Catalyst composition comprising zeolites having different silicon-aluminum molar ratios

Abstract

According to an embodiment, a catalyst composition may include from 10 wt.% to 50 wt.% of a matrix material, from 10 wt.% to 30 wt.% of a binder, and from 30 wt.% to 70 wt.% of a zeolite mixture. The zeolite mixture may include at least a first portion of a zeolite and a second portion of a zeolite. The first portion of the zeolite may consist of zeolites having a molar ratio of silicon to aluminum in a first range, and the second portion of the zeolite may consist of zeolites having a molar ratio of silicon to aluminum in a second range. The silica-alumina molar ratio range of the first portion of the zeolite does not overlap and may differ from the silica-alumina molar ratio range of the second portion of the zeolite by at least 5.

Description

Cross-reference to related applications regarding catalyst compositions containing zeolites with different silicon-to-aluminum molar ratios

[0001] This application claims the benefit of U.S. Application Serial No. 18 / 483,945, filed on October 10, 2023, the entire contents of which are incorporated herein by reference. Technical Field

[0002] The embodiments described herein generally involve chemical processing, and more specifically, catalysts. Background Technology

[0003] Porous materials, such as zeolites, are used in many petrochemical industry applications. For example, such materials can be used as catalysts in many reactions that convert hydrocarbons or other reactants from feed chemicals to product chemicals. Zeolites can be characterized by their microporous framework type. Over the past few decades, various types of zeolites have been identified, with zeolite type often described by framework type, and specific zeolite materials can be identified more specifically by various names such as ZSM-5 or Y.

[0004] Zeolite-containing catalysts and adsorbents have wide applications in many different industries. Exemplary industries include the petrochemical industry, encompassing refining, gas separation, and carbon dioxide separation and capture processes. For example, in the oil industry, zeolite-containing catalysts can be incorporated into processes such as fluidized catalytic cracking (FCC) and hydrocracking to catalyze reactions such as hydrogenation, dehydrogenation, isomerization, alkylation, and cracking. Zeolite-containing adsorbents can be used to separate paraffins or aromatic isomers, and in drying processes to remove water and other impurities from hydrocarbon streams. Summary of the Invention

[0005] Embodiments of this disclosure relate to catalyst compositions comprising zeolites with different silica-alumina molar ratios. Specifically, the catalyst composition may comprise a zeolite mixture containing a first portion of zeolite and a second portion of zeolite with different silica-alumina molar ratios. It has been found that the silica-alumina ratio of zeolites can affect the catalytic selectivity of the zeolite. For example, when the catalyst composition is used to process hydrocarbon feedstocks, zeolites with a relatively high silica-alumina ratio can improve the selectivity of the catalyst composition for light olefins. However, zeolites with a relatively high silica-alumina ratio may have a lower overall conversion of hydrocarbon feedstocks compared to catalyst compositions with a relatively low silica-alumina ratio. The embodiments described herein introduce multiple portions of zeolites with different silica-alumina ratios. In some embodiments, the catalyst composition can have improved selectivity while still maintaining sufficient overall conversion.

[0006] According to one or more embodiments disclosed herein, the catalyst composition may comprise 10 wt.% to 50 wt.% of a matrix material, 10 wt.% to 30 wt.% of a binder, and 30 wt.% to 70 wt.% of a zeolite mixture. The zeolite mixture may comprise all the zeolites in the catalyst composition. The zeolite mixture may comprise at least a first portion of zeolite and a second portion of zeolite. The first portion of zeolite may consist of zeolites with a silicon-to-aluminum molar ratio within a first range and may comprise at least 10 wt.% of the zeolite mixture. The second portion of zeolite may consist of zeolites with a silicon-to-aluminum molar ratio within a second range and may comprise at least 10 wt.% of the zeolite mixture. The silicon-to-aluminum molar ratio range of the first portion of zeolite does not overlap with the range of the second portion of zeolite and may differ by at least 5. The midpoint of the silicon-to-aluminum molar ratio range of the second portion of zeolite minus the midpoint of the silicon-to-aluminum molar ratio range of the first portion of zeolite may equal at least 15.

[0007] It should be understood that the foregoing general description and the following detailed description depict various embodiments and are intended to provide an overview or framework for understanding the nature and characteristics of the claimed subject matter. Additional features and advantages of the embodiments will be set forth in the detailed description and will be apparent in part to those skilled in the art from the description (including the drawings and claims), or will be recognized by practice of the described embodiments. The following drawings are included to provide a further understanding of the embodiments and, together with the detailed description, to explain the principles and operation of the claimed subject matter. However, the embodiments depicted in the drawings are illustrative and exemplary in nature and are not intended to limit the claimed subject matter. Attached Figure Description

[0008] The following detailed description of specific embodiments of the present disclosure is best understood when read in conjunction with the accompanying drawings, in which the same structures are indicated by the same reference numerals, and in which: FIG1 schematically depicts a reactor system according to one or more embodiments of the present disclosure.

[0009] In describing the simplified schematic diagram of Figure 1, numerous valves, temperature sensors, electronic controllers, etc., that may be used and are well known to those skilled in the art are not included. Furthermore, auxiliary components typically included in such reactor systems, such as air supplies, heat exchangers, and buffer tanks, are also excluded. However, it should be understood that these components are within the scope of this disclosure.

[0010] For the purpose of providing a simplified schematic diagram and description of the accompanying drawings, numerous valves, temperature sensors, electronic controllers, etc., that may be used in certain chemical processing operations and are well known to those skilled in the art are not included. Furthermore, auxiliary components typically included in typical chemical processing operations, such as air supply, catalyst hoppers, and flue gas treatment systems, are not depicted. Auxiliary components in hydrocracking units, such as exhaust streams, spent catalyst discharge subsystems, and catalyst replacement subsystems, are also not shown. It should be understood that these components are within the spirit and scope of the embodiments disclosed herein. However, operating components as described in this disclosure may be added to the embodiments described herein.

[0011] It should also be noted that the arrows in the accompanying drawings represent process flows. However, arrows can equivalently represent transfer lines used to transfer process flows between two or more system components. Furthermore, arrows connected to system components define an inlet or outlet in each given system component. The direction of the arrows generally aligns with the primary direction of material movement within the physical transfer line indicated by the arrow. Additionally, arrows not connecting two or more system components represent product flows leaving the depicted system or system inlet flows entering the depicted system. Product flows may be further processed in an associated chemical processing system or may be commercialized as a final product. System inlet flows may be flows transferred from an associated chemical processing system or may be untreated feed streams. Some arrows may represent recirculation flows, which are effluent streams from system components that are recycled back into the system. However, it should be understood that in some embodiments, any represented recirculation flow may be replaced by a system inlet flow of the same material, and a portion of the recirculation flow may leave the system as a system product.

[0012] Furthermore, the arrows in the accompanying drawings may schematically depict process steps that transfer a flow from one system component to another. For example, an arrow pointing from one system component to another may indicate the "transfer" of the effluent from one system component to another, which may include the "departure" or "removal" of the contents of the process flow from one system component and the "introduction" of the contents of that product flow to another system component. It should be understood that the arrows in the relevant drawings do not represent necessary or required steps.

[0013] It should be understood that, according to the embodiments presented in the accompanying drawings, an arrow between two system components may indicate that the flow is unprocessed between the two system components. In other embodiments, the flow indicated by the arrow may have substantially the same composition during its transmission between the two system components. Furthermore, it should be understood that in one or more embodiments, the arrow may indicate that at least 75 wt.%, at least 90 wt.%, at least 95 wt.%, at least 99 wt.%, at least 99.9 wt.%, or even 100 wt.% of the flow is transmitted between the system components. Therefore, in some embodiments, not all of the flow indicated by the arrow may be transmitted between the system components, for example, if a branch is present.

[0014] It should be understood that when two or more process flows intersect in the schematic flow diagram of the relevant figures, these two or more process flows are "mixed" or "combined". Mixing or combining can also include mixing by introducing two flows directly into the same reactor, separation unit, or other system component. For example, it should be understood that when two flows are depicted as being combined directly before entering a separation unit or reactor, in some embodiments, these flows may be equivalently introduced into the separation unit or reactor and mixed in the reactor.

[0015] Reference will now be made in more detail to the various embodiments, some of which are illustrated in the accompanying drawings. Detailed Implementation

[0016] One or more embodiments described herein relate to catalyst compositions comprising a zeolite mixture, the zeolite mixture comprising at least a first portion of zeolite and a second portion of zeolite, wherein the first portion of zeolite has a first range of silicon-aluminum molar ratios (“SAR”), and the second portion of zeolite has a second range of SAR, wherein the first range and the second range do not overlap and the midpoint of the second range minus the midpoint of the first range equals at least 15. Typically, such embodiments include a wider range of SAR distributions in the catalyst compared to catalysts using only a single SAR zeolite. As described herein, particularly with respect to the following embodiments, the catalysts described herein can have improved selectivity while still maintaining sufficient overall conversion.

[0017] As used throughout this disclosure, and as understood by those skilled in the art, "zeolite" or "zeolite material" generally refers to a microporous inorganic material with regular intracrystalline cavities and molecular-sized channels. Zeolites typically contain crystalline structures rather than amorphous structures. The microporous structure of zeolites can provide large surface areas and desired size / shape selectivity, which can be advantageous for catalysis. Therefore, zeolites can be used in many petrochemical industry applications, such as reactions that convert hydrocarbons or other reactants from feedstock chemicals to product chemicals via cracking.

[0018] According to one or more embodiments, zeolites can be aluminosilicates, meaning they have a crystal structure comprising silicon dioxide and aluminum oxide. When zeolites are used in chemical reactions, their silicon-to-aluminum molar ratio affects their properties. For example, when used as catalysts for processing hydrocarbon feedstocks, zeolites with a relatively high silicon-to-aluminum molar ratio may be more selective for the production of light olefins. However, zeolites with a relatively high SAR may also have a lower total hydrocarbon conversion than zeolites with a relatively low SAR. The catalyst compositions comprising zeolite mixtures disclosed herein can overcome this problem by balancing selectivity and total conversion by including zeolite portions with different SARs.

[0019] In one or more embodiments, the catalyst composition may comprise, substantially consist of, or consist of, 10 wt.% to 50 wt.% of a matrix material, 10 wt.% to 30 wt.% of a binder, and 30 wt.% to 70 wt.% of a zeolite mixture. As described herein, the zeolite mixture comprises all the zeolites in the catalyst composition. The zeolite mixture may comprise at least a first portion of zeolite and a second portion of zeolite. The first portion of zeolite consists of zeolites with a silicon-to-aluminum molar ratio within a first range. The second portion of zeolite consists of zeolites with a silicon-to-aluminum molar ratio within a second range. The silicon-to-aluminum molar ratio range of the first portion of zeolite does not overlap with that of the second portion of zeolite. The midpoint of the silicon-to-aluminum molar ratio range of the second portion of zeolite minus the midpoint of the silicon-to-aluminum molar ratio range of the first portion of zeolite equals at least 15. The first and second portions of zeolite may each constitute at least 20 wt.% of the zeolite mixture.

[0020] As described above, in one or more embodiments, the catalyst composition may comprise 30 wt.% to 70 wt.% of a zeolite mixture. For example, the catalyst composition may comprise 30 wt.% to 35 wt.% of a zeolite mixture, 35 wt.% to 40 wt.% of a zeolite mixture, 40 wt.% to 45 wt.% of a zeolite mixture, 45 wt.% to 50 wt.% of a zeolite mixture, 50 wt.% to 55 wt.% of a zeolite mixture, 55 wt.% to 60 wt.% of a zeolite mixture, 60 wt.% to 65 wt.% of a zeolite mixture, 65 wt.% to 70 wt.% of a zeolite mixture, or any combination of one or more of these ranges.

[0021] As described herein, the zeolite mixture may comprise at least a first portion of zeolite and a second portion of zeolite. In one or more embodiments, the zeolite mixture may further comprise a third portion of zeolite. In more embodiments, the zeolite mixture may further comprise a fourth portion of zeolite. Each portion of the zeolite mixture may have an SAR range that does not overlap with the SAR range of any other portion of the zeolite mixture. In one or more embodiments, the first portion of zeolite may consist of zeolite having a first SAR range, and the second portion of zeolite may consist of zeolite having a second SAR range. The midpoint of the second SAR range minus the midpoint of the first SAR range may be equal to at least 15, for example at least 20, at least 25, at least 30, at least 35, at least 40, at least 45, or even at least 50. Without being bound by theory, it is believed that a catalyst composition comprising a zeolite mixture where the midpoint of the second SAR range minus the midpoint of the first SAR range is at least 15 may have reduced selectivity or overall conversion when used to process hydrocarbon feedstocks.

[0022] As described above, the zeolite mixture may further comprise a third portion of zeolite. The third portion of zeolite may consist of zeolite having a third SAR range. The third SAR range may not overlap with the second SAR range. In one or more embodiments, the midpoint of the third SAR range minus the midpoint of the second SAR range may be at least 15, for example, at least 20, at least 25, at least 30, at least 35, at least 40, at least 45, or even at least 50. In one or more embodiments, the zeolite mixture may further comprise a fourth portion of zeolite. The fourth portion of zeolite may consist of zeolite having a fourth SAR range. The fourth SAR range may not overlap with the third SAR range. The midpoint of the fourth SAR range minus the midpoint of the third SAR range may be at least 15, for example, at least 20, at least 25, at least 30, at least 35, at least 40, at least 45, or even at least 50.

[0023] In one or more embodiments, the first and second zeolite portions may have a midpoint SAR in the range of 1 to 500, such as 1 to 25, 25 to 50, 50 to 75, 75 to 100, 100 to 125, 125 to 150, 150 to 175, 175 to 200, 200 to 225, 225 to 250, 250 to 275, 275 to 300, 300 to 325, 325 to 350, 350 to 375, 375 to 400, 400 to 425, 425 to 450, 450 to 475, 475 to 500, or any combination of one or more of these ranges. In one or more embodiments, the first zeolite portion may have an SAR of 25 to 35, and the second zeolite portion may have an SAR of 250 to 300. In other embodiments, the first zeolite fraction may have an SAR of 25 to 35, the second zeolite fraction may have an SAR of 40 to 60, and the third zeolite fraction may have an SAR of 70 to 90. In still other embodiments, the first zeolite fraction may have an SAR of 25 to 35, the second zeolite fraction may have an SAR of 70 to 90, and the third zeolite fraction may have an SAR of 250 to 300. In yet another embodiment, the first zeolite fraction may have an SAR of 40 to 60, the second zeolite fraction may have an SAR of 70 to 90, and the third zeolite fraction may have an SAR of 250 to 300.

[0024] In one or more embodiments, the SAR of the first zeolite and the SAR of the second zeolite may differ by at least 5, for example at least 10, at least 15, at least 20, at least 25, at least 30, at least 35, at least 40, at least 45 or even at least 50.

[0025] Based on the SAR of the first and second zeolites, the SAR ranges of the third and fourth zeolites can vary, but can be greater than 35 to greater than 500, for example, greater than 35 to greater than 50, greater than 50 to greater than 75, greater than 75 to greater than 100, greater than 100 to greater than 125, greater than 125 to greater than 150, greater than 150 to greater than 175, greater than 175 to greater than 200, greater than 200 to greater than 225, greater than 225 to greater than 250, greater than 250 to greater than 275, greater than 275 to greater than 300, greater than 300 to greater than 325, greater than 325 to greater than 350, greater than 350 to greater than 375, greater than 375 to greater than 400, greater than 400 to greater than 425, greater than 425 to greater than 450, greater than 450 to greater than 475, greater than 475 to greater than 500, or any combination of one or more of these ranges.

[0026] The first, second, third, and fourth portions of zeolite can include zeolites of any framework type having a suitable SAR as described above. In one or more embodiments, one or more of the first, second, third, and fourth portions of zeolite can include ZSM-5 zeolite. As used throughout this disclosure and as understood by those skilled in the art, "ZSM-5" generally refers to a zeolite having the MFI framework type according to the IZA zeolite nomenclature and consisting primarily of silica and alumina. ZSM-5 refers to "Zeolite Socony Mobil-5", a pentasil zeolite, which can be represented by the chemical formula Na n Al n Si 96-n O 192 16H2O, where 0 < n < 27. In one or more embodiments, one or more of the first, second, third, and fourth portions of zeolite can include Y zeolite. As used throughout this disclosure and as understood by those skilled in the art, "Y zeolite" and "USY" refer to zeolites having the FAU framework type according to the IZA zeolite nomenclature and consisting primarily of silica and alumina.

[0027] In one or more embodiments, each of the first portion of zeolite and the second portion of zeolite can account for at least 10 wt.% of the zeolite mixture. For example, each of the first portion of zeolite and the second portion of zeolite can account for at least 15 wt.%, at least 20 wt.%, at least 25 wt.%, at least 30 wt.%, at least 35 wt.%, at least 40 wt.%, at least 45 wt.% or even 50 wt.% of the zeolite mixture. It should be understood that the wt.% of the first portion of zeolite and the wt.% of the second portion of zeolite can be the same or different. In some embodiments, each of the first portion of zeolite and the second portion of zeolite can independently account for 10 wt.% to 90 wt.%, such as 10 wt.% to 20 wt.%, 20 wt.% to 30 wt.%, 30 wt.% to 40 wt.%, 40 wt.% to 50 wt.%, 50 wt.% to 60 wt.%, 60 wt.% to 70 wt.%, 70 wt.% to 80 wt.%, 80 wt.% to 90 wt.% or any combination of one or more of these ranges.

[0028] In one or more embodiments, the catalyst composition may comprise one or more binder materials, such as alumina-containing compounds or silica-containing compounds (including compounds containing both alumina and silica). As used throughout this disclosure, "binder material" refers to a material that can be used to "bond" or otherwise hold the zeolite and matrix together in the microspheres. The binder material can improve the abrasion resistance of the catalyst particles. For example, the binder material may comprise alumina (e.g., amorphous alumina), aluminosilicate (e.g., amorphous aluminosilicate), or silica (e.g., amorphous silica). According to one or more embodiments, the binder material may comprise boehmite. As used in this disclosure, "boehmite" refers to an aluminum-containing compound with the chemical composition AlO(OH) consisting of crystalline boehmite. Suitable boehmite includes CATAPAL® alumina, available from Sasol Limited in Johannesburg, South Africa. Boehmite also refers to aluminum hydroxide oxide, but boehmite typically contains more water than boehmite. Binder materials, such as boehmite, can be soluble in acids (e.g., monocarboxylic acids, such as nitric acid (“HNO3”) or hydrochloric acid (“HCl”)).

[0029] According to one or more embodiments, the catalyst composition may comprise 10 wt.% to 30 wt.% of a binder. For example, the catalyst composition may comprise 10 wt.% to 15 wt.% of a binder, 15 wt.% to 20 wt.% of a binder, 20 wt.% to 25 wt.% of a binder, 25 wt.% to 30 wt.% of a binder, or any combination of one or more of these ranges. It should be understood that in one or more embodiments, the catalyst composition may comprise any of the disclosed binder materials in the disclosed wt.% range. In other embodiments, the catalyst composition may comprise any combination of two or more binder materials in any amount within the disclosed wt.% range.

[0030] In one or more embodiments, the catalyst composition may comprise one or more matrix materials. As used throughout this disclosure, "matrix material" may refer to a clay material, such as kaolin. Without being bound by theory, it is believed that the matrix material of the catalyst composition possesses both physical and catalytic functions. Physical functions include providing particle integrity and abrasion resistance, acting as a heat transfer medium, and providing a porous structure to allow hydrocarbon diffusion into and out of the catalyst microspheres. The matrix also influences catalyst selectivity, product quality, and resistance to poisoning. For those reactions that directly involve relatively large molecules, the matrix material may tend to have the strongest influence on overall catalytic performance.

[0031] In one or more embodiments, the matrix material comprises kaolin. As used herein, "kaolin" refers to a clay material having a relatively large amount (e.g., at least about 50 wt.%, at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, or even at least 95 wt.%) of kaolinite, which may be represented by the chemical formula Al₂Si₂O₅(OH)₄. Kaolin is sometimes referred to as "porcelain clay". In other embodiments, the matrix material may comprise other clay materials.

[0032] In one or more embodiments, the catalyst composition may comprise 10 wt.% to 50 wt.% of a matrix material. For example, the catalyst composition may comprise 10 wt.% to 15 wt.% of a matrix material, 15 wt.% to 20 wt.% of a matrix material, 20 wt.% to 25 wt.% of a matrix material, 25 wt.% to 30 wt.% of a matrix material, 30 wt.% to 35 wt.% of a matrix material, 35 wt.% to 40 wt.% of a matrix material, 40 wt.% to 45 wt.% of a matrix material, 45 wt.% to 50 wt.% of a matrix material, or any combination of one or more of these ranges. It should be understood that in one or more embodiments, the cracking catalyst may comprise any one of the disclosed matrix materials in the disclosed wt.% range. In other embodiments, the cracking catalyst may comprise any combination of two or more matrix materials in the disclosed wt.% range.

[0033] Due to its excellent chemical inertness, high heat resistance and impact resistance, low thermal expansion, and excellent thermal conductivity, it can be added to the formulation as an additive to achieve specific properties. Metal carbides (MC) in the formulation can act as diluents, increasing the density of catalyst particles and improving their thermal conductivity. Higher thermal conductivity helps stabilize the temperature distribution of the catalyst bed and reduce hot / cold spots. In one or more embodiments, the catalyst composition may further comprise silicon carbide particles. In one or more embodiments, the catalyst composition may further comprise 1 wt.% to 40 wt.% silicon carbide particles. For example, the catalyst composition may comprise 1 wt.% to 5 wt.%, 5 wt.% to 10 wt.%, 10 wt.% to 15 wt.%, 15 wt.% to 20 wt.%, 20 wt.% to 25 wt.%, 25 wt.% to 30 wt.%, 30 wt.% to 35 wt.%, 35 wt.% to 40 wt.%, or any combination of one or more of these ranges. In one or more embodiments, the silicon carbide particles may have an average particle size of 50 nm to 900 nm. For example, silicon carbide particles may have an average particle size of 50 nm to 100 nm, 100 nm to 150 nm, 150 nm to 200 nm, 200 nm to 250 nm, 250 nm to 300 nm, 300 nm to 350 nm, 350 nm to 400 nm, 400 nm to 450 nm, 450 nm to 500 nm, 500 nm to 550 nm, 550 nm to 600 nm, 600 nm to 650 nm, 650 nm to 700 nm, 700 nm to 750 nm, 750 nm to 800 nm, 800 nm to 850 nm, 850 nm to 900 nm, or any combination of one or more of these ranges.

[0034] In one or more embodiments, the catalyst composition can be formed as particles. The particles can be shaped particles, such as spheres, or their shape can be irregular or spherical. The particle size refers to the maximum length of the particle measured along its longest distance from one side to the other. For example, the size of a spherical particle is equal to its diameter, or the maximum length of a cuboid particle is equal to the hypotenuse extending from opposite corners. The particles of the catalyst composition can have an average diameter from 0.05 micrometers to 100 micrometers, such as 0.05 micrometers to 1 micrometer, 1 micrometer to 10 micrometers, 10 micrometers to 20 micrometers, 20 micrometers to 30 micrometers, 30 micrometers to 40 micrometers, 40 micrometers to 50 micrometers, 50 micrometers to 60 micrometers, 60 micrometers to 70 micrometers, 70 micrometers to 80 micrometers, 80 micrometers to 90 micrometers, 90 micrometers to 100 micrometers, or any combination of one or more of these ranges. The average particle size can be measured using laser diffraction analysis.

[0035] In one or more embodiments, the first and second zeolite components may be present on the same particles. In other embodiments, the first and second zeolite components may each be present on different particles. In one or more embodiments, the first, second, third, and fourth zeolite components may be present on the same or different particles in any combination; for example, the first and second zeolite components may be present together on one type of particle, and the third and fourth zeolite components may be present together on another type of particle.

[0036] In one or more embodiments, the catalyst compositions of this disclosure can be used to process hydrocarbons. In one or more embodiments, a method of processing hydrocarbons may include feeding a hydrocarbon feedstock into a reactor, contacting the hydrocarbon feedstock with the catalyst composition of this disclosure to generate a product stream, and discharging the product stream from the reactor. Referring now to FIG1, an exemplary fluidized catalytic cracking (FCC) system that can be used with the catalyst compositions and methods of this disclosure is shown. In FIG1, FCC system 100 includes line 111 through which a hydrocarbon feedstock is supplied. The hydrocarbon feedstock may typically contain hydrocarbon substances. In embodiments, the hydrocarbon substance in the hydrocarbon feedstream may be crude oil. As used in this disclosure, the term "crude oil" should be understood to mean a liquid, gas, or mixture of liquids and gases, which in some embodiments includes impurities such as sulfur-containing compounds, nitrogen-containing compounds, and metallic compounds that have not undergone significant separation or reaction processes. Crude oil is different from crude oil fractions. In some embodiments, the crude oil feedstock may be a minimally treated light crude oil to provide a total metal (Ni+V) content of less than 20 parts per million (ppmw) and a Conradson carbon residue of less than 10 wt%. Such minimally treated material may be considered as crude oil as described herein.

[0037] While this specification and examples may specify crude oil as the hydrocarbon feedstock, it should be understood that the FCC system 100 described with respect to the embodiment of Figure 1 is applicable to the conversion of a variety of hydrocarbons that may be present in the hydrocarbon feedstock, including but not limited to crude oil, vacuum residue, oil sands, bitumen, atmospheric residue, vacuum gas oil, demetallized oil, naphtha stream, other hydrocarbon streams, or combinations thereof. The hydrocarbon feedstock may contain one or more non-hydrocarbon components, such as one or more heavy metals, sulfur compounds, nitrogen compounds, inorganic components, or other non-hydrocarbon compounds. If the hydrocarbon feedstock is crude oil, its American Petroleum Institute (API) density may be between 22 and 40 degrees. For example, the hydrocarbon feedstock used may be Arab Heavy crude oil (API density approximately 28 degrees), Arab Medium crude oil (API density approximately 30 degrees), Arab Light crude oil (API density approximately 33 degrees), or Arab Extra Light crude oil (API density approximately 39 degrees). It should be understood that, as used in this disclosure, "hydrocarbon feedstock" may refer to raw hydrocarbon material (such as crude oil) that has not been treated, separated or otherwise refined, or may refer to hydrocarbon material that has undergone some degree of processing (such as treatment, separation, reaction, purification or other operations) before being introduced from pipeline 111 into FCC system 100.

[0038] Generally, the composition of hydrocarbon feedstocks can contain a relatively large number of chemical substances based on their boiling points. For example, the composition of hydrocarbon feed stream 102 can make the difference between the 5 wt.% boiling point and the 95 wt.% boiling point of hydrocarbon feed stream 102 at least 100°C, at least 200°C, at least 300°C, at least 400°C, at least 500°C, or even at least 600°C.

[0039] Returning to Figure 1, the feedstock enters line 112, which delivers steam or gas for dilution. The mixture then enters riser 110, which is the reaction zone. A regenerated catalyst (which may be a catalyst composition of this disclosure) is also supplied to riser 110 via line 113. The mixing of steam or gas with the feedstock improves the selectivity for light olefins while allowing the regenerated catalyst to flow efficiently. The regenerated catalyst is supplied from regenerator 103 along line 113, which is a separate entity from riser 110. The internal temperature of regenerator 103 needs to be very high to achieve feedstock vaporization.

[0040] Steam supplied by line 112 fluidizes the feedstock and catalyst mixed at the bottom of riser 110 and moves the mixture to the top of the riser as it undergoes cracking. Because cracking is an endothermic process, the temperature of the mixture decreases, thus lowering the temperature at the top of riser 110. The product reaching the top of riser 110 then enters stripper 102, which separates the gaseous products from the solid products. To improve the efficiency of the separation process, a cyclone separator can be used. The separated gas is discharged along line 115, and the separated catalyst moves to the bottom of stripper 102. Stripping steam is supplied along line 116 to the bottom of the stripper to remove unseparated hydrocarbon reaction products. The catalyst is transferred along line 117 to regenerator 103 under the control of valve 118. In the regenerator, coke adhering to the catalyst interacts with oxidant supplied along line 120, causing the coke to be converted into carbon monoxide or carbon dioxide, which is discharged along line 119. The regenerated catalyst is supplied back to riser 110 along line 113. Valve 121 controls the amount of regenerated catalyst flowing along pipeline 113.

[0041] In the aforementioned FCC process, the cracking reaction takes place in a riser or downcomer, with the catalyst and feedstock flowing together in an entrained stream and separated using a cyclone separator and stripper. The coked catalyst is regenerated in a separate vessel operating at higher temperatures and residence times. Other suitable systems utilizing the catalyst compositions of this disclosure include those described in U.S. Patent No. 11,445,625, U.S. Patent Publication No. 2022 / 0033714, and U.S. Application No. 18 / 059,761, the entire contents of which are incorporated herein by reference.

[0042] Various embodiments of the catalyst compositions described in the examples will be further illustrated by the following examples. These examples are illustrative in nature and should not limit the subject matter of this disclosure.

[0043] Example 1 - Preparation of Catalyst Compositions Various catalyst compositions were prepared, each containing different amounts of ZSM-5 zeolite with a specific SAR. The ZSM-5 zeolite was added to a homogeneous liquid slurry formed from kaolin, alumina, and distilled water. Silica was then added to the formed gel. The mixture was mechanically mixed until a homogeneous mixture was obtained. The catalyst composition was then calcined at 550°C for 4 to 6 hours. The specific composition of the catalyst composition is recorded in Table 1. Furthermore, all examples included additional particles prepared in a similar manner to the ZSM-5 particles, but with Y zeolite added to the homogeneous liquid slurry instead of ZSM-5. The composition of these particles is recorded in Table 2.

[0044] Table 1

[0045] Table 2

[0046] Example 2 - Catalytic Testing: The conversion and selectivity of the catalyst compositions prepared in Example 1 were determined using a Micro Activity Test (MAT) device. All catalyst compositions in Table 1 were mixed with a certain amount of catalyst composition B particles from Table 2. The final formulation used in the test was obtained by physically mixing the two types of particles at a weight ratio of 50:50. Prior to the catalytic testing, all catalyst compositions were hydrothermally treated at 810°C and 100% steam for 2 to 3 hours. The test was conducted at a catalyst-to-oil ratio of 5. Arab Light crude oil was added to the reactor over a 30-second feed time and the reaction was carried out at 500°C. The results of the catalytic testing are shown in Table 3.

[0047] Table 3

[0048] As shown in Table 3, the overall conversion rates of Examples 1-12 are similar to those of Comparative Example A, which contains only a single fraction of zeolite with a single SAR. All examples except Example 12 show higher gasoline yields than Comparative Example A, and some examples, such as Example 7, exhibit both increased gasoline yields and higher light olefin yields. Overall, Examples 1-12 demonstrate that by balancing the proportions of zeolites with different SARs, selectivity for one or more target products can be improved without sacrificing overall reaction conversion.

[0049] This disclosure includes several aspects. A first aspect is a catalyst composition comprising 10 wt.% to 50 wt.% of a matrix material, 10 wt.% to 30 wt.% of a binder, and 30 wt.% to 70 wt.% of a zeolite mixture. The zeolite mixture may contain all the zeolites in the catalyst composition. The zeolite mixture may contain at least a first portion of zeolite and a second portion of zeolite. The first portion of zeolite may consist of zeolites with a silicon-to-aluminum molar ratio within a first range and may constitute at least 10 wt.% of the zeolite mixture. The second portion of zeolite may consist of zeolites with a silicon-to-aluminum molar ratio within a second range and may constitute at least 10 wt.% of the zeolite mixture. The silicon-to-aluminum molar ratio range of the first portion of zeolite does not overlap with the range of the second portion of zeolite and may differ by at least 5. The midpoint of the silicon-to-aluminum molar ratio range of the second portion of zeolite minus the midpoint of the silicon-to-aluminum molar ratio range of the first portion of zeolite may equal at least 15.

[0050] On the other hand, it is any of the foregoing aspects or a combination thereof, wherein the first portion of the zeolite has a silica-alumina molar ratio of 25 to 35, and the second portion of the zeolite has a silica-alumina molar ratio of 250 to 300.

[0051] On the other hand, it is any of the foregoing aspects or combinations thereof, wherein the zeolite mixture further comprises a third portion of zeolite, wherein: the third portion of zeolite consists of zeolites with a silicon-aluminum molar ratio in a third range, the silicon-aluminum molar ratio range of the third portion of zeolite does not overlap with the silicon-aluminum molar ratio range of the second portion of zeolite, and the midpoint of the silicon-aluminum molar ratio range of the third portion of zeolite minus the midpoint of the silicon-aluminum molar ratio range of the second portion of zeolite equals at least 15.

[0052] On the other hand, it is any of the foregoing aspects or combinations thereof, wherein the first portion of the zeolite has a silica-alumina molar ratio of 25 to 35, the second portion of the zeolite has a silica-alumina molar ratio of 40 to 60, and the third portion of the zeolite has a silica-alumina molar ratio of 70 to 90.

[0053] On the other hand, it is any of the foregoing aspects or combinations thereof, wherein the first portion of the zeolite has a silica-alumina molar ratio of 40 to 60, the second portion of the zeolite has a silica-alumina molar ratio of 70 to 90, and the third portion of the zeolite has a silica-alumina molar ratio of 250 to 300.

[0054] On the other hand, it is any of the foregoing aspects or combinations thereof, wherein the first portion of the zeolite has a silica-alumina molar ratio of 25 to 35, the second portion of the zeolite has a silica-alumina molar ratio of 70 to 90, and the third portion of the zeolite has a silica-alumina molar ratio of 250 to 300.

[0055] On the other hand, it is any of the foregoing aspects or combinations thereof, wherein the zeolite mixture further comprises a fourth portion of zeolite, wherein: the fourth portion of zeolite consists of zeolites with a silicon-aluminum molar ratio in a fourth range, the silicon-aluminum molar ratio range of the fourth portion of zeolite does not overlap with the silicon-aluminum molar ratio range of the third portion of zeolite, and the midpoint of the silicon-aluminum molar ratio range of the fourth portion of zeolite minus the midpoint of the silicon-aluminum molar ratio range of the third portion of zeolite equals at least 15.

[0056] On the other hand, it is any of the foregoing aspects or a combination thereof, wherein the midpoint of the range of the silica-alumina molar ratio of the first and second zeolites is 1 to 500.

[0057] On the other hand, it is any of the foregoing aspects or a combination thereof, wherein the zeolite mixture comprises ZSM-5 zeolite.

[0058] On the other hand, it is any of the foregoing aspects or a combination thereof, wherein the zeolite mixture comprises Y zeolite.

[0059] On the other hand, it is any of the foregoing aspects or a combination thereof, wherein the catalyst composition is formed in particulate form.

[0060] On the other hand, it is any of the foregoing aspects or a combination thereof, wherein the particles have an average particle size of 0.05 micrometers to 100 micrometers.

[0061] On the other hand, it is any of the foregoing aspects or a combination thereof, wherein the first portion of zeolite and the second portion of zeolite each exist on the same particles.

[0062] On the other hand, it is any of the foregoing aspects or a combination thereof, wherein the first portion of zeolite and the second portion of zeolite each exist on different particles.

[0063] On the other hand, it is any of the foregoing aspects or a combination of the foregoing aspects, wherein the matrix material is kaolin.

[0064] On the other hand, it is any of the foregoing aspects or a combination thereof, wherein the adhesive is silicon dioxide, aluminum oxide or a combination thereof.

[0065] On the other hand, it is any of the foregoing aspects or a combination thereof, wherein the catalyst composition further comprises 1 wt.% to 40 wt.% silicon carbide particles.

[0066] On the other hand, it is any of the foregoing aspects or a combination thereof, wherein the silicon carbide particles have an average particle size of 50 nm to 900 nm.

[0067] On the other hand, there is any of the foregoing aspects or combinations thereof, wherein the catalyst composition is substantially composed of 10 wt.% to 50 wt.% of a matrix material, 10 wt.% to 30 wt.% of a binder, and 30 wt.% to 70 wt.% of a zeolite mixture. The zeolite mixture comprises all the zeolites in the catalyst composition. The zeolite mixture comprises at least a first portion of zeolite and a second portion of zeolite. The first portion of zeolite consists of zeolites with a silicon-to-aluminum molar ratio within a first range and constitutes at least 10 wt.% of the zeolite mixture. The second portion of zeolite consists of zeolites with a silicon-to-aluminum molar ratio within a second range and constitutes at least 10 wt.% of the zeolite mixture. The silicon-to-aluminum molar ratio range of the first portion of zeolite does not overlap with and differs from the silicon-to-aluminum molar ratio range of the second portion of zeolite by at least 5. The midpoint of the silicon-to-aluminum molar ratio range of the second portion of zeolite minus the midpoint of the silicon-to-aluminum molar ratio range of the first portion of zeolite is at least 15.

[0068] Another method is a hydrocarbon processing method comprising feeding a hydrocarbon feedstock into a reactor, contacting the hydrocarbon feedstock with a catalyst composition of any of the foregoing aspects or combinations thereof to generate a product stream; and discharging the product stream from the reactor.

[0069] Having described the subject matter of this disclosure in detail and with reference to specific embodiments, it should be noted that the various details set forth in this disclosure should not be construed as implying any relation to elements that constitute essential components of the various embodiments described herein, even where specific elements are shown in each of the accompanying drawings. Rather, the appended claims should be regarded as the sole expression of the breadth of this disclosure and the respective scope of the various embodiments described herein. Furthermore, it will be apparent that various modifications and variations may be made without departing from the scope of the appended claims.

[0070] It should be noted that the term "wherein" is used as a transitional phrase in one or more of the following claims. In defining this technology, it should be noted that this term is introduced in the claims as an open-ended transitional phrase used to introduce a description of a series of features of the structure, and should be interpreted in a similar manner to the more commonly used open-ended prepositional term "comprising".

[0071] In order to define this technology, the transitional phrase “consistent essentially of…” may be introduced in the claims to limit the scope of one or more claims to the stated elements, components, materials or method steps as well as any unstated elements, components, materials or method steps, provided that such unstated elements, components, materials or method steps do not materially affect the novel features of the claimed subject matter.

[0072] It should be understood that any two quantitative values ​​assigned to a property can constitute a range for that property, and all combinations of ranges formed by all descriptive quantitative values ​​for a given property are considered in this disclosure. It should be understood that in some embodiments, the compositional range of a chemical component in a stream or reactor should be understood as including a mixture of isomers of that component. For example, specifying the compositional range of butene may include a mixture of various isomers of butene. It should be understood that these embodiments provide compositional ranges for various streams, and the total amount of isomers of a particular chemical composition can constitute a range.

Claims

1. A catalyst composition comprising: 10 wt.% to 50 wt.% of a matrix material; 10 wt.% to 30 wt.% of a binder; and 30 wt.% to 70 wt.% of a zeolite mixture, wherein: The zeolite mixture comprises all the zeolites in the catalyst composition; the zeolite mixture comprises at least a first portion of zeolite and a second portion of zeolite; the first portion of zeolite consists of zeolites with a silicon-to-aluminum molar ratio within a first range and accounts for at least 10 wt.% of the zeolite mixture; the second portion of zeolite consists of zeolites with a silicon-to-aluminum molar ratio within a second range and accounts for at least 10 wt.% of the zeolite mixture; the silicon-to-aluminum molar ratio range of the first portion of zeolite does not overlap with the silicon-to-aluminum molar ratio range of the second portion of zeolite and differs from it by at least 5; the midpoint of the silicon-to-aluminum molar ratio range of the second portion of zeolite minus the midpoint of the silicon-to-aluminum molar ratio range of the first portion of zeolite equals at least 15.

2. The catalyst composition according to claim 1, wherein, The first portion of zeolite has a silica-alumina molar ratio of 25 to 35; and the second portion of zeolite has a silica-alumina molar ratio of 250 to 300.

3. The catalyst composition according to claim 1 or claim 2, wherein, The zeolite mixture further comprises a third zeolite component, wherein: the third zeolite component consists of zeolites with a silicon-aluminum molar ratio within a third range; the silicon-aluminum molar ratio range of the third zeolite component does not overlap with the silicon-aluminum molar ratio range of the second zeolite component; and the midpoint of the silicon-aluminum molar ratio range of the third zeolite component minus the midpoint of the silicon-aluminum molar ratio range of the second zeolite component equals at least 15.

4. The catalyst composition according to claim 3, wherein, The first portion of zeolite has a silicon-to-aluminum molar ratio of 25 to 35; the second portion of zeolite has a silicon-to-aluminum molar ratio of 40 to 60; and the third portion of zeolite has a silicon-to-aluminum molar ratio of 70 to 90.

5. The catalyst composition according to claim 3, wherein, The first portion of zeolite has a silica-alumina molar ratio of 40 to 60; the second portion of zeolite has a silica-alumina molar ratio of 70 to 90; and the third portion of zeolite has a silica-alumina molar ratio of 250 to 300.

6. The catalyst composition according to claim 3, wherein, The first portion of zeolite has a silicon-to-aluminum molar ratio of 25 to 35; the second portion of zeolite has a silicon-to-aluminum molar ratio of 70 to 90; and the third portion of zeolite has a silicon-to-aluminum molar ratio of 250 to 300.

7. The catalyst composition according to claim 3, wherein, The zeolite mixture further comprises a fourth zeolite component, wherein: the fourth zeolite component consists of zeolites with a silicon-aluminum molar ratio within a fourth range; the silicon-aluminum molar ratio range of the fourth zeolite component does not overlap with the silicon-aluminum molar ratio range of the third zeolite component; and the midpoint of the silicon-aluminum molar ratio range of the fourth zeolite component minus the midpoint of the silicon-aluminum molar ratio range of the third zeolite component equals at least 15.

8. The catalyst composition according to any one of claims 1 to 7, wherein, The zeolite mixture contains ZSM-5 zeolite; the zeolite mixture contains Y zeolite; or the zeolite mixture contains both ZSM-5 zeolite and Y zeolite.

9. The catalyst composition of claim 1 according to any one of claims 1 to 8, wherein, The catalyst composition is formed in particulate form.

10. The catalyst composition according to claim 9, wherein, The first and second portions of zeolite each exist on the same particles.

11. The catalyst composition according to claim 9, wherein, The first and second parts of zeolite exist on different particles.

12. The catalyst composition according to any one of claims 1 to 11, wherein at least one of the following is true: the matrix material is kaolin; and the binder is silica, alumina, or a combination thereof.

13. The catalyst composition according to any one of claims 1 to 12, wherein, It also contains 1 wt.% to 40 wt.% silicon carbide particles.

14. A catalyst composition comprising essentially the following: 10 wt.% to 50 wt.% matrix material; The catalyst mixture comprises 10 wt.% to 30 wt.% of a binder; and 30 wt.% to 70 wt.% of a zeolite mixture, wherein the zeolite mixture contains all the zeolites in the catalyst composition; the zeolite mixture contains at least a first portion of zeolite and a second portion of zeolite; the first portion of zeolite consists of zeolites with a silicon-aluminum molar ratio in a first range; the second portion of zeolite consists of zeolites with a silicon-aluminum molar ratio in a second range; the silicon-aluminum molar ratio range of the first portion of zeolite does not overlap with the silicon-aluminum molar ratio range of the second portion of zeolite; and the midpoint of the silicon-aluminum molar ratio range of the second portion of zeolite minus the midpoint of the silicon-aluminum molar ratio range of the first portion of zeolite equals at least 15; the first portion of zeolite and the second portion of zeolite each account for at least 20 wt.% of the zeolite mixture.

15. A method for processing hydrocarbons, the method comprising: Hydrocarbon feedstock is fed into the reactor; The hydrocarbon feedstock is contacted with the catalyst composition according to claim 1 to generate a product stream; And to discharge the product stream from the reactor.

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