PROCESS FOR DIRECT CONVERSION OF CRUDE OILS TO GASOLINE

Description

BACKGROUND

Field

The present disclosure relates to processes for converting crude oils, in particular, processes for directly converting crude oils through fluidized catalytic cracking to produce gasoline.

Technical Background

Fluid Catalytic Cracking (FCC) has been the conventional process in refineries for transforming lower value feeds into gasoline. Typical hydrocarbon feeds for fluid catalytic cracking processes range from hydrocracked bottoms to heavy feed fractions such as vacuum gas oil and atmospheric residue; however, these hydrocarbon feeds are limited, at least in part, due to limitations of conventional catalysts used in fluid catalytic cracking processes. Moreover, these feeds are limited and must be obtained through costly and energy intensive refining steps. While crude oil may be a potential feedstock, the concentrations of metal, nitrogen, and sulfur in crude oil contributes to deactivation of the FCC catalysts. Further, it is extremely difficult to efficiently crack a feedstock with a wide boiling point range, such as crude oil, over a single FCC catalyst.

SUMMARY

Accordingly, there is an ongoing need for processes for converting crude oils directly to gasoline. The processes of the present disclosure include the direct processing of crude oils in a fluid catalytic cracking unit with an FCC catalyst composition to produce gasoline. In particular, the methods of the present disclosure include contacting the crude oils with an FCC catalyst composition that comprises a ZSM-5 zeolite and an ultrastable Y-type zeolite at reaction temperatures less than 580° C. In particular, the FCC catalyst composition comprises ultrastable Y-type zeolite (USY zeolite) impregnated with lanthanum, ZSM-5 zeolite impregnated with phosphorous, an alumina binder, colloidal silica, and a matrix material comprising Kaolin clay. The inclusion of the different zeolite components in the FCC catalyst composition in combination with the contacting temperature being less than 580° C., such as from 500° C. to 580° C., may increase the selectivity and yield of gasoline from the crude oil. Further, the FCC catalyst composition may demonstrate a reduced deactivation rate, which may improve the economics of gasoline production, among other features.

According to at least one aspect of the present disclosure, a process for converting crude oil to gasoline may comprise contacting a crude oil feed with a fluidized catalytic cracking (FCC) catalyst composition in a cracking reaction zone of an FCC unit at a temperature of from 500° C. to 580° C., a catalyst-to-oil weight ratio of from 2 to 40, and a contact time of from 0.1 seconds to 60 seconds. The FCC catalyst composition may comprise ultrastable Y-type zeolite (USY zeolite) impregnated with lanthanum, ZSM-5 zeolite impregnated with phosphorous, an alumina binder, colloidal silica, and a matrix material comprising Kaolin clay. The crude oil feed may be a light crude oil, an extra light crude oil, or combination thereof, and may have an API gravity of from 33 degrees to 45 degrees and a density of from 0.80 g/cm³ to 0.87 g/cm³. The contacting may cause at least a portion of hydrocarbons in the crude oil feed to undergo cracking reactions to produce an FCC effluent comprising gasoline.

Additional features and advantages of the aspects of the present disclosure will be set forth in the detailed description that follows and, in part, will be readily apparent to a person of ordinary skill in the art from the detailed description or recognized by practicing the aspects of the present disclosure.

BRIEF DESCRIPTION OF THE DRAWING

The following detailed description of the present disclosure may be better understood when read in conjunction with the following drawing in which:

FIG. 1 schematically depicts a generalized flow diagram of a fluidized catalytic cracking (FCC) system for directly converting crude oil to gasoline, according to aspects of the present disclosure; and

FIG. 2 schematically depicts a micro activity test (MAT) unit including a fixed bed quartz tubular reactor configured to simulate a reaction in a fixed bed reactor, according to aspects of the present disclosure.

For the purpose of describing the simplified schematic illustrations and descriptions of FIGS. 1-2, some of the numerous valves, temperature sensors, electronic controllers, and the like that may be employed and well known to those of ordinary skill in the art of certain chemical processing operations are not included. Further, accompanying components that are often included in chemical processing operations, such as, for example, air supplies, heat exchangers, surge tanks, catalyst hoppers, or other related systems are not depicted. It would be known that these components are within the spirit and scope of the present embodiments disclosed. However, operational components, such as those described in the present disclosure, may be added to the embodiments described in this disclosure.

It should further be noted that arrows in the drawings refer to process streams. However, the arrows may equivalently refer to transfer lines that may serve to transfer process streams between two or more system components. Additionally, arrows that connect to system components define inlets or outlets in each given system component. The arrow direction corresponds generally with the major direction of movement of the materials of the stream contained within the physical transfer line signified by the arrow. Furthermore, arrows that do not connect two or more system components signify a product stream which exits the depicted system or a system inlet stream which enters the depicted system. Product streams may be further processed in accompanying chemical processing systems or may be commercialized as end products. System inlet streams may be streams transferred from accompanying chemical processing systems or may be non-processed feedstock streams. Some arrows may represent recycle streams, which are effluent streams of system components that are recycled back into the system. However, it should be understood that any represented recycle stream, in some embodiments, may be replaced by a system inlet stream of the same material, and that a portion of a recycle stream may exit the system as a system product.

Additionally, arrows in the drawings may schematically depict process steps of transporting a stream from one system component to another system component. For example, an arrow from one system component pointing to another system component may represent “passing” a system component effluent to another system component, which may include the contents of a process stream “exiting” or being “removed” from the one system component and “introducing” the contents of that process stream to the other system component.

It should be understood that two or more process streams are “mixed” or “combined” when two or more lines intersect in the schematic flow diagrams of FIGS. 1 and 2. Mixing or combining may also include mixing by directly introducing both streams into a like reactor, separation device, or other system component. For example, it should be understood that when two streams are depicted as being combined directly prior to entering a separator or reactor, that in some embodiments, the streams could equivalently be introduced into the separator or reactor and be mixed in the reactor.

DETAILED DESCRIPTION

Reference will now be made in greater detail to various embodiments of the present disclosure, some of which are illustrated in the accompanying drawings. Whenever possible, the same reference numerals will be used throughout the drawings to refer to the same or similar parts. The present disclosure is directed to processes for directly converting crude oil through fluidized catalytic cracking to produce gasoline. Referring to FIG. 1, the processes of the present disclosure for converting crude oil to gasoline include contacting a crude oil feed 102 with a fluidized catalytic cracking (FCC) catalyst composition 114 in a cracking reaction zone 112 of an FCC unit 110 at a temperature of from 500° C. to 580° C., a catalyst-to-oil weight ratio of from 2 to 40, and a contact time of from 0.1 seconds to 60 seconds. The FCC catalyst composition 114 comprises ultrastable Y-type zeolite (USY zeolite) impregnated with lanthanum, ZSM-5 zeolite impregnated with phosphorous, an alumina binder, colloidal silica, and a matrix material comprising Kaolin clay. The crude oil feed 102 is a light crude oil, an extra light crude oil, or combination thereof, and has an API gravity of from 33 degrees to 45 degrees and a density of from 0.80 g/cm³ to 0.87 g/cm³. The contacting causes at least a portion of hydrocarbons in the crude oil feed 102 to undergo cracking reactions to produce an FCC effluent 116 comprising gasoline.

The FCC catalyst compositions and processes of the present disclosure can enable direct fluidized catalytic cracking of crude oils, such as light crude oil, extra light crude oil, or combinations thereof, to produce gasoline. The FCC catalyst compositions of the present disclosure in combination with reduced cracking temperatures of less than 580° C. can enable efficient cracking of crude oil feed streams while at the same time exhibiting a reduced rate of deactivation of the FCC catalyst composition due to contaminants and coke formation, among other features.

As used in this disclosure, the term “cracking” refers to a chemical reaction where a molecule having carbon-carbon bonds is broken into more than one molecule by the breaking of one or more of the carbon-carbon bonds; where one or more cyclic moieties in a compound, such as one or more aromatic rings or cycloalkyl groups, are converted to non-cyclic moieties; or where a molecule having carbon-carbon double bonds are reduced to carbon-carbon single bonds. As used in the present disclosure, the term “catalytic cracking” refers to cracking conducted in the presence of a catalyst.

As used in this disclosure, the term “catalyst” refers to any substance that increases the rate of a specific chemical reaction, such as cracking reactions.

As used in this disclosure, the term “used catalyst” refers to catalyst that has been contacted with reactants at reaction conditions, but has not been regenerated in a regenerator or through a regeneration process. The “used catalyst” may have coke deposited on the catalyst and may include partially coked catalyst as well as fully coked catalysts. The amount of coke deposited on the “used catalyst” may be greater than the amount of coke remaining on the regenerated catalyst following regeneration. The “used catalyst” may also include catalyst that has a reduced temperature due to contact with the reactants compared to the catalyst prior to contact with the reactants.

As used in this disclosure, the term “regenerated catalyst” refers to catalyst that has been contacted with reactants at reaction conditions and then regenerated in a regenerator or through a regeneration process to heat the catalyst to a greater temperature, oxidize and remove at least a portion of the coke from the catalyst to restore at least a portion of the catalytic activity of the catalyst, or both.

As used in this disclosure, the term “deactivated catalyst” refers to a catalyst that has lost function permanently and differs from used catalyst, in that the deactivated catalyst is generally not capable of being regenerated in the regenerator during steady state operation of the regeneration system. The deactivated catalyst can be deactivated by contaminants and/or metals in the crude oil feed or through other means.

As used in this 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, extracted directly from a subterranean formation or received from a desalting unit without having any fractions, such as naphtha, separated by distillation. A “topped crude oil” refers to a crude oil from which a portion of light hydrocarbons (hydrocarbons having a low boiling point temperature less than a threshold temperature) have been removed through a topping process.

As used in this disclosure, the terms “gasoline” and “FCC gasoline” both refer to a mixture of hydrocarbons having atmospheric boiling point temperatures in a range of from C₅ to 221° C. (i.e., from about 20° C. to 221° C.). The gasoline or FCC gasoline may comprise paraffinic, naphthenic, and aromatic hydrocarbons having from 5 carbon atoms to 12 carbon atoms.

As used in this disclosure, the terms “light cycle oil” and “LCO” both refer to a mixture of hydrocarbons having atmospheric boiling point temperatures of from 221° C. to 343° C.

As used in the present disclosure, the terms “heavy cycle oil” and “HCO” both refer to a mixture of hydrocarbons having atmospheric boiling point temperatures of greater than 343° C.

As used in this disclosure, the term “light olefins” refers to olefins having from 2 to 4 carbon atoms, where the term “olefins” has its normal meaning as understood by a person of ordinary skill in art of chemistry.

As used in this disclosure, the terms “butenes” and “mixed butenes” refers to 1-butene, cis-2-butene, trans-2-butene, isobutene, and combinations of these. As used in this disclosure, the term “normal butenes” refers to 1-butene, cis-2-butene, trans-2-butene, or any combination thereof, but not including isobutene.

As used in this disclosure, the terms “boiling point temperature”, or “boiling temperature”, or “boiling point” all refer to the temperature at which a compound or composition boils at atmospheric pressure, unless otherwise stated.

As used in this disclosure, the terms “initial boiling point” and “IBP” of a composition are defined in accordance with standard test method ASTM D2887, the entire contents of which are incorporated by reference into the present disclosure.

As used in this disclosure, the terms “final boiling point” and “FBP” of a composition are defined in accordance with standard test method ASTM D2887.

As used in this disclosure, passing a stream or effluent from one unit “directly” to another unit refers to passing the stream or effluent from the first unit to the second unit without passing the stream or effluent through any intervening reaction system or separation system that substantially changes the composition of the stream or effluent. Heat transfer devices, such as heat exchangers, preheaters, coolers, or other heat transfer equipment, and pressure devices, such as pumps, pressure regulators, compressors, or other pressure devices, are not considered to be intervening systems that change the composition of a stream or effluent, unless otherwise specifically stated in the present disclosure. Combining two streams or effluents together upstream of a process unit also is not considered to be an intervening system that changes the composition of one or both of the streams or effluents being combined. Simply dividing a stream into two streams having the same composition is also not considered to be an intervening system that changes the composition of the stream.

As used in this disclosure, the terms “upstream” and “downstream” refer to the relative positioning of unit operations with respect to the direction of flow of the process streams through the system. A first unit operation of a system is considered “upstream” of a second unit operation if process streams flowing through the system encounter the first unit operation before encountering the second unit operation. Likewise, a second unit operation is considered “downstream” of the first unit operation if the process streams flowing through the system encounter the first unit operation before encountering the second unit operation.

As used in this disclosure, the term “effluent” refers to a stream that is passed out of a reactor, a reaction zone, or a separator following a particular reaction or separation process. Generally, an effluent has a different composition than the stream that entered the separator, reactor, or reaction zone. It should be understood that when an effluent is passed to another system unit, only a portion of that effluent may be passed. For example, a slip stream (having the same composition) may carry some of the effluent away, meaning that only a portion of the effluent may enter the downstream system unit. The terms “reaction effluent” or “reactor effluent” are more particularly used to refer to streams that are passed out of a reactor or reaction zone.

As used in this disclosure, the term “high-severity conditions” refers to operating conditions of a fluid catalytic cracking system that include temperatures greater than or equal to 580° C., such as from 580° C. to 800° C., a catalyst to oil ratio greater than or equal to 1:1, or from 1:1 to 60:1, and a residence time of less than or equal to 60 seconds, or from 0.1 seconds to 60 seconds, each of which conditions may be more severe than typical operating conditions of fluid catalytic cracking systems.

As used in this disclosure, the terms “catalyst-to-oil ratio” and “CTO weight ratio” refer to the weight ratio of a catalyst to hydrocarbons in a reactor, such as in the cracking reaction zone 112 of the FCC unit 110 of the present disclosure. The catalyst-to-oil ratio of the present disclosure is calculated by dividing the mass flow rate of the FCC catalyst composition introduced to the cracking reaction zone 112 by the mass flow rate of the hydrocarbons introduced to the cracking reaction zone 112, the hydrocarbons being the crude oil feed 102.

As used in this disclosure, the term “contact time” refers to the amount of time that reactants, such as the hydrocarbons of the crude oil feed, are in contact with the FCC catalyst composition, at reaction conditions, such as at the reaction temperature.

As used in this disclosure, the term “reactor” refers to any vessel, container, conduit, or the like, 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 can include one or a plurality of “reaction zones” disposed within the reactor. The term “reaction zone” refers to a region in a reactor where a particular reaction takes place.

As used in this disclosure, the term “separation unit” refers to any separation device that at least partially separates one or more chemicals in a mixture from one another. For example, a separation unit may selectively separate different chemical species from one another, forming one or more chemical fractions. Examples of separation units include, without limitation, distillation columns, cryogenic distillation units, fractionators, flash drums, knock-out drums, knock-out pots, centrifuges, filtration devices, traps, scrubbers, expansion devices, membranes, solvent extraction devices, pressure swing adsorption units, high-pressure separators, low-pressure separators, fluid-solid separators, and the like. It should be understood that separation processes described in this disclosure may not completely separate all of one chemical consistent from all of another chemical constituent. It should be understood that the separation processes described in this disclosure “at least partially” separate different chemical components from one another, and that even if not explicitly stated, it should be understood that separation may include only partial separation. As used in this disclosure, one or more chemical constituents may be “separated” from a process stream to form a new process stream. Generally, a process stream may enter a separation unit and be divided or separated into two or more process streams of desired composition.

It should further be understood that streams may be named for the components of the stream, and the component for which the stream is named may be the major component of the stream (such as comprising from 50 weight percent (wt. %), from 70 wt. %, from 90 wt. %, from 95 wt. %, from 99 wt. %, from 99.5 wt. %, or even from 99.9 wt. % of the contents of the stream to 100 wt. % of the contents of the stream, notwithstanding any inert gases or diluents added to the stream). It should also be understood that components of a stream are disclosed as passing from one system component to another when a stream comprising that component is disclosed as passing from that system component to another system component. For example, a disclosed “gasoline stream” passing to a first system component or from a first system component to a second system component should be understood to equivalently disclose the “gasoline” itself passing to the first system component or passing from a first system component to a second system component.

The composition of feed streams and processing variables of FCC systems play a significant role on the reaction yields and heat balance within the FCC systems. Conventional FCC systems and processes can require costly refining to produce suitable feed streams. Such additional costly refining can include separating and processing of one or more fractions of a hydrocarbon feedstock before introducing the refined conventional feed into the FCC system. These additional processing steps are energy intensive and reduce the amount of viable feed from an existing hydrocarbon source. Previous systems and methods have been developed to convert crude oil to greater value chemical products and intermediates directly through catalytic cracking to attempt to overcome these limitations, such as by reducing or eliminating the processing steps needed to produce a suitable hydrocarbon feed before introduction into an FCC system. However, contaminants, metals, or both, which are often present in heavy hydrocarbon feeds such as crude oils, can deactivate the catalyst, resulting in decreased yields and increased production costs.

Accordingly, aspects of the present disclosure are directed to FCC catalyst compositions and processes for converting crude oil directly to gasoline through FCC systems using the FCC catalyst compositions in combination with reaction conditions that result in efficient cracking of the crude oil to gasoline, while resisting deactivation of the catalyst. The FCC catalyst composition of the present disclosure includes a ZSM-5 zeolite, an ultrastable Y-type zeolite, an alumina binder, a matrix material comprising Kaolin clay, and colloidal silica. The processes of the present disclosure include contacting a crude oil feed with the FCC catalyst composition in a FCC catalytic cracking system at conditions suitable for converting at least a portion of the crude oil feed to gasoline, such as a cracking temperature less than 580° C., such as from 500° C. to 580° C. The FCC catalyst compositions and reaction conditions of the processes of the present disclosure can enable the crude oil to be directly converted to gasoline efficiently while resisting deactivation, among other features.

Referring now to FIG. 1, the FCC system 100 of the present disclosure for processing a crude oil feed 102 to produce gasoline is schematically depicted. The FCC system 100 may include an FCC unit 110 and a regenerator 140. The FCC unit 110 contacts the crude oil feed 102 with the FCC catalyst composition 112 to produce a used FCC catalyst 115 and an FCC effluent 116. The regenerator 140 processes the used FCC catalyst 115 to produce a regenerated FCC catalyst 148, which can be recycled back to the FCC unit 110.

The crude oil feed 102 can include one or more types of crude oil, such as but not limited to an Arab light (AL) crude oil, an Arab extra light (AXL) crude oil, or combinations thereof. In embodiments, the crude oil feed 102 may comprise, consist of, or consist essentially of a whole crude oil or a crude oil that has undergone at least some processing, such as desalting, solids separation, scrubbing, or combinations of these, but has not been subjected to separation through distillation. For instance, the crude oil feed 102 can be a de-salted crude oil that has been subjected to a de-salting process. In embodiments, the crude oil feed 102 can include a crude oil that has not undergone pretreatment, separation (such as distillation), or other operation that changes the hydrocarbon composition of the crude oil prior to introducing the crude oil feed 102 to the FCC system 100. As used herein, the “hydrocarbon composition” of the crude oil refers to the composition of the hydrocarbon constituents of the crude oil and does not include entrained non-hydrocarbon solids, salts, water, or other non-hydrocarbon-containing constituents.

In embodiments, the crude oil feed 102 may be a light crude oil, an extra light crude oil, or a combination thereof. Light crude oils include, but are not limited to, Arab light (AL) crude oil. Extra light crude oils include, but are not limited to, Arab extra light (AXL) crude oil. The crude oil feed 102 may have an American Petroleum Institute (API) gravity of from 30 degrees to 50 degrees, such as from 30 degrees to 45 degrees, from 30 degrees to 42 degrees, from 33 degrees to 50 degrees, from 33 degrees to 45 degrees, from 33 degrees to 42 degrees, from 35 degrees to 50 degrees, from 35 degrees to 45 degrees, from 35 degrees to 42 degrees, from 38 degrees to 50 degrees, from 38 degrees to 45 degrees, from 38 degrees to 42 degrees, from 40 degrees to 50 degrees, or from 40 degrees to 45 degrees, as determined according to the standard test method in ASTM D287. The crude oil feed 102 can have a density of greater than 0.8 grams per cubic centimeter (g/cm³), greater than 0.81 g/cm³, greater than 0.82 g/cm³, or even greater than 0.85 g/cm³ as measured at 15 degrees Celsius, according to the standard test method in ASTM 287. In embodiments, the crude oil feed 102 can have a density of from 0.80 g/cm³ to 0.87 g/cm³, from 0.80 g/cm³ to 0.85 g/cm³, from 0.80 g/cm³ to 0.83 g/cm³, from 0.81 g/cm³ to 0.87 g/cm³, from 0.81 g/cm³ to 0.85 g/cm³, from 0.81 g/cm³ to 0.83 g/cm³, from 0.83 g/cm³ to 0.87 g/cm³, from 0.83 g/cm³ to 0.85 g/cm³, or from 0.85 g/cm³ to 0.87 g/cm³, as measured at 15 degrees Celsius according to the standard test method in ASTM 287.

The crude oil feed 102 may have a nitrogen content of less than or equal to 1600 parts per million by weight (ppmw), such as less than or equal to 1000 ppmw, from 0 ppmw to 1600 ppmw, or from 0 ppmw to 1000 ppmw, per unit weight of the crude oil feed 102. The nitrogen content of the crude oil feed may be determined according to the standard test method in ASTM 4629. The crude oil feed 102 may have a sulfur content of less than or equal to 2.4 weight percent (wt. %), less than or equal to 2.2 wt. %, or less than or equal to 1.8 wt. %, per unit weight of the crude oil feed 102, as determined according to the standard test method in ASTM 5453. Any nitrogen and/or sulfur in the crude oil feed 102 may react with hydrogen introduced to the FCC system 100, which may reduce the amount of hydrogen available to react with the hydrocarbon during the cracking reactions to produce gasoline. Therefore, the crude oil feed 102 has low concentrations of nitrogen, sulfur, or both.

The crude oil feed 102 may include low concentrations (less than 30 ppmw) of heavy metals, such as but not limited to vanadium, nickel, or iron. The presence of vanadium may destroy the zeolitic structures of the zeolites in the FCC catalyst composition, thereby reducing catalyst activity and selectivity towards gasoline. Vanadium may also increase hydrogen and coke production. The crude oil feed 102 may have a vanadium content of less than 30 ppmw, less than 25 ppmw, or even less than 20 ppmw, per unit weight of the crude oil feed 102. The presence of nickel in the crude oil feed 102 may promote dehydrogenation reactions and increase hydrogen and coke production. The crude oil feed 102 may have a nickel content of less than 15 ppmw, or less than or equal to 10 ppmw, per unit weight of the crude oil feed 102. The presence of iron in the crude oil feed 102 may neutralize acid sites in the catalyst and may destroy the zeolitic structures of the zeolites in the FCC catalyst composition. Iron may also make the FCC catalyst composition more sensitive to high temperature spots in the FCC system 100, such as the higher temperatures experienced during regeneration. The crude oil feed 102 may have less than 5 ppmw iron, such as less than 2 ppmw iron, per unit weight of the crude oil feed 102. The content of the various metals in the crude oil feed 102 may be determined according to the international standard test method in IP 501 from the Energy Institute.

The crude oil feed 102 may be characterized by a distillation profile determined according to the standard test method in ASTM D7169. The crude oil feed 102 may have an initial boiling point temperature (IBP) of 15° C. to 40° C., such as from 15° C. to 30° C., from 15° C. to 25° C., from 20° C. to 40° C., from 20° C. to 30° C., from 20° C. to 25° C., from 25° C. to 40° C., or from 30° C. to 40° C., as determined according to ASTM D7169. The crude oil feed 102 may have an end boiling point temperature (EBP) of less than 720° C., such as from 500° C. to 720° C., from 550° C. to 720° C., or from 600° C. to 720° C., as determined according to ASTM D7169. The crude oil feed 102 may have a 5 wt. % boiling point temperature that is less than or equal to 80° C., such as from 20° C. to 80° C., from 20° C. to 70° C., from 20° C. to 50° C., from 30° C. to 80° C., from 30° C. to 70° C., or from 30° C. to 50° C., as determined according to standard test method ASTM D7169. The crude oil feed 102 may have a 50 wt. % boiling point temperature of from 200° C. to 350° C., such as from 200° C. to 330° C. from 200° C. to 310° C., from 200° C. to 290° C., from 220° C. to 350° C., from 220° C. to 330° C., from 220° C. to 310° C., from 220° C. to 290° C., from 250° C. to 350° C., from 250° C. to 330° C., from 250° C. to 310° C., from 250° C. to 290° C., from 290° C. to 350° C., from 230° C. to 330° C., or from 290° C. to 310° C., as determined according to standard test method ASTM D7169. The crude oil feed 102 may have a 90 wt. % boiling point temperature of from 400° C. to 700° C., such as from 400° C. to 650° C. from 400° C. to 600° C., from 400° C. to 550° C., from 450° C. to 700° C., from 450° C. to 650° C., from 450° C. to 600° C., from 500° C. to 700° C., from 500° C. to 650° C., from 500° C. to 600° C., from 550° C. to 700° C., from 550° C. to 650° C., from 550° C. to 600° C., or from 600° C. to 700° C., as determined according to standard test method ASTM D7169.

The distribution of different hydrocarbons—such as paraffin compounds, naphthenes, aromatic compounds, and polyaromatic compounds (including heavy polynuclear aromatic compounds)—can influence the conversion and yield obtained from fluidized catalytic cracking of the crude oil feed 102. For instance, paraffin compounds are generally the most reactive in FCC systems and contribute to high conversion. Naphthenes are the next most reactive group of hydrocarbons in the crude oil feed 102, followed by aromatic compounds and then polyaromatic compounds. The heavy polynuclear aromatic compounds are the least reactive and do not contribute much to overall conversion and yields of gasoline by the FCC system.

In embodiments, the crude oil feed 102 can have a concentration of paraffin compounds of less than 50 wt. %, such as less than or equal to 40 wt. %, or even less than or equal to 35 wt. % per unit weight of the crude oil feed 102, as determined according to ASTM D5443. In embodiments, the crude oil feed 102 can have a concentration of paraffin compounds of from 5 wt. % to less than 50 wt. %, from 5 wt. % to 40 wt. %, from 5 wt. % to 35 wt. %, from 10 wt. % to less than 50 wt. %, from 10 wt. % to 40 wt. %, from 10 wt. % to 35 wt. %, from 20 wt. % to 50 wt. %, from 20 wt. % to 40 wt. %, or even from 20 wt. % to 35 wt. % per unit weight of the crude oil feed 102.

In embodiments, the crude oil feed 102 can have a concentration of naphthenes of from 1 wt. % to 50 wt. %, from 1 wt. % to 30 wt. %, from 1 wt. % to 25 wt. %, from 1 wt. % to 20 wt. %, from 1 wt. % to 15 wt. %, from 5 wt. % to 50 wt. %, from 5 wt. % to 30 wt. %, from 5 wt. % to 25 wt. %, from 5 wt. % to 20 wt. %, from 5 wt. % to 15 wt. %, from 10 wt. % to 50 wt. %, from 10 wt. % to 30 wt. %, from 10 wt. % to 25 wt. %, from 10 wt. % to 20 wt. %, from 10 wt. % to 15 wt. %, from 15 wt. % to 50 wt. %, from 15 wt. % to 30 wt. %, from 10 wt. % to 25 wt. %, from 15 wt. % to 20 wt. %, from 20 wt. % to 50 wt. %, from 25 wt. % to 50 wt. %, from 25 wt. % to 30 wt. %, or even from 30 wt. % to 50 wt. % per unit weight of the crude oil feed 102, as determined according to ASTM D5443.

In embodiments, the crude oil feed 102 can have a concentration of aromatic compounds of greater than or equal to 20 wt. %, greater than or equal to 30 wt. %, or even greater than or equal to 40 wt. % per unit weight of the crude oil feed 102, as determined according to ASTM D5443. The concentration of aromatic compounds in this paragraph includes polyaromatic compounds and polynuclear aromatic compounds. In embodiments, the crude oil feed 102 can have a concentration of aromatic compounds of from 20 wt. % to 90 wt. %, from 20 wt. % to 80 wt. %, from 20 wt. % to 70 wt. %, from 20 wt. % to 60 wt. %, from 20 wt. % to 50 wt. %, from 30 wt. % to 90 wt. %, from 30 wt. % to 80 wt. %, from 30 wt. % to 70 wt. %, from 30 wt. % to 60 wt. %, from 30 wt. % to 50 wt. %, from 35 wt. % to 80 wt. %, or even from 35 wt. % to 50 wt. % per unit weight of the crude oil feed 102.

In embodiments, the crude oil feed 102 comprises, consists of, or consists essentially of a light crude oil, such as AL crude oil from Saudi Arabia. The light crude oil may have an API gravity of from 30 degrees to 35 degrees, such as from 30 degrees to 34 degrees, from 30 degrees to 33 degrees, from 31 degrees to 35 degrees, from 31 degrees to 34 degrees, or from 31 degrees to 33 degrees, as determined according to the standard test method in ASTM D287. The light crude oil can have a density of from 0.85 g/cm³ to 0.87 g/cm³, from 0.85 g/cm³ to 0.86 g/cm³, or from 0.86 g/cm³ to 0.87 g/cm³, as measured at 15 degrees Celsius according to the standard test method in ASTM 287.

The light crude oil may have a nitrogen content of less than or equal to 1600 parts per million by weight (ppmw), such as less than or equal to 1000 ppmw, from 500 ppmw to 1600 ppmw, or from 500 ppmw to 1000 ppmw, per unit weight of the light crude oil. The nitrogen content of the light crude oil may be determined according to the standard test method in ASTM 4629. The light crude oil may have a sulfur content of less than or equal to 2.4 weight percent (wt. %), such as from 1.9 wt. % to 2.4 wt. %, per unit weight of the light crude oil, as determined according to the standard test method in ASTM 5453.

The light crude oil may include heavy metals, such as but not limited to vanadium, nickel, iron, or combinations thereof. The light crude oil may have a vanadium content of less than 30 ppmw, less than 25 ppmw, or even less than 20 ppmw, per unit weight of the light crude oil. The light crude oil may have a nickel content of less than 15 ppmw, or less than or equal to 10 ppmw, per unit weight of the light crude oil. The light crude oil may have less than 5 ppmw iron, such as less than 2 ppmw iron, per unit weight of the light crude oil. The content of the various metals in the light crude oil may be determined according to the standard test method in IP 501.

The light crude oil may be characterized by a distillation profile determined according to the standard test method in ASTM D7169. The light crude oil may have an initial boiling point temperature (IBP) of from 20° C. to 40° C., such as from 20° C. to 30° C., from 20° C. to 25° C., from 25° C. to 40° C., from 25° C. to 30° C., or from 30° C. to 40° C., as determined according to ASTM D7169. The light crude oil may have an end boiling point temperature (EBP) of less than 720° C., such as from 500° C. to 720° C., from 550° C. to 720° C., or from 600° C. to 720° C., as determined according to ASTM D7169. The light crude oil may have a 5 wt. % boiling point temperature of less than or equal to 80° C., such as from 20° C. to 80° C., from 20° C. to 70° C., from 20° C. to 50° C., from 30° C. to 70° C., or from 30° C. to 50° C., as determined according to standard test method ASTM D7169. The light crude oil may have a 50 wt. % boiling point temperature of from 290° C. to 350° C., such as from 290° C. to 330° C., or from 290° C. to 310° C., as determined according to standard test method ASTM D7169. The crude oil feed 102 may have a 90 wt. % boiling point temperature of from 550° C. to 700° C., such as from 550° C. to 650° C., from 550° C. to 600° C., or from 600° C. to 700° C., as determined according to standard test method ASTM D7169. Properties for an AL crude oil that may be suitable as a light crude oil for the crude oil feed 102 are provided in Table 1.

In embodiments, the crude oil feed 102 comprises, consists of, or consists essentially of an extra light crude oil, such as AXL crude oil from Saudi Arabia. The extra light crude oil may have an API gravity greater than the API gravity of the light crude oil and less than the API gravity of a gas condensate. The extra light crude oil may have an API gravity of from 35 degrees to 45 degrees, such as from 35 degrees to 42 degrees, from 38 degrees to 45 degrees, from 38 degrees to 42 degrees, from 40 degrees to 45 degrees, or from 40 degrees to 42 degrees, as determined according to the standard test method in ASTM D287. The extra light crude oil has a density that is less than the density of a light crude oil and greater than a density of a gas condensate. The extra light crude oil can have a density of less than 0.85 g/cm³, such as less than or equal to 0.84 g/cm³, less than or equal to 083 g/cm³, from 0.80 g/cm³ to 0.85 g/cm³, from 0.80 g/cm³ to 0.84 g/cm³, from 0.80 g/cm³ to 0.83 g/cm³, from 0.81 g/cm³ to 0.85 g/cm³, from 0.81 g/cm³ to 0.84 g/cm³, or from 0.81 g/cm³ to 0.83 g/cm³, as measured at 15° C. according to the standard test method in ASTM D4052.

The extra light crude oil may have a nitrogen content of less than or equal to 1000 parts per million by weight (ppmw), such as less than or equal to 800 ppmw, less than or equal to 500 ppmw, from 0 ppmw to 1000 ppmw, or from 0 ppmw to 800 ppmw, or from 0 ppmw to 500 ppmw per unit weight of the extra light crude oil, as determined according to the standard test method in ASTM 4629. The nitrogen content of the extra light crude oil may be less than the nitrogen content in a light crude oil. The extra light crude oil may have a sulfur content of less than or equal to 2.4 weight percent (wt. %), less than or equal to 2.2 wt. %, less than or equal to 2.0 wt. %, or less than or equal to 1.8 wt. %, per unit weight of the extra light crude oil, as determined according to the standard test method in ASTM 5453. The sulfur content in the extra light crude oil may be less than the sulfur content in the light crude oil. The extra light crude oil may have a vanadium content of less than 30 ppmw, less than 25 ppmw, or even less than 20 ppmw, per unit weight of the extra light crude oil. The extra light crude oil may have a nickel content of less than 15 ppmw, or less than or equal to 10 ppmw, per unit weight of the extra light crude oil. The extra light crude oil may have less than 5 ppmw iron, such as less than 2 ppmw iron, per unit weight of the extra light crude oil. The content of the various metals in the extra light crude oil may be determined according to the standard test method in IP 501.

The extra light crude oil may be characterized by a distillation profile determined according to the standard test method in ASTM D7169. The extra light crude oil may have an initial boiling point temperature (IBP) of 15° C. to 30° C., such as from 15° C. to 25° C., from 20° C. to 30° C., or from 20° C. to 25° C., as determined according to ASTM D7169. The IBP of the extra light crude oil may be less than the IBP of the light crude oil. The extra light crude oil may have an end boiling point temperature (EBP) of less than 720° C., such as from 500° C. to 720° C., from 550° C. to 720° C., or from 600° C. to 720° C., as determined according to ASTM D7169. The extra light crude oil may have a 5 wt. % boiling point temperature that is less than or equal to 80° C., such as from 20° C. to 80° C., from 20° C. to 70° C., from 20° C. to 50° C., from 30° C. to 80° C., from 30° C. to 70° C., or from 30° C. to 50° C., as determined according to standard test method ASTM D7169. The extra light crude oil may have a 50 wt. % boiling point temperature of from 200° C. to 290° C., such as from 200° C. to 280° C., from 200° C. to 270° C., from 220° C. to 290° C., from 220° C. to 280° C., from 220° C. to 270° C., from 250° C. to 290° C., from 250° C. to 280° C., or from 250° C. to 270° C., as determined according to standard test method ASTM D7169. The 50 wt. % boiling point temperature of the extra light crude oil may be less than the 50 wt. % boiling point temperature of the light crude oil. The extra light crude oil may have a 90 wt. % boiling point temperature of from 400° C. to 550° C., such as from 400° C. to 525° C. from 400° C. to 500° C., from 425° C. to 550° C., from 425° C. to 525° C., from 425° C. to 5000° C., from 450° C. to 550° C., from 450° C. to 525° C., or from 450° C. to 500° C., as determined according to standard test method ASTM D7169. The 90 wt. % boiling point temperature of the extra light crude oil may be less than the 90 wt. % boiling point temperature of the light crude oil. Properties for an AXL crude oil that may be suitable as an extra light crude oil for the crude oil feed 102 are provided in Table 1.

TABLE 1
		AL	AXL
		Crude	Crude
Analysis	Units	Oil	Oil	Test Method

American Petroleum	degree	32.8	40.5	ASTM D287
Institute (API) gravity
Density	grams per	0.860	0.822	ASTM D287
	cubic
	centimeter
	(g/cm3)
Sulfur Content	wt. %	2.088	1.697	ASTM D4294
Nitrogen Content	parts per	1523	297	ASTM D4629
	million
	by weight
	(ppmw)
Paraffins	wt. %	31	30.7	ASTM D5443
Naphthenes	wt. %	11.1	11.8	ASTM D5443
Aromatics	wt. %	44.9	37	ASTM D5443
Polyaromatics	wt. %	12.9	20.5	ASTM D5443
Sodium (Na) Content	ppmw	<1	<1	IP 501
Vanadium (V)	ppmw	17	8	IP 501
Content
Nickel (Ni) Content	ppmw	5	2	IP 501
Iron (Fe) Content	ppmw	2	<1	IP 501

Boiling Point Distribution

5% Boiling Point (BP)	° C.	37	36	ASTM D7169
10% BP	° C.	87	86	ASTM D7169
20% BP	° C.	126	125	ASTM D7169
30% BP	° C.	183	179	ASTM D7169
40% BP	° C.	238	234	ASTM D7169
50% BP	° C.	293	286	ASTM D7169
60% BP	° C.	347	337	ASTM D7169
70% BP	° C.	407	393	ASTM D7169
80% BP	° C.	473	454	ASTM D7169
90% BP	° C.	557	532	ASTM D7169
End Boiling Point	° C.	719	719	ASTM D7169
(EBP)
Weight percentages in Table 1 are based on the total weight of the crude oil.

In embodiments, the crude oil feed 102 can be a topped crude oil. As used in the present disclosure, the term “topped crude oil” refers to crude oil from which lesser boiling constituents have been removed through distillation, such as constituents having boiling point temperatures less than 180° C., less than 150° C., or even less than 120° C. In embodiments, the crude oil feed 102 comprises, consists of, or consists essentially of a topped crude oil, which has greater than or equal to 95%, greater than or equal to 98%, or even greater than or equal to 99% constituents having boiling point temperatures greater than or equal to the cut point temperature of the topping unit, such as greater than or equal to 180° C., greater than or equal to 150° C., or greater than or equal to 120° C. In embodiments, the crude oil feed 102 may be a whole crude oil that has not been subjected to a topping process or any other separation through distillation.

The processes of the present disclosure include passing the crude oil feed 102 to an FCC system 100 comprising the FCC reactor 112 which contains the FCC catalyst composition 114. The FCC catalyst composition 114 of the present disclosure includes a ZSM-5 zeolite and a Y-type zeolite. The FCC catalyst composition 114 can also include an alumina binder, a matrix material comprising Kaolin clay, and colloidal silica.

The ZSM-5 zeolite in the FCC catalyst composition 114 may be operable to crack at least a portion of the crude oil feed 102. As used in the present disclosure, “ZSM-5” refers to zeolites 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_nAl_nSi_96-nO₁₉₂·16H₂O, where 0<n<27. The molar ratio of silica to alumina in the ZSM-5 may 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 the ZSM-5 may be from 5 to 80, from 5 to 70, from 5 to 60, from 5 to 50, from 10 to 80, from 10 to 70, from 10 to 60, from 10 to 50, from 20 to 80, from 20 to 70, from 20 to 60, from 20 to 50, from 30 to 80, from 30 to 70, from 30 to 60, or from 30 to 50.

In embodiments, the ZSM-5 zeolite may have a specific surface area from 200 meters squared per gram (m²/g) to 800 m²/g. In embodiments, the specific surface area may be from 200 m²/g to 400 m²/g, from 200 m²/g to 600 m²/g, from 200 m²/g to 800 m²/g, from 300 m²/g to 400 m²/g, from 300 m²/g to 600 m²/g, from 300 m²/g to 800 m²/g, from 400 m²/g to 600 m²/g, or from 400 m²/g to 800 m²/g. The specific surface area refers to the BET surface area as determined using the Brunauer-Emmett-Teller (BET) method of surface area analysis based on gas adsorption and analysis of gas adsorption isotherms. In embodiments, the ZSM-5 zeolite, can have a total pore volume per unit weight of the ZSM-5 zeolite of 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. The total pore volume can be determined through nitrogen physisorption and analysis of nitrogen physisorption isotherms, which is a well-known method.

In embodiments, one or more of the zeolitic components of the FCC catalyst composition 114 can include one or more phosphorous-containing compounds, such as phosphorous pentoxide (P₂O₅). Without being bound by any particular theory, it is believed that phosphorus-containing compounds may stabilize the structure of the zeolitic framework structure by preventing the segregation of the framework alumina, which can improve the hydrothermal stability of the zeolitic component. This may reduce the dealumination of the zeolitic component that occurs during steaming, which can lead to a reduction in acidity and catalytic activity of the zeolitic component. In embodiments, one or more of the zeolitic components of the FCC catalyst composition 114 may include one or more phosphorous-containing compounds in an amount of from 1 wt. % to 20 wt. % based on the total weight of each zeolitic component. In embodiments, the phosphorous-containing compounds can be impregnated onto the ZSM-5 zeolite so that the ZSM-5 zeolite is impregnated with from 1 wt. % to 20 wt. % phosphorous-containing compounds based on the total weight of the ZSM-5 zeolite. In embodiments, the ZSM-5 zeolite can be impregnated with from 1 wt. % to 20 wt. % phosphorous pentoxide based on the total weight of the ZSM-5 zeolite. In embodiments, the ZSM-5 zeolite can include from 1 wt. % to 15 wt. %, from 1 wt. % to 10 wt. %, from 1 wt. % to 5 wt. %, from 5 wt. % to 20 wt. %, from 5 wt. % to 15 wt. %, from 5 wt. % to 10 wt. %, from 10 wt. % to 20 wt. %, from 10 wt. % to 15 wt. %, from 15 wt. % to 20 wt. %, from 6 wt. % to 9 wt. %, or from 7 wt. % to 8 wt. % phosphorous pentoxide based on the total weight of the ZSM-5 zeolite. In embodiments, the ZSM-5 zeolite can include about 7.5 wt. % phosphorous pentoxide based on the total weight of the ZSM-5 zeolite.

In embodiments, the FCC catalyst composition 114 can include up to 40 wt. % of the ZSM-5 zeolite based on the total weight the FCC catalyst composition 114. In embodiments, the FCC catalyst composition 114 can include up to 30 wt. %, up to 25 wt. %, or up to 20 wt. % ZSM-5 zeolite based on the total weight of the FCC catalyst composition 114. In embodiments, the FCC catalyst composition 114 can include from 1 wt. % to 40 wt. %, from 1 wt. % to 30 wt. %, from 1 wt. % to 25 wt. %, from 1 wt. % to 20 wt. %, 5 wt. % to 40 wt. %, from 5 wt. % to 30 wt. %, from 5 wt. % to 25 wt. %, from 5 wt. % to 20 wt. %, 10 wt. % to 40 wt. %, from 10 wt. % to 30 wt. %, from 10 wt. % to 25 wt. %, from 10 wt. % to 20 wt. %, from 15 wt. % to 40 wt. %, from 15 wt. % to 30 wt. %, from 15 wt. % to 25 wt. %, or from 15 wt. % to 20 wt. % of the ZSM-5 zeolite based on the total weight of the FCC catalyst composition 114.

The FCC catalyst composition 114 further includes the Y-type zeolite. In embodiments, the Y-type zeolite can comprise an ultrastable Y-type (USY) zeolite. USY zeolites can be produced via the dealumination of one or more Y-type zeolites. As used in the present disclosure, the term “Y-type zeolite” refers to a zeolite having an 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 the dealumination of the Y-type zeolite may result in a USY zeolite having a reduced number of acid sites. This reduced number of acid sites may result in a reduction of the rates of secondary reactions in the FCC system 100, such as the dehydrogenation or hydrogenation of olefins produced in the FCC system 100, when compared to Y-type zeolite that has not been dealuminated. As a result, USY zeolite may produce a greater yield of olefins and gasoline when compared to Y-type zeolite.

The molar ratio of silica to alumina in the USY zeolite can 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 can be from 5 to 80, from 5 to 50, from 5 to 25, from 5 to 10, from 10 to 80, from 10 to 50, from 10 to 25, from 25 to 80, or from 25 to 50. In embodiments, the molar ratio of silica to alumina in the USY zeolite can be about 30. In embodiments, the USY zeolite can also comprise one or more transition metals, such as zirconium, titanium, or hafnium, substituted into the framework of the zeolite. The USY zeolite can have a specific surface area of from 200 m²/g to 900 m²/g, as determined according to the BET method. In embodiments, the USY zeolite may have an average surface area of from 200 m²/g to 800 m²/g, from 300 m²/g to 900 m²/g, from 300 m²/g to 800 m²/g, from 500 m²/g to 900 m²/g, or from 500 m²/g to 800 m²/g, as determined according to the BET method. The USY zeolite may have a 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, as determined through nitrogen physisorption and analysis of nitrogen physisorption isotherms, which is a well-known method.

In embodiments, one or more of the zeolite components of the FCC catalyst composition 114 can include one or more rare earth metals or rare earth metal oxides impregnated on the zeolite, where the rare earth metal can be one or more of lanthanum, cerium, dysprosium, europium, gadolinium, holmium, lutetium, neodymium, praseodymium, promethium, samarium, scandium, terbium, thulium, ytterbium, yttrium, or combinations of these. Without being bound by any particular theory, it is believed that rare earth metals or rare earth metal oxides can improve the stability of the unit cells of the zeolite component, increase the catalytic activity of the zeolite component, or both. Moreover, it is believed that rare earth metals or rare earth metal oxides can function as vanadium traps, which act to sequester vanadium in the crude oil feed 102 and prevent deleterious effects that vanadium can have on the zeolite components of the catalyst. In embodiments, one or more of the zeolite components of the FCC catalyst composition 114 can include one or more rare earth metals or rare earth metal oxides in an amount of from 1 wt. % to 10 wt. % based on the total weight of each zeolite component. In embodiments, one or more of the zeolite components of the FCC catalyst composition 114 can be impregnated with lanthanum or lanthanum oxide. In embodiments, one or more of the zeolite components of the FCC catalyst composition 114 can include one or more lanthanum-containing compounds, such as but not limited to lanthanum oxide, in an amount of from 1 wt. % to 10 wt. %, from 1 wt. % to 7 wt. %, 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 10 wt. %, from 2 wt. % to 7 wt. %, from 2 wt. % to 5 wt. %, from 2 wt. % to 4 wt. %, from 2 wt. % to 3 wt. %, from 3 wt. % to 10 wt. %, from 3 wt. % to 7 wt. %, from 3 wt. % to 5 wt. %, from 3 wt. % to 4 wt. %, from 4 wt. % to 10 wt. %, from 4 wt. % to 7 wt. %, or from 4 wt. % to 5 wt. % based on the total weight of each zeolite component.

In embodiments, the rare earth metal or rare earth metal oxide can be impregnated on the USY zeolite of the FCC catalyst composition 114. In embodiments, the FCC catalyst composition 114 can comprise USY zeolite impregnated with lanthanum oxide (La₂O₃). In embodiments, the USY zeolite can include from 1 wt. % to 10 wt. %, from 1 wt. % to 7 wt. %, 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 10 wt. %, from 2 wt. % to 7 wt. %, from 2 wt. % to 5 wt. %, from 2 wt. % to 4 wt. %, from 2 wt. % to 3 wt. %, from 3 wt. % to 10 wt. %, from 3 wt. % to 7 wt. %, from 3 wt. % to 5 wt. %, from 3 wt. % to 4 wt. %, from 4 wt. % to 10 wt. %, from 4 wt. % to 7 wt. %, or from 4 wt. % to 5 wt. % lanthanum oxide based on the total weight of the USY zeolite. In embodiments, the USY zeolite can comprise about 2.5 wt. % lanthanum oxide based on the total weight of the USY zeolite.

In embodiments, the FCC catalyst composition 114 can include up to 40 wt. % of the USY zeolite based on the total weight the FCC catalyst composition 114. In embodiments, the FCC catalyst composition 114 can include up to 30 wt. %, or up to 25 wt. % of the USY zeolite based on the total weight of the FCC catalyst composition 114. In embodiments, the FCC catalyst composition 114 can include from 1 wt. % to 40 wt. %, from 1 wt. % to 30 wt. %, from 1 wt. % to 25 wt. %, from 5 wt. % to 40 wt. %, from 5 wt. % to 30 wt. %, from 5 wt. % to 25 wt. %, from 10 wt. % to 40 wt. %, from 10 wt. % to 30 wt. %, from 10 wt. % to 25 wt. %, from 15 wt. % to 40 wt. %, from 15 wt. % to 30 wt. %, or from 15 wt. % to 25 wt. % of the USY zeolite based on the total weight of the FCC catalyst composition 114.

In embodiments, the FCC catalyst composition 114 can 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 materials” refer to materials that serve to “glue” or otherwise hold components of the FCC catalyst composition 114 together. Binder materials can be included to improve the attrition resistance of the FCC catalyst composition 114. The binders can comprise alumina (such as amorphous alumina), silica-alumina (such as amorphous silica-alumina), or silica (such as amorphous silica). In embodiments, the binder material can comprise pseudoboehmite. As used in the present disclosure, “pseudoboehmite” refers to an aluminum-containing compound with the chemical composition AlO(OH) consisting of crystalline boehmite. While boehmite generally refers to aluminum oxide hydroxide as well, pseudoboehmite generally has a greater amount of water compared to boehmite. In embodiments, the binder material can comprise amorphous silica. The amorphous silica can be in the form of colloidal silica. As used throughout the present disclosure, the term “colloidal silica” refers to nano-sized particles of amorphous, non-porous silica. In embodiments, the FCC catalyst composition 114 can comprise an alumina binder, colloidal silica, or both.

In embodiments, the FCC catalyst composition 114 can include the one or more binders in an amount of from 5 wt. % to 30 wt. % based on the total weight of the FCC catalyst composition 114. In embodiments, the FCC catalyst composition 114 can include the one or more binders in an amount of from 5 wt. % to 25 wt. %, from 5 wt. % to 20 wt. %, from 5 wt. % to 15 wt. %, from 5 wt. % to 10 wt. %, from 10 wt. % to 25 wt. %, from 10 wt. % to 20 wt. %, from 10 wt. % to 15 wt. %, from 15 wt. % to 30 wt. %, from 15 wt. % to 25 wt. %, from 15 wt. % to 20 wt. %, from 20 wt. % to 30 wt. %, from 20 wt. % to 25 wt. %, or from 25 wt. % to 30 wt. % based on the total weight of the FCC catalyst composition 114.

In embodiments, the FCC catalyst composition 114 can include an alumina binder in an amount of from 2 wt. % to 20 wt. % based on the total weight of the FCC catalyst composition 114. In embodiments, the FCC catalyst composition 114 can include the alumina binder in an amount of from 2 wt. % to 15 wt. %, from 2 wt. % to 10 wt. %, from 5 wt. % to 20 wt. %, from 5 wt. % to 15 wt. %, from 5 wt. % to 10 wt. %, or from 7 wt. % to 9 wt. % based on the total weight of the FCC catalyst composition 114. In embodiments the FCC catalyst composition 114 can include about 8 wt. % alumina binder based on the total weight of the FCC catalyst composition 114.

In embodiments, the FCC catalyst composition 114 can include colloidal silica in an amount of from 0.5 wt. % to 10 wt. % based on the total weight of the FCC catalyst composition 114. In embodiments, the FCC catalyst composition 114 can include colloidal silica in an amount of from 0.5 wt. % to 7 wt. %, from 0.5 wt. % to 5 wt. %, from 0.5 wt. % to 4 wt. %, from 0.5 wt. % to 3 wt. %, from 0.5 wt. % to 2 wt. %, from 1 wt. % to 10 wt. %, from 1 wt. % to 7 wt. %, 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 10 wt. %, from 2 wt. % to 7 wt. %, from 2 wt. % to 5 wt. %, from 2 wt. % to 4 wt. %, or from 2 wt. % to 3 wt. % based on the total weight of the FCC catalyst composition 114. In embodiments the FCC catalyst composition 114 can include about 2 wt. % colloidal silica based on the total weight of the FCC catalyst composition 114. Without intending to be bound by any particular theory, it is believed that the colloidal silica can act as a binder and/or filler to provide additional physical strength and integrity to the FCC catalyst composition 114. Further, it is believed that the addition of colloidal silica to the FCC catalyst composition 114 can improve the attrition resistance and/or stabilize catalytic activity of the FCC catalyst composition 114.

In embodiments, the FCC catalyst composition 114 may include one or more matrix materials, which may include one or more clay materials, such as but not limited to Kaolin clay. Without being bound by any particular theory, it is believed that the matrix materials of the FCC catalyst composition 114 can serve both physical and catalytic functions. Physical functions can include providing particle integrity and attrition resistance, acting as a heat transfer medium, and providing a porous structure to allow diffusion of hydrocarbons into and out of the catalyst microspheres. The matrix materials can also affect catalyst selectivity, product quality, and resistance to poisons. The matrix materials may tend to exert its strongest influence on overall catalytic properties for those reactions that directly involve relatively large molecules.

In embodiments, the matrix materials can include Kaolin clay. As used in the present disclosure, “Kaolin clay” refers to a clay material that has 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 kaolinite, which can be represented by the chemical formula Al₂Si₂O₅(OH)₄. In embodiments, the FCC catalyst composition 114 can include one or more matrix materials in an amount of from 30 wt. % to 60 wt. % based on the total weight of each of the FCC catalyst composition 114. In embodiments, the FCC catalyst composition 114 can include from 30 wt. % to 55 wt. %, from 30 wt. % to 50 wt. %, from 30 wt. % to 45 wt. %, from 30 wt. % to 40 wt. %, from 30 wt. % to 35 wt. %, from 35 wt. % to 60 wt. %, from 35 wt. % to 55 wt. %, from 35 wt. % to 50 wt. %, from 35 wt. % to 45 wt. %, from 35 wt. % to 40 wt. %, from 40 wt. % to 60 wt. %, from 40 wt. % to 55 wt. %, from 40 wt. % to 50 wt. %, from 40 wt. % to 45 wt. %, from 45 wt. % to 60 wt. %, from 45 wt. % to 55 wt. %, from 45 wt. % to 50 wt. %, from 50 wt. % to 60 wt. %, from 50 wt. % to 55 wt. %, or from 55 wt. % to 60 wt. % matrix materials based on the total weight of the FCC catalyst composition 114.

In embodiments, the FCC catalyst composition 114 can include ZSM-5 zeolite impregnated with phosphorous, a USY zeolite impregnated with lanthanum oxide, an alumina binder, a matrix material comprising Kaolin clay, and colloidal silica. In embodiments, the ZSM-5 zeolite can be impregnated with 7.5 wt. % phosphorous pentoxide based on the total weight of the ZSM-5 zeolite. In embodiments the USY zeolite can be impregnated with 2.5 wt. % lanthanum oxide, based on the total weight of the USY zeolite.

In embodiments, the FCC catalyst composition 114 can comprise 20 wt. % ZSM-5 zeolite based on the total weight of the FCC catalyst composition 114, where the ZSM-5 zeolite is impregnated with 7.5 wt. % P₂O₅ based on the total weight of the ZSM-5 zeolite; 21 wt. % USY zeolite based on the total weight of the FCC catalyst composition 114, where the USY zeolite is impregnated with 2.5 wt. % lanthanum oxide (La₂O₃) based on the total weight of the USY zeolite; 8 wt. % alumina binder based on the total weight of the FCC catalyst composition 114; 49 wt. % Kaolin clay based on the total weight of the FCC catalyst composition 114; and 2 wt. % colloidal silica based on the total weight of the FCC catalyst composition 114. In embodiments, the FCC catalyst composition 114 can comprise a plurality of catalyst particles, where each of the plurality of catalyst particles comprises the ZSM-5 zeolite impregnated with phosphorous pentoxide, the USY zeolite impregnated with lanthanum oxide, the alumina binder, the Kaolin clay, and the colloidal silica.

The FCC catalyst composition 114 can be formed by a variety of processes. According to embodiments, the matrix material can be mixed with a fluid such as water to form a slurry, and the zeolites can be separately mixed with a fluid such as water to form a zeolite slurry. The matrix material slurry and the zeolite slurry can be combined under stirring. Separately, another slurry can be formed by combining the binder material with a fluid such as water. The binder slurry can then be combined with the slurry containing the zeolites and matrix material to form a final slurry. The final slurry can then be dried, for example by spray drying, and then calcined to produce the microparticles of the FCC catalyst composition 114.

In embodiments, the FCC catalyst composition 114 can be in the form of shaped microparticles, such as microspheres. As used in the present disclosure, the term “microparticles” refers to particles having an average particle size of from 0.1 microns and 100 microns. The size of a microparticle refers to the maximum length of a particle from one side to another, measured along the longest distance of the microparticle. For instance, a spherically-shaped microparticle has a size equal to its diameter, or a rectangular prism shaped microparticle has a maximum length equal to the hypotenuse stretching from opposite corners. Other shapes are contemplated. In embodiments, each zeolitic component of the FCC catalyst composition 114 can be included in each catalyst microparticle.

In embodiments, the FCC catalyst composition 114 can be contacted with steam prior to use in the FCC system 100. The purpose of steam treatment can be to accelerate the hydrothermal aging of the FCC catalyst composition 114 that occurs during operation of the FCC system 100 to obtain an equilibrium catalyst. Not intending to be bound by any particular theory, it is believed that the steam treatment can lead to the removal of aluminum from the framework leading to a decrease in the number of sites where framework hydrolysis can occur under hydrothermal and thermal conditions. This removal of aluminum results in an increased thermal and hydrothermal stability in dealuminated zeolites. The unit cell size can decrease as a result of dealumination, since the smaller SiO₄ tetrahedron replaces the larger AlO₄⁻ tetrahedron. The acidity of zeolites can also be affected by dealumination through the removal of framework aluminum and the formation of extra-framework aluminum species. Dealumination may affect the acidity of the zeolites by decreasing the total acidity and increasing the acid strength of the zeolite. The total acidity can decrease because of the removal of framework aluminum, which act as Brønsted acid sites. The acid strength of the zeolite may be increased because of the removal of paired acid sites or the removal of the second coordinate next nearest neighbor aluminum. The increase in the acid strength may be caused by the charge density on the proton of the OH group being highest when there is no framework aluminum in the second coordination sphere. In embodiments, the FCC catalyst composition 114 can be contacted with steam at a temperature greater than or equal to 800° C. for a period of 6 hours or greater prior to contacting the crude oil feed 102 with the FCC catalyst composition 114 in the FCC system 100.

Referring again to FIG. 1, the FCC system 100 includes the FCC unit 110 and the regenerator 140. In embodiments, the FCC system 100 can include a plurality of FCC units 110, which can be operated in series, in parallel, or a combination of both. The FCC unit 110 can include a catalyst-feed mixing zone 118, a cracking reaction zone 112, a catalyst separation zone 120, and a stripping zone 122. In embodiments, the cracking reaction zone 112 can be a downflow or “downer” reactor in which the reactants flow from the catalyst-feed mixing zone 118 downward through the cracking reaction zone 112 to the catalyst separation zone 120. Steam 117 can be introduced to the top portion of the cracking reaction zone 112 to provide additional heating to the mixture of the crude oil feed 102 and the FCC catalyst composition 114.

It should be understood that the cracking reaction zone 112 of the FCC unit 110 depicted in FIG. 1 is a simplified schematic of one particular embodiment of the cracking reaction zone 112 of a fluid catalytic cracking unit, and other configurations of the cracking reaction zone 112 may be suitable for incorporation into the FCC system 100. In embodiments, the cracking reaction zone 112 can be an up-flow cracking reaction zone. In embodiments, the cracking reaction zone 112 can include one or more riser reactors. Other embodiments may include two or more fluid catalytic cracking units operating in parallel under similar or different operating conditions.

Referring again to FIG. 1, the FCC unit 110 may be fluidly coupled to the regenerator 140. In embodiments, the regenerator 140 can be a single-zone regenerator that includes a regeneration zone 144. The used FCC catalyst 115 can be regenerated in the regeneration zone 144 to produce a regenerated FCC catalyst 148. In embodiments, the regenerator 140 can be a dual-zone regenerator that includes two separate regeneration zones (not pictured). Referring again to FIG. 1, the regenerator 140 can include a riser 142. The riser 142 can be positioned between the stripping zone 122 and the regeneration zone 144. The used FCC catalyst 115 is regenerated in the regenerator to produce the regenerated FCC catalyst 148. The regenerated FCC catalyst 148 is then passed back to the catalyst-feed mixing zone 118 as a portion of or all of the FCC catalyst composition 114.

The FCC system 100 can include a catalyst hopper 150 disposed between the regeneration zone 144 of the regenerator 140 and the FCC unit 110. The regenerated FCC catalyst 148 can be passed from the regeneration zone 144 to the catalyst hopper 150, where the regenerated FCC catalyst 148 can accumulate prior to passing from the catalyst hopper 150 to the catalyst-feed mixing zone 118 as the FCC catalyst composition 114. The regenerated FCC catalyst 148, which may be at an elevated temperature equal to or greater than the reaction temperature in the cracking reaction zone 112, can provide heat for the endothermic cracking reaction in the cracking reaction zone 112.

The FCC system 100 can be used in the processes disclosed herein for converting crude oils to gasoline. Referring again to FIG. 1, the processes of the present disclosure may include contacting the crude oil feed 102 with the FCC catalyst composition 114 in the FCC unit 110 at a temperature of from 500° C. to 580° C., a weight ratio of the FCC catalyst composition to the crude oil feed of from 2 to 10, and a contact time of from 0.1 seconds to 60 seconds. The crude oil feed 102 may have any of the compositions, properties, or other characteristics previously discussed for the crude oil feed 102. The FCC catalyst composition 114 may have any of the compositions, properties, or other features previously discussed for the FCC catalyst composition 114.

The processes may include passing the crude oil feed 102 to the catalyst-feed mixing zone 118 of the FCC unit 110. The processes may include passing the crude oil feed 102 directly to the catalyst-feed mixing zone 118 without subjecting the crude oil feed 102 to any separation process, such as separation through distillation. The processes may include mixing the crude oil feed 102 with the FCC catalyst composition 114 in the catalyst-feed mixing zone 118. The processes may include passing the mixture comprising the crude oil feed 102 and the FCC catalyst composition 114 to the cracking reaction zone 112. When the cracking reaction zone 112 is a downflow reactor, the processes may include passing the mixture of the crude oil feed 102 and the FCC catalyst composition 114 to a top portion of the cracking reaction zone 112. When the cracking reaction zone 112 is an upflow reactor, the process may include passing the mixture of the crude oil feed 102 and the FCC catalyst composition 114 to a bottom of a riser portion of the cracking reaction zone 112. In embodiments, the cracking reaction zone 112 may be an upflow reactor, and the process may include introducing a carrier gas (not shown) to the bottom of the upflow reactor, where the carrier gas facilitates upward travel of the mixture of the crude oil feed 102 and FCC catalyst composition 114 through the cracking reaction zone 112.

During steady state operation of the FCC system 100, the FCC catalyst composition 114 can be the regenerated FCC catalyst 148 that is passed to the catalyst-feed mixing zone 118 from the catalyst hopper 150. The catalyst hopper 150 can receive the regenerated FCC catalyst 148 from the regenerator 140 following regeneration of the used FCC catalyst 115. At initial start-up of the FCC system 100, the FCC catalyst composition 114 can include fresh FCC catalyst (not shown), which may be the FCC catalyst composition 114 microparticles that have not been circulated through the FCC unit 110 and the regenerator 140. Fresh FCC catalyst composition can be introduced to the catalyst hopper 150 or to the regenerator 140 periodically during operation to replenish lost FCC catalyst composition 114 microparticles or compensate for used FCC catalyst 115 that becomes permanently deactivated, such as through heavy metal accumulation in the catalyst.

Contacting the hydrocarbons from the crude oil feed 102 with the FCC catalyst composition 114 in the cracking reaction zone 112 may cause at least a portion of the hydrocarbons from the crude oil feed 102 to undergo one or more catalytic cracking reactions to form one or more cracking reaction products, which can include gasoline components. The FCC catalyst composition 114 passed to the cracking reaction zone 112 can have a temperature equal to or greater than the reaction temperature of the cracking reaction zone 112 and can transfer heat to the crude oil feed 102 to promote the endothermic cracking reactions. In embodiments, the process may include introducing steam 117 to the cracking reaction zone 112 to further increase the temperature in the cracking reaction zone 112, to increase the surface area of the crude oil feed 102 by atomizing the crude oil feed 102 into smaller droplets, to reduce the hydrocarbon partial pressure in the cracking reaction zone 112, or combinations thereof.

In embodiments, the processes may include contacting the crude oil feed 102 with the FCC catalyst composition 114 at a reaction temperature of less than 580° C. In embodiments, the process may include contacting the crude oil feed 102 with the FCC catalyst composition 114 at a reaction temperature of from 500° C. to 580° C., such as from 500° C. to 570° C., from 500° C. to 560° C., from 500° C. to 550° C., from 520° C. to 580° C., from 520° C. to 570° C., from 520° C. to 560° C., from 520° C. to 550° C., from 530° C. to 580° C., from 530° C. to 570° C., from 530° C. to 560° C., or from 530° C. to 550° C. When the reaction temperature of the cracking reaction zone 112 is greater than, for instance, 580° C., the cracking of the crude oil feed 102 over the FCC catalyst composition 114 in the cracking reaction zone 112 may result in decreased conversion of the crude oil feed 102 to gasoline components and greater conversion of the crude oil feed 102 to light olefins. In embodiments, the crude oil feed 102 can be contacted with the FCC catalyst composition 114 in the cracking reaction zone 112 at a temperature of from 500° C. to 580° C., or from 530° C. to 550° C.

The processes of the present disclosure may include contacting the crude oil feed 102 with the FCC catalyst composition 114 in the cracking reaction zone 112 at a catalyst-to-oil weight (CTO) ratio from 2 to 40, where the catalyst-to-oil weight ratio is equal to the mass flow rate of the FCC catalyst composition 114 to the cracking reaction zone 112 divided by the mass flow rate of the crude oil feed 102 to the cracking reaction zone 112. In embodiments, the crude oil feed 102 may be contacted with the FCC catalyst composition 114 in the cracking reaction zone 112 at a catalyst-to-oil weight ratio from 2 to 20, from 2 to 15, from 2 to 10, from 2 to 9, from 5 to 40, from 5 to 20, from 5 to 15, from 5 to 10, from 5 to 9, from 7 to 40, from 7 to 20, from 7 to 15, from 7 to 10, or from 7 to 9. Without intending to be bound by any particular theory, it is believed that a catalyst-to-oil weight ratio less than 2, the relative amount of the FCC catalyst composition 114 may not be sufficient to catalytically crack the crude oil feed 102 at an economically high yield.

The processes of the present disclosure may include contacting the crude oil feed 102 with the FCC catalyst composition 114 in the cracking reaction zone 112 for a contact time of from 0.1 seconds to 60 seconds. In embodiments, the processes of the present disclosure may include contacting the crude oil feed 102 with the FCC catalyst composition 114 in the cracking reaction zone 112 for a contact time of from 0.1 seconds to 30 seconds, from 0.1 seconds to 60 seconds, from 0.1 second to 40 seconds, from 0.1 second to 30 seconds, from 1 second to 60 seconds, from 1 second to 40 seconds, from 1 second to 30 seconds, from 2 seconds to 60 seconds, from 2 seconds to 40 seconds, from 2 seconds to 30 seconds, from 5 seconds to 60 seconds, from 5 seconds to 40 seconds, from 5 seconds to 30 seconds, from 10 seconds to 60 seconds, from 10 seconds to 40 seconds, from 10 seconds to 30 seconds, from 20 seconds to 60 seconds, from 20 seconds to 40 seconds, from 20 seconds to 30 seconds, or from 30 seconds to 60 seconds. Without intending to be bound by any particular theory, it is believed that a residence time less than 0.1 seconds may not provide sufficient time for hydrocarbons in the crude oil feed 102 to be sufficiently cracked by the FCC catalyst composition 114.

Referring again to FIG. 1, catalytically cracking the crude oil feed 102 through contact with the FCC catalyst composition 114 produces a mixture of the used FCC catalyst 115 and the FCC effluent 116. The processes of the present disclosure may include separating the FCC effluent 116 from the used FCC catalyst 115. Separating the FCC effluent 116 from used FCC catalyst 115 may include passing the mixture comprising the used FCC catalyst 115 and the FCC effluent 116 to the separation zone 120, such as by passing the mixture from cracking reaction zone 112 to the separation zone 120. The separation zone 120 may be configured to separate the FCC effluent 116 from the used FCC catalyst 115. In embodiments, the separation zone 120 can include one or more fluid-solid separators, such as one or more cyclones. The used FCC catalyst 125 exiting from the separation zone 120 can retain at least a portion of the FCC effluent 116, such as FCC effluent 116 that is retained in the pores of the used FCC catalyst 115, between microparticles of the used FCC catalyst 115, or both.

The processes of the present disclosure may include passing the used FCC catalyst 115, which may include a residual portion of the FCC effluent 116 retained in the used FCC catalyst 115, from the separation zone 120 to the stripping zone 122 disposed downstream of the separation zone 120. The processes may include stripping the residual portions of the FCC effluent 116 from the used FCC catalyst 115 and recovering a stripped effluent 124 from the stripping zone 122. The stripped effluent 124 can be passed to one or more downstream unit operations or combined with the FCC effluent 116 for further processing. Stripping the residual portions of the FCC effluent 116 from the used FCC catalyst 115 may include introducing a stripping gas 123, such as but not limited to steam, to the stripping zone 122 to facilitate stripping the residual portions of the FCC effluent 116 from the used FCC catalyst 115. The stripped effluent 124, which may include at least a portion of the stripping gas 123 introduced to the stripping zone 122, can be discharged from the stripping zone 122, at which point stripped effluent 124 can pass through cyclone separators (not shown) and out of the stripper vessel (not shown). The stripped effluent 124 can be directed to one or more product recovery systems in accordance with known methods in the art. The stripped effluent 124 may also be combined with one or more other streams, such as the FCC effluent 116.

Referring again to FIG. 1, the process may include, after stripping the retained portions of the FCC effluent 116 from the used FCC catalyst 115, passing the used FCC catalyst 115 to the regenerator 140. In embodiments, the used FCC catalyst 115 may be passed to the regeneration zone 144 of the regenerator 140. The process may include regenerating the used FCC catalyst 115 in the regenerator 140 to produce the regenerated FCC catalyst 148. The processes may include passing the regenerated FCC catalyst 148 back to the cracking reaction zone 112 as the FCC catalyst composition 114.

In embodiments, regenerating the used FCC catalyst 115 may include introducing the used FCC catalyst 115 and a combustion gas 146 to a bottom end of the riser 142 of the regenerator 140. The combustion gases 146 can include one or more of combustion air, oxygen, fuel gas, fuel oil, or combinations of these combustion gases. The combustion gases 146 can convey the used FCC catalyst 115 upwards through the riser 142 to the regeneration zone 144, where coke deposits and residual reactants and reaction products are at least partially or fully oxidized (combusted). The coke deposited on the used FCC catalyst 115 in the cracking reaction zone 112 may begin to oxidize in the presence of the combustion gases 146 in the riser 142 on the way upward to the regeneration zone 144. The used FCC catalyst 115 is regenerated to produce a regenerated FCC catalyst 148. During regeneration, the coke deposits on the used FCC catalyst 115 are removed and the catalyst particles are heated through combustion of the coke deposits, an additional fuel gas, or combinations of these to produce the regenerated FCC catalyst 148. The regenerated FCC catalyst 148 is then passed back to the cracking reaction zone 112 as the FCC catalyst composition 114. In embodiments, the process may include passing the regenerated FCC catalyst 148 to the catalyst hopper 150 upstream of the cracking reaction zone 112, and then passing the regenerated FCC catalyst 148 from the catalyst hopper 150 to the cracking reaction zone 112 as the FCC catalyst composition 114.

The FCC effluent 116 may include gasoline components, referred to herein as gasoline or FCC gasoline. In embodiments, the FCC effluent 116 may comprise greater than or equal to 35 wt. % gasoline based on the total weight of the FCC effluent 116, such as greater than or equal to 37 wt. %, greater than or equal to 40 wt. %, greater than or equal to 41 wt. %, greater than or equal to 42 wt. %, or even greater than or equal to 43 wt. % gasoline based on the total weight of the FCC effluent 116. In embodiments, the FCC effluent 116 may include from 35 wt. % to 60 wt. % gasoline, such as from 35 wt. % to 50 wt. %, from 37 wt. % to 60 wt. %, from 37 wt. % to 50 wt. %, from 40 wt. % to 60 wt. %, from 40 wt. % to 50 wt. %, from 42 wt. % to 60 wt. %, or from 42 wt. % to 50 wt. % gasoline per unit weight of the crude oil feed 102 introduced to the FCC system 100.

The FCC effluent 116 may also include dry gas, which is defined as hydrogen, methane, ethane, and any combinations thereof; light petroleum gases, which include C₃-C₄ alkanes, such as but not limited to propane, butane, isobutane, and combinations thereof; light olefins, such as but not limited to ethylene, propylene, butenes, or combinations thereof; light cycle oil (LCO); heavy cycle oil (HCO); or combinations thereof. The FCC effluent 116 may comprise less than 35 wt. %, less than 33 wt. %, or even less than 30 wt. % of the light olefins based on the total weight of the FCC effluent 116. In embodiments, the FCC effluent 116 may comprise less than 15 wt. %, less than 12 wt. %, less than 11 wt. %, or even less than 10 wt. % of the dry gas based on the total weight of the FCC effluent 116, where the dry gas gases comprise hydrogen (H₂), methane (C₁), and ethane (C₂).

The processes of the present disclosure include contacting the crude oil feed 102 with the FCC catalyst composition, which includes ZSM-5 zeolite impregnated with phosphorous, USY zeolite impregnated with lanthanum oxide, an alumina binder, colloidal silica, and a matrix material comprising Kaolin clay, at reaction conditions less than high-severity conditions, such as at reaction temperatures of from 500° C. to 580° C., or even 530° C. to 550° C. The combination of the FCC catalyst composition and the reduced reaction temperature of from 500° C. to 580° C. produces greater yield and selectivity towards gasoline compared to operating the FCC system 100 under high-severity conditions at temperatures of greater than 580° C. The processes of the present disclosure may upgrade the crude oil at a conversion rate of greater than or equal to 90%, greater than or equal to 91%, or even greater than or equal to 92%. The conversion is defined as 100% minus the sum of the yield of LCO and the yield of HCO (C %=100%−(Yield_LCO+Yield_HCO)).

In embodiments, the process may produce a yield of gasoline of greater than or equal to 35 wt. % per unit weight of the crude oil feed 102 introduced to the FCC system 100, such as a gasoline yield of greater than or equal to 37 wt. %, greater than or equal to 40 wt. %, greater than or equal to 42 wt. %, from 35 wt. % to 60 wt. %, from 35 wt. % to 50 wt. %, from 37 wt. % to 60 wt. %, from 37 wt. % to 50 wt. %, from 40 wt. % to 60 wt. %, from 40 wt. % to 50 wt. %, from 42 wt. % to 60 wt. %, or from 42 wt. % to 50 wt. % per unit weight of the crude oil feed 102 introduced to the FCC system 100. In embodiments, the crude oil feed 102 is extra light crude oil, such as an AXL crude oil, and the process may produce a gasoline yield of greater than or equal to 40 wt. % per unit weight of the crude oil feed 102 introduced to the FCC system 100, such as a gasoline yield of greater than or equal to 42 wt. %, greater than or equal to 43 wt. %, from 40 wt. % to 60 wt. %, from 40 wt. % to 50 wt. %, from 42 wt. % to 60 wt. %, from 42 wt. % to 50 wt. %, from 43 wt. % to 60 wt. %, or from 43 wt. % to 50 wt. % per unit weight of the crude oil feed 102 introduced to the FCC system 100.

In embodiments, the process may produce a yield of light olefins of less than or equal to 35 wt. % per unit weight of the crude oil feed 102 introduced to the FCC system 100, such as a light olefin yield of less than or equal to 32 wt. %, less than or equal to 30 wt. %, from 0 wt. % to 35 wt. %, from 0 wt. % to 32 wt. %, from 0 wt. % to 30 wt. %, from 20 wt. % to 35 wt. %, from 20 wt. % to 32 wt. %, from 20 wt. % to 30 wt. %, from 25 wt. % to 35 wt. %, from 25 wt. % to 32 wt. %, or from 25 wt. % to 30 wt. % per unit weight of the crude oil feed 102 introduced to the FCC system 100. Without being bound by any particular theory, it is believed that the reduced temperature of the FCC process favors the production of gasoline over light olefins, thereby producing a greater yield of gasoline compared to light olefins resulting from fluidized catalytic cracking of the crude oil feed 102 comprising the light crude oil, extra light crude oil, or combinations thereof.

In embodiments, the process may produce a yield of total gases (constituents that are gases at standard temperature and pressure (273 K and 1 atmosphere respectively) of less than or equal to 48 wt. % per unit weight of the crude oil feed 102 introduced to the FCC system 100, such as a total gas yield of less than or equal to 47 wt. %, less than or equal to 46 wt. %, from 0 wt. % to 48 wt. %, from 0 wt. % to 47 wt. %, from 0 wt. % to 46 wt. %, from 20 wt. % to 48 wt. %, from 20 wt. % to 47 wt. %, from 20 wt. % to 46 wt. %, from 30 wt. % to 48 wt. %, from 30 wt. % to 47 wt. %, or from 30 wt. % to 46 wt. % per unit weight of the crude oil feed 102 introduced to the FCC system 100. In embodiments, the process may produce a yield of dry gases (hydrogen, methane, ethane) of less than or equal to 15 wt. % per unit weight of the crude oil feed 102 introduced to the FCC system 100, such as a dry gas yield of less than or equal to 12 wt. %, less than or equal to 11 wt. %, from 0 wt. % to 15 wt. %, from 0 wt. % to 12 wt. %, from 0 wt. % to 11 wt. %, from 5 wt. % to 15 wt. %, from 5 wt. % to 12 wt. %, or from 5 wt. % to 11 wt. % per unit weight of the crude oil feed 102 introduced to the FCC system 100.

In embodiments, the process may produce a yield of coke of less than or equal to 8 wt. % per unit weight of the crude oil feed 102 introduced to the FCC system 100, such as a coke yield of less than or equal to 7.5 wt. %, less than or equal to 7 wt. %, less than or equal to 6 wt. %, less than or equal to 5 wt. %, from 0 wt. % to 8 wt. %, from 0 wt. % to 7.5 wt. %, from 0 wt. % to 7 wt. %, from 0 wt. % to 6 wt. %, from 0 wt. % to 5 wt. %, from 1 wt. % to 8 wt. %, from 1 wt. % to 7.5 wt. %, from 1 wt. % to 7 wt. %, from 1 wt. % to 6 wt. %, or from 1 wt. % to 5 wt. % per unit weight of the crude oil feed 102 introduced to the FCC system 100. In embodiments, the crude oil feed 102 is extra light crude oil, such as an AXL crude oil, and the process may produce a coke yield of less than or equal to 6 wt. % per unit weight of the crude oil feed 102 introduced to the FCC system 100, such as a coke yield of less than or equal to 5 wt. %, less than or equal to 4 wt. %, from 0 wt. % to 6 wt. %, from 0 wt. % to 5 wt. %, from 0 wt. % to 4 wt. %, from 1 wt. % to 6 wt. %, from 1 wt. % to 5 wt. %, or from 1 wt. % to 4 wt. % per unit weight of the crude oil feed 102 introduced to the FCC system 100.

Although the yield of coke from the processes of the present disclosure is less than the coke yield produced under high-severity conditions, the coke yield from the processes are greater than the yields of coke from fluidized catalytic cracking of conventional FCC feeds, such as atmospheric residues and vacuum gas oils. It is also noted that cracking the AL crude oil may produce greater amounts of coke compared to cracking the AXL crude oil. Producing more coke by cracking the AL crude oil may be beneficial for heat balance of the fluidized catalytic cracking operation. Conventional feeds for the FCC systems, such as atmospheric residue (AR) and vacuum gas oil (VGO), produce low amounts of coke and therefore require an injection of external heat source for satisfying the heat balance requirements of the operation. However, the injection of external heat sources increases the operational cost of the process and thus reducing the potential profits. Thus, producing additional coke by cracking the AL crude oil may improve the heat balance and reduce operational costs of the FCC process by reducing or eliminating the use of supplemental fuels for regenerating catalyst and increasing the catalyst temperature to maintain the reaction temperatures. Further, embodiments of the present disclosure may provide catalysts with a reduced deactivation rate during catalytic cracking of crude oil that is added directly to the FCC system. The reduced deactivation rate of the catalyst may improve the economics of catalytically cracking crude oil to form light olefins, among other features.

EXAMPLES

The various aspects of the present disclosure will be further clarified by the following examples. The examples are illustrative in nature and should not be understood to limit the subject matter of the present disclosure.

Example 1: Preparation of FCC Catalyst Composition

In Example 1, 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 below in Table 2.

	TABLE 2
	Chemical	Supplier
	LUDOX ® TM40 colloidal silica (SiO2)	DuPont
	Sodium hydroxide (NaOH)	Sigma Aldrich
	Y zeolite (CBV-780)	Zeolyst International
	ZSM-5 zeolite (CBV-3024E)	Zeolyst International
	Formic acid	Sigma Aldrich
	Clay	Petrobras
	Alumina, PURAL ™ SB Grade	Petrobras
	Diammonium hydrogen phosphate	Sigma Aldrich
	Lanthanum nitrate (III) hydrate	Fluka

To prepare the FCC catalyst composition of Example 1, the ZSM-5 zeolite was impregnated with 7.5 wt. % phosphorous pentoxide, and the USY zeolite was impregnated with 2.5 wt. % lanthanum oxide. The ZSM-5 zeolite had an average silica-to-alumina ratio of 30 and an average surface area of 405 m²/g. The USY zeolite had an average total pore volume per unit weight of 0.486 cm³/g. The ZSM-5 zeolite impregnated with phosphorous pentoxide and the USY zeolite impregnated with lanthanum oxide were combined with water, the alumina binder, the colloidal silica, and the Kaolin clay to produce a mixture. The mixture was stirred for 1 hour and the resulting slurry was placed in a temperature-programmed oven for drying and calcination to produce FCC catalyst composition particles. The FCC catalyst composition particles were ground to a fine powder by means of a mortar and a pestle. Then, the ground FCC catalyst composition microparticles were sieved for a fraction between 40-120 micrometers (μm) and used for characterization and evaluation. The composition of the FCC catalyst composition microparticles of Example 1 is provided in Table 3.

TABLE 3
Component	Weight %	Notes

ZSM-5	20	Phosphorus impregnated at 7.5 wt % P2O5 on
		zeolite
USY	21	Lanthanum impregnated at 2.5 wt % La2O3 on
		zeolite
Alumina	8	Pural SB from Sasol
Clay	49	Kaolin
Silica	2	Added as colloidal silica Ludox TM-40

Catalyst Testing—MAT Testing

In the Examples of the present disclosure, crude oil feed streams were catalytically cracked with the FCC catalyst composition of Example 1 using a micro activity test (MAT) instrument having a quartz reactor. The MAT instrument was obtained from Sakuragi Rikagaku (Japan). The FCC catalyst composition of Example 1 was evaluated for cracking crude oil according to standard test method ASTM D-3907.

Referring to FIG. 2, the MAT unit 300 used for the MAT testing in these examples is schematically depicted. The MAT unit 300 includes a fixed bed quartz tubular reactor 303. The catalyst 304 is loaded into the fixed bed quartz tubular reactor 303 in between layers of quartz wool 306. The catalyst 304 is steam deactivated at 810° C. for six hours prior to the reaction to hydrothermally age the catalyst 304 to mimic the equilibrium catalyst in commercial operation. The catalyst 304 in the fixed bed quartz tubular reactor 303 is heated by a furnace 322, which includes a top heater 324, a middle heater 326, and a bottom heater 328. The feed 302 is injected in the top of the fixed bed quartz tubular reactor 303 through a feed syringe. The feed 302 can be heated prior to injection with the syringe heater 318. The injection site can be heated prior to injection by the pre-heater 320. The feed 302 is in contact with the catalyst 304 for a time on stream of thirty seconds per reaction test cycle. The reaction temperature is controlled using temperature controller 316, which is integrated with the furnace 122. After contacting the feed 302 with the catalyst 304, the reaction effluent, which comprises liquid products and gaseous products, is passed out of the fixed bed quartz tubular reactor 303. The liquid products created by the reaction are collected in the liquid receiver 308, and the gaseous products created by the reaction are collected in the gas collectors 310 through water displacement. The gaseous products are then analyzed by the gas chromatograph 312. After the reaction, the catalyst 304 is stripped using nitrogen gas 314, which enters the fixed bed quartz tubular reactor at 30 cm³/min.

Examples 2-5: Cracking AL and AXL Crude Oils with the FCC Catalyst Composition

In Examples 2-5, the FCC catalyst composition of Example 1 is used to crack AL crude oil and AXL crude oil under various reaction conditions. The properties of AL crude oil and the AXL crude oil used as the crude oil feeds in Examples 2-5 are provided in Table 1. In Examples 2-5, the catalytic cracking of AL crude oil and AXL crude oil with the FCC catalyst composition of Example 1 was carried out in the MAT unit 300 according to standard test method ASTM D-3907. Prior to evaluation, the FCC catalyst composition was steamed at 810° C. for 6 hours prior to conducting the cracking reactions. The experiments were conducted in the MAT unit at 30 seconds time-on-stream (TOS). The cracking reactions were conducted at temperatures of 530° C. and 550° C. for each of the AL crude oil and the AXL crude oil. The catalyst-to-oil weight ratios for each of Examples 2-5 are provided in Table 4.

After each reaction, the FCC catalyst composition was stripped using nitrogen (N₂) at a flow rate of 30 cubic centimeters per minute (cm³/min). The liquid products were collected in a liquid receiver and the gaseous products were collected in a gas burette by water displacement and sent to the gas chromatograph (GC) for analysis. The gaseous products were analyzed by an online gas chromatography system (Agilent 7890 gas chromatograph) equipped with both FID and TCD detectors. The liquid product stream is analyzed according to the offline analytical test methods. In particular, the liquid product stream is analyzed by simulated distillation according to test method EN 15199-2 using the Agilent 7890 gas chromatograph and naphtha analysis techniques.

For the simulated distillation, the analysis was conducted for four distillation fractions: (1) light hydrocarbon gases having 1-4 carbon atoms; (2) a gasoline fraction having a boiling point range of from 20° C. to 221° C.; (3) an LCO fraction having a boiling point range of from 221° C. to 343° C.; and (4) an HCO fraction having boiling point temperatures of greater than 343° C. Coke was quantified after passing an air stream through the MAT unit at high temperatures to burn the coke into a mixture of carbon monoxide, carbon dioxide, and water, and then passing the combustion gases through a CO₂ analyzer, which included a calibrated infrared analyzer. The MAT results of Examples 2-5 for cracking the AL crude oil and the AXL crude oil over the FCC catalyst composition of Example 1 at temperatures of 530° C. and 550° C. are shown in Table 4.

Comparative Example 6: High-Severity Cracking of AXL Crude Oil

In Comparative Example 6, the AXL crude oil having the properties in Table 1 was cracked with the FCC catalyst composition under high-severity reactions conditions, which included a reaction temperature of 650° C. The catalyst-to-oil ratio for Comparative Example 6 was 8.65. Other than the reaction temperature and slight difference in catalyst-to-oil weight ratio, the cracking in Comparative Example 6 was the same as described in relation to Examples 2-5. The MAT results of Comparative Example 6 are provided in Table 4.

Comparative Example 7: High-Severity Cracking of AL Crude Oil

In Comparative Example 7, the AL crude oil having the properties in Table 1 was cracked with the FCC catalyst composition under high-severity reactions conditions, which included a reaction temperature of 640° C. The catalyst-to-oil ratio for Comparative Example 6 was 8.66. Other than the reaction temperature and slight difference in catalyst-to-oil weight ratio, the cracking in Comparative Example 7 was the same as described in relation to Examples 2-5. The MAT results of Comparative Example 7 are provided in Table 4.

Discussion of Results of Catalytic Cracking

Table 4 provides the MAT test results for the catalytic cracking conducted in Examples 2-5 and Comparative Examples 6 and 7.

	TABLE 4
	2	3	4	5	CE6	CE7

Temp. (° C.)	530	550	530	550	650	640
Time on stream (s)	30	30	30	30	30	30
Catalyst	Ex. 1	Ex. 1	Ex. 1	Ex. 1	Ex. 1	Ex. 1
Steaming conditions	810° C./	810° C./	810° C./	810° C./	810° C./	810° C./
	6 hrs	6 hrs	6 hrs	6 hrs	6hrs	6 hrs
Crude Oil Feed	AXL	AXL	AL	AL	AXL	AL
CTO Ratio	8.08	7.66	7.55	7.25	8.65	8.66
Conversion (%) (100 −	91.66	93.04	91.82	90.25	92.40	89.88
LCO − HCO)

Yields (wt. %)

Hydrogen (H2)	0.42	0.58	0.64	0.68	0.62	0.29
Methane (C1)	0.70	1.10	1.31	1.70	4.22	4.26
Ethane (C2)	0.73	0.99	1.26	1.47	2.94	3.26
Ethylene (C2═)	5.36	6.44	5.81	6.46	8.96	9.05
Propane (C3)	5.41	5.49	5.53	5.10	2.40	2.86
Propylene (C3═)	13.12	14.41	12.91	14.41	18.21	17.38
Isobutane (iC4)	5.73	5.51	5.14	4.33	1.24	1.05
Normal Butane (nC4)	2.60	2.44	3.08	2.86	1.72	0.88
Trans-2-butene (t2C4═)	2.11	2.11	1.93	2.04	2.19	2.13
1-Butene (1C4═)	1.55	1.49	1.33	1.45	1.99	1.86
Isobutene (iC4═)	3.55	3.40	3.13	3.25	3.42	3.34
Cis-2-butene (c2C4═)	1.55	1.53	1.39	1.48	1.83	1.77
1,3-Butadiene	0.02	0.03	0.03	0.03	0.10	0.13
C4 in liquid	0.69	0.55	0.44	0.46	0.035	0.04
Total Gas	43.54	46.09	43.94	45.72	49.86	48.32
Gasoline	45.47	43.38	41.46	37.13	33.40	33.13
LCO	6.43	5.35	6.02	6.83	6.41	8.34
HCO	1.91	1.61	2.15	2.92	1.19	1.78
Coke	2.64	3.57	6.43	7.40	9.15	8.44

Groups (wt. %)

Dry gas (H2, C1, C2)	7.21	9.11	9.02	10.31	16.73	16.86
LPG (C3-C4)	36.34	36.98	34.91	34.41	33.13	31.45
Light Olefins (C2═, C3═,	27.95	29.98	26.97	29.58	36.73	35.70
C4═)
C3═ and C4═	22.59	23.54	21.16	23.12	27.77	26.65
Butenes (C4═)	9.48	9.12	8.25	8.72	9.56	9.27

As shown in Table 4, cracking the AL crude oil and AXL crude oil with the FCC catalyst compositions at the reaction temperatures of 530° C. and 550° C., as in Examples 2-5, produced greater yield and selectivity towards gasoline compared to cracking at the reaction temperatures of 650° C. and 640° C., as in Comparative Examples 6 and 7, respectively. Cracking the AL crude oil and AXL crude oil with the FCC catalyst compositions at the reaction temperatures of 530° C. and 550° C., as in Examples 2-5, produced high overall conversion rates of greater than 90%. Regarding gasoline yield, the cracking in Examples 2-5 produced yields of gasoline of greater than 37 wt. %. Cracking the AXL crude oil with the FCC catalyst composition, as in Examples 2 and 3, resulted in a gasoline yield of over 43 wt. %, which is greater than the gasoline yield achieved from cracking the AL crude oil and about 10 wt. % greater than the gasoline yield achieved in Comparative Examples 6 and 7, which were conducted at the higher temperatures of 650° C. and 640° C., respectively. The gasoline yield of over 43 wt. % for cracking the AXL crude oil of Examples 2 and 3 represent about a 30% increase in gasoline yield over cracking in Comparative Examples 6 and 7, which is a significant increase in gasoline yield. As shown in Table 4, the greater gasoline yield of 45.47 wt. % was achieved at 91.66% conversion of AXL crude oil at a cracking temperature of 530° C.

The cracking in Examples 2-5 also resulted in a reduction in yield of light olefins compared to the cracking in Comparative Examples 6 and 7, which were conducted at the high-severity reaction temperatures. The cracking in Examples 2-5 at reaction temperatures of 530° C. and 550° C. resulted in yields of light olefins that were less than 30 wt. %. For comparison, the cracking of Comparative Examples 6 and 7 conducted at the greater high-severity reaction temperatures resulted in total yield of light olefins of greater than 35 wt. %. This represents around a 15% reduction in the yield of light olefins resulting from cracking at temperature of 530° C. and 550° C. compared to cracking at high-severity reaction temperatures of from 640° C. to 650° C. Without being bound by any particular theory, it is believed that the reduced temperature of the FCC process favors the production of gasoline over light olefins, thereby producing a greater yield of gasoline compared to light olefins.

Cracking the AL crude oil and AXL crude oil with the FCC catalyst composition at the reduced reaction temperatures (Examples 2-5) also reduced the yield of total gases compared to cracking the AL crude oil and AXL crude oil at the high-severity reaction temperatures (CE-6 and CE-7). The total gases refer to the mixture of constituents that are gases at standard temperature and pressure (273 K and 1 atm). For instance, the cracking of Examples 2-5 produced yields of total gases in the range of from 43.54 wt. % to 46.09 wt. % compared to total gas yield from Comparative Examples 6 and 7 of 49.86 wt. % and 48.32 wt. %. Cracking the AL crude oil and AXL crude oil with the FCC catalyst composition at the reduced reaction temperatures (Examples 2-5) also reduced the yield of dry gas (H2, C1, and C2) compared to cracking the AL crude oil and AXL crude oil at the high-severity reaction temperatures (CE-6 and CE-7). Without being bound by any particular theory, it is believed that the reduced cracking temperature of the cracking processes of the present disclosure reduces over-cracking of the hydrocarbons from AL crude oil or AXL crude oil, such as by reducing further cracking of reaction products to light gases. Thus, in the cracking processes of the present disclosure, gasoline constituents produced during cracking are not further cracked to produce light gases. As a result, the gasoline yields are increases and the light olefin and light gas yields are reduced.

Cracking the AL crude oil and AXL crude oil with the FCC catalyst composition at the reduced reaction temperatures (Examples 2-5) also reduced the amount of coke produced compared to cracking the AL crude oil and AXL crude oil at the high-severity reaction temperatures (CE-6 and CE-7). For instance, the cracking of Examples 2-5 produced coke yields in the range of from 2.64 wt. % to 7.40 wt. % compared to coke yield from Comparative Examples 6 and 7 of 9.15 wt. % and 8.44 wt. %, respectively. Thus, the lower cracking temperature is shown to result in less coke produced during the cracking reaction.

From Table 4, it is also noted that cracking the AL crude oil in Examples 4 and 5 produced greater amounts of coke compared to cracking the AXL crude oil in Examples 2 and 3. Producing more coke by cracking the AL crude oil may be beneficial for heat balance of the fluidized catalytic cracking operation.

A first aspect of the present disclosure may be directed to a process for converting crude oil to gasoline. The process may comprise contacting a crude oil feed with a fluidized catalytic cracking (FCC) catalyst composition in a cracking reaction zone of an FCC unit at a temperature of from 500° C. to 580° C., a catalyst-to-oil weight ratio of from 2 to 40, and a contact time of from 0.1 seconds to 60 seconds. The FCC catalyst composition may comprise ultrastable Y-type zeolite (USY zeolite) impregnated with lanthanum, ZSM-5 zeolite impregnated with phosphorous, an alumina binder, colloidal silica, and a matrix material comprising Kaolin clay. The crude oil feed may be a light crude oil, an extra light crude oil, or combination thereof, and may have an API gravity of from 33 degrees to 45 degrees and a density of from 0.80 g/cm³ to 0.87 g/cm³. The contacting may cause at least a portion of hydrocarbons in the crude oil feed to undergo cracking reactions to produce an FCC effluent comprising gasoline.

A second aspect of the present disclosure may include the first aspect, where the crude oil feed may have an initial boiling point from 15° C. to 40° C. and an end boiling point less than or equal to 720° C.

A third aspect of the present disclosure may include either one of the first or second aspects, where the crude oil feed may have at least one of the following: a 5 wt. % boiling point temperature of from 20° C. to 80° C.; a 50 wt. % boiling point temperature of from 200° C. to 350° C.; a 90 wt. % boiling point temperature of from 400° C. to 700° C.; or any combination thereof.

A fourth aspect of the present disclosure may include any one of the first through third aspects, where the crude oil feed may have one or more of the following: a concentration of paraffin compounds of less than 50 wt. % per unit weight of the crude oil; a concentration of aromatic compounds of greater than or equal to 20 wt. % per unit weight of the crude oil; or both.

A fifth aspect of the present disclosure may include any one of the first through fourth aspects, where the crude oil feed may have a nitrogen concentration of less than 1600 ppmw, such as less than 1000 ppmw, from 0 ppmw to 1600 ppmw, or from 0 ppmw to 1000 ppmw, per unit weight of the crude oil feed.

A sixth aspect of the present disclosure may include any one of the first through fifth aspects, where the crude oil feed may have a sulfur concentration of less than 2.2 wt. %, per unit weight of the crude oil feed.

A seventh aspect of the present disclosure may include any one of the first through sixth aspects, where the crude oil feed may have one or more of the following: less than 30 ppmw vanadium, such as less than 25 ppmw or less than 20 ppmw; less than 15 ppmw nickel, such as less than 10 ppmw nickel; less than 5 ppmw iron, such as less than 2 ppmw iron; or any combinations thereof.

An eighth aspect of the present disclosure may include any one of the first through seventh aspects, where the crude oil feed may be an extra light crude oil, such as an Arab extra light crude oil.

A ninth aspect of the present disclosure may include the eighth aspect, where the extra light crude oil may have an API gravity of from 35 degrees to 45 degrees, such as from 38 degrees to 45 degrees, from 40 degrees to 45 degrees, or from 38 degrees to 42 degrees.

A tenth aspect of the present disclosure may include either one of the eighth or ninth aspects, where the extra light crude oil may have a density of from 0.80 g/cm³ to 0.85 g/cm³, or from 0.81 g/cm³ to 0.83 g/cm³.

An eleventh aspect of the present disclosure may include any one of the eighth through tenth aspects, where the extra light crude oil may have a nitrogen concentration of less than 800 ppmw or less than 500 ppmw, per unit weight of the extra light crude oil.

A twelfth aspect of the present disclosure may include any one of the eighth through eleventh aspects, where the extra light crude oil may have a sulfur concentration of less than 2 wt. %, such as less than 1.8 wt. %, per unit weight of the extra light crude oil.

A thirteenth aspect of the present disclosure may include any one of the eighth through twelfth aspects, where the extra light crude oil may have an initial boiling point from 15° C. to 30° C. and an end boiling point less than or equal to 720° C.

A fourteenth aspect of the present disclosure may include any one of the eighth through thirteenth aspects, where the extra light crude oil may have a 50 wt. % boiling point temperature of from 200° C. to 290° C., a 90 wt. % boiling point temperature of from 400° C. to 550° C., or both.

A fifteenth aspect of the present disclosure may include any one of the eighth through fourteenth aspects, where the FCC effluent may comprise a yield of gasoline of greater than or equal to 40 wt. %, greater than or equal to 42 wt. %, or even greater than or equal to 43 wt. %, where the yield of gasoline is the mass of gasoline produced per unit weight of the extra light crude oil introduced to the FCC unit.

A sixteenth aspect of the present disclosure may include any one of the first through seventh aspects, where the crude oil feed may be a light crude oil, such as an Arab light crude oil.

A seventeenth aspect of the present disclosure may include the sixteenth aspect, where the light crude oil may have an API gravity of from 30 degrees to 35 degrees, such as from 31 degrees to 34 degrees, from 31 degrees to 33 degrees, or about 32.8 degrees.

An eighteenth aspect of the present disclosure may include either one of the sixteenth or seventeenth aspects, where the light crude oil may have a density of from 0.85 g/cm³ to 0.87 g/cm³.

A nineteenth aspect of the present disclosure may include any one of the sixteenth through eighteenth aspects, where the light crude oil may have a nitrogen concentration of from 500 ppmw to 1600 ppmw, such as from 500 ppmw to 1000 ppmw, per unit weight of the light crude oil.

A twentieth aspect of the present disclosure may include any one of the sixteenth through nineteenth aspects, where the extra light crude oil may have a sulfur concentration of less than 2.4 wt. %, such as from 1.9 wt. % to 2.4 wt. %, per unit weight of the light crude oil.

A twenty-first aspect of the present disclosure may include any one of the sixteenth through twentieth aspects, where the light crude oil may have an initial boiling point from 20° C. to 40° C. and an end boiling point less than or equal to 720° C.

A twenty-second aspect of the present disclosure may include any one of the sixteenth through twenty-first aspects, where the light crude oil may have a 50 wt. % boiling point temperature of from 290° C. to 350° C., a 90 wt. % boiling point temperature of from 550° C. to 700° C., or both.

A twenty-third, aspect of the present disclosure may include any one of the sixteenth through twenty-second aspects, where the FCC effluent may comprise a yield of gasoline of greater than 35 wt. %, where the yield of gasoline is the mass of gasoline produced per unit weight of the light crude oil introduced to the FCC unit.

A twenty-fourth aspect of the present disclosure may include any one of the first through twenty-third aspects, where the crude oil feed may be contacted with the FCC catalyst composition at a temperature of from 530° C. to 550° C.

A twenty-fifth aspect of the present disclosure may include any one of the first through twenty-fourth aspects, where the crude oil feed may be contacted with the FCC catalyst composition at a catalyst-to-oil weight ratio of from 2 to 10, from 5 to 10, from 7 to 10, or from 7 to 9.

A twenty-sixth aspect of the present disclosure may include any one of the first through twenty-fifth aspects, where the crude oil feed may be contacted with the FCC catalyst composition for a contact time of from 10 seconds to 40 seconds.

A twenty-seventh aspect of the present disclosure may include any one of the first through twenty-sixth aspects, comprising passing the crude oil feed directly to the cracking reaction zone of the FCC unit.

A twenty-eighth aspect of the present disclosure may include any one of the first through twenty-seventh aspects, where the process does not include subjecting the crude oil feed to separation by distillation upstream of the FCC unit.

A twenty-ninth aspect of the present disclosure may include any one of the first through twenty-eighth aspects, where the cracking reaction zone of the FCC unit may be a downflow reactor or an upflow reactor.

A thirtieth aspect of the present disclosure may include any one of the first through twenty-ninth aspects, further comprising separating the FCC effluent from used FCC catalyst composition downstream of the cracking reaction zone of the FCC unit, regenerating the used catalyst composition in a regenerator to produce a regenerated FCC catalyst composition, and passing the regenerated FCC catalyst composition back to an inlet of the cracking reaction zone of the FCC unit.

A thirty-first aspect of the present disclosure may include any one of the first through thirtieth aspects, where the FCC catalyst composition may comprise from 10 wt. % to 30 wt. % USY zeolite impregnated with lanthanum.

A thirty-second aspect of the present disclosure may include any one of the first through thirty-first aspects, where the FCC catalyst composition may comprise from 10 wt. % to 30 wt. % ZSM-5 zeolite impregnated with phosphorous.

A thirty-third aspect of the present disclosure may include any one of the first through thirty-second aspects, where the USY zeolite may be impregnated with from 1 wt. % to 10 wt. % lanthanum oxide based on the total weight of the USY zeolite.

A thirty-fourth aspect of the present disclosure may include any one of the first through thirty-third aspects, where the ZSM-5 zeolite may be impregnated with from 1 wt. % to 15 wt. % phosphorous pentoxide based on the total weight of the ZSM-5 zeolite.

A thirty-fifth aspect of the present disclosure may include any one of the first through thirty-fourth aspects, where the FCC catalyst composition may comprise 21 wt. % USY zeolite impregnated with lanthanum, 20 wt. % ZSM-5 zeolite impregnated with phosphorous pentoxide, 8 wt. % alumina binder, 49 wt. % Kaolin clay, and 2 wt. % colloidal silica, where the weight percentages are based on the total weight of the FCC catalyst composition.

A thirty-sixth aspect of the present disclosure may include the thirty-fifth aspect, where the USY zeolite may comprise 2.5 wt. % lanthanum oxide per unit weight of the USY zeolite.

A thirty-seventh aspect of the present disclosure may include either one of the thirty-fifth or thirty-sixth aspects, where the ZSM-5 zeolite may comprise 7.5 wt. % phosphorous pentoxide.

A thirty-eighth aspect of the present disclosure may include any one of the first through thirty-seventh aspects, where the FCC catalyst composition may comprise a plurality of catalyst particles, where each of the plurality of catalyst particles comprises the ZSM-5 zeolite impregnated with phosphorous, the USY zeolite impregnated with lanthanum, the alumina binder, the Kaolin clay, and the colloidal silica.

It is noted that any two quantitative values assigned to a property may constitute a range of that property, and all combinations of ranges formed from all stated quantitative values of a given property are contemplated in this disclosure.

It is noted that one or more of the following claims utilize the term “where” as a transitional phrase. For the purposes of defining the present technology, it is noted that this term is introduced in the claims as an open-ended transitional phrase that is used to introduce a recitation of a series of characteristics of the structure and should be interpreted in like manner as the more commonly used open-ended preamble term “comprising.”

Having described the subject matter of the present disclosure in detail and by reference to specific aspects, it is noted that the various details of such aspects should not be taken to imply that these details are essential components of the aspects. Rather, the claims appended hereto should be taken as the sole representation of the breadth of the present disclosure and the corresponding scope of the various aspects described in this disclosure. Further, it will be apparent that modifications and variations are possible without departing from the scope of the appended claims.