Modified ZSM-5 for enhanced catalytic cracking of crude oil steam to 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 metal species impregnated on the ZSM-5 zeolite wherein the metal species comprises a metal selected from the group consisting of chromium, vanadium, iron, platinum, molybdenum, cerium and nickel.

Description

Cross Reference to Related Applications

[0001] This application claims priority to U.S. Patent Application Serial No. 18 / 181,644, filed March 10, 2023, entitled “Modified ZSM-5 for Steam Enhanced Catalytic Cracking of Crude Oil to Light Olefins and Aromatics,” the entire contents of which are incorporated by reference into the present disclosure. TECHNICAL FIELD

[0002] The present 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

[0003] The global demand for higher value petrochemical products and chemical intermediates continues to grow, which remains a challenge for many integrated refineries. In particular, the production of some valuable light olefins, such as pure olefin streams, are of interest as they are considered as the building blocks for polymer synthesis, such as ethylene and propylene. In addition, light aromatic compounds, such as benzene, toluene, and mixed xylenes, can be used as fuel blending components, or can be converted to higher value chemical products and intermediates, which can be used as building blocks in chemical synthesis processes. Petrochemical feedstocks, such as crude oil, can be converted to petrochemicals, such as fuel blending components, chemical products and intermediates, such as light olefins and aromatic compounds, which are the basic intermediates for most of the petrochemical industry. Crude oil is typically processed through distillation, followed by various reforming, solvent treatment, and hydroconversion processes to produce a range of desired fuels, lubricating oil products, chemicals, chemical feedstocks, and the like. Conventional refining systems typically combine multiple complex refining units with petrochemical plants to produce higher value petrochemical products and intermediates. SUMMARY

[0004] Accordingly, there is a continuing need for cracking catalysts and processes 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. The present disclosure relates to a method for upgrading a hydrocarbon feedstock. The method includes contacting the hydrocarbon feedstock with steam in the presence of a cracking catalyst composition under reaction conditions sufficient to cause one or more cracking reactions of at least a portion of the hydrocarbons in the hydrocarbon feedstock to produce a steam catalytically cracked effluent comprising light olefins, light aromatic compounds, or both. The cracking catalyst composition includes a cracking additive comprising a metal species impregnated on a ZSM-5 zeolite, wherein the metal species includes a metal selected from the group consisting of chromium, vanadium, iron, platinum, molybdenum, cerium, and nickel. In embodiments, the cracking catalyst composition can further include a zeolite catalyst separate from the cracking additive in addition to the cracking additive.

[0005] According to one or more aspects of the present disclosure, a method for upgrading a hydrocarbon feed includes contacting a hydrocarbon feed with steam in the presence of a cracking catalyst composition under reaction conditions sufficient to cause one or more cracking reactions of at least a portion of the hydrocarbons in the hydrocarbon feed 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 metal species impregnated on a ZSM-5 zeolite, wherein the metal species comprises a metal selected from the group consisting of chromium, vanadium, iron, platinum, molybdenum, cerium, and nickel.

[0006] According to one or more other aspects of the present disclosure, a cracking catalyst composition for upgrading a hydrocarbon feed comprises a zeolite catalyst and a cracking additive comprising a metal species impregnated on a ZSM-5 zeolite, wherein the metal species comprises a metal selected from the group consisting of chromium, vanadium, iron, platinum, molybdenum, cerium, and nickel.

[0007] Additional features and advantages of aspects of the present disclosure will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art who practice the aspects of the present disclosure, and will be learned by practice of the same. BRIEF DESCRIPTION OF DRAWINGS

[0008] The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee.

[0009] The detailed description of the present disclosure will be better understood in conjunction with the appended figures, wherein: 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 the present disclosure; Figure 2 A flow diagram of a method for producing a cracking additive comprising a metal species impregnated on a ZSM-5 zeolite is depicted according to one or more embodiments shown and described in the present disclosure; Figure 3 X-ray diffraction (XRD) spectra of the FCC catalyst (E-Cat) in Comparative Example 9, which is not impregnated with a metal species, is depicted by graph; Figure 4 X-ray diffraction (XRD) spectra of the cracking additives comprising ZSM-5 impregnated with a metal species in Examples 1-7 and the zeolite catalyst in Comparative Example 8 according to one or more embodiments shown and described in the present disclosure are depicted by graph; Figure 5Graphically depicted is the function of temperature (y-axis) versus percent recovery by weight (x-axis) for AXL crude oil, a heavy fraction of AXL crude oil (BP > 350°C), and a light fraction of AXL crude oil (BP < 350°C) in simulated distillation, according to one or more embodiments shown and described herein; Figure 6 Schematically depicted is a general flow diagram of a fixed bed reactor system used to evaluate the cracking catalyst compositions of Examples 10-16, according to one or more embodiments shown and described herein; Figure 7 Graphically depicted is the product yield from cracking AXL crude oil with the cracking catalyst compositions of Examples 10-16 and Comparative Examples 17-18, according to one or more embodiments shown and described herein; Figure 8 Graphically depicted is the product yield from cracking the naphtha fraction of AXL crude oil with the cracking catalyst compositions of Examples 10-16 and Comparative Examples 17-18, according to one or more embodiments shown and described herein; Figure 9A Scanning electron microscope (SEM) images of Comparative Example 8 are shown; Figure 9B SEM images of Example 15, according to one or more embodiments shown and described herein, are shown; and Figures 9C-9F Corresponding elemental maps of Example 15, according to one or more embodiments shown and described herein, are shown, namely Si (c), Al (d), O (e), and Ce (f).

[0010] In describing Figure 1 and Figure 6 simplified schematic diagrams, many of the valves, temperature sensors, electronic controllers, etc. that are well known and can be used by those of ordinary skill in the art can not be included. In addition, accompanying components such as air supply, heat exchangers, surge tanks, etc. that are typically included in systems such as those shown in Figure 1 and Figure 6 may also not be included. However, those of ordinary skill in the art understand that these components are within the scope of the present disclosure.

[0011] In addition, Figure 1 and Figure 6The arrows in the simplified schematic diagrams refer to process streams. However, these arrows can also refer to transfer lines that can transport the process streams between two or more system components. An arrow connected to one or more system components indicates an inlet or outlet in the given system component, while an arrow connected to only one system component indicates a system outlet stream exiting the illustrated system or a system inlet stream entering the illustrated system. The direction of the arrow generally corresponds to the primary direction of movement of the process stream or the process stream contained within the physical transfer line that the arrow represents.

[0012] Figure 1 and Figure 6 The arrows in the simplified schematic diagrams can also refer to process steps that transport a process stream from one system component to another system component. For example, an arrow pointing from a first system component to a second system component can indicate that a process stream is "delivered" from the first system component to the second system component, which can include the process stream "leaving" or being "removed" from the first system component and the process stream being "introduced" to the second system component.

[0013] Various aspects will now be presented in more detail. DETAILED DESCRIPTION

[0014] The present disclosure relates to cracking catalyst compositions and methods for steam enhanced catalytic cracking of crude oil to produce a higher yield of light olefins, light aromatic compounds, or both. The methods for upgrading a hydrocarbon feed of the present disclosure include contacting a hydrocarbon feed with steam in the presence of a cracking catalyst composition in a steam catalytic cracking reactor under reaction conditions sufficient to cause one or more cracking reactions of at least a portion of the hydrocarbons in the hydrocarbon feed to produce a steam catalytic cracking effluent comprising light olefins, light aromatic compounds, or both. The cracking catalyst composition comprises a cracking additive comprising a metal species impregnated on a ZSM-5 zeolite, wherein the metal species comprises a metal selected from the group consisting of chromium, vanadium, iron, platinum, molybdenum, cerium, and nickel. In embodiments, the cracking catalyst composition can further include a zeolite catalyst combined with and distinct from the cracking additive.

[0015] The cracking additive can be prepared by a method comprising: preparing a zeolite mixture comprising ZSM-5 zeolite and water; while mixing the zeolite mixture, adding a metal precursor mixture to the zeolite mixture to produce a combined mixture, wherein the metal precursor mixture comprises a metal species precursor and water; stirring the combined mixture at a temperature of 10 degrees Celsius (°C) to 30 °C for a mixing time of 1 hour to 5 hours; while stirring, heating the combined mixture to an evaporation temperature of 30 °C to less than 100 °C; and while stirring, maintaining the combined mixture at the evaporation temperature for a period of 1 hour to 24 hours. Maintaining the combined mixture at the evaporation temperature while mixing can cause water to slowly evaporate from the combined mixture, thereby producing solid particles. Slowly evaporating water from the combined mixture while mixing can cause the metal species precursor to disperse on the surface of the ZSM-5 zeolite. The method can further comprise calcining the solid particles at a temperature of 400 °C to 800 °C for 1 hour to 12 hours to produce the cracking additive. The method of preparing the cracking additive can result in a higher degree of dispersion of the metal species on the surface of the ZSM-5 zeolite than other conventional methods of impregnating a metal or metal oxide on the surface of a zeolite. The higher degree of dispersion of the metal species on the surface of the ZSM-5 zeolite in the cracking additive can improve the conversion of crude oil in steam enhanced catalytic cracking and can improve the yield of light olefins, light aromatic compounds, or both, compared to other commercially available catalysts.

[0016] As used in the present disclosure, the term "cracking" refers to a chemical reaction in which a molecule having a carbon-carbon bond is broken into more than one molecule by breaking one or more carbon-carbon bonds, or a cyclic molecule having a carbon-carbon bond is converted into an acyclic molecule by breaking one or more carbon-carbon bonds. As used in the present disclosure, the term "catalytic cracking" refers to cracking that is performed in the presence of a catalyst. Certain catalysts can have multiple forms of catalytic activity, and invoking a catalyst for a certain specific function does not mean that the catalyst cannot have catalytic activity for other functions.

[0017] As used in the present disclosure, the term "catalyst" refers to any substance that can speed up the rate of a particular chemical reaction, such as but not limited to a cracking reaction.

[0018] As used in the present disclosure, the term "used catalyst" refers to a catalyst that has been contacted with a reactant under reaction conditions, but has not been regenerated in a regenerator or by a regeneration process. The "used catalyst" can have coke deposited on the catalyst and can include partially coked catalyst as well as fully coked catalyst. The amount of coke deposited on the "used catalyst" can be greater than the amount of coke remaining on a regenerated catalyst after regeneration. The "used catalyst" can also include a catalyst that has been reduced in temperature as a result of contact with a reactant (as compared to the catalyst prior to contact with the reactant).

[0019] As used in the present disclosure, the term "regenerated catalyst" refers to a catalyst that has been regenerated in a regenerator or by an in-place regeneration process after being contacted with a reactant under reaction conditions, which process heats the catalyst to a higher temperature, oxidizes, and removes at least a portion of the coke or other organic contaminants from the catalyst to restore at least a portion of the catalytic activity of the catalyst, or both. The "regenerated catalyst" can have less coke or organic contaminants, a higher temperature, or both, than a used catalyst; and can have a higher catalytic activity than a used catalyst. The "regenerated catalyst" can have more coke and reduced catalytic activity than a fresh catalyst that has not been contacted with a reactant in a cracking reaction zone and then regenerated.

[0020] As used throughout this disclosure, the terms "butene" or "mixed butenes" are used interchangeably and refer to a combination of one or more of isobutene, 1-butene, Trans -2-butene, or Cis -2-butene. As used throughout this disclosure, the term "normal butenes" refers to 1-butene, Trans -2-butene, or Cis -2-butene. As used throughout this disclosure, the term "2-butene" refers to Trans -2-butene, Cis -2-butene, or a combination thereof.

[0021] As used in the present disclosure, the term "initial boiling point" or "IBP" of a composition refers to the temperature at which the component with the lowest boiling temperature in the composition begins to transition from a liquid phase to a gas phase. As used in the present disclosure, the term "end boiling point" or "EBP" of a composition refers to the temperature at which the component with the highest boiling temperature in the composition transitions from a liquid phase to a gas phase. A hydrocarbon mixture can be characterized by a distillation profile, expressed in terms of the boiling temperature at which a particular weight percent of the composition transitions from a liquid phase to a gas phase.

[0022] As used in the present disclosure, the term "atmospheric boiling point temperature" refers to the boiling point temperature of a compound at atmospheric pressure.

[0023] As used in the present disclosure, the term "crude oil" or "whole crude oil" should be understood to mean a mixture of petroleum liquids, gases, or a combination of liquids and gases, including in some embodiments impurities that have not been subjected to significant separation or reaction processes, such as but not limited to sulfur-containing compounds, nitrogen-containing compounds, and metal compounds. Crude oil is different from a crude oil fraction, which is obtained by fractionating crude oil by distillation. In embodiments, the crude oil feedstock can be a minimally treated light crude oil to provide a crude oil feedstock having 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 weight percent (wt.%).

[0024] As used in the present disclosure, the term "directly" delivering a stream or effluent from one unit to another unit means delivering the stream or effluent from the first unit to the second unit without passing the stream or effluent through an intermediate reaction system or separation system that would substantially change 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, pressure regulators, compressors, or other pressure devices are not considered intermediate systems that would change the composition of the stream or effluent. Combining two streams or effluents together is also not considered to include an intermediate system that changes the composition of one or both of the combined streams or effluents.

[0025] As used in the present disclosure, the terms "downstream" and "upstream" refer to the positioning of components or unit operations in a processing system relative to the direction of flow of material through the processing system. For example, if material flowing through a processing system encounters a first component before encountering a second component, the second component is considered to be "downstream" of the first component. Likewise, if material flowing through a processing system encounters a first component before encountering a second component, the first component is considered to be "upstream" of the second component.

[0026] As used in the present 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 is different from the stream that entered the reactor, reaction zone, or separator. It will be understood that unless otherwise specified, when an effluent is delivered to another component or system, only a portion of the effluent can be delivered. For example, a slipstream or bleed stream can carry away some of the effluent, meaning that only a portion of the effluent can enter a downstream component or system. The terms "reaction effluent" and "reactor effluent" specifically refer to a stream delivered from a reactor or reaction zone.

[0027] As used in the present disclosure, the term "residence time" refers to the length of time a reactant is in contact with a catalyst under reaction conditions, such as at a reaction temperature.

[0028] As used in the present disclosure, the term "reactor" refers to any vessel, container, conduit, or the like, in which one or more chemical reactions, such as but not limited to catalytic cracking reactions, can occur between one or more reactants, optionally in the presence of one or more catalysts. One or more "reaction zones" can be provided within a reactor. The term "reaction zone" refers to a volume in a reactor in which a particular chemical reaction occurs.

[0029] As used in the present disclosure, the terms "separation unit" and "separator" refer to any separation device or collection of separation devices that at least partially separates one or more chemical constituents of a mixture from one another. For example, a separation system selectively separates different chemical constituents from one another, thereby forming one or more chemical fractions. Examples of separation systems include, but are not limited to, a distillation column, a fractionator, a flash tank, a knockout pot, a centrifuge, a decanter, a filtration device, a trap, a scrubber, an expansion device, a membrane, a solvent extraction device, an adsorption device, a chemical separator, a crystallizer, a chromatograph, a precipitator, an evaporator, a dryer, a high pressure separator, a low pressure separator, or a combination of these. The separation processes described in the present disclosure can not completely separate all of one chemical constituent from all of another chemical constituent. Rather, the separation processes described in the present disclosure "at least partially" separate different chemical constituents from one another, even if not explicitly stated, separation can include only partial separation.

[0030] It is further understood that streams can be named according to the components of the stream, and that the components used to name the stream can be the major constituents of the stream (e.g., the constituents that make up the largest portion of the stream, excluding inert dilution gases such as nitrogen, noble gases, and the like, unless otherwise noted). It is also understood that when a stream comprising a certain component is disclosed as being delivered from one system component to another system component, it is meant that the component of the stream is disclosed as being delivered from the one system component to the other system component. For example, a disclosed "hydrocarbon stream" delivered to or from a first system component to a second system component is understood to be equivalent to a disclosed "hydrocarbon" delivered to or from the first system component to the second system component.

[0031] Conventional oil refining systems include multiple unit operations to convert crude oil and other heavy hydrocarbon streams into higher value products and intermediates, such as light olefins, light aromatic compounds, or combinations thereof. Steam enhanced catalytic cracking of crude oil can directly reduce the complexity of the oil refining process, such as reducing the number of unit operations required to process the crude oil. Steam enhanced catalytic cracking generally includes contacting a hydrocarbon feed with steam in the presence of a MFI structure zeolite, such as a ZSM-5 zeolite. Steam enhanced catalytic cracking using ZSM-5 zeolites can have lower selectivity to olefins than desired.

[0032] The present disclosure relates to steam catalytic cracking of crude oil using a cracking catalyst composition comprising a cracking additive comprising a metal species impregnated on a ZSM-5 zeolite to convert hydrocarbons in the crude oil into higher value hydrocarbon products, such as, but not limited to, light olefins, light aromatic compounds, or combinations thereof. In embodiments, the cracking catalyst composition can include a zeolite catalyst different from the cracking additive in addition to the cracking additive. The cracking additive of the present disclosure has a higher dispersion of the metal species on the surface of the ZSM-5 zeolite compared to catalysts prepared by other methods. As a result, the cracking additive of the present disclosure can improve the selectivity to light olefins (such as ethylene, propylene, butylene, or combinations thereof), light aromatic compounds, or both compared to steam enhanced catalytic cracking of crude oil using a ZSM-5 zeolite without the metal species and a zeolite catalyst without the cracking additive. The present disclosure also relates to a cracking catalyst composition comprising a cracking additive, wherein the cracking additive comprises a metal species impregnated on a ZSM-5 zeolite, and a method of making a cracking additive comprising a metal species impregnated on a ZSM-5 zeolite.

[0033] Reference will now be made to Figure 1The present disclosure provides a method for converting a hydrocarbon feed 102 to light olefins, light aromatic compounds, or both, comprising: contacting the hydrocarbon feed 102 with steam in the presence of a cracking catalyst composition 132 under reaction conditions sufficient to cause one or more cracking reactions of at least a portion of the hydrocarbons in the hydrocarbon feed 102 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 metal species impregnated on a ZSM-5 zeolite. In embodiments, the cracking catalyst composition 132 can further include a zeolite catalyst different from the cracking additive, such as but not limited to a balance catalyst, in addition to the cracking additive.

[0034] The hydrocarbon feed 102 can include one or more heavy oils, such as but not limited to crude oil, bitumen, oil sands, shale oil, coal liquids, vacuum residue, tar sands, other heavy oil streams, or combinations of these. It should be understood that as used in the present disclosure, “heavy oil” refers to crude hydrocarbons that have not been previously treated by distillation, such as whole crude oil, or can refer to hydrocarbon oils that have been treated to some extent prior to being introduced into the process as the hydrocarbon feed 102. The hydrocarbon feed 102 can have a density greater than or equal to 0.80 grams per milliliter. The hydrocarbon feed 102 can have an end boiling point (EBP) greater than 565°C. The hydrocarbon feed 102 can have a nitrogen concentration less than or equal to 3000 parts per million by weight (ppmw).

[0035] In embodiments, the hydrocarbon feed 102 can be a crude oil, such as whole crude oil or synthetic crude oil. The crude oil can have an American Petroleum Institute (API) gravity of 22 degrees to 50 degrees, such as 22 degrees to 40 degrees, 25 degrees to 50 degrees, or 25 degrees to 40 degrees. For example, the hydrocarbon feed 102 can include extra light crude oil, light crude oil, medium crude oil, heavy crude oil, or combinations of these. In embodiments, the hydrocarbon feed 102 can be a light crude oil, such as but not limited to an Arab Light export crude oil. Example properties of an exemplary grade of Arab Light (AL) crude oil are provided in Table 1.

[0036] Table 1 - AL export feed example

[0037] In embodiments, the hydrocarbon feed 102 can be an Arab Extra Light (AXL) crude oil. An example boiling point distribution of an exemplary grade of AXL crude oil is provided in Table 2.

[0038] Table 2: AXL feed example

[0039] When the hydrocarbon feed 102 comprises crude oil, the crude oil can be whole crude oil, or can be crude oil that has been at least subjected to some treatment, such as desalting, solids separation, washing, or other treatment that does not change the composition of the hydrocarbons of the crude oil. For example, the hydrocarbon feed 102 can be desalted crude oil that has been subjected to desalting treatment. In embodiments, the hydrocarbon feed 102 can comprise crude oil that has not been subjected to pre-treatment, separation (such as distillation), or other operation or treatment that changes the hydrocarbon composition of the crude oil prior to introduction of the crude oil into the system 100.

[0040] In embodiments, the hydrocarbon feed 102 can be crude oil having a boiling point profile of 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 temperature at which a given weight percent of the hydrocarbon feed stream is boiling. In embodiments, the crude oil can have one or more of the following: a 5 wt% boiling temperature of less than or equal to 150°C, a 25 wt% boiling temperature of less than or equal to 225°C or less than or equal to 200°C, a 50 wt% boiling temperature of less than or equal to 500°C, less than or equal to 450°C, or less than or equal to 400°C, a 75 wt% boiling temperature of less than 600°C, less than or equal to 550°C, a 95 wt% boiling temperature of greater than or equal to 550°C or greater than or equal to 600°C, or a combination of these. In embodiments, the crude oil can have one or more of the following: a 5 wt% boiling temperature of 0°C to 100°C, a 25 wt% boiling temperature of 150°C to 250°C, a 50 wt% boiling temperature of 250°C to 400°C, a 75 wt% boiling temperature of 350°C to 600°C, and a final boiling point temperature of 500°C to 1000°C (such as 500°C to 800°C).

[0041] Referring again to Figure 1 , one embodiment of a steam catalytic cracking system 110 for steam catalytic cracking of the hydrocarbon feed 102 is schematically depicted. The steam catalytic cracking system 110 can include at least one steam catalytic cracking reactor 130. The steam catalytic cracking reactor 130 can include one or more fixed bed reactors, fluidized bed reactors, batch reactors, fluid catalytic cracking (FCC) reactors, moving bed catalytic cracking reactors, or a combination of these reactors. In embodiments, the steam catalytic cracking reactor 130 can be a fixed bed reactor. In embodiments, the steam catalytic cracking reactor 130 can include a plurality of fixed bed reactors operated in a swing 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, can also be used to contact the hydrocarbon feed 102 with steam in the presence of a cracking catalyst composition 132 to perform the steam catalytic cracking of the methods disclosed herein.

[0042] In the presence of the cracking catalyst composition 132 comprising the cracking additive of the present disclosure, the steam catalytic cracking reactor 130 is operable to contact the hydrocarbon feed 102 with steam, thereby producing a steam catalytic cracking effluent 140 comprising light olefins, light aromatic compounds, or a combination of these. As previously mentioned, the steam catalytic cracking reactor 130 can be a fixed bed catalytic cracking reactor, which can include the cracking catalyst composition 132 disposed within a steam catalytic cracking zone 134. The steam catalytic cracking reactor 130 can include a porous packing 136, such as a silica carbide packing, upstream of the steam catalytic cracking zone 134. The porous packing 136 can ensure adequate heat transfer to the hydrocarbon feed 102 and steam prior to the steam catalytic cracking reaction in the steam catalytic cracking zone 134.

[0043] Referring again to Figure 1 The hydrocarbon feed 102 can be introduced to the steam catalytic cracking reactor 130. In embodiments, the hydrocarbon feed 102 can be introduced directly to the steam catalytic cracking system 110, such as by delivering a 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 embodiments, 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-containing compounds, heavy metals, or other contaminants that can reduce the effectiveness of the cracking catalyst composition 132.

[0044] The methods disclosed herein can include introducing the hydrocarbon feed 102 to the steam catalytic cracking system 110, such as introducing the hydrocarbon feed 102 to the steam catalytic cracking reactor 130. Introducing the hydrocarbon feed 102 to the steam catalytic cracking reactor 130 can include heating the hydrocarbon feed 102 to a temperature of 35 °C to 150 °C, and then delivering the hydrocarbon feed 102 to the steam catalytic cracking reactor 130. In embodiments, the hydrocarbon feed 102 can be heated to a temperature 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.

[0045] In embodiments, delivering the hydrocarbon feed 102 to the steam catalytic cracking reactor 130 can include delivering the hydrocarbon feed 102 to a feed pump 104, where the feed pump 104 can increase the pressure of the hydrocarbon feed 102 and transport the hydrocarbon feed 102 to the steam catalytic cracking reactor 130. The flowrate of the feed pump 104 can be adjusted to deliver the hydrocarbon feed 102 to the steam catalytic cracking reactor 130 at a flowrate greater than or equal to 0.1 gallons per hour (gph) to less than or equal to 1000 gph. In embodiments, the flowrate of the feed pump 104 can be greater than or equal to 0.1 gph to less than or equal to 500 gph, 0.1 gph to less than or equal to 250 gph, 0.1 gph to less than or equal to 100 gph, 0.1 gph to less than or equal to 50 gph, 0.1 gph to less than or equal to 10 gph, 0.1 gph to less than or equal to 5 gph, 0.1 gph to less than or equal to 1 gph, 0.1 gph to less than or equal to 0.5 gph, 0.1 gph to less than or equal to 0.1 gph, 0.1 gph to less than or equal to 0.05 gph, 0.1 gph to less than or equal to 0.01 gph, 0.1 gph to less than or equal to 0.005 gph, 0.1 gph to less than or equal to 0.001 gph, 0.1 gph to less than or equal to 0.0005 gph, 0.1 gph to less than or equal to 0.0001 gph, 0.1 gph to less than or equal to 0.00005 gph, 0.1 gph to less than or equal to 0.00001 gph, 0.1 gph to less than or equal to 0.000005 gph, 0.1 gph to less than or equal to 0.000001 gph, 0.1 gph to less than or equal to 0.0000005 gph, or 0.1 gph to less than or equal to 0.0000001 gph. -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 into the steam catalytic cracking reactor 130. The hydrocarbon feed 102 can be further preheated in the feed inlet line 106 to an inlet temperature of 100°C to 250°C prior to being injected into the steam catalytic cracking reactor 130.

[0046] The water 120 can be injected into the steam catalytic cracking reactor 130 via the water feed line 122 by a water feed pump 124. The water feed line 122 can be preheated to heat the water 120 to a temperature 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 to steam in the water feed line 122 or upon contact with the hydrocarbon feed 102 in the steam catalytic cracking reactor 130. The flow rate of the water feed pump 124 can be adjusted to deliver the water 120 (liquid, steam, or both) to the steam catalytic cracking reactor 130 at a GHSV equivalent to greater than or equal to 0.1 h -1 , greater than or equal to 0.5 h -1 , greater than or equal to 1 h -1 , greater than or equal to 5 h -1 , greater than or equal to 6 h -1 , greater than or equal to 10 h -1 , or even greater than or equal to 15 h -1 . The water 120 can be introduced into the steam catalytic cracking reactor 130 at a GHSV equivalent to less than or equal to 100 h -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 water 120 can be introduced into the steam catalytic cracking reactor 130 at a GHSV equivalent to 0.1 h -1 to 100 h -1 , 0.1 h -1 to 75 h -1 , 0.1 h -1 to 50 h -1 , 0.1 h -1 to 30 h -1 , 0.1 h -1 to 20 h -1 , 1 h -1 to 100 h -1 , 1 h -1 to 75 h -1 , 1 h -1 to 50 h -1 , 1 h -1 to 30 h -1 , or 1 h -1 to 20 h-1 The flow rate of water 120 introduced into the steam catalytic cracking reactor 130 at a GHSV.

[0047] The steam generated by the injection of water 120 into the steam catalytic cracking reactor 130 can lower the hydrocarbon partial pressure, which can have a dual effect: increasing the yield of light olefins (e.g., ethylene, propylene, and butylenes), 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 butylenes are generated primarily through catalytic cracking reactions following a carbonium ion 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 lower the concentration of reactants and products, thereby favoring selectivity to light olefins. Steam can also suppress secondary reactions leading to coke formation on the catalyst surface, which favors the cracking catalyst composition to maintain high average activity.

[0048] The mass flow rate of water 120 into the steam catalytic cracking reactor 130 can be lower than the mass flow rate of the hydrocarbon feed 102 into the steam catalytic cracking reactor 130. In embodiments, the mass flow ratio of water 120 to hydrocarbon feed 102 introduced into the steam catalytic cracking reactor 130 can be less than 1, such as 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 embodiments, the mass flow ratio of water 120 to hydrocarbon feed 102 introduced into the steam catalytic cracking reactor 130 can be from 0.2 to less than 1, from 0.2 to 0.9, from 0.2 to 0.8, from 0.2 to 0.7, from 0.2 to 0.6, from 0.3 to less than 1, from 0.3 to 0.9, from 0.3 to 0.8, from 0.3 to 0.7, from 0.3 to 0.6, from 0.4 to less than 1, from 0.4 to 0.9, from 0.4 to 0.8, from 0.4 to 0.7, from 0.4 to 0.6, from 0.5 to less than 1, from 0.5 to 0.9, from 0.5 to 0.8, from 0.5 to 0.7, from 0.5 to 0.6. The mass flow ratio of water to hydrocarbon feed 102 is equal to the mass flow rate of water 120 into the steam catalytic cracking reactor 130 divided by the mass flow rate of the hydrocarbon feed 102 into the steam catalytic cracking reactor 130. In embodiments, the mass flow ratio of water 120 to hydrocarbon feed 102 introduced into the steam catalytic cracking reactor 130 can be about 0.5. In the steam catalytic cracking reactor 130, the water can be present in the form of steam.

[0049] Referring again to Figure 1In the steam catalytic cracking reactor 130, the steam catalytic cracking system 110 is operable to contact the hydrocarbon feed 102 with steam (from the water 120) in the presence of the cracking catalyst composition 132 at reaction conditions sufficient to cause one or more cracking reactions to at least a portion of the hydrocarbons in the hydrocarbon feed 102, thereby producing a steam catalytic cracking effluent 140 comprising light olefins, light aromatic compounds, or both. In embodiments, the steam catalytic cracking effluent 140 can comprise light olefins, which can include, but are not limited to, ethylene, propylene, butylene, or combinations of these. In embodiments, the steam catalytic cracking effluent 140 can comprise light aromatic compounds, which refers to compounds containing aromatic ring structures and having fewer than or equal to 11 carbon atoms. The light aromatic compounds in the steam catalytic cracking effluent 140 can include, but are not limited to, benzene, toluene, ethylbenzene, xylene, or other light aromatic compounds.

[0050] The steam catalytic cracking reactor 130 can be operated at a temperature 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 be operated at a temperature 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 be operated at a temperature of 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, 550°C to 675°C, 575°C to 750°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 embodiments, the steam catalytic cracking reactor 130 can be operated at a temperature of about 675°C. In embodiments, the steam catalytic cracking reactor 130 can be operated at a pressure of 100 kPa to 200 kPa. In embodiments, the process can be operated at atmospheric pressure (about 101 kiloPascals).

[0051] The methods of the present disclosure can include contacting the hydrocarbon feed 102 with steam (water 120) in the presence of the cracking catalyst composition 132 in the steam catalytic cracking reactor 130 for a residence time sufficient to convert at least a portion of the hydrocarbon compounds in the hydrocarbon feed 102 to light olefins, light aromatic compounds, or both. In embodiments, the methods can include contacting the hydrocarbon feed 102 with steam (water 120) in the presence of the cracking catalyst composition 132 in the steam catalytic cracking reactor 130 for a residence time of 1 second to 60 seconds (such as 1 second to 30 seconds, 1 second to 10 seconds, or about 10 seconds).

[0052] When the steam catalytic cracking reactor 130 is a fixed bed reactor, the steam catalytic cracking reactor 130 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 the flow of the hydrocarbon feed 102 and the water 120 to the steam catalytic cracking reactor 130. 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 from 2 hours to 24 hours, from 2 hours to 20 hours, from 2 hours to 16 hours, from 2 hours to 12 hours, from 2 hours to 10 hours, from 2 hours to 8 hours, from 4 hours to 24 hours, from 4 hours to 20 hours, from 4 hours to 16 hours, from 4 hours to 12 hours, from 4 hours to 10 hours, or from 4 hours to 8 hours, before the feed pump 104 and the water feed pump 124 are shut off to stop the flow of the hydrocarbon and steam to the steam catalytic cracking reactor 130.

[0053] At the end of the conversion cycle, the flow of the hydrocarbon feed 102 and the water 120 can be stopped and the cracking catalyst composition 132 can be regenerated during a regeneration cycle. In embodiments, the steam catalytic cracking system 110 can include multiple fixed bed steam catalytic cracking reactors 130 that can be operated in parallel or in series. In embodiments, the steam catalytic cracking system 110 can include 1, 2, 3, 4, 5, 6, or more than 6 steam catalytic cracking reactors 130 that can be operated in series or in parallel. Where multiple steam catalytic cracking reactors 130 are operated in parallel, one or more steam catalytic cracking reactors 130 can continue to operate during a conversion cycle while one or more of the other steam catalytic cracking reactors can be taken offline for regeneration of the cracking catalyst composition 132, thereby maintaining continuous operation of the steam catalytic cracking system 110.

[0054] Referring again to FIG. 1, 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 that accumulated during the conversion cycle. To regenerate the cracking catalyst composition 132, the hydrocarbon gas and liquid products produced 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 the hydrocarbon gas and liquid products from the fixed bed steam catalytic cracking reactor 130. The nitrogen gas can be introduced into the steam catalytic cracking reactor 130 at a gas hourly space velocity of from 10 hours -1 to 100 hours -1 .

[0055] After the hydrocarbon gas and liquid are evacuated, the steam catalytic cracking reactor 130 can be purged with nitrogen gas through the gas inlet line 112 at a gas hourly space velocity of from 10 hours -1 to 100 hours -1The air introduced into the steam catalytic cracking reactor 130 can be delivered out of the steam catalytic cracking reactor 130 through an air outlet line 142. As the air is delivered 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 hours to 5 hours. The gases produced by the air regeneration of the cracking catalyst composition 132 can be delivered out of the steam catalytic cracking reactor 130 and can be analyzed by an online gas analyzer to detect the presence or concentration of carbon dioxide produced by the de-coke of the cracking catalyst composition 132. Once the online gas analyzer measures a carbon dioxide concentration in the gases delivered out of the steam catalytic cracking reactor 130 that is less than 0.1% (by weight) or even less than 0.05% (by weight), the temperature of the steam catalytic cracking reactor 130 can be lowered from the regeneration temperature back to the reaction temperature. The flow of air through the gas inlet line 112 can be stopped. Nitrogen can be delivered through the cracking catalyst composition 132 for 15 minutes to 30 minutes to remove the air from the steam catalytic cracking reactor 130. After the treatment with nitrogen, the flow of the hydrocarbon feed 102 and the water 120 can be resumed to start 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 a different type of reactor, such as a fluidized bed reactor, a moving bed reactor, a batch reactor, a FCC reactor, or a combination of these reactors.

[0056] Referring again to Figure 1 , the steam catalytic cracking effluent 140 can be delivered out of the steam catalytic cracking reactor 130. The steam catalytic cracking effluent 140 can include one or more products and intermediates, such as but not limited to fuel gas, such as methane; saturated C2-C4hydrocarbons; light olefins; naphtha (C5-221 °C), which can include light aromatic hydrocarbon compounds; light cycle oil (LCO, 221-343 °C); heavy cycle oil (HCO, +343 °C), such as but not limited to slurry oil; coke; or a combination of these. The light olefins in the steam catalytic cracking effluent 140 can include ethylene, propylene, butylene, or a combination of these. The light aromatic hydrocarbon compounds in the steam catalytic cracking effluent 140 can include, but are not limited to, benzene, toluene, xylene, ethylbenzene, and other light aromatic hydrocarbon compounds having 6 to 11 carbon atoms.

[0057] As previously discussed, the cracking catalyst composition 132 can include, consist of, or consist essentially of a zeolite catalyst and a cracking additive, where the cracking additive is different from the zeolite catalyst. In embodiments, the zeolite catalyst can include one or more of a Y-type zeolite, a USY zeolite, a beta zeolite, a mordenite (MOR structure) zeolite, a mordenite framework inverter (MFI) zeolite, a core-shell composite containing a beta zeolite coated on an MFI zeolite framework, other types of zeolites suitable for catalyzing cracking of hydrocarbons, or combinations thereof. In embodiments, the zeolite catalyst can include an equilibrium catalyst (ECAT). As used in the present disclosure, the term “equilibrium catalyst” refers to a used zeolite catalyst from a fluid catalytic cracking (FCC) process. In embodiments, the equilibrium catalyst can include a rare earth metal, Ni, V, or combinations thereof.

[0058] In embodiments, the amount of the zeolite catalyst in the cracking catalyst composition can be from 70 wt% to 80 wt%, from 72 wt% to 80 wt%, from 74 wt% to 80 wt%, from 70 wt% to 78 wt%, from 72 wt% to 78 wt%, from 74 wt% to 78 wt%, from 70 wt% to 76 wt%, from 72 wt% to 76 wt%, or from 74 wt% to 76 wt%, based on the total amount of the cracking catalyst composition.

[0059] The cracking additive includes, consists of, or consists essentially of a metal species impregnated on a ZSM-5 zeolite. In embodiments, the ZSM-5 zeolite of the cracking additive can have a molar ratio of silica to alumina greater than or equal to 10 or greater than or equal to 20. The ZSM-5 zeolite of the cracking additive can have a molar ratio of silica to alumina less than or equal to 1500, such as less than or equal to 900, less than or equal to 600, or even less than or equal to 300. In embodiments, the ZSM-5 zeolite of the cracking additive can have a molar ratio of silica to alumina from 10 to 1500, such as from 10 to 900, from 10 to 600, from 10 to 300, from 20 to 1500, from 20 to 900, from 20 to 600, or from 20 to 300.

[0060] In embodiments, the average crystal size of the 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 a plurality of particles.

[0061] As previously discussed, the cracking additive includes a metal species impregnated on the ZSM-5 zeolite. In embodiments, the metal species can include a metal or a metal oxide. In embodiments, the metal species can include a metal selected from chromium, vanadium, iron, platinum, molybdenum, cerium, or nickel. In embodiments, the metal species can include a metal selected from the group consisting of chromium, vanadium, iron, platinum, molybdenum, cerium, and nickel. In embodiments, the cracking additive can include a single metal species including a metal selected from the group consisting of chromium, vanadium, iron, platinum, molybdenum, cerium, and nickel.

[0062] In embodiments, the metal species can be a metal oxide selected from chromium oxide, vanadium oxide, iron oxide, platinum oxide, molybdenum oxide, cerium oxide, or nickel oxide. In embodiments, the metal species can consist of a metal oxide selected from the group consisting of chromium oxide, vanadium oxide, iron oxide, platinum oxide, molybdenum oxide, cerium oxide, and nickel oxide. In embodiments, the cracking additive can include a single metal oxide selected from the group consisting of chromium oxide, vanadium oxide, iron oxide, platinum oxide, molybdenum oxide, cerium oxide, and nickel oxide.

[0063] The cracking additive can include a 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, the cracking additive can include 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%, or 2 wt% to 5 wt% of the metal species, based on the total weight of the cracking additive.

[0064] In embodiments, the cracking additive can include a metal species impregnated on a phosphorus-free ZSM-5 zeolite. In embodiments, the cracking additive can be substantially free of phosphorus, such as having less than or equal to 0.1 wt% or less than or equal to 0.01 wt% phosphorus, based on the total weight of the cracking additive.

[0065] In embodiments, the cracking additive can include cerium oxide impregnated on a ZSM-5 zeolite, which can have a molar ratio of silica to alumina of 30, and can be substantially free of phosphorus, meaning that phosphorus is not intentionally added to the cracking additive or used in the process of making the cracking additive, and any phosphorus present is in trace amounts and is introduced as a contaminant from other reagents. In embodiments, the cracking additive can have less than 1000 parts per million by weight (ppmw) of phosphorus, or less than 500 ppmw of phosphorus, or less than 100 ppmw of phosphorus. In embodiments, the cracking additive is completely free of phosphorus. The concentration of cerium oxide in the cracking additive can be from 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%, or 2 wt% to 5 wt%, or about 2 wt%, based on the total weight of the cracking additive. In embodiments, the cracking additive can consist of or consist essentially of cerium oxide impregnated on a ZSM-5 zeolite.

[0066] In embodiments, the cracking additive can be in the form of a plurality of particles. In embodiments, the average particle size of the cracking additive can be greater than or equal to 300 micrometers (pm), such as from 350 pm to 2000 pm, from 350 pm to 1500 pm, from 350 pm to 1000 pm, from 400 pm to 2000 pm, from 400 pm to 1500 pm, from 400 pm to 1000 pm, from 450 pm to 2000 pm, from 450 pm to 1500 pm, from 450 pm to 1000 pm, from 500 pm to 2000 pm, from 500 pm to 1500 pm, or from 500 pm to 1000 pm. The average particle size is determined by scanning electron microscopy (SEM) according to known methods.

[0067] In embodiments, the average surface area of the cracking additive can be from 200 square meters per gram (m 2 / g) to 400 m 2 / g, from 200 m 2 / g to 380 m 2 / g, from 200 m 2 / g to 370 m 2 / g, from 250 m 2 / g to 400 m2 / g, 250 m 2 / g to 390 m 2 / g, 250 m 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 is determined according to the Brunauer-Emmett-Teller (BET) method based on nitrogen adsorption at -195 °C on an AUTOSORB-1 instrument obtained from Quanta Chrome. Throughout this disclosure, the average surface area can be referred to as the BET surface area.

[0068] In embodiments, the average pore size of the cracking additive can be the average pore diameter of the pores having a generally cylindrical cross-section. The average pore diameter of the cracking additive can be from 3 nanometers (nm) to 10 nm, from 4 nm to 10 nm, from 3 nm to 9 nm, from 4 nm to 9 nm, from 3 nm to 8 nm, or from 4 nm to 8 nm. The average pore diameter of the cracking additive is determined by scanning electron microscopy (SEM) according to known methods.

[0069] The average pore volume of the cracking additive can be from 0.05 cubic centimeters per gram (cm 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 is determined from the measured gas adsorption isotherm by the Barrett-Joyner-Halenda model.

[0070] In embodiments, the cracking additive does not include any binder, matrix material, or other catalytic species loaded on the ZSM-5 zeolite other than the metal species.

[0071] In embodiments, the amount of the cracking additive in the cracking catalyst composition can be 20 wt% to 30 wt%, 22 wt% to 30 wt%, 24 wt% to 30 wt%, 20 wt% to 28 wt%, 22 wt% to 28 wt%, 24 wt% to 28 wt%, 20 wt% to 26 wt%, 22 wt% to 26 wt%, or 24 wt% to 26 wt%, based on the total amount of the cracking catalyst composition.

[0072] Referring now to Figure 2 The method 200 for making the cracking additive can include, in step S205, making a zeolite mixture including a ZSM-5 zeolite and water; in step S207, making a metal precursor mixture including a metal precursor and water; in step S210, adding the metal precursor mixture to the zeolite mixture while mixing the zeolite mixture to make a combined mixture; in step S220, stirring the combined mixture at a temperature of 10 degrees Celsius (°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 less than 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; in step S250, calcining the solid particles at a temperature of 400 °C to 800 °C for 1 hour to 12 hours to make the cracking additive.

[0073] 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.

[0074] In step S207 of method 200, a metal precursor mixture can be prepared by adding and mixing a metal precursor to water. 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 embodiments, the concentration of the metal precursor in the metal precursor mixture can be from 0.1% to 10% by weight, based on the total weight of the metal precursor mixture. In embodiments, the concentration of water in the metal precursor mixture can be from 90% to 99.9% by weight, based on the total weight of the metal precursor mixture. The metal precursor may include chromium(III) nitrate nonahydrate (Cr(NO3)3·9H2O), ammonium vanadate (NH4VO3), ferric(III) nitrate nonahydrate (Fe(NO3)3·9H2O), tetraammineplatinum(II) nitrate (Pt(NH3)4(NO3)2), and ammonium heptamolybdate tetraahydrate ((NH4)6Mo7O). 24 ·4H2O), cerium(III) nitrate hexahydrate (Ce(NO3)3·6H2O) or nickel nitrate hexahydrate (Ni(NO3)2·6H2O). In embodiments, the metal precursor may include only chromium(III) nitrate nonahydrate (Cr(NO3)3·9H2O), ammonium vanadate (NH4VO3), ferric(III) nitrate nonahydrate (Fe(NO3)3·9H2O), tetraammineplatinum(II) nitrate (Pt(NH3)4(NO3)2), and ammonium heptamolybdate tetrahydrate ((NH4)6Mo7O). 24 One of the following: ·4H2O), cerium(III) nitrate hexahydrate (Ce(NO3)3·6H2O) or nickel nitrate hexahydrate (Ni(NO3)2·6H2O).

[0075] In step S210 of the method 200, the metal precursor mixture can be added to the zeolite mixture while the zeolite mixture is agitated. Adding the metal precursor mixture to the zeolite mixture while the zeolite mixture is agitated can include one or more of stirring, spinning, vortexing, shaking, sonication, homogenization, blending, and the like. In embodiments, the metal precursor mixture can be added to the zeolite mixture at a rate of 0.1 milliliters per minute (mL / min) to 1.0 mL / min.

[0076] In step S220 of the method 200, the combined mixture can be agitated, which can disperse the metal precursor and the ZSM-5 zeolite throughout the combined mixture. In embodiments, the combined mixture can be agitated at a temperature 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 can be agitated for a period of time sufficient to produce a homogeneous combined mixture. In embodiments, the combined mixture can be agitated 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 agitating or mixing the combined mixture for a period of time before removing water from the combined mixture can result in a more dispersed metal species on the surface of the ZSM-5 zeolite, such as by allowing the metal precursor to penetrate into the pores of the ZSM-5 zeolite before water is removed from the combined mixture.

[0077] In step S230 of the method 200, the combined mixture can be heated to an evaporation temperature. The evaporation temperature can be below the boiling point of water at the pressure at which the heating is performed, such as below 100 °C at atmospheric pressure. In embodiments, the evaporation temperature can 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 50 °C at atmospheric pressure. The evaporation temperature can be above 100 °C as long as the pressure is adjusted accordingly to keep the combined mixture below the boiling point of water.

[0078] 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, the combined mixture can be maintained at the evaporation temperature and pressure while mixing, which can cause 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 species precursor on the surface of the ZSM-5 zeolite. In embodiments, the combined mixture can be maintained at the evaporation temperature and pressure for a period 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, 12 hours. Evaporating water from the combined mixture at an evaporation temperature (such as 30 °C to 100 °C) at atmospheric pressure for a period of 1 hour to 24 hours can result in a water evaporation rate of 1.0 grams per minute (g / min) to 10.0 g / min. Without being bound by any particular theory, it is believed that slowly removing water from the combined mixture by evaporation at a temperature below the boiling point of water at a given pressure can further improve the dispersion of the metal species on the surface of the ZSM-5 zeolite.

[0079] In embodiments, method 200 for preparing a cracking additive can further include drying the solid particles at a temperature of 50 °C to 200 °C Figure 2 In embodiments, the solid particles can be dried at a temperature 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 embodiments, the solid particles can be dried overnight.

[0080] In step S250 of method 200, after drying, the solid particles can be calcined at a temperature of 400 °C to 800 °C for a period of 1 hour to 12 hours to produce a cracking additive. In embodiments, the solid particles can be calcined at a temperature 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.

[0081] In embodiments, the cracking additive can be ion exchanged to produce a hydrogen form of the cracking additive. In the hydrogen form, Bronsted acid sites in the zeolite, also referred to as bridged OH-H groups, can form hydrogen bonds with other framework oxygen atoms in the zeolite framework. In embodiments, the method 200 of producing a cracking additive can include ion exchanging the cracking additive to produce a hydrogen form of the cracking catalyst. In embodiments, ion exchanging the cracking additive can include treating the cracking catalyst with an ammonium salt at a temperature of 50 °C to 100 °C for a period of 1 hour to 12 hours. In embodiments, the cracking additive can be treated with a 1.0 molar (M) solution of ammonium nitrate (NH4NO3). In embodiments, the cracking additive can be treated with a 0.25 normal (N) solution of ammonium nitrate. In embodiments, the cracking additive can be treated with the ammonium salt solution at a temperature 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 embodiments, the cracking additive can be treated with the ammonium salt solution 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 4.5 hours. In embodiments, the cracking additive can be treated with the ammonium salt solution at 80 °C for 4.5 hours with agitation. In embodiments, the cracking additive can be in the hydrogen form after treating the cracking catalyst.

[0082] In embodiments, the ion-exchanged hydrogen form of the cracking additive can be calcined at a temperature 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 embodiments, the ion-exchanged hydrogen form of the cracking catalyst can be 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 embodiments, the ion-exchanged hydrogen form of the cracking additive can be calcined after the ion exchange process is complete.

[0083] As previously discussed, the steam catalytic cracking effluent 140 can include one or more products and intermediates, such as, but not limited to, light hydrocarbon gases, light olefins, aromatic hydrocarbon compounds, pyrolysis oil, or combinations of these. The light olefins in the steam catalytic cracking effluent 140 can include ethylene, propylene, butylene, or combinations of these. The steam catalytic cracking effluent 140 can include light aromatic hydrocarbon compounds. The light aromatic hydrocarbon compounds can include, but are not limited to, benzene, toluene, xylene, ethylbenzene, and other light aromatic hydrocarbon compounds having 6 to 11 carbon atoms.

[0084] The steam catalytic cracking system 110 can achieve a light olefin yield of greater than or equal to 35 wt%, greater than or equal to 38 wt%, or greater than or equal to 40 wt%, based on the total weight of the stream such as the steam catalytic cracking effluent 140. In embodiments, the steam catalytic cracking system 110 can achieve a light olefin yield of 35 wt% to 60 wt%, 35 wt% to 55 wt%, 35 wt% to 50 wt%, 38 wt% to 60 wt%, 38 wt% to 55 wt%, 38 wt% to 50 wt%, 40 wt% to 60 wt%, 40 wt% to 55 wt%, or 40 wt% to 50 wt%, based on the total weight of the stream such as the steam catalytic cracking effluent 140.

[0085] The steam catalytic cracking system 110 can achieve a light aromatic compound yield of greater than or equal to 15 wt%, greater than or equal to 16 wt%, or greater than or equal to 17 wt%, based on the total weight of the stream such as the steam catalytic cracking effluent 117. In embodiments, the steam catalytic cracking system 110 can achieve a light aromatic compound yield of 15 wt% to 45 wt%, 15 wt% to 40 wt%, 15 wt% to 35 wt%, 16 wt% to 45 wt%, 16 wt% to 40 wt%, 16 wt% to 35 wt%, 17 wt% to 45 wt%, 17 wt% to 40 wt%, or 17 wt% to 35 wt%, based on the total weight of the stream such as the steam catalytic cracking effluent 140.

[0086] Referring again to Figure 1 , the steam catalytic cracking system 110 can further include a cracked 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, the steam catalytic cracking effluent 140 from each steam catalytic cracking reactor 130 can be sent to a single, shared cracked effluent separation system 150. In embodiments, each steam catalytic cracking reactor 130 can have its own dedicated cracked effluent separation system. The steam catalytic cracking effluent 140 can be sent directly from the steam catalytic cracking reactor 130 to the cracked effluent separation system 150. The cracked effluent separation system 150 can separate the steam catalytic cracking effluent 140 into one or more cracked product effluents, which can be liquid or gaseous product effluents.

[0087] Referring again to 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, centrifuges, or combinations thereof. The separation units may include one or more gas-liquid separators, one or more liquid-liquid separators, or combinations thereof.

[0088] 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.

[0089] Gaseous effluent 164 can include olefins, such as ethylene, propylene, butene, or combinations of these; light hydrocarbon gases, such as methane, ethane, propane, n-butane, isobutane, or combinations of these; other gases, such as, but not limited to, hydrogen; or combinations of these. Gaseous effluent 164 can include C2-C4 olefin products produced 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 of these), or combinations of these. Gaseous effluent 164 can include at least 90%, at least 95%, at least 98%, at least 99%, or at least 99.5% of the C2-C4 olefins from steam catalytic cracking effluent 140. Gaseous effluent 164 can 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.

[0090] In embodiments, liquid effluent 162, which includes water and hydrocarbons having greater than 5 carbon atoms, can be sent to an in-line centrifugal unit 170. In-line centrifugal unit 170 can operate to separate liquid effluent 162 into a liquid hydrocarbon effluent 172 and an aqueous effluent 174. In-line centrifugal unit 170 can operate at a rotational speed 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.

[0091] Liquid hydrocarbon effluent 172 can include hydrocarbons having a carbon atom number greater than or equal to 5 from steam catalytic cracking effluent 140. Liquid hydrocarbon effluent 172 can include small amounts of hydrocarbons having a carbon atom number less than 5, such as trace amounts of light hydrocarbons that are not separated into gaseous effluent 164. Liquid hydrocarbon effluent 172 can include light aromatic hydrocarbon compounds produced in steam catalytic cracking reactor 130, which can include, but are not limited to, benzene, toluene, mixed xylenes, ethylbenzene, and other light aromatic hydrocarbon compounds. Liquid hydrocarbon effluent 172 can further include other naphtha range hydrocarbons, kerosene, diesel, vacuum gas oil (VGO), or combinations of these. The light aromatic hydrocarbon compounds can be part of the naphtha fraction of hydrocarbon effluent 172. Liquid hydrocarbon effluent 172 can include 90%, at least 95%, at least 98%, at least 99%, or even at least 99.5% of the hydrocarbon content from liquid effluent 162. Liquid hydrocarbon effluent 172 can be sent to a downstream processing process for further conversion or separation. At least a portion of liquid hydrocarbon effluent 172 can be sent back to steam catalytic cracking reactor 130 for further conversion of hydrocarbons to olefins.

[0092] 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.

[0093] 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.

[0094] In embodiments, the FCC reactor can be operated at a reaction temperature of at least about 500°C, such as a reaction temperature of 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 feed can be catalytically cracked in the presence of steam with an FCC catalyst composition comprising the cracking additive of the present disclosure. The mass ratio of steam to hydrocarbon in the FCC reactor 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 embodiments, the residence time of the hydrocarbon feed and steam in the FCC reactor in contact with the FCC catalyst composition can be 1 second to 20 seconds, 2 seconds to 20 seconds, 5 seconds to 20 seconds, 8 seconds to 20 seconds, 1 second to 18 seconds, 2 seconds to 18 seconds, 5 seconds to 18 seconds, 8 seconds to 18 seconds, 1 second to 16 seconds, 2 seconds to 16 seconds, 5 seconds to 16 seconds, 8 seconds to 16 seconds, 1 second to 14 seconds, 2 seconds to 14 seconds, 5 seconds to 14 seconds, 8 seconds to 14 seconds, 1 second to 12 seconds, 2 seconds to 12 seconds, 5 seconds to 12 seconds, or 8 seconds to 12 seconds. In embodiments, the weight ratio of FCC catalyst composition to hydrocarbon (catalyst to 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, 7 to 10, 10 to 40, 10 to 30, 10 to 20, or 20 to 40. The cracked 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.

[0095] Examples Various aspects of the present disclosure will be further clarified by the following examples. These examples are illustrative in nature and are not to be construed as limiting the scope of the present subject matter.

[0096] Examples 1 to 7: Preparation of cracking additives comprising metal species impregnated on ZSM-5 zeolite In Examples 1 to 7, cracking additives of the present disclosure comprising different metal species impregnated on ZSM-5 zeolite were prepared. To prepare the cracking additives, first, a commercially available ZSM-5 zeolite powder (CBV3024E ZSM-5 zeolite powder from Zeolyst International with a silica to alumina ratio of 30) was calcined at 550 °C for 5 hours with 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. An appropriate amount of a metal species precursor was added to the water to produce a metal precursor mixture. While the zeolite mixture was being stirred, the metal precursor mixture was slowly added to the zeolite mixture over a period of 1 to 30 minutes to produce a combined mixture. The total amount of water of the combined mixture was 5 milliliters. The metal species precursor of each of Examples 1 to 7 is shown in Table 3. The combined mixture was stirred at ambient temperature for 3 hours and the water was removed by slow evaporation at 60 °C and atmospheric pressure with stirring to produce a solid particulate. The term “slow evaporation” of water can refer to evaporation of water at a temperature lower than the boiling point of water. The solid particulate was then dried at 100 °C overnight and subsequently calcined to a final calcination temperature of 550 °C at a heating rate of 5 °C / min in standing air for a period of 5 hours to produce the cracking additives of Examples 1 to 7 comprising metal species impregnated on ZSM-5 zeolite. The cracking additives were pelletized, sieved to a particle size of 500 µm to 1000 µm, and tested in a fixed bed reactor. The metal species and the amount of metal species in the cracking additives of each of Examples 1 to 7 are shown in Table 3.

[0097] Table 3

[0098] Comparative Example 8: ZSM-5 zeolite For Comparative Example 8, a commercially available ZSM-5 zeolite (CBV3024E) from Zeolyst International with a silica to alumina ratio of 30 was provided for comparison with the metal species impregnated on ZSM-5 zeolite of Examples 1 to 7. No metal or metal oxide was deposited on the surface of the ZSM-5 zeolite of Comparative Example 8.

[0099] The commercial ZSM-5 zeolite of Comparative Example 8 was characterized by powder X-ray diffraction (XRD). The XRD was performed on a Mini-flex II system from Rigaku using nickel-filtered CuKa radiation (l = 1.5406 Å) operating in static scan mode with a detector angular velocity of 2° per minute and a step size of 0.02°. Figure 3The X-ray diffraction (XRD) pattern of the zeolite of Comparative Example 8 is shown, indicating that the catalyst is a crystalline material with some amorphous phase in the structure. The crystalline phase is identified as mainly Faujasite.

[0100] Comparative Example 9: Equilibrated catalyst For Comparative Example 9, an equilibrium catalyst (ECAT) was provided for comparison with the catalyst additives of Examples 1 to 7.

[0101] The commercial ECAT of Comparative Example 9 was characterized by powder X-ray diffraction (XRD). The XRD was performed on a Mini-flex II system from Rigaku, using nickel filtered Cu Ka radiation (l = 1.5406 A), operating in static scan mode with a detector angular speed of 2° per minute and a step of 0.02°. Figure 4 The X-ray diffraction (XRD) pattern of the ECAT is shown, indicating that the catalyst is a crystalline material with some amorphous phase in the structure. The crystalline phase is identified as mainly Faujasite.

[0102] Characterization of metal species impregnated on ZSM-5 zeolite of Examples 1 to 7 The metal species impregnated on ZSM-5 zeolite of Examples 1 to 7 were characterized by powder X-ray diffraction (XRD) and nitrogen adsorption, ammonia temperature programmed desorption (NH3-TPD) and scanning electron microscopy (SEM) images. The XRD was performed on a Mini-flex II system from Rigaku, using nickel filtered Cu Ka radiation (l = 1.5406 A), operating in static scan mode with a detector angular speed of 2° per minute and a step of 0.02°.

[0103] As shown in Figure 3 Examples 1 to 7 exhibit characteristic peaks of the metal species impregnated on ZSM-5 zeolite in the range of 2Q = 7-10° and 2Q = 22-25°. The first peak observed is at about 2Q = 7.9°, which is a superposition of the diffractions of the -101, 011 and 101 planes, with the diffraction of the 011 plane being the main peak. The second peak observed is at about 2Q = 8.9°, which is a superposition of the diffractions of the 020, 200, -111 and 111 planes, with the diffractions of the 020 and 200 planes being dominant. As shown in Figure 3 In comparison with the ZSM-5 zeolite of Comparative Example 8, the crystallinity of the metal species impregnated on ZSM-5 zeolite of Examples 1 to 7 remains almost the same after impregnation of the metal species on the ZSM-5 zeolite. Moreover, no peaks of metal or metal oxide species were observed. This is due to the high dispersion of the nanoscale particles into the parent ZSM-5 mesopores by metal impregnation.

[0104] Furthermore, nitrogen adsorption at -195 °C was performed on Quanta Chrome's Autosorb-1. Table 4 lists physical properties such as BET surface area, average pore size, and average pore volume. All metal species impregnated on ZSM-5 zeolite in Examples 1 to 7 exhibited type I isotherms, with specific surface areas of 294–338 m² as evaluated by the BET method. 2 / g, micropore volume in the range of 0.091-0.250 cm³. 3 Within the range of / g. The high micropore volume is consistent with the high relative crystallinity of all samples. All metal species prepared in Examples 1 to 7 impregnated on ZSM-5 zeolite have a narrow pore distribution of about 5.0 nm.

[0105] Table 4: Physicochemical properties of the metal species impregnated on ZSM-5 zeolite in Examples 1 to 7, ZSM-5 zeolite in Comparative Example 8, and E-cat in Comparative Example 9.

[0106]

[0107] Examples 10 to 16 and Comparative Example 8: Preparation of cracking catalyst compositions For Example 10, a cracking catalyst was prepared by mixing 75 wt% ECAT and 25 wt% ZSM-5 zeolite impregnated with chromium oxide, based on the total amount of cracking catalyst. ECAT was the same as in Comparative Example 9. For Example 11, a cracking catalyst was prepared by mixing 75 wt% ECAT and 25 wt% ZSM-5 zeolite impregnated with vanadium oxide, based on the total amount of cracking catalyst. For Example 12, a cracking catalyst was prepared by mixing 75 wt% ECAT and 25 wt% ZSM-5 zeolite impregnated with iron oxide, based on the total amount of cracking catalyst. For Example 13, a cracking catalyst was prepared by mixing 75 wt% ECAT and 25 wt% ZSM-5 zeolite impregnated with platinum oxide, based on the total amount of cracking catalyst. For Example 14, a cracking catalyst was prepared by mixing 75 wt% ECAT and 25 wt% ZSM-5 zeolite impregnated with molybdenum oxide, based on the total amount of cracking catalyst. For Example 15, a cracking catalyst was prepared by mixing 75 wt% ECAT and 25 wt% ZSM-5 zeolite impregnated with cerium oxide, based on the total amount of cracking catalyst. For Example 16, a cracking catalyst was prepared by mixing 75 wt% ECAT and 25 wt% ZSM-5 zeolite impregnated with nickel oxide, based on the total amount of cracking catalyst.

[0108] Comparative Example 17 For Comparative Example 17, a cracking catalyst was prepared comprising 100 wt% of the ECAT of Comparative Example 9, based on the total amount of cracking catalyst. The cracking catalyst of Comparative Example 17 was evaluated for the steam catalytic cracking of a crude oil, such as AXL crude oil, at atmospheric pressure in a fixed bed reactor (FBR) system. A description of the FBR and the reaction conditions for performing the steam catalytic cracking of Comparative Example 17 is provided in Example 19.

[0109] Comparative Example 18: Cracking catalyst evaluation - thermal cracking In Comparative Example 18, the cracking catalyst of Comparative Example 17 was evaluated for the thermal catalytic cracking of a crude oil, such as AXL crude oil, at atmospheric pressure in a fixed bed reactor (FBR) system. Figure 6 The FBR system is depicted, but no steam was injected for thermal cracking. The general FBR system is described in Example 19. Figure 7 and Figure 8 The results of AXL cracking over the cracking catalyst of Comparative Example 17 are shown.

[0110] Example 19: Cracking catalyst evaluation 1 In Example 19, the cracking catalysts of Examples 10 to 16 were evaluated for the steam catalytic cracking of a crude oil, such as AXL crude oil, at atmospheric pressure in a fixed bed reactor (FBR) system. Figure 7 The results of AXL cracking over the cracking catalysts of Examples 10 to 16 and Comparative Example 17 are shown.

[0111] Referring now to Figure 6 The FBR system 300 used to perform the experiments of Example 19 is schematically depicted. A metering pump 311 was used to send AXL crude oil 301 to a fixed bed reactor 340.

[0112] The AXL crude 301 has an API of 39.3, a sulfur content of 1.6 wt%, and a total carbon content, hydrogen content, and nitrogen content of 84.3 wt%, 12.6 wt%, and 0.7 wt%, respectively. The SimDis properties of the AXL crude 301 and two fractions (AXL-350°C and AXL+350°C) were analyzed according to the ASTM D-2887 method (ASTM (2018)). The gas chromatograph (GC) used was a Shimadzu GC 2010 Plus, equipped with a flame ionization detector (FID) to determine the three fractions, namely naphtha (C5-221 °C), LCO (light cycle oil, 221-343 °C), and HCO (heavy cycle oil, +343 °C). The naphtha PIONA composition (paraffins, iso-paraffins, olefins, naphthenes, and aromatics) was determined using a Shimadzu GC equipped with a BP-1 PONA capillary column and a FID detector. As Figure 5 As shown in Table 5 and the results of the SimDis, the naphtha content was 41 wt%, while the LCO content was 26 wt%, and the HCO content was 33 wt%. The residue content (above 550 °C) of the AXL crude 301 was 4.0 wt%, and the residue content (above 550 °C) of the AXL+350°C was 14.0 wt%.

[0113] Table 5: SimDis results of the AXL crude and its two fractions

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

[0115] The catalyst bed 344 in the reaction tube 340 was moved down a few centimeters so that there was more time to preheat the AXL crude oil 301 before contacting the cracking catalyst in the catalyst bed 344. For each experiment, 1 gram (g) of cracking catalyst with a mesh size of 30-40 was placed in the center of the reaction tube 340, supported by quartz wool 343, 346 and a reactor insert 345. The quartz wool 343, 346 was placed at the bottom and top of the catalyst bed 344 to keep it in place. The height of the catalyst bed 344 was 1 cm to 2 cm. The cracking catalysts of Examples 10 to 16 and Comparative Example 17 were each used as the cracking catalyst for different experiments conducted with Example 6. Each of the cracking catalysts of Examples 10 to 16 and Comparative Example 17 was steam deactivated in the presence of steam for 6 hours at a temperature of 810 °C prior to conducting the steam catalytic cracking reaction.

[0116] After steam deactivation, the crude oil hydrocarbon feed and water / steam were introduced into the reaction tube of the FBR. The reaction occurred for 45 min to 60 min until steady state was reached. The mass ratio of steam to crude oil was 0.5 grams of steam per gram of crude oil. The crude oil was cracked at a cracking temperature of 675 °C and a weight ratio of catalyst to crude oil of 1 :2. The residence time of the crude oil and steam in the fixed bed reactor 340 was 10 seconds. The total run time for each individual experiment of Comparative Example 18 and Example 19 was 5 hours.

[0117] The cracked gaseous product 361 and liquid product 362 were characterized by off-line gas chromatography (GC) analysis using simulated distillation and naphtha analysis techniques. The reaction product stream from the cracking reaction was analyzed to determine the yields of ethylene, propylene, and butylenes. The yield analysis for Comparative Example 18 and Example 19 was as shown in Table 6 and provided in digital form in Table 6. Figure 7

[0118] Table 6: Performance evaluation results of AXL cracking of Examples 10 to 16 and Comparative Examples 17 and 18

[0119] Table 6 (continued)

[0120] Table 6 and Figure 7 ​The results show that the cracking catalysts of Examples 10 to 16 (which have the metal species impregnated on ZSM-5 zeolite of Examples 1 to 7) can directly convert crude oil into petrochemical products, such as light olefins and aromatic compounds. The results demonstrate that the metal species impregnated on ZSM-5 zeolite of Examples 1 to 7 provide high yields of light olefins, including ethylene and propylene.

[0121] Examples 10 to 17 show propylene yields of 14% to 18.3% by weight, which is higher than the propylene yields of Comparative Examples 17 and 18.

[0122] Furthermore, compared to the cracking effluent produced using the cracking catalyst of Comparative Example 18, as shown by the reduced concentration of middle distillate and heavy distillate in the cracking effluent produced using the cracking catalysts of Examples 10 to 17, Examples 10 to 17 achieved a higher conversion rate of the middle distillate portion of the hydrocarbon feed.

[0123] Example 20: Cracking catalyst evaluation 2 In Example 20, the cracking catalysts of Examples 10 to 16 and Comparative Example 17 were evaluated for steam catalytic cracking of the naphtha composition of crude oil such as AXL crude oil in a fixed-bed reaction (FBR) system at atmospheric pressure. Figure 8 The results of AXL cracking on the cracking catalysts of Examples 10 to 16 and Comparative Example 17 are shown.

[0124] Table 7: Naphtha composition (PIONA) of AXL crude oil feedstock and cracked AXL crude oil in Example 15 at 675°C

[0125] like Figure 8 As shown in Table 7, in Example 15, it was found that modification of ZSM-5 by impregnation with Ce suppressed the bimolecular mixed transfer reaction, and the higher activity could be attributed to the presence of weak acid sites, which may be the main reason for the increased activity in this type of light olefin. Furthermore, the dehydrogenation properties of Ce species improved the yields of ethylene and propylene.

[0126] In addition, such as Figure 9A As shown, Comparative Example 8 exhibits an ordered, sharp-edged, and square-shaped grain morphology, and a large crystal size of approximately less than 150 nm. In contrast, as... Figure 9B As shown in the figure, its morphology indicates that Example 15 consists of a mixture of small grains and a small amount of large particles. Figures 9C to 9F The corresponding elemental mappings for Example 15 are shown: Si(c), Al(d), O(e), and Ce(f). For example... Figures 9C to 9F As shown in the figure, the mapping shows that Ce exists on the catalyst surface and is uniformly dispersed on the catalyst surface.

[0127] A first aspect of the present disclosure can relate to a method for upgrading a hydrocarbon feed, the method comprising: contacting a hydrocarbon feed with steam in the presence of a cracking catalyst composition under reaction conditions sufficient to cause one or more cracking reactions of at least a portion of the hydrocarbons in the hydrocarbon feed to produce a steam catalytic cracking effluent comprising light olefins, light aromatic compounds, or both. The cracking catalyst composition can comprise a zeolite catalyst and a cracking additive. The cracking additive can comprise a metal species impregnated on a ZSM-5 zeolite. The zeolite catalyst can be different from the ZSM-5 zeolite of the cracking additive. The metal species can comprise a metal selected from the group consisting of chromium, vanadium, iron, platinum, molybdenum, cerium, and nickel.

[0128] A second aspect of the present disclosure can include the first aspect, wherein a molar ratio of silica to alumina of the ZSM-5 zeolite of the cracking additive can be 20 to 300.

[0129] A third aspect of the present disclosure can include any of the first or second aspects, wherein a molar ratio of silica to alumina of the ZSM-5 zeolite of the cracking additive can be 30.

[0130] A fourth aspect of the present disclosure can include any of the first to third aspects, wherein a concentration of the metal species in the cracking additive can be 0.1 weight percent (wt%) to 10 wt% or 2 wt% to 10 wt%, based on a total weight of the cracking additive.

[0131] A fifth aspect of the present disclosure can include any of the first to fourth aspects, wherein the metal species can be an elemental metal or a metal oxide.

[0132] A sixth aspect of the present disclosure can include any of the first to fifth aspects, wherein the metal species can comprise a metal oxide selected from the group consisting of chromium oxide, vanadium oxide, iron oxide, platinum oxide, molybdenum oxide, cerium oxide, and nickel oxide.

[0133] A seventh aspect of the present disclosure can include any of the first to sixth aspects, wherein the metal species can comprise a single metal oxide selected from chromium oxide, vanadium oxide, iron oxide, platinum oxide, molybdenum oxide, cerium oxide, and nickel oxide.

[0134] An eighth aspect of the present disclosure can include any of the first to seventh aspects, wherein the cracking additive can consist of the ZSM-5 zeolite and the metal species.

[0135] A ninth aspect of the present disclosure can include any of the first to eighth aspects, wherein the cracking additive can be substantially free of phosphorus.

[0136] A tenth aspect of the disclosure can include any of the first through ninth aspects, wherein the cracking additive can include cerium oxide impregnated on a ZSM-5 zeolite, a molar ratio of silica to alumina of the ZSM-5 zeolite can be 30, and the cracking additive can be substantially free of phosphorous.

[0137] An eleventh aspect of the disclosure can include any of the first through tenth aspects, wherein the cracking additive can consist essentially of cerium oxide impregnated on a ZSM-5 zeolite.

[0138] A twelfth aspect of the disclosure can include any of the first through eleventh aspects, wherein the cracking additive can consist of cerium oxide impregnated on a ZSM-5 zeolite.

[0139] A thirteenth aspect of the disclosure can include any of the first through twelfth aspects, wherein an average particle size of the cracking additive can be 300 micrometers (pm) to 2000 pm.

[0140] A fourteenth aspect of the disclosure can include any of the first through thirteenth aspects, wherein a surface area of the cracking additive can be 200 (square meters per gram) m 2 / g to 400 m 2 / g.

[0141] A fifteenth aspect of the disclosure can include any of the first through fourteenth aspects, wherein an average pore size of the cracking additive can be 3 nanometers (nm) to 10 nm.

[0142] A sixteenth aspect of the disclosure can include any of the first through fifteenth aspects, further comprising passing a hydrocarbon feed to the steam catalytic cracking reactor, wherein the hydrocarbon feed includes a crude oil having an API gravity of 25 to 50.

[0143] A seventeenth aspect of the disclosure can include any of the first through sixteenth aspects, wherein the zeolite catalyst can be a balance catalyst, such that the cracking catalyst composition includes the balance catalyst and the cracking additive.

[0144] An eighteenth aspect of the disclosure can include any of the first through seventeenth aspects, wherein an amount of the cracking additive in the cracking catalyst composition can be 20 weight percent to 30 weight percent, based on the cracking catalyst composition.

[0145] A nineteenth aspect of the disclosure can include any of the first through eighteenth aspects, wherein the hydrocarbon feed can include a whole crude oil having an API gravity of 25 to 50.

[0146] A twentieth aspect of the disclosure can include any of the first through nineteenth aspects, wherein the hydrocarbon feed can be a heavy crude oil, a light crude oil, an extra light crude oil, or a combination of these.

[0147] A twenty-first aspect of the disclosure can include any of the first through twentieth aspects, wherein the steam catalytic cracking effluent can include one or more of ethylene, propylene, butylene, or a combination of these.

[0148] A twenty-second aspect of the disclosure can include any of the first through twenty-first aspects, wherein the steam catalytic cracking effluent can include benzene, toluene, xylene, ethylbenzene, other light aromatic hydrocarbon compounds having 6 to 11 carbon atoms, or a combination of these.

[0149] A twenty-third aspect of the disclosure can include any of the first through twenty-second aspects, wherein contacting the hydrocarbon feed with steam in the presence of the cracking catalyst composition can include contacting the hydrocarbon feed with steam in the presence of the cracking catalyst composition in a cracking reactor, wherein the cracking reactor can include one or more fixed bed reactors, fluidized bed reactors, batch reactors, moving bed catalytic cracking reactors, fluid catalytic cracking (FCC) reactors, or a combination of these.

[0150] A twenty-fourth aspect of the disclosure can include any of the first through twenty-third aspects, wherein contacting the hydrocarbon feed with steam in the presence of the cracking catalyst composition can include contacting the hydrocarbon feed with steam in the presence of the cracking catalyst at a reaction temperature of 500 °C to 800 °C.

[0151] A twenty-fifth aspect of the disclosure can include any of the first through twenty-fourth aspects, wherein contacting the hydrocarbon feed with steam in the presence of the cracking catalyst composition can include contacting the hydrocarbon feed with steam in the presence of the cracking catalyst at a mass ratio of steam to hydrocarbon of 0.1 to 1.0.

[0152] A twenty-sixth aspect of the disclosure can include any of the first through twenty-fifth aspects, wherein contacting the hydrocarbon feed with steam in the presence of the cracking catalyst composition can include contacting the hydrocarbon feed with steam in the presence of the cracking catalyst composition for a residence time of 1 second to 60 seconds.

[0153] A twenty-seventh aspect of the present disclosure can include any of the first through twenty-sixth aspects, wherein the cracking additive can be prepared by a method comprising: preparing a zeolite mixture comprising ZSM-5 zeolite and water, adding a metal precursor mixture to the zeolite mixture while mixing the zeolite mixture to produce a combined mixture, wherein the metal precursor mixture comprises a metal species precursor and water; stirring the combined mixture at a temperature of 10 degrees Celsius (°C) to 30 °C for a mixing time of 1 hour to 5 hours; heating the combined mixture to an evaporation temperature of 30 °C to 100 °C while stirring; maintaining the combined mixture at the evaporation temperature for a period of 1 hour to 24 hours while stirring; wherein maintaining the combined mixture at the evaporation temperature while mixing can cause water to slowly evaporate from the combined mixture to produce solid particles, and slowly evaporating water from the combined mixture while mixing can cause the metal species precursor to disperse on a surface of the ZSM-5 zeolite; and calcining the solid particles at a temperature of 400 °C to 800 °C for 1 hour to 12 hours to produce the cracking additive.

[0154] A twenty-eighth aspect of the present disclosure can include any of the first through twenty-seventh aspects, further comprising drying the solid particles at a temperature of 50 °C to 150 °C after maintaining the combined mixture at the evaporation temperature and before calcining.

[0155] A twenty-ninth aspect of the present disclosure can include any of the first through twenty-eighth aspects, wherein the metal precursor can comprise chromium (III) nitrate nonahydrate (Cr(N03)3-9H20), ammonium vanadate (NH4VO3), iron (III) nitrate nonahydrate (Fe(N03)3-9H20), tetraammineplatinum (II) nitrate (Pt(NH3)4(N03)2), ammonium heptamolybdate tetrahydrate ((NH4)6Mo70 24 4H20), cerium (III) nitrate hexahydrate (Ce(N03)3-6H20), or nickel nitrate hexahydrate (Ni(N03)2-6H20).

[0156] A thirtieth aspect of the present disclosure can relate to a cracking catalyst composition for upgrading a hydrocarbon feed, wherein the cracking catalyst composition can comprise a zeolite catalyst and a cracking additive, the cracking additive comprising a metal species impregnated on a ZSM-5 zeolite, wherein the metal species can comprise a metal selected from the group consisting of chromium, vanadium, iron, platinum, molybdenum, cerium, and nickel, wherein the zeolite catalyst is different from the ZSM-5 zeolite of the cracking additive.

[0157] A thirty-first aspect of the present disclosure can include the thirtieth aspect, wherein a concentration of the metal species in the cracking additive can be 0.1 weight percent (wt%) to 10 wt% or 2 wt% to 10 wt%, based on a total weight of the cracking additive.

[0158] A thirty-second aspect of the disclosure can include any of the thirtieth or thirty-first aspects, wherein the zeolite catalyst can include a balance catalyst.

[0159] A thirty-third aspect of the disclosure can include any of the thirtieth through thirty-second aspects, wherein the amount of the cracking additive in the cracking catalyst composition can be 20 wt% to 30 wt% based on the cracking catalyst composition.

[0160] A thirty-fourth aspect of the disclosure can include any of the thirtieth through thirty-third aspects, wherein the amount of the zeolite catalyst in the cracking catalyst composition can be 70 wt% to 80 wt% based on the cracking catalyst composition.

[0161] A thirty-fifth aspect of the disclosure can include any of the first through twenty-ninth aspects, wherein the hydrocarbon feed can be a crude oil that can have a density greater than or equal to 0.80 grams per milliliter or an end boiling point of 500 °C to 1000 °C.

[0162] A thirty-sixth aspect of the disclosure can include any of the first through thirty-fifth aspects, wherein the cracking catalyst composition consists of the zeolite catalyst and the cracking additive, wherein the cracking additive consists of a ZSM-5 zeolite and a metal species.

[0163] It is noted that any two quantitative values that impart a certain property can constitute a range of that property, and all combinations of ranges formed by all of the quantitative values of a given property are contemplated by the disclosure.

[0164] It is noted that the following one or more claims use terminology that may

[0165] After reference to the several aspects of the present disclosure, it is noted that various details of the aspects can be changed without departing from the scope of the present disclosure. Furthermore, it is to be understood that the foregoing description is exemplary only, and not limiting. Therefore, the scope of the disclosure is not intended to be limited to the aspects presented herein, but is to be accorded with the widest scope consistent with the principles and the novel features disclosed herein.

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 contains metals impregnated on ZSM-5 zeolite; The zeolite catalyst is different from the ZSM-5 zeolite in the cracking additive; and The metals mentioned include those selected from the group consisting of chromium, vanadium, iron, platinum, molybdenum, cerium, and nickel.

2. The method according to claim 1, wherein the molar ratio of silica to alumina in the ZSM-5 zeolite of the cracking additive is 20 to 300.

3. The method according to any one of claims 1 or 2, wherein the concentration of the metal species in the cracking additive is from 0.1 wt% to 10 wt%, or from 2 wt% to 10 wt%, based on the total weight of the cracking additive.

4. The method according to any one of claims 1 to 3, wherein the metal is an elemental metal or a metal oxide.

5. The method according to any one of claims 1 to 4, wherein the metal species includes metal oxides selected from the group consisting of chromium oxides, vanadium oxides, iron oxides, platinum oxides, molybdenum oxides, cerium oxides and nickel oxides.

6. The method according to any one of claims 1 to 5, wherein the metal species includes a single metal oxide selected from chromium oxide, vanadium oxide, iron oxide, platinum oxide, molybdenum oxide, cerium oxide or nickel oxide.

7. The method according to any one of claims 1 to 6, wherein the cracking additive is composed of the ZSM-5 zeolite and the metal species.

8. The method according to any one of claims 1 to 7, wherein the cracking additive is substantially free of phosphorus.

9. The method according to any one of claims 1 to 7, wherein: The cracking additive comprises cerium oxide impregnated on the ZSM-5 zeolite. The ZSM-5 zeolite has a silica to alumina molar ratio of 30, and The cracking additives are essentially phosphorus-free.

10. The method according to any one of claims 1 to 9, wherein the cracking additive has one or more of the following properties: The average particle size ranges from 300 micrometers (µm) to 2000 µm; The surface area is 200 (square meters per gram) m² 2 / g to 400 m 2 / g; The average pore size ranges from 3 nanometers (nm) to 10 nanometers; Or any combination thereof.

11. The method according to any one of claims 1 to 10, wherein the zeolite catalyst comprises a balanced catalyst.

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

13. The method according to any one of claims 1 to 12, 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 metal-type 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; The combined mixture is held at the evaporation temperature for a period of 1 hour to 24 hours while being stirred, 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. 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.

14. The method according to any one of claims 1 to 13, further comprising delivering the hydrocarbon feed to a steam catalytic cracking reactor, wherein, The hydrocarbon feed comprises crude oil with an API gravity of 25 to 50.

15. A cracking catalyst composition for upgrading hydrocarbon feedstock, said cracking catalyst composition comprising: Zeolite catalysts; and Cracking additives, comprising metals impregnated on ZSM-5 zeolite, wherein: The zeolite catalyst is different from the ZSM-5 zeolite in the cracking additive; and The metal species include those selected from the group consisting of chromium, vanadium, iron, platinum, molybdenum, cerium, and nickel.

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