Catalyst compositions includng active lewis acid-base pairs for cracking, and hydrogenation or dehdyrogenation reactions

Abstract

A catalyst composition including a metal oxide catalyst having a surface containing M-O site pairs of the acid-base Lewis type and of balanced acid-base strength; and a cracking component. The catalyst composition as disclosed herein is used in treating a variety of feeds including, but not limited to, naphtha, pyrolysis oil, polyolefins, or a combination thereof. The bifunctional catalytic nature of the catalyst composition enables catalytic cracking as well as hydrogenation and dehydrogenation reaction for the conversion of long-chain alkanes to mixture of short chain alkanes and alkenes using a catalyst composition based on metal-oxides that avoids the use of precious metals.

Description

CATALYST COMPOSITIONS INCLUDNG ACTIVE LEWIS ACID-BASE PAIRS FOR CRACKING, AND HYDROGENATION OR DEHDYROGENATIONREACTIONSCROSS REFERENCE TO RELATED APPLICATION(S)

[0001] The present application claims priority to U.S. Provisional Patent Applications 63 / 713.303 filed on October 29, 2024 and 63 / 723,792 filed on November 22, 2024, the entire contents of which are incorporated in their entirety.FIELD OF THE INVENTION

[0002] Disclosed herein is a catalyst composition including metal oxides, active Lewis acid-base pairs and a cracking component and a method of treating reactant streams with the catalyst composition to stimulate chemical reactions. In particular, the methods may include using the catalyst composition when performing a cracking reaction and hydrogenation sequence, a dehydrogenation and cracking sequence, or a combination thereof.BACKGROUND

[0003] In the chemical industry, propene is an important intermediate for the production of a variety of compounds. For example, propene is used in the production of propylene oxide, acrylonitrile, cumene, acry lic acid, C3 and higher alcohols, or polypropylene. Historically, propene has been available primarily as a co-product from steam crackers and an off-gas product from fluid catalytic cracking units in oil refineries. These technologies have been found to be insufficient to meet the persistent growth in the market demand for propene, leading to the development of new technologies, such as dehydrogenation of propane.

[0004] In recent decades, the production of light olefins, particularly ethylene and propene, has been increasingly essential for the growing global demand for polymers, especially in high- density polyethylene and polypropylene manufacturing. Traditional methods of light olefin production include paraffin dehydrogenation, fluid catalytic cracking (FCC) and steam cracking of hydrocarbon feedstock. Paraffin dehydrogenation primarily converts light paraffins such as propane into propene, leveraging high temperatures to drive this endothermic reaction. This process is mostly applied for catalytic propane dehydrogenation (PDH), where nonlimiting representative PDH technologies include those employing platinum group metal (PGM) catalysts (e.g., Linde-BASF, Oleflex, STAR, and FCDh (DOW) processes), or Cr- containing catalysts (e.g., Catofin and FDB-4 processes). FCC, traditionally employed inAttorney Docket No. 39425-380 petroleum refining, also produces light olefins, although its effectiveness in propene generation varies, and it is limited in ethene production, contributing to less than 1% of global ethene output.

[0005] In steam cracking, light hydrocarbons, such as ethane and naphtha, are subjected to extreme temperatures, often exceeding 800°C, in the presence of steam. This process is highly endothermic, demanding a continuous supply of energy. Steam is added not only to improve olefin yields but also to reduce the hydrocarbon partial pressure, thereby minimizing the formation of undesirable carbonaceous deposits within the cracking reactors. Despite the process’s effectiveness, steam cracking faces significant challenges, particularly around energy consumption, feedstock limitations, and environmental impact.

[0006] In steam cracking, ethane is the preferred feedstock because of its higher ethene yield and relative simplicity in processing. However, the global supply of ethane is insufficient to meet the rising demand for ethene production, especially outside North America, where abundant shale gas has led to lower ethane prices. As a result, in regions where ethane is scarce or prohibitively expensive — such as Asia and Europe — the industry predominantly relies on naphtha as a feedstock. Naphtha cracking, although capable of producing ethene, is less efficient than ethane cracking; naphtha yields only about 30-35% ethene by weight, with a range of other products, including propene, butadiene, and various fuel oils, which add to operational complexity and affect overall profitability.

[0007] Further complicating the economics of naphtha cracking are the environmental and regulatory pressures that have intensified in recent years. The steam cracking of naphtha generates significant carbon dioxide emissions, both from the high-energy heating required and from the nature of the feedstock itself. Some regions, notably China, have tightened environmental regulations, limiting approvals for new naphtha-based ethene projects. Consequently, the industry urgently needs a more sustainable, efficient, and flexible pathway for producing ethene, particularly in areas dependent on naphtha as a feedstock.

[0008] Recent advances in catalytic conversion offer promising alternatives. Catalytic processes can operate at lower temperatures than traditional steam cracking, potentially reducing energy costs and carbon emissions. Furthermore, catalytic methods can be selectively tuned to favor the production of ethene over other by-products, thus improving yields. For example, oxidative dehydrogenation of ethane, while still in developmental stages, has shown potential for converting ethane to ethene with lower carbon emissions and less energy' input. However, such processes remain limited to ethane-rich regions, leaving naphtha-dependent areas without comparable alternatives.Attorney Docket No. 39425-380

[0009] An optimized catalytic process for converting naphtha into ethene and propene could provide a breakthrough solution for ethene producers in ethane-scarce regions. Such a process would ideally involve a two-step conversion: first, transforming naphtha into lighter hydrocarbons like ethane and propane, and second, selectively converting these intermediates into ethene and propene. Currently, catalyst containing zeolite and platinum (Pt) are used, but there are problems with the use of high-cost precious metal and catalyst stability during regeneration procedures that cause platinum sintering. (See, for example, US 2023 / 0399274).

[0010] There is a need for a more efficient, flexible catalyst for converting naphtha into light olefins that is both cost-effective and environmentally friendly. This catalyst should support cracking, hydrogenation, or dehydrogenation reactions, offering stability and reduced reliance on expensive precious metals. Importantly, such approach may be potentially applied for polyethylene, polypropylene, or other plastics processing via their catalytic conversion to shorter-chain hydrocarbons.SUMMARY

[0011] In an embodiment of the present disclosure, a catalyst composition is provided. The catalyst composition may include a metal oxide (MOx) catalyst having a surface containing M-0 site pairs of the acid-base Lewis type and of balanced acid-base strength; and a cracking component.

[0012] In some embodiments, the MOx catalyst may be included in an amount of about 1% to about 90% of a combined mass of the catalyst composition. In some embodiments, the cracking component may be included in an amount of about 1% to about 99%, based on a combined mass of the catalyst composition.

[0013] In some embodiments, the MOx catalyst may include a metal oxide in which M is not reducible to its zero-valent state at the conditions of catalysis.

[0014] In some embodiments, the MOx catalyst may include Lewis acid-base pairs, where M may include zirconium (Zr), cobalt (Co), gallium (Ga), zinc (Zn), cerium (Ce), yttrium (Y), titanium (Ti), or a combination thereof. In some embodiments, the MOx catalyst may include a metal comprising Zr, Y, or a combination thereof. In some embodiments, the MOx catalyst may include ZrO2. In some embodiments, the MOx catalyst may include Y2O3.

[0015] In some embodiments, the MOx catalyst may further include a rare-earth element including at least one lanthanide metal, an oxide thereof, or combinations thereof.

[0016] In some embodiments, the MOXcatalyst may further include a rare-earth metal including at least one of yttrium (Y), erbium (Er), cerium (Ce). dysprosium (Dy), gadoliniumAttorney Docket No. 39425-380(Gd), lanthanum (La), neodymium (Nd), samarium (Sm), ytterbium (Yb), Hafnium (Hf) oxides thereof, or mixtures thereof.

[0017] In some embodiments, the rare earth metal may be included in an amount of about 0.5 wt% to about 90 wt%, or about 0.5 wt% to about 50 wt%, based on total weight of the MOx catalyst.

[0018] In some embodiments, the cracking component may include a zeolite, an acid catalyst, an amorphous silica-alumina, a mesoporous acid matrix, or a combination thereof.

[0019] In some embodiments, the zeolite may include a medium pore zeolite having a 10-member ring, or a large pore zeolite having a 12-member ring.

[0020] In some embodiments, the cracking component may include a zeolite selected from the group consisting of USY zeolite, beta zeolite, ZSM-5. chabazite, SAPO-5, ferrierite, Y zeolite, ZSM-11, or mixtures thereof.

[0021] In some embodiments, the catalyst component may further include a mesoporous acid. In some embodiments, the mesoporous acid may include MCM-41, MCM- 48, MCM-50, FSM-16, FSM-21, SBA-15, or a combination thereof. In some embodiments, the MOx catalyst and the cracking component may be present as an intraparticle mixture, or an interparticle loose mixture.

[0022] In some embodiments, the catalyst composition does not include a platinum group metal.

[0023] In some embodiments, the catalyst composition may further include a trap. In some embodiments, the trap may be an oxygen trap, a water trap, a carbon dioxide trap, or a combination thereof.

[0024] In another embodiment, a method of performing a reaction is provided using a catalyst composition of the present disclosure. The method of performing a reaction may include a reaction comprises alkane dehydrogenation, alkene hydrogenation, alkene dehydrogenation, olefm-paraffin alkylation, from CO / H2 mixtures without O-rej ection as H2O or CO2, C-C bond formation via alkene oligomerization or metathesis, dehydrocyclization (alkanes / alkenes to arenes), dehydrocyclodimerization (alkanes / alkenes to arenes with a larger number of C-atoms), transfer hydrogenation, hydroformylation / carbonylation, aromatization, dearomatization, reforming, isomerization, and bifunctional reactions in which one of the aforementioned functions can be combined with a Bronsted acid function.

[0025] In yet another embodiment, a method of preparing a catalyst composition is provided. The method of preparing a catalyst composition may include mixing a zirconium containing precursor, an yttrium containing precursor, or a combination thereof with aAttorney Docket No. 39425-380 precipitant to obtain a mixture; and heating the mixture. The method may further include adding a surfactant including an organic molecule to the mixture; and separating solids from the mixture, wherein the solids include zirconium, yttrium or a combination thereof; and combining a cracking component with the solids to obtain the catalyst composition.

[0026] In some embodiments, the solids may have a molar ratio of yttrium to zirconium of 1:50 to 50: 1. In some embodiments, the method may further include washing the solids with a hydroxide, water, or a combination thereof.

[0027] In some embodiments, the method may further include drying the solids. In some embodiments, the method may further include calcining the solids.

[0028] In some embodiments, the hydroxide may include ammonium hydroxide, sodium hydroxide, or a combination thereof. In some embodiments, the hydroxide may be a solution having a pH of about 7 to about 10, or about 9.

[0029] In some embodiments, the organic molecule may include a carboxylic acid or a carboxylate anion. In some embodiments, the carboxylic acid may include lauric acid or its laureate form.

[0030] In some embodiments, the method may further include cleaning a surface of the catalyst by heating the catalyst at a temperature of about 300°C to about 800°C. In some embodiments, the cleaning does not include applying a surface cleaning reagent.

[0031] In another embodiment, a method of treating a reactant stream is provided. The method of treating a reactant stream may include feeding the reactant stream to a reactor, wherein the reactor comprises a catalyst composition of the present disclosure.

[0032] In some embodiments, the reactant stream may include naphtha, a pyrolysis oil, a polyolefin, or a combination thereof.

[0033] In some embodiments, the reactant stream may contain hydrogen. In some embodiments, the volumetric fraction of hydrogen may be betw een 0% and 100%.

[0034] In some embodiments, the reactant stream may be passed through a trap before the reactor. In some embodiments, the trap may include an impurity from the reactant stream. In some embodiments, the impurity may include oxygen (O2), water (H2O), hydrogen sulfide (H2S), carbon dioxide (CO2), carbon monoxide (CO), a sulfur containing compound, methanol, a ketone, an inorganic nitrogen compound, an organic nitrogen compound, an oxygenate, or a combination thereof.

[0035] In some embodiments, the amount of water in the reactor may be less than about2 ppm.Attorney Docket No. 39425-380

[0036] In some embodiment, the method may further include performing a hydrogenation reaction, a dehydrogenation reaction, an aromatization reaction, a cracking reaction or a combination of thereof.

[0037] In some embodiments, the method may further include feeding hydrogen to the reactor.BRIEF DESCRIPTION OF THE DRAWINGS

[0038] FIG. 1 illustrates a) Alkane / alkene equilibrium ratio in systems containing H2 at 0.1 bar pressure and ethane / ethene (red squares), propane / propene (black triangles), n- butane / n-butene (blue diamonds) or isobutane / isobutene (brown circles)5. b) Rate constants for propane dehydrogenation (black) and propene hydrogenation (blue) with comparisons to predicted hydrogenation rate constants from the dehydrogenation rate constant using gas phase thermodynamic relations (solid line).

[0039] FIG. 2 illustrates the results of «-decane reactions on MFI and a physical mixture of MFI and YSZ.Definitions:

[0040] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure, and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

[0041] As used herein, “a” or “an’’ entity refers to one or more of that entity, e.g., “a compound” refers to one or more compounds or at least one compound unless stated otherwise. As such, the terms “a” (or “an”), “one or more”, and “at least one” are used interchangeably herein.

[0042] As used herein, the term “and / or” includes any and all combinations of one or more of the associated listed items. Additionally, as used herein, “or” means “and / or.”

[0043] The term “alkyl,” as used herein, refers to a saturated straight-chain (i.e., linear or unbranched) or branched hydrocarbon chain containing carbon atoms (such as. e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms). Unless otherwise specified, alkyl groups contain 1-20 carbon atoms. In some embodiments, alkyl groups contain 1-10 carbon atoms (denoted as C1-10 alk l herein). In some embodiments, alk l groups containAttorney Docket No. 39425-3801-8 carbon atoms (denoted as Ci-s alkyl herein). In some embodiments, alkyl groups contain1-6 carbon atoms (denoted as Ci-6 alkyl herein). In some embodiments, alkyl groups contain1-4 carbon atoms (denoted as Ci-4 alkyl herein). In some embodiments, alkyl groups contain1-3 carbon atoms (denoted as Ci-3 alkyl herein). Nonlimiting examples of '‘alkyl” groups include methyl, ethyl, propyl, isopropyl, isobutyl, tert-buty l, sec-butyl, and the like.

[0044] The term “alkenyl,” as used herein, means a straight-chain (i.e., linear or unbranched) or branched hydrocarbon chain that contains at least one carbon-carbon double bond. Unless otherwise specified, alkenyl groups contain 2-20 (such as, e.g., 2-12, 2-6, or 2-4) carbon atoms. Nonlimiting examples of “alkenyl” groups include vinyl, allyl, butenyl, pentenyl, hexenyl, butadienyl, pentadienyl, hexadienyl, 2-ethylhexenyl, cyclopent-l-en-l-yl, and the like.

[0045] The term “alkynyl,” as used herein, means a straight-chain (i.e., linear or unbranched) or branched hydrocarbon chain that contains at least one carbon-carbon triple bond. Unless otherwise specified, alkynyl groups contain 2-20 (such as, e.g., 2-12, 2-6, or 2-4) carbon atoms. Nonlimiting examples of “alkynyl” groups include ethynyl, propynyl, butynyl, pentynyl, hexynyl, and the like.

[0046] The term “aryl” refers to monocyclic, bicyclic, and tricyclic ring systems having a total of five to fourteen ring members, wherein at least one ring in the system is aromatic and wherein each ring in the system contains 3 to 7 ring members. The term “aryl,” as used herein, also refers to heteroaryl ring systems as defined herein below.

[0047] As used herein, the term “catalyst composition” refers to a composition comprising a material that promotes a chemical reaction.

[0048] As used herein, the term “increase” refers to altering positively, including, but not limited to, altering positively by 1%, altering positively by 5%. altering positively by 10%, altering positively by 25%, altering positively by 30% altering positively by 50%, altering positively by 75%, altering positively by 100%, altering positively by 200%, and the like.

[0049] As used herein, the term “decrease” refers to altering negatively, including, but not limited to, altering negatively by 1%, altering negatively by 5%, altering negatively by 10%, altering negatively by 25%, altering negatively by 30%, altering negatively by 50%, altering negatively by 75%, or altering negatively by 100%.

[0050] As used herein, the term “pretreating” refers to any process in which a catalyst is contacted with a chemical, combination of chemicals, or a series of chemicals to remove an impurity from the surface of a catalyst. As used herein, the term “cleaning” refers to any process in which a catalyst is contacted with a chemical, combination of chemicals, or a seriesAttorney Docket No. 39425-380 of chemicals to activate or reactivate the catalyst to a higher activity and / or selectivity state, either before using the catalyst for the intended chemical process or at intervening points in time during use of the catalyst. In some embodiments, pretreating is carried out inside a chemical reactor. In some embodiments, pretreating is carried out outside a chemical reactor. In some embodiments, when used at intervening points during catalyst use, pretreating restores all or a portion of the activity and / or selectivity’ of the catalyst in protocols that may be denoted to those skilled in the art as catalyst regeneration treatments.

[0051] As used herein, the term “impurity free” or “substantially free” refers to stream that comprises less than about 1 wt%, less than about 0.5 wt%, less than about 0.25 wt%, less than about 0. 1 wt%, less than about 0.05 wt%, less than about 0.01 wt%, or 0 wt% of a component, such as an impurity’.

[0052] As used herein, the term “organic molecule” refers to molecules that are made of carbon and hydrogen and can include other elements. Organic molecules must contain carbon atoms covalently bonded to hydrogen atoms (C-H bonds). They usually involve oxygen and can also contain nitrogen, sulfur, phosphorous, and others. Hydrocarbons, like alkanes, alkenes and alkynes are all organic molecules and so are alcohols, carboxylic acids and carbohydrates. Many organic compounds are formed from chains of covalently linked carbon atoms yvith hydrogen atoms attached to the chain (known as a hydrocarbon backbone). This term involves, macromolecules, i.e. polymers.

[0053] As used herein, the term “surfactant” refers to a substance which tends to reduce the surface energy of a substrate w hen adsorbed to prevent particle agglomeration.

[0054] As understood herein, “naphtha” refers to a compound having a carbon range of about 5 to about 12. In some examples, “naphtha” may be light naphtha, which may include Cs to C6. In some examples, “naphtha” may be heavy naphtha, which may include C7 to C12.

[0055] As used herein, the term “polyolefins” refers to, but is not limited to, a medium range hydrocarbon, polypropylene, polyethylene, polyethylene waxes, polyisobutylene, polymethylpentene, polybutene, poly butadiene, polyisoprene, 1 -hexene, 1 -octene, medium range hydrocarbons, polyethylene waxes, or a combination thereof. In some embodiments, the polyethylene may include a low molecular weight polyethylene (LMWPE), a high molecular weight polyethylene (HMWPE), a ultra-high molecular weight polyethylene (UHMWPE), or a combination thereof.

[0056] As used herein, the term “pyrolysis” relates to a thermal decomposition or degradation of a feedstock such as plastic waste under inert conditions and results in a gas, a liquid, and a solid char fraction. During the pyrolysis, the feedstock is converted in a pyrolysisAttorney Docket No. 39425-380 unit into a great variety of chemicals including gases such as H2, Ci- to C4 alkanes, C2- to C4-alkenes, ethyne, propyne, 1 -butyne, pyrolysis oil having a boiling temperature of 25 °C to 500 °C or more and char. The direct products from such a pyrolysis are “pyrolysis gas’’ and solid products. The liquid product “pyrolysis oil” is then separated by condensation from the “pyrolysis gas”. In addition, water is formed during the pyrolysis which may be partially dispersed in the pyrolysis oil and may be partially contacted with the pyrolysis oil in a separate phase. The water formed during pyrolysis solvates various organic compounds and / or salts thereof which were also formed during the pyrolysis. The term “pyrolysis” includes slow pyrolysis, fast pyrolysis, flash pyrolysis and catalytic pyrolysis. These pyrolysis types differ regarding process temperature, heating rate, residence time, feed particle size, etc. resulting in different product quality. The pyrolysis unit may be operated adiabatically, isothermally, nonadiabatically, non-isothermally, or combinations thereof. The pyrolysis reactions of this disclosure may be carried out in a single stage or in multiple stages. For example, the pyrolysis unit can comprise two reactor vessels fluidly connected in series.

[0057] As used herein, the term “pyrolysis oil” is understood to mean any oil originating from the pyrolysis of plastic waste. The term “plastic waste” includes rubber waste such as end-of-life tires and feedstocks comprising plastic waste. The pyrolysis oil is obtained and / or obtainable from pyrolysis of such plastic waste. As used herein, the term “plastic waste” refers to any plastic material discarded after use, i.e., the plastic material has reached the end of its useful life and is considered post-consumer waste. The plastic waste can be pure polymeric plastic waste, mixed plastic waste or film waste, including soiling, adhesive materials, fillers, residues etc. The plastic waste may have an oxygen content, a nitrogen content, sulfur content, halogen content and optionally also a heavy metal content. The plastic waste can originate from any plastic material containing source. Typically, plastic waste is a mixture of different plastic materials, including hydrocarbon plastics, e.g., polyolefins such as polyethylene (HDPE, LDPE) and polypropylene, polystyrene, and copolymers thereof, etc., and polymers composed of carbon, hydrogen, and other elements such as chlorine, fluorine, oxygen, nitrogen, sulfur, silicone, etc., for example chlorinated plastics, such as polyvinylchloride (PVC), poly vinylidene chloride (PVDC), etc., nitrogen-containing plastics, such as polyamides (PA), polyurethanes (PU), acrylonitrile butadiene styrene (ABS), etc., oxy gen-containing plastics such as polyesters, e.g., polyethylene terephthalate (PET), polycarbonate (PC), etc., silicones and / or sulfur bridges crosslinked rubbers.

[0058] Typically, the plastic material comprises additives, such as processing aids, plasticizers, flame retardants, pigments, light stabilizers, lubricants, impact modifiers, antistaticAttorney Docket No. 39425-380 agents, antioxidants, etc. These additives may comprise elements other than carbon and hydrogen. For example, bromine is mainly found in connection to flame retardants. Heavy metal compounds may be used as lightfast pigments and / or stabilizers in plastics. Cadmium, zinc, and lead may be present in heat stabilizers and slip agents used in plastics manufacturing. The plastic waste can also contain residues. Residues in the sense of the invention are contaminants adhering to the plastic waste. The additives and residues are usually present in an amount of less than 50 wt.-%, preferably less than 30 wt.-%, more preferably less than 20 wt.-%, even more preferably less thanbased on the total weight of the dry weight plastic.

[0059] As used herein, the term “mixed plastic’' refers to a combination of polymers, such as polyvinyl chloride (PVC), or polyethylene terephthalate (PET), or polyolefins.DETAILED DESCRIPTION OF THE PRESENT DISCLOSURE

[0060] An optimized catalytic process for converting naphtha into ethene and propene could provide a breakthrough solution for ethene production in ethane-scarce regions. A robust and adaptable catalytic system would enable producers to manage feedstock variability, minimize unwanted by-products like methane, and adjust outputs in response to market demands. This innovation could address the critical need for an efficient, scalable, and environmentally friendly method to produce ethene from naphtha (or plastic waste), paving the way for a more resilient global ethene and propene supply chain. One possible direction for naphtha and plastic valorization is their conversion into short-chain saturated hydrocarbons in presence of hydrogen and further utilization as a feedstock for steam crackers as alternative to shale gas. This can be performed by cracking with subsequent hydrogenation of formed olefins using a bifunctional catalytic system comprised of a cracking component, which is typically a solid acid, i.e. zeolite or amorphous aluminoosilicates, and hydrogenation / dehydrogenation component, i.e. a metal oxide catalyst with surface Lewis acid-base pairs. Thus, a catalyst composition including a metal oxide catalyst and a cracking component can be effective as described herein. Importantly, this approach can be potentially applied for polyethylene and polypropylene plastics processing via their catalytic conversion to shorter-chain hydrocarbons.

[0061] It is believed by the present inventors that the platinum-based catalyst currently used can be replaced with a metal oxide to serve as a hydrogenation / dehydrogenation component in combination cracking component in, for example, a bifunctional catalyst bed.

[0062] Metal oxides, such as ZrCL. may be promising alternative catalyst compositions for heterolytic catalytic reactions (including alkane dehydrogenation and alkene hydrogenation) because of the presence of Lewis acid-base (LAB) pairs that catalyzeAttorney Docket No. 39425-380 dehydrogenation reactions (Jaegers et al. J. Am. Chem. Soc. 2024, 146, 37, 25710-25726). A major limitation in the use of metal oxides for PDH is their fast deactivation. During the dehydrogenation of hydrocarbons such as propane, the acid-base pairs of metal oxide dehydrogenation catalysts (including ZrCh) may be deactivated by (i) titration of active sites by H2O and / or CO2, which directly derive from the gas feed streams or are formed indirectly via reactions of O2 or oxygenate impurities from gas streams with propane and / or H2; and / or (ii) coke deposition resulting from the adsorption of paraffin-derived molecules on M-0 sites and their further transformations; and / or (iii) sintering and / or annealing of the catalyst particles and active sites due to exposure to high temperatures. In addition, due to facile reactions of reductants with lattice O-atoms, some metal oxide dehydrogenation catalysts, e.g., CeCh. TiCh and MoOx. may be reduced to a lower oxidation state or even the metallic state over time, potentially resulting in activation or deactivation, either through intrinsic loss of active sites, loss of site competence, or from one of the above mechanisms. Therefore, for the utilization of LAB pairs in this chemistry7, a stable active site at high temperatures is needed to avoid irreversible deactivation, which was achieved in the present disclosure.

[0063] The present disclosure relates to a catalyst composition including a metal oxide (MOx) catalyst that includes Lewis Acid Base pairs (“LAB pairs”) in combination with a cracking component. This catalyst composition is effective at cracking hydrocarbons. In particular, the catalyst composition may be used to convert streams including naphtha-range molecules, e.g. C5-C12 alkanes or large polymers (e.g.. plastics or mixed plastics), to lighter Ci- Cs hydrocarbons containing but not limited to methane, ethane, ethene, propane, propene, butane, isobutane, butenes, isobutene, etc. Without being bound by a theory7, the large molecules in the stream are believed to be cracked directly on the cracking component, and as the molecules become smaller, they can then further react with hydrogen in the presence of MOx catalyst of the present disclosure. The metal (M) of the MOx catalyst is preferably a metal element that is more cost effective than Pt-based catalysts.

[0064] The MOx catalyst may have a surface containing M-0 site pairs of the acid-base Lewis type and of balanced acid-base strength.

[0065] In some embodiments, the catalyst composition may include the MOx catalyst in an amount of about 1% to about 99% based on the total weight of the catalyst composition. In other embodiments, the MOx catalyst may be included in an amount of about 5% to about 95%, about 10% to about 90%, about 15% to about 85%, about 20% to about 80%, about 25% to about 75%, about 30% to about 70%. about 35% to about 65%, about 40% to about 60%, or about 45% to about 55%, based on the total weight of the catalyst composition.Attorney Docket No. 39425-380

[0066] In some embodiments, the catalyst composition may include the cracking component in an amount of about 1% to about 99% based on the total weight of the catalyst composition. In other embodiments, the cracking component may be included in an amount of about 5% to about 95%, about 10% to about 90%, about 15% to about 85%, about 20% to about 80%, about 25% to about 75%, about 30% to about 70%, about 35% to about 65%, about 40% to about 60%, or about 45% to about 55%, based on the total weight of the catalyst composition.

[0067] In some embodiments, the cracking component may be a solid acid catalyst. In some embodiments, the cracking component may be an aluminosilicate. In some embodiments, the cracking component may be a zeolite. In some embodiments, the cracking component may include an amorphous silica-alumina, or a mesoporous acid. In some embodiments, the cracking component may be a combination of aluminosilicate, mesoporous acid and zeolites.

[0068] In some embodiments, the MOx cataly st may include a metal oxide in which M is not reducible to its zero-valent state at the conditions of catalysis. In some embodiments, the MOx catalyst may include Lewis acid base pairs, wherein M is selected from the group consisting of zirconium (Zr), cobalt (Co), gallium (Ga), zinc (Zn), cerium (Ce), yttrium (Y), titanium (Ti), and mixtures thereof.

[0069] In some embodiments, the MOx cataly st may include Y, Zr, or a combination thereof. In some embodiments, the MOx catalyst may include yttrium oxide (Y2O3), also known as yttria, zirconium oxide (ZrO2), also known as zirconia, or a combination thereof. Presently, metal oxide or mixed metal oxide catalysts including yttrium, zirconium or a combination thereof are being developed to enhance catalytic activity and / or thermal stability. These catalysts were found to have LAB pairs that are active during hydrogenation and dehydrogenation reactions. Without wishing to be bound by theory, it is surmised that exposing and having more active LAB pair sites increases the catalytic efficiency of the metal oxide and / or mixed metal oxide catalyst containing yttrium, zirconium, or a combination thereof. Thus, such catalyst has improved reactivity, selectivity and / or lifetime. To improve activation and / or reactivity of the catalyst, a method for preparing the catalyst is described herein.

[0070] By using the method as described herein, the inventors believe that the resulting catalyst exhibited higher activity and stability at elevated temperatures when compared to reference materials synthesized using different methods and presented in the literature. Thus, the catalysts as prepared according to the method of the present disclosure can be utilized in aAttorney Docket No. 39425-380 variety of reactions that involve LAB pairs, with a particular advantage in reactions where the stability of transition states is enhanced by interactions at LAB site pairs, leading to lower activation barriers.

[0071] The present inventors have found that LAB pairs that are typically blocked by water, carbon dioxide, and other titrant species including heteroatoms can act as highly active sites in catalyzing the dehydrogenation of alkanes and reverse hydrogenation of alkenes. The sites that are most effective at stabilizing intermediates and transition states along a reaction sequence may also be those that strongly bind with reactants and / or titrants. However, the site accessibility requires that the surfaces are made and kept free of these bound molecules, such as water, carbon dioxide, or other titrant species, which are commonly present during synthesis, thermal treatment, and / or exposure to ambient air. Trace impurities, such as oxygen, water, carbon dioxide, other titrant species during reaction, or precursors which can form titrants, may also be present in the reactant streams, which can affect the accessibility of the active sites. Thus, the activity and stability of the materials have been found to be linked to the ability of the system to keep inorganic surfaces (i.e., metal oxide surfaces) free of the basic molecules and their precursors.

[0072] In some embodiments, the MOXcatalyst may further include a rare earth element including at least one lanthanide metal, an oxide thereof, or combinations thereof. In some embodiments, the MOx catalyst may further include a rare earth element including at least one of yttrium (Y). erbium (Er), cerium (Ce), dysprosium (Dy), gadolinium (Gd), lanthanum (La), neodymium (Nd), samarium (Sm), ytterbium (Yb), Hafnium (Hf), oxides thereof or mixtures thereof.

[0073] In some embodiments, the rare earth element may be included in an amount of about 0.5 wt% to about 90 wt%, based on total weight of the MOx catalyst. In some embodiments, the rare earth element may be included in an amount of about 0.5 wt% to about 50 wt%, about 1 wt% to about 85 wt%, about 1 wt% to about 45 wt%, about 5 \\t% to about 80 wt%, about 5wt% to about 40 v %, about 10 wt% to about 75 wt%, about 10 wt% to about 35 wt%, about 15 wt% to about 70 wt%. about 15 wt% to about 30 wt%, about 20 wt% to about 65 wt%, about 20 wt% to about 25 wt%, about 25 wt% to about 60 wt%, about 30 wt% to about 55 wt%, about 35 wt% to about 50 wt%, or about 40 wt% to about 45 wt%, based on total weight of the MOx catalyst.

[0074] In some embodiments, the cracking component may include a zeolite including a medium pore zeolite having a 10-member ring, or a large pore zeolite having a 12-member ring. In some embodiments, the zeolite of the cracking component may include a naturallyAttorney Docket No. 39425-380 occurring zeolite, a synthetic zeolite, or a combination thereof. In some embodiments, the zeolite may include HY, USY, dealuminated Y, RE-Y, RE-USY. ZSM-5, ZSM-AA, IM-5, MCM-68, ZSM-57, ZSM-23, CIT-5, ZDM-35, MCM-22, MCM-56, MCM-49, UZM-8, EMM- 10, ITQ-2, ITQ-30, TNU-9, ZSM-22, ZSM-18, EMM-26, Zeolite T, EMC-2, offretite, beta, ITQ-13, Zeolite A, Zeolite L, MCM-35, mordenite, ZSM-12, NU-87, ECR-1, EU-1, ZSM-50, Li-A. Na-Pl, Na-P2, Chabazite, SSZ-13, SAPO-34, zeolite RHO, SSZ-35. SAPO-5, ITQ-12, Stilbite, CIT-7, ITQ-39, Linde Q, UZM-4. Natrolite, IPC-4. ZSM-48. SSZ-61, ITQ-4, ITQ-51. Mazzite, ZSM-4, SUZ-4, SSZ-48, SSZ— 23, SAPO-1 1, SAPO-31, AIPO-18, SAPO-18, SAPO-18, SAPO-41, ITQ-7, ITQ-3, SSZ-36, MCM-58, ferrierite, Y zeolite, SAPO, or a combination thereof. In some embodiments, the zeolite may be a large-pore zeolite, for example framework types FAU, MOR and the like. In some embodiments, the zeolite may be a small-pore or / and medium-pore zeolite, for example framework types ACO, AEI, AEN, AFN, AFT, AFX, ANA, APC, APD, ATT, CHA, CDO, DDR, DFT, EAB, EDI, EPI, ERI, GIS, GOO, IHW, ITE, ITW, LEV, KFI, MER, MON, NSI, OWE, PAU, PHI, RHO, TH, SAT, SAV, SIV, THO, TSC, UEI, UFI, VNL YUG, ZON, MFI, LTA, BEA and the like. Specific examples may be ZSM-11, MFI zeolite and MCM.

[0075] In some embodiments, the cracking component may include amorphous silica- alumina, or a zeolite selected from the group consisting of USY zeolite, beta zeolite, ZSM-5, chabazite, SAPO-5, ferrierite, Y zeolite, ZSM-11, or mixtures thereof. In some embodiments, the cracking component may further include a mesoporous acid. In some embodiments, the mesoporous acid may include silica-alumina, zirconia oxides, sulfate of zirconia, or a combination thereof. In some embodiments, the mesoporous acid may include MCM-41, MCM-48, MCM-50, FSM-16, FSM-21, SBA-15, or a combination thereof.

[0076] In some embodiments, the MOx catalyst and the cracking component may be present as an intraparticle mixture, or an interparticle loose mixture.

[0077] In some embodiments, the catalyst composition does not include a platinum group metal. In some embodiments, the platinum group metal may include platinum (Pt), palladium (Pd), rhodium (Rd), ruthenium (Ru), iridium (Ir), osmium (Os), or a combination thereof.

[0078] In some embodiments, the catalyst composition may further include a catalyst, catalyst support, a catalyst binder and / or a catalyst component used in a catalyst for the dehydrogenation of hydrocarbons.

[0079] In some embodiments, a method of performing a reaction is provided. The method of performing a reaction may include using a catalyst composition as described herein. The reaction may include alkane dehydrogenation, alkene hydrogenation, alkene dehydrogenation,Attorney Docket No. 39425-380 olefin-paraffin alky lation, from CO / H2 mixtures without O-rej ection as H2O or CO2, C-C bond formation via alkene oligomerization or metathesis, dehydrocyclization (alkanes / alkenes to arenes), dehydrocyclodimerization (alkanes / alkenes to arenes with a larger number of C- atoms), transfer hydrogenation, hydroformylation / carbonylation, aromatization, dearomatization, reforming, isomerization, and bifunctional reactions in which one of the aforementioned functions can be combined with a Bronsted acid function.

[0080] In some embodiments, the reaction may occur in a batch or semi-batch configuration.

[0081] In some embodiments, the method may further include pretreating the catalyst composition in an aerobic oxidative environment before or after the cleaning with the surface cleaning reagent and treating the reactants with a trap.

[0082] In some embodiments, the method may further include pretreating the catalyst composition in an aerobic oxidative environment before the cleaning with the surface cleaning reagent and treating the reactants with a trap.

[0083] In some embodiments, the method may further include pretreating the catalyst composition in an aerobic oxidative environment after the cleaning with the surface cleaning reagent and treating the reactants with a trap to prevent titrants from re-entering the stream and blocking the most competent LAB pairs.

[0084] In an embodiment, a method of preparing a catalyst composition is provided. The method includes mixing a zirconium-containing precursor, an yttrium-containing precursor or a combination thereof with a precipitant to obtain a mixture. The method further includes heating the mixture, and adding a surfactant comprising an organic molecule to the mixture. The method then further includes separating solids from the mixture, wherein the solids include zirconium, yttrium, or a combination thereof. The method also includes combining a cracking component with the solids to obtain the catalyst composition. It is understood herein that the solids formed in the method may also refer to a metal oxide catalyst as described herein. It also may be understood that the solids and / or the metal oxide catalyst may function as a hydrogenation / dehydrogenation component in the method or systems described herein.

[0085] In some embodiments, the solids may have a molar ratio of yttrium to zirconium of about 1 :50 to about 50: 1, about 1 :45 to about 45: 1, about 1 :40 to about 40: 1, about 1:35 to about 35:1, about 1:30 to about 30: 1, about 1:25 to about 25: 1, about 1 :20 to about 20: 1, about 1 : 15 to about 15:1, about 1: 10 to about 10: 1, about 1 :5 to about 5: 1, or about 1:1.

[0086] In some embodiments, the zirconium-containing precursor, if included, may be included in an amount of about 0.05 mol / L to about 1 mol / L, about 0.1 mol / L to about 0.95Attorney Docket No. 39425-380 mol / L, about 0.2 mol / L to about 0.8 mol / L, about 0.3 mol / L to about 0.7 mol / L, or about 0.4 mol / L to about 0.6 mol / L. In some embodiments, the zirconium-containing precursor, if included, may be about 0.05 mol / L, about 0.1 mol / L, about 0.143 mol / L, about 0.2 mol / L, about 0.33 mol / L, about 0.5 mol / L, about 0.8 mol / L, about 0.857 mol / L, about 0.9 mol / L, about 0.95 mol / L or about 1 mol / L.

[0087] In some embodiments, the zirconium-containing precursor may be zirconium oxide, zirconium oxynitrate, zirconium chloride, zirconium oxychloride, zirconium acetate, zirconium oxalate, zirconium organophosphate, zirconium alkoxide, zirconium carbonate, zirconium hydroxycarbonate, zirconium carboxylate, zirconium acetylacetonate. zirconium, zirconium hydroxide, or a combination thereof.

[0088] In some embodiments, the yttrium-containing precursor, if included, may be included in an amount of about 0.05 mol / L to about 1 mol / L, about 0.1 mol / L to about 0.95 mol / L, about 0.2 mol / L to about 0.8 mol / L, about 0.3 mol / L to about 0.7 mol / L, or about 0.4 mol / L to about 0.6 mol / L. In some embodiments, the yttrium-containing precursor, if included, may be included in an amount of about 0.05 mol / L, about 0.1 mol / L, about 0.143 mol / L, about 0.2 mol / L, about 0.5 mol / L, about 0.67 mol / L, about 0.8 mol / L, about 0.857 mol / L, about 0.9 mol / L, about 0.95 mol / L or about 1 mol / L.

[0089] In some embodiments, the yttrium-containing precursor may be yttrium nitrate, yttrium chloride, yttrium acetate, yttrium oxalate, yttrium hydroxide, yttrium organophosphate, yttrium alkoxide, yttrium carbonates, yttrium hydroxy carbonate, yttrium carboxylate, yttrium acetylacetonate, yttrium, yttrium oxide, or a combination thereof.

[0090] In some embodiments, the yttrium-containing precursor, the zirconium-containing precursor, or combination thereof may be mixed with a solvent. The solvent may include an alcohol, water or a combination thereof. The alcohol may be methanol, ethanol, / 7-propanol. or isopropanol.

[0091] In some embodiments, the precipitant may include a basic compound. In some embodiments, the basic compound may include Bronsted bases and Lewis bases. For example, the basic compound may be an alkali metal hydroxide, alkaline earth metal hydroxide, ammonia, alkylammonium hydroxides, or a combination thereof. In some embodiments, the basic compound may be sodium hydroxide, potassium hydroxide, barium hydroxide, ammonia, or a combination thereof.

[0092] In some embodiments, the mixing is performed to form a homogenized mixture of components. The mixing may be formed by stirring, swaying, shaking, rolling, rotating and / or Bonification, while the precursors and precipitant are in a solvent. Thus, the mixture formedAttorney Docket No. 39425-380 with the precursors and precipitant form a suspension that is further treated so that solids are separated out.

[0093] In some embodiments, combining the cracking component and the solids may include forming an intraparticle mixture, or an interparticle loose mixture.

[0094] In some embodiments, the heating of the mixture may be carried out at a temperature in a range from about 50°C to about 450°C. In some embodiments, the heating may be at atemperature of about 50°C. about 60°C, about 70°C, about 80°C, about 90°C, about 100°C, about 110°C, about 120°C, about 130°C, about 140°C, about 150°C, about 160°C, about 170°C, about 180°C, about 190°C, about 200°C, about 210°C, about 220°C, about 230°C, about 240°C, about 250°C, about 275°C, about 300°C, about 325°C, about 350°C, about 375°C. about 400°C, about 425°C, or about 450°C. In some embodiments, the heating may be at a temperature of about 50°C to about 450°C, about 50°C to about 400°C, about 80°C to about 350°C, about 80°C to about 3000°C, about 100°C to about 250°C, or about 150°C to about 200°C. In some embodiments, the heating of the mixture may be carried out for about 1 hour to about 24 hours. In some embodiments, the heating may be carried out for about 1 hour, about 2 hours, about 3 hours, about 4 hours, about 5 hours, about 6 hours, about 7 hours, about 8 hours, about 9 hours, about 10 hours, about 11 hours, about 12 hours, about 13 hours, about 14 hours, about 15 hours, about 16 hours, about 17 hours, about 18 hours, about 19 hours, about 20 hours, about 21 hours, about 22 hours, about 23 hours, or about 24 hours.

[0095] In some embodiments of the method, the surfactant including an organic molecule may include a carboxylic acid, a carboxylate anion, a carboxylic salt, or a combination thereof. In some embodiments, the carboxylic acid may include lauric acid, or its laureate form. The organic molecule is believed to stabilize the mixture during the method of preparing so that solids may form.

[0096] In some embodiments, separating of the solids from the mixture may include filtering the solids, decanting the solids, or centrifuging the mixture, or any other method known to one of skill in the art.

[0097] In some embodiments, the method may further include washing the solids with a hydroxide, alcohol, water, or a combination thereof. The hydroxide may include ammonium hydroxide, sodium hydroxide, or a combination thereof. In an embodiment, the hydroxide is ammonium hydroxide. In another embodiment, the hydroxide is a sodium hydroxide. In some embodiments, the hydroxide may be a solution having a pH of about 7 to 10, or about 9.

[0098] In some embodiments, the method may further include drying the solids. In some embodiments, the drying may be carried out at a temperature of about 25°C to about 110°C.Attorney Docket No. 39425-380In some embodiments, the drying may be at a temperature of about 25°C, about 35°C, about 45°C, about 55°C, about 65°C, about 75°C, about 85°C. about 95°C, about 100°C. or about 110°C.

[0099] In some embodiments, the method may further include calcining the solids. In some embodiments, the calcining may be carried out at a temperature of about 300°C to about 800°C. In some embodiments, the calcining may be at a temperature of about 300°C, about 325°C, about 350°C, about 375°C, about 400°C, about 425°C, about 450°C. about 475°C, about 500°C, about 525°C, about 550°C, about 575°C, about 600°C, about 625°C, about 650°C, about 675°C, about 700°C, about 725°C, about 750°C, about 775°C, or about 800°C. In some embodiments, the calcining may be carried out for about 2 hours to about 12 hours. In other embodiments, the calcining may be carried out for about 2 hours, about 3 hours, about 4 hours, about 5 hours, about 6 hours, about 7 hours, about 8 hours, about 9 hours, about 10 hours, about 11 hours, or about 12 hours.[000100] In some embodiments, the catalyst prepared by the method of the present disclosure may include yttrium and zirconium, wherein the molar ratio of yttrium to zirconium is about 0.02 to about 50, about 0.05 to about 20, about 0.1 to about 15, about 5 to about 12, or about 8 to about 10. In some embodiments, the molar ratio of yttrium to zirconium may be about 0.02, about 0.05, about 0.1, about 0.5, about 1, about 3, about 5, about 8, about 10, about 12, about 15, about 18, about 20. about 25, about 30, about 35, about 40, about 45, or about 50.[000101] In some embodiments, the MOx catalyst may include yttrium, or zirconium, or a combination thereof as the metal. The metal oxide catalyst as described herein may have a surface with an M-0 site of the Lewis type and of balanced acid-base strength, wherein M includes yttrium or zirconium. In some embodiments, the catalyst may be a mixed metal oxide catalyst including yttrium and zirconium as the metal. The mixed metal oxide catalyst may have a surface with an M-0 site of the Lewis type and of balanced acid-base strength, wherein M includes yttrium and zirconium.[000102] In some embodiments, the cracking component may include a zeolite, an acid catalyst aluminosilicate, an amorphous silica-alumina, a mesoporous acid, or a combination thereof as described herein.[000103] In some embodiments, the method may further include mixing an additional precursor. The additional precursor may include a rare earth oxide or a rare earth metal. If included, the additional precursor may be included in an amount of 5 wt% or less, based on total weight of the catalyst.Attorney Docket No. 39425-380[000104] In some embodiments, the additional precursor may include alumina. In some embodiments, alumina may be aluminum salts, aluminum oxide hydroxides, aluminum hydroxides, alumina, or a combination thereof. In some embodiments, the alumina may be aluminum sulfates, aluminum nitrates, aluminum phosphates, aluminum chlorides, aluminum bromides, aluminum acetates, diaspore, boehmite, akdalaite, gibbsite, bayerite, doyleite, nordstrandite, or a combination thereof. In some embodiments, the alumina may include colloidal alumina, colloidal alumina oxide hydroxides, colloidal aluminum hydroxides, or a combination thereof.[000105] In some embodiments, the method may further include cleaning a surface of the catalyst from carbonaceous deposits by heating the catalyst at a temperature of about 300°C to about 800°C in the presence of O2, followed by an inert purge period of about 5 minutes to about 3 hours to remove residual O2. In some embodiments, the heating may be at a temperature of about 300°C, about 350°C, about 400°C, about 450°C, about 500°C, about 550°C, about 600°C, about 650°C, about 700°C, about 750°C, or about 800°C. In some embodiments, the inert purge period may be about 5 minutes, about 10 minutes, about 15 minutes, about 20 minutes, about 25 minutes, about 30 minutes, about 35 minutes, about 40 minutes, about 45 minutes, about 50 minutes, about 55 minutes, about 60 minutes, about 90 minutes, about 120 minutes, about 150 minutes, or about 180 minutes.[000106] In some embodiments, the cleaning of the surface removes excess water through the surface cleaning reagent reacting with the water or carbon dioxide species bound at the oxide surface.[000107] In some embodiments, the method may further include cleaning a surface of the catalyst by heating the catalyst at a temperature of about 300°C to about 800°C. In some embodiments, the heating may be at a temperature of about 300°C, about 350°C, about 400°C, about 450°C, about 500°C, about 550°C, about 600°C, about 650°C, about 700°C, about 750°C, or about 800°C.[000108] In some embodiments, the cleaning does not include applying a surface cleaning reagent. In other embodiments, when the cleaning includes heating the catalyst, it may further include applying a surface cleaning reagent.[000109] In some embodiments, a method of treating a reactant stream is provided. The method of treating a reactant stream may include feeding the reactant stream to a reactor, wherein the reactor may include a catalyst composition as described in the present disclosure. [000110] In some embodiments, the reactant stream may include naphtha, a pyrolysis oil, a polyolefin, or a combination thereof.Attorney Docket No. 39425-380[000111] In some embodiments, the catalyst composition may include a trap. In some embodiments, the trap may remove an impurity from the reactant stream. In some embodiments, the impurity may include oxygen (O2), water (H2O), hydrogen sulfide (H2S), carbon dioxide (CO2), carbon monoxide (CO), nitrogen (N2), a sulfur containing compound, methanol, a ketone, an inorganic nitrogen compound, an organic nitrogen compound, an oxygenate, or a combination thereof.[000112] In some embodiments, the amount of water and / or O2 in the reactor may be less than about 2 ppm, less than about 1.5 ppm, less than about 1 ppm, or less than about 0.5 ppm. [000113] In some embodiments, the method of treating a reactant stream may further include performing a hydrogenation reaction. In some embodiments, the method may further include feeding hydrogen to the reactor.[000114] In some embodiments, the reaction may produce a carbon product having C2-C10 chains, or a carbon product having a C2 or C3 chain.[000115] Claims or descriptions that include “or” or “and / or” between at least one members of a group are considered satisfied if one, more than one, or all of the group members are present in, employed in, or otherwise relevant to a given product or process unless indicated to the contrary or otherwise evident from the context. The disclosure includes embodiments in which exactly one member of the group is present in, employed in, or otherwise relevant to a given product or process. The disclosure includes embodiments in which more than one, or all the group members, are present in, employed in, or otherwise relevant to a given product or process.[000116] Furthermore, the disclosure encompasses all variations, combinations, and permutations in which at least one limitation, element, clause, and descriptive term from at least one of the listed claims is introduced into another claim. For example, any claim that is dependent on another claim can be modified to include at least one limitation found in any other claim that is dependent on the same base claim. Where elements are presented as lists, such as, e.g., in Markush group format, each subgroup of the elements is also disclosed, and any element(s) can be removed from the group. It should be understood that, in general, where the disclosure, or aspects of the disclosure, is / are referred to as comprising particular elements and / or features, embodiments of the disclosure or aspects of the disclosure consist, or consist essentially of, such elements and / or features. For purposes of simplicity, those embodiments have not been specifically set forth in haec verba herein. Where ranges are given (such as, e.g., from [X] to [Y]), endpoints (such as, e.g., [X] and [Y] in the phrase “from [X] to [Y]”) are included unless otherwise indicated. Furthermore, unless otherwise indicated or otherwiseAttorney Docket No. 39425-380 evident from the context and understanding of one of ordinary skill in the art, values that are expressed as ranges can assume any specific value or sub-range within the stated ranges in different embodiments of the disclosure, to the tenth of the unit of the lower limit of the range, unless the context clearly dictates otherwise.[000117] Those of ordinary skill in the art will recognize or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the disclosure described herein. Such equivalents are intended to be encompassed by the following claims.EXAMPLES[000118] The following examples are intended to be illustrative and are not meant in any way to limit the scope of the disclosure.[000119] Several tests were conducted to study a catalyst composition as described herein and its effectiveness in converting naphtha-range feedstocks to lighter alkanes. Without being bound to a theory, the acid sites present in a cracking component, such as a zeolite, enable cracking a naphtha compound (e g., w-decane) to a mixture of C2-C4 alkenes and alkanes at 723 K. At these temperatures and typical effluent conditions, having partial pressures of alkenes below 1 kPa, the hydrogenation of the alkenes present in the product mixture was favored over dehydrogenation of alkanes present in the mixture (see Figure 1). The hydrogenation reactions of these formed alkenes may be facilitated by the MOx catalysts with surface LAB pairs The presence of the catalyst composition of the present disclosure may be beneficial in three ways: i) dehydrogenation of long-chain alkane reactants to the corresponding alkene may increase the cracking rate, as alkenes are more prone to undergo catalytic cracking compared to alkanes, and ii) hydrogenation of the formed short-chain alkenes to alkanes avoids an approach to thermodynamic equilibrium for the cracking process, which limits conversion of the long-chain alkane, and iii) hydrogenation of alkenes limits the formation of arenes, tars, and carbon (via dienes / trienes) that cause catalyst deactivation.1. Reaction of n-decane using the catalyst composition[000120] Proof of concept experiments were performed utilizing w-decane as a reacting molecule on HMFI zeolite (CBV 2314 from Zeolyst, Si / Al = 12.5) and a physical mixture of HMFI and yttria-stabilized zirconia with Y:Zr ratio of 6 studied at 723 K. The results are presented in Figure 2.[000121] The nearly complete conversion (>99%) of 77-decane on MFI was observed at 723 K with 30 pmol CioH22 S'1gzeoiite‘1and led to the cracking of w-decane and the formation of aAttorney Docket No. 39425-380 mixture of primarily alkanes and alkenes in the C2-C5 range, with average carbon number equal to 3.2, and relatively small amount of Ce-Cs aromatic compounds, namely benzene, toluene, and xylenes (BTX; Table 1).Table 1 : Carbon selectivity to different product groups for / 7-decanc cracking on MFI andMFI / YZO. Reaction conditions: 723 K, 1.3 kPa n-CioH22, 100 kPa H2, 30 pmol CIOH22 S’ ^zeolite’1. For physical mixtures of MFI and YSZ, the mass ratio of former to latter was 1:9, and pretreatment in He at 923 K for 1 hour was performed prior to catalytic testing.[000122] A single C-C scission event during alkane or alkene cracking resulted in the formation of an additional alkene molecule. From this, the average carbon number of 3.2 in products indicated that on average 2 scission events take place for each / 7-decane molecules. Notably, the expected alkane / alkene ratio in products for 2 scission events is equal to 0.5 (2 new alkene molecules were formed), while observed value for MFI was slightly higher, near 0.67 (See Figure 2b). This may be explained by the formation of small amounts of aromatic compounds (BTX), which were formed from Ce-Cs alkenes by their further dehydrogenation and would otherwise lead to lower alkane / alkene ratios in the absence of alkene scavenging by aromatization. The conversion and product distribution over the MFI catalyst were stable with time on stream under the applied experimental conditions. The addition of YSZ to the catalyst bed with MFI lead to significant changes in reactivity: the average number of carbon atoms in products decreased from 3.2 with only MFI to 2.9 for the MFI / YZO mixture, indicating more extensive cracking in the bifunctional system. Notably, the products mostly include alkanes in C2-C4 range, pointing to significant hydrogenation of formed alkenes products. Also, the addition of YZO to the catalyst bed led to a higher fraction of products in C2-C3 range and lower in C4-C5 range indicating subsequent C-C scission events on products in the C4-C5 range. This was apparently facilitated by hydrogenation of formed C2 and C3 alkenes. Moreover, the formation of aromatic compounds was suppressed on MFI / YZO compared to MFI, apparently because of fast hydrogenation of alkenes, including Ce-Cs aromatic precursors. As a consequence of the fast hydrogenation, the total alkanes / alkenes ratio for MFI / YZO mixture is higher (10) and slowly decreases to around 5 over 60 ks time on stream. The suppression of hydrogenation reactions over time potentially reflects deactivation of the hydrogenationAttorney Docket No. 39425-380 component by feed impurities. From these results, it is conceivable that the hydrogenation of short-chain alkenes can circumvent potential thermodynamic limitations of C-C scission reactions.[000123] The strategy of combining dehydrogenation / hydrogenation and acid functions to convert larger alkanes to shorter ones may potentially by extended to the deconstruction of polyolefin plastics for upcycling purposes, in particular polyethylene and polypropylene. The current proposed catalytic methods of polyolefin deconstruction rely primarily on hydrogenolysis processes - treatment of plastics in presence of platinum group metals (Pt, Ru) catalyst at elevated temperatures (450-600 K) at high H2 pressure >10 bar. Hydrogenolysis lead to direct cleavage of C-C bonds and the formation of new C-H bonds. Stoichiometrically, hydrogenolysis and the described cracking and subsequent hydrogenation are macroscopically similar; however, mechanistically these two processes are very different. Thus, hydrogenolysis often lead to the formation of methane because of C-C scission at the terminal bond position. The large fraction of methane in polyolefin hydrogenolysis products is one of the challenges in plastic deconstruction via hydrogenolysis. The combination of acid-catalyzed cracking with subsequent hydrogenation has low selectivity to methane because the low stability of the primarily carbenium cation. Therefore, mainly products of long-chain alkanes conversion using this method are expected to be in C2-C4 range, similar to that demonstrated in the art. Another potential benefit of using MOXcatalysts of the present disclosure for polyolefin deconstruction is their much lower sensitivity to impurities in the feedstock, while this is a considerable problem for the state-of-the-art noble metal containing catalysts. The loss of precious metals is also a concern in polymer melts, which is avoided with catalysts of the present disclosure.[000124] Thus, the conversion of naphtha-range feedstocks using a physical mixture of M0xcatalysts of the present disclosure and a cracking component including an acid catalyst may enable the desired C-C scission to ethane steam cracker range alkanes. Potentially, large-pore zeolite, i.e. FAU-based USY used in FCC processes, may be selected to ensure the possibility of long-chain reactant molecules to access the zeolite pore system and minimize mass-transfer limitations. Polyolefin deconstruction requires that feedstock molecules, which are too large to access the acid sites within zeolite framework, first undergoing cracking outside of the zeolite framework. Thus, a mesoporous acid matrix may be utilized.

Claims

Attorney Docket No. 39425-380What is claimed is:

1. A catalyst composition comprising a metal oxide (MOx) catalyst having a surface containing M-0 site pairs of the acid-base Lewis type and of balanced acid-base strength; and a cracking component.

2. The catalyst composition of claim 1, wherein the MOXcatalyst is included in an amount of about 1% to about 90% of a combined mass of the catalyst composition.

3. The catalyst composition of claim 1 or 2, wherein the cracking component is included in an amount of about 1% to about 99%, based on a combined mass of the catalyst composition.

4. The catalyst composition of any one of the preceding claims, wherein the M0xcatalyst comprises a metal oxide in which M is not reducible to its zero-valent state at the conditions of catalysis.

5. The catalyst composition of any one of the preceding claims, wherein the MOXcatalyst comprises Lewis acid-base pairs, where M comprises zirconium (Zr), cobalt (Co), gallium (Ga), zinc (Zn), cerium (Ce), yttrium (Y), titanium (Ti), or a combination thereof.

6. The catalyst composition of any one of the preceding claims, wherein the MOx catalyst comprises a metal comprising Zr, Y, or a combination thereof.

7. The catalyst composition of any one of the preceding claims, wherein the MOx catalyst comprises ZrtZh.

8. The catalyst composition of any one of the preceding claims, wherein the MOx catalyst comprises Y2O3.Attorney Docket No. 39425-3809. The catalyst composition of any one of the preceding claims, wherein the MOx catalyst further comprises a rare-earth element comprising at least one lanthanide metal, an oxide thereof, or combinations thereof.

10. The catalyst composition of any one of the preceding claims, wherein the MOx catalyst further comprises a rare-earth metal comprising at least one of yttrium (Y), erbium (Er), cerium (Ce), dysprosium (Dy), gadolinium (Gd), lanthanum (La), neodymium (Nd), samarium (Sm), ytterbium (Yb), hafnium (Hf), oxides thereof, or mixtures thereof.

11. The catalyst composition of one of claim 9 or 10, wherein the rare earth metal is included in an amount of about 0.5 wt% to about 50 wt%. based on total weight of the MOx catalyst.

12. The catalyst composition of any one of the preceding claims, wherein the cracking component comprises a zeolite, an acid catalyst, an amorphous silica- alumina, or a combination thereof.

13. The catalyst composition of claim 12, wherein the zeolite comprises a medium pore zeolite having a 10-member ring, or a large pore zeolite having a 12-member ring.

14. The catalyst composition of claim 1 , wherein the cracking component comprises a zeolite selected from the group consisting of USY zeolite, beta zeolite, ZSM-5, chabazite, SAPO-5, ferrierite, Y zeolite, ZSM-11, or mixtures thereof.

15. The catalyst composition of any one of the preceding claims, further comprising a mesoporous acid.

16. The catalyst composition of claim 15, wherein the mesoporous acid comprises MCM- 41, MCM-48, MCM-50, FSM-16. FSM-21, SBA-15, or a combination thereof.

17. The catalyst composition of any one of the preceding claims, wherein the M0xcatalyst and the cracking component are present as an intraparticle mixture, or an interparticle loose mixture.Attorney Docket No. 39425-38018. The catalyst composition of any one of the preceding claims, wherein the composition does not include a platinum group metal.

19. A method of performing a reaction using a catalyst composition of any one of the preceding claims, wherein the reaction comprises alkane dehydrogenation, alkene hydrogenation, alkene dehydrogenation, olefm-paraffin alkylation, from CO / H2 mixtures without O-rejection as H2O or CO2, C-C bond formation via alkene oligomerization or metathesis, dehydrocyclization (alkanes / alkenes to arenes), dehydrocyclodimerization (alkanes / alkenes to arenes with a larger number of C-atoms), transfer hydrogenation, hydroformylation / carbonylation, aromatization, dearomatization, reforming, isomerization, and bifunctional reactions in which one of the aforementioned functions can be combined with a Bronsted acid function.

20. A method of preparing a catalyst composition comprising: mixing a zirconium containing precursor, an yttrium containing precursor, or a combination thereof with a precipitant to obtain a mixture; heating the mixture; adding a surfactant comprising an organic molecule to the mixture; and separating solids from the mixture, wherein the solids comprise zirconium, yttrium or a combination thereof; and combining a cracking component with the solids to obtain the catalyst composition.

21. The method of claim 20, wherein the solids have a molar ratio of yttrium to zirconium of 1:50 to 50: 1.

22. The method of claim 20 or 21, further comprising washing the solids with a hydroxide, water, or a combination thereof.

23. The method of one of claims 20-22, further comprising drying the solids.

24. The method of one of claims 20-23, further comprising calcining the solids.Attorney Docket No. 39425-38025. The method of claim 22, wherein the hydroxide comprises ammonium hydroxide, sodium hydroxide, or a combination thereof.

26. The method of claim 22, wherein the hydroxide is a solution having a pH of about 7 to about 10, or about 9.

27. The method of any one of claims 20-26, wherein the organic molecule comprises a carboxylic acid or a carboxylate anion.

28. The method of claim 27, wherein the carboxylic acid comprises lauric acid or its laureate form.

29. The method of any one of claims 20-28, further comprising cleaning a surface of the cataly st by heating the catalyst at a temperature of about 300°C to about 800°C.

30. The method of claim 29, wherein the cleaning does not include applying a surface cleaning reagent.

31. A method of treating a reactant stream comprising: feeding the reactant stream to a reactor, wherein the reactor comprises a catalyst composition according to one of claims 1-19.

32. The method of claim 31, wherein the reactant stream comprises naphtha, a py rolysis oil, a polyolefin, mixed plastics, or a combination thereof.

33. The method of claim 31 or 32, wherein the catalyst composition comprises a trap.

34. The method of claim 33, wherein the trap removes an impurity from the reactant stream.

35. The method of claim 34, wherein the impurity comprises oxygen (O2), water (H2O), hydrogen sulfide (H2S), carbon dioxide (CO2), carbon monoxide (CO), a sulfur containing compound, methanol, a ketone, an inorganic nitrogen compound, an organic nitrogen compound, an oxygenate, or a combination thereof.Attorney Docket No. 39425-38036. The method of any one of claims 31-35, wherein the amount of water in the reactor is less than about 2 ppm.

37. The method of claim 31, further comprising performing a hydrogenation reaction, a dehydrogenation reaction, an aromatization reaction, a cracking reaction or a combination of thereof.

38. The method of any one of claims 31-37, further comprising feeding hydrogen to the reactor.

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