Impregnated hierarchical pore mesoporous ZSM-5 zeolite catalyst for enhanced catalytic cracking of crude oil steam to petrochemical products

Abstract

A method for upgrading crude oil by steam enhanced catalytic cracking comprises contacting the crude oil with steam and a cracking catalyst, wherein the mass ratio of the steam to the crude oil is 0.2-1. The cracking catalyst is hierarchical mesoporous ZSM-5 zeolite impregnated with phosphorus, cerium, lanthanum and iron. Contacting a crude oil with steam and a cracking catalyst cracks a portion of the crude oil to produce light olefins, light aromatics, or both. A cracking catalyst is prepared by partially decomposing an initial ZSM-5 zeolite in a first mixture comprising sodium hydroxide and a surfactant, after decomposition, recrystallizing the zeolite component in the presence of the surfactant to produce a recrystallized ZSM-5 zeolite having a hierarchical pore structure. The recrystallized ZSM-5 zeolite is recovered and calcined to produce a hierarchical pore / mesoporous ZSM-5 zeolite, and then the hierarchical pore / mesoporous ZSM-5 zeolite is impregnated with phosphorus, lanthanum, cerium and iron.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of U.S. application serial number 17 / 956,342, filed on September 29, 2022, the entire disclosure of which is incorporated herein by reference. Technical Field

[0003] The present disclosure relates to methods and catalysts for upgrading hydrocarbons to produce higher value petrochemical products and intermediates, and in particular to methods and cracking catalyst compositions for catalytic cracking of crude oil to produce olefins, aromatics, or both. Background Art

[0004] The increasing global demand for higher value petrochemical products and chemical intermediates remains a major challenge for many integrated refineries. In particular, the production of some valuable light olefins, such as ethylene and propylene, has attracted increasing attention as pure olefin streams are considered building blocks for polymer synthesis. In addition, light aromatic compounds such as benzene, toluene and mixed xylenes can be used as fuel blending components or can be converted into higher value chemical products and intermediates, which can be used as building blocks in chemical synthesis processes. Petrochemical feeds, such as crude oil, can be converted into petrochemical products, such as fuel blending components and chemical products and intermediates, such as light olefins and light aromatic compounds, which are basic intermediates for most of the petrochemical industry. Crude oil is traditionally processed by distillation followed by various reforming, solvent treatment and hydroconversion processes to produce a range of desired fuels, lubricant products, chemicals, chemical feedstocks, etc. Conventional refining systems typically combine multiple complex refining units with petrochemical plants to produce higher value petrochemical products and intermediates. Summary of the invention

[0005] Accordingly, there is a continuing need for a cracking catalyst and method for steam-enhanced catalytic cracking crude oil feed and other hydrocarbon feeds to directly produce higher yields of light olefins, light aromatic compounds or both from crude oil using fewer processing steps. The present disclosure relates to a cracking catalyst comprising a multi-stage pore mesoporous ZSM-5 zeolite, which can be impregnated with phosphorus and a transition metal compound (such as cerium oxide, lanthanum oxide, iron oxide or a combination of these transition metal compounds). The present disclosure also relates to a method for upgrading a hydrocarbon feed (such as but not limited to crude oil) by steam-enhanced catalytic cracking using a cracking catalyst. Compared with conventional cracking catalyst compositions, the cracking catalyst of the present disclosure may be able to directly produce higher yields of light olefin products from crude oil by steam-enhanced catalytic cracking. The method of the present disclosure may be able to directly convert crude oil into light olefins, light aromatic compounds or both using fewer processing steps and operating units compared to conventional oil refining systems.

[0006] According to at least one aspect of the present disclosure, a method for upgrading crude oil by steam enhanced catalytic cracking may include contacting the crude oil with steam in the presence of a cracking catalyst, wherein the cracking catalyst may include a hierarchical mesoporous ZSM-5 zeolite impregnated with phosphorus, cerium, lanthanum and iron. The mass ratio of steam to crude oil is from 0.2 to less than 1. Contacting the crude oil with steam in the presence of a cracking catalyst may cause a cracking reaction to occur in at least a portion of the crude oil to produce a cracking effluent comprising light olefins, light aromatic compounds or both.

[0007] According to at least one other aspect of the present disclosure, a cracking catalyst for steam-enhanced catalytic cracking of hydrocarbons may include a multi-level pore mesoporous ZSM-5 zeolite impregnated with phosphorus, cerium, lanthanum and iron. The cracking catalyst can be prepared by a method comprising: providing an initial preformed ZSM-5 zeolite; decomposing a portion of the initial preformed ZSM-5 zeolite in a first mixture comprising sodium hydroxide and a surfactant; after at least partially decomposing the initial preformed ZSM-5 zeolite, recrystallizing the zeolite component in the presence of a surfactant to produce a recrystallized ZSM-5 zeolite having a multi-level pore structure; recovering the recrystallized ZSM-5 zeolite; calcining the recrystallized ZSM-5 zeolite, wherein the calcination removes the surfactant from the recrystallized ZSM-5 zeolite to produce a multi-level pore mesoporous ZSM-5 zeolite; and impregnating the multi-level pore mesoporous ZSM-5 zeolite with phosphorus, cerium, lanthanum and iron to form a cracking catalyst.

[0008] Additional features and advantages of aspects of the present disclosure will be described in subsequent specific embodiments, and for those of ordinary skill in the art, some of the additional features and advantages will be apparent from the specific embodiments or will be recognized by practicing aspects of the present disclosure. BRIEF DESCRIPTION OF THE DRAWINGS

[0009] The following detailed description of the present disclosure may be better understood when read in conjunction with the following drawings, in which:

[0010] Figure 1 schematically depicts a generalized flow diagram of a fixed bed reactor system for steam catalytic cracking of hydrocarbons to produce light olefins, light aromatics, or both, according to one or more embodiments shown and described in the present disclosure;

[0011] Figure 2 depicts a flow chart of one embodiment of a method for producing a cracking catalyst according to one or more embodiments shown and described in the present disclosure;

[0012] Figure 3schematically depicts an upflow fluid catalytic cracking (FCC) system for upgrading a hydrocarbon feed by steam enhanced fluid catalytic cracking according to one or more embodiments shown and described in the present disclosure;

[0013] Figure 4 schematically depicts a downflow fluid catalytic cracking (FCC) system for upgrading a hydrocarbon feed by steam enhanced fluid catalytic cracking according to one or more embodiments shown and described in the present disclosure;

[0014] Figure 5 graphically depicts an X-ray diffraction (XRD) pattern of a hierarchical mesoporous ZSM-5 zeolite prior to impregnation with phosphorus and transition metal compounds to produce a cracking catalyst according to one or more embodiments shown and described in the present disclosure;

[0015] Figure 6 A diagrammatic representation of one or more embodiments shown and described in the present disclosure is provided. Figure 5 a portion of the XRD spectrum in the wavelength range of 5.4 nm to 49 nm;

[0016] Figure 7 schematically depicts a generalized flow diagram of a fixed bed reactor system for evaluating cracking catalysts according to one or more embodiments shown and described in the present disclosure; and

[0017] Figure 8 The present disclosure is shown in diagram form in accordance with one or more embodiments shown and described in the present disclosure. Figure 7 The product yield obtained by steam-enhanced catalytic cracking of AXL crude oil using the composite catalyst particles of Example 5 and the commercial catalyst of Comparative Example 6 in a fixed bed reactor system.

[0018] When describing Figure 1 , 3 , 4 and Figure 7 When a simplified schematic diagram is provided, many valves, temperature sensors, electronic controllers, etc. that can be used and known by ordinary technicians in this field may not be depicted. In addition, the following may not be depicted: Figure 1 , 3 , 4 and Figure 7 The depicted system generally includes auxiliary components such as an air source, a heat exchanger, a buffer tank, etc. However, it should be understood by those skilled in the art that these components still fall within the scope of the present disclosure.

[0019] in addition, Figure 1 , 3 , 4 and Figure 7Arrows in simplified schematic diagrams of refer to process flows. However, arrows may equally refer to transfer lines that may transfer process flows between two or more system components. Arrows connected to one or more system components represent inlets or outlets in that given system component, while arrows connected only to a single system component represent system outlet flows leaving the depicted system or system inlet flows entering the depicted system. The arrow direction generally corresponds to the primary direction of movement of the process flow or process flow contained within the physical transfer line represented by the arrow.

[0020] Figure 1 , 3 , 4 and Figure 7 Arrows in simplified schematic diagrams of can also refer to method steps of transporting 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 represent "transferring" a process stream from the first system component to the second system component, which can include "leaving" or "being removed" from the first system component, as well as "introducing" or "introducing" the process stream into the second system component.

[0021] Reference will now be made in greater detail to various aspects, some of which are illustrated in the accompanying drawings. DETAILED DESCRIPTION

[0022] The present disclosure relates to a cracking catalyst and method for upgrading a hydrocarbon feed (such as but not limited to crude oil) to produce a higher yield of petrochemical products or intermediates (such as but not limited to light olefins, light aromatic compounds or both) by enhanced catalytic cracking. In particular, the present disclosure relates to a cracking catalyst that may include a multi-level pore mesoporous ZSM-5 zeolite impregnated with phosphorus, cerium, lanthanum and iron and a method for preparing the cracking catalyst. The cracking catalyst can be prepared by preparing a multi-level pore mesoporous ZSM-5 zeolite and then impregnating the multi-level pore mesoporous ZSM-5 zeolite with phosphorus, cerium, lanthanum and iron. The hierarchical mesoporous ZSM-5 zeolite can be produced by providing an initial ZSM-5 zeolite, decomposing at least a portion of the initial ZSM-5 zeolite in the presence of a surfactant, then recrystallizing the zeolite component in the presence of a surfactant to produce a recrystallized ZSM-5 zeolite, recovering the recrystallized ZSM-5 zeolite, and calcining the recrystallized ZSM-5 zeolite to remove the surfactant and produce a hierarchical mesoporous ZSM-5 zeolite having a hierarchical pore structure including both micropores and mesopores.

[0023] The method for upgrading a hydrocarbon feed by steam enhanced catalytic cracking disclosed herein may include: contacting the hydrocarbon feed with steam under reaction conditions sufficient to induce one or more cracking reactions of at least a portion of the hydrocarbons in the hydrocarbon feed in the presence of a cracking catalyst to produce a cracking effluent containing light olefins, light aromatic compounds, or both. The cracking catalyst may include a multi-level pore mesoporous ZSM-5 zeolite impregnated with phosphorus, cerium, lanthanum, and iron. The method and cracking catalyst may be able to directly convert crude oil and other heavy oils into higher value petrochemical products and intermediates, such as, but not limited to, light olefins, light aromatic compounds, or both, by steam enhanced catalytic cracking. In particular, the cracking catalyst can increase the yield of light olefins and light aromatic compounds of steam enhanced catalytic cracking of crude oil compared to conventional cracking catalysts. Compared to conventional zeolite-based cracking catalysts, the cracking catalyst disclosed herein may have high hydrothermal stability and longer activity.

[0024] As used in this disclosure, the term "cracking" refers to a chemical reaction in which a molecule having carbon-carbon bonds is broken into more than one molecule by breaking one or more of the carbon-carbon bonds. As used in this disclosure, the term "catalytic cracking" refers to cracking performed in the presence of a catalyst.

[0025] As used in this disclosure, the term "catalyst" refers to any substance that increases the rate of a particular chemical reaction, such as, but not limited to, a cracking reaction.

[0026] As used in this disclosure, the term "spent catalyst" refers to a catalyst that has been contacted with reactants under reaction conditions but has not been regenerated in a regenerator. A "spent catalyst" may have coke deposited on the catalyst and may include partially coked catalyst as well as fully coked catalyst. The amount of coke deposited on a "spent catalyst" may be greater than the amount of coke on a catalyst that is still being regenerated after regeneration. A "spent catalyst" may also include a catalyst that has a reduced temperature as a result of contact with the reactants compared to the catalyst prior to contact with the reactants.

[0027] As used in this disclosure, the term "regenerated catalyst" refers to a catalyst that has been contacted with reactants under reaction conditions and subsequently regenerated in a regenerator to heat the catalyst to a higher temperature, oxidize and remove 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. Compared to the used catalyst, the "regenerated catalyst" may have less coke or organic contaminants, a higher temperature, or both, and may have a higher catalytic activity than the used catalyst. Compared to a fresh catalyst that has not been contacted with the reactants in the reaction zone and then regenerated, the "regenerated catalyst" may have more coke and a lower catalytic activity.

[0028] As used throughout this disclosure, the term "light olefin" refers to olefinic compounds having less than or equal to 6 carbon atoms.

[0029] As used throughout this disclosure, the term "light aromatic compound" refers to a compound having an aromatic ring structure and having less than or equal to 10 carbon atoms.

[0030] As used throughout this disclosure, the terms "butenes" or "mixed butenes" are used interchangeably and refer to a combination of one or more of isobutylene, 1-butene, trans-2-butene, or cis-2-butene. As used throughout this disclosure, the term "n-butenes" refers to a combination of one or more of 1-butene, trans-2-butene, or cis-2-butene. As used throughout this disclosure, the term "2-butenes" refers to trans-2-butene, cis-2-butene, or a combination thereof.

[0031] As used in this disclosure, the term "initial boiling point" or "IBP" of a composition refers to the temperature at which the component of the composition with the lowest boiling temperature begins to transition from the liquid phase to the vapor phase. As used in this disclosure, the term "end boiling point" or "EBP" of a composition refers to the temperature at which the component with the highest boiling temperature of the composition transitions from the liquid phase to the vapor phase. A hydrocarbon mixture can be characterized by a distillation curve, which is expressed as the boiling temperature at which a specific weight percentage of the composition transitions from the liquid phase to the vapor phase.

[0032] As used in this disclosure, the term "normal pressure boiling point temperature" refers to the boiling point temperature of a compound at normal pressure.

[0033] As used in this disclosure, the term "crude oil" or "whole crude oil" is understood to refer to a mixture of liquid petroleum, petroleum gas, or a combination thereof that has not been substantially separated or reacted, including impurities in some embodiments, such as, but not limited to, sulfur-containing compounds, nitrogen-containing compounds, and metallic compounds. Crude oil is different from crude oil fractions. In certain embodiments, the crude oil feedstock can be a light crude oil that has been minimally treated 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 Conrad carbon residue of less than 5 wt.%.

[0034] As used in this disclosure, the term "directly" refers to the transfer of a material (e.g., an effluent) from a first component of a treatment system to a second component of the treatment system without passing the material through any intervening components or operating units operable to change the composition of the material. Likewise, the term "directly" also refers to the introduction of a material (e.g., a feed) into a component of a treatment system without passing the material through any preliminary components operable to change the composition of the material. Intervening or preliminary components or systems operable to change the composition of the material include reactors and separators, but are generally not intended to include heat exchangers, valves, pumps, sensors, or other auxiliary components required for the operation of a chemical process.

[0035] As used in this disclosure, the terms "downstream" and "upstream" refer to the positioning of components or operating units of 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. Similarly, 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.

[0036] As used in this disclosure, the term "effluent" refers to a stream that is transmitted from a reactor, reaction zone, or separator after a particular reaction or separation. Generally, the effluent has a different composition than the stream that enters the reactor, reaction zone, or separator. It should be understood that when the effluent is transmitted to another component or system, only a portion of the effluent may be transmitted. For example, a slipstream may carry away some of the effluent, meaning that only a portion of the effluent may enter a downstream component or system. The terms "reaction effluent" and "reactor effluent" particularly refer to a stream that is transmitted from a reactor or reaction zone.

[0037] The term "residence time" refers to the amount of time that the reactants are in contact with the catalyst under reaction conditions (eg, at the reaction temperature).

[0038] As used in this disclosure, the term "reactor" refers to any vessel, container, conduit, etc., in which one or more chemical reactions may occur between one or more reactants, optionally in the presence of one or more catalysts, such as, but not limited to, catalytic cracking reactions. One or more "reaction zones" may be disposed within a reactor. The term "reaction zone" refers to a spatial region in a reactor where a specific chemical reaction occurs.

[0039] As used in the present disclosure, the terms "separation unit" and "separator" refer to any one or more separation devices that separate one or more chemical components in a mixture at least partially from each other. For example, a separation system selectively separates different chemical components from each other to form one or more chemical fractions. Examples of separation systems include, but are not limited to, a distillation tower, a fractionator, a flash tank, a flash tower, a buffer tank, a buffer pot, a centrifuge, a decanter, a filter 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 thereof. The separation process described in the present disclosure may not completely separate all of one chemical component from all of another chemical component. Instead, the separation process described in the present disclosure "at least partially" separates different chemical components from each other, and even if not explicitly stated, the separation may include only partial separation.

[0040] It should be further understood that a stream can be named after a stream component, and the component used to name the stream can be the major component of the stream, such as the component comprising the largest fraction of the stream, but excluding diluents, such as nitrogen, inert gases, etc., unless otherwise explicitly stated. It should also be understood that when a stream comprising the component is disclosed as being transferred from one system component to another system component, the component of the stream is disclosed as being transferred from the system component to the other system component. For example, a "nitrogen gas stream" disclosed as being transferred to a first system component or from a first system component to a second system component should be understood to be equivalently disclosed as being transferred to the first system component or from a first system component to a second system component.

[0041] Traditional refinery systems include multiple operating units. Steam enhanced catalytic cracking of crude oil can directly reduce the complexity of the refining process, such as by reducing the number of operating units required to process crude oil to produce higher value petrochemical products and intermediates (such as but not limited to light olefins and light aromatic compounds). Steam enhanced catalytic cracking methods generally utilize zeolites, such as ZSM-5 zeolites, which generally have a microporous pore structure with an average pore size of less than 2 nanometers (nm). However, when directly cracking crude oil, crude oil may include a large amount of macromolecules, such as up to 30wt.% of hydrocarbons with a boiling point temperature greater than or equal to 500°C. These large hydrocarbon molecules are generally unable to reach the reaction sites in traditional microporous ZSM-5 zeolites. Macromolecules in crude oil can also block the pores in traditional ZSM-5 zeolites, which can reduce the effectiveness of traditional ZSM-5 zeolites for steam enhanced catalytic cracking of crude oil and other hydrocarbon feeds.

[0042] The present disclosure relates to the use of a cracking catalyst to steam catalytic cracking of crude oil to convert crude oil into higher value hydrocarbon products, such as but not limited to light olefins, aromatic compounds or combinations thereof. The cracking catalyst comprises a multi-level pore mesoporous ZSM-5 zeolite impregnated with phosphorus, cerium, lanthanum and iron. Metal cerium, lanthanum and iron may be present in the cracking catalyst as metal oxides. The multi-level pore mesoporous ZSM-5 zeolite in the cracking catalyst of the present disclosure may have the microporous structure characteristics of ZSM-5 zeolite, and may also have sufficiently large mesopores to increase access to reaction sites and reduce the blockage caused by macromolecules in crude oil to the reaction sites. The present disclosure also relates to a cracking catalyst and a method for making the cracking catalyst.

[0043] Reference now Figure 1The method 100 for converting a hydrocarbon feed 102 into light olefins, light aromatic compounds, or both disclosed herein comprises: contacting the hydrocarbon feed 102 with steam in the presence of a cracking catalyst 132 under reaction conditions sufficient to induce 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 132 comprises a hierarchical mesoporous ZSM-5 zeolite impregnated with phosphorus, cerium oxide, lanthanum oxide, and iron oxide.

[0044] The hydrocarbon feed 102 may include one or more heavy oils, such as, but not limited to, crude oil, asphalt, oil sands, shale oil, coal liquefaction oil, vacuum residue, tar sands, other heavy oil streams, or combinations thereof. It should be understood that, as used in the present disclosure, "heavy oil" refers to a raw hydrocarbon that has not been previously treated by distillation, such as whole crude oil, or may refer to a hydrocarbon oil that has been treated to a certain extent (such as, but not limited to, desalting) before being introduced into the method 100 as a hydrocarbon feed 102. The hydrocarbon feed 12 may have a density greater than or equal to 0.80 g / ml. The hydrocarbon feed 12 may have an end boiling point (EBP) greater than 565°C. The hydrocarbon feed 12 may have a nitrogen concentration less than or equal to 3000 parts per million by weight (ppmw).

[0045] In embodiments, hydrocarbon feed 102 can be crude oil, such as whole crude oil, synthetic crude oil or a mixture of the two. Crude oil can have an American Petroleum Institute (API) degree of 22 to 50 degrees, such as 22 to 40 degrees, 25 to 50 degrees or 25 to 40 degrees. For example, hydrocarbon feed 102 can include ultra-light crude oil, light crude oil, heavy crude oil or a combination thereof. In embodiments, hydrocarbon feed 102 can be light crude oil, such as but not limited to Arab light export crude oil. The exemplary properties of the Arab light crude oil of exemplary grade are provided in Table 1.

[0046] Table 1 Examples of Arab light export raw materials

[0047]

[0048]

[0049] In an embodiment, the hydrocarbon feed 102 may be Arabian Extra Light (AXL) crude oil. Example boiling point distributions for exemplary grades of AXL crude oil are provided in Table 2.

[0050] Table 2

[0051]

[0052]

[0053] When the hydrocarbon feed 102 includes crude oil, the crude oil can be whole crude oil, or can be crude oil that has undergone some treatment (such as desalting, solid separation, washing, or other preliminary treatment that does not involve separating the crude oil into different boiling point range fractions). For example, the hydrocarbon feed 102 can be a desalted crude oil that has been subjected to a desalting process. In an embodiment, the hydrocarbon feed 102 can include crude oil that has not been subjected to pretreatment, separation (e.g., distillation), or other operations or treatments that change the hydrocarbon composition of the crude oil before introducing the crude oil into the system 100.

[0054] In an embodiment, the hydrocarbon feed 102 may be a crude oil having a boiling point curve described as a 5wt.% boiling point temperature, a 25wt.% boiling point temperature, a 50wt.% boiling point temperature, a 75wt.% boiling point temperature, and a 95wt.% boiling point temperature. These respective boiling point temperatures correspond to the temperatures at which a given weight percentage of the hydrocarbon feed stream boils (transforms from a liquid phase to a gas phase). In an embodiment, the crude oil may have one or more of the following: a 5wt.% boiling point temperature of less than or equal to 150°C; a 25wt.% boiling point temperature of less than or equal to 225°C or less than or equal to 200°C; a 50wt.% boiling point 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 75wt.% boiling point temperature of less than 600°C, less than or equal to 550°C; a 95wt.% boiling point temperature of greater than or equal to 550°C or greater than or equal to 600°C; or a combination thereof. In an embodiment, the crude oil may have one or more of the following: a 5wt.% boiling point temperature of 0°C to 100°C; a 25wt.% boiling point temperature of 150°C to 250°C, a 50wt.% boiling point temperature of 250°C to 400°C, a 75wt.% boiling point temperature of 350°C to 600°C, and a final boiling point temperature of 500°C to 1000°C, for example 500°C to 800°C.

[0055] Reference again Figure 1, schematically depicts an embodiment of a steam catalytic cracking system 110 for steam catalytic cracking a hydrocarbon feed 102. The steam catalytic cracking system 110 may include at least one steam catalytic cracking reactor 130. The steam catalytic cracking reactor 130 may include one or more fixed bed reactors, fluidized bed reactors, batch reactors, fluidized catalytic cracking (FCC) reactors, moving bed catalytic cracking reactors, or combinations thereof. In an embodiment, the steam catalytic cracking reactor 130 may be a fixed bed reactor. In an embodiment, the steam catalytic cracking reactor 130 may include a plurality of fixed bed reactors operating in a switching mode. Herein, the operation of the steam catalytic cracking reactor 130 will be described in the context of a fixed bed reactor. However, it should be understood that other types of reactors such as fluidized bed reactors, batch reactors, FCC reactors, or moving bed reactors may also be used to contact the hydrocarbon feed 102 with a cracking catalyst to perform steam enhanced catalytic cracking in the method disclosed herein.

[0056] The steam catalytic cracking reactor 130 is operable to contact the hydrocarbon feed 102 with steam in the presence of a cracking catalyst of the present disclosure to produce a steam cracking effluent comprising light olefins, aromatic compounds, or a combination thereof. As previously described, the steam catalytic cracking reactor 130 may be a fixed bed catalytic cracking reactor, which may include a cracking catalyst 132 disposed in a steam catalytic cracking zone 134. The steam catalytic cracking reactor 130 may include a porous packing 136, such as a silicon carbide packing, upstream of the steam catalytic cracking zone 134. The porous packing 136 may ensure that sufficient heat is transferred to the hydrocarbon feed 102 and steam before the steam catalytic cracking reaction is carried out in the steam catalytic cracking zone 134.

[0057] Reference again Figure 1 , the hydrocarbon feed 102 may be introduced into the steam catalytic cracking reactor 130. In an embodiment, the hydrocarbon feed 102 may be introduced directly into the steam catalytic cracking system 110, such as by conveying the crude oil of the hydrocarbon feed 102 to the steam catalytic cracking reactor 130, without conveying the hydrocarbon feed 102 to any separation system or operating unit that changes the hydrocarbon composition of the hydrocarbon feed 102. In an embodiment, the hydrocarbon feed 102 may 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 may reduce the effectiveness of the cracking catalyst 132.

[0058] Introducing the hydrocarbon feed 102 into the steam catalytic cracking reactor 130 may include heating the hydrocarbon feed 102 to a temperature of 35°C to 150°C and then passing the hydrocarbon feed 102 to the steam catalytic cracking reactor 130. In embodiments, the hydrocarbon feed 102 may be preheated 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.

[0059] In an embodiment, delivering the hydrocarbon feed 102 to the steam catalytic cracking reactor 130 may include delivering the hydrocarbon feed 102 to a feed pump 104, wherein the feed pump 104 may increase the pressure of the hydrocarbon feed 102 and transport the hydrocarbon feed 102 to the steam catalytic cracking reactor 130. The flow rate of the feed pump 104 may be adjusted to be greater than or equal to 0.1 h per hour (h -1 ) or greater than or equal to 0.25h -1 The hydrocarbon feed 102 is injected into the steam catalytic cracking reactor 130 at a gas hourly space velocity of less than or equal to 50 h -1 , less than or equal to 25h -1 , less than or equal to 20h -1 , less than or equal to 14h -1 , less than or equal to 9h -1 Or less than or equal to 5h -1 The hydrocarbon feed 102 is injected into the steam catalytic cracking reactor 130 at a gas hourly space velocity of 0.1 h. -1 Up to 50h -1 , 0.1h -1 Until 25h -1 , 0.1h -1 Until 20h -1 , 0.1h -1 Until 14h -1 , 0.1h -1 Until 9h -1 , 0.1h -1 Until 5h -1 , 0.1h -1 Up to 4h -1 , 0.25h -1 Up to 50h -1 , 0.25h -1 Until 25h -1 , 0.25h -1 Until 20h -1 , 0.25h -1 Until 14h -1 , 0.25h -1 Until 9h -1 , 0.25h-1 Until 5h -1 , 0.25h -1 Up to 4h -1 , 1h -1 Up to 50h -1 , 1h -1 Until 25h -1 , 1h -1 Until 20h -1 , 1h -1 Until 14h -1 , 1h -1 Until 9h -1 or 1h -1 Until 5h -1 The hydrocarbon feed 102 is injected into the steam catalytic cracking reactor 130 at a gas hourly space velocity of 1.000 t / s. Before the hydrocarbon feed 102 is injected into the steam catalytic cracking reactor 130, the hydrocarbon feed 102 may be further preheated to a temperature of 100°C to 250°C in the feed inlet line 106.

[0060] Water 120 may be injected into the steam catalytic cracking reactor 130 through a feed water pump 124 through a feed water line 122. The feed water line 122 may 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 may be converted to steam in the feed water line 122 or when contacting the hydrocarbon feed 102 in the steam catalytic cracking reactor 130. The flow rate of the feed water pump 124 may be adjusted so as to be greater than or equal to 0.1 h per hour (h -1 ), greater than or equal to 0.5h -1 , greater than or equal to 1h -1 , greater than or equal to 5h -1 , greater than or equal to 6h -1 , greater than or equal to 10h -1 Or even greater than or equal to 15h -1 Water 120 (liquid, steam or both) is delivered to the steam catalytic cracking reactor 130 at a gas hourly space velocity of less than or equal to 100 h -1 , less than or equal to 75h -1 , less than or equal to 50h -1 , less than or equal to 30h -1 Or less than or equal to 20h -1 Water 120 is introduced into the steam catalytic cracking reactor 130 at a gas hourly space velocity of 0.1 h -1 Until 100h -1 , 0.1h -1 Up to 75h -1 , 0.1h -1 Up to 50h -1 , 0.1h-1 Up to 30h -1 , 0.1h -1 Until 20h -1 , 1h -1 Until 100h -1 , 1h -1 Up to 75h -1 , 1h -1 Up to 50h -1 , 1h -1 Up to 30h -1 or 1h -1 Until 20h -1 Water 120 is introduced into the steam catalytic cracking reactor 130 at a gas hourly space velocity of .

[0061] The steam produced by injecting water 120 into steam catalytic cracking reactor 130 can reduce the hydrocarbon partial pressure, which can have the dual effect of increasing light olefins (such as ethylene, propylene and butylenes) productivity and reducing the coking on the cracking catalyst. Without being intended to be limited to any particular theory, it is believed that light olefins such as propylene and mixed butylenes are mainly generated by the catalytic cracking reaction of carbocation mechanism, and because these are intermediate products, they can be subjected to secondary reactions (causing coking) such as hydrogen transfer and aromatization. Steam can improve the productivity of light olefins by suppressing these secondary bimolecular reactions, and can reduce the concentration of reactants and products, which is conducive to the selectivity of light olefins. Steam can also suppress the secondary reaction that causes catalyst surface coking, which is conducive to catalyst keeping high average activation rate. These factors may show that larger steam and oil weight ratio may be beneficial to the production of light olefins.

[0062] The mass flow rate of water 120 to the steam catalytic cracking reactor 130 may be less than the mass flow rate of the hydrocarbon feed 102 to the steam catalytic cracking reactor 130. In an embodiment, the mass flow rate ratio of water 120 (steam) to hydrocarbon feed 102 introduced into the steam catalytic cracking reactor 130 may be less than 1, e.g., 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 steam catalytic cracking reactor 130 may be 0.2 to less than 1, 0.2 to 0.9, 0.2 to 0.8, 0.2 to 0.7, 0.2 to 0.6, 0.3 to less than 1, 0.3 to 0.9, 0.3 to 0.8, 0.3 to 0.7, 0.3 to 0.6, 0.4 to less than 1, 0.4 to 0.9, 0.4 to 0.8, 0.4 to 0.7, 0.4 to 0.6, 0.5 to less than 1, 0.5 to 0.9, 0.5 to 0.8, 0.5 to 0.7, or 0.5 to 0.6. In embodiments, the mass flow ratio of water 120 to hydrocarbon feed 102 introduced into steam catalytic cracking reactor 130 may be about 0.5. In steam catalytic cracking reactor 130, water may be present as steam.

[0063] Reference again Figure 1 , the steam catalytic cracking system 110 can be operated to contact the hydrocarbon feed 102 with steam (from water 120) in the presence of a cracking catalyst 132 in the steam catalytic cracking reactor 130 under reaction conditions sufficient to induce 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. In an embodiment, the steam catalytic cracking effluent 140 may contain light olefins, which may include, but are not limited to, ethylene, propylene, mixed butenes, or a combination thereof. In an embodiment, the steam catalytic cracking effluent 140 may contain light aromatic compounds, which refer to compounds containing an aromatic ring structure and having less than or equal to 10 carbon atoms. The light aromatic compounds in the steam catalytic cracking effluent 140 may include, but are not limited to, benzene, toluene, ethylbenzene, mixed xylenes, or other light aromatic compounds.

[0064] The steam catalytic cracking reactor 130 may 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 may 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 may 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 may be operated at a temperature of about 675° C. The process may be run at atmospheric pressure (approximately 1 to 2 bar (100 kPa to 200 kPa)).

[0065] The method of the present disclosure may include contacting the hydrocarbon feed 120 with steam (water 120) in the presence of a cracking catalyst 132 in a 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 into light olefins, light aromatic compounds, or both. In an embodiment, the method may include contacting the hydrocarbon feed 102 with steam (water 120) in the presence of a cracking catalyst 132 in a steam catalytic cracking reactor 130 for a residence time of 1 second to 60 seconds, such as 5 seconds to 30 seconds or about 10 seconds.

[0066] 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 hydrocarbon feed 102 and water 120 flowing to the steam catalytic cracking reactor 130. After this period of time, the cracking catalyst 132 can be regenerated. Each conversion cycle of the steam catalytic cracking reactor 130 can be 2 hours to 24 hours, 2 hours to 20 hours, 2 hours to 16 hours, 2 hours to 12 hours, 2 hours to 10 hours, 2 hours to 8 hours, 4 hours to 24 hours, 4 hours to 20 hours, 4 hours to 16 hours, 4 hours to 12 hours, 4 hours to 10 hours, or 4 hours to 8 hours before the feed pump 104 and the feed water pump 124 are shut down to stop the flow of hydrocarbons and steam to the steam catalytic cracking reactor 130.

[0067] At the end of the conversion cycle, the flow of hydrocarbon feed 102 and water 120 can be stopped, and the cracking catalyst 132 can be regenerated during the regeneration cycle. In an embodiment, the steam catalytic cracking system 110 may include a plurality of fixed bed steam catalytic cracking reactors 130, which can be operated in parallel or in series. In an embodiment, the steam catalytic cracking system 110 may include 2, 3, 4, 5, 6 or more than 6 steam catalytic cracking reactors 130, which can be operated in series or in parallel. With a plurality of steam catalytic cracking reactors 130 operating in parallel, one or more of the steam catalytic cracking reactors 130 can continue the conversion cycle while one or more of the other steam catalytic cracking reactors 130 are offline for regenerating the cracking catalyst 132, thus maintaining continuous operation of the steam catalytic cracking system 110.

[0068] Reference again Figure 1 During the regeneration cycle, the steam catalytic cracking reactor 130 can be operated to regenerate the cracking catalyst 132. The cracking catalyst 132 can be regenerated to remove coke deposits accumulated during the conversion cycle. In order to regenerate the cracking catalyst 132, hydrocarbon gas and liquid products produced during the steam catalytic cracking process can be evacuated from the steam catalytic cracking reactor 130. Nitrogen 114 can be introduced into the steam catalytic cracking reactor 130 through the inlet line 112 to evacuate the hydrocarbon gas and liquid products from the fixed bed steam catalytic cracking reactor 130. The nitrogen gas 114 can be introduced into the steam catalytic cracking reactor 130 through the inlet line 112 to evacuate the hydrocarbon gas and liquid products from the fixed bed steam catalytic cracking reactor 130. The nitrogen gas 114 can be introduced into the steam catalytic cracking reactor 130 at a rate of 10 hours per hour (h -1 ) to 100h -1 Nitrogen 114 is introduced into the steam catalytic cracking reactor 130 at a gas hourly space velocity of .

[0069] After evacuating the hydrocarbon gas and liquid, air 116 can be introduced through the air intake line 112 at a rate of 10 hours. -1 Until 100h -1The steam catalytic cracking reactor 130 may be introduced at a gas hourly space velocity of 1.1 to 1.5 wt % into the steam catalytic cracking reactor 130. The air may be conveyed out of the steam catalytic cracking reactor 130 via the outlet line 142. While the air 116 is conveyed through the cracking catalyst 132 in the steam catalytic cracking reactor 130, the temperature of the steam catalytic cracking reactor 130 may be adjusted from the reaction temperature to a regeneration temperature of 650° C. to 750° C. for a period of 3 to 5 hours. The gas produced by the air regeneration of the cracking catalyst 132 may be conveyed out of the steam catalytic cracking reactor 130 and may be analyzed by an in-line gas analyzer to detect the presence or concentration of carbon dioxide produced by the decoking of the cracking catalyst 132. Once the concentration of carbon dioxide in the gas conveyed out of the steam catalytic cracking reactor 130 is reduced to less than 0.05 wt % to 0.1 wt % (determined by the in-line gas analyzer), the temperature of the steam catalytic cracking reactor 130 may be reduced from the regeneration temperature back to the reaction temperature. The air flow through the inlet line 112 may be stopped. The nitrogen may be passed through the cracking catalyst 132 for 15 to 30 minutes to remove air from the steam catalytic cracking reactor 130. After treatment with the nitrogen, the flow of the hydrocarbon feed 102 and the water 120 may be resumed to begin another conversion cycle of the steam catalytic cracking reactor 130. Although described herein in the context of a fixed bed reactor system, it should be understood that the steam catalytic cracking reactor 130 may be a different type of reactor, such as a fluidized bed reactor, a moving bed reactor, a batch reactor, an FCC reactor, or a combination thereof.

[0070] Reference again Figure 1 , the steam catalytic cracking effluent 140 can be transmitted out of the steam catalytic cracking reactor 130. The steam catalytic cracking effluent 140 may include one or more products and intermediates, such as but not limited to light hydrocarbon gas, light olefins, aromatic compounds, pyrolysis oil, or a combination thereof. The light olefins in the steam catalytic cracking effluent 140 may include ethylene, propylene, butene, or a combination thereof.

[0071] As previously mentioned, the cracking catalyst comprises a multi-level pore mesoporous ZSM-5 zeolite impregnated with phosphorus or a phosphorus-containing compound and one or more transition metal compounds (such as but not limited to transition metals, transition metal oxides or combinations thereof). In particular, the cracking catalyst may comprise a multi-level pore mesoporous ZSM-5 zeolite impregnated with phosphorus pentoxide, cerium oxide, lanthanum oxide and iron oxide. The cracking catalyst may be prepared by a method comprising: preparing a multi-level pore mesoporous ZSM-5 zeolite, then impregnating the multi-level pore mesoporous ZSM-5 zeolite with a phosphorus-containing compound and a transition metal compound.

[0072] Reference now Figure 2, depicts a method 200 for preparing a cracking catalyst. Method 200 may include preparing a hierarchical mesoporous ZSM-5 zeolite by the following steps: In step 210, providing an initial ZSM-5 zeolite, such as a microporous ZSM-5 zeolite; In step 220, decomposing at least a portion of the initial ZSM-5 zeolite in a first mixture comprising the initial ZSM-5 zeolite, sodium hydroxide, and a surfactant; In step 230, after decomposing at least a portion of the ZSM-5 zeolite, recrystallizing the zeolite component in the presence of the surfactant to produce a recrystallized ZSM-5 zeolite; In step 240, recovering the recrystallized ZSM-5 zeolite; and In step 250, drying and calcining the recrystallized ZSM-5 zeolite. Calcination can remove the surfactant from the recrystallized ZSM-5 zeolite to produce a hierarchical mesoporous ZSM-5 zeolite having a hierarchical pore structure. The hierarchical pore structure of the hierarchical mesoporous ZSM-5 zeolite may include micropores and mesopores.

[0073] The initial ZSM-5 zeolite is a shape-selective zeolite that can be active for catalytic cracking of hydrocarbons to produce smaller hydrocarbon molecules (such as light olefins, light aromatic compounds, or both). As used in this disclosure, "ZSM-5" refers to a zeolite having the MFI framework type according to the International Union of Pure and Applied Chemistry (IUPAC) zeolite nomenclature and composed of silica and alumina. ZSM-5 refers to "Zeolite Socony Mobil-5", and is a pentasil ring family zeolite that can be represented by the following chemical formula: Na n Al n Si 96–n O 192 ·16H 2 O, where 0 < n < 27. The initial ZSM-5 zeolite may have a microporous pore structure with an average pore diameter less than or equal to 2 nm. The initial ZSM-5 zeolite may have a silica-to-alumina molar ratio greater than or equal to 10 or greater than or equal to 20. The initial ZSM-5 zeolite may have a silica-to-alumina molar ratio less than or equal to 300, such as less than or equal to 200, less than or equal to 100, or even less than or equal to 40. In an embodiment, the initial ZSM-5 zeolite may have a silica-to-alumina molar ratio of 10 to 300, 10 to 200, 10 to 100, 10 to 50, 20 to 300, 20 to 200, 20 to 100, 20 to 50, or 50 to 300. The initial ZSM-5 zeolite may be in the form of multiple particles (such as multiple spherical particles). The initial ZSM-5 zeolite can be obtained from commercial suppliers or can be synthesized according to known methods for producing conventional microporous ZSM-5 zeolites.

[0074] The initial ZSM-5 zeolite may then be subjected to a decomposition process to decompose at least a portion of the initial ZSM-5 zeolite. As used herein, the term "decomposition" refers to decomposing the ZSM-5 framework structure into its constituent oxides, such as alumina and silica, which are then dissolved in a solution. Decomposing at least a portion of the initial ZSM-5 zeolite may include first combining the initial ZSM-5 zeolite, sodium hydroxide, and a surfactant to form a first mixture.

[0075] The first mixture may include a sufficient concentration of sodium hydroxide to decompose the zeolite framework structure of a portion of the initial ZSM-5 zeolite and dissolve the decomposed alumina and silica into the first mixture. In an embodiment, the first mixture may include a sodium hydroxide concentration of 0.2 moles (M) to 0.4M. The surfactant may be hexadecyltrimethylammonium bromide (CTAB). The first mixture may include a sufficient amount of surfactant to dissolve the components of the initial ZSM-5 zeolite after the components are decomposed and to control the formation of mesopores during recrystallization. In an embodiment, based on the gross weight of the first mixture, the first mixture may include a CTAB concentration of 4wt.% to 5wt.% or 4.45wt.%. The first mixture may have a pH greater than 9, greater than or equal to 10, greater than or equal to 10.5, or even greater than or equal to 11. The pH may be from 9.5 to 14, 9.5 to 13, 9.5 to 12.5, 9.5 to 12, 10 to 14, 10 to 13, 10 to 12.5, 10 to 12, 10.5 to 14, 10.5 to 13, 10.5 to 12.5, 10.5 to 12, 11 to 14, 11 to 13, 11 to 12.5 or even 11 to 12.

[0076] Decomposition may also include hydrothermally treating the first mixture, wherein the initial ZSM-5 zeolite is hydrothermally treated in the presence of sodium hydroxide and a surfactant so that part of the initial ZSM-5 zeolite is decomposed. Hydrothermally treating the first mixture may include heating the first mixture to a first hydrothermal treatment temperature greater than or equal to 100°C, such as a temperature of 100°C to 150°C, while stirring the first mixture. Hydrothermally treating the first mixture may also include maintaining the first mixture at a temperature greater than or equal to 100°C or 100°C to 150°C for a first hydrothermal treatment time under stirring. The first hydrothermal treatment time may be sufficient to decompose a portion but not all of the initial ZSM-5 zeolite. If the first hydrothermal treatment time is too long, all of the initial ZSM-5 zeolite may be decomposed, which may make it difficult for the zeolite component to begin recrystallization to form a multi-level pore mesoporous ZSM-5 zeolite. If the first hydrothermal treatment time is too short, insufficient decomposition of the ZSM-5 zeolite may result in insufficient formation of mesopores in the multi-level pore mesoporous ZSM-5 zeolite, which may limit the BET surface area and reduce the number of accessible reaction sites. In an embodiment, the first hydrothermal treatment time can be 10 hours to 30 hours, such as 10 hours to 24 hours, 14 hours to 30 hours, 14 hours to 24 hours, 18 hours to 30 hours, 18 hours to 24 hours, 20 hours to 30 hours, or about 24 hours.

[0077] After at least a portion of the initial ZSM-5 zeolite in the first mixture is decomposed, the alumina and silica components that are decomposed and dissolved into the first mixture can then be recrystallized in the presence of a surfactant to produce the hierarchical pore structure of the hierarchical mesoporous ZSM-5 zeolite of the present disclosure. The recrystallization of the alumina and silica components decomposed from the initial ZSM-5 zeolite in the presence of a surfactant can form a mesoporous structure while maintaining the same silica to alumina molar ratio as the initial ZSM-5 zeolite.

[0078] Recrystallizing the alumina and silica components that have been decomposed from the initial ZSM-5 zeolite may include cooling the first mixture back to room temperature. Cooling the first mixture may include cooling the first mixture to a temperature of 20°C to 50°C, such as a temperature of 25°C. After cooling, recrystallization may include adjusting the pH of the first mixture to a pH of 9.0 to produce a second mixture. The pH may be adjusted by adding a strong acid, such as, but not limited to, sulfuric acid. In an embodiment, a strong acid may be added dropwise to the first mixture until the pH reaches 9.0. In an embodiment, the pH may be adjusted with 2N sulfuric acid. The second mixture includes partially undecomposed ZSM-5 zeolite particles, a surfactant, and silica and alumina materials that decompose and dissolve in the second mixture.

[0079] After adjusting the pH, recrystallizing the ZSM-5 component may include stirring the second mixture for a second time period (10 hours to 30 hours, 10 hours to 24 hours, 14 hours to 30 hours, 14 hours to 24 hours, 18 hours to 30 hours, 18 hours to 24 hours, 20 hours to 30 hours, or about 24 hours) and then hydrothermally treating the second mixture. Hydrothermally treating the second mixture may include heating the second mixture to a second hydrothermal treatment temperature greater than or equal to 100° C. (e.g., 100° C. to 150° C.) and maintaining the second mixture at the second hydrothermal treatment temperature for a third time period under stirring. The third time period may be sufficient to recrystallize the silica and alumina components of the ZSM-5 zeolite in the presence of a surfactant to produce a recrystallized ZSM-5 zeolite having a mesoporous structure in the recrystallized portion. In an embodiment, the third time period can be 10 hours to 30 hours, 10 hours to 24 hours, 14 hours to 30 hours, 14 hours to 24 hours, 18 hours to 30 hours, 18 hours to 24 hours, 20 hours to 30 hours or about 24 hours. Stir the second mixture second time period and hydrothermally treat the second mixture for a third time period to recrystallize the aluminum oxide and silicon dioxide components in the presence of a surfactant to produce a recrystallized ZSM-5 zeolite. In particular, during recrystallization, the aluminum oxide and silicon dioxide components in the second mixture can be recrystallized in the presence of a surfactant to form a ZSM-5 zeolite layer, which has a multi-level porous structure on the outer surface of the undecomposed part of the initial ZSM-5 zeolite. The multi-level porous structure of the ZSM-5 zeolite layer recrystallized on the surface of the undecomposed part of the initial ZSM-5 zeolite can include mesopores and micropores.

[0080] After recrystallization, producing multi-level pore mesoporous ZSM-5 zeolite may include reclaiming recrystallized ZSM-5 zeolite. Reclaiming recrystallized ZSM-5 zeolite may include separating recrystallized ZSM-5 zeolite particles from the second mixture, such as but not limited to filtering the second mixture to produce a filtrate containing recrystallized ZSM-5 zeolite particles. In addition to filtering or instead of filtering, other solid-liquid separation methods may also be used. After separating recrystallized ZSM-5 zeolite particles from the second mixture, recrystallized ZSM-5 zeolite particles may be washed with water (such as distilled water or deionized water) to remove residual reagents from the surface and pores of the recrystallized ZSM-5 particles. After cleaning, the recrystallized ZSM-5 zeolite particles may be dried at a drying temperature of 80°C for a drying period of 8 to 24 hours to produce recrystallized ZSM-5 zeolite powder. The recrystallized ZSM-5 zeolite powder may then be calcined at a temperature of 500° C. to 800° C. for a calcination period of 5 to 24 hours to produce a hierarchical mesoporous ZSM-5 zeolite having a hierarchical pore structure.

[0081] In an embodiment, the multi-level pore mesoporous ZSM-5 zeolite can be ion exchanged to produce a multi-level pore mesoporous ZSM-5 zeolite in hydrogen form. In the hydrogen form, the Bronsted acid sites (also known as bridging OH-H groups) in the zeolite can form hydrogen bonds with other framework oxygen atoms in the zeolite framework. In an embodiment, the method for producing a multi-level pore mesoporous ZSM-5 zeolite may include ion exchanging the multi-level pore mesoporous ZSM-5 zeolite to produce a multi-level pore mesoporous ZSM-5 zeolite in hydrogen form. In an embodiment, ion exchanging the multi-level pore mesoporous ZSM-5 zeolite may include treating the multi-level pore mesoporous ZSM-5 zeolite with 0.25 equivalent (N) ammonium nitrate at 80°C for 5 hours. In an embodiment, multiple ion exchange processes may be performed, for example, by treating the multi-level pore mesoporous ZSM-5 zeolite with 0.25N ammonium nitrate at 80°C twice or more than twice, each time for 5 hours. In an embodiment, the multi-level pore mesoporous ZSM-5 zeolite may be in hydrogen form.

[0082] The hierarchical pore mesoporous ZSM-5 zeolite may have a silica to alumina molar ratio greater than or equal to 10, or greater than or equal to 20. The hierarchical pore mesoporous ZSM-5 zeolite may have a silica to alumina molar ratio less than or equal to 300, such as less than or equal to 200, less than or equal to 100, or even less than or equal to 40. In embodiments, the hierarchical pore mesoporous ZSM-5 zeolite may have a silica to alumina molar ratio of 10 to 300, such as 10 to 200, 10 to 100, 10 to 50, 20 to 300, 20 to 200, 20 to 100, 20 to 50, or 50 to 300. In embodiments, the hierarchical pore mesoporous ZSM-5 zeolite may have a silica to alumina molar ratio that is the same as that of the initial ZSM-5 zeolite.

[0083] Multilevel pore mesoporous ZSM-5 zeolite can be in the form of multiple particles. In embodiments, multilevel pore mesoporous ZSM-5 zeolite can have an average crystal size greater than or equal to 50nm, greater than or equal to 100nm or even greater than or equal to 200nm. Multilevel pore mesoporous ZSM-5 zeolite can have an average crystal size less than or equal to 600nm or less than or equal to 500nm. In embodiments, multilevel pore mesoporous ZSM-5 zeolite can have an average crystal size of 50nm to 600nm, 50nm to 500nm, 100nm to 600nm, 100nm to 500nm, 200nm to 600nm or 200nm to 500nm. Average crystal size is determined by scanning electron microscope (SEM) according to known methods.

[0084] As mentioned above, the multi-level pore mesoporous ZSM-5 zeolite of the cracking catalyst of the present disclosure has a multi-level pore structure including mesopores and micropores. Without being limited to any particular theory, it is believed that the presence of mesopores formed by surfactant-assisted decomposition and recrystallization can produce a mesoporous structure, which can increase the adsorption of the zeolite pore structure to larger hydrocarbon molecules from hydrocarbon feed 102, thereby achieving enhanced conversion. The presence of mesopores in the crystalline framework of the multi-level pore mesoporous ZSM-5 zeolite can be considered to be equivalent to increasing its external surface area, so that a larger number of pore openings can be used for larger reactants (such as hydrocarbon molecules with larger molecular weight). Mesopores can be used as highways to promote the transportation of molecules between micropores, and there are active reaction sites in the micropores. The formation of mesopores in the multi-level pore mesoporous ZSM-5 zeolite can also shorten the diffusion path length in the micropores, thereby improving transportation, and therefore more efficiently utilizing ZSM-5 as a catalyst. The shortened diffusion path length means that target products such as light olefins may be less prone to secondary reactions such as hydrogenation or oligomerization. The increase in molecular transport within the hierarchical mesoporous ZSM-5 zeolite of the present disclosure can reduce the probability of pore coking and can extend the life of the catalyst. It is believed that pore coking is caused by blockage of heavy aromatic compounds from the hydrocarbon feed 102, which are restricted from entering the surface pores of the microporous zeolite at higher temperatures.

[0085] In embodiments, the hierarchical mesoporous ZSM-5 zeolite may have a pore size of 550 m 2 / g to 600m 2 / g specific surface area, for example, about 572m 2 / g. The specific surface area is determined according to the Brunauer-Emmett-Teller (BET) method. In the full text of this disclosure, the specific surface area may be referred to as the BET surface area. The BET surface area of ​​the multi-level pore mesoporous ZSM-5 zeolite may include the BET surface area provided by the mesoporous structure and the BET surface area provided by the microporous structure. The BET surface area provided by the mesopores is referred to as the mesoporous BET surface area in the full text of this disclosure, which represents the surface area of ​​the mesoporous inner surface of the multi-level pore mesoporous ZSM-5 zeolite measured by the BET method. The BET surface area provided by the micropores is referred to as the micropore BET surface area in the full text of this disclosure, which represents the surface area of ​​the micropore inner surface of the multi-level pore mesoporous ZSM-5 zeolite measured by the BET method.

[0086] The hierarchical mesoporous ZSM-5 zeolite may have a mesoporous BET surface area greater than the microporous BET surface area of ​​the hierarchical mesoporous ZSM-5 zeolite. In an embodiment, the mesoporous BET surface area of ​​the hierarchical mesoporous ZSM-5 zeolite may be greater than 50% of the total BET surface area of ​​the hierarchical mesoporous ZSM-5 zeolite, for example, greater than or equal to 52% of the total BET surface area of ​​the hierarchical mesoporous ZSM-5 zeolite, or even greater than or equal to 55%. In embodiments, the mesoporous BET surface area of ​​the hierarchical mesoporous ZSM-5 zeolite may be 50% to 80%, 50% to 75%, 50% to 70%, 50% to 65%, 50% to 60%, 52% to 80%, 52% to 75%, 52% to 70%, 52% to 65%, 52% to 60%, 55% to 80%, 55% to 75%, 55% to 70%, 55% to 65%, or 55% to 60% of the total BET surface area of ​​the hierarchical mesoporous ZSM-5 zeolite. The remainder of the total BET surface area may be microporous BET surface area. In embodiments, the hierarchical mesoporous ZSM-5 zeolite may have a BET surface area of ​​300 m2 prior to impregnation with phosphorus and transition metal compounds. 2 / g to 400m 2 / g or about 325m 2 / g of mesoporous BET surface area.

[0087] Prior to impregnation with phosphorus and transition metal compounds, the hierarchical mesoporous ZSM-5 zeolite may have a pore size of 0.40 cm3 / g (cm 3 / g) to 0.50cm 3 / g or about 0.45cm 3 The total pore volume of / g. The total pore volume is determined by non-local density functional theory (NLDFT) modeling and analysis, based on the measured gas adsorption isotherm. The BET method is also used to determine the total pore volume. The total pore volume of the multi-level mesoporous ZSM-5 zeolite includes the pore volume provided by the mesopores and the pore volume provided by the micropores. The pore volume provided by the mesopores is referred to as the mesopore volume in the full text of this disclosure, and the pore volume provided by the micropores is referred to as the micropore volume in the full text of this disclosure.

[0088] The multi-level pore mesoporous ZSM-5 zeolite may have a mesoporous volume greater than the micropore volume of the multi-level pore mesoporous ZSM-5 zeolite. In an embodiment, the mesoporous volume of the multi-level pore mesoporous ZSM-5 zeolite may be greater than 50% of the total pore volume of the multi-level pore mesoporous ZSM-5 zeolite, for example, greater than or equal to 60% of the total pore volume of the multi-level pore mesoporous ZSM-5 zeolite, greater than or equal to 65% of the total pore volume, or about 67% of the total pore volume. In an embodiment, the mesoporous volume of the multi-level pore mesoporous ZSM-5 zeolite may be 60% to 80%, 60% to 75%, 60% to 70%, 65% to 80%, 65% to 75%, 65% to 70%, 67% to 80% or 67% to 75% of the total pore volume of the multi-level pore mesoporous ZSM-5 zeolite. The remainder of the total pore volume may be a micropore volume. In embodiments, the hierarchical mesoporous ZSM-5 zeolite may have a pore size of 0.25 cm prior to impregnation with phosphorus and transition metal compounds. 3 / g to 0.35cm 3 / g, 0.30cm 3 / g to 0.35cm 3 / g or about 0.31cm 3 / g of mesopore volume.

[0089] Reference again Figure 2 After synthesizing the multi-level pore mesoporous ZSM-5 zeolite, the method for manufacturing a cracking catalyst disclosed herein may further include impregnating the multi-level pore mesoporous ZSM-5 zeolite with a phosphorus-containing compound and a transition metal compound (step 260). As discussed, the cracking catalyst may further include phosphorus or a phosphorus-containing compound impregnated onto the outer surface and pore surface of the multi-level pore mesoporous ZSM-5 zeolite. The phosphorus or phosphorus-containing compound may be carried by the multi-level pore mesoporous ZSM-5 zeolite. Including phosphorus or a phosphorus-containing compound in the cracking catalyst may improve the thermal stability of the multi-level pore mesoporous ZSM-5 zeolite. In an embodiment, the phosphorus-containing compound may include phosphorus pentoxide (P pentoxide). 2 O 5 ). Phosphorus or phosphorus pentoxide can be arranged or deposited on the outer surface, pore surface, or both of the hierarchical mesoporous ZSM-5 zeolite so that the phosphorus or phosphorus pentoxide can enter the reactants that contact the cracking catalyst or diffuse into the pores of the cracking catalyst. Phosphorus or phosphorus pentoxide can be deposited on the hierarchical mesoporous ZSM-5 zeolite by known methods, such as but not limited to wet impregnation, incipient wetness impregnation, or other impregnation methods.

[0090] The cracking catalyst may include a sufficient amount of a phosphorus-containing compound such as phosphorus pentoxide to improve the thermal stability of the cracking catalyst. In an embodiment, the cracking catalyst may include 1 wt.% to 5 wt.% of a phosphorus-containing compound such as, but not limited to, phosphorus pentoxide based on the total weight of the cracking catalyst. In an embodiment, the cracking catalyst may include 1 wt.% to 4.5 wt.%, 1 wt.% to 4 wt.%, 1 wt.% to 3.5 wt.%, 1 wt.% to 3 wt.%, 1 wt.% to 2.5 wt.%, 1 wt.% to 2 wt.%, 1 wt.% to 1.5 wt.%, 1.5 wt.% to 5 wt.%, 2 wt.% to 5 wt.%, 2.5 wt.% to 5 wt.%, 3 wt.% to 5 wt.%, 3.5 wt.% to 5 wt.%, 4 wt.% to 5 wt.%, 4.5 wt.% to 5 wt.%, 1.5 wt.% to 4.5 wt.%, 2 wt.% to 4 wt.%, or 2.5 wt.% to 4 wt.% of phosphorus-containing compounds, based on the total weight of the cracking catalyst.

[0091] In embodiments, cracking catalyst can include one or more transition metals, transition metal oxides or both impregnated on the surface of multi-level pore mesoporous ZSM-5 zeolite.As previously mentioned, phosphorus or phosphorus-containing compounds can improve the thermal stability of cracking catalyst.However, the presence of phosphorus may reduce the acidity of the acidic reaction site in the multi-level pore mesoporous zeolite, which may reduce the reactivity of the reaction site.Transition metal, transition metal oxide or both can be impregnated on the multi-level pore mesoporous ZSM-5 zeolite to improve the reactivity of cracking catalyst, thereby compensating for the influence of phosphorus presence.

[0092] The transition metal, transition metal oxide or both may include one or more metal elements of the 4th to 6th periods in the IUPAC periodic table. In an embodiment, the transition metal, transition metal oxide or both may include one or more metal elements selected from the following groups: gallium (Ga), zinc (Zn), chromium (Cr), manganese (Mn), platinum (Pt), iron (Fe), molybdenum (Mo), lanthanum (La), cerium (Ce) and combinations thereof. In an embodiment, the cracking catalyst may include metal cerium, one or more cerium oxides, metal lanthanum, one or more lanthanum oxides, metal iron, one or more iron oxides or combinations thereof impregnated on the outer surface and pore surface of the multi-level pore mesoporous ZSM-5 zeolite. In an embodiment, the cracking catalyst may include cerium oxide, lanthanum oxide and iron oxide impregnated on the outer surface of the multi-level pore mesoporous ZSM-5 zeolite. The transition metal, transition metal oxide or both may be supported by the multi-level pore mesoporous ZSM-5 zeolite. The transition metal, transition metal oxide, or both can be arranged on the outer surface, pore surface, or both of the hierarchical mesoporous ZSM-5 zeolite so that the transition metal, transition metal oxide, or both can enter the reactants that contact the cracking catalyst or diffuse into the pores of the cracking catalyst. The transition metal, transition metal oxide, or both can be impregnated or deposited on the hierarchical mesoporous ZSM-5 zeolite according to known methods, such as, but not limited to, wet impregnation, incipient wetness impregnation, or other impregnation methods.

[0093] The cracking catalyst may include a sufficient amount of a transition metal, a transition metal oxide, or both to promote the production of light olefins during steam enhanced catalytic cracking. In embodiments, the cracking catalyst may include 0.01 wt.% to 30 wt.% of a transition metal, a transition metal oxide, or both, based on the total weight of the cracking catalyst. In embodiments, the cracking catalyst may include 0.01 wt.% to 25 wt.%, 0.01 wt.% to 20 wt.%, 0.01 wt.% to 15 wt.%, 0.01 wt.% to 10 wt.%, 0.01 wt.% to 5 wt.%, 0.01 wt.% to 3 wt.%, 0.1 wt.% to 30 wt.%, 0.1 wt.% to 25 wt.%, 0.1 wt.% to 20 wt.%, based on the total weight of the cracking catalyst. %, 0.1wt.% to 15wt.%, 0.1wt.% to 10wt.%, 0.1wt.% to 5wt.%, 0.1wt.% to 3wt.%, 1wt.% to 30wt.%, 1wt.% to 25wt.%, 1wt.% to 20wt.%, 1wt.% to 15wt.%, 1wt.% to 10wt.%, 1wt.% to 5wt.%, or 1wt.% to 3wt.% of a transition metal, a transition metal oxide, or both.

[0094] In an embodiment, the cracking catalyst may include cerium oxide impregnated onto a hierarchical mesoporous ZSM-5 zeolite. The cracking catalyst may include 0.01 wt.% to 20 wt.% of cerium oxide based on the total weight of the cracking catalyst. In an embodiment, the cracking catalyst may include 0.01 wt.% to 15 wt.%, 0.01 wt.% to 10 wt.%, 0.01 wt.% to 5 wt.%, 0.01 wt.% to 1 wt.%, 0.1 wt.% to 20 wt.%, 0.1 wt.% to 15 wt.%, 0.1 wt.% to 10 wt.%, 0.1 wt.% to 5 wt.%, 0.1 wt.% to 1 wt.%, 1 wt.% to 20 wt.%, 1 wt.% to 15 wt.%, 1 wt.% to 10 wt.%, or 1 wt.% to 5 wt.% of cerium oxide based on the total weight of the cracking catalyst.

[0095] In an embodiment, the cracking catalyst may include lanthanum oxide impregnated onto a hierarchical mesoporous ZSM-5 zeolite. The cracking catalyst may include 0.01 wt.% to 20 wt.% lanthanum oxide based on the total weight of the cracking catalyst. In an embodiment, the cracking catalyst may include 0.01 wt.% to 15 wt.%, 0.01 wt.% to 10 wt.%, 0.01 wt.% to 5 wt.%, 0.01 wt.% to 1 wt.%, 0.1 wt.% to 20 wt.%, 0.1 wt.% to 15 wt.%, 0.1 wt.% to 10 wt.%, 0.1 wt.% to 5 wt.%, 0.1 wt.% to 1 wt.%, 1 wt.% to 20 wt.%, 1 wt.% to 15 wt.%, 1 wt.% to 10 wt.%, or 1 wt.% to 5 wt.% lanthanum oxide based on the total weight of the cracking catalyst.

[0096] In an embodiment, the cracking catalyst may include iron oxide impregnated onto a hierarchical mesoporous ZSM-5 zeolite. The cracking catalyst may include 0.01 wt.% to 20 wt.% of iron oxide based on the total weight of the cracking catalyst. In an embodiment, the cracking catalyst may include 0.01 wt.% to 15 wt.%, 0.01 wt.% to 10 wt.%, 0.01 wt.% to 5 wt.%, 0.01 wt.% to 1 wt.%, 0.1 wt.% to 20 wt.%, 0.1 wt.% to 15 wt.%, 0.1 wt.% to 10 wt.%, 0.1 wt.% to 5 wt.%, 0.1 wt.% to 1 wt.%, 1 wt.% to 20 wt.%, 1 wt.% to 15 wt.%, 1 wt.% to 10 wt.%, or 1 wt.% to 5 wt.% of iron oxide based on the total weight of the cracking catalyst.

[0097] In embodiments, the cracking catalyst may comprise, consist of, or consist essentially of a hierarchical mesoporous ZSM-5 zeolite impregnated with 1 wt.% to 5 wt.% phosphorus pentoxide, 0.01 wt.% to 20 wt.% cerium oxide, 0.01 wt.% to 20 wt.% lanthanum oxide, and 0.01 wt.% to 20 wt.% iron oxide, wherein the weight percentages are based on the total weight of the cracking catalyst. In embodiments, the cracking catalyst may comprise, consist of, or consist essentially of a hierarchical mesoporous ZSM-5 zeolite impregnated with 3.5 wt.% phosphorus pentoxide, 1 wt.% cerium oxide, 1 wt.% lanthanum oxide, and 1 wt.% iron oxide, wherein the weight percentages are based on the total weight of the cracking catalyst.

[0098] In an embodiment, a cracking catalyst is incorporated into composite catalyst particles (comprising hierarchical mesoporous ZSM-5 zeolite impregnated with phosphorus oxide and transition metal oxide and one or more non-zeolite inorganic materials and matrix materials), and then catalyst particles are formed. The composite catalyst particles may comprise 20 wt.% to 60 wt.% of a cracking catalyst (hierarchical mesoporous ZSM-5 zeolite impregnated with P, Ce, La, Fe) based on the total weight of the composite catalyst particles. In embodiments, the composite catalyst particles may include 20 wt.% to 55 wt.%, 20 wt.% to 50 wt.%, 20 wt.% to 45 wt.%, 20 wt.% to 40 wt.%, 30 wt.% to 60 wt.%, 30 wt.% to 55 wt.%, 30 wt.% to 50 wt.%, 30 wt.% to 45 wt.%, 40 wt.% to 60 wt.%, 40 wt.% to 55 wt.%, or 40 wt.% to 50 wt.% of cracking catalyst based on the total weight of the composite catalyst particles.

[0099] In embodiments, the composite catalyst particles may include non-zeolitic inorganic materials, such as, but not limited to, non-zeolitic inorganic binders, non-zeolitic fillers, or both. The composite catalyst particles may include 15 wt.% to 60 wt.% of non-zeolitic inorganic materials based on the total weight of the composite catalyst particles. In an embodiment, the composite catalyst particles may include 15 wt.% to 20 wt.%, 15 wt.% to 30 wt.%, 15 wt.% to 40 wt.%, 15 wt.% to 50 wt.%, 20 wt.% to 30 wt.%, 20 wt.% to 40 wt.%, 20 wt.% to 50 wt.%, 20 wt.% to 60 wt.%, 30 wt.% to 40 wt.%, 30 wt.% to 50 wt.%, 30 wt.% to 60 wt.%, 40 wt.% to 50 wt.%, 40 wt.% to 60 wt.%, or 50 wt.% to 60 wt.% of non-zeolitic inorganic material, based on the total weight of the composite catalyst particles.

[0100] The non-zeolite inorganic material may include silica-based materials and alumina-based materials. The non-zeolite inorganic material may include, but is not limited to, one or more of silica sol, water glass (sodium silicate), silicic acid solution, basic aluminum chloride, aluminum dihydrogen phosphate, aluminum sol, activated alumina, porous silica, or a combination thereof. In an embodiment, the non-zeolite inorganic material may include a non-zeolite inorganic oxide, such as, but not limited to, activated alumina, porous silica, a rare earth metal oxide, or a combination thereof.

[0101] In an embodiment, the non-zeolitic inorganic material may include an alumina binder. An example of an alumina binder may include, but is not limited to, CATAPAL available from Sasol Chemicals. TM B alumina. In an embodiment, the composite catalyst particles may include a peptized alumina binder. The alumina binder may be peptized by forming a mixture including the alumina binder, water, and a peptizing agent (such as, but not limited to, formic acid), and stirring the mixture for a sufficient period of time to produce the peptized alumina binder. In an embodiment, the composite catalyst particles may include 15 wt.% to 60 wt.% of the peptized alumina binder based on the total weight of the composite catalyst particles. In embodiments, the composite catalyst particles may include 15 wt.% to 20 wt.%, 15 wt.% to 30 wt.%, 15 wt.% to 40 wt.%, 15 wt.% to 50 wt.%, 20 wt.% to 30 wt.%, 20 wt.% to 40 wt.%, 20 wt.% to 50 wt.%, 20 wt.% to 60 wt.%, 30 wt.% to 40 wt.%, 30 wt.% to 50 wt.%, 30 wt.% to 60 wt.%, 40 wt.% to 50 wt.%, 40 wt.% to 60 wt.%, or 50 wt.% to 60 wt.% of a peptized alumina binder, based on the total weight of the composite catalyst particles.

[0102] The composite catalyst particles may include one or more matrix materials. As used in the present disclosure, "matrix material" refers to clay materials such as kaolin, which are also non-zeolitic materials. Without being bound by theory, it is believed that the matrix material of the composite catalyst particles has both physical and catalytic functions. Physical functions include providing particle integrity and wear resistance, acting as a heat transfer medium, and providing a porous structure to allow hydrocarbons to diffuse into or out of the composite catalyst particles. The matrix material also affects catalyst selectivity, product quality, and anti-toxicity. In an embodiment, the matrix material includes kaolin. As used in the present disclosure, "kaolin" refers to a clay material having a relatively large amount (such as at least about 50wt.%, at least 60wt.%, at least 70wt.%, at least 80wt.%, at least 90wt.% or even at least 95wt.%) of kaolinite, which can be represented by the chemical formula Al2 Si 2 O 5 (OH) 4 In additional embodiments, the matrix material may include other clay materials.

[0103] The composite catalyst particles including cracking catalysts may include one or more matrix materials in an amount of 20 wt.% to 60 wt.% based on the total weight of the composite catalyst particles. In embodiments, the composite catalyst particles may include 20 wt.% to 55 wt.%, 20 wt.% to 50 wt.%, 20 wt.% to 45 wt.%, 20 wt.% to 40 wt.%, 30 wt.% to 60 wt.%, 30 wt.% to 55 wt.%, 30 wt.% to 50 wt.%, 30 wt.% to 45 wt.%, 40 wt.% to 60 wt.% or 40 wt.% to 50 wt.% matrix materials based on the total weight of the composite catalyst particles. In embodiments, the composite catalyst particles may include any one of the disclosed matrix materials in an amount within the disclosed weight percentage range. In embodiments, the composite catalyst particles may include a combination of any two or more matrix materials in an amount within the disclosed weight percentage range.

[0104] Composite catalyst particles can be prepared by preparing a slurry comprising water, a matrix material, a non-zeolite inorganic material (e.g., a peptized alumina binder), and a cracking catalyst comprising a hierarchical mesoporous ZSM-5 zeolite impregnated with phosphorus and a transition metal oxide. The slurry can then be spray dried and calcined at a temperature of about 550° C. for about 6 hours to produce composite catalyst particles. In an embodiment, the composite catalyst particles may have an average particle size of 20 microns to 100 microns.

[0105] As previously mentioned, the cracking catalyst of the present disclosure or the composite catalyst particles including the cracking catalyst of the present disclosure can be used to convert hydrocarbons in crude oil into higher value petrochemical products and intermediates, such as light olefins, light aromatic compounds, or both, by steam enhanced catalytic cracking. Figure 1 The steam catalytic cracking effluent 140 produced by steam enhanced catalytic cracking may have a higher yield of light olefins, such as ethylene, propylene, and mixed butenes, than effluents produced using conventional commercially available cracking catalysts.

[0106] Reference again Figure 1, the steam catalytic cracking system 110 may further include a cracking effluent separation system 150 disposed downstream of the steam catalytic cracking reactor 130. When the steam catalytic cracking system 110 includes a plurality of steam catalytic cracking reactors 130, the steam catalytic cracking effluent 140 from each steam catalytic cracking reactor 130 may be conveyed to a single shared cracking effluent separation system 150. In an embodiment, each steam catalytic cracking reactor 130 may have its own dedicated cracking effluent separation system 130. The steam catalytic cracking effluent 140 may be conveyed directly from the steam catalytic cracking reactor 130 to the cracking effluent separation system 150. The cracking effluent separation system 150 may separate the steam catalytic cracking effluent 140 into one or more cracking product effluents, which may be liquid or gaseous product effluents.

[0107] Reference again Figure 1 , the cracking effluent separation system 150 may include one or more separation units. The separation unit may include, but is not limited to, a distillation column, a fractionator, a flash tank, a buffer tank, a buffer pot, a centrifuge, a decanter, a filter 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 thereof. The separation unit may include one or more gas-liquid separators, one or more liquid-liquid separators, or a combination thereof.

[0108] In an 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, thereby condensing components of the steam catalytic cracking effluent 140 having greater than or equal to 5 carbon atoms. The gas-liquid separation unit 160 may be operated at a temperature of 10° C. to 15° C. to ensure that n-pentane and components having a boiling point temperature greater than n-pentane are condensed into the liquid effluent 162. The liquid effluent 162 may include a distillation fraction such as naphtha, kerosene, gas oil, vacuum gas oil; unconverted feedstock; residual oil; water; or a combination thereof. The liquid effluent 162 may include light aromatic compounds produced in the steam catalytic cracking reactor 130, which may include, but are not limited to, benzene, toluene, mixed xylenes, ethylbenzene, and other light aromatic compounds. The 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 greater than or equal to 5 carbon atoms in the steam catalytic cracking effluent 140. The liquid effluent 162 may include at least 95%, at least 98%, at least 99%, or even at least 99.5% of water from the steam catalytic cracking effluent 140. The liquid effluent 162 may be a two-phase stream including an oil phase and an aqueous phase miscible with the oil phase.

[0109] The gaseous effluent 164 may include olefins, such as ethylene, propylene, butene, or combinations thereof; light hydrocarbon gases, such as methane, ethane, propane, n-butane, isobutane, or combinations thereof; other gases, such as, but not limited to, hydrogen; or combinations thereof. The gaseous effluent 164 may include C produced in the steam catalytic cracking reactor 130. 2 -C 4 Olefin products such as, but not limited to, ethylene, propylene, butene (1-butene, cis-2-butene, trans-2-butene, isobutylene, or combinations thereof), or combinations thereof. The gaseous effluent 164 may include at least 90%, at least 95%, at least 98%, at least 99%, or at least 99.5% of the C olefins from the steam catalytic cracking effluent 140. 2 -C 4 Olefins. The gaseous effluent 164 may be passed to a downstream gas separation system (not shown) to further separate the gaseous effluent 164 into various product streams, such as, but not limited to, one or more olefin product streams.

[0110] The liquid effluent 162 may be a two-phase stream comprising an oil phase and an aqueous phase miscible with the oil phase. In an embodiment, the liquid effluent 162 comprising water and hydrocarbons having greater than 5 carbon atoms may be delivered to an in-line centrifugal unit 170. The in-line centrifugal unit 170 may be operable to separate the liquid effluent 162 into a liquid hydrocarbon effluent 172 and an aqueous effluent 174. The in-line centrifugal unit 170 may be operated at a rotation 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.

[0111] The liquid hydrocarbon effluent 172 may include hydrocarbons having greater than or equal to 5 carbon atoms from the steam catalytic cracking effluent 140. The liquid hydrocarbon effluent 172 may include light aromatic compounds produced in the steam catalytic cracking reactor 130, which may include, but are not limited to, benzene, toluene, mixed xylenes, ethylbenzene and other light aromatic compounds. The liquid hydrocarbon effluent 172 may also include naphtha, kerosene, diesel, vacuum gas oil (VGO) or a combination thereof. The liquid hydrocarbon effluent 172 may include at least 90%, at least 95%, at least 98%, at least 99% or even at least 99.5% of hydrocarbon components from the liquid effluent 162. The liquid hydrocarbon effluent 172 may be sent to a downstream processing process for further conversion or separation. At least a portion of the liquid hydrocarbon effluent 172 may be sent back to the steam catalytic cracking reactor 130 for further conversion into olefins. The aqueous effluent 174 may include water and water-soluble components from the liquid effluent 162. The aqueous effluent 174 may include some dissolved hydrocarbons that are soluble in the aqueous phase of the liquid effluent 162. The aqueous effluent 174 may include at least 95%, at least 98%, at least 99%, or even at least 99.5% water from the liquid effluent 162. The aqueous effluent 174 may be sent to one or more downstream processes for further processing. In an embodiment, at least a portion of the aqueous effluent 174 may be sent back to the steam catalytic cracking reactor 130 as at least a portion of the water 120 introduced into the steam catalytic cracking reactor 130.

[0112] In an embodiment, the multi-stage pore mesoporous ZSM-5 zeolite produced by the aforementioned method can be used as a catalyst in a fluidized catalytic cracking (FCC) reactor. The FCC reactor can be a fluidized bed reactor. In the FCC reactor, a cracking catalyst composed of a multi-stage pore mesoporous ZSM-5 zeolite can be contacted with a hydrocarbon feed (such as crude oil) in the presence of steam to produce light olefins, light aromatic compounds, or a combination thereof. In an embodiment, the cracking catalyst is composed of a multi-stage pore mesoporous ZSM-5 zeolite. Suitable FCC methods for catalytic cracking of crude oil in the presence of steam are disclosed in the following patent applications: U.S. Patent Application No. 17 / 009,008, U.S. Patent Application No. 17 / 009,012, U.S. Patent Application No. 17 / 009,020, U.S. Patent Application No. 17 / 009,022, U.S. Patent Application No. 17 / 009,039, U.S. Patent Application No. 17 / 009,048, and U.S. Patent Application No. 17 / 009,073, all of which are incorporated herein by reference as a whole. The hydrocarbon feed may be any of the aforementioned hydrocarbon feeds of the present disclosure. The FCC reactor may be an upflow or downflow FCC reactor. The FCC reactor system may include one or more FCC reactors and one or more catalyst regenerators.

[0113] Reference now Figure 3 , schematically depicts one embodiment of an FCC reactor system 300 including a riser FCC reactor. The FCC reactor system 300 may include an upflow FCC reactor 310 and a catalyst regeneration unit 320. As disclosed in Figure 3 As used in the context of FIG. 3 , the upflow FCC reactor 310 refers to the portion of the FCC reactor system 300 where the primary process reactions occur, such as steam enhanced fluid catalytic cracking to convert hydrocarbons to light olefins, aromatic compounds, or both. The upflow FCC reactor 310 may include a riser 312, a reaction zone 314 downstream of the riser 312, and a separation zone 316 downstream of the reaction zone 314. The FCC reactor system 300 may also include a regeneration zone 322 in a regeneration unit 320 for regenerating spent FCC catalyst.

[0114] exist Figure 3 In operation of the FCC reactor system 300, hydrocarbon feed 311 is introduced into riser 312. In an embodiment, hydrocarbon feed 311 may be combined with steam 309. Hydrocarbon feed 311 may be combined with an effective amount of heated fresh FCC catalyst or regenerated FCC catalyst in riser 312. Figure 3 and Figure 4, the term FCC catalyst refers to a cracking catalyst or composite catalyst particles comprising a multi-level pore mesoporous ZSM-5 zeolite impregnated with a phosphorus compound and a transition metal compound. The heated fresh FCC catalyst particles or regenerated FCC catalyst particles may include the cracking catalyst of the present disclosure, and may have any of the characteristics, composition or properties of the cracking catalyst described above in the present disclosure. The heated fresh FCC catalyst particles or regenerated FCC catalyst particles may be transported from the regeneration zone 322 to the riser 312 via the conduit 323. The hydrocarbon feed 311, steam 309 and FCC catalyst particles are contacted in the riser 312 and are transmitted upward to the reaction zone 314 through the riser 312. In the riser 312 and the reaction zone 314, hydrocarbons from the hydrocarbon feed 311 are contacted with steam 309 under reaction conditions in the presence of the FCC catalyst particles. Contact of hydrocarbons from hydrocarbon feed 311 with steam 309 and FCC catalyst under reactive conditions may cause at least a portion of the hydrocarbons to undergo one or more chemical reactions to form upgraded hydrocarbons, which may include light aromatics and light olefins (such as, but not limited to, ethylene, propylene, mixed butenes, or combinations thereof).

[0115] The reaction mixture including spent FCC catalyst particles, reaction products and unreacted hydrocarbons is conveyed to a separation zone 316 downstream of the reaction zone 314. In the separation zone 316, the reaction products and unreacted hydrocarbons are separated from the spent FCC catalyst particles using any suitable configuration known in the art. The reaction products, unreacted hydrocarbons and other gases separated from the spent FCC catalyst particles can be withdrawn from the separation zone 316 via a conduit 319. During the reaction, the cracking catalyst composition particles may become coked, and the coke deposits may reduce the accessibility to the active catalytic sites on the spent FCC catalyst particles. The spent FCC catalyst particles containing coke deposits from the reaction can be conveyed to the regeneration zone 322 of the regenerator 320 via a conduit 315. In the regeneration zone 322 of the regenerator 320, the coked FCC catalyst particles can be contacted with an oxygen-containing gas stream, which can enter the regeneration zone 322 via a conduit 321. The contact with the oxygen-containing gas causes the coke deposits to be burned, which removes the coke deposits from the FCC catalyst particles and heats the FCC catalyst particles. Hot regenerated FCC catalyst particles may be transferred from the regeneration zone 322 of the catalyst regeneration unit 320 to the bottom of the riser 312 via conduit 323 for mixing with the hydrocarbon feed 311 .

[0116] Reference now Figure 4, schematically depicts another embodiment of an FCC reactor system 400. The FCC reactor system 400 may include a downflow FCC reactor 410 and a catalyst regeneration unit 420. The downflow FCC reactor 410 generally refers to the unit in the reactor system 400 where the primary process reaction, such as steam enhanced fluid catalytic cracking, is performed. The downflow FCC reactor 410 may include a reaction zone 412, a separation zone 414, and a stripping zone 416. Figure 4 The reactor system 400 may further include a regeneration zone 422 in the regeneration unit 420 for regenerating the spent catalyst.

[0117] A hydrocarbon feed 411 and steam 409 may be introduced into the reaction zone 412. Heated fresh FCC catalyst particles or regenerated FCC catalyst particles may be transported from the regeneration zone 422 to the top of the reaction zone 412 through a downwardly directed conduit 423 (directed toward a hopper (not shown) located at the top of the reaction zone 412). The flow of hot FCC catalyst particles may be stabilized so that the FCC catalyst particles are uniformly directed to the mixing zone or feed injection portion of the reaction zone 412. The hydrocarbon feed 411 may be injected into the mixing zone at the top of the reaction zone 412 through a feed injection nozzle, which is typically located near the point where the regenerated FCC catalyst particles are introduced into the reaction zone 412. Multiple injection nozzles may allow the FCC catalyst particles, hydrocarbon feed 411, and steam 409 to be thoroughly and uniformly mixed. The catalytic reaction may begin immediately when the hydrocarbon feed 1 contacts the hot FCC catalyst particles.

[0118] The hydrocarbon feed 411, steam 409, and FCC catalyst particles may generally travel downward through the reaction zone 412. At the end of the reaction zone 412, the reaction vapors (reaction products, unconverted hydrocarbon feed, and carrier gas) and spent FCC catalyst particles may be conveyed to a separation zone 414 downstream of the reaction zone 412. In the separation zone 414, the spent FCC catalyst particles are separated from the reaction vapors, which include the reaction products and unreacted hydrocarbons from the hydrocarbon feed 411. The reaction vapors may be directed to various product recovery operations via conduit 419. The reaction temperature (which may be equivalent to the outlet temperature of the FCC unit 410) may be controlled by opening and closing a catalyst slide valve (not shown) that controls the flow of regenerated FCC catalyst particles from the regeneration zone 422 into the top of the reaction zone 412.

[0119] The spent FCC catalyst particles may be conveyed from separation zone 414 to stripping zone 416. In stripping zone 416, a suitable stripping gas, such as steam, may be introduced via flow line 413. Stripping zone 416 may include a plurality of baffles or structured packing (not shown) through which the downwardly flowing catalyst particles pass in countercurrent to the stripping gas. The upwardly flowing stripping gas may strip or remove any additional hydrocarbons (e.g., reaction products or unreacted hydrocarbons from the feed) that remain in the pores of the spent FCC catalyst particles or between the FCC catalyst particles.

[0120] The spent FCC catalyst particles may be transferred from the stripping zone 416 to the catalyst regeneration unit 420 via conduit 415. The spent FCC catalyst particles may be transported through the riser of the catalyst regeneration unit 420 using the lifting force from the combustion gas stream 421. The spent FCC catalyst particles may then be contacted with additional combustion air and controlled combustion in the regeneration zone 422 to remove coke deposits and heat the FCC catalyst particles to produce regenerated FCC catalyst particles. Exhaust gas may be removed from the regeneration zone 422 via conduit 425. In the regenerator, the heat generated by the combustion of any coke byproduct may be transferred to the FCC catalyst particles, which increases the temperature of the FCC catalyst to provide the heat required for the catalytic reaction in the reaction zone 412.

[0121] In embodiments, the FCC reactor may be operated at a reaction temperature of at least about 500°C, e.g., 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 may be injected into the FCC reactor. The hydrocarbon feed may be catalytically cracked in the presence of steam and a hierarchical mesoporous ZSM-5 zeolite. The mass ratio of steam to hydrocarbon in the FCC reactor can be from 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 the water in the FCC reactor. In embodiments, the residence time of the hydrocarbon feed and steam in contact with the cracking catalyst in the FCC reactor may be from 1 second to 20 seconds, from 2 seconds to 20 seconds, from 5 seconds to 20 seconds, from 8 seconds to 20 seconds, from 1 second to 18 seconds, from 2 seconds to 18 seconds, from 5 seconds to 18 seconds, from 8 seconds to 18 seconds, from 1 second to 16 seconds, from 2 seconds to 16 seconds, from 5 seconds to 16 seconds, from 8 seconds to 16 seconds, from 1 second to 14 seconds, from 2 seconds to 14 seconds, from 5 seconds to 14 seconds, from 8 seconds to 14 seconds, from 1 second to 12 seconds, from 2 seconds to 12 seconds, from 5 seconds to 12 seconds, or from 8 seconds to 12 seconds. In embodiments, the weight ratio of cracking catalyst to hydrocarbons (catalyst to oil) in the FCC reactor may be from 3 to 40, e.g., from 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 cracking effluent from the FCC reactor may be separated into various product streams, intermediate streams, and aqueous streams in a separation system downstream of the FCC reactor.

[0122] Example

[0123] Various aspects of the present disclosure will be further illustrated by the following examples. The examples are illustrative in nature and should not be construed as limiting the subject matter of the present disclosure.

[0124] Example 1-3: Synthesis of hierarchical mesoporous ZSM-5 zeolite

[0125] In Example 1-3, the multi-level mesoporous ZSM-5 zeolite with different silica to alumina molar ratios of the present disclosure is prepared. In order to prepare a cracking catalyst, 7 grams of initial preformed ZSM-5 zeolite are added to a glass reactor together with an aqueous solution of sodium hydroxide (NaOH) and a surfactant hexadecyltrimethylammonium bromide (CTAB) to produce a first mixture. Based on the gross weight of the first mixture (including CTAB, NaOH, water and initial ZSM-5 zeolite), the CTAB concentration in the first mixture is 4.45wt.%. The initial ZSM-5 zeolite of each example in Example 1-3, the molar ratio of silica to alumina in each initial ZSM-5 zeolite, and the concentration of NaOH in the first mixture are provided in Table 3.

[0126] Table 3

[0127]

[0128] For each of Examples 1-3, the initial preformed ZSM-5 zeolite was then decomposed by gradually heating a first mixture comprising ZSM-5 zeolite, NaOH and CTAB to 100°C and stirring the first mixture at 100°C for a first hydrothermal treatment period for 24 hours. After the first hydrothermal treatment, the hydrothermally treated mixture was cooled and the pH was adjusted to 9.0 by adding dilute sulfuric acid (2N (2 equivalent concentration)) to produce a second mixture. The second mixture was then stirred for 24 hours and aged for another 24 hours at 100°C. The solid product was filtered, thoroughly washed with distilled water, dried at 80°C overnight, and then calcined at 570°C for 6 hours to remove the CTAB surfactant, thereby producing the hierarchical mesoporous ZSM-5 zeolite of Examples 1-3. The hierarchical mesoporous ZSM-5 zeolite was treated twice with 0.25 equivalent (N) ammonium nitrate at 80°C for 5 hours to ion exchange the hydrogen form of the hierarchical mesoporous ZSM-5 zeolite in the hierarchical mesoporous ZSM-5 zeolite.

[0129] X-ray diffraction (XRD) was performed on the hierarchical mesoporous ZSM-5 zeolite catalyst of Example 1 including a molar ratio of silica to alumina of 40 according to a known method. Figure 5 and Figure 6 , graphically depicts the XRD spectrum of the hierarchical mesoporous ZSM-5 zeolite of Example 1. The mesoporous phase is clearly established by the low angle peaks from θ=0.2 to θ=4.5, indicating the larger pore size of the mesoporous structure. Figure 6 Provided Figure 5An enlarged view of a portion of the XRD spectrum in the wavelength range of 5.4 nm to 49 nm. Each of the hierarchical mesoporous ZSM-5 zeolites of Examples 1 to 3 had the same silica to alumina molar ratio as that of the initial preformed ZSM-5 zeolite.

[0130] The BET surface area and total pore volume of the hierarchical mesoporous ZSM-5 zeolite of Example 1 were measured. The total BET surface area of ​​the hierarchical mesoporous ZSM-5 zeolite of Example 1 was 572 m 2 / g. It was found that the mesoporous BET surface area of ​​the hierarchical mesoporous ZSM-5 zeolite of Example 1 was 325 m 2 / g, which is the part of the BET surface area contributed by the mesopores. It is found that the micropore BET surface area of ​​the hierarchical mesoporous ZSM-5 zeolite of Example 1 is 247 m 2 The mesoporous BET surface area accounts for about 57% of the total BET surface area of ​​the hierarchical mesoporous ZSM-5 zeolite of Example 1.

[0131] The total pore volume of the hierarchical mesoporous ZSM-5 zeolite of Example 1 is 0.45 cm 3 / g, where the total pore volume is determined from the measured gas adsorption isotherms by NLDFT modeling and analysis. The mesopore volume and micropore volume were also determined. The hierarchical mesoporous ZSM-5 zeolite of Example 1 was found to have a pore size of 0.14 cm 3 / g micropore volume and 0.31cm 3 The mesopore volume accounts for about 67% of the total pore volume of the hierarchical mesoporous ZSM-5 zeolite of Example 1.

[0132] Example 4: Preparation of cracking catalyst

[0133] In Example 4, a cracking catalyst was prepared, which included the hierarchical mesoporous ZSM-5 zeolite of Example 2 (a molar ratio of silica to alumina of 28) impregnated with phosphorus oxide, cerium oxide, lanthanum oxide, and iron oxide. The hierarchical mesoporous ZSM-5 zeolite of Example 2 having a molar ratio of silica to alumina of 28 was impregnated with phosphorus pentoxide and transition metal oxides by a wet impregnation method. The phosphorus pentoxide was impregnated to a content of 3.5 wt.% based on the total weight of the cracking catalyst. 2 O 5 The cracking catalyst comprises 1 wt.% of cerium oxide, 1 wt.% of lanthanum oxide and 1 wt.% of iron oxide based on the total weight of the cracking catalyst. The cracking catalyst of Example 4 is prepared by a wet impregnation method, followed by calcination to convert the transition metal precursor into a transition metal oxide.

[0134] Example 5: Preparation of composite catalyst particles containing cracking catalyst

[0135] In Example 5, composite catalyst particles were prepared using the cracking catalyst of Example 4. The composite catalyst particles of Example 5 were prepared by mixing 200 grams (dry basis) of kaolin powder with 431.92 grams of deionized water (DI water) to make a kaolin slurry. In a separate step, 200 grams (dry basis) of the cracking catalyst of Example 4 were made into a zeolite slurry with 462.59 grams of deionized water and stirred for 10 minutes. The zeolite slurry was added to the kaolin slurry and stirred for 5 minutes. Separately, a slurry of Catapal B alumina was prepared by mixing 100.0 grams (dry basis) with 194.92 grams of distilled water, and the slurry was peptized by adding 7.22 grams of concentrated formic acid (70 wt.%) and stirring for thirty minutes. The resulting peptized alumina slurry was added to the zeolite-kaolin slurry and mixed for ten minutes, producing a slurry with high viscosity in which the individual particles were still suspended. The resulting slurry consisting of about 30% solids was spray dried to produce catalyst particles having an average particle size of 20 to 100 microns. The catalyst particles were then calcined at 550° C. for 6 hours to produce composite catalyst particles of Example 5.

[0136] Comparative Example 6: UMIX 75 commercial cracking catalyst

[0137] For Comparative Example 6, a commercial cracking catalyst was provided for comparison with the composite catalyst particles of Example 5. The commercial cracking catalyst of Comparative Example 6 was prepared to include 75 wt.% of an equilibrium catalyst (ECAT) and 25 wt.% of a commercially available ZSM-5 zeolite (commercially available, such as from WR Grace and Company). ). The comparative commercial cracking catalyst may be referred to herein as "UMIX75". The commercial cracking catalyst of Comparative Example 6 does not include a multi-level pore mesoporous ZSM-5 zeolite, nor does it include a combination of phosphorus pentoxide, cerium oxide, lanthanum oxide and iron oxide impregnated on the surface of the multi-level pore mesoporous ZSM-5 zeolite.

[0138] Example 7: Cracking Catalyst Composition Evaluation

[0139] In Example 7, the composite catalyst particles including the cracking catalyst of Example 4 in Example 5 and the commercial cracking catalyst of Comparative Example 6 were evaluated at atmospheric pressure in a fixed bed reactor (FBR) system for steam catalytic cracking of AXL crude oil. The basic composition of AXL crude oil (used as hydrocarbon feed) is provided in Table 4. The cracked gaseous and liquid products were characterized by off-line gas chromatography (GC) analysis using simulated distillation and naphtha analysis techniques.

[0140] Reference now Figure 7, schematically depicting an FBR system 600 used to conduct the experiments of Example 7. AXL crude oil 601 was fed into a fixed bed reactor 640 using a metering pump 611. A constant feed rate of 2 g / h of AXL crude oil 601 was adopted. Water 602 was fed into the fixed bed reactor 640 using a metering pump 612. Water 602 was preheated using a preheater 621. A constant feed rate of 1 g / h of water 602 was adopted. Nitrogen 603 was used as a carrier gas, 65 mL / min. Nitrogen 603 was fed into the fixed bed reactor 640 using a mass flow controller (MFC) 613. Nitrogen 603 was preheated using a preheater 622. Water 602 and nitrogen 603 were mixed using a mixer 630, and the mixture was introduced into the fixed bed reactor 640. AXL crude oil 601, water 602 and nitrogen 603 were preheated to 250° C. in a preheating zone 642 before entering the reactor tube. The preheating zone 642 is preheated using a pipeline heater 631. AXL crude oil 601 is introduced from the top of the reactor 640 through an injector 641 and mixed with steam inside the upper two-thirds of the reactor tube 640 before reaching the catalyst bed 644.

[0141] Before contacting the catalyst in the catalyst bed 644, the catalyst bed 644 in the reactor tube 640 was moved down a few centimeters to provide more time for preheating of the AXL crude oil 601. For each experiment, 1 gram (g) of catalyst (composite catalyst particles of Example 5 or commercial cracking catalyst of Comparative Example 6) with a mesh size of 30-40 was placed in the center of the reactor tube 640, supported by quartz wool 643, 646 and reactor insert 645. Quartz wool 643, 646 were placed at the bottom and top of the catalyst bed 644 to hold it in place. The height of the catalyst bed 644 was 1-2 cm. The composite catalyst particles of Example 5 and the comparative cracking catalyst of Comparative Example 6 were used as cracking catalysts in different experiments conducted in Example 7, respectively. Before conducting the steam catalytic cracking reaction, the composite catalyst particles of Example 5 and the commercial cracking catalyst of Comparative Example 6 were steam deactivated at a temperature of 810°C for 6 hours in the presence of steam.

[0142] After steam deactivation, a hydrocarbon feed and water / steam comprising AXL crude oil were introduced into the reaction tubes of the FBR. The reaction was allowed to proceed for 45-60 minutes until a steady state was reached. The mass ratio of steam to crude oil was 0.5 grams of steam / gram of crude oil. The AXL crude oil was steam catalytically cracked at a cracking temperature of 675°C with a catalyst to crude oil weight ratio of 1:2. The residence time of the crude oil and steam in the fixed bed reactor 640 was 10 seconds. The total time of the flow for each individual experiment of Example 7 was 5 hours.

[0143] Reference again Figure 7, the cracking reaction product stream 645 is introduced into the gas-liquid separator 651 to separate the cracking reaction product stream 645 into cracked gaseous products 661 and liquid products 662. A wet gas flow meter 652 is placed downstream of the gas-liquid separator 651. The cracked gaseous products 661 and liquid products 662 are characterized by offline gas chromatography (GC) analysis using simulated distillation and naphtha analysis techniques. The ethylene, propylene and butene yields of the reaction product stream from the cracking reaction are analyzed. The yield analysis of Example 7 is as follows: Figure 8 The results are depicted graphically in Figure 4 and provided numerically in Table 4.

[0144] Table 4

[0145]

[0146] As shown in Table 4 and Figure 8 As shown in the results, compared with the commercially available cracking catalyst of Comparative Example 6, Example 5 contains P 2 O 5 The cracking catalyst of the hierarchical mesoporous ZSM-5 zeolite impregnated with cerium oxide, lanthanum oxide and iron oxide produced a higher yield of total light olefins (ethylene, propylene and mixed butenes). In particular, compared with the ethylene yield (17 wt.%) obtained using the commercially available cracking catalyst of Comparative Example 6, the yield of ethylene obtained using the commercially available cracking catalyst of Example 5 with P 2 O 5 The cracking catalyst comprising a hierarchical mesoporous ZSM-5 zeolite impregnated with P, cerium oxide, lanthanum oxide and iron oxide produced a significantly higher yield of ethylene (23 wt.%). Thus, compared to the yield that can be achieved with commercially available cracking catalysts, the present invention comprises a catalyst comprising a hierarchical mesoporous ZSM-5 zeolite impregnated with P, cerium oxide, lanthanum oxide and iron oxide. 2 O 5 The cracking catalyst of hierarchical mesoporous ZSM-5 zeolite impregnated with cerium oxide, lanthanum oxide and iron oxide can provide higher yield of light olefins through steam enhanced catalytic cracking.

[0147] A first aspect of the present disclosure may relate to a method for upgrading crude oil by steam enhanced catalytic cracking. The method may include contacting the crude oil with steam in the presence of a cracking catalyst, wherein the cracking catalyst may include a hierarchical mesoporous ZSM-5 zeolite impregnated with phosphorus, cerium, lanthanum and iron. The mass ratio of steam to crude oil may be from 0.2 to less than 1. Contacting the crude oil with steam in the presence of a cracking catalyst may cause a cracking reaction to occur in at least a portion of the crude oil to produce a cracking effluent comprising light olefins, light aromatic compounds or both.

[0148] A second aspect of the present disclosure may include the first aspect, wherein the phosphorus may be present in the cracking catalyst as phosphorus pentoxide, and the cracking catalyst may comprise 1 wt. % to 5 wt. % phosphorus pentoxide based on the total weight of the cracking additive.

[0149] A third aspect of the present disclosure may include any one of the first aspect or the second aspect, wherein the cracking catalyst may comprise 0.5 wt.% to 3 wt.% cerium oxide, 0.5 wt.% to 3 wt.% lanthanum oxide, and 0.5 wt.% to 3 wt.% iron oxide based on the total weight of the cracking catalyst.

[0150] A fourth aspect of the present disclosure may include any one of the first to third aspects, wherein the cracking catalyst may comprise 1 wt.% to 5 wt.% of phosphorus pentoxide, 0.5 wt.% to 3 wt.% of cerium oxide, 0.5 wt.% to 3 wt.% of lanthanum oxide, and 0.5 wt.% to 3 wt.% of iron oxide, based on the total weight of the cracking catalyst.

[0151] A fifth aspect of the present disclosure may include any one of the first to fourth aspects, wherein the cracking catalyst may comprise 3.5 wt.% phosphorus pentoxide, 1 wt.% cerium oxide, 1 wt.% lanthanum oxide, and 1 wt.% iron oxide based on the total weight of the cracking catalyst.

[0152] A sixth aspect of the present disclosure may include any one of the first to fifth aspects, including contacting crude oil with steam in the presence of a plurality of composite catalyst particles, wherein the plurality of composite catalyst particles may include a cracking catalyst, an inorganic binder, and a matrix material.

[0153] A seventh aspect of the present disclosure may include the sixth aspect, wherein the composite catalyst particle may include 20 wt.% to 60 wt.% of a cracking catalyst, 20 wt.% to 60 wt.% of a matrix material, and 15 wt.% to 60 wt.% of an inorganic binder based on the total weight of the composite catalyst particle.

[0154] An eighth aspect of the present disclosure may include any one of the sixth aspect or the seventh aspect, wherein the inorganic binder may include peptized alumina, and the matrix material includes kaolin.

[0155] A ninth aspect of the present disclosure may include any one of the first to eighth aspects, wherein the crude oil may have an American Petroleum Institute degree of 15 to 50 degrees.

[0156] The tenth aspect of the present disclosure may include any one of the first to ninth aspects, wherein the crude oil may be light crude oil, ultra-light crude oil, heavy crude oil, or a combination of these crude oils.

[0157] An eleventh aspect of the present disclosure may include any one of the first to tenth aspects, comprising contacting crude oil with steam in the presence of a cracking catalyst at a temperature of 525°C to 800°C.

[0158] A twelfth aspect of the present disclosure may include any one of the first to eleventh aspects, including contacting the crude oil with steam in the presence of a cracking catalyst for a residence time of 0.1 seconds to 60 seconds.

[0159] The thirteenth aspect of the present disclosure may include any one of the first to twelfth aspects, including: in a cracking reactor, contacting crude oil with steam in the presence of a cracking catalyst, wherein the cracking reactor may include one or more of a fixed bed reactor, a fluidized bed reactor, a batch reactor, a fluidized catalytic cracking (FCC) reactor, a moving bed catalytic cracking reactor, or a combination thereof.

[0160] A fourteenth aspect of the present disclosure may include any one of the first to thirteenth aspects, wherein the hierarchical pore mesoporous ZSM-5 zeolite may have a silica to alumina ratio of 10 to 300.

[0161] A fifteenth aspect of the present disclosure may relate to a cracking catalyst for steam enhanced catalytic cracking of hydrocarbons, the cracking catalyst comprising a hierarchical mesoporous ZSM-5 zeolite impregnated with phosphorus, cerium, lanthanum, and iron.

[0162] A sixteenth aspect of the present disclosure may include the fifteenth aspect, wherein the phosphorus may be present as phosphorus pentoxide, and the cracking catalyst may include 1 wt. % to 5 wt. % of phosphorus pentoxide based on the total weight of the cracking catalyst.

[0163] A seventeenth aspect of the present disclosure may include any one of the fifteenth aspect or the sixteenth aspect, wherein the cracking catalyst may comprise 0.5 wt.% to 3 wt.% of cerium oxide, 0.5 wt.% to 3 wt.% of lanthanum oxide, and 0.5 wt.% to 3 wt.% of iron oxide based on the total weight of the cracking catalyst.

[0164] An eighteenth aspect of the present disclosure may include any one of aspects fifteen to seventeen, wherein the cracking catalyst may comprise 1 wt.% to 5 wt.% of phosphorus pentoxide, 0.5 wt.% to 3 wt.% of cerium oxide, 0.5 wt.% to 3 wt.% of lanthanum oxide, and 0.5 wt.% to 3 wt.% of iron oxide, based on the total weight of the cracking catalyst.

[0165] A nineteenth aspect of the present disclosure may include any one of the fifteenth to eighteenth aspects, wherein the cracking catalyst may comprise 3.5 wt.% of phosphorus pentoxide, 1 wt.% of cerium oxide, 1 wt.% of lanthanum oxide, and 1 wt.% of iron oxide based on the total weight of the cracking catalyst.

[0166] A twentieth aspect of the present disclosure may include any one of the fifteenth to nineteenth aspects, wherein the hierarchical pore mesoporous ZSM-5 zeolite may have a silica to alumina ratio of 10 to 300.

[0167] The twenty-first aspect of the present disclosure may relate to a method for preparing the cracking catalyst of any one of aspects 15 to 20, wherein the method may include: providing an initial preformed ZSM-5 zeolite; decomposing a portion of the initial preformed ZSM-5 zeolite in a first mixture comprising sodium hydroxide and a surfactant; after at least partially decomposing the initial preformed ZSM-5 zeolite, recrystallizing the zeolite component in the presence of a surfactant to produce a recrystallized ZSM-5 zeolite having a multi-level pore structure; recovering the recrystallized ZSM-5 zeolite; calcining the recrystallized ZSM-5 zeolite, wherein the calcination can remove the surfactant from the recrystallized ZSM-5 zeolite to produce a multi-level pore mesoporous ZSM-5 zeolite; and impregnating the multi-level pore mesoporous ZSM-5 zeolite with phosphorus, cerium, lanthanum and iron to form a cracking catalyst.

[0168] The twenty-second aspect of the present disclosure may include the twenty-first aspect, and further include: after calcination, treating the hierarchical mesoporous ZSM-5 zeolite with 0.25 equivalent concentration (N) of ammonium nitrate at 80°C twice for 5 hours to produce the hierarchical mesoporous ZSM-5 zeolite in hydrogen form.

[0169] The twenty-third aspect of the present disclosure may include any one of the twenty-first aspect or the twenty-second aspect, wherein decomposing a portion of the initial preformed ZSM-5 zeolite may include: combining the initial preformed ZSM-5 zeolite, sodium hydroxide, and a surfactant to form a first mixture; heating the first mixture to a temperature of 100°C while stirring; and maintaining the first mixture at a temperature of 100°C and stirring for a period of 18 hours to 30 hours.

[0170] A twenty-fourth aspect of the present disclosure may include any one of aspects twenty-first to twenty-third, wherein the recrystallization of the ZSM-5 zeolite component may include: cooling the first mixture to a temperature of 20°C to 50°C; adjusting the pH of the first mixture to 9.0 to produce a second mixture; stirring the second mixture for a second period of 24 hours; and hydrothermally treating the second mixture by increasing the temperature to 100°C and stirring for a third period of 24 hours. The stirring for the second period of time and the hydrothermal treatment of the second mixture for the third period of time may recrystallize the zeolite component in the presence of a surfactant to produce a recrystallized ZSM-5 zeolite.

[0171] The twenty-fifth aspect of the present disclosure may include any one of aspects twenty-first to twenty-fourth, wherein recovering the recrystallized ZSM-5 zeolite may include: filtering the second mixture to produce a filtrate containing recrystallized ZSM-5 zeolite, washing the filtrate with distilled water, and drying the filtrate at 80° C. for a period of 8 hours to 24 hours to produce recrystallized ZSM-5 zeolite.

[0172] A twenty-sixth aspect of the present disclosure may include any one of aspects twenty-first to twenty-fifth, including calcining the recrystallized ZSM-5 zeolite at a temperature of 500° C. to 800° C. for a calcination period of 4 hours to 24 hours.

[0173] A twenty-seventh aspect of the present disclosure may include any one of aspects twenty-first to twenty-sixth, wherein the first mixture may include a sodium hydroxide concentration of 0.2 molar (M) to 0.5M.

[0174] A twenty-eighth aspect of the present disclosure may include any one of the twenty-first to twenty-seventh aspects, wherein the surfactant may include cetyltrimethylammonium bromide (CTAB).

[0175] It should be noted that any two quantitative values ​​assigned to a property may constitute a range for that property, and that all combinations of ranges formed by all of the described quantitative values ​​for a given property are contemplated in the present disclosure.

[0176] It should be noted that one or more of the following claims utilize the term "wherein" as a transition phrase. For purposes of defining the present technology, it should be noted that this term is introduced in the claims as an open transition phrase used to introduce a recitation of a series of features of a structure and should be interpreted in a manner similar to the more commonly used open-ended preamble term "comprising."

[0177] Having described the subject matter of the present disclosure in detail and with reference to particular aspects, it should be noted that the various details of these aspects should not be considered to imply that these details are essential components of the aspects. On the contrary, the claims appended hereto should be considered as the only representation of the breadth of the present disclosure and the corresponding scope of the various aspects described in the present disclosure. In addition, it is apparent that modifications and variations are possible without departing from the scope of the appended claims.

Claims

1. A cracking catalyst for steam enhanced catalytic cracking of hydrocarbons, the cracking catalyst comprising a hierarchical mesoporous ZSM-5 zeolite impregnated with phosphorus, cerium, lanthanum and iron, wherein before impregnation with the phosphorus, cerium, lanthanum and iron, the hierarchical mesoporous ZSM-5 zeolite has a diameter of 0.25 cm 3 / g to 0.35cm 3 / g of mesopore volume.

2. The cracking catalyst according to claim 1, wherein the phosphorus is present as phosphorus pentoxide, and the cracking catalyst comprises 1 wt.% to 5 wt.% of phosphorus pentoxide based on the total weight of the cracking catalyst.

3. The cracking catalyst according to claim 1 or claim 2, wherein the cracking catalyst comprises 0.5 wt.% to 3 wt.% of cerium oxide, 0.5 wt.% to 3 wt.% of lanthanum oxide and 0.5 wt.% to 3 wt.% of iron oxide based on the total weight of the cracking catalyst.

4. The cracking catalyst according to any one of the preceding claims, wherein the cracking catalyst comprises 1 wt.% to 5 wt.% of phosphorus pentoxide, 0.5 wt.% to 3 wt.% of cerium oxide, 0.5 wt.% to 3 wt.% of lanthanum oxide and 0.5 wt.% to 3 wt.% of iron oxide, based on the total weight of the cracking catalyst.

5. A method for upgrading crude oil by steam enhanced catalytic cracking, the method comprising contacting the crude oil with steam in the presence of a cracking catalyst according to any one of the preceding claims, in: The steam to crude oil mass ratio is 0.2 to less than 1; and The crude oil is contacted with steam in the presence of the cracking catalyst to cause a cracking reaction in at least a portion of the crude oil to produce a cracking effluent containing light olefins, light aromatic compounds or both.

6. A method according to any one of the preceding claims, comprising contacting the crude oil with steam in the presence of a plurality of composite catalyst particles, wherein the plurality of composite catalyst particles comprises the cracking catalyst, an inorganic binder and a matrix material.

7. The method according to any one of the preceding claims, wherein the crude oil has an American Petroleum Institute (API) degree of 15 to 50 degrees, and wherein the crude oil is a light crude oil, an extra light crude oil, a heavy crude oil, or a combination of these crude oils.

8. A method according to any one of the preceding claims, comprising contacting the crude oil with the steam in the presence of the cracking catalyst at a temperature of from 525°C to 800°C for a residence time of from 0.1 seconds to 60 seconds.

9. The method according to any one of the preceding claims, comprising contacting the crude oil with the steam in the presence of the cracking catalyst in a cracking reactor, wherein the cracking reactor comprises one or more of a fixed bed reactor, a fluidized bed reactor, a batch reactor, a fluid catalytic cracking (FCC) reactor, a moving bed catalytic cracking reactor, or a combination thereof.

10. A method for preparing a cracking catalyst according to any one of claims 1 to 4, said method include: providing an initial preformed ZSM-5 zeolite; decomposing a portion of the initial preformed ZSM-5 zeolite in a first mixture comprising sodium hydroxide and a surfactant; After at least partially decomposing the initial preformed ZSM-5 zeolite, recrystallizing the zeolite component in the presence of the surfactant to produce a recrystallized ZSM-5 zeolite having a hierarchical pore structure; recovering the recrystallized ZSM-5 zeolite; calcining the recrystallized ZSM-5 zeolite, wherein the calcining removes the surfactant from the recrystallized ZSM-5 zeolite to produce the hierarchical mesoporous ZSM-5 zeolite; as well as The hierarchical mesoporous ZSM-5 zeolite is impregnated with phosphorus, cerium, lanthanum and iron to form the cracking catalyst.

11. The method according to claim 10, further comprising treating the hierarchical mesoporous ZSM-5 zeolite with 0.25 normal (N) ammonium nitrate at 80°C twice for 5 hours after the calcination to produce the hierarchical mesoporous ZSM-5 zeolite in hydrogen form.

12. A method according to claim 10 or claim 11, wherein a portion of the initial preformed ZSM-5 zeolite is decomposed include: combining the initial preformed ZSM-5 zeolite, the sodium hydroxide, and the surfactant to form the first mixture; heating the first mixture to a temperature of 100° C. while stirring; as well as The first mixture is maintained at a temperature of 100°C and stirred for a period of 18 to 30 hours.

13. The method according to any one of claims 10 to 12, wherein the ZSM-5 zeolite component is recrystallized include: Cooling the first mixture to a temperature between 20°C and 50°C; adjusting the pH of the first mixture to 9.0 to produce a second mixture; stirring the second mixture for a second period of 24 hours; as well as The second mixture is hydrothermally treated by increasing the temperature to 100° C. and stirring for a third period of 24 hours, wherein the second period of stirring and the third period of hydrothermal treatment of the second mixture recrystallize the zeolite component in the presence of the surfactant to produce the recrystallized ZSM-5 zeolite.

14. The process according to claim 13, wherein the recrystallized ZSM-5 zeolite is recovered include: filtering the second mixture to produce a filtrate comprising the recrystallized ZSM-5 zeolite; washing the filtrate with distilled water; as well as The filtrate is dried at 80°C for a period of 8 hours to 24 hours to produce the recrystallized ZSM-5 zeolite.

15. The method of any one of claims 10-14, wherein the surfactant comprises cetyltrimethylammonium bromide (CTAB).

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