Catalyst systems and methods for making and using same

Abstract

Catalyst systems and methods for making and using the same. The catalyst system can include a plurality of catalyst particles and a plurality of catalytically inactive particles configured to be mixed with each other or mixed with each other. The catalyst particles can include a first promoter including a Group 8-10 element and Sn, Cu, Au, Ag, Ga, combinations thereof, or mixtures thereof, disposed on a support. The catalyst particles can include 0.001% to 6% by weight of a Group 8-10 element and up to 10% by weight of the first promoter, and the support can include Al and at least 0.5% by weight of a Group 2 element, based on the weight of the support. The catalytically inactive particles can be free of a Group 8-10 element. The composition of the catalytically inactive particles and the composition of the support can be the same or different.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to and the benefit of U.S. Provisional Application No. 63 / 485,956, filed February 20, 2023, the disclosure of which is incorporated herein by reference in its entirety. FIELD OF THE DISCLOSURE The present disclosure relates to catalyst systems and methods of making and using the same. More particularly, the present disclosure relates to catalyst systems comprising a plurality of catalytic particles and a plurality of catalytically inactive particles, and methods of making and using the same. [Background technology]

[0002] Catalytic reforming or dehydrogenation, dehydroaromatization, and / or dehydrocyclization of alkanes and / or alkylaromatic hydrocarbons are endothermic and equilibrium limited industrially important chemical conversion processes. 12 The reforming or dehydrogenation, dehydroaromatization and / or dehydrocyclization of alkanes and / or alkylaromatics, such as ethylbenzene, can be carried out over a variety of different catalyst compositions, 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. Catalyst preparation requires synthesis and processing steps, such as spray drying the support, calcination to form, for example, a catalyst support, and the application of a precious metal at some point during the preparation of the catalyst. The amount of catalyst used in commercial-scale processes is quite large, and the cost of applying the precious metal to the catalyst can be a significant aspect of the overall cost of preparing the catalyst. Therefore, there is a need for improved catalyst systems and methods of making and using them. The present disclosure meets this and other needs. Summary of the Invention

[0003] Catalyst systems and methods for making and using the same are provided. In some embodiments, the catalyst system can include a plurality of catalyst particles and a plurality of catalytically inactive particles configured to be mixed with each other or mixed with each other. The catalyst particles can include a Group 8-10 element and a first promoter, which can include Sn, Cu, Au, Ag, Ga, combinations thereof, or mixtures thereof, disposed on a support. The catalyst particles can include 0.001% to 6% by weight of the Group 8-10 element and up to 10% by weight of the first promoter, and the support can include Al and at least 0.5% by weight of a Group 2 element, based on the weight of the support. The catalytically inactive particles can be free of a Group 8-10 element. The composition of the catalytically inactive particles and the composition of the support can be the same or different.

[0004] In some embodiments, a process for upgrading hydrocarbons can include contacting the hydrocarbon-containing feed with a catalyst system that can include a mixture of catalyst particles and catalytically inert particles to dehydrogenate, dehydroaromatize, and dehydrocyclize at least a portion of the hydrocarbon-containing feed to produce a coked catalyst system and an effluent that can include one or more upgraded hydrocarbons and molecular hydrogen. The hydrocarbon-containing feed can be a C2-C 16 One or more linear or branched alkanes, or C4-C 16 one or more cyclic alkanes or one or more C-C 16The catalyst particles may include alkylaromatics, or mixtures thereof. The one or more upgraded hydrocarbons may include at least one of dehydrogenated hydrocarbons, dehydroaromatized hydrocarbons, and dehydrocyclized hydrocarbons. The catalyst particles may include a first promoter disposed on a support, the first promoter may include a Group 8-10 element and Sn, Cu, Au, Ag, Ga, combinations thereof, or mixtures thereof. The catalyst particles may include 0.001% to 6% by weight of a Group 8-10 element and up to 10% by weight of the first promoter, and the support may include Al and at least 0.5% by weight of a Group 2 element, based on the weight of the support. The catalytically inactive particles may be free of a Group 8-10 element. The composition of the catalytically inactive particles and the composition of the support may be the same or different. DETAILED DESCRIPTION OF THE INVENTION

[0005] Various specific embodiments, forms, and examples of the present invention will now be described, including preferred embodiments and definitions adopted herein, for purposes of understanding the claimed invention. While the following detailed description presents certain preferred embodiments, those skilled in the art will understand that these embodiments are exemplary only and that the present invention may be practiced in other ways. For purposes of determining infringement, the scope of the 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, but not necessarily all, of the inventions defined by the claims.

[0006] In this disclosure, methods are described as including at least one "step." Each step should be understood to be an act or operation that may be performed one or more times in the method, either sequentially or non-sequentially. Unless specified to the contrary or unless the context clearly dictates otherwise, multiple steps in a method may be performed sequentially in the order in which they are listed, with or without overlapping with one or more other steps, or, in some cases, in any other order. Furthermore, one or more steps, or even all steps, may be performed simultaneously with respect to materials in the same or different batches. For example, in a continuous process, the first step in the method may be performed with respect to a feedstock that is just provided at the start of the method, while the second step may be performed simultaneously with respect to an intermediate material resulting from processing of the feedstock previously provided to the method in the first step. Preferably, these steps are performed in the order in which they are listed. Unless otherwise indicated, all numbers indicating 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 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 contains a certain level of error due to the limitations of the techniques and / or devices used to obtain the measured values.

[0007] Certain embodiments and features are described herein using a set of upper numerical limits and a set of lower numerical limits, and it should be understood that ranges including any two value combinations, e.g., any lower value with any higher value, any two lower values, and / or any two higher values, are contemplated unless otherwise indicated. The indefinite article "a" or "an," as used herein, means "at least one" unless specifically specified to the contrary or unless 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 specifically specified to the contrary or unless the context clearly dictates that only one reactor or conversion zone is used.

[0008] The term "hydrocarbon" means (i) any compound consisting of hydrogen and carbon atoms, or (ii) a mixture of any 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) a mixture of any two or more such hydrocarbon compounds in (i). Thus, C2 hydrocarbons may be ethane, ethylene, acetylene, or a mixture of any two or more of these compounds in any proportion. "Cm to Cn hydrocarbons" or "Cm-Cn hydrocarbons", where m and n are positive integers and m < n, means any one of Cm, Cm+1, Cm+2, …, Cn-1, Cn hydrocarbons, or a mixture of any 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 of any two or more of these compounds in any proportion between two components and among three or more components. "Saturated C2-C3 hydrocarbons" may be ethane, propane, cyclopropane, or a mixture of any two or more of them in any proportion. "Cn+ hydrocarbons" means (i) any hydrocarbon compound containing a total of at least n carbon atoms in its molecule, or (ii) a mixture of any two or more such hydrocarbon compounds in (i). "Cn- hydrocarbons" means (i) any hydrocarbon compound containing a total of at most n carbon atoms in its molecule, or (ii) a mixture of any two or more such hydrocarbon compounds in (i). "Cm hydrocarbon stream" means a hydrocarbon stream consisting essentially of Cm hydrocarbons. "Cm-Cn hydrocarbon stream" means a hydrocarbon stream consisting essentially of Cm~Cn hydrocarbons.

[0009] For the purposes of this disclosure, the nomenclature of elements is as in Hawley's Condensed Chemical Dictionary, 16 thEd., John Wiley & Sons, Inc., (2016), Appendix V. For example, Group 2 elements include Mg, Group 8 elements include Fe, Group 9 elements include Co, Group 10 elements include Ni, and Group 13 elements include Al. The term "metalloid," as used herein, refers to the following elements: B, Si, Ge, As, Sb, Te, and At. In this disclosure, when a given element is designated as being present, that element can exist in the elemental state or as any of their chemical compounds, unless otherwise specified or clearly dictated otherwise by context. 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 may be straight-chain, branched, or cyclic. The term "aromatic" should be understood to include alkyl-substituted and unsubstituted mononuclear and polynuclear compounds, in accordance with art-recognized standards.

[0010] The term "rich in," when used in phrases such as "X-rich" or "rich in X," with reference to an output stream obtained from an apparatus, e.g., a conversion zone, means that the stream contains a higher concentration of substance X than in a feed material fed to the same apparatus to which the stream is directed. The term "lean," when used in phrases such as "X-lean" or "lean in X," with reference to an output stream obtained from an apparatus, e.g., a conversion zone, means that the stream contains a lower concentration of substance X than in a feed material fed to the same apparatus to which the stream is directed.

[0011] The term "mixed metal oxide" refers to a composition containing oxygen atoms and at least two different metal atoms mixed on an atomic scale. For example, a "mixed Mg / Al metal oxide" has O, Mg, and Al atoms mixed on an atomic scale and has the general chemical formula

number

[0012] The term "selectivity" refers to the production of a particular compound (based on moles of carbon) in a catalytic reaction. As an example, the phrase "an alkane hydrocarbon conversion reaction has 100% selectivity to olefin hydrocarbons" means that 100% of the alkane hydrocarbons (based on moles of carbon) converted in the reaction are converted to olefin hydrocarbons. When used in connection with a designated reactant, the term "conversion" refers to the amount of reactant consumed in the reaction. For example, if the designated reactant is propane, 100% conversion means that 100% of the propane is consumed in the reaction. As another example, if the designated 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 moles of carbon) is the product of the conversion and the selectivity.

[0013] As used herein, "sccm" means standard cubic centimeters per minute, which is the number of cubic centimeters (cm) of gas at standard temperature and pressure that passes through a given point in one minute. 3Standard Temperature and Pressure (STP) is a flow measurement used to indicate a temperature of 273.15 K (0°C, 32°F) and a pressure of 10 5 Refers to absolute pressure in Pa (100 kPa, 1 bar). In this disclosure, "A, B... or a combination thereof" means "A, B... or any combination of any two or more of A, B...", and "A, B... or a mixture thereof" means "A, B... or any mixture of any two or more of A, B...".

[0014] catalyst system In some embodiments, the catalyst system can include a plurality of catalyst particles and a plurality of catalytically inactive particles configured to be mixed with each other or mixed with each other. The catalyst particles can include a Group 8-10 element disposed on a support. In some embodiments, the catalyst particles can include 0.001%, 0.002%, 0.003%, 0.004%, 0.005%, 0.006%, 0.007%, 0.008%, 0.009%, 0.01%, 0.015%, 0.02%, 0.025%, 0.03%, 0.05%, 0.07%, 0.09%, 0.1%, 0.2%, 0.3%, 0.4%, or 0.5% by mass, 0.6% by mass, 0.7% by mass, 0.8% by mass, 0.9% by mass, or 1% by mass to 1.3% by mass, 1.5% by mass, 1.7% by mass, 2% by mass, 2.3% by mass, 2.5% by mass, 2.7% by mass, 3% by mass, 3. It can contain 3% by mass, 3.5% by mass, 3.7% by mass, 4% by mass, 4.3% by mass, 4.5% by mass, 4.7% by mass, 5% by mass, 5.3% by mass, 5.5% by mass, 5.7% by mass, or 6% by mass of Group 8-10 elements. In some embodiments, the Group 8-10 element can be Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, any combination thereof, or any mixture thereof. In some embodiments, the Group 8-10 element can be Pt. In some embodiments, the Group 8-10 element can be in its elemental form, a compound containing one or more Group 8-10 elements, or a combination or mixture thereof.

[0015] In some embodiments, the Group 8-10 elements in the catalyst particles can include two or more Group 8-10 elements. In such embodiments, the catalyst particles can include 0.001%, 0.002%, 0.003%, 0.004%, 0.005%, 0.006%, 0.007%, 0.008%, 0.009%, 0.01%, 0.015%, 0.02%, 0.025%, 0.03%, 0.035%, 0.04%, 0.045%, 0.05%, 0.055% by weight of Group 8-10 elements. , 0.06 mass%, 0.065 mass%, 0.07 mass%, 0.08 mass%, 0.085 mass%, 0.09 mass%, 0.095 mass%, 0.1 mass%, 0.2 mass%, 0.3 mass%, 0.4 mass%, 0.5 mass%, 0.6 mass%, 0.7 mass%, 0.8 mass%, 0.9 mass%, or 1 mass% to 2 mass%, 3 mass%, 4 mass%, 5 mass%, or 6 mass%.

[0016] The catalyst particles may also include a promoter or "first promoter" disposed on the support, which may include Sn, Cu, Au, Ag, Ga, combinations thereof, or mixtures thereof. In some embodiments, the catalyst particles may include 0.01%, 0.05%, 0.1%, 0.2%, 0.25%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1% to 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10% by weight of the promoter or first promoter disposed on the support, based on the weight of the support. In some embodiments, the promoter or first promoter may be combined with a Group 8-10 element. For example, a promoter and Pt disposed on the support may form Pt promoter clusters that may be dispersed on the support. The cocatalyst or first cocatalyst can improve the selectivity / activity / lifetime of the catalyst system for a given upgraded hydrocarbon. In some embodiments, the cocatalyst or first cocatalyst can improve the propylene selectivity of the catalyst composition when the hydrocarbon-containing feed comprises propane.

[0017] In some embodiments, the catalyst particles may optionally include one or more alkali metal elements or a first alkali metal element disposed on the support in an amount of up to 5% by weight, based on the weight of the support. In some embodiments, the catalyst particles may include 0.01%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1% to 2%, 3%, 4%, or 5% by weight of alkali metal elements disposed on the support, based on the weight of the support. The alkali metal element, if present, may be or include, but is not limited to, Li, Na, K, Rb, Cs, or combinations or mixtures thereof. In at least some embodiments, the alkali metal element may be or include K and / or Cs. In some embodiments, the alkali metal element, if present, may improve the selectivity of the catalyst composition for a given upgraded hydrocarbon.

[0018] In some embodiments, the support may be or include, but is not limited to, one or more Group 2 elements and aluminum (Al). The Group 2 element may be or include Be, Mg, Ca, Sr, Ba, combinations thereof, or mixtures thereof. In some embodiments, the Group 2 element and / or Al may be present in its elemental form. In other embodiments, the Group 2 element and / or Al may be present in the form of a compound. For example, the Group 2 element and / or Al may be present as an oxide, phosphate, halide, halate, sulfate, sulfide, borate, nitride, carbide, aluminate, carbonate, metaphosphate, selenide, tungstate, molybdate, chromite, chromate, or dichromate. In some embodiments, a mixture of any two or more compounds containing the Group 2 element and / or Al may be present in different forms.

[0019] In some embodiments, the support can include ≥0.5%, ≥1%, ≥2%, ≥3%, ≥4%, ≥5%, ≥10%, ≥20%, ≥40%, ≥80%, or ≥90% by weight of a Group 2 element, based on the weight of the support. In some embodiments, the support can include 0.5%, 3%, 5%, or 10% to 30%, 50%, 70%, or 90% by weight of a Group 2 element, based on the weight of the support.

[0020] In some embodiments, the carrier may comprise, but is not limited to, one or more of the following compounds: Mg w AlO 3+w (w is a positive number);Ca x AlO 3+x (x is a positive number);Sr y AlO 3+y (y is a positive number);Ba z AlO 3+z (z is a positive number), BeO, MgO, CaO, BaO, SrO, BeCO3, MgCO3, CaCO3, SrCO3, BaCO3, CaZrO3, Ca7ZrAl6O 18 , CaTiO3, Ca7Al6O 18 , Ca7HfAl6O 18 , BaCeO3, one or more magnesium chromates, one or more magnesium tungstates, one or more magnesium molybdates, combinations thereof and / or mixtures thereof.

[0021] Mg w AlO 3+w (w is a positive number), when present as a support or as a component of a support, can have a molar ratio of Mg to Al ranging from 0.5, 1, 2, 3, 4, or 5 to 6, 7, 8, 9, or 10. In some embodiments, Mg w AlO 3+w may include MgAl2O4, Mg2Al2O5, or a mixture thereof. x AlO 3+x(x is a positive number), when present as a support or as a component of a support, can have a molar ratio of Ca to Al in the range of 1:12, 1:4, 1:2, 2:3, 5:6, 1:1, 12:14, or 1.5:1. In some embodiments, Ca x AlO 3+x Sr can include tricalcium aluminate, dodecacalcium heptaaluminate, monocalcium aluminate, monocalcium dialuminate, monocalcium hexaaluminate, dicalcium aluminate, pentacalcium trialuminate, tetracalcium trialuminate, or any mixture thereof. y AlO 3+y (y is a positive number), when present as a support or as a component of a support, can have a molar ratio of Sr to Al ranging from 0.05, 0.3, or 0.6 to 0.9, 1.5, or 3. z AlO 3+z (z is a positive number) when present as a support or as a component of a support may have a molar ratio of Ba to Al of from 0.05, 0.3 or 0.6 to 0.9, 1.5 or 3.

[0022] In some embodiments, the Group 2 element can include Mg, and at least a portion of the Group 2 element can be in the form of MgO or a mixed metal oxide that includes Mg. In some embodiments, the support can be or include, but is not limited to, a mixed Mg / Al metal oxide. In some embodiments, the support can be or include, a mixed Mg / Al metal oxide produced or obtained by calcining hydrotalcite. In some embodiments, the support can be or include, a mixed Mg / Al metal oxide produced or obtained by calcining hydrotalcite, but with compounds of the same or similar structure made by an alternative process.

[0023] In some embodiments, the mass ratio of Group 2 element to Al in the support 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 support is a mixed Mg / Al metal oxide, the support can have a mass ratio of Mg to Al ranging from 0.001, 0.005, 0.01, 0.05, 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, or 5 to 6, 10, 12.5, 25, 50, 75, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, or 1,000. In some embodiments, the carrier is ≧0.5% by weight, ≧1% by weight, ≧2% by weight, ≧2.1% by weight, ≧2.5% by weight, ≧3% by weight, ≧3.5% by weight, ≧4% by weight, ≧4.5% by weight, ≧5% by weight, ≧ 5.5% by mass, ≧6% by mass, ≧6.5% by mass, ≧7% by mass, ≧8% by mass, ≧9% by mass, ≧10% by mass, ≧11% by mass, ≧12% by mass, ≧13% by mass, ≧14% by mass, ≧15% by mass, ≧16% by mass, ≧17% by mass, ≧18 mass%, ≧19 mass%, ≧20 mass%, ≧21 mass%, ≧22 mass%, ≧23 mass%, ≧24 mass%, ≧25 mass%, ≧26 mass%, ≧27 mass%, ≧28 mass%, ≧29 mass%, ≧30 mass%, ≧35 quality %, ≧40% by weight, ≧45% by weight, ≧50% by weight, ≧55% by weight, ≧60% by weight, ≧65% by weight, ≧70% by weight, ≧75% by weight, ≧80% by weight, ≧85% by weight or ≧90% by weight of Group 2 elements.In some embodiments, the support can comprise in the range of 0.5%, 1%, 1.5%, 2%, 2.1%, 2.3%, 2.5%, 2.7%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 13%, 15%, 17%, 19%, 21%, 23%, or 25% to 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 92.34% by weight of a Group 2 element, based on the weight of the support. In some embodiments, the support can include from 0.5%, 1%, 1.5%, 2%, 2.1%, 2.3%, 2.5%, 2.7%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, or 11% by weight Al up to 15%, 20%, 25%, 30%, 40%, 45%, or 50% by weight Al, based on the weight of the support.

[0024] In some embodiments, the support may be or include a first amount of a Group 2 element and Al in the form of a mixed Group 2 element / Al metal oxide, and a second amount of a Group 2 element in the form of an oxide of the Group 2 element. In such embodiments, the mixed Group 2 element / Al metal oxide and the oxide of the Group 2 element may be mixed on a nm scale, and the Group 2 element and Al in the mixed Group 2 element / Al metal oxide may be mixed on an atomic scale.

[0025] In other embodiments, the support may be or include a first amount of Al in the form of a Group 2 element and a mixed Group 2 element / Al metal oxide, and a second amount of Al in the form of Al2O3. In such embodiments, the mixed Group 2 element / Al metal oxide and Al2O3 may be mixed on a nm scale, and the Group 2 element and Al in the mixed Group 2 element / Al metal oxide may be mixed on an atomic scale.

[0026] In yet other embodiments, the support may be or include a first amount of Group 2 element and a first amount of Al in the form of a mixed Group 2 element / Al metal oxide, a second amount of Group 2 element in the form of an oxide of the 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 may be mixed on a nm scale, and the Group 2 element and Al in the mixed Group 2 element / Al metal oxide may be mixed on an atomic scale.

[0027] In some embodiments, the molar ratio of the Group 2 element to the total amount of any Group 8-10 elements present in the catalyst particles is from 0.24, 0.5, 1, 10, 50, 100, 300, 450, 600, 800, 1,000, 1,200, 1,500, 1,700, or 2,000 to 3,000, 3,500, 4,000, 4,500, 5,000, 5,500, 6,000, 6,500, 7,000, 7,500, 8,000, 8,500, 9,000, 9,500, 10,000 , 15,000, 20,000, 25,000, 30,000, 35,000, 40,000, 45,000, 50,000, 55,000, 60,000, 65,000, 70,000, 75,000, 80,000, 85,000, 90,000, 95,000, 100,000, 200,000, 300,000, 400,000, 500,000, 600,000, 700,000, 800,000, or 900,000.

[0028] In some embodiments, the catalyst particles may not include any Si. In other embodiments, the catalyst particles may include <0.5%, <0.45%, <0.4%, <0.35%, <0.3%, <0.25%, <0.2%, <0.15%, <0.1%, <0.09%, <0.08%, <0.07%, <0.06%, <0.05%, <0.04%, <0.03%, 0.02%, <0.01%, <0.007%, <0.005%, <0.003%, <0.001%, <0.0007%, <0.0005%, <0.0003%, or <0.0001% by weight of Si, relative to the weight of the support.

[0029] In some embodiments, the catalyst particles can have a median particle size ranging from 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, the catalyst particles have a median particle size of 0.3 g / cm when measured according to ASTM D7481-18, modified using a 10, 25, or 50 mL graduated cylinder instead of a 100 or 250 mL graduated cylinder. 3 , 0.4g / cm 3 , 0.5g / cm 3 , 0.6g / cm 3 , 0.7g / cm 3 , 0.8g / cm 3 , 0.9g / cm 3 or 1g / cm 3 to 1.1 g / cm 3 , 1.2g / cm 3 , 1.3g / cm 3 , 1.4g / cm 3 , 1.5g / cm 3 , 1.6g / cm 3 , 1.7g / cm 3 , 1.8g / cm 3 , 1.9g / cm 3 or 2 g / cm 3In some embodiments, the catalyst particles may have an apparent loose bulk density ranging from ≤5%, ≤4%, ≤3%, ≤2%, ≤1%, ≤0.7%, ≤0.5%, ≤0.4%, ≤0.3%, ≤0.2%, ≤0.1%, ≤0.07%, or ≤0.05% by weight after 1 hour, as measured in accordance with ASTM D5757-11(2017). The geometry of the catalyst particles may be predominantly spherical, and therefore, they are suitable for movement within a fluidized bed reactor. In some embodiments, the catalyst particles may have a size and density consistent with the Geldart A or Geldart B definition of a flowable solid.

[0030] In some embodiments, the catalyst particles are 2 / g, 1m 2 / g, 10m 2 / g or 100m 2 / g to 500m 2 / g, 800m 2 / g, 1,000m 2 / g or 1,500m 2 / g. The surface area of ​​the catalyst particles can be measured according to the Brunauer-Emmett-Teller (BET) method using nitrogen adsorption-desorption (liquid nitrogen temperature, 77 K) using 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.

[0031] catalytic inert particles In some embodiments, the catalytically inactive particles may be or include, but are not limited to, aluminum oxide, magnesium oxide, a second mixed Mg / Al metal oxide, quartz, silicon carbide, or mixtures thereof. In some embodiments, the composition of the catalytically inactive particles and the composition of the support in the catalyst particles may be the same or different with respect to each other. In some embodiments, the catalytically inactive particles may be the same as the catalyst particles, except that the catalytically inactive particles may not include any Group 8-10 elements. In some embodiments, the catalytically inactive particles may also include a promoter or "second promoter" disposed thereon, which may include Sn, Cu, Au, Ag, Ga, combinations thereof, or mixtures thereof. In some embodiments, the catalytically inactive particles may include 0.01%, 0.05%, 0.1%, 0.2%, 0.25%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1% to 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10% by weight of the second promoter disposed thereon, relative to the weight of the catalytically inactive particles.

[0032] In some embodiments, the catalytically inactive particles may include one or more alkali metal elements or "second" alkali metal elements disposed thereon in an amount of up to 5% by weight, based on the weight of the catalytically inactive particles. In some embodiments, the catalytically inactive particles may include 0.01%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1% to 2%, 3%, 4%, or 5% by weight of alkali metal elements disposed thereon, based on the weight of the catalytically inactive particles. The alkali metal elements, if present, may be or include, but are not limited to, Li, Na, K, Rb, Cs, or combinations or mixtures thereof. In at least some embodiments, the alkali metal elements may be or include K and / or Cs.

[0033] In some embodiments, the catalytically inactive particles may not include any Si. In other embodiments, the catalytically inactive particles may contain <0.5%, <0.45%, <0.4%, <0.35%, <0.3%, <0.25%, <0.2%, <0.15%, <0.1%, <0.09%, <0.08%, <0.07%, <0.06%, <0.05%, <0.04%, <0.03%, 0.02%, <0.01%, <0.007%, <0.005%, <0.003%, <0.001%, <0.0007%, <0.0005%, <0.0003%, or <0.0001% by weight of Si, relative to the weight of the catalytically inactive particles.

[0034] In some embodiments, the catalytically inactive particles can have a median particle size ranging from 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, the catalytically inactive particles can have a median particle size ranging from 0.3 g / cm when measured according to ASTM D7481-18, modified using a 10, 25, or 50 mL graduated cylinder instead of a 100 or 250 mL graduated cylinder. 3 , 0.4g / cm 3 , 0.5g / cm 3 , 0.6g / cm 3 , 0.7g / cm 3 , 0.8g / cm 3 , 0.9g / cm 3 or 1g / cm 3 to 1.1 g / cm 3 , 1.2g / cm 3 , 1.3g / cm 3 , 1.4g / cm 3 , 1.5g / cm 3 , 1.6g / cm 3 , 1.7g / cm 3 , 1.8g / cm 3 , 1.9g / cm 3 or 2 g / cm 3In some embodiments, the catalyst particles may have an apparent loose bulk density ranging from ≦5%, ≦4%, ≦3%, ≦2%, ≦1%, ≦0.7%, ≦0.5%, ≦0.4%, ≦0.3%, ≦0.2%, ≦0.1%, ≦0.07%, or ≦0.05% by weight after 1 hour, as measured in accordance with ASTM D5757-11(2017). The catalytically inert particles may have a predominantly spherical geometry, which may make them suitable for movement within a fluidized bed reactor. In some embodiments, the catalytically inert particles may have a size and density consistent with the Geldart A or Geldart B definition of a flowable solid.

[0035] In some embodiments, the catalytically inactive particles are 2 / g, 1m 2 / g, 10m 2 / g or 100m 2 / g to 500m 2 / g, 800m 2 / g, 1,000m 2 / g or 1,500m 2 The surface area of ​​the catalytically inactive particles can be measured according to the Brunauer-Emmett-Teller (BET) method using nitrogen adsorption-desorption (liquid nitrogen temperature, 77 K) using a Micromeritics 3flex instrument after degassing the powder at 350° C. for 4 hours. In some embodiments, the catalyst system can include catalyst particles and catalytically inactive particles in any suitable weight ratio. In some embodiments, the weight ratio of catalyst particles to catalytically inactive particles can range from 0.01:1, 0.03:1, 0.05:1, 0.07:1, 0.1:1, 0.3:1, 0.5:1, 0.7:1, or 1:1 to 1:0.7:1, 1:0.5:1, 1:0.3:1, 1:0.1, 1:0.07, 1:0.5, 1:0.3, or 1:0.1, 1:0.07, 1:0.05, 1:0.03, or 1:0.01.

[0036] The first process for making catalyst particles Methods of making catalyst particles can include preparing a slurry or gel, which can include, but is not limited to, milling, mixing, blending, combining, or otherwise contacting a Group 2 element-containing compound and a liquid medium. In some embodiments, preparing a slurry or gel can also include, but is not limited to, contacting a Group 2 element-containing compound, a liquid medium, and one or more additives.

[0037] The Group 2 element-containing compound can be in the form of an oxide, hydroxide, hydrated carbonate, salt, Group 2 element-containing clay, layered double hydroxide, phosphate, halide, halate, sulfate, sulfide, borate, nitride, carbide, aluminate, aluminosilicate, silicate, carbonate, metaphosphate, selenide, tungstate, molybdate, chromite, chromate, dichromate, silicide, or mixtures thereof. In some embodiments, the Group 2 element can be or include Mg, and the Group 2 element-containing compound can be in the form of magnesium oxide, magnesium hydroxide, hydromagnesite (inorganic hydrated magnesium carbonate, Mg(CO)(OH) 4H0), magnesium salt, magnesium-containing clay, hydrotalcite (layered double hydroxide), organomagnesium compound, or mixtures thereof.

[0038] The liquid medium may be or may include, but is not limited to, water, alcohol, acetone, chloroform, methylene chloride, dimethylformamide, dimethyl sulfoxide, glycerin, ethyl acetate, or any mixture thereof. Exemplary alcohols may be or may include, but are not limited to, methanol, ethanol, isopropanol, or any mixture thereof. The one or more additives, if present, may be or may include, but are not limited to, acids such as formic acid, lactic acid, citric acid, acetic acid, HNO, HCl, oxalic acid, stearic acid, carbonic acid, etc.; ammonia solution; bases such as NaOH, KOH; inorganic salts such as nitrates, carbonates, bicarbonates, chlorides, etc.; organic salts such as acetates, oxalates, formates, citrates, etc.; polymers such as polyvinyl alcohol, polysaccharides, binders and / or binder precursors, or any mixture thereof. Additives may 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.

[0039] In some embodiments, the binder, when present, is selected from the following: B2O3, AlBO3, Al2O3, ZrO2, TiO2, zinc aluminate, ZnO, VO, V2O3, VO2, V2O5, Ga s O t , In u O vThe binder may be or may include one or more of Mn2O3, Mn3O4, MnO, one or more molybdenum oxides, one or more tungsten oxides, one or more zeolites (where s, t, u, and v are positive integers), and mixtures and combinations thereof. When the Group 2 element is in the form of a mixed metal oxide, e.g., a mixed Mg / Al metal oxide, the additional metal in the mixed metal oxide is not considered part of the binder. For example, the support may include a mixed Mg / Al metal oxide, such as that obtained by calcining Mg / Al hydrotalcite, and such Al would not be considered part of the binder, but the support may still include Al2O3 mixed at the nm scale with the mixed Mg / Al metal oxide, and the Al2O3 would be considered the binder. The binder precursor, if present, may be or include, but is not limited to, Al2Si2O5(OH)4 (kaolin clay), aluminum chlorohydrol, boehmite, pseudoboehmite, gibbsite, bayerite, aluminum nitrate, aluminum chloride, sodium aluminate, alumina sol, silica sol, or any mixture thereof. It is known in the literature that some of the compounds herein referred to as "binders" may also be referred to as fillers, matrices, etc.

[0040] The slurry or gel can be spray-dried to produce spray-dried particles containing Group 2 elements. Spray drying refers to a process for producing a dried, particulate solid product from a slurry or gel. This process can include spraying or atomizing the slurry or gel, e.g., forming droplets into a temperature-controlled gas stream and evaporating the liquid medium from the atomized droplets to produce the 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 warm inert gas, e.g., 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 typical.

[0041] The slurry or gel can be atomized using one or more pressure nozzles (e.g., fluid nozzle atomizers), one or more pulse atomizers, one or more high-speed rotating disks (e.g., centrifugal atomizers or rotary atomizers), or any other known process. The median particle size, liquid (e.g., water) concentration, apparent loose bulk density, or any combination thereof, of the particulate solid product prepared by spray drying can be controlled, adjusted, or otherwise influenced 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 through the atomizer, the temperature of the slurry or gel, the droplet size and / or solids concentration, the dimensions of the spray dryer, or any combination thereof. It is well known in the art that various operating conditions will vary depending on the specific spray drying equipment used and can be readily determined by one of ordinary skill in the art.

[0042] The spray-dried particles may be calcined under an oxidizing atmosphere, for example, air, to produce calcined support particles comprising a Group 2 element. In some embodiments, the spray-dried particles may be calcined at a temperature ranging from 450°C, 500°C, 525°C, 550°C, 575°C, 600°C, 625°C, 650°C, or 675°C to 700°C, 725°C, 750°C, 775°C, 800°C, 850°C, 900°C, or 950°C. In some embodiments, the spray-dried particles may be calcined 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 particles may be calcined 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 particles may be calcined at a temperature ranging from 550° C. to 900° C. or 550° C. to 850° C. 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 other embodiments, the spray-dried particles may be calcined at temperatures <550°C, <540°C, <530°C, <520°C, <510°C, or <500°C for times <240 minutes, <180 minutes, <120 minutes, <90 minutes, <60 minutes, <45 minutes, <30 minutes, <25 minutes, <20 minutes, or <15 minutes.

[0043] The Group 8-10 element present in the catalyst particles can be introduced by one or more methods. For brevity and simplicity of explanation, the catalyst particle preparation is further described as including Pt as the Group 8-10 element, although any Group 8-10 element, combination thereof, or mixture thereof may be used. In some embodiments, a method of making catalyst particles can include (i) contacting at least a compound containing a Group 2 element and a liquid medium with a Pt-containing compound, such that the Pt can be present in a slurry or gel, and the catalyst system can include catalyst particles comprising calcined support particles having Pt disposed thereon. In other embodiments, a method of making catalyst particles can include (ii) depositing Pt on the spray-dried particles by contacting the spray-dried particles with a Pt-containing compound to produce spray-dried particles containing Pt, and the catalyst system can include catalyst particles comprising calcined support particles having Pt disposed thereon. In other embodiments, the method of making catalyst particles can include (iii) depositing Pt on the calcined support particles by contacting the calcined support particles with a Pt-containing compound to produce calcined support particles containing Pt, where the spray-dried particles may be calcined; the method can further include calcining the calcined support particles containing Pt to produce re-calcined support particles having Pt disposed thereon, in which case the catalyst system can include the re-calcined support particles. In some embodiments, the catalyst particles can include the calcined support particles containing Pt without an optional additional calcination step. In other embodiments, the method of making catalyst particles can include options (i), (ii), (iii), (i) and (ii), (i) and (iii), (ii) and (iii), or (i), (ii) and (iii).

[0044] In some embodiments, the Pt-containing compound may be or may include, but is not limited to, chloroplatinic acid hexahydrate, tetraammineplatinum(II) nitrate, platinum(II) acetylacetonate, platinum(II) bromide, platinum(II) iodide, platinum(II) chloride, platinum(IV) chloride, diammineplatinum(II) dichloride, ammonium tetrachloroplatinate(II), tetraammineplatinum(II) chloride hydrate, tetraammineplatinum(II) hydroxide hydrate, platinum(II) oxalate, or any mixture thereof. Other suitable compounds containing other Group 8-10 elements that can be used to prepare catalyst particles may be or may include, but are not limited to, nickel(II) chloride, palladium(II) acetate, palladium(II) nitrate, iron(II) chloride, iron(III) chloride, ruthenium(III) chloride hydrate, rhodium(III) nitrate, cobalt(II) nitrate, cobalt(II) acetate, or any mixture thereof.

[0045] The co-catalyst or first co-catalyst present in the catalyst particles can be introduced by one or more methods. In some embodiments, the method of making the catalyst particles can include (iv) contacting at least a compound containing a Group 2 element and a liquid medium with a compound including a co-catalyst element, such that the co-catalyst element is present in a slurry or gel, and the catalyst system can include catalyst particles including calcined support particles having the co-catalyst element disposed thereon. In other embodiments, the method of making the catalyst particles can include (v) depositing a compound including a co-catalyst element on the spray-dried particles to produce co-catalyst-containing spray-dried particles, and the catalyst system can include catalyst particles including calcined support particles having the co-catalyst element disposed thereon. In another embodiment, the method of making catalyst particles may include (vi) depositing a compound including a promoter element on the calcined support particles, where the spray-dried particles may be calcined to produce calcined support particles containing a promoter element, and the method may further include optionally calcining the calcined support particles containing a promoter element to produce recalcined support particles having a promoter element disposed thereon, in which case the catalyst system comprises recalcined support particles. In some embodiments, the catalyst particles may comprise calcined support particles containing a promoter element without an optional additional calcination step. In other embodiments, the method of making catalyst particles may include options (iv), (v), (vi), (iv) and (v), (iv) and (vi), (v) and (vi), or (iv), (v) and (vi). In other embodiments, the method may include any one or more of options (i), (ii), and (iii), and any one or more of options (iv), (v), and (iv). In some embodiments, the compound containing a promoter element may be or include, but is not limited to, tin(IV) chloride pentahydrate, tin(II) chloride dihydrate, tin(II) bromide, tin(IV) bromide, tin(II) acetylacetonate, tin(II) acetate, tin(IV) acetate, tin(II) oxalate, tin(IV) oxalate, silver(I) nitrate, gold(III) nitrate, copper(II) nitrate, gallium(III) nitrate, or any mixture thereof.

[0046] In some embodiments, platinum(II) oxalate and tin(II) oxalate and / or tin(IV) oxalate can be used as the Pt-containing compound and the Sn-containing compound, respectively. Tin(II) oxalate and / or tin(IV) 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 / or tin(IV) oxalate and ammonium oxalate, or ammonium oxalate and platinum oxalate, can be added to the support, followed by equilibration, drying, and / or calcination. Sn distribution throughout the support can be improved by using oxalates of Sn, including tin(II) oxalate and tin(IV) oxalate, as the Sn-containing compound.

[0047] The alkali metal element, when present in the catalyst particles, may be introduced by one or more methods. In some embodiments, the method of making the catalyst particles may include (vii) contacting at least a compound containing a Group 2 element and a liquid medium with a compound comprising an alkali metal element, such that the alkali metal element is present in a slurry or gel, and the catalyst system may include catalyst particles comprising calcined support particles having the alkali metal element disposed thereon. In other embodiments, the method of making the catalyst particles may include (viii) depositing a compound comprising an alkali metal element on the spray-dried particles to produce spray-dried particles containing the alkali metal element, and the catalyst system may include catalyst particles comprising calcined support particles having the alkali metal element disposed thereon. In another embodiment, the method of making catalyst particles may include (ix) depositing a compound containing an alkali metal element on the calcined support particles, where the spray-dried particles may be calcined to produce calcined support particles containing an alkali metal element, and the method may further include calcining the calcined support particles containing an alkali metal element to produce recalcined support particles having an alkali metal element disposed thereon, in which case the catalyst system comprises the recalcined support particles. In other embodiments, the method of making catalyst particles may include options (vii), (viii), (ix), (vii) and (viii), (vi) and (ix), (viii) and (ix), or (vii), (viii) and (iv). In other embodiments, the method of making catalyst particles may include any one or more of options (i), (ii), and (iii), any one or more of options (iv), (v), and (iv), and any one or more of options (vii), (viii), and (ix). The compound containing an alkali metal element may be or may include, but is not limited to, lithium nitrate, sodium nitrate, potassium nitrate, rubidium nitrate, cesium nitrate, or any mixture thereof.

[0048] In some embodiments, a method for making catalyst particles may include wetting calcined support particles to produce wet support particles. For example, the calcined support particles may be contacted with water to produce wet support particles. In such embodiments, the method may also include calcining the wet support particles to produce catalyst particles comprising recalcined support particles. Wetting of the calcined support may be performed at a temperature ranging from 20°C, 40°C, or 60°C to 80°C, 120°C, 140°C, 160°C, 180°C, or 200°C. The calcined support particles may be contacted with water for a period ranging from 1 minute, 5 minutes, or 10 minutes to 20 minutes, 40 minutes, 80 minutes, 160 minutes, 6 hours, 12 hours, 24 hours, or 48 hours. In some embodiments, anions such as chloride, nitrate, carbonate, bicarbonate, acetate, oxalate, formate, and / or citrate may be present during wetting.

[0049] In some embodiments, a method for making catalyst particles may include wetting spray-dried particles to produce wetted spray-dried particles. For example, the spray-dried particles may be contacted with water to produce wetted spray-dried particles. In such embodiments, the method may also include calcining the wetted spray-dried particles to produce a catalyst composition comprising calcined support particles. Wetting of the spray-dried particles may be carried out at a temperature ranging from 20°C, 40°C, or 60°C to 80°C, 120°C, 140°C, 160°C, 180°C, or 200°C. The spray-dried particles may be contacted with water for a period ranging from 1 minute, 5 minutes, or 10 minutes to 20 minutes, 40 minutes, 80 minutes, 160 minutes, 6 hours, 12 hours, 24 hours, or 48 hours. In some embodiments, anions such as chloride, nitrate, carbonate, bicarbonate, acetate, oxalate, formate, and / or citrate may be present during wetting.

[0050] In some embodiments, a method of making catalyst particles may include wetting spray-dried particles to produce wetted spray-dried particles, calcining the wetted spray-dried particles to produce calcined support particles, wetting the calcined support particles to produce wetted calcined support particles, and calcining the wetted calcined support particles to produce re-calcined support particles. Thus, the catalyst system may include spray-dried particles, calcined support particles, wetted spray-dried particles, wetted spray-dried particles that can be calcined, wetted calcined support particles, wetted calcined support particles that can be re-calcined, or any mixture thereof.

[0051] In some embodiments, catalyst particles produced by wetting calcined support particles or spray-dried particles and then calcining the wetted calcined support particles or wetted spray-dried particles can produce catalyst particles having an attrition loss after one hour, as measured in accordance with ASTM D5757-11(2017), that is less than the attrition loss after one hour of the initial calcined particles or spray-dried particles produced before the wetting step. In some embodiments, catalyst particles produced by wetting calcined support particles or spray-dried particles and then calcining the wetted support particles or wetted support particles can produce catalyst particles having an attrition loss after one hour that is 10% less, 30% less, 50% less, 70% less, 90% less, or 100% less than the attrition loss after one hour of the initial calcined particles produced before the wetting step, as measured in accordance with ASTM D5757-11(2017).

[0052] Second process for making catalyst particles In some embodiments, the catalyst particles may be catalyst particles produced solely from a spray-drying process, such that a slurry is prepared and spray-dried particles are produced from the slurry with Pt and a promoter added to the slurry, the spray-dried particles, or a combination thereof. Thus, in some embodiments, a method for making catalyst particles can include preparing a slurry or gel that can include a Group 2 element-containing compound and a liquid medium, and optionally including one or more additives described above, and spray-drying the slurry or gel to produce spray-dried support particles containing a Group 2 element. At least one of (i) and (ii) can be satisfied: (i) the Pt can be present in the slurry or gel in the form of a Pt-containing compound, and the catalyst system can include catalyst particles that include spray-dried support particles having Pt disposed thereon; and (ii) the Pt can be deposited on the spray-dried support particles by contacting the spray-dried support particles with a Pt-containing compound to produce spray-dried support particles containing Pt, and the catalyst system can include catalyst particles that include spray-dried support particles having Pt disposed thereon. At least one of (iii) and (iv) can satisfy the following: (iii) the compound including the promoter element can be present in a slurry or gel, and the catalyst system can include catalyst particles including spray-dried support particles having the promoter element disposed thereon; and (iv) the compound including the promoter element can be deposited on spray-dried support particles to produce promoter-containing spray-dried support particles, and the catalyst system can include catalyst particles including spray-dried support particles having the promoter element disposed thereon, where the promoter element includes Sn, Cu, Au, Ag, Ga, or a combination or mixture thereof. In some embodiments, an optional alkali metal element and / or binder material may also be added during synthesis of the catalyst particles, as described above.

[0053] In some embodiments, the catalyst particles may be further treated or activated in situ by adding the catalyst particles to a hydrocarbon upgrading process that subjects the catalyst particles to more severe conditions to produce catalyst particles having a higher level of activity than particles that were just spray-dried at the time of their preparation. In some embodiments, when the catalyst particles comprise catalyst particles that have been subjected to only a spray-drying step, such that a slurry is prepared and spray-dried support particles are produced from the slurry with Pt and promoter added to the slurry, spray-dried support particles, or combinations thereof, the catalyst particles may be introduced into a reaction zone, combustion zone, reduction zone, or any other location within a fluidized hydrocarbon upgrading process, some of which are further described below.

[0054] The preparation of the catalyst particles and the method of adding a Group 8-10 element such as Pt, a promoter such as Sn, an optional alkali metal element, and an optional rare earth metal element to the catalyst composition are described above. In some embodiments, the preparation of the slurry or gel, spray drying the slurry, calcining the spray-dried particles and / or the moistened calcined particles, and / or wetting of the Group 2 metal containing calcined support particles or spray-dried particles may also be carried out in accordance with U.S. Pat. Nos. 4,866,019; 6,028,023; 6,589,902; 6,593,265; 6,800,578; 7,361,264; and 7,417,005; U.S. Patent Application Publication Nos. 2004 / 0029729; 2005 / 000396; and 2016 / 0082424; WO Publication No. WO2008083563; and the published journal Wang et al., Ind. Eng. Chem. Res. 2008, 47, 5746-5750; Chubar et al., Chem. Eng. J. 2013, 234, 284-299; Valente et al., Energy Environ. Sci., 2011, 4, 4096-4107; and Julklang et al., Mater. Lett. 2017, 209, 429-432.

[0055] Method for making catalytically inactive particles In some embodiments, the catalytically inactive particles may be or include particles produced by any method suitable for producing catalytic particles, except that the addition of Group 8-10 elements may be omitted from the method. In other embodiments, the catalytically inactive particles may be or include one or more oxide compounds, such as MgO and / or Al2O3, obtained from a commercial supplier. When the catalytically inactive particles include oxides or other compounds obtained from a commercial supplier, such compounds may be calcined and / or moistened, if so desired.

[0056] The first process for upgrading hydrocarbons The initial process for upgrading hydrocarbons can include contacting a first hydrocarbon-containing feed with a catalyst system that can include a mixture of catalyst particles and catalytically inert particles to dehydrogenate, dehydroaromatize, and dehydrocyclize at least a portion of the first hydrocarbon-containing feed to produce a coked catalyst system and an effluent that can include one or more upgraded hydrocarbons and molecular hydrogen. The catalyst system and the first hydrocarbon-containing feed can be contacted in any suitable environment, such as one or more reaction zones or conversion zones disposed within one or more reactors, to produce an effluent and a coked catalyst system. The reaction zone or conversion zone can be located within, or otherwise disposed within, one or more fixed-bed reactors, one or more fluidized-bed or moving-bed reactors, one or more counter-flow reactors, or any combination thereof.

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

[0058] The first hydrocarbon-containing feed and the catalyst system can be contacted under a hydrocarbon partial pressure of at least 20 kPa (absolute), where the hydrocarbon partial pressure is less than or equal to the hydrocarbon partial pressure of any C-C hydrocarbons in the first hydrocarbon-containing feed. 16 Alkanes and any C8-C 16In some embodiments, the hydrocarbon partial pressure during contacting the first hydrocarbon-containing feed with the catalyst system can be in the range of 20 kPa (absolute), 50 kPa (absolute), 100 kPa (absolute), at least 150 kPa, at least 200 kPa, 300 kPa (absolute), 500 kPa (absolute), 750 kPa (absolute), or 1,000 kPa (absolute) to 1,500 kPa (absolute), 2,500 kPa (absolute), 4,000 kPa (absolute), 5,000 kPa (absolute), 7,000 kPa (absolute), 8,500 kPa (absolute), or 10,000 kPa (absolute), and the hydrocarbon partial pressure is determined by the total partial pressure of any C2-C4 alkyl aromatics in the first hydrocarbon-containing feed. 16 Alkanes and any C8-C 16 In other embodiments, the hydrocarbon partial pressure during contacting the first hydrocarbon-containing feed with the catalyst system can range from 20 kPa (absolute), 50 kPa (absolute), 100 kPa (absolute), 150 kPa (absolute), 200 kPa (absolute), 250 kPa (absolute), or 300 kPa (absolute) to 500 kPa (absolute), 600 kPa (absolute), 700 kPa (absolute), 800 kPa (absolute), 900 kPa (absolute), or 1,000 kPa (absolute), and the hydrocarbon partial pressure is determined by the total partial pressure of any C2-C4 alkyl aromatics in the first hydrocarbon-containing feed. 16 Alkanes and any C8-C 16 is the total alkylaromatic partial pressure.

[0059] In some embodiments, the first hydrocarbon-containing feed comprises at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, or at least 99% by volume of a single C2-C3 hydrocarbon, based on the total amount of the first hydrocarbon-containing feed. 16The first hydrocarbon-containing feed and catalyst system may comprise a single C2-C2 alkane at a pressure of at least 20 kPa (absolute), at least 50 kPa (absolute), at least 100 kPa (absolute), at least 150 kPa (absolute), at least 250 kPa (absolute), at least 300 kPa (absolute), at least 400 kPa (absolute), at least 500 kPa (absolute), or at least 1,000 kPa (absolute). 16 The contact can be carried out under pressure of an alkane, such as propane.

[0060] The first hydrocarbon-containing feed may be contacted with the catalyst system in the reaction zone or the conversion zone at any mass hourly space velocity (WHSV) effective to carry out the upgrading process. In some embodiments, the WHSV is greater than or equal to 0.01 hr -1 , 0.1 hours -1 , 1 hour -1 , 2 hours -1 , 5 hours -1 , 10 hours -1 , 20 hours -1 , 30 hours -1 or 50 hours -1 ~100 hours -1 , 250 hours -1 , 500 hours -1 or 1,000 hours -1 In some embodiments, when the hydrocarbon upgrading process includes a fluidized or otherwise mobile catalyst system, the circulation mass flow rate of the catalyst system versus any C-C 16 Alkanes and any C8-C 16 The ratio of the total amount of mass flow of alkyl aromatics may range from 1, 3, 5, 10, 15, 20, 25, 30 or 40 to 50, 60, 70, 80, 90, 100, 110, 125 or 150 on a mass to mass basis.

[0061] When the activity of a coked catalyst system falls below a desired minimum amount, the coked catalyst system, or at least a portion thereof, can be subjected to a regeneration process to produce a regenerated catalyst system. More specifically, the coked catalyst system can be contacted with one or more oxidants to effect combustion of at least a portion of the coke and produce a regenerated catalyst system and combustion gases with less coke. Depending on the specific configuration of the reactor, regeneration of the coked catalyst system can occur within the reaction zone or conversion zone, or in a combustion zone that is separate and distinct from the reaction zone or conversion zone to produce a regenerated catalyst system. For example, regeneration of the coked catalyst system can occur within the reaction zone or conversion zone when a fixed-bed or upflow reactor is used, or in a separate combustion zone that can be separate and distinct from the reaction zone or conversion zone when a fluidized-bed reactor or other circulating or fluidized-type reactor is used.

[0062] In some embodiments, the method may include contacting at least a portion of the regenerated catalyst system with a reducing gas to produce a regenerated and reduced catalyst system. An additional amount of the first hydrocarbon-containing feed may be contacted with at least a portion of the regenerated catalyst system and / or at least a portion of either the regenerated and reduced catalyst system to produce a recoke catalyst system and an additional effluent. Depending on the specific configuration of the reactor, reduction of the regenerated catalyst system may occur within the reaction or conversion zone, within the regeneration zone, or within a reduction zone that is separate and distinct from the reaction or conversion zone to produce a regenerated and reduced catalyst system. For example, reduction of the regenerated catalyst system may occur within the reaction or conversion zone when a fixed-bed or counter-flow reactor is used, or within a separate reduction zone that may be separate and distinct from the reaction or conversion zone and the regeneration zone when a fluidized-bed reactor or other circulating or fluidized-type reactor is used.

[0063] In some embodiments, the cycle time from contacting a first hydrocarbon-containing feed with the catalyst system to contacting an additional amount of the first hydrocarbon-containing feed with the regenerated catalyst system may be ≦5 hours. The first cycle begins by contacting the catalyst system with the first hydrocarbon-containing feed, then with at least an oxidizing gas to produce a regenerated catalyst system, or with at least an oxidizing gas and an optional reducing gas to produce a regenerated catalyst system, and the first cycle ends by contacting the regenerated catalyst system 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 catalyst system to contacting an additional amount of the first hydrocarbon-containing feed with the regenerated catalyst system may, in some embodiments, be ≦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.

[0064] The oxidant may be or may include, but is not limited to, O2, O3, CO2, HO, or mixtures thereof. In some embodiments, to increase coke removal from the catalyst system, an excess of oxidant may be used over that required to combust 100% of the coke on the catalyst system, thereby reducing the time required for coke removal and resulting in an increased yield of upgraded product produced in a given time period. Using pure O2 as the oxidant may facilitate capture and sequestration of CO2 produced during combustion in one or more downstream CO2 capture systems.

[0065] The coked catalyst system and the oxidant may be contacted with each other at a temperature ranging from 500°C, 550°C, 600°C, 650°C, 700°C, 750°C, or 800°C to 900°C, 950°C, 1000°C, 1050°C, or 1100°C to produce a regenerated catalyst system. In some embodiments, the coked catalyst system and the oxidant may be contacted with each other at a temperature ranging from 500°C to 1100°C, 600°C to 1000°C, 650°C to 950°C, 700°C to 900°C, or 750°C to 850°C to produce a regenerated catalyst system.

[0066] The coking catalyst system and oxidant may be contacted with each other for a time period of ≦2 hours, ≦1 hour, ≦30 minutes, ≦10 minutes, ≦5 minutes, ≦1 minute, ≦30 seconds, ≦10 seconds, ≦5 seconds, or ≦1 second. For example, the coking catalyst system and oxidant may be contacted with each other for a time period ranging from 2 seconds to 2 hours. In some embodiments, the coking catalyst system and oxidant may be contacted for a time period sufficient to remove ≧50%, ≧75%, ≧90%, or >99% by weight of any coke disposed on the catalyst system. In some embodiments, the time that the coking catalyst system and the oxidant are in contact with each other may be shorter than the time that the catalyst system is in contact with the first hydrocarbon-containing feed to produce an effluent and a coked catalyst system. For example, the time that the coking catalyst system and the oxidant are in contact with each other may be at least 90%, at least 60%, at least 30%, or at least 10% shorter than the time that the catalyst system is in contact with the first hydrocarbon-containing feed to produce an effluent. In other embodiments, the time that the coking catalyst system and the oxidant are in contact with each other may be longer than the time that the catalyst system is in contact with the first hydrocarbon-containing feed to produce an effluent and a coked catalyst system. For example, in some embodiments, the coking catalyst system and the oxidant may be contacted with each other for a time that 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 the catalyst system contacts the first hydrocarbon-containing feed to produce the effluent.

[0067] The coking catalyst system and the oxidant may be contacted with each other under an oxidant partial pressure ranging 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 system can range from 20 kPa (absolute), 50 kPa (absolute), 100 kPa (absolute), 150 kPa (absolute), 200 kPa (absolute), 250 kPa (absolute), or 300 kPa (absolute) to 500 kPa (absolute), 600 kPa (absolute), 700 kPa (absolute), 800 kPa (absolute), 900 kPa (absolute), or 1,000 kPa (absolute) to produce a regenerated catalyst system.

[0068] Without wishing to be bound by theory, it is believed that at least a portion of the Group VIII-III elements present in / on the coked catalyst particles may undergo agglomeration relative to the catalyst system prior to contact with the first hydrocarbon-containing feed. During combustion of at least a portion of the coke on the coked catalyst system, it is believed that at least a portion of the Group VIII-III elements may be redispersed around the support of the catalyst particles. Redispersion of at least a portion of any agglomerated Group VIII-III elements may improve the stability of the catalyst system over multiple cycles.

[0069] In some embodiments, at least a portion of the Group 8-10 elements in the regenerated catalyst system may be in a higher oxidation state than the Group 8-10 elements in the catalyst system contacted with the first hydrocarbon-containing feed and than the Group 8-10 elements in the coked catalyst system. Thus, as noted above, in some embodiments, the method may include contacting at least a portion of the regenerated catalyst system with a reducing gas to produce a regenerated and reduced catalyst system. Suitable reducing gases (reducing agents) may be or include, but are not limited to, H, CO, CH, CH, CH, CH, CH, steam, or mixtures thereof. In some embodiments, the reducing agent may be mixed with an inert gas, such as Ar, Ne, He, N, CO, HO, or mixtures thereof. In such embodiments, at least a portion of the Group 8-10 elements in the regenerated and reduced catalyst system may be reduced to a lower oxidation state, e.g., elemental state, than the Group 8-10 elements in the regenerated catalyst system. In this embodiment, an additional amount of the first hydrocarbon-containing feed may be contacted with at least a portion of the regenerated catalyst system and / or at least a portion of the regenerated and reduced catalyst system.

[0070] In some embodiments, the regenerated catalyst system and reducing gas may be contacted at a temperature ranging from 400° C., 450° C., 500° C., 550° C., 600° C., 620° C., 650° C., or 670° C. to 720° C., 750° C., 800° C., or 900° C. The regenerated catalyst system and reducing gas may be contacted for a time ranging from 1 second, 5 seconds, 10 seconds, 20 seconds, 30 seconds, or 1 minute to 10 minutes, 30 minutes, or 60 minutes. The regenerated catalyst system and reducing gas may be contacted under a reducing agent partial pressure of from 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 during contact with the regenerated catalyst system to produce a regenerated catalyst system may 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).

[0071] At least a portion of the regenerated catalyst system, the regenerated and reduced catalyst system, the fresh or unused catalyst system, or a mixture thereof can be contacted with an additional amount of the first hydrocarbon-containing feed in the reaction zone or conversion zone to produce additional effluent and additional coked catalyst system. As specified above, in some embodiments, the cycle time from contacting the first hydrocarbon-containing feed with the catalyst system to contacting the additional amount of the first hydrocarbon-containing feed with at least a portion of the regenerated catalyst system and / or the regenerated and reduced catalyst system, and optionally with the fresh or unused catalyst system, can be ≦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.

[0072] In some embodiments, as specified above, one or more additional feeds, e.g., one or more sweep fluids, may be utilized between the flow of the first hydrocarbon-containing feed and the oxidant, between the oxidant and the optional reducing gas (if used), between the oxidant and the additional first hydrocarbon-containing feed, and / or between the reducing gas and the additional first hydrocarbon-containing feed. The sweep fluid may purge or otherwise drive away undesirable materials, such as non-combustible particulates, including soot, from the reactor, among other things. In some embodiments, the additional feed may be inert under dehydrogenation, dehydroaromatization, and dehydrocyclization, combustion, and / or reducing conditions. Suitable sweep fluids may be or include, but are not limited to, N2, He, Ar, CO2, HO, CO2, CH4, or mixtures thereof. In some embodiments, when the method utilizes a sweep fluid, the period or time during which the sweep fluid is used may 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 catalyst system may remain sufficiently active and stable after a large number of cycles, e.g., at least 15, at least 20, at least 30, at least 40, at least 50, at least 60, at least 70, at least 100, at least 125, at least 150, at least 175, or at least 200 cycles, with each cycle lasting <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 may be from 5 seconds, 30 seconds, 1 minute, or 5 minutes to 10 minutes, 20 minutes, 30 minutes, 45 minutes, 50 minutes, 70 minutes, 2 hours, 3 hours, 4 hours, or 5 hours. In some embodiments, after catalyst performance has stabilized (sometimes the first few cycles may have relatively poor or relatively good performance, but the performance may eventually stabilize), the method may, when the first hydrocarbon-containing feed comprises propane, produce a yield of a first upgraded hydrocarbon product, e.g., propylene, at an upgraded hydrocarbon, e.g., propylene, selectivity of ≧75%, ≧80%, ≧85%, ≧90%, ≧93%, or ≧95% upon initial contact with the first hydrocarbon-containing feed, and upon completion of the final cycle (at least 15 cycles in total), have a second upgraded hydrocarbon product yield, which may be at least 90%, at least 93%, at least 95%, at least 97%, at least 98%, at least 99%, at least 99.5%, or at least 100%, with an upgraded hydrocarbon, e.g., propylene, selectivity of ≧75%, ≧80%, ≧85%, or ≧90%, ≧93%, or ≧95%.

[0074] In some embodiments, when the first hydrocarbon-containing feed comprises propane and the upgraded hydrocarbon comprises propylene, contacting the first hydrocarbon-containing feed with the catalyst system may produce a propylene yield of ≥ 52%, ≥ 53%, ≥ 55%, ≥ 57%, ≥ 60%, ≥ 62%, ≥ 63%, ≥ 64%, ≥ 65%, or ≥ 66%, with a propylene selectivity of ≥ 75%, ≥ 80%, ≥ 85%, ≥ 90%, ≥ 93%, or ≥ 95%, for at least 15, at least 20, at least 30, at least 40, at least 50, at least 60, at least 70, at least 100 cycles, at least 125 cycles, at least 150 cycles, at least 175 cycles, or at least 200 cycles. In other embodiments, when the first hydrocarbon-containing feed comprises at least 70% by volume 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), a propylene yield of ≥ 52%, ≥ 53%, ≥ 55%, ≥ 57%, ≥ 60%, ≥ 62%, ≥ 63%, ≥ 64%, ≥ 65%, or ≥ 66% can be obtained with a propylene selectivity of ≥ 75%, ≥ 80%, ≥ 85%, ≥ 90%, ≥ 93%, or ≥ 95% for at least 15, at least 20, at least 30, at least 40, at least 50, at least 60, at least 70, at least 100, at least 125, at least 150, at least 175, or at least 200 cycles. It is believed that the propylene yield can be further increased to ≥67%, ≥68%, ≥70%, ≥72%, ≥75%, ≥77%, ≥80%, or ≥82% with a propylene selectivity of ≥75%, ≥80%, ≥85%, ≥90%, ≥93%, or ≥95% for ≥15 cycles, ≥20 cycles, ≥30 cycles, ≥40 cycles, ≥50 cycles, ≥60 cycles, ≥70 cycles, ≥100 cycles, ≥125 cycles, ≥150 cycles, ≥175 cycles, or ≥200 cycles by further optimizing the composition of the support and / or adjusting one or more process conditions.In some embodiments, a propylene yield can be obtained when the catalyst system is contacted with the first hydrocarbon-containing feed at a temperature of ≥620°C, ≥630°C, ≥640°C, ≥650°C, ≥655°C, ≥660°C, ≥670°C, ≥680°C, ≥690°C, ≥700°C, or ≥750°C for ≥15 cycles, ≥20 cycles, ≥30 cycles, ≥40 cycles, ≥50 cycles, ≥60 cycles, ≥70 cycles, ≥100 cycles, ≥125 cycles, ≥150 cycles, ≥175 cycles, or ≥200 cycles.

[0075] In some embodiments, when a fluidized-bed reactor or other circulating or fluidized-type reactor is used, the catalyst system including a mixture of catalyst particles and catalytically inert particles can be introduced into any location or combination of locations in the reactor system. In some embodiments, the catalyst system can be introduced into the reaction zone or conversion zone, the regeneration zone, the reduction zone, if present, or any location between any two or any combination of these zones. In some embodiments, when a fluidized-bed reactor or other circulating or fluidized-type reactor is used, the catalyst particles and catalytically inert particles can be introduced into the reactor system separately so that the catalyst system can be formed within the reactor system. In such embodiments, the catalyst particles and catalytically inert particles can be introduced into the same zone or different zones, or a first portion of the catalyst particles and / or catalytically inert particles can be introduced into the reactor system at a first location and a second portion of the catalyst particles and / or catalytically inert particles can be introduced into the reactor system at a second location.

[0076] During the process for upgrading hydrocarbons, the mass ratio of catalyst particles to catalytically inert particles can be adjusted and used to adjust or control the composition of the effluent recovered from the reactor system. In some embodiments, the amount of catalyst particles, the amount of catalytically inert particles, or both the amount of catalyst particles and the amount of catalytically inert particles can be adjusted while the first hydrocarbon-containing feed is contacting the catalyst system. In some embodiments, the mass ratio of catalyst particles to catalytically inert particles can be increased or decreased by adjusting the amount of catalyst particles and / or catalytically inert particles while the first hydrocarbon-containing feed is contacting the catalyst system.

[0077] Suitable systems for carrying out the processes disclosed herein can include systems known in the art, such as fixed bed reactors as disclosed in WO Publication No. WO2017078894, fluidized riser reactors and / or downer reactors as disclosed in 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, and countercurrent reactors as disclosed in U.S. Pat. No. 8,754,276; U.S. Patent Application Publication No. 2015 / 0065767; and WO Publication No. WO2013169461.

[0078] First hydrocarbon-containing feed The first hydrocarbon-containing feed may include, but is not limited to, one or more alkane hydrocarbons, such as C-C 16 Linear or branched alkanes and / or C4-C 16 Cyclic alkanes and / or one or more alkyl aromatic hydrocarbons, e.g., C-C 16 In some embodiments, the first hydrocarbon-containing feed may be or may include alkyl aromatics. In some embodiments, the first hydrocarbon-containing feed may be or may include any C2-C6 alkyl aromatics in the first hydrocarbon-containing feed. 16 Alkanes and any C8-C 16The first hydrocarbon-containing feed may contain 0.1% to 50% by volume of water vapor based on the total amount of alkyl aromatics. In another embodiment, the first hydrocarbon-containing feed may contain any C2-C 16 Alkanes and any C8-C 16 It may contain <0.1% by volume of water vapor based on the total amount of alkyl aromatics, or it may contain no water vapor.

[0079] C2-C 16 The alkane may be or may include, but is not limited to, ethane, propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, n-heptane, 2-methylhexane, 2,2,3-trimethylbutane, cyclopentane, cyclohexane, methylcyclopentane, ethylcyclopentane, n-propylcyclopentane, 1,3-dimethylcyclohexane, or mixtures thereof. For example, the first hydrocarbon-containing feed may include propane, which may be dehydrogenated to produce propylene and / or isobutane, and isobutane may be dehydrogenated to produce isobutylene. In another example, the first hydrocarbon-containing feed may include liquefied petroleum gas (LP-gas), which may be in the gas phase when contacted with the catalytic system. In some embodiments, the hydrocarbons in the first hydrocarbon-containing feed may consist essentially of a single alkane, such as propane. In some embodiments, the first hydrocarbon-containing feed contains ≥ 50 mol%, ≥ 75 mol%, ≥ 95 mol%, ≥ 98 mol%, or ≥ 99 mol% of a single C-C hydrocarbon, based on the total moles of all hydrocarbons in the first hydrocarbon-containing feed. 16In some embodiments, the first hydrocarbon-containing feed comprises at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 97%, or at least 99% by volume of a single C2-C alkane, based on the total amount of the first hydrocarbon-containing feed. 16 It may include alkanes such as propane.

[0080] C8-C 16 The alkyl aromatic may be or may include, but is not limited to, ethylbenzene, propylbenzene, butylbenzene, one or more ethyltoluenes, or mixtures thereof. In some embodiments, the first hydrocarbon-containing feed contains ≥ 50 mol%, ≥ 75 mol%, ≥ 95 mol%, ≥ 98 mol%, or ≥ 99 mol% of a single C-C hydrocarbon, based on the total mass of all hydrocarbons in the first hydrocarbon-containing feed. 16 The hydrocarbons may include alkyl aromatics such as ethylbenzene. In some embodiments, the ethylbenzene may be dehydrogenated to produce styrene. Thus, in some embodiments, the initial process for upgrading hydrocarbons disclosed herein may include propane dehydrogenation, butane dehydrogenation, isobutane dehydrogenation, pentane dehydrogenation, pentane dehydrocyclization to cyclopentadiene, naphtha reforming, ethylbenzene dehydrogenation, ethyltoluene dehydrogenation, and the like.

[0081] In some embodiments, the first hydrocarbon-containing feed can be diluted with one or more diluents, such as, for example, one or more inert gases. Suitable inert gases can be or include, but are not limited to, Ar, Ne, He, N2, CO2, CH4, or mixtures thereof. When the hydrocarbon-containing feed includes a diluent, the first hydrocarbon-containing feed can be used to remove any C2-C4 hydrocarbons in the first hydrocarbon-containing feed. 16 Alkanes and any C8-C16 The diluent may comprise from 0.1%, 0.5%, 1% or 2% by volume up to 3%, 8%, 16% or 32% by volume based on the total amount of alkyl aromatic.

[0082] In some embodiments, the first hydrocarbon-containing feed may also include H. In some embodiments, when the first hydrocarbon-containing feed includes H, the H to any C-C 16 Alkanes and any C8-C 16 The ratio of the total amount of 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. In other embodiments, H2 may be introduced into the reactor system as a feed that is separate and distinct from the first hydrocarbon-containing feed.

[0083] In some embodiments, the first hydrocarbon-containing feed and the environment within the reactor system may be substantially free of any water vapor, e.g., any C2-C4 hydrocarbons in the first hydrocarbon-containing feed. 16 Alkanes and any C8-C 16 The amount of water vapor may be <0.1% by volume, based on the total amount of alkylaromatic aromatics. In other embodiments, the first hydrocarbon-containing feed may include water vapor, and / or water vapor may be introduced into the reactor system as a feed that is separate from the first hydrocarbon-containing feed. For example, the first hydrocarbon-containing feed, or when introduced separately from the first hydrocarbon-containing feed, may be present in the reactor system in a manner that does not affect the water vapor content of any C2-C4 alkylaromatic hydrocarbons in the first hydrocarbon-containing feed. 16 Alkanes and any C8-C 16 The water vapor may comprise 0.1%, 0.3%, 0.5%, 0.7%, 1%, 3%, or 5% to 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50% by volume of water vapor relative to the total amount of alkyl aromatics. In other embodiments, the first hydrocarbon-containing feed, or if introduced separately from the first hydrocarbon-containing feed, the environment within the reactor system may be such that any C2-C4 hydrocarbons in the first hydrocarbon-containing feed are present.16 Alkanes and any C8-C 16 The reactor system may contain ≦50%, ≦45%, ≦40%, ≦35%, ≦30%, ≦25%, ≦20%, or ≦15% by volume of water vapor relative to the total amount of alkylaromatic aromatics. In other embodiments, the first hydrocarbon-containing feed, or if introduced separately from the first hydrocarbon-containing feed, the environment within the reactor system may contain ≦50%, ≦45%, ≦40%, ≦35%, ≦30%, ≦25%, ≦20%, or ≦15% by volume of water vapor. 16 Alkanes and any C8-C 16 It may contain at least 1 vol%, at least 3 vol%, at least 5 vol%, at least 10 vol%, at least 15 vol%, at least 20 vol%, at least 25 vol%, or at least 30 vol% water vapor based on the total amount of alkyl aromatics.

[0084] In some embodiments, the first hydrocarbon-containing feed may contain sulfur, or sulfur may be introduced as a separate feed separated from the first hydrocarbon-containing feed. For example, the first hydrocarbon-containing feed may contain sulfur in the range of 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 may 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. The sulfur in the first hydrocarbon-containing feed, if present, can be or include, but is not limited to, one or more mercaptans such as H2S, dimethyl disulfide, or any mixture thereof.

[0085] In some embodiments, the first hydrocarbon-containing feed and the environment within the reaction or conversion zone may be substantially free of or may not contain molecular oxygen. In some embodiments, the first hydrocarbon-containing feed may contain ≦5 mol%, ≦3 mol%, or ≦1 mol% molecular oxygen (O). It is believed that providing a first hydrocarbon-containing feed that is substantially free of molecular oxygen inhibits oxidation reactions that would otherwise consume at least a portion of the alkanes and / or alkylaromatics in the first hydrocarbon-containing feed.

[0086] First upgrade hydrocarbon recovery and use In some embodiments, the first upgraded hydrocarbons in the effluent can contain at least one upgraded hydrocarbon, such as olefins, water, unreacted hydrocarbons, molecular hydrogen, etc. The upgraded hydrocarbons can be recovered or otherwise obtained by any convenient process, for example, by one or more conventional processes. One such process can include cooling and / or compressing the effluent to condense at least a portion of any water and any heavy hydrocarbons that may be present, leaving the olefins and at least a portion of any unreacted alkanes or alkylaromatics primarily in the vapor phase. The olefins and unreacted alkanes or alkylaromatics can then be removed from the reaction product in one or more separation drums. For example, the dehydrogenation product can be separated from the unreacted first hydrocarbon-containing feed using one or more separators or distillation columns.

[0087] In some embodiments, the recovered olefins, such as propylene, can be used to produce polymers, for example, the recovered propylene can be polymerized to produce polymers having segments or units derived from the recovered propylene, such as polypropylene, ethylene-propylene copolymers, etc. 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 elastomeric polymers, such as butyl rubber.

[0088] The second process for upgrading hydrocarbons The second process for upgrading hydrocarbons can include contacting the second hydrocarbon-containing feed with a catalyst system, which can include a mixture of catalyst particles and catalytically inert particles, to reform at least a portion of the second hydrocarbon-containing feed and produce a coked catalyst system and an effluent, which can include carbon monoxide and molecular hydrogen. The catalyst system and the second hydrocarbon-containing feed can be contacted in any suitable environment, such as one or more reaction or conversion zones disposed within one or more reactors, to produce an effluent and a coked catalyst system. The reaction or conversion zone can be disposed within or otherwise located within one or more fixed-bed reactors, one or more fluidized or moving-bed reactors, one or more counter-flow reactors, or any combination thereof. For clarity and brevity, the reforming reaction will be discussed in the context of a fluidized-bed reactor; however, it should be understood that a fixed-bed reactor, a counter-flow reactor, a moving-bed reactor, or any other reactor can be used to perform the reforming of the second hydrocarbon-containing feed.

[0089] Reformed hydrocarbons can be produced using a reforming reaction through a continuous or discontinuous reaction process. In some embodiments, the reaction process can include a reforming step, e.g., an endothermic reaction, and a regeneration step, e.g., an exothermic reaction, operated continuously while a fluidized catalyst is transported between the reforming and regeneration sections of a reactor. The endothermic reaction can include hydrocarbon reforming in the presence of a catalytic system. Unused hydrocarbons and regenerated fluidized catalyst particles and catalytically inactive particles can enter the reforming section. After spending some time in the reforming section, the hydrocarbons can be converted to reformed products, at least a portion of which can exit the reforming section along with the spent catalytic system. The reformed products and unreacted feed can be separated from the spent catalytic system 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 catalytic system can be sent to the regeneration section for regeneration. The exothermic regeneration reaction can be the reaction of an oxidant and, optionally, a fuel under combustion conditions to produce a regenerated catalytic system and flue gas. After regeneration, the regenerated catalyst system may be separated from the flue gas by one or more separators and transported back to the reforming zone, where it may be combined with additional hydrocarbon feed and enter the reforming zone to begin further reforming reactions. The reforming process may convert CO and / or HO and hydrocarbons, such as CH, into a synthesis gas containing H and CO. The regeneration process may combust reactants, such as coke disposed on the spent catalyst system, and / or optional fuel and oxidant, to generate heat for heating the regenerated catalyst system, which may provide heat that can be used to drive the reforming reactions. In some embodiments, the catalyst system may be heated to an average temperature ranging from 600°C, 700°C, or 800°C to 1,000°C, 1,300°C, or 1,600°C during the regeneration process.

[0090] Exemplary fuels may be or 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. The oxidant may be or include O. In some embodiments, the oxidant may be or include air, O-enriched air, O-depleted air, or any other suitable O-containing stream.

[0091] Regeneration of a catalyst system can correspond to removing coke from particles in the catalyst system. In some embodiments, during reforming, a portion of the feed introduced into the reforming zone can form coke. This coke can potentially block access to catalytic sites (e.g., metal sites) on catalyst particles in the catalyst system. During regeneration, at least a portion of the coke produced during reforming can be removed as CO or CO2. Regeneration of a catalyst system can also correspond to redispersing any agglomerated active phase of the catalyst, such as Group 8-10 elements.

[0092] Second hydrocarbon-containing feed The second hydrocarbon-containing feed may comprise one or more reformable C-C hydrocarbons, such as, but not limited to, alkanes, alkenes, cycloalkanes, alkylaromatics, etc. 16The second hydrocarbon-containing feed may be or may include methane, ethane, propane, butane, pentane, or any mixture thereof. In some embodiments, the second hydrocarbon-containing feed may be or may include methane, ethane, propane, butane, pentane, or a mixture thereof. In some embodiments, the second hydrocarbon-containing feed may be exposed to the catalyst system at a pressure less than 35 kPa gauge pressure. For example, the second hydrocarbon-containing feed may be exposed to the catalyst system at a pressure ranging from 0.7 kPa gauge pressure, 2 kPa gauge pressure, 3.5 kPa gauge pressure, 5 kPa gauge pressure, or 10 kPa gauge pressure to 15 kPa gauge pressure, 20 kPa gauge pressure, 25 kPa gauge pressure, or 30 kPa gauge pressure. In other embodiments, the second hydrocarbon-containing feed may be exposed to the catalyst system at a pressure ranging from 35 kPa gauge pressure to 15 MPa gauge pressure. In still other embodiments, the second hydrocarbon-containing feed can be exposed to the catalyst system under pressures ranging 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 still other embodiments, the second hydrocarbon-containing feed can be exposed to the catalyst system under pressures less than 2.8 MPa gauge, less than 2.5 MPa gauge, less than 2.2 MPa gauge, or less than 2 MPa gauge.

[0093] The reforming reaction of a second hydrocarbon-containing feed, e.g., CH, can be carried out in the presence of HO (steam reforming), CO (dry reforming), or both HO and CO (bi-reforming). Example stoichiometries for steam reforming, dry reforming, and bi-reforming of CH are shown in Equations (1)-(3). (1) Dry reforming: CH4 + CO2 = 2CO + 2H2 (2) Steam reforming: CH4 + H2O = CO + 3H2 (3) Double reforming: 3CH4 + 2H2O + CO2 = 4CO + 8H2 As shown in equations (1)-(3), dry reforming can produce a lower ratio of H to CO than steam reforming. Reforming reactions conducted using only steam can generally produce syngas with an H:CO molar ratio of about 3, such as 2.5 to 3.5. In contrast, reforming reactions conducted using only CO can generally produce syngas with an H:CO molar ratio of approximately 1 or even lower. By using a combination of CO and HO during reforming, the reforming reaction can be controlled to produce a wide range of H to CO ratios in the resulting syngas.

[0094] It should also be noted that the ratio of H to CO in the syngas may also depend on the water-gas shift equilibrium. While the stoichiometries in equations (1)-(3) indicate ratios of approximately 1 or approximately 3 for dry reforming and steam reforming, respectively, the equilibrium amounts of H and CO in the syngas may differ from the reaction stoichiometry. The equilibrium amounts may be determined based on the water-gas shift equilibrium, which is related to the concentrations of H, CO, CO, and HO based on the reaction shown in equation (4). (4) H2O + CO ←→ H2 + CO2

[0095] In some embodiments, the catalyst system can also function as a water-gas shift catalyst. Thus, if the reaction environment producing H and CO also contains HO and / or CO, the initial stoichiometry from the reforming reaction may vary based on the water-gas shift equilibrium. However, this equilibrium is also temperature-dependent, with higher temperatures favoring the production of CO and HO. As a result, the ratio of H to CO produced during synthesis gas formation is constrained by the water-gas shift equilibrium at the temperature of the reaction zone where synthesis gas is produced. The ability to adjust the H:CO molar ratio of the syngas provides a flexible process that can be combined with a wide range of syngas upgrading processes. Exemplary syngas upgrading processes can include, but are not limited to, the Fischer-Tropsch process, synthesis of methanol and / or other alcohols, e.g., one or more C1-C4 alcohols, fermentation processes, separation methods that can separate hydrogen to produce H2-rich products, dimethyl ether, and combinations thereof. These syngas upgrading processes are well known to those skilled in the art. In some embodiments, the upgraded products can include, but are not limited to, methanol, synthetic crude, diesel, lubricating oil, wax, olefins, dimethyl ether, other chemicals, or any combination thereof.

[0096] Suitable systems for carrying out the reforming of the second hydrocarbon-containing feed include fixed bed reactors as disclosed in WO Publication No. WO2017078894, fluidized riser reactors as disclosed in 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. The reactors may include systems known in the art, such as a downer reactor and / or a downer reactor, and countercurrent reactors as disclosed in 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 WO Publication No. WO2013169461.

[0097] Particularly in the context of one or more fluidized or moving-bed reactors, during the first and / or second hydrocarbon upgrading process, at least a portion of the Group VIII elements may potentially be transferred from the catalyst particles to the catalytically inactive particles by contacting each other. Similarly, if the catalyst particles and the catalytically inactive particles are mixed prior to introduction into the reactor system, at least a portion of the Group VIII elements may also be transferred from the catalyst particles to the catalytically inactive particles. Such transfer of the Group VIII elements may convert at least a portion of the catalytically inactive particles to the catalyst particles. Thus, in some embodiments, the mass ratio of catalyst particles to catalytically inactive particles may also be adjusted during the hydrocarbon conversion process by transferring a portion of the Group VIII elements from the catalyst particles to the catalytically inactive particles.

[0098] Feed and Energy The first and second hydrocarbon-containing feeds described herein can be derived from either a fossil fuel source or a non-fossil fuel source. For example, propane can be a product or by-product of a process that uses biomass as a feed. The fuels described in this discussion can also be derived from either a fossil fuel source or a non-fossil fuel source. For example, methane or H2 can be a product or by-product of a process that uses biomass as a feed. The fuels described in this discussion can also be made from renewable energy, such as renewable electricity. For example, renewable electricity can be used to produce H2 by electrolysis of water. The energy used in the methods described herein can also be supplied by renewable electricity instead of fuel. [Example]

[0099] The above discussion can be further illustrated with reference to the following non-limiting examples. The catalysts and selected inert particles used in Examples 1-6 were prepared according to the following procedure: Support particles of mixed Mg / Al metal oxide (PURALOX® MG80 / 150, Sasol) were dried in air at 550°C for 3 hours. The dried support was immersed in an appropriate amount of chloroplatinic acid solution, an appropriate amount of SnCl4 solution in water, or both. After 24 hours at room temperature, the immersed material was dried in air at 110°C for 6 hours and calcined in air at 800°C for 12 hours to produce the final particles containing Pt, Sn, or both Pt and Sn. In Examples 1-6, fixed-bed experiments using the catalysts were conducted at approximately 100 kPa (absolute). A gas chromatograph (GC) was used to measure the composition of the reactor effluent. The concentrations of each component in the reactor effluent were then used to calculate C3H6 yields and selectivities. C3H6 yields and selectivities reported in these examples were calculated on a moles of carbon basis. In each example, the appropriate amount of catalyst was mixed with the appropriate amount of quartz diluent and loaded into a quartz reactor. The amount of diluent was determined so that the quartz reactor and the catalyst bed (catalyst + diluent) overlapping the isothermal zone of the catalyst bed were nearly isothermal during operation. The dead volume of the reactor was filled with quartz chips / rods.

[0100] The process steps in Examples 1 to 6 were as follows: 1. An inert gas was flushed through the system. 2. Dry air at a flow rate of 83.9 sccm was flowed through the bypass of the reaction zone while simultaneously flowing the inert gas through the reaction zone. The reaction zone was heated to a regeneration temperature of 800°C. 3. Next, 83.9 sccm of dry air was flowed through the reaction zone for 10 minutes to regenerate the catalyst. 4. An inert gas was flushed through the system. 5. An H2-containing gas having 10% by volume H2 and 90% by volume Ar was flowed through the bypass of the reaction zone at a flow rate of 46.6 sccm for a certain period of time while simultaneously flowing the inert gas through the reaction zone. Next, this was followed by flowing the H2-containing gas through the reaction zone for 3 seconds at 800°C. 6. An inert gas was flushed through the system. During this process, the temperature of the reaction zone was varied from 800°C to the reaction temperature of 670°C. 7. A hydrocarbon-containing (HC gas) feed containing 81% by volume C3H8, 9% by volume inert gas (Ar or Kr), and 10% by volume water vapor was flowed through the reaction zone bypass at a flow rate of 17.6 sccm for a fixed period of time while the inert gas was simultaneously flowed through the reaction zone. The hydrocarbon-containing feed was then flowed through the reaction zone for 10 minutes at 670°C. GC sampling of the reaction effluent began immediately after the feed was switched from the reaction zone bypass to the reaction zone. The above process steps were repeated in cycles.

[0101] Although this example utilized a fixed bed reactor, a fluidized bed reactor or process could equally be utilized, and without wishing to be bound by theory, it is expected that the interaction of the active catalyst portion of the catalyst system in a fluidized bed reactor will interact more effectively with catalytically inactive particles, whether they be mixed Mg / Al metal oxides, Sn-doped mixed Mg / Al metal oxides, or other catalytically inactive particles.

[0102] [Table 1] Example 2 vs. Example 1 demonstrates the advantages of using mixed Mg / Al metal oxide particles as catalytically inactive particles compared to quartz.

[0103] Compared with Examples 1 and 2, which utilized quartz or undoped mixed Mg / Al metal oxide particles as the inert, Examples 3 and 4, which utilized catalytically inactive Sn-doped mixed Mg / Al metal oxide particles, demonstrated higher yields and selectivities. Thus, based on Examples 3 and 4, it appears that the catalytically inactive Sn-doped mixed Mg / Al metal oxide particles enhance the activity of the catalytically active particles and / or become catalytically active by transferring some of the Pt from the catalytic particles to the catalytically inactive particles, turning the catalytically inactive particles into catalytically active particles. Example 5 vs. Example 3 shows the effect of increasing the amount of catalytic particles by 10% to 20% by weight relative to the amount of catalytically inactive particles. The increased amount of catalytic particles significantly improved the yield. Example 6 shows that including an order of magnitude more catalyst particles (using 0.3 g of catalyst particles versus 0.03 g of catalyst particles in Examples 1-4) but at a lower Pt concentration (0.05 wt % versus 0.3 wt % in Examples 1-4) results in a significant improvement in yield.

[0104] List of embodiments The present disclosure can further include the following non-limiting embodiments. A1. A method for upgrading hydrocarbons, comprising: (I) contacting a hydrocarbon-containing feed with a catalyst system comprising a mixture of catalyst particles and catalytically inert particles to at least partially reform the hydrocarbon-containing feed to produce a coked catalyst system and a synthesis gas comprising H2 and CO, wherein the hydrocarbon-containing feed is selected from one or more C1-C 161. A method for producing a catalytically inert feed comprising: contacting a hydrocarbon-containing feed and a catalyst system at a temperature of 400°C or greater, the catalyst system comprising a hydrocarbon and HO, CO, or a mixture of HO and CO, wherein the hydrocarbon-containing feed and the catalyst system comprise a first promoter comprising a Group 8-10 element and Sn, Cu, Au, Ag, Ga, combinations or mixtures thereof, disposed on a support, the catalyst particles comprising 0.001% to 6% by weight of the Group 8-10 element and up to 10% by weight of the first promoter, the support comprising Al and at least 0.5% by weight of a Group 2 element based on the weight of the support, the catalytically inert particles being free of the Group 8-10 element, and the composition of the catalytically inert particles and the composition of the support being the same or different. A2. (II) The method of A1, further comprising the step of contacting at least a portion of the coked catalyst system with an oxidizing agent to effect combustion of at least a portion of the coke to produce a regenerated catalyst system having less coke and combustion gases. A3. (III) The method of A2, further comprising the step of contacting the fuel with an oxidizer and a coking catalyst system to effect at least partial combustion of the fuel. A4. The process of A2 or A3, further comprising the step of (IV) contacting an additional amount of a hydrocarbon-containing feed with at least a portion of the regenerated catalyst system to produce a recoked catalyst system and an additional effluent. A5. Any of the methods of A1-A4, wherein the hydrocarbon-containing feed is contacted with the catalyst system in a fluidized bed reactor. A6. Any of the methods of A1-A4, wherein the hydrocarbon-containing feed is contacted with the catalyst system in a fixed bed reactor. A7. Any of the methods of A1-A4, wherein the hydrocarbon-containing feed is contacted with the catalyst system in a counter-flow reactor.

[0105] A8. Any of the methods A1 to A7, wherein the catalyst particles in the catalyst system contain from 0.001%, 0.001%, 0.01%, 0.1%, 0.15%, or 0.2% to 0.4%, 0.6%, 0.8%, 1%, 2%, 3%, 4%, 5%, or 6% by weight of a Group 8 to 10 element relative to the weight of the support. A9. Any of the methods A1 to A8, wherein the Group 8 to 10 element includes Pt. A10. Any of the methods of A1-A9, wherein the catalyst system further comprises an alkali metal element, including Li, Na, K, Rb, Cs, combinations thereof, or mixtures thereof, disposed on the support in an amount of up to 5% by weight, based on the weight of the support. A11. The process of any of A1-A10, wherein the catalyst system is in the form of particles having a size and particle density consistent with the Geldart A or Geldart B definition of a flowable solid. A12. The method of any one of A1-A11, wherein the mass ratio of Group 2 element to Al in the support is in the range of 0.001, 0.01, 0.1, or 1 to 6, 12.5, 100, or 1,000. A13. The method of any one of A1 to A12, wherein the Group 2 element includes Mg, and at least a portion of the Mg is in the form of MgO or a mixed metal oxide including Mg. A14. The method of any one of A1 to A13, wherein the Group 2 element includes Mg, and at least a portion of the Mg and at least a portion of the Al are in the form of a mixed Mg / Al metal oxide.

[0106] A15. Any of the methods A1 to A14, wherein the Group 2 element includes Mg, and at least a portion of the Mg and at least a portion of the Al are in the form of a mixed Mg / Al metal oxide, and the mass ratio of Mg to Al in the mixed Mg / Al metal oxide is in the range of 0.001, 0.01, 0.1, or 1 to 6, 12.5, 100, or 1,000. A16. Any of the methods A1 to A15, wherein at least a portion of the Group 2 element is in the form of an oxide of the Group 2 element, at least a portion of the Al is in the form of Al2O3, and the oxide of the Group 2 element and Al2O3 are mixed on the nm scale. A17. Any of the methods A1 to A16, wherein the Group 2 element includes Mg, at least a portion of the Mg is in the form of MgO, at least a portion of the Al is in the form of Al2O3, and the oxides of MgO and Al2O3 are mixed on the nm scale.

[0107] A18. Any of the methods A1-A17, further comprising at least one of the following steps: reacting at least a portion of the synthesis gas under effective Fischer-Tropsch conditions in the presence of a Fischer-Tropsch catalyst to produce an upgraded product, wherein the Fischer-Tropsch catalyst comprises a shifting Fischer-Tropsch catalyst or a non-shifting Fischer-Tropsch catalyst; subjecting at least a portion of the synthesis gas to a fermentation process to produce alcohols, organic acids, or mixtures thereof; contacting at least a portion of the synthesis gas with a catalyst to produce at least one C1-C4 alcohol; and separating H2 from the synthesis gas to produce an H2-rich product.

[0108] Various terms are defined above. To the extent that a term used in the claims is not defined above, the broadest definition given to that term by one of ordinary skill in the art should be given, as reflected in at least one printed publication or issued patent. Furthermore, all patents, test procedures, and other documents cited in this application are incorporated by reference in their entirety to the extent such disclosure is not inconsistent with this application and for all jurisdictions in which such incorporation is permitted. While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, which scope is defined by the following claims.

Claims

1. 1. A catalyst system comprising a plurality of catalytic particles and a plurality of catalytically inactive particles adapted to be mixed with each other or mixed with each other, the catalyst particles comprise a first promoter comprising a Group 8-10 element and Sn, Cu, Au, Ag, Ga, combinations thereof, or mixtures thereof disposed on a support; the catalyst particles comprise 0.001% to 6% by weight of a Group 8 to 10 element and up to 10% by weight of a first promoter; the support comprises Al and at least 0.5% by weight of a Group 2 element relative to the weight of the support; the catalytically inactive particles are free of Group 8-10 elements; The composition of the catalytically inactive particles and the composition of the support are the same or different; Catalyst system.

2. 10. The catalyst system of claim 1, wherein the support comprises a first mixed Mg / Al metal oxide.

3. 3. The catalyst system of claim 2, wherein the mass ratio of Mg to Al in the first mixed Mg / Al metal oxide ranges from 0.001 to 1,000.

4. 4. The catalyst system of any one of claims 1 to 3, wherein the catalytically inactive particles comprise aluminum oxide, magnesium oxide, a second mixed Mg / Al metal oxide, or a mixture thereof.

5. 5. A catalyst system according to claim 1, wherein the catalyst particles contain <0.2% by weight of Si, relative to the weight of the support, and the catalytically inactive particles contain <0.2% by weight of Si, relative to the weight of the catalytically inactive particles.

6. 6. The catalyst system of any one of claims 1 to 5, wherein the catalytically inactive particles comprise a second promoter disposed thereon, the second promoter comprising Sn, Cu, Au, Ag, Ga, combinations thereof or mixtures thereof, and the catalytically inactive particles comprise up to 10 wt. % of the second promoter, based on the weight of the catalytically inactive particles prior to adding the second promoter thereto.

7. 7. The catalyst system of claim 6, wherein the first promoter and the second promoter each comprise Sn.

8. 8. The catalyst system of claim 1, wherein the Group 8-10 element comprises Pt.

9. the Group 8 to 10 element includes Pt; the first promoter comprises Sn; the support comprises a first mixed Mg / Al metal oxide; the catalytically inactive particles comprise a second mixed Mg / Al metal oxide; the mass ratio of Mg to Al in the first mixed Mg / Al metal oxide and the mass ratio of Mg to Al in the second mixed Mg / Al metal oxide are independently in the range of 0.001 to 1,000; the catalytically inactive particles include a second promoter disposed thereon, the second promoter comprising Sn, Cu, Au, Ag, Ga, combinations thereof, or mixtures thereof; The catalytically inactive particles contain up to 10% by weight of the second promoter, based on the weight of the catalytically inactive particles before adding the second promoter thereto; 10. The catalyst system of claim 1.

10. Catalyst system according to any one of claims 1 to 9, wherein the mass ratio of catalytic particles to catalytically inactive particles is in the range of 0.01:1 to 1:0.

01.

11. 1. A method for upgrading hydrocarbons, comprising: contacting the hydrocarbon-containing feed with a catalyst system comprising a mixture of catalyst particles and catalytically inert particles to one or more of dehydrogenation, dehydroaromatization, and dehydrocyclization of at least a portion of the hydrocarbon-containing feed to produce a coked catalyst system and an effluent comprising one or more upgraded hydrocarbons and molecular hydrogen; The hydrocarbon-containing feed is 2 -C 16 one or more linear or branched alkanes, or C 4 -C 16 one or more cyclic alkanes or one or more C 8 -C 16 alkyl aromatics, or mixtures thereof; the one or more upgraded hydrocarbons comprise at least one of dehydrogenated hydrocarbons, dehydrogenated aromatized hydrocarbons, and dehydrogenated cyclized hydrocarbons; the catalyst particles comprise a first promoter comprising a Group 8-10 element and Sn, Cu, Au, Ag, Ga, combinations thereof, or mixtures thereof disposed on a support; the catalyst particles comprise 0.001% to 6% by weight of a Group 8 to 10 element and up to 10% by weight of a first promoter; the support comprises Al and at least 0.5% by weight of a Group 2 element relative to the weight of the support; the catalytically inactive particles are free of Group 8-10 elements; the composition of the catalytically inactive particles and the composition of the support are the same or different; A method comprising:

12. 12. The method of claim 11, wherein the mixture of catalyst particles and catalytically inactive particles is disposed in a fixed bed within the reactor.

13. 12. The method of claim 11, wherein the mixture of catalyst particles and catalytically inactive particles is in the form of fluidized particles disposed within a reactor.

14. 14. The method of claim 13, wherein the catalyst particles and catalytically inert particles are introduced separately into the reactor such that a mixture of the catalyst particles and catalytically inert particles is formed in the reactor.

15. 15. The method of claim 14, further comprising adjusting the amount of catalyst particles, catalytically inert particles, or both catalyst particles and catalytically inert particles during contact of the hydrocarbon-containing feed with the catalyst system.

16. 16. The method of claim 15, wherein the mass ratio of catalytic particles to catalytically inactive particles is in the range of 0.01:1 to 1:0.

01.

17. The method of any one of claims 11 to 16, wherein the support comprises a first mixed Mg / Al metal oxide.

18. 18. The method of claim 17, wherein the mass ratio of Mg to Al in the first mixed Mg / Al metal oxide is in the range of 0.001 to 1,000.

19. The method of any one of claims 11 to 17, wherein the catalytically inactive particles comprise aluminum oxide, magnesium oxide, a second mixed Mg / Al metal oxide, or a mixture thereof.

20. the Group 8 to 10 element includes Pt; the first promoter comprises Sn; the catalytically inactive particles comprise aluminum oxide, magnesium oxide, mixed Mg / Al metal oxides, or mixtures thereof; the catalyst particles contain <0.2 wt. % Si, based on the weight of the support; the catalytically inactive particles contain <0.2 wt. % Si, based on the weight of the catalytically inactive particles; the catalytically inactive particles include a second promoter disposed thereon, the second promoter comprising Sn, Cu, Au, Ag, Ga, combinations thereof, or mixtures thereof; The catalytically inactive particles contain up to 10% by weight of the second promoter, based on the weight of the catalytically inactive particles before adding the second promoter thereto; The method according to any one of claims 11 to 19.

21. The hydrocarbon-containing feed and catalyst system are contacted at a hydrocarbon partial pressure of at least 20 kPa (absolute) at a temperature in the range of 300°C to 900°C, and the hydrocarbon partial pressure is such that the C 2 -C 16 Alkanes and any C 8 -C 16 21. The method of any one of claims 11 to 20, wherein the total partial pressure of the alkyl aromatics.

22. contacting at least a portion of the coked catalyst system with an oxidant to effect combustion of at least a portion of the coke to produce a regenerated catalyst system having less coke and combustion gases; contacting an additional amount of hydrocarbon-containing feed with at least a portion of the regenerated catalyst system to produce a recoked catalyst system and an additional effluent; The method of any one of claims 11 to 21, further comprising:

23. 23. The method of claim 22, further comprising contacting at least a portion of the low-coke regenerated catalyst system with a reducing gas to produce a regenerated and reduced catalyst system, and contacting an additional amount of hydrocarbon-containing feed with at least a portion of the regenerated and reduced catalyst system to produce a recoked catalyst system and an additional effluent.

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