Method for firing a catalyst

Abstract

A method for firing a catalyst. The method may include a step of performing a first firing on a synthesized catalyst containing Pt disposed on a carrier, the first firing including exposing the catalyst to a first reducing gas or a first oxidizing gas to produce a first fired catalyst. The method may include a step of performing a cycle firing on the first fired catalyst, the cycle firing including exposing the first fired catalyst to a second reducing gas and a second oxidizing gas to produce a cycle fired catalyst. The method may include a step of performing a final firing on the first fired catalyst or the cycle fired catalyst, the final firing including exposing the first fired catalyst or the cycle fired catalyst to a third reducing gas or a third oxidizing gas. At least one of the cycle firing and the final firing can be performed. The fired catalyst can be obtained at the end of the cycle firing or at the end of the final firing.

Description

Technical Field

[0001] Cross - Reference to Related Applications This application claims priority and the benefit thereof to U.S. Provisional Application No. 63 / 357,729, filed on July 1, 2022, the disclosure of which is hereby incorporated by reference in its entirety. The present disclosure relates to a method of calcining a synthesized catalyst. More particularly, the present disclosure relates to calcining a synthesized catalyst comprising Pt disposed on a support to produce a calcined catalyst.

Background Art

[0002] The catalytic reforming or dehydrogenation, dehydrogenative aromatization, and / or dehydrogenative cyclization of alkanes and / or alkyl aromatic hydrocarbons are industrially important chemical conversion processes that are endothermic and limited by equilibrium. Alkanes, for example, C1 - C 12 The reforming or dehydrogenation, dehydrogenative aromatization, and / or dehydrogenative cyclization of alkanes and / or alkyl aromatics, such as ethylbenzene, can be carried out by various different catalysts, such as 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.

[0003] After synthesis, the synthesized catalyst usually needs to be pretreated or conditioned before it can be used in a commercial reactor. One of the conditioning processes involves equilibration at room temperature, typically using a flowing or stagnant gas, to enable any liquid precursors to disperse within the catalyst. Another conditioning process involves drying, typically at a temperature below calcination, using a flowing gas or vacuum, to allow most of the volatile components to escape from the catalyst. Another conditioning process involves calcination, typically at a higher temperature than drying in a flowing gas or vacuum, to convert the precursors in the catalyst to active species or species that are structurally / chemically closer to the active species. These conditioning processes improve the performance of the as-synthesized catalyst, but such improvements are not as desirable as hoped. Therefore, there is a need for an improved process for conditioning the synthesized catalyst. The present disclosure meets this need and other needs. SUMMARY OF THE INVENTION

[0004] A method for firing a synthesized catalyst is provided. In some embodiments, the method for firing a catalyst may include a step of subjecting a synthesized catalyst containing Pt disposed on a support to a first firing, wherein the first firing includes exposing the synthesized catalyst to a first reducing gas under reducing conditions or a first oxidizing gas under oxidizing conditions to produce a first fired catalyst. The synthesized catalyst can contain <0.05 wt% Pt based on the mass of the non-volatile matter of the catalyst. The method may include a step of subjecting the first fired catalyst to a cyclic firing, wherein the cyclic firing includes exposing the first fired catalyst to a second reducing gas under reducing conditions and a second oxidizing gas under oxidizing conditions for n cycles to produce a cyclically fired catalyst. The variable n may be an integer. The cyclic firing can start with the second oxidizing gas when the first firing uses the first reducing gas. The cyclic firing can start with the second reducing gas when the first firing uses the first oxidizing gas. When n ≥ 2, the composition of the second reducing gas used in each cyclic firing may be the same or different, and the composition of the second oxidizing gas used in each cyclic firing may be the same or different. The method may include a step of subjecting the first fired catalyst or the cyclically fired catalyst to a final firing, wherein the final firing can include exposing the first fired catalyst or the cyclically fired catalyst to a third reducing gas under reducing conditions or a third oxidizing gas under oxidizing conditions. At least one of the cyclic firing and the final firing can be performed. When the final firing is performed, the third oxidizing gas can be used when the first firing uses the first reducing gas or when the cyclic firing ends with the second reducing gas. When the final firing is performed, the third reducing gas can be used when the first firing uses the first oxidizing gas or when the cyclic firing ends with the second oxidizing gas. The reducing conditions used for the first firing, optional cyclic firing, and optional final firing can independently include heating the catalyst at a temperature in the range of 500 °C to 850 °C for a time in the range of 30 seconds to 10 hours.The oxidation conditions used for the initial firing, optional cycle firing, and optional final firing can independently include heating the catalyst for a time in the range of 30 seconds to 10 hours and at a temperature in the range of 350°C to 850°C. The fired catalyst can be obtained at the end of the cycle firing or at the end of the final firing.

[0005] In one embodiment, a method of firing a catalyst includes the step of subjecting synthesized catalyst particles, which can contain Pt disposed on a support, to a first firing, where the first firing can include exposing the catalyst particles to a first reducing gas under reducing conditions or a first oxidizing gas under oxidizing conditions to produce first fired catalyst particles. The synthesized catalyst particles can have a size and particle density that conform to the definition of Geldart A of a fluidizable solid. The method can include the step of subjecting the first fired catalyst particles to a cyclic firing, where the cyclic firing can include exposing the first fired catalyst particles to a second reducing gas under reducing conditions and a second oxidizing gas under oxidizing conditions for n cycles to produce cyclic fired catalyst particles. The variable n can be an integer. The cyclic firing can start with the second oxidizing gas when the first firing uses the first reducing gas. The cyclic firing can start with the second reducing gas when the first firing uses the first oxidizing gas. When n ≥ 2, the composition of the second reducing gas used for each cyclic firing can be the same or different, and the composition of the second oxidizing gas used for each cyclic firing can be the same or different. The method can include the step of subjecting the first fired catalyst particles or the cyclic fired catalyst particles to a final firing, where the final firing can include exposing the first fired catalyst particles or the cyclic fired catalyst particles to a third reducing gas under reducing conditions or a third oxidizing gas under oxidizing conditions. At least one of the cyclic firing and the final firing can be performed. When the final firing is performed, the third oxidizing gas can be used when the first firing uses the first reducing gas or when the cyclic firing ends with the second reducing gas. When the final firing is performed, the third reducing gas can be used when the first firing uses the first oxidizing gas or when the cyclic firing ends with the second oxidizing gas. The reducing conditions used for the first firing, optional cyclic firing, and optional final firing can independently include heating the catalyst particles at a temperature in the range of 500 °C to 850 °C for a time in the range of 30 seconds to 10 hours.The oxidation conditions used for the initial firing, optional cycle firing, and optional final firing can independently include heating the catalyst particles for a time in the range of 30 seconds to 10 hours and at a temperature in the range of 350°C to 850°C. The fired catalyst particles can be obtained at the end of the cycle firing or at the end of the final firing.

Mode for Carrying Out the Invention

[0006] Various specific embodiments, forms, and examples of the present invention will be described hereinafter, including the preferred embodiments and definitions employed herein, for the purpose of understanding the claimed invention. The following detailed description presents specific preferred embodiments, but those skilled in the art will understand that these embodiments are merely illustrative and that the present invention may be practiced in other ways. For the purpose of determining infringement, the scope of the present invention refers to any one or more of the appended claims, including equivalents and elements or limitations equivalent to those recited. Any reference to "the present invention" may refer to one or more of the inventions defined by the claims, but not necessarily all of them.

[0007] In the present disclosure, a method is described as including at least one "step". Each step is to be understood as an action or operation that may be performed one or more times, continuously or discontinuously, in the method. Unless otherwise specified or the context clearly indicates otherwise, multiple steps in a method may be performed sequentially in the order in which they are listed, with one or more other steps overlapping or not overlapping, or, in some cases, in any other order. Further, one or more steps, or even all steps, may be performed simultaneously with respect to the same batch or different batches of material. For example, in a continuous process, the first step in the method is performed with respect to the raw material just supplied at the start of the method, while the second step may be performed simultaneously with respect to the intermediate material resulting from the treatment of the raw material previously supplied to the method in the first step. Preferably, these steps are performed in the order described.

[0008] Unless otherwise indicated, all numbers expressing quantities in this disclosure should be understood to be modified in all instances by the term "about." It should also be understood that the exact numerical values used in the specification and claims also 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 includes a certain level of error due to the limitations of the techniques and / or apparatus used to obtain the measured values.

[0009] 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 ranges including any combination of two values, e.g., any combination of any lower value and any higher value, any combination of two lower values, and / or any combination of two higher values, are contemplated unless otherwise indicated. As used herein, the indefinite articles "a" or "an" mean "at least one" unless specifically designated to the contrary or the context clearly dictates 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 there is a contrary designation or the context clearly indicates that only one reactor or conversion zone is used.

[0010] The term "hydrocarbon" means (i) any compound consisting of hydrogen atoms and carbon atoms, or (ii) any mixture of two or more such compounds in (i). The term "Cn hydrocarbon", where n is a positive integer, means (i) any hydrocarbon compound containing a total of n carbon atoms in its molecule, or (ii) any mixture of two or more such hydrocarbon compounds in (i). Thus, C2 hydrocarbons may be ethane, ethylene, acetylene, or any mixture in any proportion of at least two of these compounds. "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" may be any one of ethane, ethylene, acetylene, propane, propene, propyne, propadiene, cyclopropane, and any mixture in any proportion of two or more of these compounds between two components and between three or more components. "Saturated C2-C3 hydrocarbons" may be ethane, propane, cyclopropane, or any mixture of two or more of them in any proportion. The term "Cn+ hydrocarbon" 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 in (i). The term "Cn- hydrocarbon" 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 in (i). The term "Cm hydrocarbon stream" means a hydrocarbon stream consisting essentially of Cm hydrocarbons. The term "Cm-Cn hydrocarbon stream" means a hydrocarbon stream consisting essentially of Cm-Cn hydrocarbons.

[0011] For the purposes of this disclosure, the nomenclature of the elements is as in Hawley’s Condensed Chemical Dictionary, 16 thIt conforms to the version of the periodic table (new notation) presented in Appendix V of John Wiley & Sons, Inc., (2016), Ed. For example, Group 2 elements include Mg, Group 8 elements include Fe, Group 9 elements include Co, Group 10 elements include Ni, and Group 13 elements include Al. The term "metalloid", as used herein, refers to the following elements: B, Si, Ge, As, Sb, Te, and At. In the present disclosure, when a given element is indicated as present, the element can exist in elemental form or, unless otherwise specified or clearly indicated by context, in any of its chemical compounds.

[0012] The term "alkane" means a saturated hydrocarbon. The term "cyclic alkane" means a saturated hydrocarbon that contains a cyclic carbon ring within its molecular structure. Alkanes can be straight-chain, branched, or cyclic. The term "aromatic" should be understood to include alkyl-substituted as well as unsubstituted, mononuclear and polynuclear compounds, in accordance with what is recognized in the art. The term "rich in", when used in phrases such as "X-rich" or "rich in X", with respect to a device, e.g., an effluent stream obtained from a conversion zone, means that the stream contains the substance X at a higher concentration than in the feed material supplied to the same device from which this stream is derived. The term "lean in", when used in phrases such as "X-lean" or "lean in X", with respect to a device, e.g., an effluent stream obtained from a conversion zone, means that the stream contains the substance X at a lower concentration than in the feed material supplied to the same device from which this stream is derived.

[0013] The term "mixed metal oxide" is a composition containing oxygen atoms and at least two different metal atoms mixed at the atomic scale. For example, "mixed Mg / Al metal oxide" has O, Mg, and Al atoms mixed at the atomic scale and a general chemical formula [Number] It is substantially the same as, or coincides with, a composition obtained by calcining a Mg / Al hydrotalcite having (A is a counter anion of negative charge n, x is in the range of >0 to <1, and m is ≧0). A substance formed by mixing nm-sized MgO particles and nm-sized Al2O3 particles together is not a mixed metal oxide because Mg atoms and Al atoms are not mixed at the atomic scale but rather at the nm scale. The terms "calcination" and "calcining" refer to heating a substance, such as a synthesized catalyst or support, to a temperature of 350 °C or higher under any atmosphere, such as an oxidizing atmosphere, an inert atmosphere, or a reducing atmosphere. The term "calcined" refers to a substance, such as a synthesized catalyst or support, that has been subjected to the calcination / calcining step.

[0014] The term "selectivity" refers to the formation of a specific compound (based on the number of moles of carbon) in a catalytic reaction. As an example, the statement "The alkane hydrocarbon conversion reaction has 100% selectivity to olefin hydrocarbons" means that 100% of the alkane hydrocarbons (based on the number of moles of carbon) converted in the reaction are converted to olefin hydrocarbons. When used in relation to a specified reactant, the term "conversion rate" means the amount of the reactant consumed in the reaction. For example, if the specified reactant is propane, a 100% conversion rate means that 100% of the propane is consumed in the reaction. In another example, if the specified reactant is propane and 1 mole of propane is converted to 1 mole of methane and 1 mole of ethylene, the selectivity to methane is 33.3% and the selectivity to ethylene is 66.7%. The yield (based on the number of moles of carbon) is the product of the conversion rate and the selectivity.

[0015] As used herein, "sccm" means standard cubic centimeters per minute, which is the cubic centimeters of gas at standard temperature and pressure passing a given point within one minute (cm 3) It is a flow measurement value used to indicate a number. Standard temperature and pressure (STP) refer to a temperature of 273.15 K (0 °C) and an absolute pressure of 10 5 Pa (100 kPa, 1 bar). In the present disclosure, "A, B... or a combination thereof" means "A, B..., or any combination of two or more of A, B...", and "A, B..., or a mixture thereof" means "A, B..., or any mixture of two or more of A, B...".

[0016] Method for firing a catalyst When upgrading one or more hydrocarbons, for example, when dehydrogenating an alkane to produce an olefin, a synthesized catalyst used for this purpose, if a firing process is first applied to produce a fired catalyst, when contacted with one or more alkanes under dehydrogenation conditions, surprisingly and unexpectedly, it has been found that it can show significantly improved performance compared to a synthesized catalyst that has not been subjected to the firing process. In some embodiments, the synthesized catalyst can include Pt disposed on a support. In some embodiments, the synthesized catalyst can contain <0.05 wt%, <0.045 wt%, <0.04 wt%, <0.035 wt% or <0.03 wt% of Pt based on the mass of the non-volatile matter of the catalyst. In other embodiments, the synthesized catalyst can be in the form of catalyst particles having a size and particle density that conform to the Geldart A definition of a fluidizable solid, and can contain 0.001 wt% to 6 wt% of Pt based on the mass of the non-volatile matter of the catalyst.

[0017] As used herein, the term "synthesized catalyst" refers to a catalyst containing Pt disposed on a support and not subjected to a temperature of 350 °C or higher. However, the support may be subjected to a temperature exceeding 350 °C before adding Pt, but once Pt is disposed on the support, it should be understood that this synthesized catalyst has not been heated to a temperature of 350 °C or higher until a calcination process is performed. It should also be understood that the "synthesized catalyst" may be subjected to equilibration and / or drying as long as the "synthesized catalyst" has not been heated to a temperature of 350 °C or higher.

[0018] Since the synthesized catalyst has not been subjected to a temperature of 350 °C or higher, the synthesized catalyst can contain one or more volatile compounds adsorbed on its surface and / or one or more compounds that can form and desorb volatile compounds at a higher temperature, such as when the synthesized catalyst is heated to a temperature of 350 °C or higher under another atmosphere such as an oxidative atmosphere, a reducing atmosphere, or an inert atmosphere. As used herein, the term "mass of the non-volatile matter of the catalyst" refers to the residual mass of the synthesized catalyst or the synthesized catalyst after being conditioned in some way after being heated to a temperature of 900 °C under flowing air. The mass of the non-volatile matter of the catalyst can be measured by thermogravimetric analysis. A typical thermogravimetric analysis procedure is as follows: Place 10 - 20 mg of the solid to be analyzed on a platinum pan of a TGA550 manufactured by TA Instruments. Monitor and record the mass of this solid with a microbalance connected to the platinum pan. The temperature of the platinum pan and the solid can be ramped from 25 °C to 900 °C at a gradient rate of 5 °C / min under a constant air flow. Once the solid reaches a temperature of 900 °C, the residual mass of the solid becomes the "mass of the non-volatile matter of the solid".

[0019] Exemplary volatile compounds include, but are not limited to, CO, H2, CO2, H2O, SO3, SO2, HCl, H2S, CH4, one or more alcohols, acetone, chloroform, methylene chloride, dimethylformamide, dimethyl sulfoxide, glycerin, ethyl acetate, or any mixture thereof, or may contain these. In some embodiments, when the synthesized catalyst contains CO2 and / or H2O, such volatile compounds can be adsorbed from the ambient environment. In some embodiments, when the synthesized catalyst contains CO2, H2O, one or more alcohols, acetone, chloroform, methylene chloride, dimethylformamide, dimethyl sulfoxide, glycerin, ethyl acetate, or any mixture thereof, such volatile compounds can be adsorbed thereon during the preparation of the synthesized catalyst. For example, the method of making the synthesized catalyst can include forming a slurry consisting of a support and / or one or more compounds from which the support can be derived, one or more Pt-containing compounds, and optionally one or more additional compounds, such as a promoter-containing compound, where the liquid medium can include water, one or more alcohols, and / or other liquid media. In some embodiments, when the metal-containing compound added to the support contains chlorides, such as chloroplatinic acid in the case of platinum or tin(IV) chloride in the case of tin, the chlorides may react with H2O molecules to form HCl, and HCl desorbs from the synthesized catalyst when the synthesized catalyst is heated to a temperature above 350°C. In some embodiments, when the metal-containing compound added to the support contains sulfates, such as tin(II) sulfate in the case of tin, the sulfates may decompose to form SO2, and SO2 desorbs from the synthesized catalyst when the synthesized catalyst is heated to a temperature above 350°C.

[0020] A method of firing a synthesized catalyst may include a step of subjecting the synthesized catalyst to a first firing, where the first firing can include exposing the synthesized catalyst to a first reducing gas under reducing conditions or a first oxidizing gas under oxidizing conditions to produce a first fired catalyst. In some embodiments, when subjecting the synthesized catalyst to the first firing, the synthesized catalyst can include one or more adsorbed volatile compounds. The first fired catalyst can have a lesser amount of adsorbed volatile compounds compared to the synthesized catalyst.

[0021] The method of firing the catalyst can also include at least one of two additional steps, namely cycle firing and / or final firing. At least one of cycle firing and final firing can be performed. In some embodiments, the first fired catalyst can be subjected to cycle firing in n cycles, where n can be an integer. In some embodiments, n can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or more. In other embodiments, the first fired catalyst can be subjected to a final firing. In still other embodiments, the first fired catalyst can be subjected to cycle firing followed by final firing. The fired catalyst can be obtained at the end of cycle firing or at the end of final firing. Optional cycle firing can include exposing the first fired catalyst to a second reducing gas under reducing conditions and a second oxidizing gas under oxidizing conditions for n cycles. The variable n is an integer. Cycle firing can start with the second oxidizing gas when the first firing uses the first reducing gas, or cycle firing can start with the second reducing gas when the first firing uses the first oxidizing gas. When n ≥ 2, the composition of the second reducing gas used in each cycle firing can be the same or different, and the composition of the second oxidizing gas used in each cycle firing can be the same or different.

[0022] In other embodiments, the method of firing the catalyst may include the step of optionally subjecting the initially fired catalyst to a final firing, where the optional final firing can include exposing the initially fired catalyst or the cyclically fired catalyst to a third reducing gas under reducing conditions or to a third oxidizing gas under oxidizing conditions. When the final firing is carried out, when the first firing uses a first reducing gas, or when the cyclic firing ends with a second reducing gas, a third oxidizing gas can be used. When the final firing is carried out, when the first firing uses a first oxidizing gas, or when the cyclic firing ends with a second oxidizing gas, a third reducing gas can be used.

[0023] In some embodiments, the temperature under reducing conditions used for the initial firing, optional cyclic firing, and optional final firing may be equal to or higher than the temperature under oxidizing conditions used for the initial firing, optional cyclic firing, and optional final firing. In some embodiments, the total time under reducing conditions used for the initial firing, optional cyclic firing, and optional final firing may be longer than the total time under oxidizing conditions used for the initial firing, optional cyclic firing, and optional final firing.

[0024] The reduction conditions used for the initial firing, optional cycle firing, and optional final firing can independently include heating the catalyst at a temperature in the range 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 reduction conditions used for the initial firing, optional cycle firing, and optional final firing can independently include heating the catalyst for a time in the range 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 reduction conditions used for the initial firing, optional cycle firing, and optional final firing can independently include heating the catalyst under an absolute pressure in the range from 30 kPa, 60 kPa, or 90 kPa to 150 kPa, 300 kPa, or 600 kPa. It has been found by microscopic analysis that incorporating a reduction firing step into the method of firing the synthesized catalyst described herein can improve the distribution of the promoter (Sn) on the support when the catalyst is synthesized using the promoter.

[0025] It should be understood that the composition, temperature, and / or pressure of the reducing gas can vary during any given firing step, i.e., the initial firing, cycle firing, and final firing. For example, if the initial firing starts with a first reducing gas, this composition can start with a reducing gas containing about 10 vol% H2 and can be switched to a reducing gas containing 100 vol% H2. Similarly, the initial firing can start at a temperature of 550 °C for a first time and can be heated up to a temperature of 575 °C during a second time of the initial firing step. It should be understood that if an optional cycle firing is used and n ≥ 2, the composition, temperature, time, and / or pressure of the second reducing gas used between each of the reduction conditions in the cycle firing can be the same or different with respect to each other and can also vary during any given cycle firing step.

[0026] The oxidation conditions used for the initial firing, optional cycle firing, and optional final firing can independently include heating the catalyst at a temperature in the range from 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 oxidation conditions used for the initial firing, optional cycle firing, and optional final firing can independently include heating the catalyst for a time in the range 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 oxidation conditions used for the initial firing, optional cycle firing, and optional final firing can independently include heating the catalyst under an absolute pressure in the range from 30 kPa, 60 kPa or 90 kPa to 150 kPa, 300 kPa or 600 kPa.

[0027] It should be understood that the composition, temperature and / or pressure of the oxidizing gas can vary during any given firing step, namely the initial firing, cycle firing and final firing. For example, if the initial firing starts with a first oxidizing gas, this composition can start with an oxidizing gas containing 10 vol% O2 and can be switched to a reducing gas containing 21 vol% O2, such as air. Similarly, the initial firing can start at a temperature of 450 °C for a first time and can be heated up to a temperature of 475 °C during a second time of the initial firing step. If an optional cycle firing is used and n ≥ 2, the composition, temperature, time and / or pressure of the second oxidizing gas used during each of the oxidation conditions in the cycle firing can be the same as or different from each other and can also vary during any given cycle firing step.

[0028] The first reducing gas, the second reducing gas, and the third reducing gas may independently be, but are not limited to, H2, CO, CH4, C2H6, C3H8, C2H4, C3H6, water vapor, or any mixture thereof, or may contain these. In some embodiments, the first, second, and third reducing gases may independently be mixed with one or more inert gases. Suitable inert gases may be, but are not limited to, He, Ne, Ar, N2, CO2, CH4, or any mixture thereof, or may contain these. In some embodiments, the composition of the first, second, and third reducing gases can be changed during the first firing, during the reduction conditions in the cycle firing, and during the reduction conditions in the final firing, or otherwise can vary. For example, the first firing can start with a reducing gas containing 100% H2 and can be changed to a reducing gas containing 10% H2 or any other amount of H2 during the first firing. In other embodiments, the composition of the first, second, and third reducing gases can be maintained constant during the first firing, during the reduction conditions in the cycle firing, and during the reduction conditions in the final firing.

[0029] The first oxidizing gas, the second oxidizing gas, and the third oxidizing gas may independently be, but are not limited to, O2, O3, CO2, water vapor, or any mixture thereof, or may contain these. In some embodiments, the first, second, and third oxidizing gases may independently be mixed with one or more inert gases. Suitable inert gases may be, but are not limited to, He, Ne, Ar, N2, CO2, CH4, or any mixture thereof, or may contain these. In some embodiments, the composition of the first, second, and third oxidizing gases can be changed during the first firing, during the oxidation conditions in the cycle firing, and during the oxidation conditions in the final firing. For example, the first firing can start with a reducing gas containing 100% O2 and can be changed to a reducing gas containing about 21% O2, such as air, or any other amount of O2 during the first firing. In other embodiments, the composition of the first, second, and third oxidizing gases can be maintained constant during the first firing, during the oxidation conditions in the cycle firing, and during the oxidation conditions in the final firing. Firing on an industrial scale typically uses a box furnace, a belt firing machine, or a rotary firing machine. The firing may also be assisted by microwave / ultrasonic simultaneous treatment.

[0030] Synthesized catalyst In some embodiments, the synthesized catalyst may contain 0.001 wt%, 0.002 wt%, 0.003 wt%, 0.004 wt%, 0.005 wt%, 0.006 wt%, 0.007 wt%, 0.008 wt%, 0.009 wt%, 0.01 wt%, 0.015 wt%, 0.02 wt%, 0.025 wt%, 0.03 wt%, 0.035 wt%, 0.04 wt%, 0.045 wt%, 0.05 wt%, 0.055 wt%, 0.06 wt%, 0.065 wt%, 0.07 wt%, 0.075 wt%, 0.08 wt%, 0.085 wt%, 0.09 wt%, 0.095 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt% or 1 wt% - 2 wt%, 3 wt%, 4 wt%, 5 wt% or 6 wt% of Pt disposed on the carrier with respect to the mass of the non-volatile matter of the catalyst. In other embodiments, the synthesized catalyst may contain ≦5.5 wt%, ≦4.5 wt%, ≦3.5 wt%, ≦2.5 wt%, ≦1.5 wt%, ≦1 wt%, ≦0.9 wt%, ≦0.8 wt%, ≦0.7 wt%, ≦0.6 wt%, ≦0.5 wt%, ≦0.4 wt%, ≦0.3 wt%, ≦0.2 wt%, ≦0.15 wt%, ≦0.1 wt%, ≦0.09 wt%, ≦0.08 wt%, ≦0.07 wt%, ≦0.06 wt%, ≦0.05 wt%, ≦0.045 wt%, ≦0.04 wt%, ≦0.035 wt%, ≦0.03 wt%, ≦0.025 wt%, ≦0.02 wt%, ≦0.015 wt%, ≦0.01 wt%, ≦0.009 wt%, ≦0.008 wt%, ≦0.007 wt%, ≦0.006 wt%, ≦0.005 wt%, ≦0.004 wt%, ≦0.003 wt%, ≦0.002 or ≦0.001 wt% of Pt disposed on the carrier with respect to the mass of the non-volatile matter of the catalyst.In some embodiments, the synthesized catalyst can contain Pt disposed on the support in an amount of >0.0001 wt%, >0.0005 wt%, >0.001 wt%, >0.003 wt%, >0.005 wt%, >0.007 wt%, >0.009 wt%, >0.01 wt%, >0.02 wt%, >0.04 wt%, >0.06 wt%, >0.08 wt%, >0.1 wt%, >0.13 wt%, >0.15 wt%, >0.17 wt%, >0.2 wt%, >0.2 wt%, >0.23 wt%, >0.25 wt%, >0.27 wt% or >0.3 wt% and <0.5 wt%, <1 wt%, <2 wt%, <3 wt%, <4 wt%, <5 wt% or <6 wt% based on the mass of the non-volatile matter of the catalyst.

[0031] In some embodiments, the synthesized catalyst may also include Ni, Pd, or a combination thereof, or a mixture thereof, disposed on a support. When Ni, Pd, or a combination thereof, or a mixture thereof is also disposed on the support, the synthesized catalyst may contain, based on the mass of the non-volatile matter of the catalyst, a total amount of Pt and any Ni and / or any Pd disposed on the support 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%, 0.055 wt%, 0.06 wt%, 0.065 wt%, 0.07 wt%, 0.075 wt%, 0.08 wt%, 0.085 wt%, 0.09 wt%, 0.095 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt% or 1 wt% to 2 wt%, 3 wt%, 4 wt%, 5 wt% or 6 wt%. In some embodiments, the active component of the synthesized catalyst capable of performing one or more of the reforming or dehydrogenation, dehydrogenative aromatization, and dehydrogenative cyclization of the hydrocarbon-containing feed can include Pt or Pt and Ni and / or Pd. It should be understood that the active component may not be active or may not be as active as the calcined catalyst obtained at the end of the cycle calcination or the end of the final calcination. It should also be understood that Pt, and when present, Ni and / or Pd can exist in the synthesized catalyst in elemental form and / or in the form of a compound containing Pt, and when present, a compound containing Ni, and / or a compound containing Pd.

[0032] In some embodiments, the synthesized catalyst can contain a promoter disposed on the support in an amount of up to 10 wt% relative to the mass of the non-volatile matter of the catalyst. The promoter may be, but is not limited to, Sn, Cu, Au, Ag, Ga, or combinations thereof, or mixtures thereof, or may include these. In some embodiments, the promoter can bind to Pt and / or, if present, Ni and / or Pd. For example, the promoter and Pt disposed on the support can form clusters of Pt-promoter that can be dispersed on the support. The promoter can improve the selectivity / activity / lifetime of the catalyst with respect to a given higher hydrocarbon. In some embodiments, the promoter can improve the propylene selectivity of the catalyst when the hydrocarbon-containing feed contains propane. The synthesized catalyst can contain the promoter in an amount from 0.01 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt% or 1 wt% to 3 wt%, 5 wt%, 7 wt% or 10 wt% relative to the mass of the non-volatile matter of the catalyst. It should be understood that the promoter may not be bound to Pt and / or, if present, Ni and / or Pd, or may not be very strongly bound to these, compared to the calcined catalyst obtained at the end of the cycle calcination or the end of the final calcination. It should also be understood that the promoter can be present in elemental form in the synthesized catalyst and / or can be present in the form of compounds containing the promoter.

[0033] In some embodiments, the synthesized catalyst may contain one or more alkali metal elements disposed on the support in an amount of up to 5% by weight, based on the weight of the non-volatile matter of the catalyst. The alkali metal element, when present, is not limited to, but may be, for example, Li, Na, K, Rb, Cs, or a combination thereof, or a mixture thereof, or may include these. In at least some embodiments, the alkali metal element can be or can include K and / or Cs. In some embodiments, the alkali metal element, when present, can improve the selectivity of the catalyst particles for a given higher hydrocarbon. The synthesized catalyst can contain the alkali metal element in an amount from 0.01% by weight, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4% by weight, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight or 1% by weight to 2% by weight, 3% by weight, 4% by weight or 5% by weight, based on the weight of the non-volatile matter of the catalyst. It should be understood that the alkali metal element, when present, can be in elemental form and / or in the form of a compound containing the alkali metal element.

[0034] The support is not limited to, but may be, for example, one or more Group 2 elements, or a combination thereof, or a mixture thereof, or may include these. In some embodiments, the Group 2 element can be present in elemental form. In other embodiments, the Group 2 element can be present in the form of a compound. For example, the Group 2 element can be present as an oxide, phosphate, halide, eitelite, 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 containing the Group 2 element can be present in different forms. For example, the first compound may be an oxide, and the second compound may be an aluminate, in which case the first compound and the second compound contain the same or different Group 2 elements from each other.

[0035] The synthesized catalyst can contain Group 2 elements in an amount of ≥0.5 wt%, ≥1 wt%, ≥2 wt%, ≥3 wt%, ≥4 wt%, ≥5 wt%, ≥6 wt%, ≥7 wt%, ≥8 wt%, ≥9 wt%, ≥10 wt%, ≥11 wt%, ≥12 wt%, ≥13 wt%, ≥14 wt%, ≥15 wt%, ≥16 wt%, ≥17 wt%, ≥18 wt%, ≥19 wt%, ≥20 wt%, ≥21 wt%, ≥22 wt%, ≥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% based on the mass of the non-volatile matter of the catalyst. In some embodiments, the synthesized catalyst contains Group 2 elements in the range of 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 mass of the non-volatile matter of the catalyst. In some embodiments, the molar ratio of the Group 2 element to the present Pt, or Pt and any Ni and / or Pd, can be in the range of 0.24, 0.5, 1, 10, 50, 100, 300, 450, 600, 800, 1,000, 1,200, 1,500, 1,700 or 2,000 to 3,000, 3,500, 4,000, 4,500, 5,000, 5,500, 6,000, 6,500, 7,000, 7,500, 8,000, 8,500, 9,000, 9,500, 10,000, 15,000, 20,000, 25,000, 30,000, 35,000, 40,000, 45,000, 50,000, 55,000, 60,000, 65,000, 70,000, 75,000, 80,000, 85,000, 90,000, 95,000, 100,000, 200,000, 300,000, 400,000, 500,000, 600,000, 700,000, 800,000 or 900,000.

[0036] In some embodiments, the carrier can contain Group 2 elements and Al and can be in the form of an Al metal oxide having O, Mg, and Al atoms mixed on a mixed Group 2 element / atomic scale. In some embodiments, the carrier can be, or can contain, Group 2 elements and Al in the form of an oxide of a Group 2 element or one or more oxides that can be mixed on an nm scale and in the form of Al2O3. In some embodiments, the carrier can be, or can contain, oxides of Group 2 elements, such as MgO and Al2O3, mixed on an nm scale.

[0037] In some embodiments, the carrier can be, or can contain, a first amount of Group 2 elements and Al in the form of a mixed Group 2 element / Al metal oxide and a second amount of Group 2 elements in the form of an oxide of a Group 2 element. In such embodiments, the mixed Group 2 element / Al metal oxide and the oxide of the Group 2 element can be mixed on an nm scale, and the Group 2 elements and Al in the mixed Group 2 element / Al metal oxide can be mixed on an atomic scale. In other embodiments, the carrier can be, or can contain, a first amount of Group 2 elements and a first amount of Al in the form of a mixed Group 2 element / Al metal oxide, a second amount of Group 2 elements and a second amount of Al in the form of an oxide of a Group 2 element, and a second amount of Al in the form of Al2O3. In such embodiments, the mixed Group 2 element / Al metal oxide, the oxide of the Group 2 element, and Al2O3 can be mixed on an nm scale, and the Group 2 elements and Al in the mixed Group 2 element / Al metal oxide can be mixed on an atomic scale.

[0038] In some embodiments, when the carrier contains Group 2 elements and Al, the mass ratio of Group 2 elements to Al in the carrier may range from 0.001, 0.005, 0.01, 0.05, 0.1, 0.15, 0.2, 0.3, 0.5, 0.7 or 1 to 3, 6, 12.5, 25, 50, 75, 100, 200, 300, 400, 500, 600, 700, 800, 900 or 1,000. In some embodiments, when the carrier contains Al, the synthesized catalyst may contain 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 mass of the non-volatile matter of the catalyst.

[0039] In some embodiments, the carrier includes, but is not limited to, 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, one or more of combinations and mixtures thereof, or may contain these. In some embodiments, the Group 2 element can contain Mg, and at least a portion of the Group 2 element can be in the form of MgO or a mixed oxide containing MgO. In some embodiments, the support may be, but is not limited to, a MgO - Al2O3 mixed metal oxide, or may contain these. In some embodiments, when the support is a MgO - Al2O3 mixed metal oxide, this support can have a Mg to Al molar ratio equal to 20, 10, 5, 2, 1 to 0.5, 0.1 or 0.01.

[0040] Mg w Al2O 3+w (where w is a positive number), when present as a support or as a component of a support, can have a Mg to Al molar ratio in the range from 0.5, 1, 2, 3, 4 or 5 to 6, 7, 8, 9 or 10. In some embodiments, Mg w Al2O 3+w can contain MgAl2O4, Mg2Al2O5, or a mixture thereof. Ca x Al2O 3+x (where x is a positive number), when present as a support or as a component of an inorganic support, can have a Ca to Al molar ratio in the range of 1:12, 1:4, 1:2, 2:3, 5:6, 1:1, 12:14 or 1.5:1. In some embodiments, Ca x Al2O 3+x can contain tricalcium aluminate, dodecacalcium heptaaluminate, monocalcium aluminate, monocalcium 16alite16nate, monocalcium hexaaluminate, dicalcium aluminate, pentacalcium trialuminate, tetracalcium trialuminate, or any mixture thereof. Sr y Al2O 3+y(where y is a positive number) can have an Sr to Al molar ratio in the range of 0.05, 0.3 or 0.6 to 0.9, 1.5 or 3 when present as a carrier or as a component of a carrier. Ba z Al2O 3+z (where z is a positive number) can have a Ba to Al molar ratio in the range of 0.05, 0.3 or 0.6 to 0.9, 1.5 or 3 when present as a carrier or as a component of a carrier.

[0041] In some embodiments, the carrier can also contain, but is not limited to, at least one metal element and / or at least one metalloid element selected from groups other than Group 2 and Group 10, and / or at least one compound thereof, where the at least one metal element and / or the at least one metalloid element is not one of the alkali metal elements or one of the promoter elements. When the carrier also contains a compound of a metal element and / or a metalloid element selected from groups other than Group 2 and Group 10 and the at least one metal element and / or the at least one metalloid element is not one of the alkali metal elements or one of the promoter elements, the compound can be present in the carrier as an oxide, phosphate, halide, eolite, 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 the at least one metalloid element selected from groups other than Group 2 and Group 10, and / or at least one compound thereof can be, but is not limited to, one or more rare earth elements, i.e., elements having an atomic number of 21, 39 or 57 - 71, or can include these.

[0042] The carrier contains at least one metal element and / or at least one metalloid element selected from groups other than Group 2 and Group 10, and / or at least one compound thereof. When 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, in some embodiments, the at least one metal element and / or at least one metalloid element can function as a binder and can be referred to as a "binder". Whether it is at least one metal element and / or at least one metalloid element selected from groups other than Group 2 and Group 10, and / or at least one compound thereof, when 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 the sake of clarity and ease of explanation, the at least one metal element and / or at least one metalloid element selected from groups other than Group 2 and Group 10 is further described herein as a "binder". In some embodiments, when the carrier contains a binder, the synthesized catalyst can contain a binder in the range from 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% based on the mass of the non-volatile matter of the catalyst.

[0043] In some embodiments, suitable compounds containing a binder include, but are not limited to, the following: B2O3, AlBO3, Al2O3, SiO2, ZrO2, TiO2, SiC, Si3N4, aluminosilicate, 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 (s, t, u and v are positive integers) and one or more of their mixtures and combinations, or can include these.

[0044] In some embodiments, the synthesized catalyst can be in the form of a monolithic structure. In other embodiments, the synthesized catalyst can be in the form of particles. In some embodiments, the synthesized catalyst particles can 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 or 500 μm. In some embodiments, when the synthesized catalyst particles are measured in accordance with ASTM D7481-18 modified using a 10, 25 or 50 mL volumetric cylinder instead of a 100 or 250 mL volumetric cylinder, it is 0.3 g / cm 3 , 0.4 g / cm 3 , 0.5 g / cm 3 , 0.6 g / cm 3 , 0.7 g / cm 3 , 0.8 g / cm 3 , 0.9 g / cm 3 or 1 g / cm 3 to 1.1 g / cm 3 , 1.2 g / cm 3 , 1.3 g / cm 3 , 1.4 g / cm 3 , 1.5 g / cm 3 , 1.6 g / cm 3 , 1.7 g / cm 3 , 1.8 g / cm 3 , 1.9 g / cm 3 or 2 g / cm 3It can have an apparent bulk density in the range up to. In some embodiments, the synthesized catalyst particles, when measured in accordance with ASTM D5757-11(2017), can have a consumption 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% after 1 hour. The geometric shape of the synthesized catalyst particles is mostly spherical, and thus they are suitable for moving within a fluidized bed reactor. In some embodiments, the synthesized catalyst particles can have a size and density that conform to the definition of Geldart A or Geldart B of a fluidizable solid.

[0045] In some embodiments, the synthesized catalyst particles are 0.1 m 2 / g, 1 m 2 / g, 10 m 2 / g or 100 m 2 / g to 500 m 2 / g, 800 m 2 / g, 1,000 m 2 / g or 1,500 m 2 It can have a surface area in the range up to. The surface area of the synthesized catalyst particles can be measured in accordance with the Brunauer-Emmett-Teller (BET) method using nitrogen adsorption-desorption (at the temperature of liquid nitrogen, 77 K) with a Micromeritics 3flex instrument after degassing the powder at 350 °C for 4 hours. More information on this method can be found, for example, in “Characterization of Porous Solids and Powders: Surface Area, Pore Size and Density,” S. Lowell et al., Springer, 2004.

[0046] Method for preparing the synthesized catalyst The method of making the synthesized catalyst is not limited to the following, but can include steps of preparing a slurry or gel that can include, but is not limited to, milling, mixing, blending, combining, or otherwise contacting a compound containing a Group 2 element and a liquid medium. In some embodiments, the preparation of the slurry or gel can also include, but is not limited to, contacting a compound containing a Group 2 element, a liquid medium, and one or more additives. In other embodiments, the preparation of the slurry or gel can include, but is not limited to, contacting a compound containing a Group 2 element, a liquid medium, a binder or binder precursor, and optionally one or more additives.

[0047] The compound containing a Group 2 element can be in the form of an oxide, hydroxide, hydrated carbonate, salt, clay containing a Group 2 element, layered double hydroxide, phosphate, halide, halate, sulfate, sulfide, borate, nitride, carbide, aluminate, aluminosilicate, silicate, carbonate, metaphosphate, selenide, tungstate, molybdate, chromite, chromate, dichromate, silicide, or a mixture thereof. In some embodiments, the Group 2 element can be, or can include, Mg, and the compound containing a Group 2 element can be in the form of magnesium oxide, magnesium hydroxide, hydrotalcite (inorganic hydrated magnesium carbonate, Mg5(CO3)4(OH)2·4H2O), magnesium salts, magnesium-containing clays, hydrotalcite (layered double hydroxide), organomagnesium compounds, or a mixture thereof. In some embodiments, the Group 2 element can be, or can include, Mg, and the compound containing a Group 2 element can be in the form of magnesium oxide after calcination, magnesium hydroxide after calcination, hydrotalcite (inorganic hydrated magnesium carbonate, Mg5(CO3)4(OH)2·4H2O) after calcination, magnesium salts after calcination, magnesium-containing clays after calcination, hydrotalcite (layered double hydroxide) after calcination, organomagnesium compounds after calcination, or a mixture thereof.

[0048] The liquid medium may be, but is not limited to, water, alcohol, acetone, chloroform, methylene chloride, dimethylformamide, dimethyl sulfoxide, glycerin, ethyl acetate, or any mixture thereof, or may contain these. Exemplary alcohols may be, but are not limited to, methanol, ethanol, isopropanol, or any mixture thereof, or may contain these. The binder, if present, may be the above binder or may contain this. The binder precursor, if present, may be, but is not limited to, Al2Si2O5(OH)4 (kaolin clay), aluminum chlorohydrol, boehmite, pseudo-boehmite, gibbsite, bayertite, aluminum nitrate, aluminum chloride, sodium aluminate, alumina sol, silica sol, or any mixture thereof, or may contain these. It is known in the literature that some of the compounds herein referred to as "binder" may also be referred to as filler, matrix, additive, etc. One or more additives, if present, may be, but are not limited to, acids such as formic acid, lactic acid, citric acid, acetic acid, HNO3, HCl, oxalic acid, stearic acid, carbonic acid, bases such as ammonia solution, NaOH, KOH, inorganic salts such as nitrates, carbonates, bicarbonates, chlorides, organic salts such as acetates, oxalates, formates, citrates, polymers such as polyvinyl alcohol, polysaccharides, or any mixture thereof, or may contain these. The additives can help improve the chemical / physical properties of the spray-dried material and / or improve the rheological properties of the slurry / gel to facilitate spray drying.

[0049] A slurry or gel can be spray dried to produce spray dried carrier particles containing Group 2 elements. Spray drying refers to the process of producing a dried particulate solid product from a slurry or gel. This process can include the steps of spraying or atomizing the slurry or gel, for example, forming droplets in a temperature-controlled gas stream and evaporating the liquid medium from the atomized droplets to produce a particulate solid product. For example, in a spray drying process, the slurry or gel can be atomized into droplets and mixed with warm air or a heated 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 typically be near or above the boiling temperature of the liquid. An outlet air temperature of about 60 °C to about 120 °C can be common.

[0050] The slurry or gel can be atomized with one or more pressure nozzles (e.g., fluid nozzle atomizers), one or more pulse sprayers, one or more high-speed rotating disks (e.g., centrifugal atomizers or rotary atomizers), or any other known process. The median particle size, liquid (e.g., water) concentration, apparent bulk density, or any combination thereof of the particulate solid product prepared by spray drying can be controlled, adjusted, or otherwise affected by one or more operating conditions and / or parameters of the spray dryer. Exemplary operating conditions can include, but are not limited to, the feed rate and temperature of the gas stream, the speed of the atomizer, the feed rate of the slurry or gel by the atomizer, the temperature of the slurry or gel, the size and / or solids concentration of the droplets, the dimensions of the spray dryer, or any combination thereof. It is well known in the art that the various operating conditions will vary depending on the specific spray drying apparatus used and can be readily determined by one of ordinary skill in the art.

[0051] In some embodiments, the spray-dried carrier particles can be fired in an oxidizing atmosphere, such as air, to produce fired carrier particles containing Group 2 elements. In some embodiments, the spray-dried carrier particles can be fired at a temperature in the range 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 higher. In some embodiments, the spray-dried carrier particles can be fired at a temperature of ≤ 950 °C, ≤ 900 °C, ≤ 850 °C, ≤ 800 °C, ≤ 750 °C, ≤ 700 °C, ≤ 650 °C, ≤ 600 °C or ≤ 550 °C, ≤ 525 °C, ≤ 500 °C, ≤ 475 °C or ≤ 460 °C. In some embodiments, the spray-dried carrier particles can be fired for a time 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 can be fired in the presence of oxygen, such as air. In some embodiments, the spray-dried particles can be fired for a time of ≤ 240 minutes, ≤ 180 minutes, ≤ 120 minutes, ≤ 90 minutes, ≤ 60 minutes, ≤ 45 minutes, ≤ 30 minutes, ≤ 25 minutes, ≤ 20 minutes or ≤ 15 minutes at a temperature in the range of 550 °C to 900 °C or 550 °C to 850 °C. In other embodiments, the spray-dried particles are fired for a time of ≤ 240 minutes, ≤ 180 minutes, ≤ 120 minutes, ≤ 90 minutes, ≤ 60 minutes, ≤ 45 minutes, ≤ 30 minutes, ≤ 25 minutes, ≤ 20 minutes or ≤ 15 minutes at a temperature of ≤ 550 °C, ≤ 540 °C, ≤ 530 °C, ≤ 520 °C, ≤ 510 °C or ≤ 500 °C.

[0052] Pt, and when present, Ni and / or Pd, which are present in the synthesized catalyst, can be introduced in one or two ways. For simplicity, Pt is described, but in addition to Pt, Ni-containing compounds and / or Pd-containing compounds can also be used. In some embodiments, the method of making the synthesized catalyst can include the step of contacting at least a compound containing a Group 2 element and a liquid medium with a Pt-containing compound such that Pt can be present in a slurry or gel and the synthesized catalyst can include spray-dried catalyst particles having Pt disposed thereon carried by particles. In such embodiments, the spray-dried particles may be the synthesized catalyst, or the spray-dried particles can be subjected to equilibration and / or drying at a temperature not ≧350° C. to produce the synthesized catalyst.

[0053] In other embodiments, the method of making the synthesized catalyst can include the step of 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 can be contacted with the Pt-containing compound in the presence of a liquid medium to produce a mixture, and the solid fraction can be recovered by filtration. The Pt-containing compound may be, but is not limited to, hexahydrate chloroplatinic acid, tetraammineplatinum(II) nitrate, platinum(II) acetylacetonate, platinum(II) bromide, platinum(II) iodide, platinum(II) chloride, platinum(IV) chloride, platinum(II) dichloride diamine, ammonium tetrachloroplatinate(II), tetraammineplatinum(II) chloride hydrate, tetraammineplatinum(II) hydroxide hydrate, or any mixture thereof, or may include these. Suitable Ni and Pd-containing compounds may be, but are not limited to, nickel(II) chloride, palladium(II) acetate, palladium(II) nitrate, or mixtures thereof, or may include these.

[0054] The promoter and / or alkali metal element that may be present in the synthesized catalyst can be introduced by the same method as the method by which Pt can be introduced. Compounds containing a promoter element are not limited to the following, but may be, or may contain, tin(II) oxide, tin(IV) oxide, tin(IV) chloride pentahydrate, tin(II) chloride dihydrate, tin(II) bromide, tin(IV) bromide, tin(II) acetylacetonate, tin(II) acetate, tin(IV) acetate, silver(I) nitrate, gold(III) nitrate, copper(II) nitrate, gallium(III) nitrate, or any mixture thereof. Compounds containing an alkali metal element are not limited to the following, but may be, or may contain, lithium nitrate, sodium nitrate, potassium nitrate, rubidium nitrate, cesium nitrate, or any mixture thereof.

[0055] In some embodiments, platinum(II) oxalate and tin(II) oxalate can be used as the Pt-containing compound and the Sn-containing compound. Tin(II) oxalate can be dissolved in an aqueous solution containing ammonium oxalate or an aqueous solution containing ammonium oxalate and platinum oxalate. An aqueous solution containing tin(II) oxalate and ammonium oxalate or ammonium oxalate and platinum oxalate can be added to the support, and then equilibration, drying, and / or calcination can be performed. The distribution of Sn throughout the support can be improved by using a stannous oxalate of Sn containing tin(II) oxalate and tin(IV) oxalate as the Sn-containing compound. The use of platinum(II) oxalate and tin(II) oxalate as the Pt-containing compound and the Sn-containing compound on various supports for various applications is described in U.S. Patent No. 8,569,203.

[0056] The first process for upgrading hydrocarbons The first process for upgrading hydrocarbons can include contacting a first hydrocarbon-containing feed with a calcined catalyst to perform one or more of dehydrogenation, dehydroaromatization, and dehydrocyclization of at least a portion of the first hydrocarbon-containing feed, to produce an effluent that can contain a coked catalyst and one or more upgraded hydrocarbons and molecular hydrogen. The calcined catalyst and the first hydrocarbon-containing feed can be contacted with each other within any suitable environment, such as one or more reaction zones or conversion zones disposed within one or more reactors, to produce the effluent and the coked catalyst. The reaction zone or conversion zone may be disposed within one or more fixed-bed reactors, one or more fluidized-bed reactors or moving-bed reactors, one or more countercurrent reactors, or any combination thereof, or alternatively, may be placed within these.

[0057] The first hydrocarbon-containing feed and the calcined catalyst can be contacted at a temperature in the range from 300 °C, 350 °C, 400 °C, 450 °C, 500 °C, 550 °C, 600 °C, 620 °C, 650 °C, 660 °C, 670 °C, 680 °C, 690 °C or 700 °C to 725 °C, 750 °C, 760 °C, 780 °C, 800 °C, 825 °C, 850 °C, 875 °C or 900 °C. In some embodiments, the first hydrocarbon-containing feed and the calcined catalyst can be contacted at a temperature of at least 620 °C, at least 650 °C, at least 660 °C, at least 670 °C, at least 680 °C, at least 690 °C or at least 700 °C to 725 °C, 750 °C, 760 °C, 780 °C, 800 °C, 825 °C, 850 °C, 875 °C or 900 °C. The first hydrocarbon-containing feed can be introduced into the reaction zone or conversion zone for a time of ≤ 3 hours, ≤ 2.5 hours, ≤ 2 hours, ≤ 1.5 hours, ≤ 1 hour, ≤ 45 minutes, ≤ 30 minutes, ≤ 20 minutes, ≤ 10 minutes, ≤ 5 minutes, ≤ 1 minute, ≤ 30 seconds, ≤ 10 seconds, ≤ 5 seconds or ≤ 1 second or ≤ 0.5 second and contacted with the calcined catalyst therein. In some embodiments, the first hydrocarbon-containing feed can be contacted with the calcined catalyst for a time in the range from 0.1 second, 0.5 second, 0.7 second, 1 second, 30 seconds, 1 minute, 5 minutes or 10 minutes to 30 minutes, 50 minutes, 70 minutes, 1.5 hours, 2 hours or 3 hours.

[0058] The first hydrocarbon-containing feed and the calcined catalyst can be contacted under a hydrocarbon partial pressure of at least 20 kPa (absolute), where the hydrocarbon partial pressure is any C2-C in the first hydrocarbon-containing feed 16 alkane and any C8-C 16It is the total partial pressure of alkyl aromatics. In some embodiments, the hydrocarbon partial pressure during contacting the first hydrocarbon-containing feed with the calcined catalyst can be in the range from 20 kPa (absolute), 50 kPa (absolute), 100 kPa (absolute), at least 150 kPa, at least 200 kPa, 300 kPa (absolute), 500 kPa (absolute), 750 kPa (absolute) or 1,000 kPa (absolute) to 1,500 kPa (absolute), 2,500 kPa (absolute), 4,000 kPa (absolute), 5,000 kPa (absolute), 7,000 kPa (absolute), 8,500 kPa (absolute) or 10,000 kPa (absolute), and the hydrocarbon partial pressure is all C2-C in the first hydrocarbon-containing feed 16 alkanes and all C8-C 16 It is the total partial pressure of alkyl aromatics. In other embodiments, the hydrocarbon partial pressure during contacting the hydrocarbon-containing feed with the calcined catalyst can be in the range from 20 kPa (absolute), 50 kPa (absolute), 100 kPa (absolute), 150 kPa (absolute), 200 kPa (absolute), 250 kPa (absolute) or 300 kPa (absolute) to 500 kPa (absolute), 600 kPa (absolute), 700 kPa (absolute), 800 kPa (absolute), 900 kPa (absolute) or 1,000 kPa (absolute), and the hydrocarbon partial pressure is all C2-C in the first hydrocarbon-containing feed 16 alkanes and all C8-C 16 It is the total partial pressure of alkyl aromatics.

[0059] In some embodiments, the first hydrocarbon-containing feed is at least 60% by volume, at least 65% by volume, at least 70% by volume, at least 75% by volume, at least 80% by volume, at least 85% by volume, at least 90% by volume, at least 95% by volume or at least 99% by volume of a single C2-C with respect to the total amount of the first hydrocarbon-containing feed 16Alkanes, such as propane, can be included. The first hydrocarbon-containing feed and the calcined catalyst are at least 20 kPa (absolute), at least 50 kPa (absolute), at least 100 kPa (absolute), at least 150 kPa (absolute), at least 250 kPa (absolute), at least 300 kPa (absolute), at least 400 kPa (absolute), at least 500 kPa (absolute) or at least 1,000 kPa (absolute) of a single C2-C 16 alkanes, such as propane, can be contacted under pressure.

[0060] The first hydrocarbon-containing feed can be contacted with the calcined catalyst in the reaction zone or conversion zone at any mass hourly space velocity (WHSV) effective to effect an upgrading process. In some embodiments, the WHSV is 0.01 h -1 , 0.1 h -1 , 1 h -1 , 2 h -1 , 5 h -1 , 10 h -1 , 20 h -1 , 30 h -1 or 50 h -1~ 100 h -1 , 250 h -1 , 500 h -1 or 1,000 h -1 or less. In some embodiments, where the hydrocarbon upgrading process includes a fluidized or otherwise mobile calcined catalyst, the ratio of the circulating mass flow rate of the calcined catalyst to the total mass flow rate of any C2-C 16 alkanes and any C8-C 16 alkyl aromatics can range from 1, 3, 5, 10, 15, 20, 25, 30 or 40 to 50, 60, 70, 80, 90, 100, 110, 125 or 150 on a mass-to-mass basis.

[0061] If the activity of the coking catalyst drops below the desired minimum amount, the coking catalyst or at least a part thereof can be subjected to a regeneration process to produce a regenerated catalyst. More specifically, the coking catalyst can be contacted with one or more oxidants to effect combustion of at least a part of the coke, producing a regenerated catalyst with less coke and combustion gas. The regeneration of the coking catalyst can be carried out within the reaction zone or conversion zone, or within a combustion zone isolated from and separated from the reaction zone or conversion zone, depending on the specific configuration of the reactor, to produce a regenerated catalyst. For example, the regeneration of the coking catalyst can be carried out within the reaction zone or conversion zone when a fixed bed reactor or a countercurrent reactor is used, or within a separate combustion zone that can be isolated from and separated from the reaction zone or conversion zone when a fluidized bed reactor or other cyclic or fluidized type of reactor is used. In some embodiments, fuel can be added to the combustion zone to generate heat that can be used to heat the coking catalyst. Exemplary fuels 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 oil, gasoline, diesel, kerosene, volatiles, and / or other combustible compounds, or may include these. In some embodiments, the regeneration process can include a step of burning fuel within the combustion zone and then flowing a relatively dry oxidant into the combustion zone to produce a regenerated catalyst. In some embodiments, the regeneration process can include a step of burning fuel with the coking catalyst within a first combustion zone to produce at least a partially regenerated catalyst, a step of transporting the at least partially regenerated catalyst to a second combustion zone, and a step of flowing a relatively dry oxidant into the second combustion zone to produce a regenerated catalyst. Examples of dry oxidants include air containing <2% by volume of water vapor.

[0062] In some embodiments, the method may 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 hydrocarbon-containing feed can be contacted with at least a portion of either the regenerated catalyst and / or at least a portion of the regenerated and reduced catalyst to produce a recoked catalyst and additional effluent.

[0063] In some embodiments, the cycle time from contacting the hydrocarbon-containing feed with the calcined catalyst to contacting an additional amount of the hydrocarbon-containing feed with the regenerated catalyst may be ≤ 5 hours. The first cycle begins by contacting the calcined catalyst with a first hydrocarbon-containing feed and then either contacting with at least an oxidizing gas to produce a regenerated catalyst or contacting with at least an oxidizing gas and an optional reducing gas to produce a regenerated and reduced catalyst, and the first cycle is ended by contacting the regenerated catalyst with an additional amount of the first hydrocarbon-containing feed. If one or more additional feeds (described in more detail below) are utilized between the flow of the first hydrocarbon-containing feed and the oxidizing gas, between the oxidizing gas and the reducing gas (if used), between the oxidizing gas and the additional amount of the first hydrocarbon-containing feed, and / or between the reducing gas (if used) and the additional amount of the first hydrocarbon-containing feed, the time during which such strip gas is utilized is included in the time included in the cycle time. Thus, the cycle time from contacting the first hydrocarbon-containing feed with the calcined catalyst to contacting an additional amount of the hydrocarbon-containing feed with the regenerated catalyst may be, in some embodiments, ≤ 5 hours, ≤ 4 hours, ≤ 3 hours, ≤ 2 hours, ≤ 1 hour, ≤ 55 minutes, ≤ 50 minutes or ≤ 45 minutes.

[0064] The oxidizing agent may be, but is not limited to, O2, O3, CO2, H2O, or a mixture thereof, or may contain these. In some embodiments, in order to increase the coke removal rate from the catalyst, an excess amount of oxidizing agent can be used compared to the oxidizing agent required to burn 100% of the coke on the coked catalyst, and as a result, the time required for coke removal can be shortened, leading to an improvement in the yield of upgraded products produced within a given time. Using pure O2 as the oxidizing agent can facilitate the capture and isolation of CO2 generated during combustion in one or more downstream CO2 recovery systems.

[0065] The coked catalyst and the oxidizing agent can be brought into contact with each other at a temperature in the range from 500 °C, 550 °C, 600 °C, 650 °C, 700 °C, 750 °C or 800 °C to 900 °C, 950 °C, 1,000 °C, 1,050 °C or 1,100 °C to produce a regenerated catalyst. In some embodiments, the coked catalyst and the oxidizing agent can be brought into contact with each other 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.

[0066] The coked catalyst and the oxidizing agent can be brought into contact with each other for a time of ≤2 hours, ≤1 hour, ≤30 minutes, ≤10 minutes, ≤5 minutes, ≤1 minute, ≤30 seconds, ≤10 seconds, ≤5 seconds or ≤1 second. For example, the coked catalyst and the oxidizing agent can be brought into contact with each other for a time in the range of 2 seconds to 2 hours. In some embodiments, the coked catalyst and the oxidizing agent can be brought into contact for a time sufficient to remove ≥50% by mass, ≥75% by mass or ≥90% by mass or >99% of any coke disposed on the coked catalyst. In some embodiments, the time for the coking catalyst and the oxidant to contact each other may be shorter than the time for the calcined / regenerated catalyst to contact the hydrocarbon-containing feed to produce the effluent and the coking catalyst. For example, the time for the coking catalyst and the oxidant to contact each other may be at least 90%, at least 60%, at least 30%, or at least 10% shorter than the time for the calcined / regenerated catalyst to contact the hydrocarbon-containing feed to produce the effluent. In other embodiments, the time for the coking catalyst and the oxidant to contact each other may be longer than the time for the calcined / regenerated catalyst to contact the hydrocarbon-containing feed to produce the effluent and the coking catalyst. For example, the time for the coking catalyst and the oxidant to contact each other may be at least 50%, at least 100%, at least 300%, at least 500%, at least 1,000%, at least 10,000%, at least 30,000%, at least 50,000%, at least 75,000%, at least 100,000%, at least 250,000%, at least 500,000%, at least 750,000%, at least 1,000,000%, at least 1,250,000%, at least 1,500,000%, or at least 1,800,000% longer than the time for the calcined / regenerated catalyst to contact the hydrocarbon-containing feed to produce the effluent.

[0067] The coked catalyst and the oxidant can be brought into contact with each other under an oxidant partial pressure in the range from 20 kPa (absolute), 50 kPa (absolute), 100 kPa (absolute), 300 kPa (absolute), 500 kPa (absolute), 750 kPa (absolute) or 1,000 kPa (absolute) to 1,500 kPa (absolute), 2,500 kPa (absolute), 4,000 kPa (absolute), 5,000 kPa (absolute), 7,000 kPa (absolute), 8,500 kPa (absolute) or 10,000 kPa (absolute). In other embodiments, the oxidant partial pressure during contact with the coked catalyst is in the range from 20 kPa (absolute), 50 kPa (absolute), 100 kPa (absolute), 150 kPa (absolute), 200 kPa (absolute), 250 kPa (absolute) or 300 kPa (absolute) to 500 kPa (absolute), 600 kPa (absolute), 700 kPa (absolute), 800 kPa (absolute), 900 kPa (absolute) or 1,000 kPa (absolute) in order to produce a regenerated catalyst.

[0068] Although not wishing to be bound by theory, at least a portion of the Pt disposed on the coked catalyst and, if present, Ni and / or Pd is thought to be at risk of agglomeration compared to the calcined / regenerated catalyst prior to contact with the first hydrocarbon-containing feed. While at least a portion of the coke on the coked catalyst is burning, at least a portion of the Pt and, if present, any Ni and / or Pd can be redispersed around the support. By redispersing any agglomerated Pt and, if present, at least a portion of Ni and / or Pd, the activity of the catalyst can be increased over a number of cycles and its stability improved.

[0069] In some embodiments, at least a portion of the Pt in the regenerated catalyst, and Ni and / or Pd if present, may be in a higher oxidation state compared to the Pt in the catalyst contacted with the first hydrocarbon-containing feed, and Ni and / or Pd if present, and compared to the Pt in the coked catalyst, and Ni and / or Pd if present. Thus, as noted above, in some embodiments, the method may include contacting at least a portion of the regenerated catalyst with a reducing gas to produce a regenerated and reduced catalyst. Suitable reducing gases (reducing agents) may include, but are not limited to, H2, CO, CH4, C2H6, C3H8, C2H4, C3H6, steam, or mixtures thereof, or may contain these. In some embodiments, the reducing agent can be mixed with an inert gas such as Ar, Ne, He, N2, CO2, H2O, or mixtures thereof. In such embodiments, at least a portion of the Pt in the regenerated and reduced catalyst, and Ni and / or Pd if present, can be reduced to a lower oxidation state, for example, the elemental state, compared to the Pt in the regenerated catalyst, and Ni and / or Pd if present. In this embodiment, an additional amount of hydrocarbon-containing feed can be contacted with at least a portion of the regenerated catalyst and / or at least a portion of the regenerated and reduced catalyst.

[0070] In some embodiments, the regenerated catalyst and the reducing gas can be contacted at a temperature in the range of 400 °C, 450 °C, 500 °C, 550 °C, 600 °C, 620 °C, 650 °C or 670 °C to 720 °C, 750 °C, 800 °C or 900 °C. The regenerated catalyst and the reducing gas can be contacted for a time in the range of 1 second, 5 seconds, 10 seconds, 20 seconds, 30 seconds or 1 minute to 10 minutes, 30 minutes or 60 minutes. The regenerated catalyst and the reducing gas can be contacted under a reducing agent partial pressure in the range of 20 kPa (absolute), 50 kPa (absolute) or 100 kPa (absolute), 300 kPa (absolute), 500 kPa (absolute), 750 kPa (absolute) or 1,000 kPa (absolute) to 1,500 kPa (absolute), 2,500 kPa (absolute), 4,000 kPa (absolute), 5,000 kPa (absolute), 7,000 kPa (absolute), 8,500 kPa (absolute) or 10,000 kPa (absolute). In other embodiments, the reducing agent partial pressure while contacting the regenerated catalyst to produce 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).

[0071] At least a portion of the regenerated catalyst, the regenerated and reduced catalyst, the new or unused catalyst, or a mixture thereof can be contacted with an additional amount of the first hydrocarbon-containing feed within the reaction zone or conversion zone to produce additional effluent and additional coked catalyst. As noted above, in some embodiments, the cycle time from contacting the hydrocarbon-containing feed with the calcined / regenerated catalyst to contacting the additional amount of the hydrocarbon-containing feed with at least a portion of the regenerated catalyst, and / or the regenerated and reduced catalyst, and optionally the new or unused catalyst, can be ≤ 5 hours, ≤ 4 hours, ≤ 3 hours, ≤ 2 hours, ≤ 1 hour, ≤ 55 minutes, ≤ 50 minutes or ≤ 45 minutes.

[0072] In some embodiments, as noted above, one or more additional feeds, e.g., one or more sweep fluids, can be utilized between the flow of the first hydrocarbon-containing feed and the oxidant, between the oxidant and an optional reducing gas (if used), between the oxidant and an additional first hydrocarbon-containing feed, and / or between the reducing gas and an additional first hydrocarbon-containing feed. The sweep fluid can, inter alia, purge or otherwise expel undesirable substances, such as non-combustible particulates including soot, from the reactor. In some embodiments, the additional feed can be inert under dehydrogenation, dehydroaromatization and dehydrocyclization, combustion and / or reducing conditions. Suitable sweep fluids may include, but are not limited to, N2, He, Ar, CO2, H2O, CO2, CH4 or mixtures thereof, or may contain these. In some embodiments, when the method utilizes a sweep fluid, the period or time during which the sweep fluid is used can range from 1 second, 5 seconds, 10 seconds, 20 seconds, 30 seconds or 1 minute to 10 minutes, 30 minutes or 60 minutes.

[0073] In some embodiments, the fired / regenerated catalyst can maintain a sufficiently active and stable state after a number of cycles, such as at least 15, at least 20, at least 30, at least 40, at least 50, at least 60, at least 70, at least 100 cycles, at least 125 cycles, at least 150 cycles, at least 175 cycles or at least 200 cycles, and each cycle time is ≤ 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 has stabilized (sometimes the first few cycles can have relatively poor or relatively good performance, but the performance can ultimately stabilize), when the hydrocarbon-containing feed contains propane, the method, when first contacted with the first hydrocarbon-containing feed, can produce a first upgraded hydrocarbon product, such as propylene, with a selectivity for upgraded hydrocarbons of ≥ 75%, ≥ 80%, ≥ 85% or ≥ 90% or > 95%, and at the completion of the last cycle (at least 15 cycles in total), can have a second upgraded hydrocarbon product yield with a selectivity for upgraded hydrocarbons of ≥ 75%, ≥ 80%, ≥ 85% or ≥ 90% or > 95%, such as propylene, and the yield of the first upgraded hydrocarbon product can be at least 90%, at least 93%, at least 95%, at least 97%, at least 98%, at least 99%, at least 99.5% or at least 100%.

[0074] In some embodiments, when the first hydrocarbon-containing feed contains propane and the upgraded hydrocarbon contains propylene, contacting the hydrocarbon-containing feed with a calcined / regenerated catalyst can result in a propylene selectivity of ≧75%, ≧80%, ≧85%, ≧90%, ≧93% or ≧95% and a propylene yield of 48%, ≧49%, ≧50%, ≧51%, ≧52%, ≧53%, ≧54%, ≧55%, ≧56%, ≧57%, ≧58%, ≧59%, ≧60%, ≧61%, ≧62%, ≧63%, ≧64%, ≧65%, ≧66%, ≧67%, ≧68% or ≧69%. In some embodiments, when the hydrocarbon-containing feed contains propane and the upgraded hydrocarbon contains propylene, contacting the hydrocarbon-containing feed with a calcined / regenerated catalyst can result in a propylene selectivity of at least 75%, at least 80%, at least 85%, at least 90% or at least 95% and 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% for between at least 15, at least 20, at least 30, at least 40, at least 50, at least 60, at least 70, at least 100 cycles, at least 125 cycles, at least 150 cycles, at least 175 cycles or at least 200 cycles.In other embodiments, when the hydrocarbon-containing feed contains 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% of propane based on the total amount of the first hydrocarbon-containing feed and is contacted under a propane partial pressure of at least 20 kPa (absolute), at least 75%, at least 80%, at least 85%, at least 90% or at least 95% propylene selectivity can be achieved, and 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% can be obtained. 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% with at least 75%, at least 80%, at least 85%, at least 90% or at least 95% propylene selectivity during 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 by further optimizing the composition of the carrier and / or adjusting one or more process conditions.In some embodiments, 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 for between 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, a propylene yield can be obtained.

[0075] Suitable systems for practicing the methods disclosed herein can include systems well known in the art, such as the 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 the fluidized riser reactors and / or downer reactors disclosed in U.S. Patent Application Publication Nos. 2004 / 0082824; 2008 / 0194891; and the countercurrent reactors disclosed in U.S. Patent No. 8,754,276; U.S. Patent Application Publication No. 2015 / 0065767; and WO Publication No. WO2013169461.

[0076] The first hydrocarbon-containing feed is not limited to, but can be one or more alkane hydrocarbons, such as C2-C 16 linear or branched alkanes and / or C4-C 16 cyclic alkanes, and / or one or more alkyl aromatic hydrocarbons, such as C8-C 16 alkyl aromatics or can include them. In some embodiments, the first hydrocarbon-containing feed is any C2-C in the hydrocarbon-containing feed 16 alkane and any C8-C 16The total amount of alkylaromatics may contain 0.1% to 50% by volume of steam. In other embodiments, the first hydrocarbon-containing feed is any C2-C in the hydrocarbon-containing feed 16 alkane and any C8-C 16 The total amount of alkylaromatics can contain <0.1% by volume of steam or may not contain steam.

[0077] C2-C 16 The alkanes include, but are not limited to, ethane, propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, n-heptane, 2-methylhexane, 2,2,3-trimethylbutane, cyclopentane, cyclohexane, methylcyclopentane, ethylcyclopentane, n-propylcyclopentane, 1,3-dimethylcyclohexane or mixtures thereof, or may include these. For example, the first hydrocarbon-containing feed can contain propane, which can be dehydrogenated to produce propylene and / or isobutane, and isobutane can be dehydrogenated to produce isobutylene. In another example, the first hydrocarbon-containing feed can contain liquefied petroleum gas (LP gas), which can be present in the gas phase when contacted with a catalyst. In some embodiments, the first hydrocarbon in the hydrocarbon-containing feed can consist of a substantially single alkane such as propane. In some embodiments, the hydrocarbon-containing feed is ≧50 mol%, ≧75 mol%, ≧95 mol%, ≧98 mol% or ≧99 mol% of a single C2-C based on the total mass of all hydrocarbons in the first hydrocarbon-containing feed 16 alkane, for example, propane. In some embodiments, the first hydrocarbon-containing feed is at least 50% by volume, at least 55% by volume, at least 60% by volume, at least 65% by volume, at least 70% by volume, at least 75% by volume, at least 80% by volume, at least 85% by volume, at least 90% by volume, at least 95% by volume, at least 97% by volume or at least 99% by volume of a single C2-C based on the total amount of the first hydrocarbon-containing feed16 It may contain alkanes, for example, propane.

[0078] C8-C 16 The alkyl aromatics may be, but are not limited to, ethylbenzene, propylbenzene, butylbenzene, one or more ethyltoluenes, or mixtures thereof, or may contain these. In some embodiments, the hydrocarbon-containing feed is ≧50 mol%, ≧75 mol%, ≧95 mol%, ≧98 mol% or ≧99 mol% of a single C8-C based on the total mass of all hydrocarbons in the first hydrocarbon-containing feed 16 It may contain alkyl aromatics, for example, ethylbenzene. In some embodiments, ethylbenzene can be dehydrogenated to produce styrene. Thus, in some embodiments, the first process for upgrading the 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.

[0079] In some embodiments, the first hydrocarbon-containing feed can be diluted with one or more diluents, such as one or more inert gases. Suitable inert gases may be, but are not limited to, Ar, Ne, He, N2, CO2, CH4, or mixtures thereof, or may contain these. When the hydrocarbon-containing feed contains a diluent, the hydrocarbon-containing feed is any C2-C in the hydrocarbon-containing feed 16 Alkanes and any C8-C 16 It can contain diluents from 0.1% by volume, 0.5% by volume, 1% by volume or 2% by volume to 3% by volume, 8% by volume, 16% by volume or 32% by volume based on the total amount of all alkyl aromatics.

[0080] In some embodiments, the first hydrocarbon-containing feed can also contain H2. In some embodiments, when the first hydrocarbon-containing feed contains H2, H2 to any C2-C 16The ratio of the total amount of alkanes and any C8-C 16 alkyl aromatics may range from 0.1, 0.3, 0.5, 0.7 or 1 to 2, 3, 4, 5, 6, 7, 8, 9 or 10.

[0081] In some embodiments, the first hydrocarbon-containing feed is any C2-C in the hydrocarbon-containing feed 16 alkanes and any C8-C 16 alkyl aromatics may contain substantially no water vapor (e.g., <0.1% by volume of water vapor). In other embodiments, the first hydrocarbon-containing feed can contain water vapor. For example, the first hydrocarbon-containing feed is any C2-C in the first hydrocarbon-containing feed 16 alkanes and any C8-C 16 alkyl aromatics may contain from 0.1% by volume, 0.3% by volume, 0.5% by volume, 0.7% by volume, 1% by volume, 3% by volume or 5% by volume to 10% by volume, 15% by volume, 20% by volume, 25% by volume, 30% by volume, 35% by volume, 40% by volume, 45% by volume or 50% by volume of water vapor. In other embodiments, the first hydrocarbon-containing feed is any C2-C in the first hydrocarbon-containing feed 16 alkanes and any C8-C 16 alkyl aromatics may contain ≦50% by volume, ≦45% by volume, ≦40% by volume, ≦35% by volume, ≦30% by volume, ≦25% by volume, ≦20% by volume or ≦15% by volume of water vapor. In other embodiments, the first hydrocarbon-containing feed is any C2-C in the first hydrocarbon-containing feed 16 alkanes and any C8-C 16 alkyl aromatics may contain at least 1% by volume, at least 3% by volume, at least 5% by volume, at least 10% by volume, at least 15% by volume, at least 20% by volume, at least 25% by volume or at least 30% by volume of water vapor.

[0082] In some embodiments, the first hydrocarbon-containing feed can contain sulfur. For example, the first hydrocarbon-containing feed can contain sulfur in the range of from 0.5 ppm, 1 ppm, 5 ppm, 10 ppm, 20 ppm, 30 ppm, 40 ppm, 50 ppm, 60 ppm, 70 ppm, or 80 ppm to 100 ppm, 150 ppm, 200 ppm, 300 ppm, 400 ppm, or 500 ppm. In other embodiments, the first hydrocarbon-containing feed can contain sulfur in the range of 1 ppm to 10 ppm, 10 ppm to 20 ppm, 20 ppm to 50 ppm, 50 ppm to 100 ppm, or 100 ppm to 500 ppm. Sulfur in the first hydrocarbon-containing feed, if present, is not limited to, but can be, for example, one or more mercaptans, H2S, dimethyldisulfide, or any mixture thereof, or can include these.

[0083] In some embodiments, the first hydrocarbon-containing feed can substantially not contain or can not contain molecular oxygen. In some embodiments, the first hydrocarbon-containing feed can contain up to 5 mol%, up to 3 mol%, or up to 1 mol% of molecular oxygen (O2). By supplying a first hydrocarbon-containing feed that substantially does not contain molecular oxygen, an oxidation reaction that would otherwise consume at least a portion of the alkanes and / or alkyl aromatics in the first hydrocarbon-containing feed is thought to be prevented.

[0084] Recovery and Use of the First Upgraded Hydrocarbon In some embodiments, the first upgraded hydrocarbon can include at least one upgraded hydrocarbon, such as olefins, water, unreacted hydrocarbons, molecular hydrogen, etc. The first upgraded hydrocarbon can be recovered by any convenient process, for example, by one or more conventional processes, or alternatively, obtained. One such process can include cooling and / or compressing the effluent to condense at least a portion of any water and any heavy hydrocarbons present, leaving the olefins and any unreacted alkanes or alkyl aromatics primarily in the vapor phase. Next, the olefins and unreacted alkanes, or alkyl aromatic hydrocarbons, can be removed from the reaction product in one or more separation drums. For example, one or more separators or distillation columns can be used to separate the dehydrogenation product from the unreacted first hydrocarbon-containing feed.

[0085] In some embodiments, the recovered olefins, such as propylene, can be used in the production of polymers. For example, the recovered propylene can be polymerized to produce polymers having segments or units derived from the recovered propylene, such as polypropylene, ethylene-propylene copolymers, etc. For example, the recovered isobutene can be used to produce one or more of oxygenates such as methyl tert-butyl ether, fuel additives such as diisobutene, and synthetic elastomer polymers such as butyl rubber.

[0086] Second process for upgrading hydrocarbons The second process for upgrading hydrocarbons can include contacting a second hydrocarbon-containing feed with a calcined catalyst comprising catalyst particles having Pt disposed on a support and optionally a promoter, to effect reforming of at least a portion of the second hydrocarbon-containing feed and produce an effluent that can include a coking catalyst and carbon monoxide and molecular hydrogen. The calcined catalyst and the second hydrocarbon-containing feed can be contacted with each other within any suitable environment, such as one or more reaction zones or conversion zones disposed within one or more reactors, to produce the effluent and the coking catalyst. The reaction zone or conversion zone can be disposed within one or more fixed bed reactors, one or more fluidized bed reactors or moving bed reactors, one or more countercurrent reactors or any combination thereof, or alternatively, can be disposed within these. For clarity and brevity of explanation, the reforming reaction is discussed in the context of a fluidized bed reactor, but it should be understood that a fixed bed reactor, countercurrent reactor or moving bed reactor, or any other reactor can be used to effect reforming of the second hydrocarbon-containing feed.

[0087] Using a reforming reaction, reformed hydrocarbons can be produced by a continuous reaction process or a discontinuous reaction process. In some embodiments, this reaction process can include a reforming step, e.g., an endothermic reaction, and a regeneration step, e.g., an exothermic reaction, that operate continuously while the fluidized catalyst is transported between the reforming zone and the regeneration zone of the reactor. The endothermic reaction can include hydrocarbon reforming in the presence of a calcined catalyst. Unused hydrocarbons and regenerated fluidized catalyst particles can enter the reforming zone. The hydrocarbons can be converted to reformed products that, after spending some time in the reforming zone, can at least partially exit the reforming zone with the spent catalyst. The reformed products and unreacted feed can be separated from the spent catalyst by one or more separation devices. The reformed products and unreacted feed from the separation device can proceed downstream for further purification while the spent catalyst can be sent to the regeneration zone for regeneration. The exothermic regeneration reaction can be a reaction of an oxidizer and optionally a fuel under combustion conditions that produces a regenerated catalyst and flue gas. After regeneration, the regenerated catalyst is separated from the flue gas by one or more separation devices and transported back to the reforming zone where it can merge with additional hydrocarbon feed and enter the reforming zone to initiate further reforming reactions. The reforming step can convert CO2 and / or H2O and hydrocarbons, e.g., CH4, to synthesis gas containing H2 and CO. The regeneration step can generate heat to heat the regenerated catalyst such that reactants, e.g., coke deposited on the spent catalyst, and / or optionally a fuel and an oxidizer are combusted to provide heat that can be used to drive the reforming reaction. In some embodiments, the catalyst can be heated to an average temperature in the range of 600 °C, 700 °C, or 800 °C to 1,000 °C, 1,300 °C, or 1,600 °C during the regeneration step.

[0088] Exemplary fuels 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 oil, gasoline, diesel, kerosene, volatiles, and / or other combustible compounds, or may include these. The oxidant may be O2 or may contain this. In some embodiments, the oxidant may be air, air rich in O2, air depleted of O2, or any other suitable O2-containing stream, or may include these.

[0089] Regeneration of the catalyst can correspond to removing coke from the catalyst particles. In some embodiments, during reforming, a portion of the feed introduced into the reforming zone may form coke. This coke can potentially block access to the catalyst sites (such as metal sites) of the catalyst. During regeneration, at least a portion of the coke generated during reforming can be removed as CO or CO2. Regeneration of the catalyst can also correspond to redispersion of any aggregated active phase of the catalyst such as Pt.

[0090] The second hydrocarbon-containing feed includes, but is not limited to, one or more reformable C1-C such as alkanes, alkenes, cycloalkanes, alkyl aromatics, etc. 16It may be a hydrocarbon or any mixture thereof, or it can contain these. In some embodiments, the second hydrocarbon-containing stream may be or may contain methane, ethane, propane, butane, pentane, or a mixture thereof. In some embodiments, the second hydrocarbon-containing feed can be exposed to the catalyst under a pressure of less than 35 kPa gauge. For example, the second hydrocarbon-containing feed can be exposed to the catalyst under a pressure in the range from 0.7 kPa gauge, 2 kPa gauge, 3.5 kPa gauge, 5 kPa gauge, or 10 kPa gauge to 15 kPa gauge, 20 kPa gauge, 25 kPa gauge, or 30 kPa gauge. In other embodiments, the second hydrocarbon-containing feed can be exposed to the catalyst under a pressure in the range of 35 kPa gauge to 15 MPa gauge. In still other embodiments, the second hydrocarbon-containing feed can be exposed to the catalyst under a pressure in the range from 0.7 kPa gauge, 2 kPa gauge, 5 kPa gauge, 20 kPa gauge, 35 kPa gauge, 50 kPa gauge, or 100 kPa gauge to 200 kPa gauge, 1 MPa gauge, 3 MPa gauge, 5 MPa gauge, 10 MPa gauge, or 15 MPa gauge. In yet other embodiments, the second hydrocarbon-containing feed can be exposed to the catalyst under a pressure of less than 2.8 MPa gauge, less than 2.5 MPa gauge, less than 2.2 MPa gauge, or less than 2 MPa gauge.

[0091] The reforming reaction of the second hydrocarbon-containing feed, for example, CH4, can be carried out in the presence of H2O (steam reforming), in the presence of CO2 (dry reforming), or in the presence of both H2O and CO2 (bi-reforming). Examples of the stoichiometry for the steam reforming, dry reforming, and bi-reforming of CH4 are shown in formulas (1) to (3). (1) Dry reforming: CH4 + CO2 = 2CO + 2H2 (2) Steam reforming: CH4 + H2O = CO + 3H2 (3) Bi-reforming: 3CH4 + 2H2O + CO2 = 4CO + 8H2 As shown in Formulas (1) to (3), dry reforming can produce H2 with a lower ratio to CO than steam reforming. The reforming reaction carried out using only steam can generally produce synthesis gas having an H2:CO molar ratio of about 3, such as 2.5 to 3.5. In contrast, the reforming reaction carried out using only CO2 can generally produce synthesis gas having an H2:CO molar ratio that is approximately 1 or even lower. By using a combination of CO2 and H2O during reforming, the reforming reaction can be controlled to produce a wide range of H2 to CO ratios in the resulting synthesis gas.

[0092] It should also be noted that the ratio of H2 to CO in the synthesis gas can also depend on the water-gas shift equilibrium. The stoichiometry in Formulas (1) to (3) shows ratios of approximately 1 or approximately 3 for dry reforming and steam reforming, respectively, but the equilibrium amounts of H2 and CO in the synthesis gas can differ from the stoichiometry of the reaction. The equilibrium amounts can be determined based on the water-gas shift equilibrium, which is related to the concentrations of H2, CO, CO2, and H2O based on the reaction shown in Formula (4). (4) H2O + CO ←→ H2 + CO2

[0093] In some embodiments, the calcined catalyst can also act as a water-gas shift catalyst. Thus, when the reaction environment for producing H2 and CO also contains H2O and / or CO2, the initial stoichiometry from the reforming reaction can change based on the water-gas shift equilibrium. However, this equilibrium also depends on temperature, and the higher the temperature, the more favorable it is for the production of CO and H2O. As a result, the ratio of H2 to CO that occurs during the formation of the synthesis gas is restricted by the water-gas shift equilibrium at the temperature of the reaction zone where the synthesis gas is produced. By being able to adjust the H2:CO molar ratio of the synthesis gas, a flexible process can be realized that can be combined with a wide range of synthesis gas upgrading processes. Exemplary synthesis gas upgrading processes include, but are not limited to, the Fischer-Tropsch process, the synthesis of methanol and / or other alcohols, such as one or more C1-C4 alcohols, fermentation processes, separation methods capable of separating hydrogen to produce a hydrogen-rich product, dimethyl ether, and combinations thereof. These synthesis gas upgrading processes are well known to those skilled in the art. In some embodiments, the upgraded product can include, but is not limited to, methanol, synthetic crude oil, diesel, lubricating oil, wax, olefin, dimethyl ether, other chemicals, or any combination thereof.

[0094] Suitable systems for carrying out the reforming of the second hydrocarbon-containing feed include fixed bed reactors disclosed in WO Publication No. WO2017078894, U.S. Pat. Nos. 3,888,762; 7,102,050; 7,195,741; 7,122,160; and 8,653,317; and U.S. Patent Application Publication Nos. 2004 / 0082824; 2008 / 0194891; fluidized riser reactors and / or downer reactors, and U.S. Pat. Nos. 7,740,829; 8,551,444; 8,754,276; 9,687,803; and 10,160,708; and U.S. Patent Application Publication Nos. 2015 / 0065767 and 2017 / 0137285; and countercurrent reactors disclosed in WO Publication No. WO2013169461, and can include systems well known in the art.

Examples

[0095] The above discussion can be further explained with reference to the following non-limiting examples. The synthesized catalyst 1 was prepared according to the following procedure. Calcined hydrotalcite support particles (23.0 g; MgO:Al2O3 = 71 / 29 w / w) having physical properties matching 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 an 8% chloroplatinic acid solution, 2.97 g of a 23.65% tin(IV) chloride pentahydrate, and 20 ml of DI water was prepared. With stirring, this aqueous mixture was slowly added to the above slurry. After the addition was complete, the mixture was stirred for an additional 10 minutes, and then the solid fraction was recovered by filtration. Next, the solid was dried in air at 110 °C for 6 hours. After drying, the solid still contained a significant amount of volatile compounds and / or compounds that could form volatile compounds upon heat treatment at temperatures higher than 110 °C. The mass of the non-volatile matter of the catalyst was measured by thermogravimetric analysis (TGA) in an oxidative environment (air) by heating the synthesized catalyst to a temperature of 900 °C. The synthesized catalyst 1 had Pt and Sn loadings of approximately 0.05 wt% and 1.0 wt%, respectively, based on the mass of the non-volatile matter of the catalyst.

[0096] Nine individual samples of the synthesized catalyst 1 were obtained and individually calcined under nine different calcination processes to obtain calcined catalysts (Examples 1 - 9). The calcination processes were as follows. Calcination 1 (Example 1; (O)): 1. Under a flow of 46.6 sccm of air, the reaction zone temperature was raised 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.

[0097] Calcination 2 (Example 2; (O)): 1. Under a flow of 46.6 sccm of air, the reaction zone temperature was raised 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. Firing 3 (Example 3; (R)): 1. Under a 46.6 sccm air flow, the reaction zone temperature was raised from room temperature to 110 °C at 30 °C / min, and the catalyst particles were dried at 110 °C for 0.5 h. 2. Next, the reaction zone temperature was raised from 110 °C to 600 °C at 30 °C / min under an inert gas flow. 3. Under a 10% H2 flow in 46.6 sccm argon, the catalyst particles were fired at 600 °C for 2.5 h to produce fired catalyst particles. Firing 4 (Example 4; (OR)): 1. Under a 46.6 sccm air flow, the reaction zone temperature was raised from room temperature to 450 °C at 30 °C / min, and the catalyst particles were fired at 450 °C for 0.5 h. 2. The reaction zone temperature was raised from 450 °C to 600 °C at 30 °C / min under an inert gas flow. 3. Under a 10% H2 flow in 46.6 sccm argon, the catalyst particles were fired at 600 °C for 2.5 h to produce fired catalyst particles.

[0098] Firing 5 (Example 5; (OR)): 1. Under a 46.6 sccm air flow, the reaction zone temperature was raised from room temperature to 550 °C at 30 °C / min, and the catalyst particles were fired at 550 °C for 0.5 h. 2. Next, the reaction zone temperature was raised from 550 °C to 600 °C at 30 °C / min under an inert gas flow. 3. Under a 10% H2 flow in 46.6 sccm argon, the catalyst particles were fired at 600 °C for 2.5 h to produce fired catalyst particles. Firing 6 (Example 6; (OR)): 1. Under a 46.6 sccm air flow, the reaction zone temperature was raised from room temperature to 800 °C at 30 °C / min, and the catalyst particles were fired at 800 °C for 0.5 h. 2. Next, the reaction zone temperature was lowered from 800 °C to 600 °C at 30 °C / min under an inert gas flow. 3. Under a 10% H2 flow in 46.6 sccm argon, the catalyst particles were fired at 600 °C for 2.5 h to produce fired catalyst particles.

[0099] Firing 7 (Example 7; (OR)): 1. Under a 46.6 sccm air flow, the reaction zone temperature was raised from room temperature to 550 °C at a rate of 30 °C / min, and the catalyst particles were fired at 550 °C for 0.5 hour. 2. Next, the reaction zone temperature was raised from 550 °C to 600 °C at a rate of 30 °C / min under an inert gas flow. 3. Under a 10% H2 flow in 46.6 sccm of argon, the catalyst particles were fired at 600 °C for 1.25 hours to produce fired catalyst particles. Firing 8 (Example 8; (OR)): 1. Under a 46.6 sccm air flow, the reaction zone temperature was raised from room temperature to 550 °C at a rate of 30 °C / min, and the catalyst particles were fired at 550 °C for 0.5 hour. 2. Next, the reaction zone temperature was raised from 550 °C to 600 °C at a rate of 30 °C / min under an inert gas flow. 3. Under a 10% H2 flow in 46.6 sccm of argon, the catalyst particles were fired at 600 °C for 5 hours to produce fired catalyst particles.

[0100] Firing 9 (Example 9; (OROR)): 1. Under a 46.6 sccm air flow, the reaction zone temperature was raised from room temperature to 550 °C at a rate of 30 °C / min, and the catalyst particles were fired at 550 °C for 0.25 hour. 2. Next, the reaction zone temperature was raised from 550 °C to 600 °C at a rate of 30 °C / min under an inert gas flow. 3. Under a 10% H2 flow in 46.6 sccm of argon, the catalyst particles were fired at 600 °C for 0.625 hour. 4. Next, the system was purged with an inert gas. 5. Next, under a 46.6 sccm air flow, the reaction zone temperature was lowered from 600 °C to 550 °C at a rate of 30 °C / min, and the catalyst particles were fired at 550 °C for 0.25 hour. 6. The reaction zone temperature was raised from 550 °C to 600 °C at a rate of 30 °C / min under an inert gas flow. 7. Under a 10% H2 flow in 46.6 sccm of argon, the catalyst particles were fired at 600 °C for 0.625 hours to produce fired catalyst particles.

[0101] The fixed-bed experiments using the fired catalysts of Examples 1 to 9 were carried out at approximately 100 kPa (absolute). The composition of the reactor effluent was measured using a gas chromatograph (GC). Next, the C3H6 yield and selectivity were calculated using the concentrations of each component in the reactor effluent. The C3H6 yield and selectivity at the start of the reaction were Y, respectively.ini and S ini Represent as and report as percentages in the following table. The C3H6 yields and selectivities reported in the examples were calculated based on the number of moles of carbon. In each example, 0.3 g of catalyst (on a non-volatile basis) was mixed with an appropriate amount of silicon carbide and loaded into a quartz reactor. The amount of SiC was determined, and in this way, the catalyst bed (catalyst + SiC) overlapping the isothermal zone of the quartz reactor and the catalyst bed was made to be almost isothermal during operation. The dead volume of the reactor was filled with quartz rods.

[0102] The process steps of the examples were as follows: 1. An inert gas was vigorously flowed through this system. 2. 83.9 sccm of dry air was flowed through the bypass of the reaction zone while an inert gas was flowed through the reaction zone. 3. The reaction zone was heated to a regeneration temperature of 800 °C. 4. Next, 83.9 sccm of air was flowed through the reaction zone for 10 minutes to regenerate the catalyst. 5. An inert gas was vigorously flowed through this system. 6. 46.6 sccm of H2-containing gas (10 vol% H2 and 90 vol% Ar) was flowed through the bypass of the reaction zone for a certain period while an inert gas was flowed through the reaction zone. Next, after that, the H2-containing gas was flowed through the reaction zone at 800 °C for 3 seconds. An inert gas was vigorously flowed through this system. During this process, the temperature of the reaction zone was changed from 800 °C to a reaction temperature of 670 °C. 7. A hydrocarbon-containing (HC gas) feed containing 81 vol% C3H8, 9 vol% Ar, and 10 vol% steam was flowed through the bypass of the reaction zone at a flow rate of 17.6 sccm for a certain time while an inert gas was flowed through the reaction zone. Next, the hydrocarbon-containing feed was flowed through the reaction zone at 670 °C for 10 minutes. Sampling for GC of the reaction effluent was started immediately after switching the feed from the bypass of the reaction zone to the reaction zone. 8. The above process steps 1 to 7 were repeated for 14 cycles. Stable performance was obtained after 8 cycles.

[0103] [Table 1]

[0104] Comparison between Firings 1 and 2 and between 3 - 9 suggests that reductive firing can be more effective than oxidative firing. Comparison between Firings 1 and 2 and between Firings 4 - 9 shows that reductive firing after oxidative firing can help significantly increase the C3H6 yield. For example, Firings 4, 5, 7, and 8 resulted in catalysts with excellent performance, while Firing 6 resulted in a catalyst with slightly poorer performance. Comparison between Firings 4 - 8 shows that oxidative firing is preferably not carried out at temperatures that are too high or too low. Comparison between Firings 5, 7, and 8 shows that reductive firing should preferably not be too long or too short. Comparison between Firings 5 and 9 shows that advantages can be obtained by dividing oxidative firing and reductive firing into two repeated cycles while keeping the total period constant.

[0105] Three additional samples of the synthesized Catalyst 1 were obtained and fired under three additional firing processes to obtain fired catalysts (Examples 10 - 12). The firing processes were as follows. Firing 10 (Example 10, (OROR)): 1. Under a 46.6 sccm air flow, the reaction zone temperature was raised from room temperature to 600 °C at 30 °C / min, and the catalyst particles were fired at 600 °C for 0.25 h. 2. Next, the system was purged with an inert gas. 3. Under a 10% H2 flow in 46.6 sccm argon, the catalyst particles were fired at 600 °C for 0.625 h. 4. The system was purged with an inert gas. 5. Under a 46.6 sccm air flow, the catalyst particles were fired at 600 °C for 0.25 h. 6. Next, the system was purged with an inert gas. 7. Under a 10% H2 flow in 46.6 sccm argon, the catalyst particles were fired at 600 °C for 0.625 h to produce fired catalyst particles.

[0106] Firing 11 (Example 11; (OROR)): 1. Under a 46.6 sccm air flow, the reaction zone temperature was raised from room temperature to 550 °C at 30 °C / min, and the catalyst particles were fired at 550 °C for 0.25 h. 2. The reaction zone temperature was raised from 550 °C to 650 °C at 30 °C / min under an inert gas flow. 3. Under a 10% H2 flow in 46.6 sccm argon, the catalyst particles were fired at 650 °C for 0.625 h. 4. The system was purged with an inert gas. 5. Under a 46.6 sccm air flow, the reaction zone temperature was lowered from 650 °C to 550 °C at 30 °C / min, and the catalyst particles were fired at 550 °C for 0.25 h. 6. The reaction zone temperature was raised from 550 °C to 650 °C at 30 °C / min under an inert gas flow. 7. Under a 10% H2 flow in 46.6 sccm argon, the catalyst particles were fired at 650 °C for 0.625 h to produce fired catalyst particles.

[0107] Firing 12 (Example 12; (OROROROR)): 1. Under a 46.6 sccm air flow, the reaction zone temperature was raised from room temperature to 600 °C at 30 °C / min, and the catalyst particles were fired at 600 °C for 5 min. 2. The system was purged with an inert gas. 3. Under a 10% H2 flow in 46.6 sccm argon, the catalyst particles were fired at 600 °C for 15 min. 4. The system was purged with an inert gas. 5. Under a 46.6 sccm air flow, the catalyst particles were fired at 600 °C for 5 min. 6. The system was purged with an inert gas. 7. Under a 10% H2 flow in 46.6 sccm argon, the catalyst particles were fired at 600 °C for 15 min. 8. Steps 4 - 7 were repeated twice. 9. The system was purged with an inert gas. 10. Under a 46.6 sccm air flow, the catalyst particles were fired at 600 °C for 5 min. 11. The system was purged with an inert gas. 12. Under a 10% H2 flow in 46.6 sccm argon, the catalyst particles were fired at 600 °C for 20 min to produce fired catalyst particles. The fixed-bed experiments using the fired catalysts of Examples 10 to 12 were carried out at approximately 100 kPa (absolute). The same procedure used for the fired catalysts of Examples 1 to 9 was used for the fired catalysts of Examples 10 to 12. These results are shown in Figure 2 below. It should be noted that the reactor used to conduct the fixed-bed experiments in Examples 10 to 12 was different from the reactor used in Examples 1 to 9. Therefore, the results shown in Tables 1 and 2 should not be compared with each other regarding the performance of the catalysts because the reactors are not the same.

[0108]

Table 2

[0109] Comparison between Examples 10 and 12 shows that even when oxidative calcination and reductive calcination were divided into 5 repeated cycles while maintaining the whole period constant, it did not bring advantages regarding the C3H6 yield. Comparison between Examples 10 and 11 shows that when the temperature during oxidative calcination was decreased from 600 °C to 550 °C and the temperature during reductive calcination was increased from 600 °C to 650 °C, the C3H6 yield was improved.

[0110] 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 deionized (DI) water to prepare a slurry. An aqueous mixture containing 0.32 g of an 8% chloroplatinic acid solution, 5.95 g of 23.65% tin(IV) chloride pentahydrate, and 40 ml of DI water was prepared. With stirring, this aqueous mixture was slowly added to the above slurry. After the addition was complete, the mixture was stirred for an additional 10 minutes, and then the solid fraction 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 significant amount of volatile compounds or compounds that could form volatile compounds upon heat treatment at temperatures higher than 300 °C. The mass of the non-volatile matter of the catalyst was quantified by thermogravimetric analysis (TGA) in an oxidative environment (air) by heating the synthesized catalyst to a temperature of 900 °C. The synthesized catalyst 2 had Pt and Sn loadings of approximately 0.025 wt% and 1.0 wt%, respectively, based on the mass of the non-volatile matter of the catalyst.

[0111] Four individual samples of the synthesized catalyst 2 were obtained and individually calcined under four different calcination processes to obtain calcined catalysts (Examples 13 - 16). The calcination processes were as follows. Calcination 13 (Example 13; (O)): 1. Under a flow of 46.6 sccm of air, the reaction zone temperature was raised from room temperature to 550 °C at 30 °C / min, and the catalyst particles were calcined at 550 °C for 0.5 hour to produce calcined catalyst particles. Calcination 14 (Example 14; (OR)): 1. Under a flow of 46.6 sccm of air, the reaction zone temperature was raised from room temperature to 550 °C at 30 °C / min, and the catalyst particles were calcined at 550 °C for 0.5 hour. 2. Next, the reaction zone temperature was raised from 550 °C to 650 °C at 30 °C / min under a flow of inert gas. 3. Under a flow of 46.6 sccm of 100% H2, the catalyst particles were calcined at 650 °C for 1.25 hours to produce calcined catalyst particles. Firing 15 (Example 16; (OR)): 1. Under a 46.6 sccm air flow, the reaction zone temperature was raised from room temperature to 550 °C at a rate of 30 °C / min, and the catalyst particles were fired at 550 °C for 0.5 h. 2. Next, the reaction zone temperature was raised from 550 °C to 650 °C at a rate of 30 °C / min under an inert gas flow. 3. Under a 10% H2 flow in 46.6 sccm of argon, the catalyst particles were fired at 650 °C for 1.25 h to produce fired catalyst particles.

[0112] Firing 16 (Example 16; (ORO)): 1. Under a 46.6 sccm air flow, the reaction zone temperature was raised from room temperature to 550 °C at a rate of 30 °C / min, and the catalyst particles were fired at 550 °C for 0.5 h. 2. The reaction zone temperature was raised 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 fired at 650 °C for 1.25 h. 4. The system was purged with an inert gas. 5. Under a 46.6 sccm air flow, the reaction zone temperature was lowered from 650 °C to 550 °C at a rate of 30 °C / min, and the catalyst particles were fired at 550 °C for 0.5 h to produce fired catalyst particles.

[0113] The fixed-bed experiments using the fired catalysts of Examples 13 to 16 were carried out at approximately 100 kPa (absolute). The same procedure used for the fired catalysts of Examples 1 to 9 was used for the fired catalysts of Examples 13 to 16.

Table 3

[0114] From Table 3, it is suggested that when a combination of reductive firing / oxidative firing is used, the C3H6 yield can still be improved in the case of a catalyst having 0.025 mass% of Pt and a slightly different MgO:Al2O3 ratio compared to the synthesized catalyst 1. However, in the case of the synthesized catalyst 2, probably because the MgO:Al2O3 ratio of catalyst 2 (77 / 23 w / w) is higher than that of the synthesized catalyst 1 (71 / 29 w / w), 100% H2 was required instead of 10% H2 to achieve the highest C3H6 yield.

[0115] List of Embodiments The present disclosure can further include the following non-limiting embodiments. A1. A method of firing a catalyst, comprising the step of subjecting a synthesized catalyst containing Pt disposed on a support to a firing process, the firing process heating the synthesized catalyst at a first temperature for a first time in a first atmosphere and heating the synthesized catalyst at a second temperature for a second time in a second atmosphere to produce a fired catalyst, the synthesized catalyst containing <0.05% by mass of Pt based on the mass of the non-volatile matter of the catalyst, (i) the first atmosphere contains a first oxidizing gas, the first temperature is in the range of 350°C to 850°C, the first time is in the range of 30 seconds to 10 hours, the second atmosphere contains a first reducing gas, the second temperature is in the range of 500°C to 850°C, and the second time is in the range of 30 seconds to 10 hours, or (ii) the first atmosphere contains a first reducing gas, the first temperature is in the range of 500°C to 850°C, the first time is in the range of 30 seconds to 10 hours, the second atmosphere contains a first oxidizing gas, the second temperature is in the range of 350°C to 850°C, and the second time is in the range of 30 seconds to 10 hours.

[0116] A2. The method of A1, wherein the first oxidizing gas contains O2, O3, CO2, water vapor or a mixture thereof, and the first reducing gas contains H2, CO, CH4, C2H6, C3H8, C2H4, C3H6, water vapor or a mixture thereof. A3. When first subjecting the synthesized catalyst to a firing process, the synthesized catalyst contains one or more volatile compounds, and the one or more volatile compounds contain adsorbed CO2, adsorbed H2O, adsorbed ethanol or a mixture thereof, the method of A1 or A2. A4. The first atmosphere contains a first oxidizing gas, the second atmosphere contains a first reducing gas, and the method further includes the step of heating the synthesized catalyst at a third temperature for a third time in a third atmosphere to produce a fired catalyst, 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 is in the range of 30 seconds to 10 hours, the method according to any one of A1 to A3.

[0117] A5. The method of A4 further includes a step of heating the synthesized catalyst at a fourth temperature for a fourth time under a fourth atmosphere to produce a calcined catalyst, wherein the fourth atmosphere contains a second reducing gas, the fourth temperature ranges from 500 °C to 850 °C, and the fourth time ranges from 30 seconds to 10 hours. A6. The method of A5, wherein the second oxidizing gas contains O2, O3, CO2, water vapor, or a mixture thereof, and the second reducing gas contains H2, CO, CH4, C2H6, C3H8, C2H4, C3H6, water vapor, or a mixture thereof.

[0118] A7. The method according to any one of A1 to A3, wherein the first atmosphere contains a first reducing gas, the second atmosphere contains a first oxidizing gas, and the method further includes a step of heating the synthesized catalyst at a third temperature for a third time under a third atmosphere to produce a calcined catalyst, wherein the third atmosphere contains a second reducing gas, the third temperature ranges from 500 °C to 850 °C, and the third time ranges from 30 seconds to 10 hours. A8. The method of A7 further includes a step of heating the synthesized catalyst at a fourth temperature for a fourth time under a fourth atmosphere to produce a calcined catalyst, wherein the fourth atmosphere contains a second oxidizing gas, the fourth temperature ranges from 350 °C to 850 °C, and the fourth time ranges from 30 seconds to 10 hours. A9. The method of A8, wherein the second reducing gas contains H2, CO, CH4, C2H6, C3H8, C2H4, C3H6, water vapor, or a mixture thereof, and the second oxidizing gas contains O2, O3, CO2, water vapor, or a mixture thereof.

[0119] A10. The method according to any one of A1 to A9, wherein the synthesized catalyst further contains a promoter containing Sn, Cu, Au, Ag, Ga, a combination thereof, or a mixture thereof disposed on a carrier, the carrier contains at least 0.5% by mass of a Group 2 element, and the values of the mass percentages are all based on the mass of the non-volatile matter of the catalyst. A11. The method of A10, wherein the Group 2 element contains Mg, and at least a part of the Group 2 element is in the form of MgO or a mixed metal oxide containing Mg. A12. The method of A10, wherein the support further contains a Group 13 element, the promoter contains Sn, the Group 2 element contains Mg, the Group 13 element contains Al, and the support contains a mixed Mg / Al metal oxide. 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 conform to the definition of Geldart A of a fluidizable solid. A14. The method of any one of A1 - A13, wherein when the calcined catalyst is contacted with propane under dehydrogenation conditions, it produces a propylene selectivity of ≥90% and a propylene yield of ≥48%. A15. The method of any one of A1 - A14, wherein the composition of the first atmosphere and the composition of the second atmosphere each independently remain constant or vary over the first time and the second time, respectively.

[0120] B1. A method of calcining a catalyst, comprising subjecting synthesized catalyst particles containing Pt disposed on a support to a calcination process, the calcination process including heating the synthesized catalyst particles at a first temperature for a first time under a first atmosphere and heating the synthesized catalyst particles at a second temperature for a second time under a second atmosphere to produce calcined catalyst particles, the synthesized catalyst particles having a size and particle density that conform to the definition of Geldart A of a fluidizable solid, and (i) the first atmosphere contains a first oxidizing gas, the first temperature is in the range of 350°C to 850°C, the first time is in the range of 30 seconds to 10 hours, the second atmosphere contains a first reducing gas, the second temperature is in the range of 500°C to 850°C, and the second time is in the range of 30 seconds to 10 hours, or (ii) the first atmosphere contains a first reducing gas, the first temperature is in the range of 500°C to 850°C, the first time is in the range of 30 seconds to 10 hours, the second atmosphere contains a first oxidizing gas, the second temperature is in the range of 350°C to 850°C, and the second time is in the range of 30 seconds to 10 hours.

[0121] B2. The method of B1, wherein the first oxidizing gas contains O2, O3, CO2, water vapor, or a mixture thereof, and the first reducing gas contains H2, CO, CH4, C2H6, C3H8, C2H4, C3H6, water vapor, or a mixture thereof. B3. A method of B1 or B2, wherein when the catalyst particles are first subjected to a firing process, the catalyst particles contain one or more volatile compounds, and the one or more volatile compounds include adsorbed CO2, adsorbed H2O, adsorbed ethanol, or a mixture thereof. B4. The first atmosphere contains a first oxidizing gas, the second atmosphere contains a first reducing gas, and the method includes a step of heating the synthesized catalyst particles at a third temperature for a third time under a third atmosphere to produce fired catalyst particles, the third atmosphere further contains a second oxidizing gas, the third temperature is in the range of 350 °C to 850 °C, and the third time is in the range of 30 seconds to 10 hours, any one of the methods of B1 - B3.

[0122] B5. The method according to claim B4, further including a step of heating the synthesized catalyst particles at a fourth temperature for a fourth time under a fourth atmosphere to produce fired catalyst particles, 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 is in the range of 30 seconds to 10 hours. B6. The method of B5, wherein the second oxidizing gas includes O2, O3, CO2, water vapor, or a mixture thereof, and the second reducing gas includes H2, CO, CH4, C2H6, C3H8, C2H4, C3H6, water vapor, or a mixture thereof. B7. The first atmosphere contains a first reducing gas, the second atmosphere contains a first oxidizing gas, and the method further includes a step of heating the synthesized catalyst particles at a third temperature for a third time under a third atmosphere to produce fired catalyst particles, 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 is in the range of 30 seconds to 10 hours, any one of the methods of B4 - B6.

[0123] B8. The method of B7, further including a step of heating the synthesized catalyst particles at a fourth temperature for a fourth time under a fourth atmosphere to produce fired catalyst particles, 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 is in the range of 30 seconds to 10 hours. The method of B8, wherein the second reducing gas contains H2, CO, CH4, C2H6, C3H8, C2H4, C3H6, water vapor, or a mixture thereof, and the second oxidizing gas contains O2, O3, CO2, water vapor, or a mixture thereof. The method according to any one of B1 - B9, wherein the synthesized catalyst particles further contain, at most 10% by mass, a promoter containing Sn, Cu, Au, Ag, Ga, a combination thereof, or a mixture thereof, disposed on a support, the support contains at least 0.5% by mass of a Group 2 element, and the values of the mass percentages are all relative to the mass of the non-volatile matter of the catalyst.

[0124] The method of B10, wherein the Group 2 element contains Mg, and at least a part of the Group 2 element is in the form of MgO or a mixed metal oxide containing Mg. The method of B10, wherein the support further contains a Group 13 element, the promoter contains Sn, the Group 2 element contains Mg, the Group 13 element contains Al, and the support contains a mixed Mg / Al metal oxide. The method according to any one of B1 - B12, wherein when the calcined catalyst particles are contacted with propane under dehydrogenation conditions, a propylene selectivity of ≧90% and a propylene yield of ≧48% are produced.

[0125] The method according to any one of B1 - B13, wherein the composition of the first atmosphere and the composition of the second atmosphere each independently remain constant or vary over the first time and the second time, respectively.

[0126] C1. A method for upgrading hydrocarbons, comprising the step of subjecting a synthesized catalyst containing Pt disposed on a carrier to a first calcination, wherein the first calcination comprises exposing the synthesized catalyst to a first reducing gas under reducing conditions or a first oxidizing gas under oxidizing conditions to produce a first calcined catalyst, and the synthesized catalyst has, relative to the mass of the non-volatile matter of the catalyst, <0.Including steps and containing 0.5 mass% of Pt; the method including a step of subjecting the first-fired catalyst to cyclic firing, the cyclic firing including exposing the first-fired catalyst to a second reducing gas under reducing conditions and a second oxidizing gas under oxidizing conditions for n cycles to produce a cyclic-fired catalyst, where n is an integer, the cyclic firing starting with the second oxidizing gas when the first firing uses a first reducing gas, the cyclic firing starting with the second reducing gas when the first firing uses a first oxidizing gas, and when n ≥ 2, the composition of the second reducing gas used in each cyclic firing may be the same or different, and the composition of the second oxidizing gas used in each cyclic firing may be the same or different; the method including a step of subjecting the first-fired catalyst or the cyclic-fired catalyst to final firing, the final firing including exposing the first-fired catalyst or the cyclic-fired catalyst to a third reducing gas under reducing conditions or a third oxidizing gas under oxidizing conditions, where at least one of the cyclic firing and the final firing is performed, and when the final firing is performed, the third oxidizing gas is used when the first firing uses the first reducing gas or when the cyclic firing ends with the second reducing gas, and the third reducing gas is used when the first firing uses the first oxidizing gas or when the cyclic firing ends with the second oxidizing gas, the reducing conditions used in the first firing, optional cyclic firing, and optional final firing independently include heating the catalyst at a temperature in the range of 500 °C to 850 °C for a time in the range of 30 seconds to 10 hours, and the oxidizing conditions used in the first firing, optional cyclic firing, and optional final firing independently include heating the catalyst at a temperature in the range of 350 °C to 850 °C for a time in the range of 30 seconds to 10 hours, the fired catalyst being obtained at the end of the cyclic firing or the end of the final firing; the method including a step of contacting a hydrocarbon-containing feed with the fired catalyst to perform one or more of dehydrogenation, dehydroaromatization, and dehydrocyclization of at least a part of the hydrocarbon-containing feed to produce a coked catalyst composition and an effluent containing one or more upgraded hydrocarbons and molecular hydrogen, where the hydrocarbon-containing feed is one or more C2-C.16 a straight-chain or branched alkane, or one or more C4-C 16 cyclic alkane, or one or more C8-C 16 alkylaromatic, or a mixture thereof, wherein a hydrocarbon-containing feed and a calcined catalyst are contacted at a temperature in the range of 300 °C to 900 °C for a time of ≦ 3 hours under a hydrocarbon partial pressure of at least 20 kPa (absolute), the hydrocarbon partial pressure being the total partial pressure of any C2-C 16 alkane and any C8-C 16 alkylaromatic in the hydrocarbon-containing feed, and one or more upgraded hydrocarbons are included, the method comprising the step of

[0127] C2. further comprising the steps of contacting at least a portion of the coked catalyst with an oxidizing agent to effect combustion of at least a portion of the coke to produce a regenerated catalyst with less coke and combustion gas, and contacting an additional amount of the hydrocarbon-containing feed with at least a portion of the regenerated catalyst to produce a recoked catalyst and further effluent, the cycle time from contacting the hydrocarbon-containing feed with the calcined catalyst to contacting the additional amount of the hydrocarbon-containing feed with the regenerated catalyst being ≦ 5 hours, the method of C1.

[0128] D1. A method for upgrading hydrocarbons, comprising the step of subjecting synthetic catalyst particles containing Pt disposed on a support to a first calcination, wherein the first calcination comprises exposing the catalyst particles to a first reducing gas under reducing conditions or a first oxidizing gas under oxidizing conditions to produce first calcined catalyst particles, and the synthetic catalyst particles have a size and particle density that conform to the definition of Geldart A of a fluidizable solid; the method may comprise the step of subjecting the first calcined catalyst particles to a cyclic calcination, wherein the cyclic calcination comprises exposing the first calcined catalyst particles to a second reducing gas under reducing conditions and a second oxidizing gas under oxidizing conditions for n cycles to produce cyclic calcined catalyst particles, n is an integer, the cyclic calcination is started with the second oxidizing gas when the first calcination uses the first reducing gas, the cyclic calcination is started with the second reducing gas when the first calcination uses the first oxidizing gas, and 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 include a step of subjecting the first-fired catalyst particles or the cycle-fired catalyst particles to a final firing, wherein the final firing includes exposing the first-fired catalyst particles or the cycle-fired catalyst particles to a third reducing gas under reducing conditions or to a third oxidizing gas under oxidizing conditions. At least one of the cycle firing and the final firing is performed. When the final firing is performed, when the first firing uses a first reducing gas, or when the cycle firing ends with a second reducing gas, a third oxidizing gas is used. When the final firing is performed, when the first firing uses a first oxidizing gas, or when the cycle firing ends with a second oxidizing gas, a third reducing gas is used. The reducing conditions used for the first firing, optional cycle firing, and optional final firing independently include heating the catalyst particles for a time in the range of 30 seconds to 10 hours at a temperature in the range of 500 °C to 850 °C. The oxidizing conditions used for the first firing, optional cycle firing, and optional final firing independently include heating the catalyst particles for a time in the range of 30 seconds to 10 hours at a temperature in the range of 350 °C to 850 °C. The fired catalyst particles are obtained at the end of the cycle firing or the end of the final firing. The method is a step of contacting a hydrocarbon-containing feed with the fired catalyst to produce a coked catalyst composition and an effluent containing one or more upgraded hydrocarbons and molecular hydrogen for performing one or more of dehydrogenation, dehydroaromatization, and dehydrocyclization of at least a part of the hydrocarbon-containing feed, wherein the hydrocarbon-containing feed contains one or more C2-C; 16 linear or branched alkanes, or one or more C4-C 16 cyclic alkanes, or one or more C8-C 16 alkyl aromatics, or a mixture thereof, and contacting the hydrocarbon-containing feed and the fired catalyst at a hydrocarbon partial pressure of at least 20 kPa (absolute) for a time of ≤ 3 hours at a temperature in the range of 300 °C to 900 °C, wherein the hydrocarbon partial pressure is for any C2-C in the hydrocarbon-containing feed 16 alkanes and any C8-C 16A method comprising a step of being the total partial pressure of an alkyl aromatic, wherein one or more upgraded hydrocarbons contain at least one of a dehydrogenated hydrocarbon, a dehydrogenated aromatized hydrocarbon, and a dehydrogenated cyclized hydrocarbon.

[0129] D2. A method according to D1, further comprising the steps of contacting at least a portion of the coking catalyst with an oxidizing agent to produce a regenerated catalyst with less coke and combustion gas for burning at least a portion of the coke, and contacting an additional amount of hydrocarbon-containing feed with at least a portion of the regenerated catalyst to produce a recoked catalyst and further 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.

[0130] Various terms are defined above. To the extent that terms used in the claims are not defined above, the broadest definition given to those terms by one of ordinary skill in the art, as reflected in at least one printed publication or issued patent, shall be given. Further, all patents, test procedures, and other documents cited in this application are hereby incorporated by reference in their entirety to the extent that such disclosure is not inconsistent with this application and in all jurisdictions in which such incorporation is permitted by law.

[0131] The foregoing is directed to embodiments of the invention, but other and further embodiments of the invention may be devised without departing from the basic scope thereof, which is determined by the following claims.

Claims

1. A method for firing a catalyst, comprising: a step of subjecting a synthesized catalyst containing Pt disposed on a carrier to a first firing, the first firing including exposing the synthesized catalyst to a first reducing gas under reducing conditions or a first oxidizing gas under oxidizing conditions to produce a first fired catalyst, the synthesized catalyst containing the Pt at < 0.05% by mass based on the mass of the non-volatile matter of the catalyst; optionally, a step of subjecting the first fired catalyst to a cyclic firing, the cyclic firing including exposing the first fired catalyst to a second reducing gas under reducing conditions and a second oxidizing gas under oxidizing conditions for n cycles to produce a cyclically fired catalyst, where n is an integer, when the first firing uses the first reducing gas, the cyclic firing is started with the second oxidizing gas, when the first firing uses the first oxidizing gas, the cyclic firing is started with the second reducing gas, when n ≥ 2, the composition of the second reducing gas used in each cyclic firing may be the same or different, and the composition of the second oxidizing gas used in each cyclic firing may be the same or different; optionally, a step of subjecting the first fired catalyst or the cyclically fired catalyst to a final firing, the final firing including exposing the first fired catalyst or the cyclically fired catalyst to a third reducing gas under reducing conditions or a third oxidizing gas under oxidizing conditions; at least one of the cyclic firing and the final firing is performed; when the final firing is performed, when the first firing uses the first reducing gas, or when the cyclic firing is performed and ends with the second reducing gas, the third oxidizing gas is used; when the final firing is performed, when the first firing uses the first oxidizing gas, or when the cyclic firing is performed and ends with the second oxidizing gas, the third reducing gas is used; the reducing conditions used in the first firing, the optional cyclic firing, and the optional final firing each independently include heating the catalyst for a time in the range of 30 seconds to 10 hours at a temperature in the range of 500°C to 850°C; the oxidizing conditions used in the first firing, the optional cyclic firing, and the optional final firing each independently include heating the catalyst for a time in the range of 30 seconds to 10 hours at a temperature in the range of 350°C to 850°C, and the fired catalyst is obtained at the end of the cyclic firing or the end of the final firing. Claim 2 The first oxidizing gas, the second oxidizing gas if used, and the third oxidizing gas if used contain O 2 , O 3 , CO 2 , water vapor, or a mixture thereof independently, and the first reducing gas, the second reducing gas if used, and the third reducing gas if used contain H 2 , CO, CH 4 , C 2 H 6 , C 3 H 8 , C 2 H 4 , C 3 H 6 , water vapor, or a mixture thereof independently, the method according to claim 1. Claim 3 The reduction conditions used for the initial firing, optional cycle firing, and optional final firing independently include heating the catalyst at a temperature in the range of 550°C to 700°C for a time in the range of 5 minutes to 1 hour, The oxidation conditions used for the initial firing, optional cycle firing, and optional final firing independently include heating the catalyst at a temperature in the range of 400°C to 600°C for a time in the range of 5 minutes to 1 hour, The method according to claim 1 or claim 2. Claim 4 The temperature under the reduction conditions used for the initial firing, optional cycle firing, and optional final firing is equal to or higher than the temperature under the oxidation conditions used for the initial firing, optional cycle firing, and optional final firing, according to any one of claims 1 to 3. The method described in the item. Claim 5 The total time under the reduction conditions used for the initial firing, optional cycle firing, and optional final firing is longer than the total time under the oxidation conditions used for the initial firing, optional cycle firing, and optional final firing, according to any one of claims 1 to 4. The method described in the item. Claim 6 When the synthesized catalyst is subjected to the first calcination, the synthesized catalyst contains one or more volatile compounds, and the one or more volatile compounds are adsorbed CO 2 , adsorbed H 2 O, adsorbed ethanol, or a mixture thereof, the method according to any one of claims 1 to 5. Claim 7 The synthesized catalyst further contains a promoter containing Sn, Cu, Au, Ag, Ga, a combination thereof, or a mixture thereof, disposed on a carrier, up to 10% by mass, The synthesized catalyst contains at least 0.5% by mass of a Group 2 element, All the mass percentage values are based on the mass of the non-volatile matter of the catalyst The method according to any one of claims 1 to 6. Claim 8 The Group 2 element contains Mg, At least a part of the Group 2 element is in the form of MgO or a mixed metal oxide containing Mg, The method according to claim 7. Claim 9 The carrier further contains a Group 13 element, The promoter contains Sn, The Group 2 element contains Mg, The Group 13 element contains Al, The carrier contains a mixed Mg / Al metal oxide, The method according to claim 7. Claim 10 The synthesized catalyst is in the form of particles having a size and particle density that conform to the definition of Geldart A of a fluidized solid, according to any one of claims 1 to 9. The method described in the item. Claim 11 When the calcined catalyst is contacted with propane under dehydrogenation conditions, it produces a propylene selectivity of ≧90% and a propylene yield of ≧48%, according to any one of claims 1 to 10. The method described in the item. Claim 12 The method according to any one of claims 1 to 11, wherein the synthesized catalyst contains 0.001% to 0.045% by mass of the Pt based on the mass of the non-volatile matter of the catalyst.

13. The method according to any one of claims 1 to 12, wherein both cycle firing and final firing are performed.

14. The composition of the first oxidizing gas, the composition thereof when the second oxidizing gas is used, and the composition thereof when the third oxidizing gas is used are each maintained constant or vary independently during the initial firing, cycle firing, and final firing, respectively, in the method according to any one of claims 1 to 13.

15. The composition of the first reducing gas, the composition thereof when the second reducing gas is used, and the composition thereof when the third reducing gas is used are each maintained constant or vary independently during the initial firing, cycle firing, and final firing, respectively, in the method according to any one of claims 1 to 14.

16. A method for firing a catalyst, wherein the method includes a step of subjecting synthesized catalyst particles containing Pt disposed on a carrier to an initial firing, the initial firing including exposing the catalyst particles to a first reducing gas under reducing conditions or a first oxidizing gas under oxidizing conditions to produce initial fired catalyst particles, and the synthesized catalyst particles having a size and particle density that conform to the definition of Geldart A of a fluidizable solid. The method may include a step of subjecting the initial fired catalyst particles to a cycle firing, the cycle firing including exposing the initial fired catalyst particles to a second reducing gas under reducing conditions and a second oxidizing gas under oxidizing conditions during n cycles to produce cycle fired catalyst particles. n is an integer. The cycle firing starts with the second oxidizing gas when the first reducing gas is used in the initial firing. The cycle firing starts with the second reducing gas when the first oxidizing gas is used in the initial firing. When n ≥ 2, the composition of the second reducing gas used in each cycle firing is the same or different, and the composition of the second oxidizing gas used in each cycle firing is the same or different. The method may include a step of subjecting the first-fired catalyst particles or the cycle-fired catalyst particles to a final firing, the final firing including exposing the first-fired catalyst particles or the cycle-fired catalyst particles to a third reducing gas under reducing conditions or to a third oxidizing gas under oxidizing conditions. At least one of cycle firing and final firing is performed. When the final firing is performed, if the first firing uses a first reducing gas, or when the cycle firing is performed and ends with a second reducing gas, a third oxidizing gas is used. When the final firing is performed, if the first firing uses a first oxidizing gas, or when the cycle firing is performed and ends with a second oxidizing gas, a third reducing gas is used. The reducing conditions used for the first firing, optional cycle firing, and optional final firing independently include heating the catalyst particles at a temperature in the range of 500°C to 850°C for a time in the range of 30 seconds to 10 hours. The oxidizing conditions used for the first firing, optional cycle firing, and optional final firing independently include heating the catalyst particles at a temperature in the range of 350°C to 850°C for a time in the range of 30 seconds to 10 hours. A method in which the fired catalyst particles are obtained at the end of cycle firing or at the end of final firing.

17. The first oxidizing gas, the second oxidizing gas if used, and the third oxidizing gas if used contain, independently, O 2 , O 3 , CO 2 , water vapor, or a mixture thereof, and the first reducing gas, the second reducing gas if used, and the third reducing gas if used contain, independently, H 2 , CO, CH 4 , C 2 H 6 , C 3 H 8 , C 2 H 4 , C 3 H 6 , water vapor, or a mixture thereof, the method according to claim 16.

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

19. The method according to any one of claims 16 to 18, wherein the temperature under the reducing conditions used for the first firing, optional cycle firing, and optional final firing is equal to or higher than the temperature under the oxidizing conditions used for the first firing, optional cycle firing, and optional final firing.

20. The method according to any one of claims 16 to 19, wherein the total time under the reducing conditions used for the first firing, optional cycle firing, and optional final firing is longer than the total time under the oxidizing conditions used for the first firing, optional cycle firing, and optional final firing.

21. When the synthesized catalyst particles are subjected to the first firing, the synthesized catalyst particles contain one or more volatile compounds, and the one or more volatile compounds are adsorbed CO 2 , adsorbed H 2 O, adsorbed ethanol, or a mixture thereof, the method according to any one of claims 16 to 20. Claim 22 The synthesized catalyst particles further contain, at most 10% by mass, of a promoter containing Sn, Cu, Au, Ag, Ga, a combination thereof, or a mixture thereof, disposed on a carrier, The synthesized catalyst particles contain at least 0.5% by mass of a Group 2 element, All of the mass percentage values are based on the mass of the non-volatile matter of the catalyst, The method according to any one of claims 16 to 21. Claim 23 The Group 2 element contains Mg, At least a part of the Group 2 element is in the form of MgO or a mixed metal oxide containing Mg, The method according to claim 22. Claim 24 The carrier further contains a Group 13 element, The promoter contains Sn, The Group 2 element contains Mg, The Group 13 element contains Al, The carrier contains a mixed Mg / Al metal oxide, The method according to claim 22. Claim 25 When the calcined catalyst particles are contacted with propane under dehydrogenation conditions, a propylene selectivity of ≧90% and a propylene yield of ≧48% are produced. The method according to any one of claims 16 to 24. Claim 26 The synthesized catalyst particles contain 0.001% to 6% by mass of the Pt, based on the mass of the non-volatile matter of the catalyst. The method according to any one of claims 16 to 25. Claim 27 Both cycle calcination and final calcination are performed. The method according to any one of claims 16 to 26. Claim 28 The composition of the first oxidizing gas, the composition thereof when the second oxidizing gas is used, and the composition thereof when the third oxidizing gas is used are each maintained constant or vary independently during the first calcination, the cycle calcination, and the final calcination. The method according to any one of claims 16 to 27. Claim 29 The composition of the first reducing gas, the composition thereof when the second reducing gas is used, and the composition thereof when the third reducing gas is used are each maintained constant or vary independently during the first calcination, the cycle calcination, and the final calcination. The method according to any one of claims 16 to 28.

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