Process and bimetallic cracking additive for steam enhanced catalytic cracking of crude oil to produce light olefins and aromatics

Abstract

A process for upgrading a hydrocarbon feed comprises contacting the hydrocarbon feed with steam in the presence of a cracking catalyst composition under reaction conditions sufficient to cause at least a portion of the hydrocarbons in the hydrocarbon feed to undergo one or more cracking reactions to produce a steam catalytic cracking effluent comprising light olefins, light aromatic compounds, or both, wherein: the cracking catalyst composition comprises a cracking additive comprising a ZSM-5 zeolite, a first metal species and a second metal species wherein the first metal species and the second metal species are impregnated on the ZSM-5 zeolite, the first metal species comprising a metal or a metal oxide comprising the first metal, and the second metal species comprising a second metal; the second metal species comprises a metal or a metal oxide, the metal or metal oxide comprising a second metal, and the second metal is different from the first metal.

Description

Cross-references to related applications

[0001] This application claims priority to U.S. Patent Application Serial No. 18 / 181,648, filed March 10, 2023, entitled “Method for Steam-Enhanced Catalytic Cracking of Crude Oil to Produce Light Olefins and Aromatics and Bimetallic Cracking Additives,” the entire contents of which are incorporated herein by reference. Technical Field

[0002] This disclosure relates to methods and catalysts for processing hydrocarbon materials, and in particular to methods and cracking catalyst compositions for steam-enhanced catalytic cracking of crude oil to produce olefins, aromatic compounds, or both. Background Technology

[0003] The growing global demand for higher-value petrochemical products and chemical intermediates remains a significant challenge for many integrated refineries. In particular, the production of valuable light olefins such as ethylene and propylene is of particular interest, as pure olefin streams are considered fundamental materials for polymer synthesis. Furthermore, light aromatic compounds, such as benzene, toluene, and mixed xylenes, can be used as fuel blending components or converted into higher-value chemical products and intermediates that can serve as base materials in chemical synthesis methods. Petrochemical feedstocks such as crude oil can be converted into petrochemicals, such as fuel blending components, chemical products, and intermediates, such as light olefins and aromatic compounds, which are fundamental intermediates in much of the petrochemical industry. Crude oil is typically distilled and then subjected to various reforming, solvent treatment, and hydroconversion processes to produce a range of desired fuels, lubricants, chemicals, and chemical feedstocks. Traditional refining systems often combine multiple complex refining units with petrochemical plants to produce higher-value petrochemical products and intermediates. Summary of the Invention

[0004] Therefore, there is a ongoing need for cracking catalysts and methods for steam-enhanced catalytic cracking of crude oil feedstocks and other hydrocarbon feedstocks to produce higher yields of light olefins, light aromatic compounds, or both. This disclosure relates to a method for upgrading hydrocarbon feedstocks. The method includes contacting the hydrocarbon feedstock with steam in the presence of a cracking catalyst composition under reaction conditions sufficient to cause at least a portion of the hydrocarbons in the feedstock to undergo one or more cracking reactions to produce a steam catalytic cracking effluent comprising light olefins, light aromatic compounds, or both. The cracking catalyst composition comprises a bimetallic cracking additive. The cracking additive comprises ZSM-5 zeolite, a first metal type, and a second metal type, wherein the first metal type and the second metal type are impregnated on the ZSM-5 zeolite. The first metal type may comprise a metal or metal oxide comprising a first metal selected from the group consisting of chromium, iron, platinum, molybdenum, cerium, lanthanum, and zinc. The second metal type may comprise a metal or metal oxide comprising a second metal different from the first metal, and the second metal may be selected from the group consisting of chromium, iron, platinum, molybdenum, cerium, lanthanum, and zinc. In embodiments, the cracking catalyst composition may further include a zeolite catalyst, which is different from the cracking additive and is used in combination with the cracking additive.

[0005] According to one or more aspects of this disclosure, a method for upgrading a hydrocarbon feedstock includes: contacting the hydrocarbon feedstock with steam in the presence of a cracking catalyst composition under reaction conditions sufficient to cause at least a portion of the hydrocarbons in the hydrocarbon feedstock to undergo one or more cracking reactions, to produce a steam catalytic cracking effluent comprising light olefins, light aromatic compounds, or both. The cracking catalyst composition comprises a cracking additive. The cracking additive comprises ZSM-5 zeolite, a first metal type, and a second metal type. The first metal type and the second metal type are impregnated on the ZSM-5 zeolite. The first metal type comprises a metal or metal oxide comprising a first metal selected from the group consisting of chromium, iron, platinum, molybdenum, cerium, lanthanum, and zinc. The second metal type comprises a metal or metal oxide comprising a second metal selected from the group consisting of chromium, iron, platinum, molybdenum, cerium, lanthanum, and zinc. The second metal is different from the first metal.

[0006] According to one or more other aspects of this disclosure, a cracking additive for upgrading hydrocarbon feedstock comprises ZSM-5 zeolite, a first metal type, and a second metal type. The first and second metal types are impregnated onto the ZSM-5 zeolite. The first metal type comprises a metal or metal oxide comprising a first metal selected from the group consisting of chromium, iron, platinum, molybdenum, cerium, lanthanum, and zinc. The second metal type comprises a metal or metal oxide comprising a second metal selected from the group consisting of chromium, iron, platinum, molybdenum, cerium, lanthanum, and zinc. The second metal is different from the first metal.

[0007] According to one or more other aspects of this disclosure, a cracking catalyst composition for upgrading a hydrocarbon feedstock comprises a zeolite catalyst and a cracking additive comprising ZSM-5 zeolite, a first metal type, and a second metal type. The first and second metal types are impregnated onto the ZSM-5 zeolite. The first metal type comprises a metal or metal oxide comprising a first metal selected from the group consisting of chromium, iron, platinum, molybdenum, cerium, lanthanum, and zinc. The second metal type comprises a metal or metal oxide comprising a second metal selected from the group consisting of chromium, iron, platinum, molybdenum, cerium, lanthanum, and zinc. The second metal is different from the first metal.

[0008] Additional features and advantages of various aspects of this disclosure will be set forth in the following detailed description, and some features and advantages will be apparent to those skilled in the art from the detailed description or will be recognized by practice of various aspects of this disclosure. Attached Figure Description

[0009] The patent or application documents must contain at least one color drawing. The Patent Office will, upon request and after payment of the necessary fees, provide a copy of the publication of this patent or patent application with the color drawing.

[0010] A better understanding of the detailed description of this disclosure can be achieved by reading in conjunction with the following accompanying figures, in which: Figure 1 A general flow diagram of a fixed-bed reactor system for steam catalytic cracking of crude oil to produce light olefins and light aromatic compounds is schematically depicted according to one or more embodiments shown and described in this disclosure. Figure 2 A flowchart is depicted of a method for producing a cracking additive comprising a first metal species and a second metal species impregnated on ZSM-5 zeolite, according to one or more embodiments shown and described in this disclosure. Figure 3 A general flow diagram of a fixed-bed reactor system for evaluating a cracking catalyst composition comprising cracking additives for steam catalytic cracking of crude oil is schematically depicted according to one or more embodiments shown and described in this disclosure. Figure 4 The product yields obtained by steam catalytic cracking of AXL crude oil using the cracking catalyst compositions of Examples 8 to 13 and Comparative Example 14, according to one or more embodiments shown and described in this disclosure, are illustrated by graphs. Figure 5A SEM images of Embodiment 6 according to one or more embodiments shown and described in this disclosure are presented; and Figure 5B-5FThe corresponding element mappings of Embodiment 6, namely Si(b), Al(c), O(d), Fe(e), and Ce(f), according to one or more embodiments shown and described in this disclosure are illustrated.

[0011] In description Figure 1 and Figure 3 In simplified schematic diagrams, many valves, temperature sensors, electronic controllers, etc., which are well known to and likely used by those skilled in the art, may not be included. Furthermore, they are typically included in, for example... Figure 1 and Figure 3 Accompanying components in the illustrated system, such as air supply units, heat exchangers, and buffer tanks, may not be included. However, those skilled in the art will understand that these components are all within the scope of this disclosure.

[0012] also, Figure 1 and Figure 3 In the simplified diagram, the arrows indicate process flows. However, these arrows can also refer to transfer lines, which transfer process flows between two or more system components. Arrows connected to one or more system components indicate inlets or outlets within a given system component, while arrows connected to only one system component indicate system outlet flows leaving the system or system inlet flows entering the system. The direction of the arrows generally corresponds to the primary direction of movement of the process flow represented by the arrow or the process flow contained within the physical transfer line.

[0013] Figure 1 and Figure 3 Arrows in a simplified diagram can also indicate process steps that transfer a process flow from one system component to another. For example, an arrow pointing from a first system component to a second system component can indicate "delivering" a process flow from the first system component to the second system component. This can include the process flow "leaving" or being "removed" from the first system component, as well as "introducing" the process flow into the second system component.

[0014] The various aspects will now be described in more detail, some of which are shown in the accompanying drawings. Detailed Implementation

[0015] This disclosure relates to a cracking catalyst composition comprising a cracking additive and a method for steam-enhanced catalytic cracking of crude oil using the cracking catalyst composition to produce higher yields of light olefins, light aromatic compounds, or both. The method for upgrading a hydrocarbon feedstock includes contacting the hydrocarbon feedstock with steam in a steam catalytic cracking reactor, in the presence of the cracking catalyst composition, under reaction conditions sufficient to cause at least a portion of the hydrocarbons in the hydrocarbon feedstock to undergo one or more cracking reactions, to produce a steam catalytic cracking effluent comprising light olefins, light aromatic compounds, or both. The cracking catalyst composition comprises at least a cracking additive, which may be a bimetallic cracking additive. The cracking additive may comprise a first metal and a second metal, both impregnated on ZSM-5 zeolite. The first metal may comprise a metal or metal oxide comprising a first metal selected from the group consisting of chromium, iron, platinum, molybdenum, cerium, lanthanum, and zinc. The second metal may comprise a metal or metal oxide comprising a second metal selected from the group consisting of chromium, iron, platinum, molybdenum, cerium, lanthanum, and zinc. The second metal is different from the first metal. In embodiments, the cracking catalyst composition may further include a zeolite catalyst that is different from the cracking additive and is combined with the cracking additive.

[0016] Cracking additives can be prepared by methods including: preparing a zeolite mixture comprising ZSM-5 zeolite and water; simultaneously adding a metal precursor mixture to the zeolite mixture to produce a combined mixture, wherein the metal precursor mixture comprises a first metal precursor, a second metal precursor, and water; stirring the combined mixture at a temperature of 10°C to 30°C for a mixing time of 1 hour to 5 hours; simultaneously heating the combined mixture to an evaporation temperature and pressure, such as an evaporation temperature of 30°C to below 100°C at atmospheric pressure; and simultaneously maintaining the combined mixture at the evaporation temperature and pressure for a period of 1 hour to 24 hours. Maintaining the combined mixture at the evaporation temperature and pressure during mixing allows water to slowly evaporate from the combined mixture, thereby producing solid particles. Simultaneous slow evaporation of water from the combined mixture during mixing allows the metal precursors to disperse on the surface of the ZSM-5 zeolite. The method may further include calcining the solid particles at a temperature of 400°C to 800°C for 1 hour to 12 hours to produce the cracking additive. Compared to other conventional methods that impregnate metals or metal oxides onto zeolite surfaces, this method for preparing cracking additives allows for a higher degree of dispersion of the two metal species on the ZSM-5 zeolite surface. Compared to other commercially available catalysts, the higher dispersion of the two metal species on the ZSM-5 zeolite surface in this cracking additive can improve the conversion rate of crude oil in steam-enhanced catalytic cracking and increase the yield of light olefins, light aromatics, or both.

[0017] As used in this disclosure, the term "cracking" refers to a chemical reaction in which molecules having carbon-carbon bonds break down into more than one molecule by breaking one or more carbon-carbon bonds, or where cyclic molecules having carbon-carbon bonds are converted into acyclic molecules by breaking one or more carbon-carbon bonds. As used in this disclosure, the term "catalytic cracking" refers to cracking carried out in the presence of a catalyst. Some catalysts may possess multiple forms of catalytic activity, and the fact that a catalyst is activated for a particular function does not mean that the catalyst cannot be catalytically active for other functions.

[0018] As used in this disclosure, the term "catalyst" refers to any substance that can accelerate the rate of a particular chemical reaction (such as, but not limited to, cracking).

[0019] As used in this disclosure, the term "used catalyst" refers to a catalyst that has been in contact with reactants under reaction conditions but has not been regenerated in a regenerator or through a regeneration process. The "used catalyst" may have deposited coke on it and may include partially coked catalysts as well as fully coked catalysts. The amount of coke deposited on the "used catalyst" may be greater than the amount of coke remaining on the regenerated catalyst after regeneration. The "used catalyst" may also include a catalyst whose temperature has decreased due to contact with reactants (compared to the catalyst before contact with reactants).

[0020] As used in this disclosure, the term "regenerated catalyst" refers to a catalyst that is regenerated in a regenerator or by an in-place regeneration process after contact with reactants under reaction conditions, which involves heating the catalyst to a higher temperature, oxidizing it, and removing at least a portion of the coke or other organic contaminants from the catalyst to restore at least a portion of the catalyst's catalytic activity, or both. A "regenerated catalyst" may have less coke or organic contaminants, a higher temperature, or both, than a used catalyst; and may have higher catalytic activity than a used catalyst. Compared to a new catalyst that is not contacted with reactants in the cracking reaction zone and then regenerated, a "regenerated catalyst" may have more coke and reduced catalytic activity.

[0021] As used throughout this disclosure, the terms "butene" or "mixed butene" are used interchangeably and refer to isobutene, 1-butene, trans -2-Butene or Cis One or more combinations of -2-butenes. As used throughout this disclosure, the term "normal butenes" refers to 1-butene, trans -2-Butene or Cis One or more combinations of 2-butene. As used throughout this disclosure, the term "2-butene" refers to trans -2-Butene, Cis -2-Butene or combinations thereof.

[0022] As used in this disclosure, the term "initial boiling point" or "IBP" for a composition refers to the temperature at which the component with the lowest boiling point in the composition begins to change from the liquid phase to the gas phase. As used in this disclosure, the term "final boiling point" or "EBP" for a composition refers to the temperature at which the component with the highest boiling point in the composition changes from the liquid phase to the gas phase. Hydrocarbon mixtures can be characterized by a distillation profile, expressed as the boiling point temperature at which a specific weight percentage of the composition changes from the liquid phase to the gas phase.

[0023] As used in this disclosure, the term "atmospheric boiling point temperature" refers to the boiling point temperature of a compound at atmospheric pressure.

[0024] As used in this disclosure, the terms "crude oil" or "whole crude oil" should be understood to mean a liquid, gas, or mixture of liquids and gases, and in some embodiments, includes impurities that have not undergone significant separation or reaction processes, such as, but not limited to, sulfur compounds, nitrogen compounds, and metallic compounds. Crude oil differs from crude oil fractions, which are obtained by fractionating crude oil through distillation. In embodiments, the crude oil feedstock may be a minimally processed light crude oil to provide a crude oil feedstock with a total metal (Ni+V) content of less than 5 parts per million by weight (ppmw) and a Conradson carbon residue of less than 5 wt.%.

[0025] As used in this disclosure, delivering a stream or effluent “directly” from one unit to another means delivering the stream or effluent from the first unit to the second unit without passing through an intermediate reaction system or separation system that would significantly alter the composition of the stream or effluent. Heat transfer devices (such as heat exchangers, preheaters, coolers, condensers, or other heat transfer equipment) and pressure devices (such as pumps, regulators, compressors, or other pressure devices) are not considered intermediate systems that would alter the composition of the stream or effluent. Combining two streams or effluents is also not considered an intermediate system that involves altering the composition of one or both of the combined streams or effluents.

[0026] As used in this disclosure, the terms "downstream" and "upstream" refer to the location of a component or unit operation in a processing system relative to the direction of material flow through the processing system. For example, if material flowing through the processing system encounters a first component before encountering a second component, the second component is considered "downstream" of the first component. Similarly, if material flowing through the processing system encounters a first component before encountering a second component, the first component is considered "upstream" of the second component.

[0027] As used in this disclosure, the term "effluent" refers to a stream delivered from a reactor, reaction zone, or separator after a particular reaction or separation. Typically, the composition of the effluent differs from that of the stream entering the reactor, reaction zone, or separator. It should be understood that, unless otherwise stated, when an effluent is delivered to another component or system, only a portion of the effluent may be delivered. For example, a slipstream or bleed stream may carry away some effluent, meaning that only a portion of the effluent may enter a downstream component or system. The terms "reaction effluent" and "reactor effluent" specifically refer to streams delivered from a reactor or reaction zone.

[0028] As used in this disclosure, the term "residence time" refers to the length of time that a reactant is in contact with a catalyst under reaction conditions (such as reaction temperature).

[0029] As used in this disclosure, the term "reactor" refers to any vessel, container, conduit, etc., in which one or more chemical reactions, such as, but not limited to, catalytic cracking reactions, can occur between one or more reactants in the presence of one or more catalysts. One or more "reaction zones" may be provided within the reactor. The term "reaction zone" refers to the volume within the reactor where a specific chemical reaction occurs.

[0030] As used in this disclosure, the terms "separation unit" and "separator" refer to any separation device or assembly of separation devices that at least partially separates one or more chemical components in a mixture from one another. For example, a separation system selectively separates different chemical components from one another to form one or more chemical fractions. Examples of separation systems include, but are not limited to, distillation columns, fractionators, flash tanks, separating tanks, knock-out pots, centrifuges, decanters, filters, traps, scrubbers, expansion devices, membranes, solvent extraction devices, adsorption devices, chemical separators, crystallizers, chromatographs, precipitators, evaporators, dryers, high-pressure separators, low-pressure separators, or combinations thereof. The separation processes described in this disclosure may not completely separate all of one chemical component from all of another chemical component. Rather, the separation processes described in this disclosure "at least partially" separate different chemical components from one another, and even if not explicitly stated, separation may include only partial separation.

[0031] It should be further understood that a stream may be named according to its components, and the components used to name the stream may be the main components of the stream (e.g., the components that constitute the largest portion of the stream, excluding inert diluent gases such as nitrogen, rare gases, etc., unless otherwise stated). It should also be understood that when a stream containing a certain component is disclosed as being delivered from one system component to another system component, it means that the component of the stream is disclosed as being delivered from said one system component to said other system component. For example, a disclosure of a “hydrocarbon stream” being delivered to or from a first system component to a second system component should be understood as equivalent to a disclosure of a “hydrocarbon” being delivered to or from a first system component to a second system component.

[0032] Traditional refining systems consist of multiple unit operations. Steam-enhanced catalytic cracking of crude oil can directly reduce the complexity of the refining process, such as reducing the number of unit operations required to process crude oil. Steam-enhanced catalytic cracking typically involves contacting the hydrocarbon feedstock with steam in the presence of a mordenite framework inverted (MFI) zeolite (such as ZSM-5). The selectivity for olefins in steam-enhanced catalytic cracking using ZSM-5 zeolite may be lower than expected.

[0033] This disclosure relates to the steam catalytic cracking of crude oil using a cracking catalyst composition to convert crude oil into higher-value hydrocarbon products, such as, but not limited to, light olefins, light aromatic compounds, or combinations thereof. The cracking catalyst composition may include at least a cracking additive having a first metal species and a second metal species impregnated on ZSM-5 zeolite. In embodiments, in addition to the cracking additive, the cracking catalyst composition may further include a zeolite catalyst different from the cracking additive. Without being bound by any particular theory, it is believed that the cracking additive prepared by the improved wet impregnation method of this disclosure allows for greater dispersibility of the first and second metal species on the ZSM-5 zeolite surface compared to cracking additives prepared by other standard impregnation methods. Therefore, the cracking additive of this disclosure can improve the selectivity for light olefins (such as ethylene, propylene, butene, or combinations thereof), light aromatic compounds, or both, compared to steam-enhanced catalytic cracking of crude oil using ZSM-5 zeolite without metal species or zeolite catalysts without cracking additives. This disclosure also relates to a cracking additive comprising a first metal type and a second metal type impregnated on ZSM-5 zeolite, and a method for preparing the cracking additive.

[0034] For reference Figure 1The method disclosed herein for converting hydrocarbon feed 102 into light olefins, light aromatic compounds, or both includes: contacting the hydrocarbon feed 102 with steam in the presence of a cracking catalyst composition 132 under reaction conditions sufficient to cause at least a portion of the hydrocarbons in the hydrocarbon feed 102 to undergo one or more cracking reactions, to produce a steam catalytic cracking effluent 140 comprising light olefins, light aromatic compounds, or both, wherein the cracking catalyst composition 132 comprises a cracking additive having a first metal type and a second metal type impregnated on ZSM-5 zeolite. In embodiments, in addition to the cracking additive, the cracking catalyst composition 132 may further comprise a zeolite catalyst different from the cracking additive, such as, but not limited to, a balanced catalyst.

[0035] Hydrocarbon feed 102 may include one or more heavy oils, such as, but not limited to, crude oil, bitumen, oil sands, shale oil, coal slurry, vacuum residue, tar sands, other heavy oil streams, or combinations thereof. It should be understood that, as used in this disclosure, "heavy oil" refers to crude hydrocarbons that have not undergone prior distillation, such as whole crude oil, or may refer to hydrocarbon oils that have undergone some degree of processing before being introduced into process 100 as hydrocarbon feed 102. The density of hydrocarbon feed 102 may be greater than or equal to 0.80 g / mL. The final boiling point (EBP) of hydrocarbon feed 102 may be greater than 565°C. The nitrogen concentration of hydrocarbon feed 102 may be less than or equal to 3000 parts per million (ppmw).

[0036] In this embodiment, hydrocarbon feed 102 may be crude oil, such as whole crude oil or synthetic crude oil. The American Petroleum Institute (API) gravity of the crude oil may be between 22 and 50 degrees, such as 22 to 40 degrees, 25 to 50 degrees, or 25 to 40 degrees. For example, hydrocarbon feed 102 may include extra light crude oil, light crude oil, medium crude oil, heavy crude oil, or a combination thereof. In this embodiment, hydrocarbon feed 102 may be light crude oil, such as, but not limited to, Arab Light export crude oil. Example characteristics of exemplary grades of Arab Light (AL) crude oil are provided in Table 1.

[0037] Table 1 - Examples of AL Export Raw Materials

[0038] In this implementation, hydrocarbon feed 102 may be Arab Extra Light (AXL) crude oil. Table 2 provides examples of the boiling point distribution of exemplary grades of AXL crude oil.

[0039] Table 2: Examples of AXL Raw Materials

[0040] When hydrocarbon feed 102 contains crude oil, the crude oil can be pure crude oil or crude oil that has undergone at least some treatment, such as desalting, solids separation, washing, or other treatments that do not alter the hydrocarbon composition of the crude oil. For example, hydrocarbon feed 102 can be desalted crude oil that has undergone desalting treatment. In embodiments, hydrocarbon feed 102 may include crude oil that has not undergone pretreatment, separation (e.g., distillation), or other operations or treatments that alter the hydrocarbon composition of the crude oil before it is introduced into system 100.

[0041] In an embodiment, the hydrocarbon feed 102 may be crude oil having the following boiling point profile: 5% wt% boiling temperature, 25% wt% boiling temperature, 50% wt% boiling temperature, 75% wt% boiling temperature, and 95% wt% boiling temperature. These respective boiling temperatures correspond to the temperatures at which a given weight percentage of the hydrocarbon feed stream boils. In an embodiment, the crude oil may have one or more of the following: 5% wt% boiling temperature less than or equal to 150°C; 25% wt% boiling temperature less than or equal to 225°C or less than or equal to 200°C; 50% wt% boiling temperature less than or equal to 500°C, less than or equal to 450°C, or less than or equal to 400°C; 75% wt% boiling temperature less than 600°C or less than or equal to 550°C; 95% wt% boiling temperature greater than or equal to 550°C or greater than or equal to 600°C; or combinations thereof. In the implementation, the crude oil may have one or more of the following: 5% by weight boiling temperature of 0°C to 100°C, 25% by weight boiling temperature of 150°C to 250°C, 50% by weight boiling temperature of 250°C to 400°C, 75% by weight boiling temperature of 350°C to 600°C, and a final boiling point temperature of 500°C to 1000°C (e.g., 500°C to 800°C).

[0042] Refer again Figure 1 This illustration schematically depicts one embodiment of a steam catalytic cracking system 110 for steam catalytic cracking of hydrocarbon feed 102. The steam catalytic cracking system 110 may include at least one steam catalytic cracking reactor 130. The steam catalytic cracking reactor 130 may include one or more fixed-bed reactors, fluidized-bed reactors, batch reactors, fluidized-catalytic cracking (FCC) reactors, moving-bed catalytic cracking reactors, or combinations thereof. In one embodiment, the steam catalytic cracking reactor 130 may be a fixed-bed reactor. In another embodiment, the steam catalytic cracking reactor 130 may include multiple fixed-bed reactors operating in an oscillating mode. The operation of the steam catalytic cracking reactor 130 will be described herein in the context of a fixed-bed reactor. However, it should be understood that other types of reactors, such as fluidized-bed reactors, batch reactors, FCC reactors, or moving-bed reactors, may also be used to contact the hydrocarbon feed 102 with steam in the presence of a cracking catalyst composition 132, thereby performing the steam catalytic cracking of the methods disclosed herein.

[0043] In the presence of a cracking catalyst composition comprising the cracking additives of this disclosure, a steam catalytic cracking reactor 130 is operable to contact a hydrocarbon feed 102 with steam, thereby producing a steam catalytic cracking effluent 140 comprising light olefins, light aromatic compounds, or combinations thereof. As previously described, the steam catalytic cracking reactor 130 may be a fixed-bed catalytic cracking reactor, which may include a cracking catalyst composition 132 disposed within a steam catalytic cracking zone 134. The steam catalytic cracking reactor 130 may include a porous packing material 136, such as silica-carbide packing, upstream of the steam catalytic cracking zone 134. The porous packing material 136 ensures adequate heat transfer to the hydrocarbon feed 102 and the steam prior to the steam catalytic cracking reaction in the steam catalytic cracking zone 134.

[0044] Refer again Figure 1 The hydrocarbon feed 102 can be introduced into the steam catalytic cracking reactor 130. In one embodiment, the hydrocarbon feed 102 can be introduced directly into the steam catalytic cracking system 110, for example, by delivering the crude oil of the hydrocarbon feed 102 to the steam catalytic cracking reactor 130, without delivering the hydrocarbon feed 102 to any separation system or unit operation that would alter the hydrocarbon composition of the hydrocarbon feed 102. In another embodiment, the hydrocarbon feed 102 can be treated upstream of the steam catalytic cracking system 110 to remove contaminants, such as, but not limited to, nitrogen compounds, sulfur compounds, heavy metals, or other contaminants that could reduce the effectiveness of the cracking catalyst composition 132.

[0045] The methods disclosed herein may include introducing hydrocarbon feed 102 into a steam catalytic cracking system 110, such as introducing hydrocarbon feed 102 into a steam catalytic cracking reactor 130. Introducing hydrocarbon feed 102 into the steam catalytic cracking reactor 130 may include heating hydrocarbon feed 102 to a temperature of 35°C to 150°C and then delivering hydrocarbon feed 102 into the steam catalytic cracking reactor 130. In embodiments, hydrocarbon feed 102 may be heated to temperatures of 40°C to 150°C, 45°C to 150°C, 50°C to 150°C, 35°C to 145°C, 40°C to 145°C, 45°C to 145°C, 35°C to 140°C, 40°C to 140°C, or 45°C to 140°C.

[0046] In one embodiment, delivering the hydrocarbon feed 102 to the steam catalytic cracking reactor 130 may include delivering the hydrocarbon feed 102 to a feed pump 104, wherein the feed pump 104 may increase the pressure of the hydrocarbon feed 102 and deliver the hydrocarbon feed 102 to the steam catalytic cracking reactor 130. The flow rate of the feed pump 104 may be adjusted to deliver the hydrocarbon feed 102 at a rate greater than or equal to 0.1 h⁻¹. -1) or greater than or equal to 0.25 h -1 The gas hourly space velocity (GHSV) is injected into the steam catalytic cracking reactor 130. The hydrocarbon feed 102 can be injected at a GHSV of less than or equal to 50 h⁻¹. -1 Less than or equal to 25 h -1 Less than or equal to 20 h -1 Less than or equal to 14h -1 9 h or less -1 or less than or equal to 5 h -1 GHSV is injected into the steam catalytic cracking reactor 130. Hydrocarbon feed 102 can be introduced via feed inlet line 106 at a rate of 0.1 h⁻¹. -1 Up to 50 h -1 0.1 h -1 Up to 25 hours -1 0.1 h -1 Up to 20 h -1 0.1h -1 up to 14 hours -1 0.1 h -1 up to 9 h -1 0.1 h -1 up to 5 hours -1 0.1 h -1 up to 4 hours -1 0.25 h -1 Up to 50 h -1 0.25 h -1 Up to 25 hours -1 0.25 h -1 Up to 20 h -1 0.25 h -1 up to 14 hours -1 0.25 h -1 up to 9 h -1 0.25 h -1 up to 5 hours -1 0.25 h -1 up to 4h -1 1 h -1 Up to 50 h -1 1 h -1 Up to 25 hours -1 1 h -1 Up to 20 h -1 1 h -1 up to 14 hours -1 1 h -1 up to 9 h -1 or 1 hour -1 up to 5 hours -1GHSV is injected into the steam catalytic cracking reactor 130. Before injecting the hydrocarbon feed 102 into the steam catalytic cracking reactor 130, the hydrocarbon feed 102 can be further preheated to an inlet temperature of 100°C to 250°C in the feed inlet line 106.

[0047] Water 120 can be injected into the steam catalytic cracking reactor 130 via water feed pump 124 and water feed line 122. Water feed line 122 can be preheated to heat the water 120 to temperatures of 50°C to 175°C, 50°C to 150°C, 60°C to 175°C, or 60°C to 170°C. The water 120 can be converted into steam upon contact with hydrocarbon feed 102 in water feed line 122 or in steam catalytic cracking reactor 130. The flow rate of water feed pump 124 can be adjusted to deliver water 120 (liquid, steam, or both) at a rate equivalent to or greater than 0.1 h⁻¹. -1 ≥0.5 h -1 1 h or more -1 5 h or more -1 6 h or more -1 ≥10 h -1 or even greater than or equal to 15 h -1 The GHSV flow rate is fed to the steam catalytic cracking reactor 130. Water 120 can be fed at a flow rate equivalent to less than or equal to 100 h⁻¹. -1 Less than or equal to 75 h -1 Less than or equal to 50 h -1 Less than or equal to 30 h -1 or less than or equal to 20 h -1 The GHSV flow rate is introduced into the steam catalytic cracking reactor 130. Water 120 can be introduced at a flow rate equivalent to 0.1 h⁻¹. -1 Up to 100 h -1 0.1 h -1 Up to 75 h -1 0.1 h -1 Up to 50 h -1 0.1 h -1 Up to 30 h -1 0.1 h -1 Up to 20 h -1 1 h -1 Up to 100 h -1 1 h -1 Up to 75 h -1 1 h -1 Up to 50 h -1 1 h -1 Up to 30 h -1 or 1 hour -1 Up to 20 h-1 The GHSV flow rate is introduced into the steam catalytic cracking reactor 130.

[0048] Injecting water 120 into the steam-catalytic cracking reactor 130 generates steam, which reduces hydrocarbon partial pressure. This has a dual effect: increasing the yield of light olefins (e.g., ethylene, propylene, and butene) and reducing coke formation on the cracking catalyst composition 132. Without being bound by any particular theory, it is believed that light olefins such as propylene and butene are primarily generated through catalytic cracking reactions following a carbocation mechanism, and since these are intermediate products, they can undergo secondary reactions, such as hydrogen transfer and aromatization (leading to coke formation). Steam can increase the yield of light olefins by suppressing these secondary bimolecular reactions and can reduce the concentrations of reactants and products, thus favoring selectivity for light olefins. Steam can also suppress secondary reactions that lead to coke formation on the catalyst surface, which helps maintain a high average activity of the cracking catalyst composition.

[0049] The mass flow rate of water 120 entering the steam catalytic cracking reactor 130 can be lower than the mass flow rate of hydrocarbon feed 102 entering the steam catalytic cracking reactor 130. In an embodiment, the mass flow ratio of water 120 to hydrocarbon feed 102 introduced into the steam catalytic cracking reactor 130 can be less than 1, for example, less than or equal to 0.9, less than or equal to 0.8, less than or equal to 0.7, or less than or equal to 0.6. In this embodiment, the mass flow rate ratio of water 120 to hydrocarbon feed 102 introduced into the steam catalytic cracking reactor 130 can be 0.2 to less than 1, 0.2 to 0.9, 0.2 to 0.8, 0.2 to 0.7, 0.2 to 0.6, 0.3 to less than 1, 0.3 to 0.9, 0.3 to 0.8, 0.3 to 0.7, 0.3 to 0.6, 0.4 to less than 1, 0.4 to 0.9, 0.4 to 0.8, 0.4 to 0.7, 0.4 to 0.6, 0.5 to less than 1, 0.5 to 0.9, 0.5 to 0.8, 0.5 to 0.7, or 0.5 to 0.6. The mass flow rate ratio of water to hydrocarbon feed 102 is equal to the mass flow rate of water 120 entering the steam catalytic cracking reactor 130 divided by the mass flow rate of hydrocarbon feed 102 entering the steam catalytic cracking reactor 130. In this embodiment, the mass flow ratio of water 120 introduced into the steam catalytic cracking reactor 130 to hydrocarbon feed 102 can be approximately 0.5. In the steam catalytic cracking reactor 130, water may be present in the form of steam.

[0050] Refer again Figure 1In a steam catalytic cracking reactor 130, in the presence of a cracking catalyst composition 132, a steam catalytic cracking system 110 is operable to contact a hydrocarbon feed 102 with steam (from water 120) under reaction conditions sufficient to cause at least a portion of the hydrocarbons in the hydrocarbon feed 102 to undergo one or more cracking reactions, thereby producing a steam catalytic cracking effluent 140 comprising light olefins, light aromatic compounds, or both. In embodiments, the steam catalytic cracking effluent 140 may comprise light olefins, which may include, but are not limited to, ethylene, propylene, butene, or combinations thereof. In embodiments, the steam catalytic cracking effluent 140 may comprise light aromatic compounds, which are compounds containing a single aromatic ring structure and having 11 or fewer carbon atoms. The light aromatic compounds in the steam catalytic cracking effluent 140 may include, but are not limited to, benzene, toluene, ethylbenzene, xylene, or other light aromatic compounds.

[0051] The steam catalytic cracking reactor 130 can operate at temperatures greater than or equal to 525°C, greater than or equal to 550°C, greater than or equal to 575°C, or even greater than or equal to 600°C. The steam catalytic cracking reactor 130 can operate at temperatures less than or equal to 800°C, less than or equal to 750°C, less than or equal to 700°C, or even less than or equal to 675°C. The steam catalytic cracking reactor 130 can operate at temperatures ranging from 525°C to 800°C, 525°C to 750°C, 525°C to 700°C, 525°C to 675°C, 550°C to 750°C, 550°C to 700°C, 555°C to 675°C, 575°C to 700°C, 575°C to 675°C, 600°C to 750°C, 600°C to 700°C, or 600°C to 675°C. In one embodiment, the steam catalytic cracking reactor 130 can operate at a temperature of approximately 675°C. In another embodiment, the steam catalytic cracking reactor 130 can operate at a pressure of 100 kPa to 200 kPa. In yet another embodiment, the process can operate at atmospheric pressure (approximately 101 kPa).

[0052] The method disclosed herein may include, in a steam catalytic cracking reactor 130, contacting a hydrocarbon feed 102 with steam (water 120) for a residence time sufficient to convert at least a portion of the hydrocarbon compounds in the hydrocarbon feed 102 into light olefins, light aromatic compounds, or both, in the presence of a cracking catalyst composition 132. In embodiments, the method may include, in a steam catalytic cracking reactor 130, contacting a hydrocarbon feed 102 with steam (water 120) for a residence time of 1 second to 60 seconds (e.g., 1 second to 30 seconds, 1 second to 10 seconds, or about 10 seconds) in the presence of the cracking catalyst composition 132.

[0053] When the steam catalytic cracking reactor 130 is a fixed-bed reactor, it can be operated in a semi-continuous manner. For example, during a conversion cycle, the steam catalytic cracking reactor 130 can be operated for a period of time with hydrocarbon feed 102 and water 120 flowing to it. After a period of time, the cracking catalyst composition 132 can be regenerated. Each conversion cycle of the steam catalytic cracking reactor 130 can be 2 hours to 24 hours, 2 hours to 20 hours, 2 hours to 16 hours, 2 hours to 12 hours, 2 hours to 10 hours, 2 hours to 8 hours, 4 hours to 24 hours, 4 hours to 20 hours, 4 hours to 16 hours, 4 hours to 12 hours, 4 hours to 10 hours, or 4 hours to 8 hours before shutting off the feed pump 104 and water feed pump 124 to stop the flow of hydrocarbons and steam to the steam catalytic cracking reactor 130.

[0054] At the end of the conversion cycle, the flow of hydrocarbon feed 102 and water 120 can be stopped, and the cracking catalyst composition 132 can be regenerated during the regeneration cycle. In an embodiment, the steam catalytic cracking system 110 may include multiple fixed-bed steam catalytic cracking reactors 130, which may operate in parallel or in series. In an embodiment, the steam catalytic cracking system 110 may include one, two, three, four, five, six, or more than six steam catalytic cracking reactors 130, which may operate in series or in parallel. When multiple steam catalytic cracking reactors 130 are operating in parallel, one or more steam catalytic cracking reactors 130 may continue to operate in the conversion cycle, while one or more of the other steam catalytic cracking reactors 130 may be taken offline for regeneration of the cracking catalyst composition 132, thereby maintaining the continuous operation of the steam catalytic cracking system 110.

[0055] Refer again Figure 1 During the regeneration cycle, the steam catalytic cracking reactor 130 can be operated to regenerate the cracking catalyst composition 132, thereby removing coke deposits accumulated during the conversion cycle. To regenerate the cracking catalyst composition 132, hydrocarbon gases and liquid products generated by the steam catalytic cracking process can be evacuated from the steam catalytic cracking reactor 130. Nitrogen gas can be introduced into the steam catalytic cracking reactor 130 through the gas inlet line 112 to evacuate hydrocarbon gases and liquid products from the fixed-bed steam catalytic cracking reactor 130. Nitrogen gas can be introduced at a rate of 10 kilometres per hour (h). -1 ) to 100 h -1 The gas hourly space velocity is introduced into the steam catalytic cracking reactor 130.

[0056] After the hydrocarbon gas and liquid are discharged, they can be discharged through gas inlet pipeline 112 at a rate of 10 h. -1 Up to 100 h -1Air is introduced into the steam catalytic cracking reactor 130 at a gas hourly space velocity (GHSV). The air can be delivered out of the steam catalytic cracking reactor 130 via air outlet line 142. During the delivery of air through the cracking catalyst composition 132 in the steam catalytic cracking reactor 130, the temperature of the steam catalytic cracking reactor 130 can be raised from the reaction temperature to a regeneration temperature of 650°C to 750°C for a period of 3 to 5 hours. The gas generated by the air regeneration of the cracking catalyst composition 132 can be delivered out of the steam catalytic cracking reactor 130 and analyzed by an online gas analyzer to detect the presence or concentration of carbon dioxide generated by the decoking of the cracking catalyst composition 132. Once the online gas analyzer detects that the carbon dioxide concentration in the gas delivered from the steam catalytic cracking reactor 130 has dropped below 0.1% (by weight) or even below 0.05% (by weight), the temperature of the steam catalytic cracking reactor 130 can be reduced from the regeneration temperature back to the reaction temperature. The flow of air through the gas inlet line 112 can be stopped. Nitrogen gas can be delivered through the cracking catalyst composition 132 for 15 to 30 minutes to remove air from the steam catalytic cracking reactor 130. After nitrogen treatment, the flow of hydrocarbon feed 102 and water 120 can be restored to begin another conversion cycle of the steam catalytic cracking reactor 130. Although described herein in the context of a fixed-bed reactor system, it should be understood that the steam catalytic cracking reactor 130 can be of different types of reactors, such as a fluidized-bed reactor, a moving-bed reactor, a batch reactor, an FCC reactor, or a combination of these reactors.

[0057] Refer again Figure 1 The steam catalytic cracking effluent 140 can be delivered from the steam catalytic cracking reactor 130. The steam catalytic cracking effluent 140 may include one or more products and intermediates, such as, but not limited to, fuel gas, such as methane; saturated C2-C4 hydrocarbons; light olefins; naphtha (C5-221°C), which may include light aromatic compounds; light cycle oil (LCO, 221-343°C); heavy cycle oil (HCO, +343°C), such as, but not limited to, slurry oil; coke; or combinations thereof. The light olefins in the steam catalytic cracking effluent 140 may include ethylene, propylene, butene, or combinations thereof. The light aromatic compounds in the steam catalytic cracking effluent 140 may include, but are not limited to, benzene, toluene, xylene, ethylbenzene, and other light aromatic compounds having 6 to 11 carbon atoms.

[0058] As discussed above, the cracking catalyst composition 132 includes a cracking additive. In embodiments, the cracking catalyst composition 132 may further include a zeolite catalyst different from the cracking additive. In embodiments, the cracking catalyst composition 132 may comprise, or consist of, a zeolite catalyst and a cracking additive, or substantially consist of a zeolite catalyst and a cracking additive, wherein the cracking additive is different from the zeolite catalyst.

[0059] In embodiments, the zeolite catalyst may comprise one or more of the following: Y-type zeolite, USY zeolite, β-zeolite, mordenite (MOR) structured zeolite, mordenite framework inverted (MFI) zeolite, other types of zeolite suitable for catalytic cracking of hydrocarbons, core-shell composites containing β-zeolite coated on an MFI zeolite framework, or combinations thereof. In embodiments, the zeolite catalyst may include a balanced catalyst (ECAT). As used herein, the terms "balanced catalyst" or "ECAT" refer to a used zeolite catalyst from a fluidized catalytic cracking (FCC) process. In embodiments, the balanced catalyst may comprise rare earth metals, Ni, V, or combinations thereof.

[0060] In an embodiment, based on the total amount of the cracking catalyst composition, the amount of zeolite catalyst in the cracking catalyst composition may be 70% to 80% by weight, 72% to 80% by weight, 74% to 80% by weight, 70% to 78% by weight, 72% to 78% by weight, 74% to 78% by weight, 70% to 76% by weight, 72% to 76% by weight, or 74% to 76% by weight.

[0061] The cracking additive comprises a first metal type and a second metal type uniformly impregnated on ZSM-5 zeolite, and is composed of, or substantially composed of, the first metal type and the second metal type uniformly impregnated on ZSM-5 zeolite. In embodiments, the ZSM-5 zeolite of the cracking additive may have a silica to alumina molar ratio greater than or equal to 10 or greater than or equal to 20. The ZSM-5 zeolite of the cracking additive may have a silica to alumina molar ratio less than or equal to 1500, for example, less than or equal to 900, less than or equal to 600, or even less than or equal to 300. In an embodiment, the ZSM-5 zeolite of the cracking additive may have a molar ratio of silica to alumina of 10 to 1500, such as 10 to 900, 10 to 600, 10 to 300, 20 to 1500, 20 to 900, 20 to 600, or 20 to 300.

[0062] In embodiments, the average crystal size of ZSM-5 zeolite can be greater than or equal to 150 nanometers (nm), such as 160 nm to 1000 nm, 160 nm to 950 nm, 160 nm to 900 nm, 190 nm to 1000 nm, 190 nm to 950 nm, 190 nm to 900 nm, 190 nm to 800 nm, 190 nm to 700 nm, 190 nm to 250 nm, 210 nm to 1000 nm, 210 nm to 950 nm, 210 nm to 900 nm, 210 nm to 800 nm, 800 nm to 1000 nm, 900 nm to 1000 nm, or 900 nm to 950 nm. The average crystal size is determined by scanning electron microscopy (SEM) according to known methods. In embodiments, the ZSM-5 zeolite of the cracking additive can be in the form of multiple particles.

[0063] As discussed above, the cracking additive comprises a first metal type and a second metal type impregnated on ZSM-5 zeolite. In embodiments, the first metal type may include a metal or a metal oxide. The metal or metal oxide of the first metal type may include a first metal selected from the group consisting of chromium, iron, platinum, molybdenum, cerium, lanthanum, and zinc. In embodiments, the first metal type may be a metal oxide selected from the group consisting of chromium oxide, iron oxide, platinum oxide, molybdenum oxide, cerium oxide, lanthanum oxide, and zinc oxide.

[0064] The cracking additive may include a first metal species at a concentration sufficient to increase the yield of light olefins, light aromatic compounds, or both, when steam catalytic cracking is performed using the cracking additive. In embodiments, based on the total weight of the cracking additive, the cracking additive may contain 0.1 wt% to 10 wt%, 0.1 wt% to 8 wt%, 0.1 wt% to 5 wt%, 1 wt% to 10 wt%, 1 wt% to 8 wt%, 1 wt% to 5 wt%, 2 wt% to 10 wt%, 2 wt% to 8 wt%, 2 wt% to 5 wt%, or 1 wt% to 2 wt% of the first metal species.

[0065] In an embodiment, the second metal type may include a metal or a metal oxide. The metal or metal oxide of the second metal type may include a second metal selected from the group consisting of chromium, iron, platinum, molybdenum, cerium, lanthanum, and zinc. The second metal of the second metal type differs from the first metal of the first metal type. In an embodiment, the second metal type may be a metal oxide selected from the group consisting of chromium oxide, iron oxide, platinum oxide, molybdenum oxide, cerium oxide, lanthanum oxide, and zinc oxide, wherein the metal oxide of the second metal type differs from the metal oxide of the first metal type.

[0066] The cracking additive may include a second metal species at a concentration sufficient to increase the yield of light olefins, light aromatic compounds, or both when using the cracking additive for steam catalytic cracking. In embodiments, based on the total weight of the cracking additive, the cracking additive may contain 0.1 wt% to 10 wt%, 0.1 wt% to 8 wt%, 0.1 wt% to 5 wt%, 1 wt% to 10 wt%, 1 wt% to 8 wt%, 1 wt% to 5 wt%, 2 wt% to 10 wt%, 2 wt% to 8 wt%, 2 wt% to 5 wt%, or 1 wt% to 2 wt% of the second metal species.

[0067] In one embodiment, the first metal of the first metal species in the cracking additive can be platinum, molybdenum, cerium, or zinc, while the second metal of the second metal species in the cracking additive can be lanthanum, iron, or chromium. In another embodiment, the first metal species in the cracking additive can be platinum oxide, molybdenum oxide, cerium oxide, or zinc oxide, while the second metal species in the cracking additive can be lanthanum oxide, iron oxide, or chromium oxide. In yet another embodiment, the cracking additive may include platinum oxide and lanthanum oxide impregnated on ZSM-5 zeolite, platinum oxide and iron oxide impregnated on ZSM-5 zeolite, molybdenum oxide and iron oxide impregnated on ZSM-5 zeolite, cerium oxide and chromium oxide impregnated on ZSM-5 zeolite, zinc oxide and chromium oxide impregnated on ZSM-5 zeolite, or cerium oxide and iron oxide impregnated on ZSM-5 zeolite.

[0068] In one embodiment, based on the total weight of the cracking additive, the cracking additive may contain 1% by weight of platinum oxide and 2% by weight of lanthanum oxide impregnated on ZSM-5 zeolite. In another embodiment, based on the total weight of the cracking additive, the cracking additive may contain 1% by weight of platinum oxide and 2% by weight of iron oxide impregnated on ZSM-5 zeolite. In another embodiment, based on the total weight of the cracking additive, the cracking additive may contain 2% by weight of molybdenum oxide and 2% by weight of iron oxide impregnated on ZSM-5 zeolite. In another embodiment, based on the total weight of the cracking additive, the cracking additive may contain 2% by weight of cerium oxide and 2% by weight of chromium oxide impregnated on ZSM-5 zeolite. In another embodiment, based on the total weight of the cracking additive, the cracking additive may contain 2% by weight of chromium oxide and 1% by weight of zinc oxide impregnated on ZSM-5 zeolite. In yet another embodiment, based on the total weight of the cracking additive, the cracking additive may contain 2% by weight of cerium oxide and 2% by weight of iron oxide impregnated on ZSM-5 zeolite.

[0069] In one embodiment, the cracking additive may include a first metal species and a second metal species impregnated on ZSM-5 zeolite, but excludes phosphorus. In another embodiment, the cracking additive may be substantially phosphorus-free, for example, having less than or equal to 0.1% by weight or less than or equal to 0.01% by weight of phosphorus based on the total weight of the cracking additive.

[0070] In embodiments, the cracking additive may comprise cerium oxides and iron oxides impregnated on ZSM-5 zeolite, wherein the molar ratio of silica to alumina in the zeolite may be 30, and the cracking additive may be substantially phosphorus-free, meaning that phosphorus is not intentionally added to the cracking additive or used in the method of preparing the cracking additive, and any phosphorus present is in trace amounts and is introduced as a contaminant of other reagents. In embodiments, the cracking additive may have less than 1000 parts by weight per million parts (ppmw) of phosphorus, or less than 500 ppmw of phosphorus, or less than 100 ppmw of phosphorus. In embodiments, the cracking additive is completely phosphorus-free. The concentration of cerium oxides in the cracking additive may be 2% by weight based on the total weight of the cracking additive. The concentration of iron oxides in the cracking additive may be 2% by weight based on the total weight of the cracking additive. In embodiments, the cracking additive may consist substantially of cerium oxides and iron oxides impregnated on ZSM-5 zeolite. In embodiments, the cracking additive may consist of cerium oxides and iron oxides impregnated on ZSM-5 zeolite.

[0071] In one embodiment, the cracking additive may include zinc oxide and chromium oxide impregnated on ZSM-5 zeolite, wherein the molar ratio of silica to alumina in the zeolite may be 30, and the cracking additive may be substantially phosphorus-free. Based on the total weight of the cracking additive, the concentration of zinc oxide in the cracking additive may be 1% by weight, and the concentration of chromium oxide in the cracking additive may be 2% by weight. In another embodiment, the cracking additive may consist substantially of zinc oxide and chromium oxide impregnated on ZSM-5 zeolite.

[0072] In embodiments, the cracking additive may be in the form of multiple particles. In embodiments, the average particle size of the cracking additive may be greater than or equal to 300 micrometers (µm), for example, 350 µm to 2000 µm, 350 µm to 1500 µm, 350 µm to 1000 µm, 400 µm to 2000 µm, 400 µm to 1500 µm, 400 µm to 1000 µm, 450 µm to 2000 µm, 450 µm to 1500 µm, 450 µm to 1000 µm, 500 µm to 2000 µm, 500 µm to 1500 µm, or 500 µm to 1000 µm. The average particle size is determined by scanning electron microscopy (SEM) according to known methods.

[0073] In this embodiment, the average surface area of ​​the cracking additive can be 200 square meters per gram (m²). 2 / g) to 400 m 2 / g、200 m 2 / g to 380 m 2 / g、200 m 2 / g to 370 m 2 / g、250 m 2 / g to 400 m 2 / g、250 m 2 / g to 390 m 2 / g、250m 2 / g to 380 m 2 / g、250 m 2 / g to 370 m 2 / g、300 m 2 / g to 400 m 2 / g、300 m 2 / g to 390 m 2 / g、300 m 2 / g to 380 m 2 / g or 300 m 2 / g to 370 m 2 / g. The average surface area was determined according to the Brunauer-Emmett-Teller (BET) method, based on nitrogen adsorption performed at -195 °C on an AUTOSORB-1 instrument obtained from Quanta Chrome. Throughout this disclosure, the average surface area may be referred to as the BET surface area.

[0074] In this embodiment, the average pore size of the cracking additive can be the average pore diameter of a pore having a generally cylindrical cross-section. The average pore diameter of the cracking additive can be 3 nm to 10 nm, 4 nm to 10 nm, 3 nm to 9 nm, 4 nm to 9 nm, 3 nm to 8 nm, or 4 nm to 8 nm. The average pore diameter of the cracking additive is determined by scanning electron microscopy (SEM) according to known methods.

[0075] The average pore volume of the cracking additive can be 0.05 square centimeters per gram (cm²). 3 / g) to 0.5 cm 3 / g, 0.06 cm 3 / g to 0.5 cm 3 / g, 0.07 cm 3 / g to 0.5 cm 3 / g, 0.08 cm 3 / g to 0.5 cm 3 / g, 0.09 cm 3 / g to 0.5 cm 3 / g, 0.05 cm 3 / g to 0.3 cm 3 / g, 0.06 cm 3 / g to 0.3 cm 3 / g, 0.07 cm 3 / g to 0.3 cm 3 / g, 0.08 cm 3 / g to 0.3 cm 3 / g, 0.09 cm 3 / g to 0.3 cm 3 / g, 0.05 cm 3 / g to 0.1 cm 3 / g, 0.06 cm 3 / g to 0.1 cm 3 / g, 0.07 cm 3 / g to 0.1 cm 3 / g, 0.08 cm 3 / g to 0.1 cm 3 / g or 0.09 cm 3 / g to 0.1 cm 3 / g. The average pore volume of the cracking additive was determined by measuring the gas adsorption isotherm using the Barrett-Joyner-Halenda model.

[0076] In this embodiment, the cracking additive does not include any binder, matrix material, or other catalysts other than metals loaded on ZSM-5 zeolite.

[0077] In an embodiment, based on the total amount of the cracking catalyst composition, the amount of cracking additive in the cracking catalyst composition may be 20% to 30% by weight, 22% to 30% by weight, 24% to 30% by weight, 20% to 28% by weight, 22% to 28% by weight, 24% to 28% by weight, 20% to 26% by weight, 22% to 26% by weight, or 24% to 26% by weight.

[0078] For reference Figure 2 The method 200 for preparing cracking additives may include: in step S205, preparing a zeolite mixture comprising ZSM-5 zeolite and water; in step S207, preparing a metal precursor mixture comprising a first metal precursor, a second metal precursor, and water; in step S210, adding the metal precursor mixture to the zeolite mixture while mixing the zeolite mixture to prepare a combined mixture; in step S220, stirring the combined mixture at a temperature of 10°C to 30°C for a mixing time of 1 hour to 5 hours; in step S230, heating the combined mixture to an evaporation temperature of 30°C to below 100°C while stirring at atmospheric pressure; in step S240, maintaining the combined mixture at the evaporation temperature and atmospheric pressure for a period of 1 hour to 24 hours; and in step S250, calcining the solid particles at a temperature of 400°C to 800°C for 1 hour to 12 hours to produce cracking additives.

[0079] In step S205 of method 200, a zeolite mixture comprising ZSM-5 zeolite and water can be prepared by adding zeolite powder containing ZSM-5 zeolite to water. In an embodiment, the concentration of zeolite powder in the zeolite mixture can be from 10% by weight (wt%) to 50% by weight, based on the total weight of the zeolite mixture. In an embodiment, the concentration of water in the zeolite mixture can be from 50% by weight to 90% by weight, based on the total weight of the zeolite mixture. In an embodiment, method 200 for preparing cracking additives may further include calcining the zeolite powder before producing the zeolite mixture. In an embodiment, the zeolite powder can be calcined at temperatures of 400°C to 800°C, 400°C to 600°C, 500°C to 800°C, 500°C to 600°C, or 550°C. In an embodiment, the zeolite powder can be calcined for a period of 1 hour to 12 hours, 1 hour to 10 hours, 2 hours to 12 hours, 2 hours to 10 hours, or 8 hours.

[0080] In step S207 of method 200, a metal precursor mixture can be prepared by adding a first metal precursor and a second metal precursor to water and mixing them. The preparation of the metal precursor mixture in step S207 can be performed concurrently with the preparation of the zeolite mixture in step S205. In an embodiment, the concentration of the first metal precursor in the metal precursor mixture can be from 0.1 wt% to 10 wt%, based on the total weight of the metal precursor mixture. In an embodiment, the concentration of the second metal precursor in the metal precursor mixture can be from 0.1 wt% to 10 wt%, based on the total weight of the metal precursor mixture. In an embodiment, the concentration of water in the metal precursor mixture can be from 80 wt% to 99.8 wt% or from 90 wt% to 99 wt%, based on the total weight of the metal precursor mixture.

[0081] First-metal precursors may include chromium(III) nitrate nonhydrate (Cr(NO3)3·9H2O), ferric(III) nitrate nonhydrate (Fe(NO3)3·9H2O), tetraammineplatinum(II) nitrate (Pt(NH3)4(NO3)2), and ammonium heptamolybdate tetrahydrate ((NH4)6Mo7O). 24 The precursors for the second metal species may include cerium(III) nitrate hexahydrate (Ce(NO3)3·6H2O), lanthanum(III) nitrate hexahydrate (La(NO3)3·6H2O), or zinc(NO3) nitrate hexahydrate (Zn(NO3)2·6H2O). 24 The precursors are cerium(III) nitrate hexahydrate (Ce(NO3)3·6H2O), lanthanum nitrate hexahydrate (La(NO3)3·6H2O), or zinc nitrate hexahydrate (Zn(NO3)2·6H2O). The precursor of the second metal species may be different from that of the first metal species.

[0082] In step S210 of method 200, a metal precursor mixture may be added to the zeolite mixture while it is being stirred. Adding the metal precursor mixture to the zeolite mixture while it is being stirred may include one or more of the following methods: stirring, swirling, vortexing, shaking, ultrasonic treatment, homogenization, and blending. In an embodiment, the metal precursor mixture may be added to the zeolite mixture at a rate of 0.1 mL / min to 1.0 mL / min.

[0083] In step S220 of method 200, the combined mixture may be stirred, which may disperse the first metal species precursor, the second metal species precursor, and ZSM-5 zeolite throughout the combined mixture. In embodiments, the combined mixture may be stirred at temperatures of 10°C to 30°C, 10°C to 25°C, 15°C to 30°C, or 15°C to 25°C. The combined mixture may be stirred for a period of time sufficient to produce a homogeneous combined mixture. In embodiments, the combined mixture may be stirred for 1 hour to 5 hours, 1 hour to 4 hours, 2 hours to 5 hours, 2 hours to 4 hours, or 3 hours. Without being bound by any particular theory, it is believed that stirring or mixing the combined mixture for a period of time before removing water from the combined mixture may result in greater dispersion of the first and second metal species on the surface of the ZSM-5 zeolite, for example, by allowing the first metal species precursor, the second metal species precursor, or both to penetrate into the porous structure of the ZSM-5 zeolite before removing water from the combined mixture.

[0084] In step S230 of method 200, the combined mixture may be heated to an evaporation temperature. This evaporation temperature may be lower than the boiling point of water at the pressure under which heating is performed, for example, lower than 100°C at atmospheric pressure. In embodiments, at atmospheric pressure, the evaporation temperature may be 10°C to below 100°C, 10°C to 90°C, 10°C to 80°C, 10°C to 70°C, 10°C to 60°C, 20°C to below 100°C, 20°C to 90°C, 20°C to 80°C, 20°C to 70°C, 20°C to 60°C, 30°C to below 100°C, 30°C to 90°C, 30°C to 80°C, 30°C to 70°C, 30°C to 60°C, 40°C to below 100°C, 40°C to 90°C, 40°C to 80°C, 40°C to 70°C, 40°C to 60°C, or about 50°C. Evaporation temperatures can exceed 100°C, provided the pressure is adjusted accordingly to keep the combined mixture below the boiling point of water.

[0085] In step S240 of method 200, the combined mixture can be maintained at the evaporation temperature and pressure for a period of 1 hour to 24 hours while stirring. In step S240 of method 200, maintaining the combined mixture at the evaporation temperature and pressure while mixing allows water to slowly evaporate from the combined mixture, thereby producing solid particles. In step S240 of method 200, water can be slowly evaporated from the combined mixture while mixing disperses the metal precursors on the surface of ZSM-5 zeolite. In embodiments, the combined mixture can be maintained at the evaporation temperature and pressure for periods of 1 hour to 24 hours, 1 hour to 20 hours, 1 hour to 16 hours, 2 hours to 24 hours, 2 hours to 20 hours, 2 hours to 16 hours, 5 hours to 24 hours, 5 hours to 20 hours, 5 hours to 16 hours, 2 hours to 24 hours, 8 hours to 20 hours, 8 hours to 16 hours, and 12 hours. Evaporating water from a combined mixture at atmospheric pressure and at evaporation temperatures (e.g., 30°C to 100°C) for a period of 1 to 24 hours can result in water evaporation rates ranging from 1.0 g / min to 10.0 g / min. Without being bound by any particular theory, it is believed that the slow removal of water from the combined mixture by evaporation at a temperature below the boiling point of water under given pressure can further improve the dispersibility of the first and second metal species on the ZSM-5 zeolite surface.

[0086] In an embodiment, the method 200 for preparing cracking additives may further include drying solid particles at a temperature of 50°C to 200°C. Figure 2 (Not shown in the text). In an embodiment, the solid particles may be dried at temperatures of 50°C to 200°C, 50°C to 100°C, 70°C to 200°C, 70°C to 100°C, or 90°C. In an embodiment, the solid particles may be dried overnight.

[0087] In step S250 of method 200, after drying, the solid particles can be calcined at a temperature of 400°C to 800°C for 1 hour to 12 hours to produce a cracking additive. In embodiments, the solid particles can be calcined at temperatures of 400°C to 800°C, 400°C to 600°C, 500°C to 800°C, 500°C to 600°C, or about 550°C. In embodiments, the solid particles can be calcined for a period of 1 hour to 12 hours, 1 hour to 10 hours, 2 hours to 12 hours, 2 hours to 10 hours, or 8 hours.

[0088] In embodiments, the cracking additive may be ion-exchanged to produce a hydrogen form of the cracking additive. In the hydrogen form, the Brønsted acid sites in the zeolite, also known as bridging OH–H groups, can form hydrogen bonds with other skeletal oxygen atoms in the zeolite framework. In embodiments, the method 200 for producing the cracking additive may include ion-exchanging the cracking additive to produce a hydrogen form of the cracking catalyst. In embodiments, ion-exchanging the cracking additive may include treating the cracking catalyst with an ammonium salt at a temperature of 50°C to 100°C for 1 hour to 12 hours. In embodiments, the cracking additive may be treated with a 1.0 mol (M) ammonium nitrate (NH4NO3) solution. In embodiments, the cracking additive may be treated with an ammonium nitrate solution of a 0.25 equivalence (N) concentration. In embodiments, the cracking additive may be treated with an ammonium salt solution at temperatures of 50°C to 100°C, 50°C to 90°C, 70°C to 100°C, 70°C to 90°C, or 80°C. In one embodiment, the cracking additive can be treated with an ammonium salt solution for a period of 1 to 12 hours, 1 to 8 hours, 2 to 12 hours, 2 to 8 hours, or 4.5 hours. In another embodiment, the cracking additive can be treated with an ammonium salt solution at 80°C for 4.5 hours with stirring. In yet another embodiment, after treatment, the cracking additive may be in the hydrogen form.

[0089] In some embodiments, the cracking additive in the form of ion-exchanged hydrogen can be calcined at temperatures of 400°C to 800°C, 400°C to 600°C, 500°C to 800°C, 500°C to 600°C, or 550°C. In some embodiments, the cracking catalyst in the form of ion-exchanged hydrogen can be further calcined for a period of 1 hour to 12 hours, 1 hour to 8 hours, 2 hours to 12 hours, 2 hours to 8 hours, or 5 hours. In some embodiments, the cracking additive in the form of ion-exchanged hydrogen can be calcined after the ion exchange process is completed.

[0090] As discussed above, steam catalytic cracking effluent 140 may include one or more products and intermediates, such as, but not limited to, light hydrocarbon gases, light olefins, aromatic compounds, pyrolysis oil, or combinations thereof. Light olefins in steam catalytic cracking effluent 140 may include ethylene, propylene, butene, or combinations thereof. Steam catalytic cracking effluent 140 may include light aromatic compounds. Light aromatic compounds may include, but are not limited to, benzene, toluene, xylene, ethylbenzene, and other light aromatic compounds having 6 to 11 carbon atoms.

[0091] Based on the total weight of the steam catalytic cracking effluent 140, the steam catalytic cracking system 110 can achieve a yield of light olefins (ethylene, propylene, and butene) greater than or equal to 35 wt%, greater than or equal to 37 wt%, greater than or equal to 39 wt%, or greater than or equal to 40 wt%. In an embodiment, based on the total weight of the steam catalytic cracking effluent 140, the steam catalytic cracking system 110 can achieve light olefin yields of 35 wt% to 60 wt%, 35 wt% to 55 wt%, 35 wt% to 50 wt%, 35 wt% to 45 wt%, 37 wt% to 60 wt%, 37 wt% to 55 wt%, 37 wt% to 50 wt%, 37 wt% to 45 wt%, 39 wt% to 60 wt%, 39 wt% to 55 wt%, 39 wt% to 50 wt%, 39 wt% to 45 wt%, 40 wt% to 60 wt%, 40 wt% to 55 wt%, 40 wt% to 50 wt%, or 40 wt% to 45 wt%.

[0092] Based on the total weight of a stream such as steam catalytic cracking effluent 140, the steam catalytic cracking system 110 can achieve a yield of light aromatic compounds greater than or equal to 15 wt%, greater than or equal to 18 wt%, or greater than or equal to 20 wt%. In embodiments, based on the total weight of a stream such as steam catalytic cracking effluent 140, the steam catalytic cracking system 110 can achieve yields of light aromatic compounds ranging from 15 wt% to 30 wt%, 15 wt% to 28 wt%, 15 wt% to 26 wt%, 18 wt% to 30 wt%, 18 wt% to 28 wt%, 18 wt% to 26 wt%, 20 wt% to 30 wt%, 20 wt% to 28 wt%, or 20 wt% to 26 wt%.

[0093] Refer again Figure 1 The steam catalytic cracking system 110 may further include a cracking effluent separation system 150 disposed downstream of the steam catalytic cracking reactor 130. When the steam catalytic cracking system 110 includes multiple steam catalytic cracking reactors 130, steam catalytic cracking effluent 140 from each steam catalytic cracking reactor 130 may be fed to a single shared cracking effluent separation system 150. In an embodiment, each steam catalytic cracking reactor 130 may have its own dedicated cracking effluent separation system. The steam catalytic cracking effluent 140 may be fed directly from the steam catalytic cracking reactor 130 to the cracking effluent separation system 150. The cracking effluent separation system 150 may separate the steam catalytic cracking effluent 140 into one or more cracking product effluents, which may be liquid product or gaseous product effluents.

[0094] Refer again Figure 1The cracking effluent separation system 150 may include one or more separation units. These separation units may include, but are not limited to, distillation columns, fractionators, flash tanks, separators, liquid separators, centrifuges, decanters, filters, traps, scrubbers, expansion devices, membranes, solvent extraction devices, adsorption devices, chemical separators, crystallizers, chromatographs, precipitators, evaporators, dryers, high-pressure separators, low-pressure separators, or combinations thereof. The separation units may include one or more gas-liquid separators, one or more liquid-liquid separators, or combinations thereof.

[0095] In one embodiment, the cracking effluent separation system 150 may include a gas-liquid separation unit 160 and a centrifugal unit 170 located downstream of the gas-liquid separation unit 160. The gas-liquid separation unit 160 is operable to separate the steam catalytic cracking effluent 140 into a liquid effluent 162 and a gaseous effluent 164. The gas-liquid separation unit 160 is operable to reduce the temperature of the steam catalytic cracking effluent 140 to condense components in the steam catalytic cracking effluent 140 having five or more carbon atoms. The gas-liquid separation unit 160 may operate at a temperature of 10°C to 15°C to ensure that n-pentane and components with boiling points higher than n-pentane condense into the liquid effluent 162. The liquid effluent 162 may include distilled fractions such as naphtha, kerosene, gas oil, vacuum gas oil; unconverted feedstock; residue; water; or combinations thereof. Liquid effluent 162 may include light aromatic compounds produced in steam catalytic cracking reactor 130, including but not limited to benzene, toluene, mixed xylenes, ethylbenzene, and other light aromatic compounds. Liquid effluent 162 may include at least 95%, at least 98%, at least 99%, or even at least 99.5% of the hydrocarbon components having 5 or more carbon atoms in steam catalytic cracking effluent 140. Liquid effluent 162 may include at least 95%, at least 98%, at least 99%, or even at least 99.5% of water from steam catalytic cracking effluent 140.

[0096] Gaseous effluent 164 may comprise: olefins, such as ethylene, propylene, butene, or combinations thereof; light hydrocarbon gases, such as methane, ethane, propane, n-butane, isobutane, or combinations thereof; other gases, such as, but not limited to, hydrogen; or combinations thereof. Gaseous effluent 164 may include C2-C4 olefin products generated in steam catalytic cracking reactor 130, such as, but not limited to, ethylene, propylene, butene (1-butene, cis-2-butene, trans-2-butene, isobutene, or combinations thereof) or combinations thereof. Gaseous effluent 164 may comprise at least 90%, at least 95%, at least 98%, at least 99%, or at least 99.5% of C2-C4 olefins from steam catalytic cracking effluent 140. Gaseous effluent 164 may be sent to a downstream gas separation system (not shown) to further separate gaseous effluent 164 into various product streams, such as, but not limited to, one or more olefin product streams.

[0097] In one embodiment, a liquid effluent 162 comprising water and hydrocarbons having more than five carbon atoms may be fed to an in-line centrifuge unit 170. The in-line centrifuge unit 170 is operable to separate the liquid effluent 162 into a liquid hydrocarbon effluent 172 and an aqueous effluent 174. The in-line centrifuge unit 170 may operate at speeds of 2500 rpm to 5000 rpm, 2500 rpm to 4500 rpm, 2500 rpm to 4000 rpm, 3000 rpm to 5000 rpm, 3000 rpm to 4500 rpm, or 3000 rpm to 4000 rpm to separate the hydrocarbon phase from the aqueous phase.

[0098] Liquid hydrocarbon effluent 172 may include hydrocarbons with 5 or more carbon atoms from steam catalytic cracking effluent 140. Liquid hydrocarbon effluent 172 may include small amounts of hydrocarbons with fewer than 5 carbon atoms, such as trace amounts of light hydrocarbons not separated into gaseous effluent 164. Liquid hydrocarbon effluent 172 may include light aromatic compounds produced in steam catalytic cracking reactor 130, which may include, but are not limited to, benzene, toluene, mixed xylenes, ethylbenzene, and other light aromatic compounds. Liquid hydrocarbon effluent 172 may further include other naphtha range hydrocarbons, kerosene, diesel, vacuum gas oil (VGO), or combinations thereof. Light aromatic compounds may be a portion of the naphtha fraction of hydrocarbon effluent 172. Liquid hydrocarbon effluent 172 may include 90%, at least 95%, at least 98%, at least 99%, or even at least 99.5% of the hydrocarbon composition from liquid effluent 162. Liquid hydrocarbon effluent 172 may be sent to downstream processing for further conversion or separation. At least a portion of the liquid hydrocarbon effluent 172 can be returned to the steam catalytic cracking reactor 130 for further conversion of hydrocarbons into olefins.

[0099] Aqueous effluent 174 may include water and water-soluble components from liquid effluent 162. Aqueous effluent 174 may include dissolved hydrocarbons soluble in the aqueous phase of liquid effluent 162. Aqueous effluent 174 may contain at least 95%, at least 98%, at least 99%, or even at least 99.5% water from liquid effluent 162. Aqueous effluent 174 may be sent to one or more downstream processes for further treatment. In an embodiment, at least a portion of aqueous effluent 174 may be returned to steam catalytic cracking reactor 130 as at least a portion of the water 120 introduced into steam catalytic cracking reactor 130.

[0100] In embodiments, the cracking additive comprising a metal species impregnated on ZSM-5 zeolite is prepared by the previously described method and can be used as at least a portion of the FCC catalyst composition for a fluidized bed catalytic cracking (FCC) reactor. The FCC reactor may be a fluidized bed reactor. In the FCC reactor, the FCC catalyst composition comprising the cracking additive of this disclosure may be contacted with a hydrocarbon feedstock (e.g., crude oil) in the presence of steam to produce light olefins, light aromatic compounds, or combinations thereof. In embodiments, the cracking additive included in the FCC catalyst composition may consist of a metal species impregnated on ZSM-5 zeolite. FCC methods suitable for catalytic cracking of crude oil in the presence of steam are disclosed in U.S. Patent Application Nos. 17 / 009,008, 17 / 009,012, 17 / 009,020, 17 / 009,022, 17 / 009,039, 17 / 009,048, and 17 / 009,073, all of which are incorporated herein by reference in their entirety. The hydrocarbon feedstock can be any hydrocarbon feedstock previously discussed in this disclosure. The FCC reactor can be an upflow or downflow FCC reactor. The FCC reactor system may include one or more FCC reactors and one or more catalyst regenerators.

[0101] In embodiments, the FCC reactor can be operated at a reaction temperature of at least about 500°C, such as 500°C to 800°C, 550°C to 800°C, 600°C to 800°C, 650°C to 800°C, 500°C to 750°C, 550°C to 750°C, 600°C to 750°C, 650°C to 750°C, 500°C to 700°C, 550°C to 700°C, 600°C to 700°C, or 650°C to 700°C. Steam can be injected into the FCC reactor. The hydrocarbon feedstock can be catalytically cracked in the presence of steam using an FCC catalyst composition comprising the cracking additives disclosed herein. In an FCC reactor, the mass ratio of steam to hydrocarbons can be 0.2 to 0.8, 0.3 to 0.8, 0.4 to 0.8, 0.5 to 0.8, 0.2 to 0.7, 0.3 to 0.7, 0.4 to 0.7, 0.5 to 0.7, 0.2 to 0.6, 0.3 to 0.6, 0.4 to 0.6, or 0.5 to 0.6. Steam can refer to all water in the FCC reactor. In the embodiments, the residence time of the hydrocarbon feed and steam in contact with the FCC catalyst composition in the FCC reactor can be 1 to 20 seconds, 2 to 20 seconds, 5 to 20 seconds, 8 to 20 seconds, 1 to 18 seconds, 2 to 18 seconds, 5 to 18 seconds, 8 to 18 seconds, 1 to 16 seconds, 2 to 16 seconds, 5 to 16 seconds, 8 to 16 seconds, 1 to 14 seconds, 2 to 14 seconds, 5 to 14 seconds, 8 to 14 seconds, 1 to 12 seconds, 2 to 12 seconds, 5 to 12 seconds, or 8 to 12 seconds. In embodiments, the weight ratio of the FCC catalyst composition to hydrocarbons (catalyst and oil) in the FCC reactor can be 3 to 40, such as 3 to 30, 3 to 20, 5 to 40, 5 to 30, 5 to 20, 5 to 10, 7 to 40, 7 to 30, 7 to 20, 10 to 40, 10 to 30, 10 to 20, or 20 to 40. The cracking effluent from the FCC reactor can be separated into various product streams, intermediate streams, and aqueous streams in a separation system downstream of the FCC reactor.

[0102] Example Various aspects of this disclosure will be further illustrated by the following examples. These examples are illustrative in nature and should not be construed as limiting the subject matter of this disclosure.

[0103] Examples 1 to 6: Preparation of cracks containing a first metal species and a second metal species impregnated on ZSM-5 zeolite Chemical additives In Examples 1 to 6, cracking additives comprising different metal species impregnated on ZSM-5 zeolite were prepared according to the present disclosure. To prepare the cracking additives, commercially available ZSM-5 zeolite powder (CBV3024E ZSM-5 zeolite powder from Zeolyst International, with a silica to alumina ratio of 30) was first calcined at 550°C for 5 hours at a heating rate of 5°C / min. Then, 5 grams of the calcined ZSM-5 zeolite powder was mixed with water to produce a zeolite mixture. Appropriate amounts of a first metal species precursor and a second metal species precursor were added to the water to produce a metal precursor mixture. While stirring the zeolite mixture, the metal precursor mixture was slowly added to the zeolite mixture over 1 to 30 minutes to produce a combined mixture. The total water volume of the combined mixture was 5 ml. The first and second metal species precursors for each of Examples 1 to 6 are shown in Table 3. The combined mixture was stirred at ambient temperature for 3 hours, and water was removed by slow evaporation at 60°C and atmospheric pressure under stirring to produce solid particles. The term "slow evaporation" of water refers to evaporation at a temperature below the boiling point of water. The solid particles were then dried overnight at 100°C, followed by calcination in standing air at a heating rate of 5°C / min to a final calcination temperature of 550°C, which was held for 5 hours to produce the cracking additives of Examples 1 to 6, comprising a first metal species and a second metal species impregnated on ZSM-5 zeolite. The cracking additives were granulated, sieved to a particle size of 500 µm to 1000 µm, and tested in a fixed-bed reactor. The first metal species and the second metal species, and their amounts, in each of Examples 1 to 6 are shown in Table 3.

[0104] Figure 5A The SEM image of Example 6 is shown. Figures 5B to 5F The corresponding elemental mapping for Example 6 is shown, namely Si(b), Al(c), O(d), Fe(e), and Ce(f). As shown in Figures 5(a) to 5(f), both Ce and Fe are present on the catalyst surface and are uniformly dispersed on the catalyst surface.

[0105] Table 3

[0106] Table 3 (continued)

[0107] Comparative Example 7: Balanced Catalyst For Comparative Example 7, a balanced catalyst (ECAT) was provided for comparison with the catalyst additives of Examples 1 to 6.

[0108] Examples 8-13 and Comparative Example 7: Preparation of cracking catalyst compositions In Examples 8 to 13, cracking catalyst compositions were prepared by mixing 75 wt% of ECAT with 25 wt% of each cracking additive from Examples 1 to 6. The ECAT was the same as in Comparative Example 7. For Example 8, a cracking catalyst composition was prepared by mixing 75 wt% of ECAT with 25 wt% of a cracking additive from Example 1 containing platinum oxide and lanthanum oxide impregnated on ZSM-5 zeolite. For Example 9, a cracking catalyst composition was prepared by mixing 75 wt% of ECAT with 25 wt% of a cracking additive from Example 2 containing platinum oxide and iron oxide impregnated on ZSM-5 zeolite. For Example 10, a cracking catalyst composition was prepared by mixing 75 wt% of ECAT with 25 wt% of a cracking additive from Example 3 containing molybdenum oxide and iron oxide impregnated on ZSM-5 zeolite. For Example 11, a cracking catalyst composition was prepared by mixing 75 wt% of ECAT with 25 wt% of a cracking additive comprising cerium oxide and chromium oxide impregnated on ZSM-5 zeolite, as described in Example 4. For Example 12, a cracking catalyst composition was prepared by mixing 75 wt% of ECAT with 25 wt% of a cracking additive comprising zinc oxide and chromium oxide impregnated on ZSM-5 zeolite, as described in Example 5. For Example 13, a cracking catalyst composition was prepared by mixing 75 wt% of ECAT with 25 wt% of a cracking additive comprising cerium oxide and iron oxide impregnated on ZSM-5 zeolite, as described in Example 6.

[0109] Comparative Example 14 For Comparative Example 14, a cracking catalyst was prepared comprising 100% by weight of ECAT from Comparative Example 7, based on the total amount of the cracking catalyst. Comparative Example 17 was evaluated for crude oil steam catalytic cracking, such as with AXL crude oil, in a fixed-bed reactor (FBR) system at atmospheric pressure. A description of the FBR and the reaction conditions for carrying out the steam catalytic cracking of Comparative Example 17 is provided in Example 15.

[0110] Example 15: Evaluation of cracking catalysts In Example 15, the cracking catalyst compositions of Examples 8 to 13 and Comparative Example 14 were evaluated for steam catalytic cracking of crude oil (e.g., AXL crude oil) in a fixed-bed reactor (FBR) system at atmospheric pressure. Figure 4 The results of cracking AXL crude oil on the cracking catalyst compositions of Examples 8 to 13 and Comparative Example 14 are shown.

[0111] For reference Figure 3The FBR system 300 used for the experiment of Example 13 is schematically depicted. AXL crude oil 301 is fed to the fixed bed reactor 340 using a metering pump 311.

[0112] AXL crude oil 301 has an API value of 39.3, a sulfur content of 1.6 wt%, and total carbon, hydrogen, and nitrogen contents of 84.3 wt%, 12.6 wt%, and 0.7 wt%, respectively. The simulated distillation (SimDis) performance of AXL crude oil 301 and two fractions (AXL-350℃ and AXL+350℃) was analyzed according to ASTM D-2887 (ASTM (2018)). A Shimadzu GC 2010 Plus equipped with a flame ionization detector (FID) was used to determine the three fractions: naphtha (C5-221℃), LCO (light cycle oil, 221-343℃), and HCO (heavy cycle oil, +343℃). The pIONA composition (alkanes, isoalkanes, alkenes, cycloalkanes, and aromatics) of the naphtha was determined using a Shimadzu GC equipped with a BP-1 PONA capillary column and an FID detector. As shown in Table 4, the SimDis results indicate that the naphtha content is 41% by weight, the LCO content is 26% by weight, and the HCO content is 33% by weight. The residue content of AXL crude oil 301 (above 550°C) is 4.0% by weight, and the residue content of AXL+350°C (above 550°C) is 14.0% by weight.

[0113] Table 4: Simulated distillation results of AXL crude oil and its three fractions

[0114] The constant feed rate of AXL crude oil 301 is 2 g / h. Water 302 is fed to the fixed-bed reactor 340 using metering pump 312. The water 302 is preheated using preheater 321. The constant feed rate of water 302 is 1 g / h. Nitrogen 303 is used as the carrier gas at a flow rate of 65 mL / min. Nitrogen 303 is fed to the fixed-bed reactor 340 using mass flow controller (MFC) 313. The nitrogen 303 is preheated using preheater 322. The water 302 and nitrogen 303 are mixed using mixer 330 and the mixture is introduced into the fixed-bed reactor 340. Before entering the reaction tube, AXL crude oil 301, water 302, and nitrogen 303 are preheated to 250°C in preheating zone 342. Preheating zone 342 is preheated using inline heater 331. Crude oil 301 is introduced from the top of reactor 340 through injector 341 and mixed with steam at the top two-thirds of the reaction tube before reaching the catalyst bed 344.

[0115] The catalyst bed 344 in the reaction tube 340 is moved downwards by a few centimeters to allow more time for preheating of AXL crude oil 301 before contact with the cracking catalyst composition in the catalyst bed 344. For each experiment, 1 gram (g) of the cracking catalyst composition with a mesh size of 30-40 is placed in the center of the reaction tube 340, supported by quartz wool 343, 346 and reactor insert 345. Quartz wool 343, 346 is placed at the bottom and top of the catalyst bed 344 to keep it in place. The height of the catalyst bed 344 is 1 cm to 2 cm. The cracking catalyst compositions of Examples 7 to 12 were each used as the cracking catalyst compositions for different experiments conducted in Example 13. Before carrying out the steam catalytic cracking reaction, each cracking catalyst composition of Examples 7 to 12 was steam deactivated at 810°C for 6 hours in the presence of steam.

[0116] After steam deactivation, crude oil hydrocarbon feed and water / steam are introduced into the FBR reactor tube. The reaction occurs for 45 to 60 minutes until steady state is reached. The mass ratio of steam to crude oil is 0.5 g steam per gram of crude oil. The crude oil is cracked at a cracking temperature of 675°C and a catalyst-to-crude oil weight ratio of 1:2. The residence time of crude oil and steam in the fixed-bed reactor 340 is 10 seconds. The total run time for each individual experiment in Example 13 is 5 hours.

[0117] Cracking product stream 345 is introduced into gas-liquid separator 351. A wet test meter 352 is placed downstream of gas-liquid separator 351. The gaseous products 361 and liquid products 362 from the cracking reaction are characterized by offline gas chromatography (GC) analysis using simulated distillation and naphtha analysis techniques. The reaction product streams from the cracking reaction are analyzed to determine the yields of ethylene, propylene, and butene. Yield analysis in Example 15 is as follows. Figure 4 As shown in the image.

[0118] Figure 4 The results show that the cracking catalysts of Examples 8 to 13 (which have the first and second metal species impregnated on ZSM-5 zeolite as in Examples 1 to 6) can directly convert crude oil into petrochemical products, such as light olefins and aromatic compounds. The results demonstrate that the first and second metal species impregnated on ZSM-5 zeolite in Examples 1 to 6 provide high yields of light olefins, including ethylene and propylene.

[0119] Examples 8 to 13 show ethylene yields of 16.4% to 19.8% by weight, higher than the propylene yield of Comparative Example 14. Examples 8 to 13 show propylene yields of 15.3% to 18.8% by weight, higher than the propylene yield of Comparative Example 14. Examples 8 to 13 show yields of ethylene, propylene, and butene that are higher than the yields of ethylene, propylene, and butene in Comparative Example 14.

[0120] Furthermore, compared to the cracking effluent produced using the cracking catalyst of Comparative Example 14, as shown by the reduced concentration of middle distillate and heavy distillate in the cracking effluent produced using the cracking catalysts of Examples 8 to 13, Examples 8 to 13 achieved a higher conversion rate of the middle distillate portion of the hydrocarbon feed.

[0121] A first aspect of this disclosure relates to a method for upgrading a hydrocarbon feedstock, the method comprising: contacting the hydrocarbon feedstock with steam in the presence of a cracking catalyst composition under reaction conditions sufficient to cause at least a portion of the hydrocarbons in the hydrocarbon feedstock to undergo one or more cracking reactions, to produce a steam catalytic cracking effluent comprising light olefins, light aromatic compounds, or both. The cracking catalyst composition may comprise a zeolite catalyst and a cracking additive. The cracking additive may comprise ZSM-5 zeolite, a first metal type, and a second metal type. The first and second metal types may be impregnated onto the ZSM-5 zeolite. The first metal type may comprise a metal or metal oxide comprising a first metal selected from the group consisting of chromium, iron, platinum, molybdenum, cerium, lanthanum, and zinc. The second metal type may comprise a metal or metal oxide comprising a second metal selected from the group consisting of chromium, iron, platinum, molybdenum, cerium, lanthanum, and zinc. The second metal may be different from the first metal.

[0122] The second aspect of this disclosure may include the first aspect, wherein the molar ratio of silica to alumina in ZSM-5 zeolite may be 20 to 80.

[0123] The third aspect of this disclosure may include either the first or the second aspect, wherein the molar ratio of silica to alumina in ZSM-5 zeolite may be 30.

[0124] The fourth aspect of this disclosure may include any one of the first to third aspects, wherein the concentration of the first metal species in the cracking additive may be from 0.1 wt% to 10 wt% or from 2 wt% to 10 wt% based on the total weight of the cracking additive.

[0125] The fifth aspect of this disclosure may include any one of the first to fourth aspects, wherein the concentration of the second metallic substance in the cracking additive may be 0.1 wt% to 10 wt% or 2 wt% to 10 wt% based on the total weight of the cracking additive.

[0126] The sixth aspect of this disclosure may include any one of the first to fifth aspects, wherein the first metal of the first metal class may be platinum, molybdenum, cerium or zinc, and the second metal of the second metal class may be lanthanum, iron or chromium.

[0127] The seventh aspect of this disclosure may include any one of the first to sixth aspects, wherein the first metal type may be a metal oxide selected from the group consisting of chromium oxide, iron oxide, platinum oxide, molybdenum oxide, cerium oxide, lanthanum oxide and zinc oxide, and the second metal type may be a metal oxide selected from the group consisting of chromium oxide, iron oxide, platinum oxide, molybdenum oxide, cerium oxide, lanthanum oxide and zinc oxide.

[0128] The eighth aspect of this disclosure may include any one of the first to seventh aspects, wherein the first metal may be platinum oxide, molybdenum oxide, cerium oxide or zinc oxide, and the second metal may be lanthanum oxide, iron oxide or chromium oxide.

[0129] The ninth aspect of this disclosure may include any one of the first to eighth aspects, wherein the cracking additive may be substantially phosphorus-free, or may have less than 1000 ppmw, less than 500 ppmw, or even less than 100 ppmw of phosphorus based on the total weight of the cracking additive.

[0130] The tenth aspect of this disclosure may include any one of the first to ninth aspects, wherein the cracking additive may comprise platinum oxide and lanthanum oxide impregnated on ZSM-5 zeolite, platinum oxide and iron oxide impregnated on ZSM-5 zeolite, molybdenum oxide and iron oxide impregnated on ZSM-5 zeolite, cerium oxide and chromium oxide impregnated on ZSM-5 zeolite, zinc oxide and chromium oxide impregnated on ZSM-5 zeolite, or cerium oxide and iron oxide impregnated on ZSM-5 zeolite.

[0131] The eleventh aspect of this disclosure may include any one of the first to tenth aspects, wherein the cracking additive may comprise cerium oxide and iron oxide impregnated on ZSM-5 zeolite or zinc oxide and chromium oxide impregnated on ZSM-5 zeolite, the molar ratio of silica to alumina in ZSM-5 zeolite may be 30, and the cracking additive may be substantially phosphorus-free.

[0132] The twelfth aspect of this disclosure may include any one of the first to eleventh aspects, wherein the cracking additive may consist substantially of cerium oxides and iron oxides impregnated on ZSM-5 zeolite or zinc oxides and chromium oxides impregnated on ZSM-5 zeolite.

[0133] The thirteenth aspect of this disclosure may include any one of the first to twelfth aspects, wherein the cracking additive may consist of cerium oxides and iron oxides impregnated on ZSM-5 zeolite or zinc oxides and chromium oxides impregnated on ZSM-5 zeolite.

[0134] The fourteenth aspect of this disclosure may include any one of the first to thirteenth aspects, wherein the amount of cracking additive in the cracking catalyst composition may be 20% to 30% by weight based on the cracking catalyst composition.

[0135] The fifteenth aspect of this disclosure may include any one of the first to fourteenth aspects, wherein the zeolite catalyst in the cracking catalyst composition may further comprise a balanced catalyst.

[0136] The sixteenth aspect of this disclosure may include any one of the first to fifteenth aspects, wherein the amount of equilibrium catalyst in the cracking catalyst composition may be 70% to 80% by weight based on the cracking catalyst composition.

[0137] The seventeenth aspect of this disclosure may include any one of the first to sixteenth aspects, wherein the cracking catalyst composition comprises a balance catalyst and a cracking additive, is composed of a balance catalyst and a cracking additive, or is substantially composed of a balance catalyst and a cracking additive.

[0138] The eighteenth aspect of this disclosure may include any one of the first to seventeenth aspects, wherein the zeolite catalyst is different from the ZSM-5 zeolite used as a cracking additive.

[0139] The nineteenth aspect of this disclosure may include any one of the first to eighteenth aspects, and further includes delivering a hydrocarbon feedstock to a steam catalytic cracking reactor.

[0140] The twentieth aspect of this disclosure may include any one of the first to nineteenth aspects, wherein the hydrocarbon feed comprises whole crude oil with an API gravity between 25 and 50.

[0141] The twentieth aspect of this disclosure may include any one of the first to twentieth aspects, wherein the hydrocarbon feedstock may be heavy crude oil, light crude oil, extra-light crude oil, or a combination thereof.

[0142] The 22nd aspect of this disclosure may include any one of the first to 22nd aspects, wherein the steam catalytic cracking effluent may contain olefins, and the olefins may contain one or more of ethylene, propylene, butene, or a combination thereof.

[0143] The twentieth aspect of this disclosure may include any one of the first to twenty-second aspects, wherein the steam catalytic cracking effluent may contain benzene, toluene, xylene, ethylbenzene, other light aromatic compounds having 6 to 11 carbon atoms, or combinations thereof.

[0144] The 24th aspect of this disclosure may include any one of the first to 23 aspects, wherein contacting the hydrocarbon feed with steam in the presence of the cracking catalyst composition may be performed in a steam catalytic cracking reactor, wherein the steam catalytic cracking reactor may include one or more of a fixed-bed reactor, a fluidized-bed reactor, a batch reactor, a moving-bed catalytic cracking reactor, a fluidized-catalytic cracking (FCC) reactor, or a combination thereof.

[0145] The 25th aspect of this disclosure may include any one of the first to 24th aspects, wherein contacting the hydrocarbon feed with steam in the presence of the cracking catalyst composition may include contacting the hydrocarbon feed with steam in the presence of the cracking catalyst at a reaction temperature of 500°C to 800°C.

[0146] The 26th aspect of this disclosure may include any one of the first to 25 aspects, wherein contacting the hydrocarbon feed with steam in the presence of the cracking catalyst composition may include contacting the hydrocarbon feed with steam at a steam-to-hydrocarbon mass ratio of 0.1 to 1.0 in the presence of the cracking catalyst.

[0147] The 27th aspect of this disclosure may include any one of the first to 26 aspects, wherein contacting the hydrocarbon feed with steam in the presence of the cracking catalyst composition may include a residence time of 1 second to 60 seconds in the presence of the cracking catalyst composition.

[0148] The twentieth aspect of this disclosure relates to a cracking additive for upgrading hydrocarbon feedstocks, wherein the cracking additive may comprise ZSM-5 zeolite, a first metal type, and a second metal type. The first and second metal types may be impregnated onto the ZSM-5 zeolite. The first metal type may comprise a metal or metal oxide comprising a first metal selected from the group consisting of chromium, iron, platinum, molybdenum, cerium, lanthanum, and zinc. The second metal type may comprise a metal or metal oxide comprising a second metal selected from the group consisting of chromium, iron, platinum, molybdenum, cerium, lanthanum, and zinc. The second metal may be different from the first metal.

[0149] The 29th aspect of this disclosure may include the 28th aspect, wherein the cracking additive can be prepared by a method comprising: preparing a zeolite mixture comprising ZSM-5 zeolite and water; simultaneously mixing the zeolite mixture and adding a metal precursor mixture to the zeolite mixture to produce a combined mixture, wherein the metal precursor mixture comprises a first metal precursor, a second metal precursor, and water; stirring the combined mixture at a temperature of 10°C to 30°C for a mixing time of 1 hour to 5 hours; simultaneously heating the combined mixture to an evaporation temperature of 30°C to 100°C; and simultaneously maintaining the combined mixture at the evaporation temperature for a period of 1 hour to 24 hours, wherein: maintaining the combined mixture at the evaporation temperature during mixing allows water to slowly evaporate from the combined mixture to produce solid particles, and simultaneously allowing water to slowly evaporate from the combined mixture during mixing allows the metal precursor to be dispersed on the surface of the ZSM-5 zeolite. The method for preparing the cracking additive may further include calcining the solid particles at a temperature of 400°C to 800°C for 1 hour to 12 hours to produce the cracking additive.

[0150] The twentieth or thirtieth aspect of this disclosure may include any one of the twenty-eighth or twenty-ninth aspects, further comprising drying the solid particles at a temperature of 50°C to 150°C after the combined mixture has been kept at an evaporation temperature and before calcination.

[0151] The thirty-first aspect of this disclosure may include any one of the twenty-eighth to thirtieth aspects, wherein the first metal precursor and the second metal precursor may each include chromium(III) nitrate nonhydrate (Cr(NO3)3·9H2O), ferric(III) nitrate nonhydrate (Fe(NO3)3·9H2O), tetraammineplatinum(II) nitrate (Pt(NH3)4(NO3)2), and ammonium heptamolybdate tetrahydrate ((NH4)6Mo7O). 24 ·4H2O), cerium(III) nitrate hexahydrate (Ce(NO3)3·6H2O), lanthanum nitrate hexahydrate (La(NO3)3·6H2O) or zinc nitrate hexahydrate (Zn(NO3)2·6H2O).

[0152] The thirty-second aspect of this disclosure relates to a cracking catalyst composition for upgrading hydrocarbon feedstocks, the cracking catalyst composition comprising a zeolite catalyst and a cracking additive, wherein the cracking additive comprises ZSM-5 zeolite, a first metal type, and a second metal type. The first and second metal types may be impregnated onto the ZSM-5 zeolite. The first metal type may comprise a metal or a metal oxide comprising a first metal selected from the group consisting of chromium, iron, platinum, molybdenum, cerium, lanthanum, and zinc. The second metal type may comprise a metal or a metal oxide comprising a second metal selected from the group consisting of chromium, iron, platinum, molybdenum, cerium, lanthanum, and zinc. The second metal may be different from the first metal.

[0153] The thirtieth to thirty-third aspects of this disclosure may include any one of the twenty-eighth to thirty-second aspects, wherein, based on the total weight of the cracking additive, the concentration of the first metal species in the cracking additive may be from 0.1 wt% to 10 wt% or from 2 wt% to 10 wt%.

[0154] The 34th aspect of this disclosure may include any one of the 28th to 33rd aspects, wherein the concentration of the second metal species in the cracking additive may be 0.1 wt% to 10 wt% or 2 wt% to 10 wt% based on the total weight of the cracking additive.

[0155] The thirty-fifth aspect of this disclosure may include any one of the twenty-eighth to thirty-fourth aspects, wherein the zeolite catalyst may include a balanced catalyst.

[0156] The thirty-sixth aspect of this disclosure may include any one of the twenty-eighth to thirty-fifth aspects, wherein the amount of cracking additive in the cracking catalyst composition may be 20% to 30% by weight based on the cracking catalyst composition.

[0157] The thirty-seventh aspect of this disclosure may include any one of the twenty-eighth to thirty-sixth aspects, wherein the amount of zeolite catalyst in the cracking catalyst composition may be 70% to 80% by weight based on the cracking catalyst composition.

[0158] The thirty-eighth aspect of this disclosure may include any one of the twenty-eighth to thirty-seventh aspects, wherein the zeolite catalyst is different from the ZSM-5 zeolite used as a cracking additive.

[0159] It should be noted that any two quantitative values ​​assigned to a certain characteristic can constitute a range of that characteristic, and all combinations of ranges formed by all said quantitative values ​​of a given characteristic are within the scope of this disclosure.

[0160] It should be noted that one or more of the following claims use the term "wherein" as a transitional phrase. In defining this technology, it should be noted that this term is introduced in the claims as an open transitional phrase to introduce a description of a series of features of the structure, and should be understood in the same way as the more commonly used open prepositional term "comprising".

[0161] Having referenced to specific aspects and described the subject matter of this disclosure in detail, it should be noted that the various details of these aspects should not be construed as implying that such details are essential components of these aspects. Rather, the appended claims should be considered the sole expression of the breadth of this disclosure and the corresponding scope of the aspects described herein. Furthermore, it will be apparent that modifications and variations may be made without departing from the scope of the appended claims.

Claims

1. A method for upgrading a hydrocarbon feedstock, the method comprising: In the presence of a cracking catalyst composition, the hydrocarbon feed is contacted with steam under reaction conditions sufficient to cause at least a portion of the hydrocarbons in the hydrocarbon feed to undergo one or more cracking reactions, to produce a steam catalytic cracking effluent comprising light olefins, light aromatic compounds, or both, wherein: The cracking catalyst composition comprises a zeolite catalyst and a cracking additive; The cracking additive comprises ZSM-5 zeolite, a first metal type, and a second metal type; The first metal type and the second metal type are impregnated onto the ZSM-5 zeolite; The first metal species comprises a metal or metal oxide, wherein the metal or metal oxide comprises a first metal selected from the group consisting of chromium, iron, platinum, molybdenum, cerium, lanthanum and zinc; The second metal category comprises a metal or metal oxide, said metal or metal oxide comprising a second metal selected from the group consisting of chromium, iron, platinum, molybdenum, cerium, lanthanum, and zinc; and The second metal is different from the first metal.

2. The method according to claim 1, wherein the molar ratio of silica to alumina in the ZSM-5 zeolite is 20 to 80.

3. The method according to any one of claims 1 or 2, wherein: Based on the total weight of the cracking additive, the concentration of the first metal species in the cracking additive is from 0.1% to 10% by weight or from 2% to 10% by weight. Based on the total weight of the cracking additive, the concentration of the second metal species in the cracking additive is 0.1% to 10% by weight or 2% to 10% by weight; Or both.

4. The method according to any one of claims 1 to 3, wherein: The first metal in the first metal class is platinum, molybdenum, cerium, or zinc; and The second metal in the second metal category is lanthanum, iron, or chromium.

5. The method according to any one of claims 1 to 4, wherein: The first metal type is a metal oxide selected from the group consisting of chromium oxide, iron oxide, platinum oxide, molybdenum oxide, cerium oxide, lanthanum oxide, and zinc oxide; and The second metal type is a metal oxide selected from the group consisting of chromium oxide, iron oxide, platinum oxide, molybdenum oxide, cerium oxide, lanthanum oxide, and zinc oxide.

6. The method according to any one of claims 1 to 5, wherein: The first metal is platinum oxide, molybdenum oxide, cerium oxide, or zinc oxide; and The second metal is lanthanum oxide, iron oxide, or chromium oxide.

7. The method according to any one of claims 1 to 6, wherein, The cracking additive comprises: Platinum oxide and lanthanum oxide impregnated on the ZSM-5 zeolite; Platinum oxides and iron oxides impregnated on the ZSM-5 zeolite; Molybdenum oxide and iron oxide impregnated on the ZSM-5 zeolite; Cerium oxide and chromium oxide impregnated on the ZSM-5 zeolite; Zinc oxide and chromium oxide impregnated on the ZSM-5 zeolite; or Cerium oxides and iron oxides impregnated on the ZSM-5 zeolite.

8. The method according to any one of claims 1 to 7, wherein: The cracking additive comprises cerium oxides and iron oxides impregnated on the ZSM-5 zeolite, or zinc oxides and chromium oxides impregnated on the ZSM-5 zeolite. The ZSM-5 zeolite has a silica to alumina molar ratio of 30, and The cracking additive is essentially phosphorus-free.

9. The method according to any one of claims 1 to 8, wherein the cracking additive is substantially composed of cerium oxide and iron oxide impregnated on the ZSM-5 zeolite or zinc oxide and chromium oxide impregnated on the ZSM-5 zeolite.

10. The method according to any one of claims 1 to 9, wherein the cracking additive consists of cerium oxide and iron oxide impregnated on the ZSM-5 zeolite or zinc oxide and chromium oxide impregnated on the ZSM-5 zeolite.

11. The method according to any one of claims 1 to 10, wherein, Based on the cracking catalyst composition, the amount of the cracking additive in the cracking catalyst composition is 20% to 30% by weight.

12. The method according to any one of claims 1 to 11, wherein the hydrocarbon feed is delivered to a steam catalytic cracking reactor, wherein the hydrocarbon feed comprises whole crude oil with an API gravity between 25 and 50.

13. A cracking additive for upgrading hydrocarbon feedstock, said cracking additive comprising ZSM-5 zeolite, a first metal type, and a second metal type, wherein: The first metal type and the second metal type are impregnated onto the ZSM-5 zeolite; The first metal species comprises a metal or metal oxide, wherein the metal or metal oxide comprises a first metal selected from the group consisting of chromium, iron, platinum, molybdenum, cerium, lanthanum and zinc; The second metal category comprises a metal or metal oxide, said metal or metal oxide comprising a second metal selected from the group consisting of chromium, iron, platinum, molybdenum, cerium, lanthanum, and zinc; and The second metal is different from the first metal.

14. The cracking additive according to claim 13, wherein the cracking additive is prepared by a method comprising: Prepare a zeolite mixture comprising the ZSM-5 zeolite and water; While mixing the zeolite mixture, a metal precursor mixture is added to the zeolite mixture to produce a combined mixture, wherein the metal precursor mixture comprises a first metal precursor, a second metal precursor, and water; The combined mixture is stirred at a temperature of 10°C to 30°C for 1 to 5 hours. While stirring, the combined mixture is heated to an evaporation temperature of 30°C to 100°C; While stirring, the combined mixture is maintained at the evaporation temperature for a period of 1 hour to 24 hours, wherein: While mixing, the combined mixture is maintained at the evaporation temperature, allowing water to slowly evaporate from the combined mixture, thereby producing solid particles; as well as While mixing, water is slowly evaporated from the combined mixture, causing the metal precursors to disperse on the surface of the ZSM-5 zeolite. as well as The solid particles are calcined at a temperature of 400°C to 800°C for 1 to 12 hours to produce the cracking additive.

15. A cracking catalyst composition for upgrading hydrocarbon feedstock, wherein the cracking catalyst composition comprises a zeolite catalyst and the cracking additive of claim 13, wherein, The zeolite catalyst is different from the ZSM-5 zeolite in the cracking additive.

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