Method for treating sulfur-containing whole crude oil

Abstract

In accordance with embodiments described herein, a method of treating a whole crude oil feed stream may include feeding the whole crude oil feed stream to a fluid catalytic cracking unit and contacting an adsorbent material and a cracking catalyst. The adsorbent material may adsorb at least a portion of the sulfur of the whole crude oil feed stream, and at least a portion of the whole crude oil feed stream may be catalytically cracked to produce coke deposited on the cracking catalyst. The method may also include feeding the sorbent material and the cracking catalyst to a regenerator, wherein the sorbent material and the cracking catalyst contact an oxygen-containing gas at a temperature sufficient to remove at least a portion of the sulfur on the sorbent material and combust at least a portion of the coke on the cracking catalyst.

Description

[0001] Cross - Reference to Related Applications

[0002] This application claims priority to U.S. Patent Application No. 18 / 052,447, filed on November 3, 2022, with the invention title "Method for Processing Sulfur - Containing Whole Crude Oil", the entire content of which is incorporated herein by reference. Technical Field

[0003] Embodiments of the present disclosure generally relate to chemical processing, and more particularly to processes and systems for utilizing fluid catalytic cracking feed chemicals. Background Art

[0004] Ethylene, propylene, butene, butadiene, and aromatic compounds such as benzene, toluene, and xylene are basic intermediates in most of the petrochemical industry. They are typically obtained by thermal cracking (or steam pyrolysis) of petroleum gas and distillate oils (such as naphtha, kerosene, or even diesel). These compounds are also produced by the fluid catalytic cracking (FCC) process in refineries, in which traditional heavy feeds (such as gas oils or residues) are converted. Typical FCC feeds range from hydrocracked bottom oil to heavy feed fractions such as vacuum gas oil and atmospheric residue; however, these feeds are limited. Due to the limitation of these traditional feeds, there is a market demand for the above - mentioned chemical intermediates. Summary of the Invention

[0005] According to the embodiments described herein, whole crude oil (as opposed to downstream refined petrochemical products) can be converted into products such as olefins and aromatics by fluid catalytic cracking. However, these whole crude oil feeds contain sulfur, which, if not removed, will have an adverse effect on the products. Methods for cracking whole crude oil while simultaneously reducing sulfur are described herein. In these embodiments described herein, an adsorbent material is used in the FCC process, where the adsorbent material is sometimes mixed with the cracking catalyst and passed together with the cracking catalyst between the FCC unit and the regenerator. In the regenerator, the sulfur content on the adsorbent material can be reduced so that the treatment can be continuously repeated. In such embodiments, there is no need to remove sulfur through pretreatment such as hydrotreating. For example, in some embodiments described herein, no external hydrogen is introduced into the fluid catalytic cracking unit, and there is no need to hydrogen - treat the adsorbent material or the catalyst before the adsorbent material or the catalyst enters the FCC unit. In addition, the spent adsorbent material and the spent catalyst can be sent to the same regenerator and regenerated under the same regeneration conditions. Finally, the adsorbent material and the catalyst are capable of sufficiently removing sulfur and catalytic cracking components from the stream containing whole crude oil, where the whole crude oil does not need to be separated before entering the fluid catalytic cracking unit.

[0006] According to the embodiments described herein, a method for processing a whole crude oil feed stream can include feeding the whole crude oil feed stream into a fluid catalytic cracking unit and contacting the whole crude oil feed stream with an adsorbent material and a cracking catalyst in the fluid catalytic cracking unit. The cracking catalyst can include zeolite. The whole crude oil feed stream may contain sulfur. Further, when in the fluid catalytic cracking unit, the adsorbent material can adsorb at least a portion of the sulfur of the whole crude oil feed stream such that the sulfur content on the adsorbent material increases. Further, at least a portion of the whole crude oil feed stream is catalytically cracked to produce one or more products and coke deposited on the cracking catalyst. The method can further include feeding the adsorbent material and the cracking catalyst containing coke into a regenerator, wherein the adsorbent material and the cracking catalyst can be contacted with an oxygen-containing gas at a regenerator temperature sufficient to remove at least a portion of the sulfur on the adsorbent material and burn at least a portion of the coke on the cracking catalyst. The method can further include feeding the adsorbent material and the cracking catalyst from the regenerator into the fluid catalytic cracking unit.

[0007] Additional features and advantages of the embodiments will be set forth in the detailed description which follows, and in part will be obvious from the description, or can be learned by practice of the techniques described in the foregoing including the detailed description, the claims and the drawings.

[0008] Brief Description of the Drawings

[0009] The following detailed description of specific embodiments of the present disclosure can be best understood when read in conjunction with the following drawings, in which like structures are denoted by like reference numerals and in which:

[0010] Figure 1 is a general schematic diagram of a hydrocarbon feed conversion system according to one or more embodiments described in the present disclosure.

[0011] For simplicity of description of the schematic diagrams and the associated drawings, many valves, temperature sensors, electronic controllers, etc. that are used and known to those of ordinary skill in the art in certain chemical processing operation fields are not included. Further, the accompanying components that are typically included in chemical processing operations are not depicted, e.g., a gas source, a catalyst hopper, and a flue gas treatment system. The accompanying components in the hydrocracking unit (e.g., an exhaust stream, a spent catalyst discharge subsystem, and a catalyst replacement subsystem) are also not shown. It should be understood that these components are within the spirit and scope of the disclosed embodiments herein. However, operating components such as those described in the present disclosure can be added to the embodiments described in the present disclosure.

[0012] It should also be noted that the arrows in the drawings refer to the process flow. However, the arrows can equivalently refer to the transfer pipelines that can be used to transfer process steam between two or more system components. In addition, the arrows connected to the system components define the inlets or outlets in each given system component. The arrow direction generally corresponds to the main movement direction of the material of the flow contained within the physical transfer pipeline represented by the arrow. In addition, the arrows that do not connect two or more system components represent the product stream leaving the depicted system or the system feed stream entering the depicted system. The product stream can be further processed in an accompanying chemical processing system or can be commercialized as a final product. The system feed stream can be a stream transferred from an accompanying chemical processing system or can be an unprocessed raw material stream. Some arrows can represent recycle streams, which are the effluent streams that are recycled back to the system components in the system. However, it should be understood that in some embodiments, any represented recycle stream can be replaced by a system feed stream of the same material, and a portion of the recycle stream can leave the system as a system product.

[0013] In addition, the arrows in the drawings can schematically depict the process steps of transferring a flow from one system component to another. For example, an arrow pointing from one system component to another can represent "transferring" the system component effluent to another system component, which can include the contents of the process flow that "leave" or "are removed" from one system component and the introduction of the contents of the product stream "into" another system component.

[0014] It should be understood that according to the embodiments presented in the relevant drawings, the arrow between two system components can indicate that the flow is not processed between the two system components. In other embodiments, the flow represented by the arrow may have substantially the same composition during the transfer between the two system components. In addition, it should be understood that in one or more embodiments, the arrow can indicate that at least 75 wt.%, at least 90 wt.%, at least 95 wt.%, at least 99 wt.%, at least 99.9 wt.%, or even 100 wt.% of the flow is transferred between the system components. Therefore, in some embodiments, only a portion of the flow represented by the arrow can be transferred between the system components, for example, if there is a tail flow.

[0015] It should be understood that when two or more lines intersect in the schematic flow diagram of the relevant drawing, two or more process flows are "mixed" or "combined". The mixing or combination can also include mixing by directly introducing two flows into a similar reactor, separation device, or other system component. For example, it should be understood that when two flows are depicted as being directly combined before entering a separator or reactor, in some embodiments, the flows may be equivalent to being introduced into the separator or reactor and mixed in the reactor.

[0016] Reference will now be made in more 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 like parts. Detailed Description

[0017] Reference will now be made in more detail to various embodiments. Referring Figure 1 , a hydrocarbon feed conversion system 100 is depicted in which the presently disclosed methods may be carried out. According to one or more embodiments, a method for processing a whole crude oil feed stream 102 may include feeding the whole crude oil feed stream 102 into a fluid catalytic cracking unit 130, where the whole crude oil feed stream 102 contacts an adsorbent material and a cracking catalyst in the fluid catalytic cracking unit 130. As described in detail herein, the adsorbent material and the cracking catalyst may be circulated between the fluid catalytic cracking unit 130 and a regenerator 140.

[0018] As used in the present disclosure, the term "fluid catalytic cracking unit" refers to a vessel or other similar object in which one or more cracking chemical reactions occur among one or more reactants in the presence of one or more catalysts. Solids (such as catalysts) in the fluid catalytic cracking unit 130 typically operate in a fluidized flow manner. "Cracking" as used in the present disclosure generally refers to a chemical reaction in which carbon-carbon bonds are broken. For example, by breaking one or more carbon-carbon bonds, a molecule having carbon-carbon bonds is broken into multiple molecules, or a compound including an alkyl or cyclic moiety (such as an alkane, cycloalkane, naphthalene, aromatic compound, etc.) is converted into an olefin compound and / or a compound that does not include a cyclic moiety or includes fewer cyclic moieties than before cracking. In addition, the fluid catalytic cracking unit 130 may include multiple zones. For example, the fluid catalytic cracking unit 130 may include a mixing zone in which one or more reactants may be mixed with any catalyst and / or adsorbent material present in the fluid catalytic cracking unit 130; a reaction and adsorption zone in which one or more reactants may react with one or more catalysts and one or more adsorbent materials; and a separation zone in which one or more catalysts and one or more adsorbent materials may be separated from the remaining contents of the fluid catalytic cracking unit 130.

[0019] As used in the present disclosure, the term "catalyst" may refer to any substance that increases the rate of a specific chemical reaction. The catalysts described in the present disclosure may be used to facilitate various reactions, such as but not limited to cracking (including aromatics cracking). The term "cracking catalyst" refers to a catalyst that is operable to carry out the above-described cracking reactions, but is not limited to only carrying out these types of reactions.

[0020] As used in the present disclosure, the term "adsorbent material" refers to any composition that is capable of adsorbing at least a portion of an unwanted substance (such as sulfur) from a feed stream.

[0021] As used herein, the term "regenerator" refers to any suitable combustion device into which combustion gas (such as air or other oxygen-containing gas stream) is introduced and flue gas is discharged. The combustion gas may include one or more of combustion air, oxygen, fuel gas, fuel oil, other components, or any combination thereof. In a regenerator (such as regenerator 140), coke that may be deposited on the catalyst may be at least partially oxidized (burned) in the presence of the combustion gas to form at least carbon dioxide and water. In some embodiments, the coke deposit on the catalyst may be completely oxidized in regenerator 140. Other organic compounds (such as residual cracking reaction products) may also be oxidized in the presence of the combustion gas in regenerator 140. Other gases, such as carbon monoxide, may be formed during the oxidation of the coke in regenerator 140. The oxidation of the coke deposit generates heat, which may be transferred to and retained by the regenerated catalyst when transferred to other devices.

[0022] As generally described herein, the cracking catalyst and adsorbent material can be in a "spent" or "regenerated" state. The spent state is generally after undergoing a cracking reaction in FCC unit 130, and the regenerated state is generally after regeneration in regenerator 140. For example, stream 106 typically includes spent cracking catalyst and spent adsorbent material, while stream 110 typically includes regenerated cracking catalyst and regenerated adsorbent material.

[0023] As used herein, the term "spent catalyst" generally refers to a catalyst that has been introduced and passed through a cracking reaction zone to crack hydrocarbon materials (such as a whole crude oil feed stream), but has not been regenerated in regenerator 140. Generally, the activity of the spent catalyst is significantly reduced, for example, due to the deposition of coke on the catalyst. The "spent catalyst" may have coke deposited on the catalyst and may include partially coked catalyst as well as fully coked catalyst. The amount of coke deposited on the "spent catalyst" may be greater than the amount of coke remaining on the regenerated catalyst after regeneration. As used herein, the term "regenerated catalyst" generally refers to a catalyst that has been introduced into the cracking reaction zone and then regenerated in a regenerator (such as regenerator 140) to heat the catalyst to a higher temperature, oxidize and remove at least a portion of the coke in the catalyst to restore at least a portion of the catalytic activity of the catalyst, or both.

[0024] As used in this disclosure, the term "spent adsorbent material" refers to an adsorbent material that has adsorbed at least a portion of sulfur from a sulfur-containing stream. The spent adsorbent material may have a higher sulfur adsorption amount after contacting the full crude oil feed stream 102 in the fluid catalytic cracking unit 130 as compared to when the adsorbent material was first introduced into the fluid catalytic cracking unit 130. Generally, the sulfur adsorption activity of the spent adsorbent material decreases because more sites on the adsorbent material have already bound to sulfur. The amount of sulfur adsorbed on the spent adsorbent material may be greater than the amount of sulfur adsorbed on the adsorbent material after regeneration. As used in this disclosure, the term "regenerated adsorbent material" generally refers to an adsorbent material that has been introduced into the cracking reaction zone and regenerated in a regenerator (such as regenerator 140) to remove adsorbed sulfur. Generally, the regenerated adsorbent material has an increased sulfur adsorption activity because more sites are no longer bound to sulfur.

[0025] It should also be understood that a stream can be named according to the components of the stream, and the named component of the stream can be the main component of the stream (e.g., 50 weight percent (wt.%), 70 wt.%, 90 wt.%, 95 wt.%, 99 wt.%, 99.5 wt.%, or even 99.9 wt.% to 100 wt.% of the stream content). It should also be understood that when a stream containing the component is disclosed as flowing from one system component to another system component, the component of the stream is also disclosed as flowing from one system component to another system component. For example, an "propylene stream" disclosed as flowing from a first system component to a second system component should be understood to equivalently disclose "propylene" etc. flowing from the first system component to the second system component.

[0026] Referring again to Figure 1 , a hydrocarbon feed conversion system 100 is schematically depicted. The hydrocarbon feed conversion system 100 may include a fluid catalytic cracking unit 130 and a regenerator 140. The hydrocarbon feed conversion system 100 generally receives a full crude oil feed stream 102 to produce at least one product stream 104.

[0027] In one or more embodiments, the hydrocarbon feed conversion system 100 includes a fluid catalytic cracking (FCC) unit 130, where at least a portion of the full crude oil feed stream 102 enters the FCC unit 130 and contacts cracking catalyst and adsorbent material at relatively high temperature and pressure. As the full crude oil feed stream 102 contacts the heated catalyst and cracks into lighter products, carbonaceous deposits (commonly referred to as coke) form on the catalyst. The coke deposits formed on the catalyst may reduce the catalytic activity of the catalyst and even deactivate the catalyst. Catalyst deactivation may result in the catalyst losing its catalytic effectiveness. The spent catalyst with coke deposits can be separated from the cracking reaction products, the removable hydrocarbons removed, and then sent to a regenerator 140. Additionally, the full crude oil feed stream 102 contacts the adsorbent material in the FCC unit 130, where the adsorbent material adsorbs at least a portion of the sulfur from the full crude oil feed stream 102, such that the sulfur content on the adsorbent material increases and the sulfur content in the full crude oil feed stream 102 decreases. The adsorbent material can be separated from the other contents present in the FCC unit 130 and sent to the regenerator 140. In some embodiments, the spent catalyst with coke deposits and the adsorbent material that has adsorbed at least a portion of the sulfur from the full crude oil feed stream 102 can be sent to the regenerator 140 in one stream and / or processed in the regenerator 140 simultaneously under the same conditions. The regenerator 140 can be operated such that coke burns off the catalyst in the presence of an oxygen-containing gas, thereby producing a regenerated catalyst with catalytic effect.

[0028] The term "catalytically effective" refers to the ability of the regenerated catalyst to increase the rate of the cracking reaction. The term "catalytic activity" refers to the degree to which the regenerated catalyst increases the rate of the cracking reaction and may be related to the number of available catalytically active sites on the catalyst. For example, coke deposits on the catalyst may cover or block the catalytically active sites on the spent catalyst, thereby reducing the number of available catalytically active sites, which may reduce the catalytic activity of the catalyst. After regeneration, the regenerated catalyst may have coke equal to or less than 10 wt.%, 5 wt.%, or even 1 wt.% based on the total weight of the regenerated catalyst. Additionally, the regenerator 140 can be operated such that at least a portion of the sulfur adsorbed on the adsorbent material is removed, resulting in the adsorbent material having more active sites available to adsorb sulfur components again. The regenerated catalyst and the regenerated adsorbent material can then be recycled back to the FCC unit 130.

[0029] In one or more embodiments, the whole crude oil feed stream 102 generally may comprise whole crude oil. As used herein, the term "whole crude oil" should be understood as a mixture of petroleum liquids, gases, solids, or combinations thereof, including in some embodiments impurities that have not undergone significant separation or reaction processes, such as sulfur-containing compounds, nitrogen-containing compounds, and metal compounds. Whole crude oil is distinguished from crude oil fractions. In certain embodiments, the whole crude oil may be a minimally treated light crude oil to provide a crude oil feedstock having a total metal (Ni + V) content of less than 10 parts per million by weight (ppmw) and a Conradson carbon residue of less than 5 wt.%. For example, minimal treatment may include hydrotreating to remove, for example, heavy metals, etc.

[0030] In one or more embodiments, the whole crude oil feed stream 102 is whole crude oil having an American Petroleum Institute (API) gravity of 15 degrees to 50 degrees. For example, the whole crude oil feed stream 102 utilized may be Arabian heavy crude oil (API gravity of about 28°), Arabian medium crude oil (API gravity of about 30°), Arabian light crude oil (API gravity of about 33°), or Arabian extra light crude oil (API gravity of about 39°).

[0031] Generally, the contents of the whole crude oil feed stream 102 may include a relatively diverse variety of chemicals based on boiling point and have the characteristics of unprocessed crude oil that has not been separated into fractions. For example, the whole crude oil feed stream 102 may have a composition such that the difference between the 5 wt.% boiling point and the 95 wt.% boiling point of the whole crude oil feed stream 102 is at least 100 °C, at least 200 °C, at least 300 °C, at least 400 °C, at least 500 °C, or even at least 600 °C, such as 50 °C to 1000 °C, 100 °C to 750 °C, 150 °C to 600 °C, 150 °C to 500 °C, 150 °C to 400 °C, 150 °C to 900 °C, 250 °C to 800 °C, or 350 °C to 700 °C.

[0032] Before introducing the whole crude oil feed stream 102 into the fluid catalytic cracking unit 130, one or more supplemental feed streams (not shown) may be added to the whole crude oil feed stream 102. As previously described, in one or more embodiments, the whole crude oil feed stream 102 may be whole crude oil. In one or more embodiments, the whole crude oil feed stream 102 may be whole crude oil and one or more supplemental feed streams, the supplemental feed stream including one or more of vacuum residue, tar sands, asphalt, atmospheric residue, vacuum gas oil, demetallized oil, naphtha stream, other hydrocarbon streams, or combinations of these materials, which may be added to the whole crude oil feed stream 102 upstream of the fluid catalytic cracking unit 130.

[0033] In one or more embodiments, the sulfur content of the total crude oil feed stream 102 can be from 0.5 wt.% to 15 wt.%. For example, in some embodiments, the sulfur content of the total crude oil feed stream 102 can be from 0.5 wt.% to 12.5 wt.%, from 0.5 wt.% to 10 wt.%, from 0.5 wt.% to 7.5 wt.%, from 2.5 wt.% to 15 wt.%, from 5 wt.% to 15 wt.%, from 7.5 wt.% to 15 wt.%, from 0.5 wt.% to 4.5 wt.%, from 0.5 wt.% to 4 wt.%, from 0.5 wt.% to 3.5 wt.%, from 0.5 wt.% to 3 wt.%, from 0.5 wt.% to 2.5 wt.%, from 0.5 wt.% to 2 wt.%, from 0.5 wt.% to 1.5 wt.%, from 1 wt.% to 5 wt.%, from 1.5 wt.% to 5 wt.%, from 2 wt.% to 5 wt.%, from 2.5 wt.% to 5 wt.%, from 3 wt.% to 5 wt.%, from 3.5 wt.% to 5 wt.%, from 4 wt.% to 5 wt.%, from 1 wt.% to 4 wt.%, or from 1.5 wt.% to 3.5 wt.%.

[0034] Still referring to Figure 1, the total crude oil feed stream 102 recycled from the regenerator 140 and the recycled catalyst and adsorbent stream 110 can enter the fluid catalytic cracking unit 130. In some embodiments, the fluid catalytic cracking unit 130 can be a riser such that the adsorbent material and cracking catalyst present in the fluid catalytic cracking unit 130 move in an upward direction during the treatment process. The fluid catalytic cracking unit 130 can include a mixing zone 132, a cracking and adsorption zone 134, and a separation zone 136. The total crude oil feed stream 102, the adsorbent material, and / or the cracking catalyst can enter the fluid catalytic cracking unit 130 in the mixing zone 132, where the total crude oil feed stream 102, the adsorbent material, and / or the cracking catalyst can be fully mixed. Then, the total crude oil feed stream 102, the adsorbent material, and / or the cracking catalyst can be fed into the cracking and adsorption zone 134, where the total crude oil feed stream 102, the adsorbent material, and / or the cracking catalyst can be contacted under operating conditions that result in a catalytic cracking reaction between the total crude oil feed stream 102 and the cracking catalyst and the adsorption of sulfur in the total crude oil feed stream 102 onto the adsorbent material. Then, the total crude oil feed stream 102, the adsorbent material, and / or the cracking catalyst can be fed into the separation zone 136, where the cracking catalyst containing coke deposits and the adsorbent material with a higher sulfur adsorption concentration are at least partially separated from the total crude oil feed stream 102 and one or more of the formed products. The one or more formed products can be output from the fluid catalytic cracking unit 130 in the form of a product stream 104. The separated adsorbent material and cracking catalyst can then be sent to the regenerator 140 as a spent catalyst and adsorbent material stream 106. It should be understood that when the total crude oil feed stream 102, the adsorbent material, and / or the cracking catalyst are in the mixing zone 132 and the separation zone 136, the adsorbent material can adsorb sulfur from the total crude oil feed stream 102, and the cracking catalyst can undergo a catalytic reaction with the total crude oil feed stream 102; however, in one or more embodiments, the catalytic reaction of the cracking catalyst and the sulfur adsorption of the adsorbent material are mostly achieved in the cracking and adsorption zone 134.

[0035] According to one or more embodiments, the fluid catalytic cracking unit 130 can be operated at a temperature of 150°C to 1000°C. For example, in some embodiments, the fluid catalytic cracking unit 130 can be operated at a temperature of 150°C to 850°C, 150°C to 650°C, 150°C to 500°C, 350°C to 1000°C, 500°C to 1000°C, 750°C to 1000°C, 350°C to 650°C, 400°C to 650°C, 450°C to 650°C, 500°C to 650°C, 550°C to 650°C, 300°C to 600°C, 300°C to 550°C, 300°C to 500°C, 300°C to 450°C, 350°C to 600°C, 400°C to 550°C, or 450°C to 500°C.

[0036] The product stream 104 can include a mixture of cracked hydrocarbon materials, which can be further separated into one or more higher value petrochemical products and recovered from the system. For example, the product stream 104 can include one or more of cracked gas oil, cracked gasoline, cracked naphtha, mixed butenes, butadiene, propylene, ethylene, other olefins, ethane, methane, other petrochemical products, or combinations thereof. The cracked gasoline can be further processed to obtain aromatic hydrocarbons, such as benzene, toluene, xylene, or other aromatic hydrocarbons.

[0037] In one or more embodiments, the fluid catalytic cracking unit 130 can be operated such that no external hydrogen is introduced into the fluid catalytic cracking unit 130. In other words, the catalytic cracking reaction between the full crude oil feed stream 102 and the cracking catalyst and the adsorption of sulfur in the full crude oil feed stream 102 on the adsorbent material can be achieved without introducing a stream consisting primarily of hydrogen into the fluid catalytic cracking unit 130. It should be understood that a small amount of hydrogen may be naturally present in the fluid catalytic cracking unit 130, but a stream consisting essentially of hydrogen or primarily of hydrogen will not be introduced into the fluid catalytic cracking unit 130. Additionally, prior to the full crude oil feed stream 102 and the adsorbent material entering the fluid catalytic cracking unit 130, it is not necessary to pretreat the full crude oil feed stream 102 and / or the adsorbent material with hydrogen. The full crude oil feed stream 102 and / or the adsorbent material do not need to be contacted with a stream consisting primarily of hydrogen prior to entering the fluid catalytic cracking unit 130 in order for the full crude oil feed stream 102 and the cracking catalyst to react sufficiently and for the adsorbent material to sufficiently adsorb sulfur from the full crude oil feed stream 102 onto the adsorbent material.

[0038] In one or more embodiments, the regenerator 140 can treat the cracking catalyst and the adsorbent material by contacting the components with an oxygen-containing stream 108 at the regenerator temperature to produce a regenerated catalyst and a regenerated adsorbent material. The oxygen-containing gas can be any gas containing at least 0.1 mol% oxygen, such as air. The regenerator 140 can treat the catalyst by removing coke (i.e., at least most of the coke) and raising the catalyst temperature (e.g., by burning the coke). As used herein, "removing" coke from the catalyst means removing at least a portion of the coke, although some residual coke may still remain on the catalyst, as would be understood by one of ordinary skill in the art. The catalyst that can be recycled from the regenerator 140 to the fluid catalytic cracking unit 130 can be the regenerated catalyst and thus has a relatively high catalytic activity. The regenerator 140 can treat the adsorbent material such that the adsorbent material can desorb at least a portion of the sulfur adsorbed onto the adsorbent material from the full crude oil feed stream 102.

[0039] In one or more embodiments, the adsorbent material used in the hydrocarbon feed conversion system 100 can be any composition comprising one or more silicon oxides, one or more aluminum oxides, one or more nickel oxides, and / or one or more zinc oxides. The silicon oxide can be silica (silicon dioxide), silicon monoxide, or a combination thereof. The aluminum oxide can be aluminum(I) oxide, aluminum(II) oxide, aluminum(III) oxide (bauxite), or a combination thereof. The nickel oxide can be nickel(II) oxide, nickel(III) oxide, or a combination thereof. The zinc oxide can have the chemical formula ZnO and be in the wurtzite crystal form, the sphalerite crystal form, or a combination thereof. The surface of the adsorbent material can have various bonds between at least aluminum, silicon, nickel, zinc, and oxygen atoms such that one or more of the Al-O, Si-O, Ni-O, and Zn-O bonds are present on the surface of the adsorbent material. It is understood that there are many ways to manufacture an adsorbent material comprising one or more silicon oxides, one or more aluminum oxides, one or more nickel oxides, and / or one or more zinc oxides, and these different methods are contemplated in this application.

[0040] Without being bound by a particular theory, it is generally believed that when the adsorbent material contacts the sulfur-containing whole crude oil feed stream 102 in the fluid catalytic cracking unit 130, the sulfur in the whole crude oil feed stream 102 will react with at least a portion of the Zn-O and Ni-O bonds present on the surface of the adsorbent material such that at least a portion of the oxygen atoms are removed and replaced by sulfur atoms, such that new Zn-S and Ni-S bonds appear on the surface of the adsorbent material, thereby adsorbing at least a portion of the sulfur in the whole crude oil feed stream 102. When the spent adsorbent material (i.e., the adsorbent material that has adsorbed at least a portion of the sulfur in the whole crude oil feed stream 102) is sent to the regenerator 140 and contacted with an oxygen-containing gas, at least a portion of the Zn-S and Ni-S bonds on the surface of the spent adsorbent material will react with the oxygen in the oxygen-containing gas, thereby removing at least a portion of the sulfur adsorbed on the adsorbent material and replacing at least a portion of the sulfur with oxygen to increase the amount of Zn-O and Ni-O bonds on the surface of the regenerated adsorbent material.

[0041] The regenerator 140 can operate at a regenerator temperature of 350°C to 1500°C. For example, in one or more embodiments, the regenerator 140 can be operated at the following regenerator temperatures: 350° to 1250°C, 350°C to 1000°C, 350°C to 750°C, 500°C to 1500°C, 750°C to 1500°C, 1000°C to 1500°C, 600°C to 850°C, 650°C to 850°C, 700°C to 850°C, 550°C to 850°C, 750°C to 850°C, 550°C to 800°C, 550°C to 750°C, 550°C to 700°C, 550°C to 650°C, or 650°C to 750°C.

[0042] In one or more embodiments, the adsorbent material comprises one or more nickel oxides in an amount of 1 wt.% to 50 wt.% relative to the total weight of the adsorbent material. For example, in some embodiments, the adsorbent material comprises one or more nickel oxides in an amount of 1.5 wt.% to 50 wt.%, 2 wt.% to 50 wt.%, 2.5 wt.% to 50 wt.%, 3 wt.% to 50 wt.%, 3.5 wt.% to 50 wt.%, 4 wt.% to 50 wt.%, 4.5 wt.% to 50 wt.%, 5 wt.% to 50 wt.%, 10 wt.% to 50 wt.%, 15 wt.% to 50 wt.%, 20 wt.% to 50 wt.%, 25 wt.% to 50 wt.%, 1 wt.% to 40 wt.%, 1 wt.% to 30 wt.%, 1 wt.% to 20 wt.%, 1 wt.% to 10 wt.%, 1 wt.% to 7.5 wt.%, 1 wt.% to 5 wt.%, 1 wt.% to 4.5 wt.%, 1 wt.% to 4 wt.%, 1 wt.% to 3.5 wt.%, 1 wt.% to 3 wt.%, 1 wt.% to 2.5 wt.%, 1 wt.% to 2 wt.%, 2 wt.% to 40 wt.%, 2.5 wt.% to 25 wt.%, or 5 wt.% to 20 wt.% relative to the total weight of the adsorbent material.

[0043] In one or more embodiments, the adsorbent material comprises one or more zinc oxides in an amount of 1 wt.% to 50 wt.% relative to the total weight of the adsorbent material. For example, in some embodiments, the adsorbent material comprises one or more zinc oxides in an amount of 1.5 wt.% to 50 wt.%, 2 wt.% to 50 wt.%, 2.5 wt.% to 50 wt.%, 3 wt.% to 50 wt.%, 3.5 wt.% to 50 wt.%, 4 wt.% to 50 wt.%, 4.5 wt.% to 50 wt.%, 5 wt.% to 50 wt.%, 10 wt.% to 50 wt.%, 15 wt.% to 50 wt.%, 20 wt.% to 50 wt.%, 25 wt.% to 50 wt.%, 1 wt.% to 40 wt.%, 1 wt.% to 30 wt.%, 1 wt.% to 20 wt.%, 1 wt.% to 10 wt.%, 1 wt.% to 7.5 wt.%, 1 wt.% to 5 wt.%, 1 wt.% to 4.5 wt.%, 1 wt.% to 4 wt.%, 1 wt.% to 3.5 wt.%, 1 wt.% to 3 wt.%, 1 wt.% to 2.5 wt.%, 1 wt.% to 2 wt.%, 2 wt.% to 40 wt.%, 2.5 wt.% to 25 wt.%, or 5 wt.% to 20 wt.% relative to the total weight of the adsorbent material.

[0044] In one or more embodiments, the adsorbent material comprises from 8 wt.% to 12 wt.% of one or more nickel oxides, from 18 wt.% to 22 wt.% of one or more zinc oxides, and from 65 wt.% to 70 wt.% of one or more aluminum oxides, based on the total weight of the adsorbent material. In one or more embodiments, the adsorbent material comprises 10 wt.% of one or more nickel oxides, 21.4 wt.% of one or more zinc oxides, and 68.6 wt.% of one or more aluminum oxides, based on the total weight of the adsorbent material.

[0045] The catalyst used in the hydrocarbon feed conversion system 100 may include one or more fluid catalytic cracking catalysts suitable for a fluid catalytic cracking unit 130. The catalyst may be a heat carrier and may provide heat transfer to the fluid catalytic cracking unit 130. The catalyst may also have a plurality of catalytically active sites, such as acidic sites, to facilitate cracking reactions. For example, in an embodiment, the catalyst may be a highly active FCC catalyst having high catalytic activity. Examples of fluid catalytic cracking catalysts suitable for the hydrocarbon feed conversion system 100 may include, but are not limited to, zeolites, silica-alumina catalysts, carbon monoxide combustion promoter additives, bottom cracking additives, light olefin production additives, other catalyst additives, or combinations of these components. Zeolites that may be used as at least a portion of the cracking catalyst may include, but are not limited to, Y, REY, USY, RE-USY zeolites, or combinations of these zeolites. The catalyst may also include shaped selective catalyst additives, such as ZSM-5 zeolite crystals or other pentasil-type catalyst structures, which are commonly used in other FCC processes to produce light olefins and / or increase the octane number of FCC gasoline. In one or more embodiments, the catalyst may include a mixture of ZSM-5 zeolite crystals and cracking catalyst zeolites and a matrix structure of a typical FCC cracking catalyst. In one or more embodiments, the catalyst may be a mixture of Y and ZSM-5 zeolite catalysts embedded in clay, alumina, and a binder.

[0046] In one or more embodiments, at least a portion of the catalyst can be modified to include one or more rare earth elements (the 15 elements of the lanthanide series of the IUPAC periodic table plus scandium and yttrium), alkaline earth metals (Group 2 of the IUPAC periodic table), transition metals, phosphorus, fluorine, or any combination of these elements, which can increase the olefin yield in the fluid catalytic cracking unit 130. Transition metals may include "elements whose atoms have a partially filled d subshell, or which can give rise to cations with an incomplete d subshell" [IUPAC, Compendium of Chemical Terminology, 2nd ed. ("the Gold Book") (1997). Online corrected version: (2006 -) "transition element"]. One or more transition metals or metal oxides can also be impregnated onto the catalyst. The metal or metal oxide can include one or more metals from Groups 6 - 10 of the IUPAC periodic table. In some embodiments, the metal or metal oxide can include one or more of molybdenum, rhenium, tungsten, or any combination thereof. In one or more embodiments, a portion of the catalyst can be impregnated with tungsten oxide.

[0047] Examples

[0048] Examples are provided herein that may disclose one or more embodiments of the present disclosure. However, these examples should not be considered as limiting the claimed embodiments provided below.

[0049] Example 1 - Desulfurization Test of Adsorbent Material

[0050] Multiple adsorbent materials were formed and then tested in a fixed - bed continuous - flow reactor. One adsorbent material (calcined NiZn / Al 2 O 3 ) was synthesized from oxides of nickel, zinc, and aluminum, where the content of nickel oxide in the adsorbent material was 1 wt.% to 50 wt.% of the total weight of the adsorbent material, and the content of zinc oxide in the adsorbent material was also 1 wt.% to 50 wt.% of the total weight of the adsorbent material. Another adsorbent material (Ni / Al 2 O 3 ) was synthesized only from nickel oxide and aluminum oxide. These two adsorbent materials were evaluated by contacting a model oil (a 2 wt.% thiophene - hexane solution with a sulfur concentration of 20,000 ppm) in a fixed - bed continuous - flow reactor, and then the sulfur content was analyzed using an ANTEK nitrogen and sulfur analyzer. The reaction conditions included a temperature of 500 °C, ambient pressure, a 2 wt.% thiophene - hexane solution at 1 mL / min, 0.77 g of the adsorbent material, and an oil - to - adsorbent material weight hourly space velocity (WHSV) of 500 hr -1 , and the ratio of oil to adsorbent material was approximately 7. The conversion was calculated using Equation 1 below, where S in is the sulfur content before entering the reactor, and S outis the sulfur content after leaving the reactor:

[0051]

[0052] Table 1 below shows the sulfur conversion achieved for each adsorbent material. It is noteworthy that, compared with the NiZn / Al 2 O 3 adsorbent material, the calcined Ni / Al 2 O 3 adsorbent material achieved a higher conversion rate.

[0053] Table 1 - Desulfurization Conversion Rate of Test Adsorbent Material

[0054]

[0055] Example 2 - Regeneration Test of Adsorbent Material

[0056] Then, the calcined NiZn / Al 2 O 3 adsorbent material and the Ni / Al 2 O 3 adsorbent material were tested under regeneration conditions, including contacting the adsorbent material with air at a temperature of about 700 °C for about 10 minutes after the test of Example 1. Then, the adsorbent material was recycled for the test of Example 1 again. No signs of damage were observed for the calcined NiZn / Al 2 O 3 adsorbent material, and it was able to achieve a desulfurization conversion rate and olefin product yield similar to those in the first cycle. In contrast, compared with the first cycle, signs of damage were indeed observed for the Ni / Al 2 O 3 adsorbent material, and the desulfurization conversion rate and olefin product yield decreased significantly.

[0057] The present disclosure includes one or more non-limiting aspects. A first aspect includes a method for processing a whole crude oil feed stream, the method comprising: feeding the whole crude oil feed stream into a fluid catalytic cracking unit and contacting the whole crude oil feed stream with an adsorbent material and a cracking catalyst in the fluid catalytic cracking unit, wherein the cracking catalyst comprises a zeolite, wherein the whole crude oil feed stream comprises sulfur, and wherein in the fluid catalytic cracking unit: the adsorbent material adsorbs at least a portion of the sulfur of the whole crude oil feed stream such that the sulfur content on the adsorbent material increases; and at least a portion of the whole crude oil feed stream is catalytically cracked to produce one or more products and coke deposited on the cracking catalyst; and feeding the adsorbent material and the cracking catalyst comprising coke into a regenerator, wherein the adsorbent material and the cracking catalyst are contacted with an oxygen-containing gas at a regenerator temperature sufficient to remove at least a portion of the sulfur on the adsorbent material and burn at least a portion of the coke on the cracking catalyst; and feeding the adsorbent material and the cracking catalyst from the regenerator into the fluid catalytic cracking unit.

[0058] A second aspect includes any of the above aspects, wherein the adsorbent material and the cracking catalyst are mixed in the fluid catalytic cracking unit.

[0059] A third aspect includes any of the above aspects, wherein the regenerator temperature is from 550 °C to 850 °C.

[0060] A fourth aspect includes any of the above aspects, wherein the regenerator temperature is from 650 °C to 750 °C.

[0061] A fifth aspect includes any of the above aspects, wherein the adsorbent material and the cracking catalyst are mixed in the regenerator.

[0062] A sixth aspect includes any of the above aspects, wherein no external hydrogen is introduced into the fluid catalytic cracking unit.

[0063] A seventh aspect includes any of the above aspects, wherein the whole crude oil feed stream is not pretreated with hydrogen before entering the fluid catalytic cracking unit; and the adsorbent material is not pretreated with hydrogen before entering the fluid catalytic cracking unit.

[0064] An eighth aspect includes any of the above aspects, wherein the adsorbent material comprises one or more aluminum oxides, one or more nickel oxides, and one or more zinc oxides.

[0065] A ninth aspect includes any of the above aspects, wherein the adsorbent material comprises one or more nickel oxides in an amount of 1 wt.% to 50 wt.% based on the total weight of the adsorbent material.

[0066] The tenth aspect includes any of the above aspects, wherein the adsorbent material comprises one or more zinc oxides in an amount of 1 wt.% to 50 wt.% based on the total weight of the adsorbent material.

[0067] The eleventh aspect includes any of the above aspects, wherein the adsorbent material comprises one or more nickel oxides in an amount of 10 wt.% based on the total weight of the adsorbent material, one or more zinc oxides in an amount of 21.4 wt.% based on the total weight of the adsorbent material, and one or more aluminum oxides in an amount of 68.6 wt.% based on the total weight of the adsorbent material.

[0068] The twelfth aspect includes any of the above aspects, wherein the sulfur content of the whole crude oil feed stream is 0.5 wt.% to 5 wt.%.

[0069] The thirteenth aspect includes any of the above aspects, wherein the one or more products include olefins, aromatics, or a combination thereof.

[0070] The fourteenth aspect includes any of the above aspects, wherein the fluid catalytic cracking unit operates at a temperature of 300 °C to 650 °C.

[0071] The fifteenth aspect includes any of the above aspects, wherein the fluid catalytic cracking unit operates at a temperature of 450 °C to 550 °C.

[0072] The sixteenth aspect includes any of the above aspects, wherein the whole crude oil feed stream comprises crude oil having an American Petroleum Institute (API) gravity of 15 degrees to 50 degrees.

[0073] The seventeenth aspect includes any of the above aspects, wherein the whole crude oil feed stream comprises Arabian heavy crude oil, Arabian medium crude oil, Arabian light crude oil, or Arabian extra light crude oil.

[0074] The eighteenth aspect includes any of the above aspects, wherein the adsorbent material and the cracking catalyst are fluidized in the fluid catalytic cracking unit.

[0075] The nineteenth aspect includes any of the above aspects, wherein the cracking catalyst and the adsorbent material are present in the fluid catalytic cracking unit at a weight ratio of the cracking catalyst to the adsorbent material of 95:5 to 80:20.

[0076] The twentieth aspect includes any of the above aspects, wherein the adsorbent material includes one or more aluminum oxides, one or more nickel oxides, and one or more zinc oxides; the adsorbent material includes one or more nickel oxides in an amount of 1 wt.% to 50 wt.% based on the total weight of the adsorbent material; the adsorbent material includes one or more zinc oxides in an amount of 1 wt.% to 50 wt.% based on the total weight of the adsorbent material; the whole crude oil feed stream includes crude oil with an American Petroleum Institute (API) gravity of 15 degrees to 50 degrees; and the sulfur content of the whole crude oil feed stream is 0.5 wt.% to 5 wt.%.

[0077] The subject matter of the present disclosure has been described in detail with reference to specific embodiments. It should be understood that any detailed description of the components or features of an embodiment does not necessarily mean that the component or feature is essential for a particular embodiment or any other embodiment. In addition, those skilled in the art should understand that various modifications and variations can be made to the described embodiments without departing from the spirit and scope of the claimed subject matter.

[0078] It should be noted that one or more of the following claims use the term "wherein" as a transitional phrase. To define the present technology, it should be noted that this term is introduced in the claims as an open transitional phrase for introducing a recitation of a series of characteristics of a structure, and should be interpreted in a manner similar to the more commonly used open preamble term "comprising".

[0079] It should be understood that when a first component is described as "comprising" a second component, it is contemplated that in some embodiments, the first component "consists of" or "consists essentially of" the second component. It should also be understood that when a first component is described as "comprising" a second component, it is contemplated that in some embodiments, the first component comprises at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or even at least 99% of the second component (wherein % can be wt.% or mol%).

[0080] To describe and define the technology of the present invention, it should be noted that the variables mentioned herein are "functions" of a parameter or another variable, and it does not mean that the variable is merely a function of the listed parameter or variable. On the contrary, the reference herein to a variable as a "function" of the listed parameter is intended to be open-ended, such that the variable can be a function of a single parameter or multiple parameters.

[0081] It should also be noted that the recitation herein of "at least one" component, element, etc. should not be used to infer that the alternative use of the article "a" or "an" should be limited to a single component, element, etc.

[0082] It should be understood that any two quantitative values assigned to a property can form a range of that property, and all combinations of ranges formed by all such quantitative values of a given property are contemplated in the present disclosure.

Claims

1. A method for processing a whole crude oil feed stream, the method comprising: feeding the whole crude oil feed stream into a fluid catalytic cracking unit and contacting the whole crude oil feed stream with an adsorbent material and a cracking catalyst in the fluid catalytic cracking unit, wherein the cracking catalyst comprises zeolite, wherein the whole crude oil feed stream comprises sulfur, and wherein in the fluid catalytic cracking unit: the adsorbent material adsorbs at least a portion of the sulfur in the whole crude oil feed stream such that the sulfur content on the adsorbent material increases; and catalytically cracking at least a portion of the whole crude oil feed stream to produce one or more products and coke deposited on the cracking catalyst; and feeding the adsorbent material and the cracking catalyst comprising coke into a regenerator, wherein the adsorbent material and the cracking catalyst are contacted with an oxygen-containing gas at a regenerator temperature sufficient to remove at least a portion of the sulfur on the adsorbent material and burn at least a portion of the coke on the cracking catalyst; and feeding the adsorbent material and the cracking catalyst from the regenerator into the fluid catalytic cracking unit.

2. The method according to claim 1, wherein the adsorbent material and the cracking catalyst are mixed in the fluid catalytic cracking unit.

3. The method according to claim 1 or 2, wherein the regenerator temperature is from 550 °C to 850 °C.

4. The method according to any one of claims 1 to 3, wherein the adsorbent material and the cracking catalyst are mixed in the regenerator.

5. The method according to claim 4, wherein the adsorbent material and the cracking catalyst are regenerated under the same regeneration conditions.

6. The method according to any one of claims 1 to 5, wherein no external hydrogen is introduced into the fluid catalytic cracking unit.

7. The method according to any one of claims 1 to 6, wherein: the whole crude oil feed stream is not pretreated with hydrogen before entering the fluid catalytic cracking unit; and the adsorbent material is not pretreated with hydrogen before entering the fluid catalytic cracking unit.

8. The method according to any one of claims 1 to 7, wherein the adsorbent material comprises one or more aluminum oxides, one or more nickel oxides, and one or more zinc oxides.

9. The method according to claim 7, wherein the adsorbent material comprises one or more nickel oxides in an amount of 1 wt.% to 50 wt.% based on the total weight of the adsorbent material and / or one or more zinc oxides in an amount of 1 wt.% to 50 wt.% based on the total weight of the adsorbent material.

10. The method according to claim 7, wherein the adsorbent material comprises one or more nickel oxides in an amount of 10 wt.% based on the total weight of the adsorbent material, one or more zinc oxides in an amount of 21.4 wt.% based on the total weight of the adsorbent material, and one or more aluminum oxides in an amount of 68.6 wt.% based on the total weight of the adsorbent material.

11. The method according to any one of claims 1 to 10, wherein the one or more products comprise olefins, aromatics, or a combination thereof.

12. The method according to any one of claims 1 to 11, wherein the fluid catalytic cracking unit is operated at a temperature of 300 °C to 650 °C.

13. The method according to any one of claims 1 to 12, wherein the adsorbent material and the cracking catalyst are fluidized in the fluid catalytic cracking unit.

14. The method according to any one of claims 1 to 13, wherein the cracking catalyst and the adsorbent material are present in the fluid catalytic cracking unit in a weight ratio of the cracking catalyst to the adsorbent material of 95:5 to 80:

20.

15. The method according to any one of claims 1 to 14, wherein: the adsorbent material comprises one or more aluminum oxides, one or more nickel oxides, and one or more zinc oxides; the adsorbent material comprises one or more nickel oxides in an amount of 1 wt.% to 50 wt.% based on the total weight of the adsorbent material; the adsorbent material comprises one or more zinc oxides in an amount of 1 wt.% to 50 wt.% based on the total weight of the adsorbent material; the full crude oil feed stream comprises crude oil having an American Petroleum Institute (API) gravity of 15 degrees to 50 degrees; and the sulfur content of the full crude oil feed stream is 0.5 wt.% to 5 wt.%.

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