mixed metal oxide containing Mg.

24. The method of claim 22, wherein: The carrier further comprises a Group 13 element, The accelerator comprises Sn, The Group 2 element includes Mg, The Group 13 element includes Al, and The support comprises a mixed Mg / Al metal oxide.

25. The process of any one of claims 16-24, wherein the calcined catalyst particles produce a propylene yield of ≥ 48% with a propylene selectivity of ≥ 90% when the calcined catalyst particles are contacted with propane under dehydrogenation conditions.

26. The method of any one of claims 16-25, wherein the synthesized catalyst particles comprise 0.001 wt% to 6 wt% Pt based on the non-volatile weight of the catalyst.

27. The method of any one of claims 16-26, wherein both the cyclic calcination and the final calcination are performed.

28. The method of any one of claims 16 to 27, wherein the composition of the first oxidizing gas, the composition of the second oxidizing gas if used, and the composition of the third oxidizing gas if used, are independently kept constant or varied during the initial calcination, during the cyclic calcination, and during the final calcination, respectively.

29. The method of any one of claims 16 to 28, wherein the composition of the first reducing gas, the composition of the second reducing gas if used, and the composition of the third reducing gas if used, are independently kept constant or changed during the initial calcination, during the cyclic calcination, and during the final calcination, respectively.

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