Process and catalyst formulation for cracking crude oil

Abstract

A process for converting a crude oil can include contacting the crude oil with one or more hydrotreating catalysts to produce a hydrotreated effluent, and contacting the hydrotreated effluent with a fluid catalytic cracking (FCC) catalyst composition in an FCC system to produce a cracked effluent comprising at least olefins. The crude oil may have an API specific gravity of 25 to 29. The FCC system can be operated at a temperature greater than or equal to 580 DEG C, the weight ratio of the FCC catalyst composition to the crude oil is from 2: 1 to 10: 1, and the residence time is from 0.1 second to 60 seconds. The FCC catalyst composition may include an ultra-stable Y-type zeolite (USY zeolite) impregnated with lanthanum; a ZSM-5 zeolite impregnated with phosphorus; an alumina binder; colloidal silicon dioxide; and a matrix material comprising kaolin.

Description

[0001] Cross - reference to related applications

[0002] This application claims the benefit of U.S. Patent Application Serial No. 18 / 053,809, filed on November 9, 2022, the entire disclosure of which is incorporated herein by reference. Technical Field

[0003] The present disclosure relates to methods and catalyst formulations for processing petroleum-based materials, particularly methods and catalyst compositions for cracking hydrocarbon feeds to produce chemical intermediates. Background Art

[0004] The growing global demand for light 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 drawn increasing attention because pure olefin streams are considered the building blocks for polymer synthesis. The production of light olefins depends on several process variables, such as feed type, operating conditions, and catalyst type. Despite the options available for producing higher yields of propylene and light olefins, a significant amount of research activity in this field is still ongoing. For example, light olefins are generally produced by thermal cracking (or steam cracking) of petroleum gases and fractions, such as naphtha, kerosene, or gas oil. Light olefins can also be produced by fluid catalytic cracking processes. Generally, the hydrocarbon feeds for fluid catalytic cracking processes are in the range of hydrocracked bottoms to heavy feed fractions, such as vacuum gas oil and atmospheric residue; however, the supply of these hydrocarbon feeds is limited and, at least in part, due to the limitations of conventional catalysts and processes used in fluid catalytic cracking processes. Summary of the Invention

[0005] Accordingly, there is a continuing need for integrated methods capable of producing intermediate chemical compounds from crude oil. The methods of the present disclosure include contacting a crude oil feed with one or more hydrotreating catalysts to form a hydrotreated effluent. The methods of the present disclosure further include contacting the hydrotreated effluent with an FCC catalyst composition. In particular, the methods of the present disclosure include contacting the hydrotreated effluent with an FCC catalyst composition comprising ZSM-5 zeolite and ultrastable Y zeolite. The inclusion of these different zeolite components can allow for increased selectivity and yield of light olefins, suitable for the entire range of some unconventional hydrocarbon feeds for fluid catalytic cracking processes, such as crude oil. In addition, the FCC catalyst composition may exhibit a reduced deactivation rate, which can improve the economics of light olefin production, as well as other characteristics.

[0006] According to at least one embodiment of the present disclosure, a method for converting crude oil may include contacting the crude oil with one or more hydrotreating catalysts to produce a hydrotreated effluent, and contacting the hydrotreated effluent with a fluid catalytic cracking (FCC) catalyst composition in an FCC system to produce a cracked effluent containing at least olefins. The crude oil may have an API gravity of 25 to 29. The FCC system may be operated at a temperature of greater than or equal to 580 °C, the weight ratio of the FCC catalyst composition to the crude oil is 2:1 to 10:1, and the residence time is 0.1 second to 60 seconds. The FCC catalyst composition may include ultrastable Y zeolite (USY zeolite) impregnated with lanthanum, ZSM-5 zeolite impregnated with phosphorus, an alumina binder, colloidal silica, and a matrix material containing kaolin.

[0007] Additional features and advantages of embodiments of the present disclosure will be set forth in the detailed description below, and in part, will be readily apparent to those of ordinary skill in the art from the detailed description, or recognized by practicing the embodiments of the present disclosure.

[0008] Brief description of the drawings

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

[0010] Figure 1 A general flow diagram of a system for converting a hydrocarbon feed to produce olefins according to one or more aspects of the present disclosure is schematically depicted.

[0011] When describing Figure 1 a simplified schematic diagram, many valves, temperature sensors, electronic controllers, etc. that may be used and are well known to those of ordinary skill in the art are not included. In addition, accompanying components (such as air supply devices, heat exchangers, surge tanks, etc.) that are typically included in those systems as Figure 1 shown are also not included. However, those of ordinary skill in the art understand that these components are within the scope of the present disclosure.

[0012] Now, various aspects will be referred to in more detail, some of which are shown in the drawings. Detailed Description

[0013] The present disclosure relates to methods and catalysts for upgrading crude oil by hydrotreating and fluid catalytic cracking to produce higher value chemical products and intermediates, such as but not limited to light olefins, aromatic compounds, and combinations thereof. The methods of the present disclosure enable the conversion of heavy hydrocarbon feeds comprising crude oil (such as Arabian heavy crude oil). The methods and FCC catalyst compositions of the present disclosure can effectively crack crude oil feed streams while exhibiting a reduced deactivation rate due to contaminants and coke formation and other characteristics.

[0014] Definitions

[0015] As used in the present disclosure, the term "API" refers to the American Petroleum Institute.

[0016] As used in the present disclosure, the term "cracking" refers to a chemical reaction in which a molecule having a carbon-carbon bond is broken into more than one molecule by the breaking of one or more carbon-carbon bonds; in which a compound comprising a ring portion (such as an aromatic) is converted into a compound that does not comprise a ring portion; or in which a molecule having a carbon-carbon double bond is reduced to a carbon-carbon single bond. As used in the present disclosure, the term "catalytic cracking" refers to cracking that occurs in the presence of a catalyst. Some catalysts may have multiple forms of catalytic activity, and referring to a catalyst by one particular function does not imply that the catalyst cannot have catalytic activity for other functions.

[0017] As used in the present disclosure, the term "catalyst" refers to any substance that increases the rate of a specific chemical reaction (such as a cracking reaction).

[0018] As used in the present disclosure, the term "crude oil" refers to a mixture of petroleum liquids and gases, including impurities (such as sulfur-containing compounds, nitrogen-containing compounds, and metal compounds), which is extracted directly from underground formations or received from a desalting unit without any fractions (such as naphtha) separated by distillation.

[0019] As used in the present disclosure, the term "naphtha" refers to an intermediate mixture of hydrocarbon-containing materials from crude oil refining and having atmospheric boiling points from 36 degrees Celsius (°C) to 220 °C. Naphtha can comprise: light naphtha, which comprises hydrocarbon-containing materials having atmospheric boiling points from 36 °C to 80 °C; intermediate naphtha, which comprises hydrocarbon-containing materials having atmospheric boiling points from 80 °C to 140 °C; and heavy naphtha, which comprises hydrocarbon-containing materials having atmospheric boiling points from 140 °C to 200 °C. Naphtha can comprise alkanes, cycloalkanes, and aromatic hydrocarbons having from 4 to 11 carbon atoms.

[0020] As used in this disclosure, the term "direct" means delivering a material (such as an effluent) from a first component of a system to a second component of the system without passing the material through any intermediate component or system that is operable to change the composition of the material. Similarly, the term "direct" also means introducing a material (such as a feed) into a component of a system without passing the material through any preparatory component that is operable to change the material components. Intermediate or preparatory components or systems that are operable to change the composition of the material may include reactors and separators, but generally are not intended to include heat exchangers, valves, pumps, sensors, or other auxiliary components required to operate a chemical process. Additionally, combining two streams upstream of a second component rather than delivering each stream separately to the second component is not considered an intermediate or preparatory component that is operable to change the material components.

[0021] As used in this disclosure, the terms "downstream" and "upstream" refer to the positioning of a component or system relative to the direction of flow of a material through the system. For example, if a material flowing through the system encounters a first component before it encounters a second component, the second component may be considered "downstream" of the first component. Similarly, if a material flowing through the system encounters a first component before it encounters a second component, the first component may be considered "upstream" of the second component.

[0022] As used in this disclosure, the term "effluent" means a stream that is delivered 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 an effluent is delivered to another component or system, only a portion of the effluent can be delivered. For example, a slipstream may carry away some of the effluent, meaning that only a portion of the effluent can enter a downstream component or system. The terms "reaction effluent" and "reactor effluent" specifically refer to a stream that is delivered from a reactor or reaction zone.

[0023] As used in this disclosure, the term "high severity conditions" refers to the operating conditions of a fluid catalytic cracking system (such as an FCC system), which include a temperature greater than or equal to 580 °C or from 580 °C to 750 °C, a catalyst-to-oil ratio greater than or equal to 1:1 or from 1:1 to 60:1, and a residence time less than or equal to 60 seconds or from 0.1 second to 60 seconds, each condition being potentially more severe than the general operating conditions of a fluid catalytic cracking system.

[0024] As used in this disclosure, the term "catalyst-to-oil ratio" or "CTO weight ratio" refers to the weight ratio of catalyst to a process stream containing hydrocarbons.

[0025] The term "residence time" refers to the amount of time that reactants are in contact with a catalyst under reaction conditions (such as at the reaction temperature).

[0026] As used in this disclosure, the term "reactor" refers to any vessel, container, conduit, etc. in which a chemical reaction (such as catalytic cracking) occurs between one or more reactants, optionally in the presence of one or more catalysts. A reactor may include one or more "reaction zones" disposed within the reactor. The term "reaction zone" refers to the region within the reactor where a specific reaction occurs.

[0027] As used in this disclosure, the terms "separation unit" and "separator" refer to any separation device that at least partially separates one or more chemical components in a mixture 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, distillation columns, fractionators, flash tanks, separation drums, separation vessels, centrifuges, filtration devices, traps, scrubbers, expansion devices, membranes, solvent extraction devices, high-pressure separators, low-pressure separators, or combinations thereof. The separation methods described in this disclosure may not completely separate all of one chemical component from all of another chemical component. Rather, the separation methods described in this disclosure "at least partially" separate different chemical components from each other, and separation may include only partial separation even if not explicitly stated.

[0028] It should be further understood that a stream can be named according to the components of the stream, and the components used to name the stream can be the major components of the stream (such as comprising from 50 wt%, 70 wt%, 90 wt%, 95 wt%, 99 wt%, 99.5 wt% or 99.9 wt% to 100 wt% of the content of the stream). It should also be understood that when a stream containing a component is disclosed as being delivered from one system component to another system component, that component of the stream is disclosed as being delivered from that system component to another system component. For example, a disclosed "heavy oil stream" being delivered to a first system component or from a first system component to a second system component should be understood as equivalently disclosing "heavy oil" being delivered to a first system component or from a first system component to a second system component.

[0029] The composition of the feed stream and the processing variables of the FCC system play important roles in the reaction yields and heat balance within the system. Conventional FCC systems and methods may require expensive refining to produce a suitable feed stream. Such additional expensive refining can include separating and treating one or more fractions of the hydrocarbon feedstock prior to introducing the refined conventional feed into the FCC system. These additional processing steps are energy intensive and reduce the viable feed quantity from existing hydrocarbon sources. Previous systems and methods that have been developed have attempted to overcome these limitations by directly converting crude oil into higher value chemical products and intermediates via catalytic cracking, such as by reducing or eliminating the processing steps required to produce a suitable hydrocarbon feed prior to introducing it into the FCC system. However, contaminants, metals, or both present in heavy hydrocarbon feeds, such as crude oil, can deactivate the catalyst, resulting in reduced yields and increased production costs.

[0030] Embodiments

[0031] Accordingly, embodiments of the present disclosure relate to an integrated method that, through the combination of hydrotreating and FCC, uses reaction conditions and catalyst compositions that facilitate the efficient treatment and cracking of crude oil while resisting catalyst deactivation to directly convert crude oil into higher value chemical products and intermediates (such as, but not limited to, olefins and aromatic compounds). The FCC catalyst compositions of the present disclosure can include ZSM-5 zeolite, ultrastable Y zeolite, alumina binder, a matrix material including kaolin, and colloidal silica. The method of the present disclosure can include contacting a crude oil feed stream with one or more hydrotreating catalysts to form a hydrotreated effluent. The method can further include contacting the hydrotreated effluent with an FCC catalyst composition in an FCC catalytic cracking system to convert at least a portion of the hydrotreated effluent feed stream into light olefins, aromatic compounds, or both. The hydrotreated effluent can be contacted with the FCC catalyst composition under highly severe conditions. The method of the present invention enables the direct and efficient conversion of crude oil into light olefins, aromatic compounds, or both, while having characteristics such as resistance to deactivation.

[0032] Reference is now made to Figure 1 , a method 100 for converting crude oil according to the present disclosure can include contacting crude oil 102 with one or more hydrotreating catalysts 112 to produce a hydrotreated effluent 104, and contacting the hydrotreated effluent 104 with a fluid catalytic cracking (FCC) catalyst composition 122 in an FCC system 120 to produce a cracked effluent 126 comprising at least olefins.

[0033] The feedstock of the present method 100 can be crude oil 102. The "crude oil" 102 can be a crude hydrocarbon that has not been previously treated (such as by one or more of distillation, cracking, hydrotreating, desalting, or dehydration). In an embodiment, the crude oil 102 may have undergone at least some treatment, such as desalting, solid separation, washing, or a combination thereof, but has not undergone distillation. For example, the crude oil 102 can be desalted crude oil that has undergone desalting treatment. In an embodiment, before introducing the crude oil 102 into the method 100, the crude oil 102 may not have been pretreated, separated (such as by distillation), or otherwise operated on to change the hydrocarbon composition of the crude oil. As used herein, the "hydrocarbon composition" of crude oil refers to the composition of the hydrocarbon components of the crude oil 102, excluding entrained non-hydrocarbon solids, salts, water, or other non-hydrocarbon components.

[0034] The crude oil 102 can have an American Petroleum Institute (API) gravity of 25 to 30. For example, the crude oil can have an API gravity of 25 to 29, 25 to 28, 26 to 30, 26 to 29, 26 to 28, 27 to 30, 27 to 28, or any subset thereof. At a temperature of 15 degrees Celsius, the crude oil can have a density greater than 0.8 grams per milliliter (g / ml), greater than 0.82 g / ml, greater than 0.84 g / ml, 0.86 g / ml, 0.88 g / ml, 0.8 g / ml to 1.0 g / ml, 0.84 g / ml to 0.96 g / ml, 0.86 g / ml to 0.93 g / ml, 0.87 g / ml to 0.902 g / ml, 0.87 g / ml to 0.89 g / ml, or any subset thereof. According to some embodiments, the crude oil 102 can be Arabian heavy crude oil. The properties of a representative grade of Arabian heavy crude oil can be found in Table 2-3.

[0035] The crude oil 102 can have an initial boiling point of 30°C to 50°C. For example, the crude oil 102 can have an initial boiling point of 30°C to 45°C, 30°C to 40°C, 30°C to 35°C, 35°C to 50°C, 40°C to 50°C, 45°C to 50°C, or any subset thereof. The initial boiling point can be determined according to the standard test method ASTM D7169.

[0036] The crude oil 102 can have a final boiling point (also referred to herein as "EBP" and "FBP") greater than 720 degrees Celsius. For example, the crude oil 102 can have a final boiling point greater than 740°C, greater than 760°C, greater than 780°C, greater than 800°C, greater than 850°C, greater than 900°C, greater than 950°C, or greater than 1000°C. The crude oil 102 can have a final boiling point less than 2000°C, less than 1800°C, less than 1600°C, less than 1400°C, less than 1200°C, less than 1000°C, less than 900°C, less than 800°C, less than 750°C, or any subset thereof. The final boiling point can be determined according to the standard test method ASTM D7169.

[0037] At least 50 wt% of the crude oil 102 may have a boiling point temperature of 300 °C or higher. For example, the crude oil may have 50 wt% with a boiling point temperature in the range of 300 °C to 500 °C, 300 °C to 475 °C, 300 °C to 450 °C, 300 °C to 425 °C, 300 °C to 400 °C, 300 °C to 375 °C, 350 °C to 500 °C, 350 °C to 475 °C, 350 °C to 450 °C, 350 °C to 425 °C, 350 °C to 400 °C, 350 °C to 375 °C, 375 °C to 500 °C, 375 °C to 475 °C, 375 °C to 450 °C, 375 °C to 425 °C, 375 °C to 400 °C, or any subset thereof. The boiling point temperature of 50 wt% can be determined according to the standard test method ASTM D7169.

[0038] The crude oil 102 may have a nitrogen concentration of less than or equal to 5000 parts per million by weight (ppmw). For example, the crude oil 102 may have a nitrogen concentration of less than 4500 ppmw, less than 4000 ppmw, less than 3500 ppmw, less than 3000 ppmw, less than 2500 ppmw, less than 2000 ppmw, 1000 ppmw to 5000 ppmw, 1000 ppmw to 4000 ppmw, 1000 ppmw to 3000 ppmw, 1000 ppmw to 2000 ppmw, or any subset thereof. The nitrogen concentration of the crude oil 102 can be determined according to the standard test method ASTM D4629.

[0039] The crude oil 102 may have a concentration of paraffinic compounds of less than 50 wt% per unit weight of the crude oil. For example, the crude oil 102 may have a concentration of paraffinic compounds of less than or equal to 40 wt%, less than or equal to 35 wt%, less than or equal to 30 wt%, less than or equal to 25 wt%, less than or equal to 20 wt%, less than or equal to 15 wt%, less than or equal to 10 wt%, or even less than or equal to 5 wt% per unit weight of the hydrocarbon feed. In an embodiment, the crude oil 102 may have a concentration of paraffinic compounds per unit weight of the crude oil 102 in the range of 5 wt% to less than 50 wt%, 5 wt% to 40 wt%, 5 wt% to 35 wt%, 5 wt% to 30 wt%, 5 wt% to 25 wt%, 5 wt% to 20 wt%, 10 wt% to less than 50 wt%, 10 wt% to 40 wt%, 10 wt% to 35 wt%, 10 wt% to 30 wt%, 10 wt% to 25 wt%, or even 10 wt% to 20 wt%. The paraffin content of the crude oil 102 can be determined according to ASTM 5443.

[0040] The crude oil 102 may have a concentration of aromatic compounds greater than or equal to 20% by weight per unit weight of the crude oil. For example, as determined according to ASTM 5443, the crude oil 102 may have a concentration of aromatic compounds greater than or equal to 30% by weight, greater than or equal to 40% by weight, or even greater than or equal to 50% by weight per unit weight of the crude oil 102. In an embodiment, the crude oil 102 may have a concentration of aromatic compounds per unit weight of the crude oil 102 from 20% by weight to 90% by weight, 20% by weight to 80% by weight, 20% by weight to 70% by weight, 30% by weight to 90% by weight, 30% by weight to 80% by weight, 30% by weight to 70% by weight, 40% by weight to 90% by weight, 40% by weight to 80% by weight, 40% by weight to 70% by weight, 50% by weight to 90% by weight, 50% by weight to 80% by weight, 50% by weight to 70% by weight, or any subset thereof.

[0041] The crude oil 102 may have a concentration of naphthenes greater than or equal to 10% by weight per unit weight of the crude oil. For example, as determined according to ASTM 5443, the crude oil 102 may have a concentration of naphthenes greater than or equal to 15% by weight, greater than or equal to 20% by weight, greater than or equal to 25% by weight, or greater than or equal to 27% by weight per unit weight of the crude oil 102. In an embodiment, the crude oil 102 may have a concentration of naphthenes per unit weight of the crude oil 102 from 25% by weight to 60% by weight, 25% by weight to 50% by weight, 25% by weight to 40% by weight, 25% by weight to 35% by weight, 27% by weight to 60% by weight, 27% by weight to 50% by weight, 27% by weight to 40% by weight, 27% by weight to 35% by weight, or any subset thereof.

[0042] In some embodiments, the crude oil 102 may be topped crude oil. As used in the present disclosure, the term "topped crude oil" refers to crude oil from which the lower boiling components have been removed by distillation, such as components having a boiling point temperature below 180 °C or even below 160 °C. The crude oil 102 may comprise, consist of, or consist essentially of topped crude oil having greater than or equal to 95%, greater than or equal to 98%, or even greater than or equal to 99% of the components having a boiling point temperature greater than or equal to 160 °C or greater than or equal to 180 °C, depending on the fractionation point temperature of the topping unit.

[0043] In an embodiment, one or more make-up feeds (not shown) may be mixed with the crude oil 102 before introducing the crude oil 102 to one or more hydrotreating catalysts, or in addition to the crude oil 102, one or more make-up feeds may be independently introduced to one or more hydrotreating catalysts 112. In an alternative embodiment, the crude oil 102 may be independently introduced to one or more hydrotreating catalysts 112 in the absence of any other such feeds.

[0044] The crude oil 102 may be contacted with one or more hydrotreating catalysts 112 in a hydrotreating system 110. The hydrotreating system 110 may be a single reactor or a series of directly connected reactors. In the presence of more than one hydrotreating catalyst 112, the catalysts may be arranged in different beds, the catalysts may be placed in separate reactors, or the catalysts may be mixed in a single reactor. The crude oil 102 may contact one or more hydrotreating catalysts 112 in a downward flow manner.

[0045] One or more hydrotreating catalysts 112 may include one or more of a hydrodemetallization (also referred to as “HDM”) catalyst, a hydrodesulfurization (also referred to as “HDS”) catalyst, and a hydrodearomatization (also referred to as “HAD”) catalyst. In some embodiments, one or more hydrotreating catalysts 112 may include a hydrodemetallization catalyst, a hydrodesulfurization catalyst, and a hydrodearomatization catalyst. In further embodiments, one or more hydrotreating catalysts 112 may further include a hydrodenitrogenation catalyst, a hydrodeoxygenation catalyst, or both.

[0046] One or more hydrotreating catalysts 112 may be arranged in any order. For example, one or more hydrotreating catalysts 112 may be arranged such that the crude oil 102 first contacts the HDM catalyst, then the HDS catalyst, and then the HDA catalyst. Optionally, one or more hydrotreating catalysts 112 may be arranged such that the crude oil contacts the HDM, then the HDA, and then the HDS; or contacts the HDS, HDA, HDM; or contacts the HDS, then the HDM, and then the HDA; or contacts the HDA, then the HDS, and then the HDM; or contacts the HDA, then the HDM, and then the HDS catalyst. In some embodiments, the HDM and HDS catalysts may be placed upstream of the HDA catalyst. Without being limited by theory, it is believed that placing the HDA catalyst after the HDS catalyst and the HDM catalyst may protect the HDA catalyst from deactivation.

[0047] In alternative embodiments, there may be only one or two of the one or more hydrotreating catalysts 112. The one or more hydrotreating catalysts 112 may be arranged such that the crude oil contacts the HDM and then the HDA, or contacts the HDA and then the HDM, or contacts the HDS and then the HDA, or contacts the HDA and then the HDS, or contacts the HDM and then the HDS, or contacts the HDS and then the HDM catalyst.

[0048] In embodiments where the catalysts form a mixed bed, the crude oil may contact the one or more hydrotreating catalysts 112 in a random or simultaneous manner.

[0049] The HDM catalyst may comprise one or more metals from Groups 5, 6, or 8 - 10 of the IUPAC Periodic Table. For example, the HDM catalyst may comprise molybdenum. The HDM catalyst may further comprise a support material, and the metal may be disposed on the support material. The support material may be γ - alumina or silica / alumina extrudates, spheres, cylinders, beads, pellets, and combinations thereof. In some embodiments, the HDM catalyst may comprise a γ - alumina support having a surface area of 100 square meters per gram (m 2 / g) to 160 m 2 / g, such as 100 m 2 / g to 130 m 2 / g, or 130 m 2 / g to 160 m 2 / g. In one embodiment, the HDM catalyst may comprise a molybdenum metal catalyst on an alumina support (sometimes referred to as a "Mo / Al2O3 catalyst"). It should be understood that throughout this disclosure, the metals contained in any disclosed catalyst may be present as sulfides or oxides or even other compounds.

[0050] In some embodiments, the HDM catalyst may comprise 0.5 wt% to 12 wt% of an oxide or sulfide of molybdenum, such as 2 wt% to 10 wt% or 3 wt% to 7 wt% of an oxide or sulfide of molybdenum, and 88 wt% to 99.5 wt% of alumina, such as 90 wt% to 98 wt% or 93 wt% to 97 wt% of alumina.

[0051] The HDM catalyst may have a relatively large pore volume, such as at least 0.8 cubic centimeters per gram (cm 3 / g) (e.g., at least 0.9 cm 3 / g or even at least 1.0 cm 3 / g). The pore size of the HDM catalyst can be predominantly macroporous (i.e., having a pore size greater than 50 nanometers (nm)). Without being bound by theory, it is believed that such pore structure and volume can provide a large capacity for the absorption of metals and optionally dopants on the surface of the HDM catalyst. In one embodiment, the HDM catalyst can include a dopant comprising one or more compounds that include elements selected from the group consisting of boron, silicon, halogens, phosphorus, and combinations thereof.

[0052] Exemplary HDM catalysts can include KFR-22 from Albermarle Corp.

[0053] The HDS catalyst can comprise one or more metals from Groups 5, 6, or 8-10 of the IUPAC Periodic Table. The HDS catalyst can comprise one or more metals from Group 6 of the IUPAC Periodic Table and one metal from Group 8-10 of the IUPAC Periodic Table. Examples of Group 6 metals include molybdenum and tungsten, and examples of Group 8-10 metals include nickel and cobalt. The HDS catalyst can further comprise a support material, and the metals can be disposed on the support material. In some embodiments, the HDS catalyst can comprise Mo and Ni on an alumina support (sometimes referred to as a “Mo-Ni / Al2O3 catalyst”). The HDS catalyst can also contain a dopant selected from the group consisting of boron, phosphorus, halogens, silicon, and combinations thereof. In one or more embodiments, the HDS catalyst can comprise: 10 wt% to 18 wt% of an oxide or sulfide of molybdenum, such as 11 wt% to 17 wt% or 12 wt% to 16 wt% of an oxide or sulfide of molybdenum; 1 wt% to 7 wt% of an oxide or sulfide of nickel, such as 2 wt% to 6 wt% or 3 wt% to 5 wt% of an oxide or sulfide of nickel; and 75 wt% to 89 wt% of alumina, such as 77 wt% to 87 wt% or 79 wt% to 85 wt% of alumina.

[0054] The HDS catalyst can have a surface area of 140 m 2 / g to 200 m 2 / g, such as 140 m 2 / g to 170 m 2 / g, or 170 m 2 / g to 200 m 2 / g. The HDS catalyst can have an intermediate pore volume of 0.5 cm 3 / g to 0.7 cm 3 / g, such as 0.6 cm 3 / g. The HDS catalytic converter can generally comprise a mesoporous structure having a pore size in the range of 12 nm to 50 nm.

[0055] Exemplary HDS catalysts can include KFR-33 from Albermarle Corp.

[0056] The HDA catalyst can comprise one or more metals from Groups 5, 6, 8, 9, or 10 of the IUPAC Periodic Table. In some embodiments, the HDA catalyst can comprise one or more metals from Group 5 or Group 6 of the IUPAC Periodic Table, and one or more metals from Groups 8, 9, or 10 of the IUPAC Periodic Table. In some embodiments, the HDA catalyst can comprise molybdenum or tungsten from Group 6 and nickel or cobalt from Groups 8, 9, or 10. The HDA catalyst can further comprise a support material (such as zeolite), and the metal can be disposed on the support material. In one embodiment, the HDA catalyst can comprise a tungsten and nickel metal catalyst on a mesoporous zeolite support (sometimes referred to as a "W-Ni / mesoporous zeolite catalyst"). In another embodiment, the HDA catalyst can comprise a molybdenum and nickel metal catalyst on a mesoporous zeolite support (sometimes referred to as a "Mo-Ni / mesoporous zeolite catalyst"). The zeolite support material can not be limited to any particular type of zeolite. However, zeolites such as Y, β, AWLZ-15, LZ-45, Y-82, Y-84, LZ-210, LZ-25, silicalite, or mordenite framework zeolites are contemplated to be suitable for use in the HDA catalysts described herein.

[0057] The support material of the HDA catalyst (i.e., mesoporous zeolite) can be characterized as mesoporous by having an average pore diameter of 2 nm to 50 nm. Without being bound by theory, it is believed that relatively large-sized pores (i.e., mesoporosity) allow larger molecules to diffuse inside the zeolite, which is thought to enhance the reaction activity and selectivity of the catalyst. As the pore diameter increases, aromatic-containing molecules can more easily diffuse into the catalyst, and aromatic cracking can be increased. For example, in some conventional embodiments, the feedstock converted by the hydrotreating catalyst can be: vacuum gas oil; light cycle oil from, for example, a fluid catalytic cracking reactor; or coker unit gas oil from, for example, a coking unit. Compared to the molecular sizes of these oils, the molecular sizes in heavy oils (such as crude oil and atmospheric residue), which can be the feedstock of the present method and system, are relatively small. Heavy oils generally cannot diffuse inside conventional zeolites and cannot be converted at the active sites located inside the zeolites. Therefore, zeolites with larger pore diameters (i.e., mesoporous zeolites) can allow larger molecules of heavy oils to overcome diffusion limitations and can facilitate the reaction and conversion of larger molecules of heavy oils.

[0058] In one or more embodiments, the HDA catalyst can comprise: 18 wt% to 28 wt% of a sulfide or oxide of tungsten, such as 20 wt% to 27 wt% or 22 wt% to 26 wt% of tungsten or a sulfide or oxide of tungsten; 2 wt% to 8 wt% of an oxide or sulfide of nickel, such as 3 wt% to 7 wt% or 4 wt% to 6 wt% of an oxide or sulfide of nickel; and 5 wt% to 40 wt% of a mesoporous zeolite, such as 10 wt% to 35 wt% or 10 wt% to 30 wt% of a zeolite. In another embodiment, the HDA catalyst can comprise: 12 wt% to 18 wt% of an oxide or sulfide of molybdenum, such as 13 wt% to 17 wt% or 14 wt% to 16 wt% of an oxide or sulfide of molybdenum; 2 wt% to 8 wt% of an oxide or sulfide of nickel, such as 3 wt% to 7 wt% or 4 wt% to 6 wt% of an oxide or sulfide of nickel; and 5 wt% to 40 wt% of a mesoporous zeolite, such as 10 wt% to 35 wt% or 10 wt% to 30 wt% of a mesoporous zeolite.

[0059] It should be understood that some embodiments of the presently described methods and systems can utilize an HDA catalyst that includes a mesoporous zeolite (i.e., having an average pore diameter of 2 nm to 50 nm). However, in other embodiments, the average pore diameter of the zeolite can be less than 2 nm (i.e., microporous).

[0060] Exemplary HDA catalysts can include KFR-70 from Albermarle Corp.

[0061] The crude oil 102 can be contacted with one or more hydrotreating catalysts 112 at a temperature of at least 300 °C, at least 325 °C, at least 350 °C, at least 375 °C, or at least 400 °C. The crude oil 102 can be contacted with one or more hydrotreating catalysts 112 at a temperature below 1000 °C, below 800 °C, below 600 °C, below 500 °C, or below 450 °C.

[0062] The crude oil 102 can be contacted with one or more hydrotreating catalysts 112 in the presence of hydrogen. For example, the atmosphere in which the crude oil 102 is contacted with one or more hydrotreating catalysts 112 can be at least 10 mol% hydrogen, at least 25 mol% hydrogen, at least 50 mol% hydrogen, at least 75 mol% hydrogen, at least 90 mol% hydrogen, or even at least 99 mol% hydrogen.

[0063] The crude oil 102 can be contacted with one or more hydrotreating catalysts 112 at a pressure of at least 75 bar, at least 100 bar, at least 125 bar, or at least 150 bar.

[0064] The crude oil can be contacted with one or more hydrotreating catalysts at a hydrogen / oil ratio of at least 600. For example, the crude oil can be contacted with one or more hydrotreating catalysts at a hydrogen / oil ratio of at least 800, at least 1000, at least 1200, from 600 to 1500, from 800 to 1400, from 1100 to 1300, or any subset thereof.

[0065] The crude oil 102 can be at a liquid hourly space velocity (LHSV) greater than 0.1 h -1 , greater than 0.2 h -1 , greater than 0.25 h -1 , greater than 0.28 h -1 , less than 0.5 h -1 , less than 0.4 h -1 , less than 0.35 h -1 , less than 0.32 h -1 , 0.1 h -1 to 0.5 h -1 , 0.2 h -1 to 0.4 h -1 , 0.25 h -1 to 0.35 h -1 , 0.28 h -1 to 0.32 h -1 or any subset thereof and contacted with one or more hydrotreating catalysts 112.

[0066] The hydrotreated effluent 104 can be fed directly from the hydrotreating system 110 to the FCC system 120. In an alternative embodiment, the hydrotreated effluent 104 can undergo additional processing steps between leaving the hydrotreating system 110 and being fed to the FCC system 120.

[0067] At least 50 wt% of the hydrotreated effluent 104 can have a boiling point temperature of at least 300 °C, such as at least 310 °C or at least 315 °C. At least 50 wt% of the hydrotreated effluent 104 can have a boiling point temperature less than 400 °C, less than 380 °C, less than 360 °C, less than 340 °C, or less than 325 °C. The boiling point temperature of 50 wt% can be determined according to the standard test method ASTM D7169.

[0068] The hydrotreated effluent 104 can have a nitrogen content that is less than 30%, less than 25%, less than 20%, less than 15%, or less than 10% of the nitrogen content of the crude oil 102. The nitrogen content can be measured according to the standard test method ASTM D-4629.

[0069] The hydrotreated effluent 104 may have a sulfur content that is less than 20%, less than 15%, less than 10%, less than 5%, less than 4%, or less than 3% of the sulfur content of the crude oil 102. The sulfur content may be measured according to the standard test method ASTM D-4294.

[0070] The method of the present disclosure includes delivering the hydrotreated effluent 104 from a hydroprocessing unit 110 to a FCC system 120 that includes a FCC catalyst composition 122. The hydrotreated effluent 104 may be delivered directly to the FCC system 120. In some embodiments, the FCC system 120 may be a downflow FCC system. In alternative embodiments, the FCC system 120 may be an upflow FCC system.

[0071] The FCC system may be operated at a temperature greater than or equal to 580 °C. For example, the FCC system may be operated at a temperature greater than 600 °C, greater than 620 °C, greater than 640 °C, or greater than 645 °C.

[0072] The FCC catalyst 122 may contact the hydrotreated effluent 104 under high severity reaction conditions. For example, the FCC catalyst 122 may contact the hydrotreated effluent 104 at a reaction temperature greater than 580 °C, such as 580 °C to 750 °C, 580 °C to 740 °C, 580 °C to 720 °C, 580 °C to 700 °C, 580 °C to 680 °C, 580 °C to 660 °C, 580 °C to 650 °C, 600 °C to 750 °C, 600 °C to 740 °C, 600 °C to 720 °C, 600 °C to 700 °C, 600 °C to 680 °C, 600 °C to 660 °C, 600 °C to 650 °C, 620 °C to 750 °C, 620 °C to 740 °C, 620 °C to 720 °C, 620 °C to 700 °C, 620 °C to 680 °C, 620 °C to 660 °C, or 620 °C to 650 °C. When the reaction temperature is higher than, for example, 750 °C, compared to embodiments where the reaction temperature is lower than 750 °C, the hydrotreated effluent 104 may undergo increased thermal cracking and decreased catalytic cracking. Without being bound by theory, it is believed that thermal cracking of the hydrotreated effluent can increase the yield of ethylene and decrease the yield of other products. In embodiments, the hydrotreated effluent may contact the FCC catalyst composition 122 at a temperature of 600 °C to 650 °C. Catalytic cracking of the hydrotreated effluent 104 in the fluid catalytic cracking unit 120 can produce a greater amount of desired products (such as light olefins and aromatics).

[0073] The weight ratio of the FCC catalyst composition to the crude oil may be from 2:1 to 10:1, such as 2:1 to 8:1, 2:1 to 6:1, 2:1 to 4:1, 4:1 to 10:1, 6:1 to 10:1, or 8:1 to 10:1.

[0074] The fluid catalytic cracking system 120 can be operated at a catalyst-to-oil (CTO) weight ratio of from 2:1 to 10:1, where the catalyst-to-oil weight ratio is the weight ratio of the FCC catalyst composition 122 to the hydrotreated effluent 104 in a unit volume of the reaction mixture comprising the hydrotreated effluent 104 and the FCC catalyst composition 122. For example, the fluid catalytic cracking system 120 can be operated at a catalyst-to-oil weight ratio of from 2:1 to 3:1, from 2:1 to 5:1, from 2:1 to 10:1, from 3:1 to 5:1, or from 5:1 to 10:1. Without being bound by theory, it is believed that a catalyst-to-oil weight ratio less than 2:1 may not provide a sufficient amount of catalyst to catalytically crack the hydrotreated effluent 104 at an economically high yield. It is believed that a catalyst-to-oil weight ratio greater than 10:1 may not be economically practical for scale-up in commercial applications.

[0075] The hydrotreated effluent 104 can be contacted with the FCC catalyst composition 122 for a residence time of from 0.1 second to 60 seconds. For example, the hydrotreated effluent can be contacted with the FCC catalyst composition for the following residence times: from 5 seconds to 60 seconds, from 10 seconds to 60 seconds, from 20 seconds to 60 seconds, from 30 seconds to 60 seconds, from 40 seconds to 60 seconds, from 50 seconds to 60 seconds, from 0.1 second to 50 seconds, from 0.1 second to 40 seconds, from 0.1 second to 30 seconds, from 0.1 second to 20 seconds, from 0.1 second to 10 seconds, from 10 seconds to 50 seconds, from 20 seconds to 40 seconds, or any subset thereof. Without intending to be bound by any particular theory, it is believed that a residence time less than 0.1 second may not provide sufficient time for the hydrocarbons in the hydrotreated effluent 104 to be sufficiently cracked by the FCC catalyst composition 122.

[0076] The FCC catalyst composition 122 can comprise ultrastable Y zeolite (USY zeolite) impregnated with lanthanum, ZSM-5 zeolite impregnated with phosphorus, an alumina binder, colloidal silica, and a matrix material comprising kaolin.

[0077] The FCC catalyst composition can comprise from 1 wt% to 40 wt% of ZSM-5 zeolite impregnated with phosphorus, from 1 wt% to 40 wt% of USY zeolite impregnated with lanthanum, from 2 wt% to 20 wt% of an alumina binder, from 0.5 wt% to 5 wt% of colloidal silica, and from 30 wt% to 70 wt% of a matrix material, or any subset thereof.

[0078] According to some embodiments, the FCC catalyst composition may comprise 19 wt% to 23 wt% of lanthanum-impregnated USY zeolite, 18 wt% to 22 wt% of phosphorus-impregnated ZSM-5 zeolite, 6 wt% to 10 wt% of alumina binder, 47 wt% to 51 wt% of kaolin, and 0.1 wt% to 4 wt% of colloidal silica, wherein the weight percentages are based on the total weight of the FCC catalyst composition.

[0079] According to some specific embodiments, the FCC catalyst composition 122 may comprise: about 20 wt% of ZSM-5 zeolite based on the total weight of the FCC catalyst composition 122, wherein the ZSM-5 zeolite is impregnated with about 7.5 wt% of P2O5 based on the total weight of the ZSM-5 zeolite; about 21 wt% of USY zeolite based on the total weight of the FCC catalyst composition 122, wherein the USY zeolite is impregnated with about 2.5 wt% of lanthanum oxide (La2O3) based on the total weight of the USY zeolite; about 8 wt% of alumina binder based on the total weight of the FCC catalyst composition 122; about 49 wt% of kaolin based on the total weight of the FCC catalyst composition 122; and about 2 wt% of colloidal silica based on the total weight of the FCC catalyst composition 122.

[0080] The ZSM-5 zeolite in the FCC catalyst composition 122 is operable to crack at least a portion of the hydrotreated effluent 104 to produce one or more light olefins (such as ethylene and propylene). Without being bound by any particular theory, it is believed that the ZSM-5 zeolite may have a greater tendency to crack relatively light hydrocarbons, such as those present in the hydrotreated effluent 104 and those produced by the catalytic cracking of heavier hydrocarbons by Y-type zeolite. Thus, when compared to an FCC catalyst that does not include ZSM-5 zeolite, the addition of ZSM-5 zeolite can increase the yield of products (such as light olefins). As used in the present disclosure, "ZSM-5" refers to a zeolite having an MFI framework type according to the IUPAC zeolite nomenclature and consisting of silica and alumina. ZSM-5 refers to "Zeolite Socony Mobil-5" and is a pentasil family zeolite that can be represented by the chemical formula Na n Al n Si 96–n O 192 ·16H2O, where 0 < n < 27. The molar ratio of silica to alumina in ZSM-5 can be at least 5, at least 10, at least 25, at least 30, or even at least 50. In embodiments, the molar ratio of silica to alumina in ZSM-5 can be 5 to 50, 5 to 40, 5 to 35, 10 to 50, 10 to 40, 10 to 35, 20 to 50, 20 to 40, 20 to 35, 30 to 50, or 30 to 40.

[0081] The ZSM-5 zeolite may have an average surface area of from 200 square meters per gram (m 2 / g) to 800 m 2 / g. In an embodiment, the average surface area may be from 200 m 2 / g to 400 m 2 / g, from 200 m 2 / g to 600 m 2 / g, from 200 m 2 / g to 800 m 2 / g, from 300 m 2 / g to 400 m 2 / g, from 300 m 2 / g to 600 m 2 / g, from 300 m 2 / g to 800 m 2 / g, from 400 m 2 / g to 600 m 2 / g, or from 400 m 2 / g to 800 m 2 / g. In an embodiment, the ZSM-5 zeolite may have the following average total pore volume per unit weight of the ZSM-5 zeolite: from 0.010 milliliters per gram (mL / g) to 0.500 mL / g, such as from 0.050 mL / g to 0.500 mL / g, from 0.010 mL / g to 0.300 mL / g, or from 0.050 mL / g to 0.300 mL / g.

[0082] One or more zeolite components of the FCC catalyst composition 122 may include one or more phosphorus-containing compounds, such as phosphorus pentoxide (P2O5). Without being bound by any particular theory, it is believed that the phosphorus-containing compounds may stabilize the structure of the zeolite framework by preventing the segregation of framework alumina, which can improve the hydrothermal stability of the zeolite component. This may reduce the dealumination of the zeolite component that occurs during the steaming process, which may lead to a decrease in the acidity and catalytic activity of the zeolite component.

[0083] One or more zeolite components of the FCC catalyst composition 122 may include one or more phosphorus-containing compounds in an amount of 1 wt% to 20 wt% based on the total weight of each zeolite component. In an embodiment, the phosphorus-containing compound may be impregnated onto the ZSM-5 zeolite such that the ZSM-5 zeolite is impregnated with a phosphorus-containing compound in an amount of 1 wt% to 20 wt% based on the total weight of the ZSM-5 zeolite. For example, the ZSM-5 zeolite may be impregnated with phosphorus pentoxide in an amount of 1 wt% to 20 wt% based on the total weight of the ZSM-5 zeolite. In an embodiment, the ZSM-5 zeolite may include phosphorus pentoxide in an amount of 1 wt% to 15 wt%, 1 wt% to 10 wt%, 1 wt% to 5 wt%, 5 wt% to 20 wt%, 5 wt% to 15 wt%, 5 wt% to 10 wt%, 10 wt% to 20 wt%, 10 wt% to 15 wt%, 15 wt% to 20 wt%, 6 wt% to 9 wt% or 7 wt% to 8 wt% based on the total weight of the ZSM-5 zeolite. In a specific embodiment, the ZSM-5 zeolite may include phosphorus pentoxide in an amount of about 7.5 wt% based on the total weight of the ZSM-5 zeolite.

[0084] The FCC catalyst composition 122 may include up to 40 wt% of ZSM-5 zeolite based on the total weight of the FCC catalyst composition 122. For example, the FCC catalyst composition 122 may include up to 30 wt%, up to 25 wt% or up to 20 wt%, 1 wt% to 40 wt%, 1 wt% to 30 wt%, 1 wt% to 25 wt%, 1 wt% to 20 wt%, 5 wt% to 40 wt%, 5 wt% to 30 wt%, 5 wt% to 25 wt%, 5 wt% to 20 wt%, 10 wt% to 40 wt%, 10 wt% to 30 wt%, 10 wt% to 25 wt%, 10 wt% to 20 wt%, 15 wt% to 40 wt%, 15 wt% to 30 wt%, 15 wt% to 25 wt% or 15 wt% to 20 wt% of the phosphorus-impregnated ZSM-5 zeolite.

[0085] The FCC catalyst composition 122 may include a Y-type zeolite. The Y-type zeolite of the FCC catalyst composition 122 may be operable to produce one or more olefins from hydrocarbons in the hydrotreated effluent 104. The Y-type zeolite may comprise an ultrastable Y-type (USY) zeolite. The USY zeolite may be produced via dealumination of one or more Y-type zeolites. As used in the present disclosure, the term "Y-type zeolite" refers to a zeolite having a FAU framework type according to the IUPAC zeolite nomenclature and consisting of silica and alumina. Without being bound by any particular theory, it is believed that dealumination of the Y-type zeolite may result in a reduction in the number of acid sites of the USY zeolite. When compared with the undealuminated Y-type zeolite, this reduction in the number of acid sites may result in a decrease in the rate of secondary reactions (such as dehydrogenation or hydrogenation of olefins produced in the FCC system 120) in the FCC system 120. Thus, the USY zeolite may produce a higher olefin yield when compared with the Y-type zeolite.

[0086] The molar ratio of silica to alumina in the USY zeolite may be greater than or equal to 5, greater than or equal to 10, greater than or equal to 25, or even greater than or equal to 50. In embodiments, the molar ratio of silica to alumina in the USY zeolite may be from 5 to 50, from 5 to 25, from 5 to 10, from 10 to 50, from 10 to 25, or from 25 to 50. In embodiments, the molar ratio of silica to alumina in the USY zeolite may be about 30. In embodiments, the USY zeolite may further comprise one or more transition metals substituted into the framework of the zeolite, such as zirconium, titanium, or hafnium.

[0087] The USY zeolite may have an average surface area of 200 m 2 / g to 900 m 2 / g. For example, the USY zeolite may have an average surface area of 200 m 2 / g to 800 m 2 / g, 300 m 2 / g to 900 m 2 / g, 300 m 2 / g to 800 m 2 / g, 300 m 2 / g to 700 m 2 / g, 300 m 2 / g to 600 m 2 / g, 300 m 2 / g to 500 m 2 / g, 350 m 2 / g to 450 m 2 / g, 500 m 2 / g to 900 m 2 / g or 500 m 2 / g to 800 m 2 / g.

[0088] The USY zeolite may have an average total pore volume per unit weight of the USY zeolite of from 0.050 mL / g to 0.600 mL / g, such as from 0.050 mL / g to 0.500 mL / g.

[0089] One or more zeolite components of the FCC catalyst composition 122 may include one or more rare earth metals or rare earth metal oxides, where the rare earth metal may be one or more of lanthanum, cerium, dysprosium, europium, gadolinium, holmium, lutetium, neodymium, praseodymium, promethium, samarium, scandium, terbium, thulium, ytterbium, yttrium, or combinations thereof. Without being bound by any particular theory, it is believed that the rare earth metal or metal oxide may enhance the stability of the unit cell of the zeolite component, increase the catalytic activity of the zeolite component, or both. Additionally, it is believed that the rare earth metal or metal oxide may act as a vanadium trap, which serves to sequester vanadium in the feed and prevent the deleterious effects that vanadium may have on the zeolite component of the catalyst. One or more zeolite components of the FCC catalyst composition 122 may include one or more rare earth metals in an amount of from 1 wt% to 5 wt% based on the total weight of each zeolite component. One or more zeolite components of the FCC catalyst composition 122 may be impregnated with lanthanum or lanthanum oxide.

[0090] One or more zeolite components of the FCC catalyst composition 122 may include one or more lanthanum-containing compounds, such as but not limited to lanthanum oxide, in an amount of from 1 wt% to 5 wt%, from 1 wt% to 4 wt%, from 1 wt% to 3 wt%, from 1 wt% to 2 wt%, from 2 wt% to 5 wt%, from 2 wt% to 4 wt%, from 2 wt% to 3 wt%, from 3 wt% to 5 wt%, from 3 wt% to 4 wt%, or from 4 wt% to 5 wt% based on the total weight of each zeolite component.

[0091] The rare earth or rare earth oxide may be impregnated on the USY zeolite of the FCC catalyst composition 122. The FCC catalyst composition 122 may comprise a USY zeolite impregnated with lanthanum oxide (La2O3). For example, the USY zeolite may include lanthanum oxide in an amount of from 1 wt% to 5 wt%, from 1 wt% to 4 wt%, from 1 wt% to 3 wt%, from 1 wt% to 2 wt%, from 2 wt% to 5 wt%, from 2 wt% to 4 wt%, from 2 wt% to 3 wt%, from 3 wt% to 5 wt%, from 3 wt% to 4 wt%, or from 4 wt% to 5 wt% based on the total weight of the USY zeolite. In some specific embodiments, the USY zeolite may comprise about 2.5 wt% of lanthanum oxide based on the total weight of the USY zeolite.

[0092] The FCC catalyst composition may include up to 40 wt% of USY zeolite based on the total weight of the FCC catalyst composition 122. For example, the FCC catalyst composition 122 may include up to 30 wt% or up to 25 wt%, 1 wt% to 40 wt%, 1 wt% to 30 wt%, 1 wt% to 25 wt%, 5 wt% to 40 wt%, 5 wt% to 30 wt%, 5 wt% to 25 wt%, 10 wt% to 40 wt%, 10 wt% to 30 wt%, 10 wt% to 25 wt%, 15 wt% to 40 wt%, 15 wt% to 30 wt% or 15 wt% to 25 wt% of lanthanum-impregnated USY zeolite based on the total weight of the FCC catalyst composition 122.

[0093] The FCC catalyst composition 122 may include one or more binder materials, such as alumina-containing compounds or silica-containing compounds (including compounds containing alumina and silica). As used in the present disclosure, "binder material" refers to a material used to "glue" or otherwise hold the components of the FCC catalyst composition 122. Binder materials may be included to improve the attrition resistance of the FCC catalyst composition 122. The binder may comprise alumina (such as amorphous alumina), silica-alumina (such as amorphous silica-alumina) or silica (such as amorphous silica). According to one or more embodiments, the binder material may comprise pseudoboehmite. As used in the present disclosure, "pseudoboehmite" refers to an aluminum-containing compound having a chemical composition of AlO(OH) and consisting of crystalline boehmite. Although boehmite generally also refers to hydroxyaluminum oxide, pseudoboehmite generally has a greater amount of water than boehmite. In an embodiment, the binder material may comprise amorphous silica. The amorphous silica may be in the form of colloidal silica. As used throughout the present disclosure, the term "colloidal silica" refers to nanoscale particles of amorphous, non-porous silica. In an embodiment, the FCC catalyst composition 122 may comprise an alumina binder, colloidal silica, or both.

[0094] The FCC catalyst composition 122 may include one or more binders in an amount of 5 wt% to 30 wt% based on the total weight of the FCC catalyst composition 122. For example, the FCC catalyst composition 122 may include one or more binders in an amount of 5 wt% to 25 wt%, 5 wt% to 20 wt%, 5 wt% to 15 wt%, 5 wt% to 10 wt%, 10 wt% to 25 wt%, 10 wt% to 20 wt%, 10 wt% to 15 wt%, 15 wt% to 30 wt%, 15 wt% to 25 wt%, 15 wt% to 20 wt%, 20 wt% to 30 wt%, 20 wt% to 25 wt% or 25 wt% to 30 wt% based on the total weight of the FCC catalyst composition 122.

[0095] The FCC catalyst composition 122 may include alumina binder in an amount of 2 wt% to 20 wt% based on the total weight of the FCC catalyst composition 122. For example, the FCC catalyst composition 122 may include alumina binder in an amount of 2 wt% to 15 wt%, 2 wt% to 10 wt%, 5 wt% to 20 wt%, 5 wt% to 15 wt%, 5 wt% to 10 wt%, or 7 wt% to 9 wt% based on the total weight of the FCC catalyst composition 122. In an embodiment, the FCC catalyst composition 122 may include alumina binder in an amount of about 8 wt% based on the total weight of the FCC catalyst composition 122.

[0096] The FCC catalyst composition 122 may include colloidal silica in an amount of 0.5 wt% to 5 wt% based on the total weight of the FCC catalyst composition 122. For example, the FCC catalyst composition 122 may include colloidal silica in an amount of 0.5 wt% to 4 wt%, 0.5 wt% to 3 wt%, 0.5 wt% to 2 wt%, 1 wt% to 4 wt%, 1 wt% to 3 wt%, 1 wt% to 2 wt%, 2 wt% to 4 wt%, or 2 wt% to 3 wt% based on the total weight of the FCC catalyst composition 122. In an embodiment, the FCC catalyst composition 122 may include colloidal silica in an amount of about 2 wt% based on the total weight of the FCC catalyst composition 122. Without wishing to be bound by any particular theory, it is believed that colloidal silica may be used as a binder and / or filler to provide additional physical strength and integrity to the FCC catalyst. Additionally, it is believed that adding colloidal silica to the FCC catalyst may improve the abrasion resistance of the FCC catalyst and / or stabilize its catalytic activity.

[0097] In an embodiment, the FCC catalyst composition 122 may include one or more matrix materials, which may include one or more clay materials, such as but not limited to kaolin. Without wishing to be bound by any particular theory, it is believed that the matrix material of the FCC catalyst composition 122 may provide both physical and catalytic functions. The physical functions may include providing particle integrity and abrasion resistance, acting as a heat transfer medium, and providing a porous structure to allow hydrocarbon diffusion into or out of the catalyst microspheres. The matrix material may also affect catalyst selectivity, product quality, and toxicity resistance. For those reactions directly involving relatively large molecules, the matrix material may tend to have its strongest influence on the overall catalytic performance.

[0098] The matrix material may include kaolin. As used herein, "kaolin" refers to a clay material having a relatively large amount (such as at least about 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, at least 90 wt% or at least 95 wt%) of kaolin, which can be represented by the chemical formula Al2Si2O5(OH)4. One or more matrix materials may comprise at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, at least 90 wt%, at least 95 wt% or even at least 99 wt% of kaolin.

[0099] The FCC catalyst composition 122 may include one or more matrix materials in an amount of 30 wt% to 60 wt% based on the total weight of each FCC catalyst composition 122. The FCC catalyst composition 122 may include 30 wt% to 70 wt%, 30 wt% to 60 wt%, 30 wt% to 50 wt%, 30 wt% to 45 wt%, 30 wt% to 40 wt%, 30 wt% to 35 wt%, 35 wt% to 60 wt%, 35 wt% to 55 wt%, 35 wt% to 50 wt%, 35 wt% to 45 wt%, 35 wt% to 40 wt%, 40 wt% to 60 wt%, 40 wt% to 55 wt%, 40 wt% to 50 wt%, 40 wt% to 45 wt%, 45 wt% to 60 wt%, 45 wt% to 55 wt%, 45 wt% to 50 wt%, 50 wt% to 60 wt%, 50 wt% to 55 wt% or 55 wt% to 60 wt% of matrix material based on the total weight of the FCC catalyst composition 122.

[0100] The FCC catalyst composition 122 may include kaolin in an amount of 30 wt% to 60 wt% based on the total weight of each FCC catalyst composition 122. For example, the FCC catalyst composition 122 may include 30 wt% to 70 wt%, 30 wt% to 60 wt%, 30 wt% to 50 wt%, 30 wt% to 45 wt%, 30 wt% to 40 wt%, 30 wt% to 35 wt%, 35 wt% to 60 wt%, 35 wt% to 55 wt%, 35 wt% to 50 wt%, 35 wt% to 45 wt%, 35 wt% to 40 wt%, 40 wt% to 60 wt%, 40 wt% to 55 wt%, 40 wt% to 50 wt%, 40 wt% to 45 wt%, 45 wt% to 60 wt%, 45 wt% to 55 wt%, 45 wt% to 50 wt%, 50 wt% to 60 wt%, 50 wt% to 55 wt% or 55 wt% to 60 wt% of kaolin based on the total weight of the FCC catalyst composition 122.

[0101] The FCC catalyst composition 122 may comprise a plurality of catalyst particles, each of the plurality of catalyst particles comprising ZSM-5 zeolite impregnated with phosphorus pentoxide, USY zeolite impregnated with lanthanum oxide, an alumina binder, kaolin, and colloidal silica.

[0102] The FCC catalyst composition 122 can be formed by various methods. According to one embodiment, a matrix material can be mixed with a fluid (such as water) to form a slurry, and the zeolite can be separately mixed with a fluid (such as water) to form a slurry. The matrix material slurry and the zeolite slurry can be combined under agitation. Additionally, by combining a binder material with a fluid (such as water), another slurry can be formed. Then, the binder slurry can be combined with the slurry containing the zeolite and the matrix material to form a final slurry. The final slurry can then be dried, for example, by spraying, and then calcined to produce the particulates of the cracking catalyst.

[0103] In an embodiment, the FCC catalyst composition 122 can be in the form of shaped particulates, such as microspheres. As used in the present disclosure, a "particulate" refers to a particle having an average particle size of from 0.1 micrometer to 100 micrometers. The size of the particulate refers to the maximum length of the particle measured along the longest distance of the particulate from one side to the other side. For example, a spherical particulate has a size equal to its diameter, or a rectangular prismatic particulate has a size equal to the maximum length of the hypotenuse extending from opposite corners. In an embodiment, each zeolite component of the FCC catalyst composition 122 can be included in each catalyst particulate. However, in other embodiments, particulates can be mixed, where the particulates contain only a portion of the FCC catalyst composition 122. For example, a mixture of two particulate types can be included in the FCC catalyst composition 122, where one particulate type includes only ZSM-5 and the other particulate type includes only USY zeolite.

[0104] The FCC catalyst composition 122 can be contacted with steam before being used in the FCC system 120. The purpose of the steam treatment can be to accelerate the hydrothermal aging of the FCC catalyst composition 122 that occurs during the operation of the FCC system 120 to obtain an equilibrium catalyst. Without intending to be bound by any particular theory, it is believed that the steam treatment can cause the removal of aluminum from the framework, thereby reducing the number of sites where framework hydrolysis can occur under hydrothermal and thermal conditions. This removal of aluminum results in an increase in the thermal stability and hydrothermal stability of the dealuminated zeolite. Since smaller SiO4 tetrahedra replace larger AlO4 -The tetrahedron, so dealumination can lead to a decrease in the unit cell size. Dealumination can also affect the acidity of zeolites by removing framework aluminum and forming additional framework aluminum species. Dealumination can affect the acidity of zeolites by reducing the total acidity and increasing the acid strength of the zeolites. The total acidity can be reduced due to the removal of framework aluminum that acts as Bronsted acid sites. The acid strength of the zeolites can be increased because paired acid sites are removed or second-coordinated sub-nearest neighbor aluminum is removed. The increase in acid strength can be attributed to the highest charge density on the proton of the OH group when there is no framework aluminum in the second coordination sphere. In an embodiment, before contacting the hydrocracking effluent 104 with the FCC catalyst composition 122 in the FCC system 120, the FCC catalyst composition 122 can be contacted with steam at a temperature of greater than or equal to 800 °C for 6 hours or a longer period.

[0105] In an embodiment, before introducing the hydrotreated effluent 104 into the FCC catalyst 122, one or more supplemental feed streams can be combined with the hydrotreated effluent 104. One or more supplemental feed streams can be added to contact the FCC catalyst 122 simultaneously with the hydrotreated effluent 104. The supplemental feed stream can include one or more of vacuum residue, tar sands, asphalt, atmospheric residue, vacuum gas oil, de-metallized oil, naphtha stream, or a combination thereof.

[0106] The hydrocarbons from the hydrocracking effluent 104 can be contacted with the FCC catalyst composition 122, which can cause at least a portion of the hydrocarbons from the hydrocracking effluent 104 to undergo one or more catalytic cracking reactions to form one or more cracked reaction products that can include one or more olefins.

[0107] As previously described, embodiments of the present disclosure include contacting the hydrotreated effluent 104 with an FCC catalyst composition 122 that includes a ZSM-5 zeolite impregnated with phosphorus, a USY zeolite impregnated with lanthanum oxide, an alumina binder, colloidal silica, and a matrix material containing kaolin. Incorporating two or more different zeolite components can increase the selectivity and yield of the FCC process to produce light olefins across the entire range of some unconventional hydrocarbon feeds (such as crude oil) used in fluid catalytic cracking processes. Compared to conventional FCC catalysts, the FCC catalyst composition 122 can be particularly suitable for catalytic cracking of crude oil under high severity reaction conditions to produce a higher olefin yield. Without being bound by any particular theory, it is believed that the different zeolite components can have sufficient activity to promote the catalytic cracking of lighter hydrocarbons and be mild enough to avoid excessive catalytic cracking (such as the continuous cracking of light olefins and light aromatic product compounds). This balanced activity provided by the mixture of zeolite components can increase the yield of products (such as light olefins) from the catalytic cracking of both light and heavy hydrocarbons present in crude oil.

[0108] Cracked effluent

[0109] The cracked effluent 126 may comprise at least 15 wt% light olefins. Light olefins refer to olefins having 2 to 4 carbon atoms. For example, the cracked effluent may comprise at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 35 wt%, at least 40 wt% or at least 43 wt% light olefins.

[0110] The cracked effluent 126 may comprise at least 2 wt% C2 olefins. For example, the cracked effluent may comprise at least 4 wt%, at least 6 wt% or at least 8 wt% C2 olefins.

[0111] The cracked effluent 126 may comprise at least 2 wt% C3 olefins. For example, the cracked effluent may comprise at least 5 wt%, at least 10 wt%, at least 15 wt% or at least 20 wt% C3 olefins.

[0112] The cracked effluent 126 may comprise at least 2 wt% C4 olefins. For example, the cracked effluent may comprise at least 5 wt%, at least 10 wt%, at least 12 wt% C4 olefins.

[0113] The cracked effluent 126 may comprise at least 5 wt% gasoline-range products. For example, the cracked effluent may comprise at least 10 wt%, at least 20 wt%, at least 25 wt% or at least 30 wt% gasoline-range products.

[0114] In addition, embodiments of the present disclosure may provide a catalyst with a reduced deactivation rate during the catalytic cracking of crude oil directly added to an FCC system. The reduction in the catalyst deactivation rate may improve the economics of catalytically cracking crude oil to form light olefins, among other characteristics.

[0115] Examples

[0116] Various aspects of the present disclosure will be further illustrated by the following examples. These examples are illustrative in nature and should not be construed as limiting the subject matter of the present disclosure.

[0117] Example 1: Hydroprocessing of Arabian heavy crude oil

[0118] In Example 1, Arabian heavy crude oil was introduced into a three-stage hydrotreating unit. The first stage was the KFR-22 hydrodemetallization catalyst commercially available from Albermarle Corp. The second stage was the KFR-33 hydrodesulfurization catalyst commercially available from Albermarle Corp. The third stage was the KFR-70 hydrodearomatization catalyst from Albermarle Corp. The crude oil was introduced at the top and flowed downward to contact the KFR-22, then the KFR-33, then the KFR-70, and then left the bottom of the reactor as the hydrotreated effluent. The reactor conditions are shown in Table 1.

[0119] The properties of the crude oil and the hydrotreated effluent are shown in Tables 2-3. As shown in the tables, the density, nitrogen, and sulfur contents were determined according to the American Society for Testing and Materials (ASTM) procedures. The Fe, Na, Ni, and V contents were determined by inductively coupled plasma according to ASTM D5185-18. It can be seen that the hydrotreating resulted in at least a 99.7% reduction in sulfur concentration and a 96.9% reduction in nitrogen concentration. This further resulted in at least a 93% reduction in Ni and a 98% reduction in vanadium.

[0120] Arabian heavy crude oil has an IBP of 102 °C, an FBP greater than 720 °C, a paraffin content of 22 wt%, a naphthene content of 10.5 wt%, an aromatic content of 45.3 wt%, and a polyaromatic content of 22.1 wt%.

[0121] Both Arabian heavy crude oil and the hydrotreated effluent were subjected to simulated distillation according to ASTM D-7169. The results are given in Table 3.

[0122] Table 1

[0123] Temperature (°C) 400 Pressure (bar) 150 <![CDATA[Liquid hourly space velocity (h -1 )]]> 0.30 Oil flow rate ml / h 45 <![CDATA[H2 flow rate (L / h)]]> 54

[0124] Table 2

[0125] Arabian heavy crude oil Hydroprocessed effluent Test method Density @ 15.6 °C <![CDATA[0.8920g / cm 3 > 0.8416 ASTM D - 4052 N 1952 ppm 59.6 ppm ASTM D - 4629 S 2.68 wt% 0.008 wt% ASTM D - 4294 Fe <10 ppm < 1 ppm IP 501 Na 1 ppm <1 ppm IP 501 Ni 16 ppm < 1 ppm IP 501 V 51 ppm <1 ppm IP 501

[0126] Table 3

[0127]

[0128] Example 2: Preparation of FCC catalyst composition

[0129] In Example 2, an FCC catalyst composition according to the present disclosure was prepared. The materials used in preparing the FCC catalyst composition of Example 1 are provided in Table 4 below.

[0130] Table 4

[0131]

[0132] To prepare the FCC catalyst composition of Example 2, ZSM-5 zeolite (CBV-3024-E commercially available from Zeolyst International) was impregnated with 7.5 wt% of phosphorus pentoxide, and USY zeolite (CBV-780 commercially available from Zeolyst International) was impregnated with 2.5 wt% of lanthanum oxide. The ZSM-5 zeolite had an average silica-alumina ratio of 30 and had an average surface area of 405 m 2 / g. The USY zeolite had an average total pore volume per unit weight of 0.486 cm 3 / g. The ZSM-5 zeolite impregnated with phosphorus pentoxide and the USY zeolite impregnated with lanthanum oxide were combined with water, alumina binder, colloidal silica, and kaolin to produce a mixture. The mixture was stirred for 1 hour, and the resulting slurry was placed in a programmed oven for drying and calcination to produce FCC catalyst composition particles. The FCC catalyst composition particles were ground into a fine powder using a mortar and pestle. Then, the ground FCC catalyst composition microparticles were sieved to obtain the fraction between 40 - 120 micrometers (μm) and used for characterization and evaluation. The composition of the FCC catalyst composition microparticles of Example 2 is provided in Table 4.

[0133] Table 4

[0134] Component wt% Notes ZSM - 5 20 <![CDATA[Phosphorus is impregnated on zeolite at 7.5 wt% P2O5]]> USY 21 <![CDATA[Lanthanum is impregnated on zeolite with 2.5 wt% La2O3]]> Alumina 8 Pural SB from Sasol Clay 49 Kaolin Silica 2 Ludox TM - 40 added as colloidal silica

[0135] Example 3: FCC of the hydroprocessed effluent of Example 1

[0136] In Example 3, the performance of the FCC catalyst composition of Example 2 for cracking the hydrotreated effluent produced from hydrotreated Arabian heavy crude oil in Example 1 was evaluated. The properties of the Arabian heavy crude oil used in the example are shown in Table 2 - 3 as before. Catalytic cracking was carried out using the FCC catalyst composition of Example 2 in a quartz tube reactor in a Sakuragi Rikagaku (Japan) Micro Activity Test (MAT) instrument. The FCC catalyst composition of Example 2 for cracking the hydrotreated effluent of Example 1 was evaluated according to the standard test method ASTM D-3907. Before the evaluation, the FCC catalyst composition was steamed at 810 °C for 6 hours and then subjected to the cracking reaction. The experiment was carried out in the MAT unit with a run time (TOS) of 30 seconds. The cracking reaction was carried out at a temperature of 650 °C and at a catalyst-oil weight ratio of about 5.

[0137] After each reaction, the FCC catalyst composition particles were stripped with nitrogen (N2) at a flow rate of 30 milliliters per minute (mL / min). The liquid product was collected in a liquid receiver, and the gaseous product was collected in a gas burette by water displacement and sent to a gas chromatograph (GC) for analysis. The used catalyst was used to measure the amount of coke produced from the reaction.

[0138] The MAT results of the hydrotreated effluent of Example 1 cracked over the FCC catalyst composition of Example 2 are shown in Table 5. It can be seen that a high light olefin yield of greater than 42 wt% was obtained using the FCC catalyst composition of Example 2.

[0139] Table 5

[0140]

[0141]

[0142] Comparative Example 1

[0143] The Arabian heavy crude oil of Example 1 was used and a comparative example was carried out according to the method of Example 3. The comparative example did not undergo hydrotreatment. The FCC cracking results of the comparative example are given in Table 6.

[0144] Table 6

[0145]

[0146]

[0147] Compared with cracking the hydrotreated Arabian heavy crude oil in Example 1, the comparative example showed a lower yield of light olefins from cracking the Arabian heavy crude oil (untreated). It is shown here that hydrotreatment improves the reactivity of the crude oil by converting chemically inert polyaromatics into reactive alkanes and cycloalkanes.

[0148] Example 4: Evaluation of contaminants on equilibrium catalyst

[0149] In Example 4, the deactivation rates of the FCC catalyst compositions of Example 3 and Comparative Example 1 were evaluated. Industrially, FCC catalyst deactivation is evaluated based on the nickel (Ni) and vanadium (V) contents accumulated on the equilibrium catalyst (E-Cat). After the catalyst has been continuously circulated between the regenerator and the FCC reactor for several days, it can be considered an E-Cat. The deactivation of FCC catalysts is mainly promoted by two factors, namely steam and feed contaminants. Industrially, the deactivation of FCC catalysts is evaluated by taking E-Cat samples from the FCC system and analyzing the Ni and V contents of the samples. In Example 3 and Comparative Example 1, the FCC catalyst compositions were delivered once through the MAT unit and may not fully represent industrial E-Cat. Optionally, the FCC catalyst composition of Example 1 was steam deactivated at 810 °C for 6 hours and can thus be considered representative of industrial E-Cat.

[0150] In addition to steam deactivating the catalyst, equations established in the literature based on the metal balance around the unit (metal 入 - metal 出 = accumulated metal) were used to estimate how much Ni and V would accumulate on the FCC catalyst composition of Example 1 at equilibrium. For example, the Fluid Catalytic Cracking Handbook, 4th Edition, Sadeghbeigi (2020) provides equations for estimating Ni and V accumulation on FCC catalysts. These equations estimate the Ni and V contents on the E-Cat based on the levels of Ni and V in the feed (AL crude oil in these examples) and the daily catalyst addition rate. The first-order differential equation (Equation 1) with the solution C a M e is as follows:

[0151]

[0152] Where:

[0153] Me = E-cat metal content, parts per million by weight (ppmw);

[0154] A = (W × M f ) / Ca;

[0155] W = feed rate, pounds per day (lb / day);

[0156] M f = feed metal, ppmw;

[0157] C a = catalyst addition rate, lb / day;

[0158] M0 = initial metal on the E-cat, ppmw;

[0159] T = time, days;

[0160] I = catalyst inventory, pounds (lb.); and

[0161] B = catalyst addition rate, pounds of catalyst per barrel of feed, where one barrel equals 42 U.S. gallons.

[0162] At steady state, the concentration of any metal on the catalyst is approximated using the following equation (Equation 2):

[0163] M e = (141.5 / (131.5 + °API 进料 ) × 350.4 × M f ) / B (Equation 2);

[0164] where °API 进料 = American Petroleum Institute gravity of the feed, degrees.

[0165] The feed rate of the crude oil is 76,500 barrels per day. After implementing the above equation, it was found that when using the method of Comparative Example 1, a feed of 85 tons per day of fresh catalyst was required to maintain the deactivation limit of Ni+V below 10,000 ppm in the calculated FCC catalyst composition. Using the method of Example 3 and the same feed rate, only 30 tons per day of fresh catalyst was required to achieve an equilibrium Ni+V of less than 2000 ppm. It is believed that this is because the feed of the FCC in Comparative Example 1 had a Ni+V content of 67 ppm, while the feed of the FCC in Example 3 had a Ni+V content of less than 2 ppm after hydrotreating.

[0166] Aspect

[0167] According to a first aspect of the present disclosure, a method for converting crude oil comprises contacting the crude oil with hydrogen and one or more hydrotreating catalysts to produce a hydrotreated effluent, wherein the crude oil has an API gravity of 25 to 29; and contacting the hydrotreated effluent with a fluid catalytic cracking (FCC) catalyst composition in an FCC system to produce a cracked effluent comprising at least olefins, wherein the FCC system is operated at a temperature greater than or equal to 580 °C, the weight ratio of the FCC catalyst composition to the crude oil is 2:1 to 10:1, and the residence time is 0.1 second to 60 seconds, and wherein the FCC catalyst composition comprises: ultrastable Y zeolite (USY zeolite) impregnated with lanthanum; ZSM-5 zeolite impregnated with phosphorus; an alumina binder; colloidal silica; and a matrix material comprising kaolin.

[0168] According to a second aspect of the present disclosure, alone or in combination with any of the foregoing aspects, one or more hydrotreating catalysts comprise one or more of a hydrodemetallization catalyst, a hydrodesulfurization catalyst, or a hydrodearomatization catalyst.

[0169] According to a third aspect of the present disclosure, alone or in combination with any of the foregoing aspects, one or more hydrotreating catalysts comprise a hydrodemetallization catalyst, a hydrodesulfurization catalyst, and a hydrodearomatization catalyst.

[0170] According to a fourth aspect of the present disclosure, alone or in combination with any of the foregoing aspects, the FCC catalyst composition comprises 10 wt% to 30 wt% of USY zeolite impregnated with lanthanum.

[0171] According to a fifth aspect of the present invention, alone or in combination with any of the foregoing aspects, the FCC catalyst composition comprises 10 wt% to 40 wt% of ZSM-5 zeolite impregnated with phosphorus.

[0172] According to a sixth aspect of the present disclosure, alone or in combination with any of the foregoing aspects, the USY zeolite is impregnated with 1 wt% to 5 wt% of lanthanum oxide based on the total weight of the USY zeolite.

[0173] According to a seventh aspect of the present disclosure, alone or in combination with any of the foregoing aspects, the ZSM-5 zeolite is impregnated with 1 wt% to 15 wt% of phosphorus pentoxide based on the total weight of the ZSM-5 zeolite.

[0174] According to an eighth aspect of the present invention, the FCC catalyst composition comprises 19 wt% to 23 wt% of USY zeolite impregnated with lanthanum, 18 wt% to 22 wt% of ZSM-5 zeolite impregnated with phosphorus, 6 wt% to 10 wt% of an alumina binder, 47 wt% to 51 wt% of kaolin, and 0.1 wt% to 4 wt% of colloidal silica, wherein the weight percentages are based on the total weight of the FCC catalyst composition.

[0175] According to a ninth aspect of the present disclosure, alone or in combination with any of the foregoing aspects, the crude oil has a density greater than 0.8 grams per milliliter at 15 degrees Celsius.

[0176] According to a tenth aspect of the present disclosure, alone or in combination with any of the foregoing aspects, the crude oil has an initial boiling point of 30 degrees Celsius to 50 degrees Celsius and a final boiling point greater than 720 degrees Celsius.

[0177] According to an eleventh aspect of the present disclosure, alone or in combination with any of the foregoing aspects, at least 50 wt% of the crude oil has a boiling point temperature greater than or equal to 300 degrees Celsius.

[0178] According to a twelfth aspect of the present disclosure, alone or in combination with any of the foregoing aspects, the crude oil has a concentration of paraffinic compounds less than 50 wt% per unit weight of the crude oil.

[0179] According to a thirteenth aspect of the present disclosure, alone or in combination with any of the foregoing aspects, the crude oil has a concentration of aromatic compounds of greater than or equal to 20% by weight per unit weight of the crude oil.

[0180] According to a fourteenth aspect of the present disclosure, alone or in combination with any of the foregoing aspects, the crude oil is Arabian heavy crude oil.

[0181] According to a fifteenth aspect of the present disclosure, alone or in combination with any of the foregoing aspects, the hydrotreated effluent is contacted with an FCC catalyst composition at a temperature of 600 °C to 700 °C.

[0182] According to a sixteenth aspect of the present disclosure, alone or in combination with any of the foregoing aspects, the hydrotreated effluent is contacted with an FCC catalyst composition for a residence time of 20 seconds to 40 seconds.

[0183] According to a seventeenth aspect of the present disclosure, alone or in combination with any of the foregoing aspects, the FCC system is a downflow FCC system.

[0184] According to an eighteenth aspect of the present disclosure, alone or in combination with any of the foregoing aspects, the crude oil is contacted with one or more hydrotreating catalysts 112 at a temperature of at least 350 °C.

[0185] According to a nineteenth aspect of the present disclosure, alone or in combination with any of the foregoing aspects, the crude oil has an API gravity of 27 to 28.

[0186] According to a twentieth aspect of the present disclosure, alone or in combination with any of the foregoing aspects, one or more hydrotreating catalysts 112 comprise a hydrodemetallization catalyst, a hydrodesulfurization catalyst, and a hydrodearomatization catalyst; and the FCC catalyst composition comprises a plurality of catalyst particles, wherein each of the plurality of catalyst particles comprises ZSM-5 zeolite impregnated with phosphorus, USY zeolite impregnated with lanthanum, an alumina binder, kaolin, and colloidal silica.

[0187] It should be noted that any two quantitative values assigned to a property may constitute a range of that property, and all combinations of ranges formed by all the said quantitative values of a given property are contemplated in the present disclosure.

[0188] It should be noted that one or more of the appended claims use the term "wherein" as a transitional phrase. For the purposes of defining the present technology, it should be noted that this term is introduced in the claims as an open transitional phrase for introducing a listing of a series of features of a structure and should be interpreted in a manner similar to the more common open preamble term "comprising".

[0189] After the subject matter of the present disclosure has been described in detail and with reference to specific aspects, it should be noted that the various details of these aspects should not be taken as implying that these details are essential components of these aspects. Rather, the appended claims should be regarded as the sole 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 obvious that modifications and variations can be made without departing from the scope of the appended claims.

Claims

1. A method for converting crude oil, comprising: Contacting crude oil with hydrogen and one or more hydrotreating catalysts to produce a hydrotreated effluent, wherein, The crude oil has an API gravity of 25 to 29; And Contacting the hydrotreated effluent with a fluid catalytic cracking (FCC) catalyst composition in an FCC system to produce a cracked effluent containing at least olefins, wherein the FCC system is operated at a temperature of greater than or equal to 580 °C, the weight ratio of the FCC catalyst composition to the crude oil is 2:1 to 10:1, and the residence time is 0.1 second to 60 seconds, and Wherein the FCC catalyst composition comprises: Ultra-stable Y zeolite (USY zeolite) impregnated with lanthanum; ZSM-5 zeolite impregnated with phosphorus; Alumina binder; Colloidal silica; and A matrix material containing kaolin.

2. The method according to claim 1, wherein The one or more hydrotreating catalysts comprise one or more of a hydrodemetallization catalyst, a hydrodesulfurization catalyst, or a hydrodearomatization catalyst.

3. The method according to claim 1, wherein The one or more hydrotreating catalysts comprise a hydrodemetallization catalyst, a hydrodesulfurization catalyst, and a hydrodearomatization catalyst.

4. The method according to claim 1, wherein Contacting the crude oil with the one or more hydrotreating catalysts at a temperature of at least 350 °C.

5. The method according to claim 1, wherein: The FCC catalyst composition comprises 10 wt% to 30 wt% of USY zeolite impregnated with lanthanum; The USY zeolite is impregnated with 1 wt% to 5 wt% of lanthanum oxide based on the total weight of the USY zeolite; The FCC catalyst composition comprises 10 wt% to 40 wt% of ZSM-5 zeolite impregnated with phosphorus; And The ZSM-5 zeolite is impregnated with 1 wt% to 15 wt% of phosphorus pentoxide based on the total weight of the ZSM-5 zeolite.

6. The method according to claim 1, wherein The FCC catalyst composition comprises 19 wt% to 23 wt% of the USY zeolite impregnated with lanthanum, 18 wt% to 22 wt% of the ZSM-5 zeolite impregnated with phosphorus, 6 wt% to 10 wt% of the alumina binder, 47 wt% to 51 wt% of the kaolin, and 0.1 wt% to 4 wt% of the colloidal silica, wherein the weight percentages are based on the total weight of the FCC catalyst composition.

7. The method according to claim 1, wherein The FCC system is a downflow FCC system.

8. The method according to claim 1, wherein Contacting the hydrotreated effluent with the FCC catalyst composition at a temperature of 600 °C to 700 °C, and contacting the hydrotreated effluent with the FCC catalyst composition for a residence time of 0.1 second to 60 seconds.

9. The method according to any one of claims 1 to 8, wherein The crude oil is Arabian heavy crude oil.

10. The method according to any one of claims 1 to 8, wherein The API gravity of the crude oil is 27 to 28.

11. The method according to any one of claims 1 to 8, wherein, The crude oil has a density greater than 0.8 g / ml at 15 degrees Celsius.

12. The method according to any one of claims 1 to 8, wherein The crude oil has an initial boiling point of 30 °C to 50 °C and a final boiling point greater than 720 °C.

13. The method according to any one of claims 1 to 8, wherein, At least 50 wt% of the crude oil has a boiling point temperature greater than or equal to 300 °C.

14. The method according to any one of claims 1 to 8, wherein, The crude oil has a concentration of paraffinic compounds less than 50 wt% per unit weight of the crude oil.

15. The method according to any one of claims 1 to 8, wherein The crude oil has a concentration of aromatic compounds greater than or equal to 20 wt% per unit weight of the crude oil.

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