FCC catalyst composition for fluid catalytic cracking and method of using the FCC catalyst composition

Abstract

The fluid catalytic cracking catalyst composition (FCC catalyst composition) comprises a framework-substituted ultrastable Y-type zeolite (USY zeolite) having one or more transition metals substituted into the framework of the USY zeolite and an FCC zeolite cracking additive. A method for upgrading a hydrocarbon feed comprises contacting the hydrocarbon feed with the FCC catalyst composition of the present disclosure under reaction conditions sufficient to upgrade at least a portion of the hydrocarbon feed. The method for upgrading a hydrocarbon feed comprises passing the hydrocarbon feed through a fluid catalytic cracking unit and contacting the hydrocarbon feed with the FCC catalyst composition in the fluid catalytic cracking unit under reaction conditions sufficient to cause at least a portion of the hydrocarbon feed to undergo cracking reactions and produce a cracked reaction mixture comprising spent FCC catalyst composition and a cracked effluent containing one or more olefins.

Description

Description of Related Applications

[0001] This application claims priority to U.S. Patent Application No. 16 / 919,336, filed July 2, 2020, entitled "FCC CATALYST COMPOSITIONS FOR FLUID CATALYTIC CRACKING AND METHODS OF USING THE FCC CATALYST COMPOSITIONS," which is incorporated herein by reference in its entirety. [Technical field]

[0002] The present disclosure relates generally to processes for upgrading hydrocarbons, and more particularly to catalyst compositions for upgrading hydrocarbons and fluid catalytic cracking processes for upgrading hydrocarbons using the catalyst compositions. [Background technology]

[0003] Petrochemical feeds such as crude oil can be converted into chemical products and intermediates such as olefins and aromatics, which are the basic intermediates for most of the petrochemical industry. The increasing global demand for light olefins and aromatics remains a major challenge for many integrated refineries. There is an increasing focus on the production of some valuable light olefins, especially ethylene, propene, and butene, since pure olefin streams are considered as building blocks for polymer synthesis. In addition, aromatics such as benzene, toluene, ethylbenzene, and xylene can be useful intermediates for the synthesis of polymers and other organic compounds, as well as for fuel additives. Summary of the Invention

[0004] Fluid catalytic cracking (FCC) units are the main hydrocarbon conversion units in modern oil refineries. FCC units can primarily produce gasoline in conventional FCC units or propylene in high severity FCC units. Conventional FCC units can operate at temperatures between 500 degrees Celsius (°C) and 550°C and catalyst to oil ratios between 3.0:1 and 6.0:1. On the other hand, advanced FCC units can operate at temperatures between 600°C and 650°C and catalyst to oil ratios greater than 6.0:1. In advanced FCC units, hydrocarbons may be converted to gasoline with an FCC catalyst, which can then be converted to olefins with an additive for the FCC catalyst. The olefins may include ethylene, propylene, butene, or combinations thereof.

[0005] In the FCC process, hydrocarbons are catalytically cracked over an acidic catalyst maintained in a fluidized state. The catalyst can be continuously regenerated. One of the main products from such a process is typically gasoline. Other products such as liquid petroleum gas and cracked gas oil may also be produced in small amounts. Gasoline and other hydrocarbon products can be further upgraded to light olefins such as ethylene, propylene, butene, or combinations thereof during the FCC process. Coke deposited on the catalyst is burned off at high temperatures in the presence of air before recycling the regenerated catalyst back to the reaction zone. Despite many advances in the FCC process, the industry is constantly seeking improved catalyst materials, especially those that can increase the conversion to desired products.

[0006] Thus, there remains a need for fluid catalytic cracking catalyst compositions and methods for upgrading hydrocarbons to increase the efficiency of the cracking process and improve the yield of valuable products such as light olefins. The present disclosure relates to fluid catalytic cracking (FCC) catalyst compositions comprising framework-substituted ultra-stable Y-type zeolites and FCC zeolite cracking additives. These FCC catalyst compositions may be characterized by reduced dry gas and coke production and greater cracking activity compared to conventional cracking catalysts commonly used in FCC units. The FCC catalyst compositions of the present disclosure can significantly increase the conversion of hydrocarbon feed to desired products such as light olefins and gasoline.

[0007] According to one or more embodiments of the present disclosure, an FCC catalyst composition may include a framework-substituted USY zeolite that includes one or more transition metals substituted into the framework of the USY zeolite. The FCC catalyst composition may further include from 1 weight percent to 50 weight percent of an FCC zeolite cracking additive, based on the total weight of the FCC catalyst composition.

[0008] In one or more other embodiments of the present disclosure, a method for upgrading a hydrocarbon feed may include contacting the hydrocarbon feed with an FCC catalyst composition at reaction conditions sufficient to upgrade at least a portion of the hydrocarbon feed. The FCC catalyst composition may further include a framework-substituted USY zeolite and 1 to 50 weight percent of an FCC zeolite cracking additive, based on the total weight of the FCC catalyst composition. The framework-substituted USY zeolite may include hafnium, zirconium, titanium, or a combination thereof, substituted into the framework of the framework-substituted USY zeolite.

[0009] In yet another embodiment of the disclosure, a method for upgrading a hydrocarbon feed may include passing the hydrocarbon feed through a fluid catalytic cracking unit. The method may further include contacting the hydrocarbon feed with an FCC catalyst composition in the fluid catalytic cracking unit under reaction conditions sufficient to cause at least a portion of the hydrocarbon feed to undergo a cracking reaction. The cracking reaction may produce a cracking reaction mixture comprising a spent FCC catalyst composition and a cracked effluent comprising one or more olefins. The FCC catalyst composition may comprise a framework-substituted USY zeolite comprising hafnium, zirconium, titanium, or a combination thereof substituted on the framework of the framework-substituted USY zeolite. The FCC catalyst composition may further comprise 1 weight percent to 50 weight percent of an FCC zeolite cracking additive, based on the total weight of the FCC catalyst composition. The method may further include passing the cracked reaction mixture through a catalyst separation device that separates the cracked reaction mixture into a spent FCC catalyst composition and a cracked effluent, and allowing the cracked effluent to flow from the fluid catalytic cracking unit.

[0010] Additional features and advantages of the techniques described in this disclosure are set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from that description, or will be learned by practicing the techniques as described in this disclosure, including the following detailed description, the claims, and the accompanying drawings. [Brief description of the drawings]

[0011] The following detailed description of specific embodiments of the present disclosure can be best understood when read in conjunction with the following drawings, where like structure is indicated with like reference numerals and in which: [Figure 1] FIG. 1 is a generalized flow diagram of a system for upgrading a hydrocarbon feed according to one or more embodiments shown and described in this disclosure. [Diagram 2]FIG. 1 is a generalized flow diagram of another system for upgrading a hydrocarbon feed according to one or more embodiments shown and described in this disclosure. The simplified schematic diagrams and descriptions of FIGS. 1-2 may be used for illustrative purposes and do not include the numerous valves, temperature sensors, electronic controls, etc. that are well known to those skilled in the art of a particular chemical processing operation. Additionally, ancillary components often included in a chemical processing operation, such as, for example, air intakes, heat exchangers, surge tanks, catalyst hoppers, or other associated systems, are not shown. It will be understood that these components are within the spirit and scope of the presently disclosed embodiments. However, operational components such as those described in this disclosure may be added to the embodiments described in this disclosure.

[0012] It is further noted that the arrows in the drawings refer to process streams. However, the arrows may equivalently refer to transfer lines that may serve to transfer process vapors between two or more system components. Additionally, the arrows connecting to system components define an inlet or outlet at each given system component. The direction of the arrows generally coincides with the primary direction of movement of the flowing material contained within the physical transfer line represented by the arrow. Additionally, arrows that do not connect two or more system components refer to product streams exiting the depicted system or system inlet streams entering the depicted system. The product streams may be further processed in an associated chemical processing system or commercialized as an end product. The system inlet streams may be streams transferred from an associated chemical processing system or unprocessed feed streams. Some arrows may represent recycle streams that are output streams of system components and recycled back into the system. However, it should be understood that in some embodiments, any of the depicted recycle streams may be replaced with a system inlet stream of the same material and some of the recycle streams may exit the system as a system product.

[0013] Additionally, arrows in the drawings may generally depict process steps that transport a stream from one system component to another. For example, an arrow pointing from one system component to another may represent "passing" the effluent of the system component to another, which may include the contents of a process stream being "exited" or "removed" from one system component and the contents of its product stream being "introduced" to another system component.

[0014] It should be understood that where two or more lines intersect in the schematic flow diagrams of Figures 1-2, two or more process streams are "mixed" or "combined." Mixing or combining may also include mixing by directly introducing both streams into a similar reactor, separator, or other system component. For example, where two streams are depicted as being combined directly prior to entering a separation unit or reactor, it should be understood that in some embodiments the streams may equivalently be introduced into a separation unit or reactor and mixed in the reactor.

[0015] Reference will now be made in detail to various embodiments of the present disclosure, several embodiments of which are illustrated in the accompanying drawings. Wherever possible, the same reference numbers will be used throughout the drawings to refer to the same or like parts. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] The present disclosure relates to a fluid catalytic cracking catalyst composition and a method for upgrading hydrocarbons by cracking a hydrocarbon feed using the fluid catalytic cracking catalyst composition. In particular, the present disclosure relates to a fluid catalytic cracking catalyst composition (FCC catalyst composition) comprising a framework-substituted ultrastable Y-type zeolite (framework-substituted USY zeolite) and an FCC zeolite cracking additive. The present disclosure also relates to a method for upgrading a hydrocarbon feed using the FCC catalyst composition. The method may include contacting the hydrocarbon feed with the FCC catalyst composition in a fluid catalytic cracking unit under reaction conditions sufficient to upgrade at least a portion of the hydrocarbon feed to produce one or more olefins.

[0017] The various FCC catalyst compositions and methods for upgrading hydrocarbons disclosed herein can increase the efficiency of the fluid catalytic cracking process compared to conventional catalysts used in FCC processes. That is, the various FCC catalyst compositions and methods for upgrading hydrocarbons disclosed herein can increase the conversion of the hydrocarbon feed and increase the yield of desired products such as light olefins (ethylene, propylene, butene, or combinations thereof) and gasoline. The various FCC catalyst compositions and methods for upgrading hydrocarbons disclosed herein can also reduce the production of dry gas and coke.

[0018] As used in this disclosure, a "catalyst" can refer to any substance that increases the rate of a particular chemical reaction. The catalysts and catalyst components described in this disclosure can be used to promote a variety of reactions, such as, but not limited to, cracking, aromatic cracking, or combinations thereof.

[0019] As used in this disclosure, "cracking" can refer to a chemical reaction in which a molecule having a carbon-carbon bond is broken into multiple molecules by breaking one or more of the carbon-carbon bonds; a compound containing a cyclic moiety, such as an aromatic compound, is converted to a compound that does not contain a cyclic moiety; or a molecule having a carbon-carbon double bond is reduced to a carbon-carbon single bond. A catalyst can have multiple forms of catalytic activity, and referring to a catalyst in one particular functionality does not mean that the catalyst is not catalytically active with respect to other functionalities.

[0020] As used throughout this disclosure, the term "light olefin" may refer to one or more of ethylene, propylene, butene, or combinations thereof.

[0021] As used throughout this disclosure, the term "butene" can refer to one or more isomers of butene, such as one or more of 1-butene, trans-2-butene, cis-2-butene, isobutene, or a mixture of these isomers. As used throughout this disclosure, the term "normal butene" can refer to one or more of 1-butene, trans-2-butene, cis-2-butene, or a mixture of these isomers, but does not include isobutene. As used throughout this disclosure, the term "2-butene" can refer to trans-2-butene, cis-2-butene, or a mixture of these two isomers.

[0022] As used throughout this disclosure, the terms "crude oil" or "whole crude oil" can refer to crude oil received directly from an oil field or from a desalting unit without any fractions being separated by distillation.

[0023] As used throughout this disclosure, the terms "upstream" and "downstream" can refer to the relative positioning of unit operations with respect to the flow direction of a process stream. A first unit operation in a system is considered to be "upstream" of a second unit operation if a process stream flowing through the system encounters the first unit operation before encountering the second unit operation. Similarly, a second unit operation is considered to be "downstream" of a first unit operation if a process stream flowing through the system encounters the first unit operation before encountering the second unit operation.

[0024] As used in this disclosure, passing a stream or effluent "directly" from one unit to another may refer to passing the stream or effluent from a first unit to a second unit without passing the stream or effluent through an intervening reaction or separation system that would substantially alter the composition of the stream or effluent. Heat transfer devices, such as heat exchangers, preheaters, chillers, condensers, or other heat transfer equipment, and pressure devices, such as pumps, pressure regulators, compressors, or other pressure devices, are not considered to be intervening systems that alter the composition of the stream or effluent. The combination of two streams or effluents with each other is also not considered to constitute an intervening system that alters the composition of one or both of the combined streams or effluents.

[0025] As used in this disclosure, the term "effluent" can refer to a stream that is discharged from a reactor, reaction zone, or separation unit after a particular reaction or separation. In general, the effluent has a different composition than the stream that entered the separation unit, reactor, or reaction zone. It should be understood that if the effluent is passed to another system unit, only a portion of that system stream may be passed through. For example, a slip stream may carry away some of the effluent, meaning that only a portion of the effluent may enter a downstream system unit. The term "reaction effluent" can be used more specifically to refer to a stream that is discharged from a reactor or reaction zone.

[0026] It should be further understood that a stream may be named for a component of that stream, and that the component for which the stream is named may be the majority component of the stream (e.g., from 50 mass percent (wt %), from 70 mass %, from 90 mass %, from 95 mass %, from 99 mass %, from 99.5 mass %, or even from 99.9 mass % to 100 mass % of the stream's content). A component of a stream should also be understood to be disclosed as being passed from one system component to another if a stream containing that component is disclosed as being passed from one system component to another. For example, a "hydrogen stream" disclosed as passing to a first system component or from a first system component to a second system component is intended to equivalently disclose "hydrogen" passing to the first system component or from the first system component to the second system component.

[0027] As previously mentioned, the FCC catalyst composition of the present disclosure comprises a framework-substituted USY zeolite having one or more transition metals substituted into the framework of the USY zeolite. The FCC catalyst composition may also comprise 1 wt.% to 50 wt.% of an FCC zeolite cracking additive based on the total weight of the FCC catalyst composition. The FCC catalyst composition of the present disclosure may be used alone or in combination with other fluid catalytic cracking catalyst materials in FCC processes for converting hydrocarbons to gasoline, olefins, or other useful products and intermediates.

[0028] The framework-substituted USY zeolite may be a USY zeolite containing one or more transition metal atoms that form at least a portion of the framework of the USY zeolite. The framework-substituted USY zeolite is a USY zeolite in which silicon and aluminum atoms form the zeolite framework, and a portion of the aluminum atoms forming the zeolite framework are replaced with transition metal atoms, such as hafnium, zirconium, titanium atoms, or combinations thereof. The framework-substituted USY zeolite may contain 0.1% to 5% by weight of each transition metal based on the total weight of the framework-substituted USY zeolite. For example, the framework-substituted USY zeolite may contain 0.1% to 4% by weight, 0.2% to 4% by weight, or 0.3% to 3% by weight of each transition metal based on the total weight of the framework-substituted USY zeolite. The framework-substituted USY zeolite may contain 0.1% to 15% by weight of the transition metal based on the total weight of the framework-substituted USY zeolite. For example, the framework-substituted USY zeolite may contain 0.1% to 12.5%, 0.5% to 10%, or 1.0% to 7.5% by weight of transition metal based on the total weight of the framework-substituted USY zeolite. The amount of transition metal substituted in the framework-substituted USY zeolite may include both transition metal atoms substituted for aluminum atoms in the zeolite framework and transition metal atoms not substituted for aluminum atoms but supported on the inner surfaces of the pores of the framework-substituted USY zeolite.

[0029] The one or more transition metals may include hafnium, zirconium, titanium, or a combination thereof. In an embodiment, the one or more transition metals include hafnium. In an embodiment, the framework substituted USY zeolite may include zirconium, titanium, or zirconium and titanium. In an embodiment, the framework substituted USY zeolite may include hafnium, zirconium, or hafnium and zirconium. At least a portion of the hafnium, zirconium, titanium, or a combination of these transition metals may be supported on or associated with the interior surfaces of the pores of the USY zeolite in the form of a metal oxide, e.g., hafnium oxide particles, zirconium oxide particles, titanium oxide particles, or a combination thereof. The metal oxide of hafnium, zirconium, titanium, or a combination thereof may be associated with the interior surfaces of the mesopores of the USY zeolite.

[0030] In embodiments, examples of suitable compounds of hafnium may include hafnium nitrate, hafnium chloride, hafnium fluoride, hafnium bromide, and hafnium oxalate. Examples of suitable compounds of zirconium may include zirconium sulfate, zirconium nitrate, and zirconium chloride. Examples of suitable compounds of titanium may include titanium sulfate, titanium acetate, titanium chloride, titanium nitrate, and titanium lactate.

[0031] Framework substitution of transition metal atoms into the framework of framework-substituted USY zeolites can be confirmed, for example, by X-ray fluorescence, radio frequency plasma optical emission spectroscopy, atomic absorption spectroscopy, ultraviolet-visible-near infrared spectroscopy (UV-Vis-NIR), Fourier transform infrared spectroscopy (FT-IR), or nuclear magnetic resonance spectroscopy (NMR).

[0032] Framework-substituted USY zeolites are generally zeolites having a molecular weight of 2.430 nanometers to 2.450 nanometers, e.g., 2.432 nm to 2.434 nm, 2.432 nm to 2.436 nm, 2.432 nm to 2.438 nm, 2.432 nm to 2.440 nm, 2.432 nm to 2.442 nm, 2.432 nm to 2.444 nm, 2.432 nm to 2.446 nm, 2.432 nm to 2.448 nm, 2.434 nm to 2.436 nm, 2.434 nm m to 2.438nm, 2.434nm to 2.440nm, 2.434nm to 2.442nm, 2.434nm to 2.444nm, 2.434nm to 2.446nm, 2.434nm to 2.448nm, 2.434nm to 2.450nm, 2.436nm to 2.438nm, 2.436nm to 2.440nm, 2.436nm to 2.442nm, 2.436nm to 2.444nm, 2.436nm to 2.446nm, 2.436 nm to 2.448nm, 2.436nm to 2.450nm, 2.438nm to 2.440nm, 2.438nm to 2.442nm, 2.438nm to 2.444nm, 2.438nm to 2.446nm, 2.438nm to 2.448nm, 2.438nm to 2.450nm, 2.440nm to 2.442nm, 2.440nm to 2.444nm, 2.440nm to 2.446nm, 2.440nm to 2.448nm, 2.4 The crystal lattice constant may be 40 nm to 2.450 nm, 2.442 nm to 2.444 nm, 2.442 nm to 2.446 nm, 2.442 nm to 2.448 nm, 2.442 nm to 2.450 nm, 2.444 nm to 2.446 nm, 2.444 nm to 2.448 nm, 2.444 nm to 2.450 nm, 2.446 nm to 2.448 nm, 2.446 nm to 2.450 nm, or 2.448 nm to 2.450 nm. The crystal lattice constant may be measured using ASTM method D3942. A crystal lattice constant less than 2.430 nm may tend to reduce the activity of the FCC catalyst composition. Without intending to be bound by any particular theory, the activity of the FCC catalyst composition may be reduced due to the high SiO2 / Al2O3 molar ratio in the framework structure and the small number of solid acid sites that serve as active sites for cracking.Similarly, due to the crystal lattice constant of more than 2.450 nm, the crystal structure of the framework-substituted USY zeolite may be destroyed during the FCC reaction. Without intending to be bound by any particular theory, it is believed that the destruction of the crystal structure of the framework-substituted USY zeolite during the FCC reaction occurs due to low thermal resistance, which may also result in a decrease in the activity of the FCC catalyst composition.

[0033] Framework-substituted USY zeolites may have specific surface areas of 600 to 900 meters squared per gram, as determined by the Brunauer-Emmett-Teller (BET) method. 2 / g to 875m 2 / g, 600m 2 / g to 850m 2 / g, 600m 2 / g to 825m 2 / g, 600m 2 / g to 800m 2 / g, 600m 2 / g to 775m 2 / g, 600m 2 / g to 750m 2 / g, 600m 2 / g to 725m 2 / g, 600m 2 / g to 700m 2 / g, 600m 2 / g to 675m 2 / g, 600m 2 / g to 650m 2 / g, 600m 2 / g to 625m 2 / g, 625m 2 / g to 900m 2 / g, 650m 2 / g to 900m 2 / g, 675m 2 / g to 900m 2 / g, 700m 2 / g to 900m 2 / g, 725m 2 / g to 900m 2 / g, 750m 2 / g to 900m 2 / g, 775m2 / g to 900m 2 / g, 800m 2 / g to 900m 2 / g, 825m 2 / g to 900m 2 / g, 850m 2 / g to 900m 2 / g, or 875m 2 / g to 900m 2 / g. 2 At specific surface areas below 900 m / g, the number of solid acid sites with effective catalytic activity during the FCC reaction will decrease. 2 Specific surface areas greater than 100 / g would be impractical due to production limitations, however, advantages may be found as advances in the processing of zeolite materials are discovered.

[0034] Framework-substituted USY zeolites may have high silica (SiO2) to alumina (Al2O3) molar ratios of 5:1 to 100:1. For example, the framework substituted USY zeolite may have a molar ratio of SiO2 to Al2O3 of 10:1 to 100:1, 20:1 to 100:1, 30:1 to 100:1, 40:1 to 100:1, 50:1 to 100:1, 60:1 to 100:1, 70:1 to 100:1, 80:1 to 100:1, 90:1 to 100:1, 5:1 to 90:1, 5:1 to 80:1, 5:1 to 70:1, 5:1 to 60:1, 5:1 to 50:1, 5:1 to 40:1, 5:1 to 30:1, 5:1 to 20:1, 5:1 to 10:1, 10:1 to 95:1, 15:1 to 90:1, 20:1 to 85:1, or 25:1 to 80:1. A molar ratio of SiO2 to Al2O3 less than 5:1 will not result in an effective pore volume. Without intending to be bound by any particular theory, it is believed that the ineffective pore volume will reduce the cracking activity. Similarly, a molar ratio of SiO2 to Al2O3 greater than 100:1 will reduce the number of solid acid sites. Without intending to be bound by any particular theory, it is believed that a reduced number of solid acid sites will reduce the cracking activity.

[0035] To produce a framework-substituted USY zeolite, some of the aluminum atoms in the USY zeolite can be replaced with hafnium atoms, zirconium atoms, titanium atoms, or a combination thereof. The framework-substituted USY zeolite can be produced by calcining the USY zeolite at a temperature of 500° C. to 700° C. A suspension containing the calcined USY zeolite and having a liquid-solid mass ratio of 5 to 15 can then be formed. An inorganic or organic acid can be added such that the pH of the solution is 1.0 to 2.0. A solution containing a transition metal, such as hafnium, zirconium, or titanium, can then be mixed with the suspension. The mixture containing the suspension and the transition metal solution can be neutralized, for example, with aqueous ammonia, to a pH of about 7.0.

[0036] USY zeolite can be used as a raw material for the process of preparing framework-exchanged USY zeolite. USY zeolite can be a commercially available USY zeolite or can be prepared from Y zeolite. The process of preparing USY zeolite is known to those skilled in the art. For example, one of the processes of preparing the above USY zeolite may include exchanging sodium ions with ammonium ions by conventional methods such as dispersing Y zeolite in water to prepare a suspension, adding ammonium sulfate to the suspension, washing the solid material with water, washing the solid material with an aqueous ammonium sulfate solution at a temperature of 40° C. to 80° C., washing the solid material with water at a temperature of 40° C. to 95° C., and drying the solid material at a temperature of 100° C. to 180° C. for about 30 minutes. Thus, ammonium-exchanged Y zeolite, NH4-, in which about 50% by mass to 70% by mass of Na contained in the Y zeolite is replaced with NH4, is obtained. 50から70 Y is generated.

[0037] Next, the ammonium-exchanged Y-type zeolite (NH4- 50から70Hydrogen-type Y zeolite (HY) can be prepared by calcining the initial Y zeolite (Na-Y). Next, ammonium-exchanged Y zeolite (NH4-Y) is prepared by ion-exchanging about 80% to 97% of the Na contained in the initial Y zeolite (Na-Y) with NH4. 80から97 The hydrogen Y zeolite obtained above can be dispersed in water at a temperature between 40° C. and 95° C. to prepare a suspension, and ammonium sulfate is added to the suspension. The suspension can then be stifled at a temperature between 40° C. and 95° C. for 10 minutes to 3 hours. The solid material can then be washed with water at a temperature between 40° C. and 95° C., then with an aqueous solution of ammonium sulfate at a temperature between 40° C. and 95° C., followed by washing with water at a temperature between 40° C. and 80° C. The solid material is then dried at a temperature between 100° C. and 180° C. for 30 minutes to 30 hours. In an embodiment, the final ammonium ion exchange rate will be 90% or more.

[0038] The thus obtained ammonium-exchanged Y-type zeolite (NH4- 80から97 USY) can be calcined, for example, at 500° C. to 700° C. in a saturated steam atmosphere for 10 minutes to 10 hours. Thus, USY zeolites can be prepared having a crystal lattice constant of 2.430 nanometers to 2.450 nanometers, a specific surface area of ​​600 square meters per gram to 900 square meters per gram, and a specific surface area of ​​5:1 to 100:1.

[0039] In the method for producing the framework-substituted USY zeolite of the present disclosure, non-framework aluminum can be removed from the above-mentioned USY zeolite to obtain a USY zeolite having a crystal lattice constant of 2.430 nanometers to 2.450 nanometers. The non-framework aluminum can be removed, for example, by dispersing the above-mentioned USY zeolite in water at a temperature of 40° C. to 95° C. to prepare a suspension, adding sulfuric acid to the suspension, and stilting the suspension for 10 minutes to 3 hours while maintaining the temperature at 40° C. to 95° C. to dissolve the non-framework aluminum. After dissolving the non-framework aluminum, the suspension can be filtered, and the residue on the filter can be washed with purified water at a temperature of 40° C. to 95° C. and dried at a temperature of 100° C. to 145° C., thereby obtaining a USY zeolite from which non-framework aluminum has been removed.

[0040] In the method of producing the framework-substituted USY zeolite of the present disclosure, the USY zeolite can be calcined at a temperature of 500° C. to 700° C., such as 550° C. to 650° C. The calcination period is typically not critical as long as the target framework-substituted USY zeolite is obtained. In an embodiment, the calcination period can be from 30 minutes to 10 hours. In an embodiment, the calcination atmosphere for calcining the USY zeolite is air.

[0041] The calcined USY zeolite can then be framework substituted with hafnium, titanium, zirconium, or combinations thereof. To framework substitute the calcined USY zeolite, the calcined USY zeolite can be suspended in water at a temperature of 20° C. to 30° C. to form a suspension. The liquid-solid mass ratio can be in the range of 5:1 to 15:1, such as 8:1 to 12:1. An inorganic or organic acid can then be added to the suspension such that the pH of the suspension is controlled in the range of 1.0 to 2.0. The pH of the suspension can be controlled in the range of 1.0 to 2.0 to prevent precipitation during mixing of the aqueous solution of the hafnium compound, zirconium compound, titanium compound, or combinations thereof with the suspension of the USY zeolite. The inorganic acid may include, but is not limited to, sulfuric acid, nitric acid, or hydrochloric acid. The organic acid may include, but is not limited to, carboxylic acid. A solution containing the hafnium compound, zirconium compound, titanium compound, or combinations thereof can then be added to the suspension and mixed.

[0042] The mixing of the aqueous solution of hafnium compounds, zirconium compounds, titanium compounds, or combinations thereof with the suspension of USY zeolite can be carried out by gradually adding the aqueous solution of hafnium compounds, zirconium compounds, titanium compounds, or combinations thereof to the suspension of USY zeolite. After completing the addition of the aqueous solution to the suspension, the solution can be mixed, for example, by stirring at ambient conditions (about 25°C) for 3 to 5 hours. After the mixing is completed, the mixed solution can be neutralized by adding an alkaline compound, such as, but not limited to, aqueous ammonia, so that the pH is controlled at 7.0 to 7.5. The resulting framework-substituted USY zeolite can be filtered, washed with water, and dried at a temperature of 80°C to 180°C.

[0043] The FCC catalyst composition may include 5% to 60% by weight of framework-substituted USY zeolite based on the total weight of the FCC catalyst composition. In embodiments, the FCC catalyst composition of the present disclosure includes 5% to 10%, 5% to 15%, 5% to 20%, 5% to 25%, 5% to 30%, 5% to 35%, 5% to 40%, 5% to 45%, 5% to 50%, 5% to 55%, 10% to 15%, 10% to 20%, 10% to 25%, 10% to 30%, 10% to 35%, 10% to 40%, 10% to 45%, 10% to 50%, 10% to 55%, 10% to 15%, 10% to 20%, 10% to 25%, 10% to 30%, 10% to 35 ... 5% by weight, 10% to 40% by weight, 10% to 45% by weight, 10% to 50% by weight, 10% to 55% by weight, 10% to 60% by weight, 15% to 20% by weight, 15% to 25% by weight, 15% to 30% by weight, 15% to 35% by weight, 15% to 40% by weight, 15% to 45% by weight, 15% to 50% by weight, 15% to 55% by weight, 20% to 25% by weight, 20% to 30% by weight, 20% to 35% by weight, 20% to 40% by weight %, 20% to 45% by weight, 20% to 50% by weight, 20% to 55% by weight, 20% to 60% by weight, 25% to 30% by weight, 25% to 35% by weight, 25% to 40% by weight, 25% to 45% by weight, 25% to 50% by weight, 25% to 55% by weight, 25% to 60% by weight, 30% to 35% by weight, 30% to 40% by weight, 30% to 45% by weight, 30% to 50% by weight, 30% to 55% by weight, 30% to 60% by weight %, 35% to 40%, 35% to 45%, 35% to 50%, 35% to 55%, 35% to 60%, 40% to 45%, 40% to 50%, 40% to 55%, 40% to 60%, 45% to 50%, 45% to 55%, 45% to 60%, 50% to 55%, 50% to 60%, or 55% to 60% by weight of framework substituted USY zeolite.

[0044] In addition to the framework-replaced USY zeolite, the FCC catalyst composition may also include an additive for FCC zeolite cracking. This additive for FCC zeolite cracking may include one or more of MFI framework zeolite, MEL framework zeolite, beta framework zeolite, mordenite framework zeolite, or a combination thereof. Further, the FCC catalyst composition may include any other olefin-selective additive.

[0045] In an embodiment, the additive for FCC zeolite cracking may include an MFI framework additive. In some embodiments, the MFI framework additive may include ZSM-5 zeolite. As used in this disclosure, "MFI framework zeolite" refers to a zeolite having an MFI framework type according to the IUPAC zeolite nomenclature and consisting of silica and alumina. ZSM-5 zeolite is referred to as "Zeolite Socony Mobil-5" and has the chemical formula Na n Al n Si 96-n O 192 ·16H2O and can be represented as a pentasil-type zeolite. In other embodiments, the additive for FCC zeolite cracking may include an MEL framework zeolite. This MEL framework zeolite may be ZSM-11 zeolite. ZSM-11 zeolite is referred to as "Zeolite Socony Mobil-11" and has the chemical formula Na n Al n Si 96-n O 192 ·16H2O and can be represented as a pentasil-type zeolite.

[0046] In embodiments, the FCC catalyst composition may be present in an amount of from 1% to 5%, from 1% to 10%, from 1% to 15%, from 1% to 20%, from 1% to 25%, from 1% to 30%, from 1% to 35%, from 1% to 40%, from 1% to 45%, from 5% to 10%, from 5% to 15%, from 5% to 20%, from 5% to 25%, from 5% to 5%, from 5% to 6%, from 5% to 7%, from 5% to 8%, from 5% to 9%, from 5% to 10%, from 5% to 15%, from 5% to 20%, from 5% to 25%, from 5% to 10%, from 5% to 15%, from 5% to 20%, from 5% to 25%, from 5% to 30%, from 5% to 35%, from 5% to 40%, from 5% to 4 ... % to 30% by weight, 5% to 35% by weight, 5% to 40% by weight, 5% to 45% by weight, 5% to 50% by weight, 10% to 15% by weight, 10% to 20% by weight, 10% to 25% by weight, 10% to 30% by weight, 10% to 35% by weight, 10% to 40% by weight, 10% to 45% by weight, 10% to 50% by weight, 15% to 20% by weight, 15% to 25% by weight, 15% to to 30% by mass, 15% to 35% by mass, 15% to 40% by mass, 15% to 45% by mass, 15% to 50% by mass, 20% to 25% by mass, 20% to 30% by mass, 20% to 35% by mass, 20% to 40% by mass, 20% to 45% by mass, 20% to 50% by mass, 25% to 30% by mass, 25% to 35% by mass, 25% to 40% by mass, 25% to 45% by mass, 25% by mass In some embodiments, the FCC catalyst composition may comprise from 1% to 50% by weight of the FCC zeolite cracking additive, such as from 30% to 35% by weight, from 30% to 40% by weight, from 30% to 45% by weight, from 30% to 45% by weight, from 30% to 50% by weight, from 35% to 40% by weight, from 35% to 45% by weight, from 35% to 50% by weight, from 40% to 45% by weight, from 40% to 50% by weight, or from 45% to 50% by weight.

[0047] The FCC catalyst composition may contain from 15 wt.% to 60 wt.% of an inorganic filler, based on the total weight of the FCC catalyst composition. For example, the FCC catalyst composition may comprise from 15% to 20% by weight, from 15% to 25% by weight, from 15% to 30% by weight, from 15% to 35% by weight, from 15% to 40% by weight, from 15% to 45% by weight, from 15% to 50% by weight, from 15% to 55% by weight, from 20% to 25% by weight, from 20% to 30% by weight, from 20% to 35% by weight, from 20% to 40% by weight, from 20% to 45% by weight, from 20% to 50% by weight, from 20% to 55% by weight, from 20% to 60% by weight, from 25% to 30% by weight, from 25% to 35% by weight, from 25% to 40% by weight, from 25% to 45% by weight, from 25% to 50% by weight, from 25% to 55% by weight, from 25 ...55% by weight, from 25% to 60% by weight, from 25% to from 55%, 25% to 60%, 30% to 35%, 30% to 40%, 30% to 45%, 30% to 50%, 30% to 55%, 30% to 60%, 35% to 40%, 35% to 45%, 35% to 50%, 35% to 55%, 35% to 60%, 40% to 45%, 40% to 50%, 40% to 55%, 40% to 60%, 45% to 50%, 45% to 55%, 45% to 60%, 50% to 55%, 50% to 60%, or 55% to 60% by weight of inorganic filler. The inorganic filler may be silica-based or alumina-based. The inorganic filler may include one or more of silica sol, water glass (sodium silicate), silicic acid liquid, basic aluminum chloride, aluminum biphosphate, alumina sol, activated alumina, porous silica, metal scavengers, or combinations thereof. In an embodiment, the inorganic filler may be a silica sol containing SiO2. A silica sol containing SiO2 at a concentration of 10 to 15 percent by weight can be prepared by simultaneously and successively adding water glass containing SiO2 at a concentration ranging from 12 to 23 percent by weight and sulfuric acid having a concentration ranging from 20 to 30 percent by weight.A solution obtained by dissolving one or more kinds of microcrystalline alumina such as gibbsite, boehmite, or bayerite in an acidic solution can be used as an aluminum compound filler. Basic aluminum chloride has the formula (1): [Al2(OH) n Cl 6-n m (1) (where 0 < n < 6 and 1 < m < 10, and the symbol m represents a natural number) and can be represented by

[0048] Aluminum dihydrogen phosphate or primary aluminum phosphate, also called aluminum metaphosphate, is represented by Al(H2PO4)3. Alumina sol may be produced, for example, by adjusting the pH of pseudo-boehmite alumina with an acid. The inorganic oxide can be activated alumina, porous silica, rare earth metal compounds, and metal scavengers (metal capturers).

[0049] ​An FCC catalyst composition may include one or more matrix materials. As used in this disclosure, "matrix material" may refer to a clay material, such as kaolin. Without intending to be bound by theory, it is believed that the matrix material of an FCC catalyst composition may perform both physical and catalytic functions. Physical functions include providing particle integrity and attrition resistance, acting as a heat transfer medium, and providing a porous structure that allows for the diffusion of hydrocarbons into and out of the catalyst microspheres. The matrix may also affect catalyst selectivity, product quality, and poison resistance. The matrix material will tend to have the strongest effect on overall catalytic activity for reactions directly involving relatively large molecules. In an embodiment, the matrix material includes kaolin. As used in this disclosure, "kaolin" refers to a clay material having a relatively large amount of kaolinite (such as at least about 50% by weight, at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight, or even at least 95% by weight). Kaolinite may be represented by the chemical formula Al2Si2O5(OH)4. In additional embodiments, the matrix material may include other clay materials.

[0050] The FCC catalyst composition may include one or more matrix materials in an amount of 30% to 60% by weight based on the total weight of the FCC catalyst composition. In embodiments, the FCC catalyst composition may include 30% to 55%, 30% to 50%, 30% to 45%, 30% to 40%, 30% to 35%, 35% to 60%, 40% to 60%, 45% to 60%, 50% to 60%, or 55% to 60% by weight of matrix materials based on the total weight of the FCC catalyst composition. In embodiments, the FCC catalyst composition may include any single disclosed matrix material in an amount in the disclosed weight percent range. In embodiments, the FCC catalyst composition may include any two or more matrix materials in combination in an amount in the disclosed weight percent range.

[0051] In an embodiment, the FCC catalyst composition may include a rare earth oxide having a chemical formula of RE2O3, where RE is a rare earth metal. The rare earth metal of the rare earth metal oxide may include one or more of cerium (Ce), lanthanum (La), praseodymium (Pr), neodymium (Nd), or combinations thereof. The FCC catalyst composition may include 0.0 wt.% to 6.0 wt.% of a rare earth oxide based on the total weight of the FCC catalyst composition. The FCC catalyst composition may include 0.0 wt.% to 0.5 wt.%, 0.0 wt.% to 1.0 wt.%, 0.0 wt.% to 1.5 wt.%, 0.0 wt.% to 2.0 wt.%, 0.0 wt.% to 2.5 wt.%, 0.0 wt.% to 3.0 wt.%, 0.0 wt.% to 4 wt.%, 0.0 wt.% to 5 wt.%, 0.5 wt.% to 1.0 ... 5% to 1.5% by weight, 0.5% to 2.0% by weight, 0.5% to 2.5% by weight, 0.5% to 3.0% by weight, 0.5% to 4.0% by weight, 0.5% to 5.0% by weight, 0.5% to 6.0% by weight, 1.0% to 1.5% by weight, 1.0% to 2.0% by weight, 1.0% to 2.5% by weight, 1.0% to 3.0% by weight %, 1.0% to 4.0% by mass, 1.0% to 5.0% by mass, 1.0% to 6.0% by mass, 1.5% to 2.0% by mass, 1.5% to 2.5% by mass, 1.5% to 3.0% by mass, 1.5% to 4.0% by mass, 1.5% to 5.0% by mass, 1.5% to 6.0% by mass, 2.0% to 2.5% by mass, 2.0% to 3.0% by mass It may contain 0.0%, 2.5% to 3.0%, 2.0% to 4.0%, 2.0% to 5.0%, 2.0% to 6.0%, 3.0% to 4.0%, 3.0% to 5.0%, 3.0% to 6.0%, 4.0% to 5.0%, or 4.0% to 6.0% by weight of rare earth metal oxides.

[0052] The FCC catalyst composition of the present disclosure may be in the form of shaped microparticles, such as microspheres. As stated, "microparticle" refers to a particle having a size of 0.1 micrometer to 100 micrometers. The size of a microparticle refers to the maximum length of the particle from one side to another, measured along the longest distance of the microparticle. For example, a spherically shaped microparticle has a size equal to the diameter, while a parallelepiped shaped microparticle has a maximum length equal to the hypotenuse extending from the opposite corner.

[0053] According to an embodiment, all of the zeolites of the FCC catalyst composition (framework-substituted USY zeolite and FCC zeolite cracking additive) may be included in each microparticle. However, in other embodiments, the microparticles may be mixed, where the microparticles contain only a portion of the FCC catalyst composition. For example, a mixture of two microparticle types may be included in the FCC catalyst composition, where one type of microparticle contains framework-substituted USY zeolite and another type of microparticle contains the FCC zeolite cracking additive.

[0054] The FCC catalyst composition can be formed by a variety of processes. In an embodiment, the matrix material can be mixed with a fluid such as water to form a slurry, and the framework-substituted USY zeolite and the FCC zeolite cracking additive can be mixed separately with a fluid such as water to form a slurry. The matrix material slurry and the zeolite slurry can be mixed under stirring. Separately, an inorganic filler material can be mixed with a fluid such as water to form a separate slurry. The inorganic filler slurry can then be mixed with the matrix material and zeolite-containing slurry to form a total slurry. The total slurry can be dried, for example by spraying, and then calcined to produce small particles of the FCC catalyst composition. According to another embodiment, the framework-substituted USY zeolite and the FCC zeolite cracking additive can be mixed while drying to produce small particles of the FCC catalyst composition.

[0055] In one or more embodiments, the FCC catalyst composition can be formed by first adding activated alumina to a silica sol. Then, a slurry of the framework-substituted USY zeolite can be prepared with 20% to 30% by weight sulfuric acid. The framework-substituted USY zeolite slurry can have a pH ranging from 3 to 5. Similarly, a slurry of the FCC zeolite cracking additive can be prepared. The activated alumina and silica sol can be mixed with the framework-substituted USY zeolite slurry and the FCC zeolite cracking additive slurry to form a slurry mixture. The slurry mixture can then be spray-dried to form spherical particles. After spray-drying, the spherical particles can be washed. The spherical particles can then be contacted with an aqueous solution of rare earth metal chloride for ion exchange, such that the FCC catalyst composition includes 0% to 6% by weight of rare earth metal oxide, based on the weight of the framework-substituted USY zeolite. Finally, the spherical particles can be dried to produce the FCC catalyst composition.

[0056] The FCC catalyst composition of the present disclosure can be incorporated into a system for upgrading hydrocarbons by fluid catalytic cracking. Referring to FIG. 1, one embodiment of a reactor system 100 that can be suitable for use in the method of upgrading a hydrocarbon feed of the present disclosure is shown generally. However, it should be understood that other reactor system configurations may be suitable for the method described in this disclosure. The reactor system 100 includes an FCC unit 110 and a catalyst regeneration unit 120. As used in this disclosure in the context of FIG. 1, the FCC unit 110 generally refers to the portion of the reactor system 100 in which the reactions of the main process, such as upgrading a hydrocarbon feed to form light olefins, take place. The FCC unit 110 can include a riser section 112, a reaction zone 114, and a separation zone 116. The reactor system 100 can also include a regeneration zone 122 for regenerating spent catalyst.

[0057] In an embodiment, the hydrocarbon feed 111 may be introduced into the reaction zone 114 along with steam or other suitable gas (not shown) for atomization of the feed. The hydrocarbon feed 111 may be mixed with and contacted with an effective amount of heated fresh or regenerated catalyst particles. The heated fresh or regenerated catalyst particles may be the FCC catalyst composition of the present disclosure and may have any of the characteristics, compositions, or properties previously described in this disclosure for the FCC catalyst composition. The heated fresh or regenerated catalyst particles may be conveyed from the regeneration zone 122 through a conduit 123. The hydrocarbon feed 111 may be contacted with the FCC catalyst composition and then passed to the reaction zone 114. In a continuous process, the mixture of the FCC catalyst composition and the hydrocarbon feed 111 may proceed upward through the riser section 112 to the reaction zone 114. In the riser section 112 and the reaction zone 114, the hydrocarbons of the hydrocarbon feed 111 may be contacted with the particles of the FCC catalyst composition at reactive conditions. Hydrocarbons from the hydrocarbon feed 111 may be contacted with particles of the FCC catalyst composition under reactive conditions to cause at least a portion of the hydrocarbons to react and undergo cracking reactions to form upgraded hydrocarbons, which may include light olefins such as, but are not limited to, ethylene, propylene, butene, or combinations thereof.

[0058] During the reaction, the particles of the FCC catalyst composition may become coked, which may limit or eliminate access to the active catalytic sites of the particles of the FCC catalyst composition. The reaction products may be separated from the coked catalyst particles using any suitable configuration known in the art. This separation may occur in a zone generally referred to as separation zone 116, which may be located above reaction zone 114. The reaction products may be removed through conduit 119. The particles of the FCC catalyst composition containing coke deposits from the reaction may be passed through conduit 115 to regeneration zone 122.

[0059] In the regeneration zone 122, the coked FCC catalyst composition particles can be contacted with an oxygen-containing gas stream, which can enter the regeneration zone 122 through conduit 121. The regeneration zone 122 can be operated in a configuration under conditions known in FCC operations. For example, the regeneration zone 122 can be operated as a fluidized bed to produce a regeneration exhaust gas containing combustion products, which can be discharged through conduit 125. The hot regenerated FCC catalyst composition particles can be transported from the regeneration zone 122 of the catalyst regeneration unit 120 through conduit 123 to the bottom of the riser section 112 for mixing with the hydrocarbon feed 111, as described above.

[0060] Referring to FIG. 2, one embodiment of an exemplary reactor system 200 that may be suitable for use in the method of upgrading a hydrocarbon feed described in the present disclosure is shown generally. Again, it should be understood that other reactor system configurations may be suitable for the method described in the present disclosure. The reactor system 200 may generally include a number of components, such as an FCC unit 210 and a catalyst regeneration unit 220. As used in the present disclosure in the context of FIG. 2, the FCC unit 210 generally refers to the unit of the reactor system 200 in which the reactions of the main process, such as upgrading a hydrocarbon feed to form light olefins, take place. The FCC unit 210 may include a reaction zone 212, a separation zone 2124, and a stripper zone 216. As used in the context of FIG. 2, the reactor system 200 may also include a regeneration zone 222 for regenerating spent catalyst.

[0061] In an embodiment, the hydrocarbon feed 211 may be introduced into the reaction zone 212 through a downer section of the reactor system 200 along with steam or other suitable gas (not shown) for atomization of the feed. An effective amount of heated fresh or regenerated particles of FCC catalyst composition from the regeneration zone 222 may be conveyed to the top of the reaction zone 212. The heated fresh or regenerated particles of FCC catalyst composition from the regeneration zone 222 may be conveyed through a downwardly directed conduit, commonly referred to as a transfer line or standpipe. 223 The hot FCC catalyst composition particles may be conveyed through a feed nozzle to a withdrawal or hopper (not shown) at the top of the reaction zone 212. The flow of hot FCC catalyst composition particles may typically be stabilized to be uniformly directed into the mixing zone or feed injection portion of the reaction zone 212. The hydrocarbon feed 211 may typically be injected into the mixing zone through a feed injection nozzle located proximate to the point where the regenerated FCC catalyst composition particles are introduced into the reaction zone 212. These multiple injection nozzles allow thorough and uniform mixing of the FCC catalyst composition particles with the hydrocarbon feed 211. Once the hydrocarbon feed 211 contacts the hot FCC catalyst composition particles, the catalytic reaction may begin.

[0062] The hydrocarbon product reaction vapors may flow through the remainder of reaction zone 212 to separation zone 214. The hydrocarbon products and unreacted hydrocarbons may be directed to various product recovery sections via conduit 219. In embodiments, a quench jet (not shown) may be provided near the bottom of reaction zone 212 or just prior to separation zone 214, if needed for temperature control. The quench jet may rapidly slow down or stop the catalytic reaction.

[0063] The reaction temperature (which will be equal to the outlet temperature of the FCC unit 210) can be controlled by opening and closing a catalyst slide valve (not shown), which can control the flow of particles of regenerated FCC catalyst composition from the regeneration zone 222 to the top of the reaction zone 212.

[0064] A stripper zone 216 may also be present to separate the particles of the FCC catalyst composition from the hydrocarbon products and unreacted hydrocarbons. The particles of the FCC catalyst composition from the separation zone 214 may pass to the stripper zone 216. In the stripper zone 216, a suitable stripping gas, such as steam, may be introduced through flow line 213. The stripper zone 216 may include a number of baffles or structured packings (not shown) through which the downwardly flowing catalyst particles pass countercurrently to the stripping gas. The upwardly flowing stripping gas may strip or remove any excess hydrocarbons remaining within the pores of the catalyst particles or between the catalyst particles. The particles of the stripped or spent FCC catalyst composition may pass from the stripper zone 216 through a conduit 215 to a catalyst regeneration unit 220. The particles of the stripped or spent FCC catalyst composition may be transported by lift from the combustion air stream 221 through a lift riser of the catalyst regeneration unit 220. The particles of the stripped or spent FCC catalyst composition may then be contacted with additional combustion air in regeneration zone 222 and undergo controlled combustion of any accumulated coke. Flue gas may be removed from regeneration zone 222 through conduit 225. In the regenerator, heat from the combustion of any coke by-products may be conducted to the particles of the FCC catalyst composition, thereby increasing the temperature required to supply heat to the catalytic reaction in reaction zone 212.

[0065] A method for upgrading a hydrocarbon feed may include contacting the hydrocarbon feed with an FCC catalyst composition at reaction conditions sufficient to upgrade at least a portion of the hydrocarbon feed, where the FCC catalyst composition comprises a framework-substituted USY zeolite and from 1 weight percent to 50 weight percent of an FCC zeolite cracking additive, based on the total weight of the FCC catalyst composition. The framework-substituted USY zeolite may comprise hafnium, zirconium, titanium, or combinations thereof substituted into the framework of the framework-substituted USY zeolite.

[0066] The hydrocarbon feed may include one or more of crude oil, synthetic crude oil, bitumen, oil sands, shale oil, coal liquids, naphtha, diesel, vacuum gas oil, vacuum resid, demetalized oil, deasphalted oil, coker gas oil, cycle oil, light oil, or combinations thereof. In embodiments, the hydrocarbon feed may be derived from one or more of crude oil, synthetic crude oil, bitumen, oil sands, shale oil, coal liquids, naphtha, diesel, vacuum gas oil, vacuum resid, demetalized oil, deasphalted oil, coker gas oil, cycle oil, light oil, or combinations thereof. The hydrocarbon feed may have an atmospheric boiling range of 350° C. or greater. As used in this disclosure, "atmospheric boiling range" may refer to the temperature interval from the initial boiling point to the final boiling point, where the initial boiling point refers to the temperature at which the first drop of distillation product is obtained and the final boiling point refers to the temperature at which the highest boiling point compound vaporizes.

[0067] In an embodiment, the hydrocarbon feed may include a hydrocracking recycle stream or an unconverted bottoms stream from a hydrocracking unit having the following properties as shown in Table 1.

[0068] [Table 1]

[0069] The hydrocarbon feed may be contacted with the FCC catalyst composition at a temperature of 450° C. to 700° C. The hydrocarbon feed may be contacted with the FCC catalyst composition at a temperature of 450° C. to 500° C., 450° C. to 550° C., 450° C. to 650° C., 500° C. to 550° C., 500° C. to 600° C., 500° C. to 650° C., 500° C. to 700° C., 550° C. to 600° C., 550° C. to 650° C., 550° C. to 700° C., 600° C. to 650° C., 600° C. to 700° C., or 650° C. to 700° C.

[0070] The hydrocarbon feed can be contacted with the FCC catalyst composition at a pressure of from 0.1 to 1 megapascal (MPa). The hydrocarbon feed may be contacted with the FCC catalyst composition at a pressure of 0.1 MPa to 0.2 MPa, 0.1 MPa to 0.3 MPa, 0.1 MPa to 0.4 MPa, 0.1 MPa to 0.5 MPa, 0.1 MPa to 0.6 MPa, 0.1 MPa to 0.7 MPa, 0.1 MPa to 0.8 MPa, 0.1 MPa to 0.9 MPa, 0.3 MPa to 0.4 MPa, 0.3 MPa to 0.5 MPa, 0.3 MPa to 0.6 MPa, 0.3 MPa to 0.7 MPa, 0.3 MPa to 0.8 MPa, 0.3 MPa to 0.9 MPa, 0.3 MPa to 1.0 MPa, 0.5 MPa to 0.6 MPa, 0.5 MPa to 0.7 MPa, 0.5 MPa to 0.8 MPa, 0.5 MPa to 0.9 MPa, or 0.5 MPa to 1.0 MPa.

[0071] The hydrocarbon feed may be contacted with the FCC catalyst composition at the reaction temperature for a residence time (total time the hydrocarbon feed spends in contact with the FCC catalyst composition) of 0.1 to 60 seconds (s). The hydrocarbon feed may be contacted with the FCC catalyst composition at the reaction temperature for a residence time of 0.1 to 10 s, 0.1 to 20 s, 0.1 to 30 s, 0.1 to 40 s, 0.1 to 50 s, 10 to 20 s, 10 to 30 s, 10 to 40 s, 10 to 50 s, 10 to 60 s, 20 to 30 s, 20 to 40 s, 20 to 50 s, 20 to 60 s, 30 to 40 s, 30 to 50 s, 30 to 60 s, 40 to 50 s, 40 to 60 s, or 50 to 60 s.

[0072] The hydrocarbon feed can be contacted with the FCC catalyst composition at a mass ratio of the hydrocarbon feed to the FCC catalyst composition of from 1:2 to 1:30. For example, the hydrocarbon feed can be contacted with the FCC catalyst composition at a mass ratio of the hydrocarbon feed to the FCC catalyst composition of from 1:1 to 1:15, from 1:1 to 1:10, or from 1:8 to 1:20.

[0073] The cracked effluent may contain increased concentrations of one or more of the following compared to the hydrocarbon feed: gasoline, light cycle oil (LCO), heavy cycle oil (HCO), total gas (C4 and below), dry gas (C2 and below), liquefied petroleum gas (C3-C4), ethylene, propylene, and butenes.

[0074] The framework-substituted USY zeolite may include 0.1% to 5% by weight of a transition metal, based on the weight of the framework-substituted USY zeolite. The one or more transition metals may include hafnium, titanium, zirconium, or combinations thereof. In embodiments, the one or more transition metals include hafnium. The one or more transition metals may further include zirconium or titanium. In embodiments, the framework-substituted USY zeolite has a crystal lattice constant of 2.430 nm to 2.450 nm, a crystal lattice constant of 600 m 2 / g to 900m 2 / g, a molar ratio of SiO2 to Al2O3 from 5:1 to 100:1, or a combination of these properties.

[0075] The FCC catalyst composition may include 5% to 60% by weight of framework-substituted USY zeolite based on the weight of the FCC catalyst composition. The FCC catalyst composition may further include 15% to 60% by weight of an inorganic filler based on the total weight of the FCC catalyst composition. The inorganic filler may include silica sol, basic aluminum chloride, aluminum biphosphate, alumina sol, kaolin, clay, activated alumina, porous silica, rare earth oxide, metal scavenger, or combinations thereof. The FCC catalyst composition may further include a rare earth oxide having a chemical formula of RE2O3, and may include 0% to 6.0% by weight of the rare earth oxide based on the weight of the framework-substituted USY zeolite. In embodiments, the rare earth metal of the rare earth oxide may include one or more of cerium, lanthanum, praseodymium, neodymium, or combinations thereof. The FCC catalyst composition may have any other characteristics, compositions, or properties previously described in this disclosure for the FCC catalyst composition.

[0076] Referring again to Figures 1-2, a method of upgrading a hydrocarbon feed may include passing the hydrocarbon feed through a fluid catalytic cracking unit (FCC unit); contacting the hydrocarbon feed with an FCC catalyst composition in the FCC unit under reaction conditions sufficient to cause at least a portion of the hydrocarbon feed to undergo cracking reactions to produce a cracked reaction mixture comprising a spent FCC catalyst composition and a cracked effluent comprising one or more olefins, the FCC catalyst composition comprising a framework-substituted USY zeolite comprising hafnium, zirconium, titanium, or a combination thereof substituted into the framework of the framework-substituted USY zeolite, and 1 weight percent to 50 weight percent of an FCC zeolite cracking additive based on the total weight of the FCC catalyst composition; passing the cracked reaction mixture through a catalyst separation device that separates the cracked reaction mixture into a spent FCC catalyst composition and a cracked effluent; and passing the cracked effluent from the fluid catalytic cracking unit. In an embodiment, the fluid catalytic cracking unit may be a downer reactor or a riser reactor. The FCC catalyst composition may have any other characteristics, composition, or properties previously described in this disclosure for the FCC catalyst composition. The FCC unit may include any of the characteristics or operating conditions previously described in this disclosure for the FCC unit.

[0077] The description and examples are Things and Although presented in terms of whole crude oil or desalted crude oil as a crude oil conversion, it should be understood that the systems and processes described in this disclosure could be applied to the conversion of a wide variety of heavy oils, including, but not limited to, crude oil, vacuum resid, tar sands, bitumen, atmospheric resid, vacuum gas oil, or other heavy oils. EXAMPLES

[0078] Various embodiments of the FCC catalyst compositions and methods for upgrading hydrocarbons are further clarified by the following examples, which are illustrative in nature and should not be construed as limiting the subject matter of the present disclosure.

[0079] Example 1: FCC Catalyst Compositions (Framework-Substituted USY Zeolite with and without FCC Zeolite Cracking Additive) In Example 1, two sets of Advanced Cracking Evaluation (ACE) tests were performed using a feed sample of unconverted hydrocracked bottom stream, the properties of which are shown in Table 1. The ACE unit is described in detail in U.S. Pat. No. 6,069,012. The activity of the FCC catalyst composition was determined according to ASTM method D7964, entitled "Standard Test Method for Determining Activity of Fluid Catalytic Cracking (FCC) Catalysts in a Fluidized Bed." The first test was performed with a framework-substituted USY zeolite, in which a portion of the aluminum framework was substituted with zirconium and titanium. The second test was performed with an FCC catalyst composition comprising the same framework-substituted USY zeolite as the first test and an FCC zeolite cracking additive according to the present disclosure. The FCC catalyst composition comprised 90 wt. % framework-substituted USY zeolite and 10 wt. % FCC zeolite cracking additive. The FCC zeolite cracking additive comprised an MFI framework zeolite.

[0080] The catalysts (framework-substituted USY zeolite and FCC catalyst compositions) were conditioned according to ASTM method D4463 entitled "Guide for Metals Free Steam Deactivation of Fresh Fluid Cracking Catalyst". Each catalyst (framework-substituted USY zeolite and FCC catalyst composition) was first calcined at 500° C. for 4 hours under nitrogen flow. The temperature was then increased at a rate of 5° C. per minute. After the temperature reached 810° C., the nitrogen flow was continued for 30 minutes, after which the nitrogen flow was stopped and replaced with a steam flow. Water was fed to the preheat zone of the steamer at a rate of 3 liters per hour. With steam flowing at ambient pressure, the temperature was increased to 810° C. and maintained at this temperature for 6 hours.

[0081] For each test, 5.0 to 11.0 grams of catalyst (framework substituted USY zeolite or FCC catalyst composition) were transferred to the reactor where it was heated to the full reaction temperature of 600° C. with nitrogen gas flowing from the bottom through the feed injector to keep the catalyst particles fluidized. When the catalyst bed temperature was within ±1° C. of the 600° C. reaction temperature, the hydrocarbon feed was injected at an injection rate of 1.5 grams per minute for an injection time of 45 seconds. The tests were run at 600° C. with a hydrocarbon feed to catalyst ratio of 4.5 to 9.8 for a residence time of 45 seconds.

[0082] All gaseous products are passed through a liquid container, C 5+ The hydrocarbons were condensed and the non-condensable products were passed to a gas container. After stripping was completed, the reactor temperature was increased to 650°C and the nitrogen was changed to air to regenerate the catalyst. During regeneration, the flue gas from the regeneration process was passed through a CO2 analyzer and the total amount of coke produced was calculated from the flue gas flow rate and CO2 concentration.

[0083] The hydrocarbon gas products were analyzed using an Agilent Micro GC equipped with four TCD detectors. Gas from the start of feed injection to liquid stripping was collected in a glass bottle by water displacement. The displacement water was collected in a container mounted on a balance. The mass difference before and after was used to determine the volume of gas. After stripping was completed, approximately 250 ml of gas was used to purge the sampling line and the GC analysis was performed by the software. Nitrogen, hydrogen, all C 1~4 All components in the gaseous product stream were analyzed, including hydrocarbons, and some C5 and C6 hydrocarbons. During data processing, the C5 and heavier products were added to the gasoline product.

[0084] Simulated distillation of the liquid products was performed using a Varian GC equipped with an FID detector according to ASTM D-2887. Three different liquid fractions were considered: gasoline (C5-<221°C), light cycle oil (LCO-221°C to 343°C), and heavy cycle oil (HCO->343°C). Conversions and yields were calculated using the mass percentages of the liquid products.

[0085] The FCC catalyst composition containing the framework-substituted USY zeolite and the FCC zeolite cracking additive resulted in higher conversions than the framework-substituted USY zeolite without the FCC zeolite cracking additive. The FCC catalyst composition containing the FCC zeolite cracking additive achieved conversions as high as 91% by weight, whereas the framework-substituted USY zeolite without the FCC zeolite cracking additive achieved only 87% conversion. Table 2 shows the product changes between the two tests at 87% by weight conversion. A positive change reflects an increase in the amount of a particular product in the FCC catalyst composition containing the FCC zeolite cracking additive compared to the framework-substituted USY zeolite without the FCC zeolite cracking additive, whereas a negative change reflects a lower amount of a particular product in the FCC catalyst composition containing the FCC zeolite cracking additive compared to the framework-substituted USY zeolite without the FCC zeolite cracking additive.

[0086] [Table 2]

[0087] As can be seen from Table 2, when the FCC catalyst composition containing the FCC zeolite cracking additive is used, the gasoline yield, LCO yield, and coke amount are reduced. At the same time, when the FCC catalyst composition containing the FCC zeolite cracking additive is used, the yields of HCO, total gas, dry gas, LPG, ethylene, propylene, and butene are all increased. In particular, the provided FCC catalyst composition increases the yield of light olefins such as ethylene, propylene, and butene compared with the framework-substituted USY zeolite itself. In addition, as mentioned above, when the FCC catalyst composition containing the FCC zeolite cracking additive is used, the overall conversion is 4 mass% higher compared with the FCC catalyst composition without the FCC zeolite cracking additive.

[0088] One or more embodiments of the present disclosure are described herein. A first embodiment of the present disclosure may include a fluid catalytic cracking (FCC) catalyst composition, the FCC catalyst composition comprising a framework-substituted USY zeolite comprising one or more transition metals substituted into the framework of the USY zeolite; and 1 weight percent to 50 weight percent of an FCC zeolite cracking additive, based on the total weight of the FCC catalyst composition.

[0089] A second embodiment of the present disclosure may include the first embodiment, wherein the framework-substituted USY zeolite includes 0.1 weight percent to 5 weight percent of each transition metal based on the weight of the framework-substituted USY zeolite.

[0090] A third aspect of the present disclosure may include any of the first or second aspects, wherein the one or more transition metals include hafnium, zirconium, titanium, or a combination thereof.

[0091] A fourth aspect of the present disclosure may include any one of the first to third aspects, wherein the one or more transition metals include hafnium.

[0092] A fifth embodiment of the present disclosure may include any one of the first to fourth embodiments, wherein the framework-substituted USY zeolite has a crystal lattice parameter of 2.430 nanometers to 2.450 nanometers.

[0093] A sixth embodiment of the present disclosure may include any one of the first to fifth embodiments, wherein the framework-substituted USY zeolite has a specific surface area of ​​600 square meters per gram to 900 square meters per gram.

[0094] A seventh embodiment of the present disclosure may include any one of the first to sixth embodiments, wherein the framework-substituted USY zeolite has a molar ratio of SiO2 to Al2O3 from 5:1 to 100:1.

[0095] An eighth embodiment of the present disclosure may include any one of the first to seventh embodiments, wherein the FCC catalyst composition comprises 5 weight percent to 60 weight percent of the framework-substituted USY zeolite, based on the total weight of the FCC catalyst composition.

[0096] A ninth embodiment of the present disclosure may include the eighth embodiment, further comprising 15 to 60 weight percent of an inorganic filler, based on the total weight of the FCC catalyst composition.

[0097] A tenth embodiment of the present disclosure may include the ninth embodiment, wherein the inorganic filler comprises one or more of silica sol, basic aluminum chloride, aluminum biphosphate, alumina sol, activated alumina, porous silica, a metal scavenger, or combinations thereof.

[0098] An eleventh embodiment of the present disclosure may include the tenth embodiment, further comprising 0.0 to 6.0 weight percent of a rare earth oxide, based on the total weight of the FCC catalyst composition.

[0099] A twelfth aspect of the present disclosure may include the eleventh aspect, wherein the rare earth metal of the rare earth oxide includes one or more of cerium, lanthanum, praseodymium, neodymium, or combinations thereof.

[0100] A thirteenth embodiment of the present disclosure may include any one of the first through twelfth embodiments, wherein the FCC catalyst composition comprises 5 weight percent to 15 weight percent of the FCC zeolite cracking additive, based on the total weight of the FCC catalyst composition.

[0101] A fourteenth aspect of the present disclosure can include any one of the first to thirteenth aspects, wherein the FCC zeolite cracking additive comprises an MFI framework zeolite.

[0102] A fifteenth embodiment of the present disclosure can include any one of the first to fourteenth embodiments, wherein the FCC zeolite cracking additive comprises a ZSM-5 zeolite.

[0103] A sixteenth aspect of the present disclosure may include a method for upgrading a hydrocarbon feed comprising contacting the hydrocarbon feed with an FCC catalyst composition at reaction conditions sufficient to upgrade at least a portion of the hydrocarbon feed, the FCC catalyst composition comprising a framework-substituted USY zeolite and 1 weight percent to 50 weight percent of an FCC zeolite cracking additive based on the total weight of the FCC catalyst composition, the framework-substituted USY zeolite comprising hafnium, zirconium, titanium, or a combination thereof substituted onto the framework of the framework-substituted USY zeolite.

[0104] A seventeenth embodiment of the present disclosure may include the sixteenth embodiment, wherein the hydrocarbon feed is contacted with the FCC catalyst composition at a temperature from 450 degrees Celsius to 700 degrees Celsius.

[0105] An eighteenth embodiment of the present disclosure may include any of the sixteenth or seventeenth embodiments, wherein the hydrocarbon feed is contacted with the FCC catalyst composition at a pressure of 0.1 to 1 megapascal.

[0106] A nineteenth embodiment of the present disclosure may include any one of the sixteenth to eighteenth embodiments, wherein the hydrocarbon feed is contacted with the FCC catalyst composition at the reaction temperature for a residence time of from 0.1 seconds to 60 seconds.

[0107] A twentieth embodiment of the present disclosure may include any one of the sixteenth to nineteenth embodiments, wherein the hydrocarbon feed comprises one or more of crude oil, syncrude oil, bitumen, oil sands, shale oil, coal liquids, naphtha, diesel, vacuum gas oil, vacuum resid, demetalized oil, deasphalted oil, coker gas oil, cycle oil, diesel, or combinations thereof.

[0108] A twenty-first embodiment of the present disclosure may include the twentieth embodiment, wherein the hydrocarbon feed has an atmospheric pressure boiling range of 350 degrees Celsius or greater.

[0109] A twenty-second embodiment of the present disclosure may include any one of the sixteenth to twenty-first embodiments, wherein the hydrocarbon feed is contacted with the FCC catalyst composition in a mass ratio of hydrocarbon feed to FCC catalyst composition of 1:2 to 1:30.

[0110] A twenty-third embodiment of the present disclosure may include any one of the sixteenth to twenty-second embodiments, wherein the framework-substituted USY zeolite includes 0.1 weight percent to 5 weight percent of each transition metal based on the weight of the framework-substituted USY zeolite.

[0111] A twenty-fourth embodiment of the present disclosure can include any one of the sixteenth to twenty-third embodiments, wherein the framework-substituted USY zeolite includes hafnium.

[0112] A twenty-fifth embodiment of the present disclosure may include the twenty-fourth embodiment, wherein the framework-substituted USY zeolite includes zirconium or titanium.

[0113] A twenty-sixth embodiment of the present disclosure may include any one of the sixteenth to twenty-fifth embodiments, wherein the framework-substituted USY zeolite has a crystal lattice parameter of 2.430 nanometers to 2.450 nanometers.

[0114] A twenty-seventh embodiment of the present disclosure can include any one of the sixteenth to twenty-sixth embodiments, wherein the framework-substituted USY zeolite has a specific surface area of ​​600 square meters per gram to 900 square meters per gram.

[0115] A twenty-eighth embodiment of the present disclosure may include any one of the sixteenth to twenty-seventh embodiments, wherein the framework-substituted USY zeolite has a molar ratio of SiO2 to Al2O3 from 5:1 to 100:1.

[0116] A twenty-ninth embodiment of the present disclosure can include any one of the sixteenth to twenty-eighth embodiments, wherein the FCC catalyst composition comprises 5 weight percent to 60 weight percent of the framework-substituted USY zeolite, based on the total weight of the FCC catalyst composition.

[0117] A thirtieth embodiment of the present disclosure may include the twenty-ninth embodiment, further comprising 15 to 60 weight percent of an inorganic filler, based on the total weight of the FCC catalyst composition.

[0118] A thirty-first embodiment of the present disclosure may include the thirtieth embodiment, wherein the inorganic filler comprises one or more of basic silica sol, aluminum chloride, aluminum biphosphate, alumina sol, activated alumina, porous silica, a metal scavenger, or combinations thereof.

[0119] A thirty-second embodiment of the present disclosure may include the thirty-first embodiment, wherein the FCC catalyst composition further comprises 0.0 to 6.0 weight percent of a rare earth oxide having a chemical formula of RE2O3, based on the total weight of the FCC catalyst composition.

[0120] A thirty-third embodiment of the present disclosure may include the thirty-second embodiment, wherein the rare earth metal of the rare earth oxide includes one or more of cerium, lanthanum, praseodymium, neodymium, or combinations thereof.

[0121] A thirty-fourth embodiment of the present disclosure may include any one of the sixteenth to thirty-third embodiments, wherein the FCC catalyst composition comprises 5 weight percent to 15 weight percent of the FCC zeolite cracking additive, based on the total weight of the FCC catalyst composition.

[0122] A thirty-fifth embodiment of the present disclosure can include any one of the sixteenth to thirty-fourth embodiments, wherein the FCC zeolite cracking additive comprises an MFI framework zeolite.

[0123] A thirty-sixth embodiment of the present disclosure can include any one of the sixteenth to thirty-fifth embodiments, wherein the FCC zeolite cracking additive comprises a ZSM-5 zeolite.

[0124] A thirty-seventh aspect of the present disclosure may include a method of upgrading a hydrocarbon feed, comprising the steps of: passing the hydrocarbon feed through a fluid catalytic cracking unit; contacting the hydrocarbon feed with an FCC catalyst composition in the fluid catalytic cracking unit under reaction conditions sufficient to cause at least a portion of the hydrocarbon feed to undergo cracking reactions to produce a cracked reaction mixture comprising a spent FCC catalyst composition and a cracked effluent comprising one or more olefins, wherein the FCC catalyst composition comprises a framework-substituted USY zeolite comprising hafnium, zirconium, titanium, or a combination thereof substituted on the framework of the framework-substituted USY zeolite, and 1 weight percent to 50 weight percent of an FCC zeolite cracking additive, based on the total weight of the FCC catalyst composition; passing the cracked reaction mixture through a catalyst separation device that separates the cracked reaction mixture into a spent FCC catalyst composition and a cracked effluent; and allowing the cracked effluent to flow from the fluid catalytic cracking unit.

[0125] A thirty-eighth embodiment of the present disclosure may include the thirty-seventh embodiment, wherein the hydrocarbon feed is contacted with the FCC catalyst composition at a temperature from 450 degrees Celsius to 700 degrees Celsius.

[0126] A thirty-ninth embodiment of the present disclosure may include any of the thirty-seventh or thirty-eighth embodiments, wherein the hydrocarbon feed is contacted with the FCC catalyst composition at a pressure of 0.1 to 1 megapascal.

[0127] A fortieth embodiment of the present disclosure may include any one of the thirty-seventh to thirty-ninth embodiments, wherein the hydrocarbon feed is contacted with the FCC catalyst composition at the reaction temperature for a residence time of from 0.1 seconds to 60 seconds.

[0128] A forty-first embodiment of the present disclosure may include any one of the thirty-seventh to fortieth embodiments, wherein the hydrocarbon feed comprises one or more of crude oil, syncrude oil, bitumen, oil sands, shale oil, coal liquids, naphtha, diesel, vacuum gas oil, vacuum resid, demetalized oil, deasphalted oil, coker gas oil, cycle oil, diesel, or combinations thereof.

[0129] A forty-second embodiment of the present disclosure may include the forty-first embodiment, wherein the hydrocarbon feed has an atmospheric pressure boiling range of 350 degrees Celsius or greater.

[0130] A forty-third embodiment of the present disclosure may include any one of the thirty-seventh to forty-second embodiments, wherein the hydrocarbon feed is contacted with the FCC catalyst composition in a mass ratio of hydrocarbon feed to FCC catalyst composition of 1:2 to 1:30.

[0131] A forty-fourth embodiment of the present disclosure may include any one of the thirty-seventh to forty-third embodiments, wherein the fluid catalytic cracking unit is a downer reactor.

[0132] A forty-fifth embodiment of the present disclosure may include any one of the thirty-seventh to forty-fourth embodiments, wherein the fluid catalytic cracking unit is a riser reactor.

[0133] A forty-sixth embodiment of the present disclosure may include any one of the thirty-seventh to forty-fifth embodiments, wherein the framework-substituted USY zeolite includes 0.1 to 5 weight percent of each transition metal based on the weight of the framework-substituted USY zeolite.

[0134] A forty-seventh embodiment of the present disclosure can include any one of the thirty-seventh to forty-sixth embodiments, wherein the framework-substituted USY zeolite includes hafnium.

[0135] A forty-eighth embodiment of the present disclosure may include the forty-seventh embodiment, wherein the framework-substituted USY zeolite includes zirconium or titanium.

[0136] A forty-ninth embodiment of the present disclosure may include any one of the thirty-seventh to forty-eighth embodiments, wherein the framework-substituted USY zeolite has a crystal lattice parameter of 2.430 nanometers to 2.450 nanometers.

[0137] A fiftieth embodiment of the present disclosure can include any one of the thirty-seventh to forty-ninth embodiments, wherein the framework-substituted USY zeolite has a specific surface area of ​​600 to 900 square meters per gram.

[0138] A fifty-first embodiment of the present disclosure may include any one of the thirty-seventh to fiftieth embodiments, wherein the framework-substituted USY zeolite has a molar ratio of SiO2 to Al2O3 from 5:1 to 100:1.

[0139] A fifty-second embodiment of the present disclosure may include any one of the thirty-seventh to fifty-first embodiments, wherein the FCC catalyst composition comprises 5 weight percent to 60 weight percent of the framework-substituted USY zeolite, based on the weight of the FCC catalyst composition.

[0140] A fifty-third embodiment of the present disclosure may include the fifty-second embodiment, further comprising 15 to 60 weight percent of an inorganic filler, based on the total weight of the FCC catalyst composition.

[0141] A fifty-fourth embodiment of the present disclosure may include the fifty-third embodiment, wherein the inorganic filler comprises one or more of silica sol, basic aluminum chloride, aluminum biphosphate, alumina sol, activated alumina, porous silica, a metal scavenger, or combinations thereof.

[0142] A fifty-fifth embodiment of the present disclosure may include the fifty-fourth embodiment, wherein the FCC catalyst composition further comprises 0.0 to 6.0 weight percent of a rare earth oxide, based on the total weight of the FCC catalyst composition, the rare earth oxide having a chemical formula of RE2O3.

[0143] A fifty-sixth embodiment of the present disclosure may include the fifty-fifth embodiment, wherein the rare earth metal of the rare earth oxide includes one or more of cerium, lanthanum, praseodymium, neodymium, or combinations thereof.

[0144] A fifty-seventh embodiment of the present disclosure may include any one of the thirty-seventh to fifty-sixth embodiments, wherein the FCC catalyst composition comprises 5 weight percent to 15 weight percent of the FCC zeolite cracking additive, based on the total weight of the FCC catalyst composition.

[0145] A fifty-eighth embodiment of the present disclosure can include any one of the thirty-seventh to fifty-seventh embodiments, wherein the FCC zeolite cracking additive comprises an MFI framework zeolite.

[0146] A fifty-ninth embodiment of the present disclosure can include any one of the thirty-seventh to fifty-eighth embodiments, wherein the FCC zeolite cracking additive comprises a ZSM-5 zeolite.

[0147] Please note that one or more of the following claims utilizes the transitional phrase "herein." Please note that for purposes of defining the present technology, this term is introduced into the claims as an open-ended transitional phrase used to introduce a recitation of a series of features of a structure, and should be interpreted in a similar manner to the more commonly used open-ended postscript "comprising."

[0148] It should be understood that any two quantitative values ​​given for a property may constitute a range for that property, and all combinations of ranges formed from all recited quantitative values ​​for a given property are contemplated in this disclosure.

[0149] Although the subject matter of the present disclosure has been described in detail and with reference to specific embodiments, it should be noted that various details described in the present disclosure should not be interpreted as implying that these details relate to elements that are essential components of the various embodiments described in the present disclosure, even if a particular element is illustrated in each of the drawings accompanying this description. Rather, the claims appended hereto should be considered as solely representing the breadth of the present disclosure and the corresponding scope of the various embodiments described in the present disclosure. Moreover, it will be apparent that modifications and variations are possible without departing from the scope of the appended claims. Preferred embodiments of the present invention will be described below in detail. EMBODIMENT 1 1. A fluid catalytic cracking (FCC) catalyst composition comprising: a framework-substituted USY zeolite comprising one or more transition metals substituted into the framework of the USY zeolite; and 1 weight percent to 50 weight percent of an FCC zeolite cracking additive, based on the total weight of the FCC catalyst composition; 1. An FCC catalyst composition comprising: EMBODIMENT 2 2. The FCC catalyst composition of embodiment 1, wherein the one or more transition metals comprise hafnium, zirconium, titanium, or a combination thereof. EMBODIMENT 3 3. The FCC catalyst composition according to embodiment 1 or 2, wherein the framework-substituted USY zeolite has a crystal lattice constant of 2.430 nanometers to 2.450 nanometers and a specific surface area of ​​600 square meters per gram to 900 square meters per gram. EMBODIMENT 4 4. The FCC catalyst composition of any one of embodiments 1 to 3, wherein the FCC catalyst composition comprises 5 to 60 weight percent of the framework-substituted USY zeolite, based on the total weight of the FCC catalyst composition. EMBODIMENT 5 5. The FCC catalyst composition of any one of embodiments 1 to 4, wherein the FCC zeolite cracking additive comprises an MFI framework zeolite, or more preferably a ZSM-5 zeolite. EMBODIMENT 6 1. A method for upgrading a hydrocarbon feed comprising: contacting the hydrocarbon feed with an FCC catalyst composition under reaction conditions sufficient to upgrade at least a portion of the hydrocarbon feed; the FCC catalyst composition comprises a framework-substituted USY zeolite and 1 weight percent to 50 weight percent of an FCC zeolite cracking additive, based on the total weight of the FCC catalyst composition, the framework-substituted USY zeolite comprising hafnium, zirconium, titanium, or a combination thereof, substituted into the framework of the framework-substituted USY zeolite; The method comprising: EMBODIMENT 7 7. The method of upgrading a hydrocarbon feed according to embodiment 6, wherein the hydrocarbon feed is contacted with the FCC catalyst composition at a temperature of 450 degrees Celsius to 700 degrees Celsius, for a residence time of 0.1 seconds to 60 seconds, and in a mass ratio of hydrocarbon feed to FCC catalyst composition of 1:2 to 1:30. EMBODIMENT 8 A method for upgrading a hydrocarbon feed according to embodiment 6 or 7, wherein the framework-substituted USY zeolite comprises zirconium or titanium. EMBODIMENT 9 9. The method for upgrading a hydrocarbon feed according to any one of embodiments 6 to 8, wherein the FCC catalyst composition comprises 5 to 60 weight percent of the framework-substituted USY zeolite, based on the total weight of the FCC catalyst composition. EMBODIMENT 10 10. The method for upgrading a hydrocarbon feed according to any one of embodiments 6 to 9, further comprising 15 to 60 weight percent of an inorganic filler, based on the total weight of the FCC catalyst composition. EMBODIMENT 11 11. The method for upgrading a hydrocarbon feed according to any one of embodiments 6 to 10, wherein the FCC zeolitic cracking additive comprises an MFI framework zeolite, or more preferably a ZSM-5 zeolite. EMBODIMENT 12 1. A method for upgrading a hydrocarbon feed comprising: passing the hydrocarbon feed through a fluid catalytic cracking unit; contacting the hydrocarbon feed with an FCC catalyst composition in the fluid catalytic cracking unit under reaction conditions sufficient to cause at least a portion of the hydrocarbon feed to undergo cracking reactions to produce a cracked reaction mixture comprising a spent FCC catalyst composition and a cracked effluent comprising one or more olefins; The FCC catalyst composition comprises: a framework-substituted USY zeolite comprising hafnium, zirconium, titanium, or a combination thereof substituted into the framework of the framework-substituted USY zeolite; and 1 weight percent to 50 weight percent of an FCC zeolite cracking additive, based on the total weight of the FCC catalyst composition; A process comprising: passing the cracked reaction mixture through a catalyst separation unit that separates the cracked reaction mixture into the spent FCC catalyst composition and the cracked effluent; and allowing the cracked effluent to exit the fluid catalytic cracking unit; The method includes: EMBODIMENT 13 13. The method of upgrading a hydrocarbon feed according to embodiment 12, wherein the hydrocarbon feed is contacted with the FCC catalyst composition at a mass ratio of hydrocarbon feed to FCC catalyst composition of from 1:2 to 1:30. EMBODIMENT 14 14. A method for upgrading a hydrocarbon feed according to embodiment 12 or 13, wherein the FCC catalyst composition comprises from 5 to 60 weight percent of the framework-substituted USY zeolite, based on the weight of the FCC catalyst composition. EMBODIMENT 15 15. The method for upgrading a hydrocarbon feed according to any one of embodiments 12 to 14, wherein the FCC zeolite cracking additive comprises an MFI framework zeolite. [Explanation of symbols]

[0150] 100, 200 Reactor system 110, 210 FCC units 111, 211 Hydrocarbon feed 112 Riser part 114, 212 Reaction Zone 115, 119, 121, 123, 215, 219, 225 conduit 116, 214 Separation Zone 120, 220 Catalyst regeneration unit 122, 222 Regeneration Zone 216 Stripper Zone

Claims

1. 1. A fluid catalytic cracking (FCC) catalyst composition comprising: a framework-substituted USY zeolite comprising one or more transition metals substituted into the framework of the USY zeolite; 1 to 50 weight percent of an FCC zeolite cracking additive, based on the total weight of the FCC catalyst composition, the FCC zeolite cracking additive comprising a ZSM-5 zeolite; and 35 to 60 weight percent of an inorganic filler, based on the total weight of the FCC catalyst composition, comprising one or more of silica sol, basic aluminum chloride, aluminum biphosphate, alumina sol, activated alumina, porous silica, a metal scavenger, or combinations thereof; 1. An FCC catalyst composition comprising:

2. The FCC catalyst composition of claim 1 , wherein the one or more transition metals comprise hafnium, zirconium, titanium, or a combination thereof.

3. 2. The FCC catalyst composition of claim 1, wherein the framework-substituted USY zeolite has a crystal lattice parameter of 2.430 nanometers to 2.450 nanometers and a specific surface area of ​​600 square meters per gram to 900 square meters per gram.

4. 2. The FCC catalyst composition of claim 1, wherein the FCC catalyst composition comprises from 5 to 60 weight percent of the framework-substituted USY zeolite, based on the total weight of the FCC catalyst composition.

5. The FCC catalyst composition of any one of claims 1 to 4, wherein the FCC catalyst composition comprises a plurality of microparticles, each of the plurality of microparticles comprising the framework-substituted USY zeolite, the FCC zeolite cracking additive, and the inorganic filler.

6. 1. A method for upgrading a hydrocarbon feed comprising: contacting the hydrocarbon feed with an FCC catalyst composition under reaction conditions sufficient to upgrade at least a portion of the hydrocarbon feed; The FCC catalyst composition comprises: a framework-substituted USY zeolite comprising hafnium, zirconium, titanium, or a combination thereof substituted into the framework of the framework-substituted USY zeolite; 1 to 50 weight percent of an FCC zeolite cracking additive, based on the total weight of the FCC catalyst composition, the FCC zeolite cracking additive comprising a ZSM-5 zeolite; and 35 to 60 weight percent of an inorganic filler, based on the total weight of the FCC catalyst composition, comprising one or more of silica sol, basic aluminum chloride, aluminum biphosphate, alumina sol, activated alumina, porous silica, a metal scavenger, or combinations thereof; A process comprising: The method comprising:

7. 7. The method of claim 6, wherein the hydrocarbon feed is contacted with the FCC catalyst composition at a temperature of from 450 degrees Celsius to 700 degrees Celsius, for a residence time of from 0.1 seconds to 60 seconds, and in a mass ratio of hydrocarbon feed to FCC catalyst composition of from 1:2 to 1:

30.

8. 7. The method of claim 6, wherein the framework-substituted USY zeolite contains zirconium or titanium.

9. 7. The method of claim 6, wherein the FCC catalyst composition comprises from 5 to 60 weight percent of the framework-substituted USY zeolite, based on the total weight of the FCC catalyst composition.

10. The method of claim 6 further comprising 15 to 60 weight percent of an inorganic filler, based on the total weight of the FCC catalyst composition.

11. The method of any one of claims 6 to 10, wherein the FCC catalyst composition comprises a plurality of microparticles, each of the plurality of microparticles comprising the framework-substituted USY zeolite, the FCC zeolite cracking additive, and the inorganic filler.

12. passing the hydrocarbon feed through a fluid catalytic cracking unit; contacting the hydrocarbon feed with an FCC catalyst composition in the fluid catalytic cracking unit under reaction conditions sufficient to cause at least a portion of the hydrocarbon feed to undergo cracking reactions to produce a cracked reaction mixture comprising a spent FCC catalyst composition and a cracked effluent comprising one or more olefins; passing the cracked reaction mixture through a catalyst separation unit that separates the cracked reaction mixture into the spent FCC catalyst composition and the cracked effluent; and allowing the cracked effluent to exit the fluid catalytic cracking unit; The method of claim 6, comprising:

13. 13. The process of claim 12, wherein the hydrocarbon feed is contacted with the FCC catalyst composition at a mass ratio of hydrocarbon feed to FCC catalyst composition of from 1:2 to 1:

30.

14. 14. The method of claim 12 or 13, wherein the FCC catalyst composition comprises from 5 weight percent to 60 weight percent of the framework-substituted USY zeolite, based on the weight of the FCC catalyst composition.

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