Multi-zone catalytic cracking of crude oil

Abstract

A method of treating a hydrocarbon feed may include: fractionating the hydrocarbon feed into a light stream, an intermediate stream, a heavy stream, and a residual stream; hydrotreating the residual stream to form a hydrotreated residual stream; and feeding the light stream, the intermediate stream, the heavy stream, and the hydrotreated residual stream to a single fluid catalytic cracking (FCC) reaction zone, thereby producing a product stream comprising light olefins. The light stream and hydrotreated residual stream may be exposed to more harsh FCC cracking conditions than the intermediate stream, and the intermediate stream may be exposed to more harsh FCC cracking conditions than the specific gravity stream. The FCC reaction zone may be operated in a flow configuration, and may be operated under high severity conditions.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. patent application No. 18 / 163,328, filed on February 2, 2023, entitled “Multi-Zone Catalytic Cracking of Crude Oil,” the entire contents of which are incorporated herein by reference. Technical Field

[0003] The present disclosure relates to processes for processing petroleum-based materials, particularly processes for cracking hydrocarbon feeds to produce light olefins. Background Art

[0004] The growing global demand for light chemical intermediates remains a major challenge for many integrated refineries. In particular, the production of valuable light olefins, such as ethylene and propylene, has attracted increasing attention, as pure olefin streams are considered building blocks for polymer synthesis. The production of light olefins depends on several process variables, such as feed type, operating conditions, and catalyst type. Although there are options available for producing higher yields of propylene and light olefins, considerable research activity in this area is still ongoing.

[0005] Light olefins are generally produced by thermal cracking (or steam cracking) of petroleum gas and distillates (such as naphtha, kerosene or gas oil). Light olefins can also be produced by fluid catalytic cracking processes. Generally, the hydrocarbon feeds used in fluid catalytic cracking processes range from hydrocracked bottoms to heavy feed fractions (such as vacuum gas oil and atmospheric residue); however, the supply of these hydrocarbon feeds is limited, at least in part due to limitations of the methods used in fluid catalytic cracking processes. Summary of the Invention

[0006] Therefore, there is a continuing need for an integrated process capable of producing intermediate compounds from a hydrocarbon feed, such as crude oil. The method of the present disclosure comprises fractionating the hydrocarbon feed into a plurality of streams, contacting one stream with one or more hydrotreating catalysts to form a hydrotreated effluent. The method of the present disclosure further comprises contacting the hydrotreated effluent and the other streams with an FCC catalyst composition. In particular, the method of the present disclosure comprises: fractionating the hydrocarbon feed into a light stream, an intermediate stream, a heavy stream, and a residual stream; hydrotreating the residual stream; merging the hydrotreated residual stream with the light stream; and introducing the combined stream into a fluid catalytic cracking unit (FCC). The intermediate stream and the heavy stream can be introduced into different points in the same FCC so that they experience lower severity than the combined light stream and the hydrotreated residual stream.

[0007] According to at least one embodiment of the present disclosure, a method for processing a hydrocarbon feed may include: fractionating the hydrocarbon feed into a light stream, an intermediate stream, a heavy stream, and a residual stream; hydrotreating the residual stream to form a hydrotreated residual stream; and feeding the light stream, the intermediate stream, the heavy stream, and the hydrotreated residual stream to a single fluid catalytic cracking (FCC) reaction zone to produce a product stream comprising light olefins. The light stream and the hydrotreated residual stream may be exposed to FCC cracking conditions that are more severe than the intermediate stream. The intermediate stream may be exposed to FCC cracking conditions that are more severe than the heavy stream. The FCC reaction zone may be configured in a downflow manner and operated under high severity conditions. The light stream may contain hydrocarbons boiling at less than 200°C. The intermediate stream may contain hydrocarbons boiling at 200°C to 371°C. The heavy stream may contain hydrocarbons boiling at 371°C to 540°C. The residual stream may contain hydrocarbons boiling at more than 540°C.

[0008] Additional features and advantages of the embodiments of the present disclosure will be set forth in the detailed description that follows, and in part, will be readily apparent to those skilled in the art from the detailed description or learned by practicing the embodiments of the present disclosure.

[0009] BRIEF DESCRIPTION OF THE DRAWINGS

[0010] The following detailed description of the present disclosure may be better understood when read in conjunction with the following drawings, in which:

[0011] Figure 1 A generalized flow diagram of a system for converting a hydrocarbon feed to produce olefins according to one or more aspects of the present disclosure is schematically depicted.

[0012] When describing Figure 1 The simplified schematic diagram does not include many valves, temperature sensors, electronic controllers, etc. that may be used and are familiar to those of ordinary skill in the art. In addition, it does not include the Figure 1 Accompanying components in those systems are shown, such as air supply, heat exchangers, surge tanks, etc. However, one of ordinary skill in the art understands that these components are within the scope of the present disclosure.

[0013] Reference will now be made in detail to various aspects, some of which are illustrated in the accompanying drawings. DETAILED DESCRIPTION

[0014] The present disclosure relates to methods and catalysts for upgrading hydrocarbon feeds, such as crude oil, to produce higher value chemical products and intermediates, such as, but not limited to, light olefins, aromatic compounds, and combinations thereof, by hydroprocessing and fluid catalytic cracking (FCC). The methods and FCC catalyst compositions of the present disclosure enable efficient cracking of feed streams, such as those comprising crude oil, by utilizing hydroprocessing and steric effects within an FCC, such as a downflow FCC.

[0015] definition

[0016] As used in this disclosure, the term "API" refers to the American Petroleum Institute.

[0017] As used in this disclosure, the term "ASTM" refers to the American Society for Testing and Materials.

[0018] As used in this disclosure, the term "cracking" refers to a chemical reaction in which a molecule having carbon-carbon bonds is broken into more than one molecule by breaking one or more carbon-carbon bonds; in which a compound including a cyclic moiety (such as an aromatic hydrocarbon) is converted into a compound that does not include a cyclic moiety; or in which a molecule having a carbon-carbon double bond is reduced to a carbon-carbon single bond. As used in this disclosure, the term "catalytic cracking" refers to cracking performed in the presence of a catalyst. Some catalysts can have multiple forms of catalytic activity, and invoking a catalyst by one specific function does not render the catalyst inactive for other functions.

[0019] As used in this disclosure, the term "catalyst" refers to any substance that increases the rate of a particular chemical reaction, such as a cracking reaction.

[0020] 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 metallic compounds, that is extracted directly from an underground formation or received from a desalting unit, without having any fractions separated by distillation, such as naphtha.

[0021] As used in this disclosure, the term "naphtha" refers to an intermediate mixture of hydrocarbonaceous materials derived from crude oil refining and having an atmospheric boiling point of 36 degrees Celsius (° C.) to 220° C. Naphtha may include light naphtha, which includes hydrocarbonaceous materials having an atmospheric boiling point of 36° C. to 80° C.; intermediate naphtha, which includes hydrocarbonaceous materials having an atmospheric boiling point of 80° C. to 140° C.; and heavy naphtha, which includes hydrocarbonaceous materials having an atmospheric boiling point of 140° C. to 200° C. Naphtha may include paraffins, cycloparaffins, and aromatics having 4 to 11 carbon atoms.

[0022] As used in this disclosure, the term "directly" refers to the delivery of a material (such as an effluent) from a first component of a system to a second component of the system without passing the material through any intermediate component or system that is operable to change the composition of the material. Similarly, the term "directly" also refers to the introduction of a material (such as a feed) into a component of a system without passing the material through any preliminary component that is operable to change the composition of the material. Intermediate or preliminary components or systems that are operable to change the composition of the material may include reactors and separators, but are generally not intended to include heat exchangers, valves, pumps, sensors, or other auxiliary components required to operate a chemical process. In addition, merging two streams together upstream of a second component, rather than delivering each stream separately to the second component, is not considered an intermediate or preliminary component that is operable to change the composition of the material.

[0023] As used in this disclosure, the terms "downstream" and "upstream" refer to the positioning of a component or system relative to the direction of material flow through the system. For example, if material flowing through a system encounters a first component before encountering a second component, the second component can be considered "downstream" of the first component. Similarly, if material flowing through a system encounters the first component before encountering the second component, the first component can be considered "upstream" of the second component.

[0024] As used in this disclosure, the term "effluent" refers to the stream delivered from a reactor, reaction zone or separator after a specific reaction or separation. Typically, the effluent has a composition different from the stream entering the reactor, reaction zone or separator. It should be understood that when the effluent is delivered to another component or system, only a portion of the effluent can be delivered. For example, a tail stream may take away some effluent, which means that only a portion of the effluent can enter a downstream component or system. The terms "reaction effluent" and "reactor effluent" particularly refer to the stream delivered from a reactor or reaction zone.

[0025] As used in this disclosure, the term "high severity conditions" refers to operating conditions of a fluid catalytic cracking system (such as an FCC system), which include a temperature greater than or equal to 580°C or from 580°C to 750°C, a catalyst to oil ratio greater than or equal to 1:1 or from 1:1 to 60:1, and a residence time less than or equal to 60 seconds or from 0.1 seconds to 60 seconds, each of which may be more severe than typical operating conditions of a fluid catalytic cracking system.

[0026] As used in this disclosure, the term "catalyst to oil ratio" or "CTO weight ratio" refers to the weight ratio of catalyst to a process stream comprising hydrocarbons.

[0027] The term "residence time" refers to the amount of time that the reactants are in contact with the catalyst under reaction conditions, such as at the reaction temperature.

[0028] As used in this disclosure, the term "reactor" refers to any vessel, container, conduit, etc., in which a chemical reaction (such as catalytic cracking) occurs between one or more reactants, optionally in the presence of one or more catalysts. A reactor may include one or more "reaction zones" disposed within the reactor. The term "reaction zone" refers to an area of ​​a reactor where a specific reaction occurs.

[0029] As used in this disclosure, the terms "separation unit" and "separator" refer to any separation device that at least partially separates one or more chemical components in a mixture from one another. For example, a separation system selectively separates different chemical components from one another to form one or more chemical fractions. Examples of separation systems include, but are not limited to, a distillation column, a fractionator, a flash tank, a knockout drum, a knockout drum, a centrifuge, a filter unit, a collector, a scrubber, an expansion unit, a membrane, a solvent extraction unit, a high-pressure separator, a low-pressure separator, or a combination of these. The separation methods described in this disclosure may not completely separate all of one chemical component from all of another chemical component. Rather, the separation methods described in this disclosure "at least partially" separate different chemical components from one another, and separation may include only partial separation even if not explicitly stated.

[0030] As used herein, the term "light olefins" refers to olefins having 2 to 4 carbon atoms (containing at least one double bond). For example, light olefins may include ethylene, propylene, and butene.

[0031] It should be further understood that a stream can be named according to a component of the stream, and the component used to name the stream can be the major component of the stream (e.g., comprising from 50%, 70%, 90%, 95%, 99%, 99.5%, or 99.9% by weight of the contents of the stream to 100% by weight of the contents of the stream). It should also be understood that when a stream comprising a component is disclosed as being delivered from one system component to another system component, the component of the stream is disclosed as being delivered from that system component to the other system component. For example, a disclosed "heavy oil stream" being delivered to a first system component or from a first system component to a second system component should be understood to equivalently disclose the delivery of "heavy oil" to the first system component or from the first system component to the second system component.

[0032] The composition of the feed stream and the processing variables of the FCC system play an important role in the reaction yield and heat balance in the system. Conventional FCC systems and methods may require expensive refining to produce suitable feed streams. This extra expensive refining may include separating and processing one or more fractions of the hydrocarbon feed before the refined conventional feed is introduced into the FCC system. These extra processing steps are energy intensive and have reduced the feasible feed amount from existing hydrocarbon sources. Previous systems and methods that have been developed have directly converted crude oil into more valuable chemical products and intermediates through catalytic cracking in an attempt to overcome these limitations, such as by reducing or eliminating the processing steps required to produce suitable hydrocarbon feed before being introduced into the FCC system. However, pollutants, metals or both present in the heavy hydrocarbon feed (such as crude oil) can deactivate the catalyst, causing a reduction in yield and an increase in production costs.

[0033] Implementation Method

[0034] Thus, embodiments of the present disclosure relate to integrated processes for converting crude oil directly into higher value chemical products and intermediates, such as, but not limited to, olefins and aromatics, through a combination of hydroprocessing and FCC using the reaction configurations described herein.

[0035] The method 100 for processing a hydrocarbon feed 105 may include fractionating 110 the hydrocarbon feed 105 into a light stream 115, an intermediate stream 120, a heavy stream 125, and a residue stream 130. The method may further include hydrotreating 135 the residue stream 130 to form a hydrotreated residue stream 140. The light stream 115, the intermediate stream 120, the heavy stream 125, and the hydrotreated residue stream 140 may then be fed to a single fluid catalytic cracking (FCC) reaction zone to produce a product stream comprising light olefins.

[0036] hydrocarbon feed

[0037] The hydrocarbon feed 105 of present method 100 can be crude oil, such as whole crude oil." crude oil " can be the crude hydrocarbon that has not previously experienced treatment (such as by one or more of distillation, cracking, hydrotreating, desalination or dehydration).In an embodiment, crude oil may have experienced at least some treatments, such as desalination, solid separation, washing or these combinations, but not yet experienced distillation.For example, crude oil may be the desalted crude oil through desalting.In an embodiment, before crude oil is introduced into method 100, crude oil may not have the operation of pre-treatment, separation (such as distillation) or other hydrocarbon composition that changes crude oil.As used herein, " hydrocarbon composition " of crude oil refers to the composition of the hydrocarbon component of crude oil, does not include the non-hydrocarbon solids, salt, water or other non-hydrocarbon components that are carried away.

[0038] The hydrocarbon feed 105, such as crude oil, may have an American Petroleum Institute (API) gravity of 25 to 55. For example, the hydrocarbon feed 105 may have an API gravity of 45 to 55, 50 to 52, 25 to 35, 27 to 29, 30 to 32, 32 to 34, 27 to 32, or any subset thereof. At a temperature of 15 degrees Celsius, the hydrocarbon feed 105 may have a density greater than 0.8 grams per milliliter (g / ml), greater than 0.82 g / ml, greater than 0.84 g / ml, 0.86 g / ml, 0.88 g / ml, greater than 0.90 g / ml, greater than 0.91 g / ml, 0.8 g / ml to 1.0 g / ml, 0.84 g / ml to 0.96 g / ml, 0.86 g / ml to 0.93 g / ml, 0.88 g / ml to 0.92 g / ml, 0.9 g / ml to 0.92 g / ml, or any subset thereof. According to some embodiments, the hydrocarbon feed 105 may be Arabian heavy crude oil, Arabian medium crude oil, Arabian light crude oil, or Arabian extra light crude oil.

[0039] The hydrocarbon feed 105 may have an initial boiling point of 30° C. to 50° C. For example, the hydrocarbon feed 105 may have an initial boiling point of 30° C. to 45° C., 30° C. to 40° C., 30° C. to 35° C., 35° C. to 50° C., 40° C. to 50° C., 45° C. to 50° C., or any subset thereof. The initial boiling point may be determined according to standard test method ASTM D7169.

[0040] The hydrocarbon feed 105 may have an end boiling point (also referred to herein as "EBP" and "FBP") greater than 720 degrees Celsius. For example, the hydrocarbon feed 105 may have an end boiling point greater than 740°C, greater than 760°C, greater than 780°C, greater than 800°C, greater than 850°C, greater than 900°C, greater than 950°C, or greater than 1000°C. The hydrocarbon feed 105 may have an end boiling point less than 2000°C, less than 1800°C, less than 1600°C, less than 1400°C, less than 1200°C, less than 1000°C, less than 900°C, less than 800°C, less than 750°C, or any subset thereof. The end boiling point may be determined according to standard test method ASTM D7169.

[0041] At least 50 wt% of the hydrocarbon feed 105 may have a boiling point temperature greater than or equal to 300° C. For example, the hydrocarbon feed 105 may have a 50 wt% boiling point temperature of 300° C. to 500° C., 300° C. to 475° C., 300° C. to 450° C., 300° C. to 425° C., 300° C. to 400° C., 300° C. to 375° C., 350° C. to 500° C., 350° C. to 475° C., 350° C. to 450° C., 350° C. to 425° C., 350° C. to 400° C., 350° C. to 375° C., 375° C. to 500° C., 375° C. to 475° C., 375° C. to 450° C., 375° C. to 425° C., 375° C. to 400° C., or any subset thereof. The 50 wt% boiling point temperature may be determined according to standard test method ASTM D7169.

[0042] The hydrocarbon feed 105 may have a nitrogen concentration of less than or equal to 5,000 parts per million by weight (ppmw). For example, the hydrocarbon feed 105 may have a nitrogen concentration of less than 4,500 ppmw, less than 4,000 ppmw, less than 3,500 ppmw, less than 3,000 ppmw, less than 2,500 ppmw, less than 2,000 ppmw, 1,000 ppmw to 5,000 ppmw, 1,000 ppmw to 4,000 ppmw, 1,000 ppmw to 3,000 ppmw, 1,000 ppmw to 2,000 ppmw, or any subset thereof. The nitrogen concentration of the hydrocarbon feed 105 may be determined according to standard test method ASTM D4629.

[0043] The hydrocarbon feed 105 may have a paraffinic compound concentration of less than 50 wt.% per unit weight of the hydrocarbon feed 105. For example, the hydrocarbon feed 105 may have a paraffinic compound concentration of less than or equal to 40 wt.%, less than or equal to 35 wt.%, less than or equal to 30 wt.%, less than or equal to 25 wt.%, less than or equal to 20 wt.%, less than or equal to 15 wt.%, less than or equal to 10 wt.%, or even less than or equal to 5 wt.% per unit weight of the hydrocarbon feed. In an embodiment, the hydrocarbon feed 105 may have a paraffin compound concentration of 5 wt% to less than 50 wt%, 5 wt% to 40 wt%, 5 wt% to 35 wt%, 5 wt% to 30 wt%, 5 wt% to 25 wt%, 5 wt% to 20 wt%, 10 wt% to less than 50 wt%, 10 wt% to 40 wt%, 10 wt% to 35 wt%, 10 wt% to 30 wt%, 10 wt% to 25 wt%, or even 10 wt% to 20 wt% per unit weight of the hydrocarbon feed 105. The paraffin content of the hydrocarbon feed 105 may be determined according to ASTM 5443.

[0044] The hydrocarbon feed 105 may have an aromatics concentration of greater than or equal to 20 wt % per unit weight of the hydrocarbon feed 105. For example, the hydrocarbon feed 105 may have an aromatics concentration of greater than or equal to 30 wt %, greater than or equal to 40 wt %, or even greater than or equal to 50 wt % per unit weight of the hydrocarbon feed 105 as determined according to ASTM 5443. In embodiments, the hydrocarbon feed 105 may have an aromatics concentration of between 20 wt % and 90 wt %, between 20 wt % and 80 wt %, between 20 wt % and 70 wt %, between 30 wt % and 90 wt %, between 30 wt % and 80 wt %, between 30 wt % and 70 wt %, between 40 wt % and 90 wt %, between 40 wt % and 80 wt %, between 40 wt % and 70 wt %, between 50 wt % and 90 wt %, between 50 wt % and 80 wt %, between 50 wt % and 70 wt %, or any subset thereof, per unit weight of the hydrocarbon feed 105.

[0045] The hydrocarbon feed 105 may have a cycloparaffin concentration greater than or equal to 25 wt% per unit weight of the hydrocarbon feed 105. For example, the hydrocarbon feed 105 may have a cycloparaffin concentration greater than or equal to 27 wt% per unit weight of the hydrocarbon feed 105 as determined according to ASTM 5443. In embodiments, the hydrocarbon feed 105 may have a cycloparaffin concentration per unit weight of the hydrocarbon feed 105 of from 25 wt% to 60 wt%, from 25 wt% to 50 wt%, from 25 wt% to 40 wt%, from 25 wt% to 35 wt%, from 27 wt% to 60 wt%, from 27 wt% to 50 wt%, from 27 wt% to 40 wt%, from 27 wt% to 35 wt%, or any subset thereof.

[0046] In some embodiments, the hydrocarbon feed 105 may be a topped crude oil. As used herein, the term "topped crude oil" refers to crude oil from which lower boiling components have been removed by distillation, such as components having a boiling temperature below 180° C. or even below 160° C. The hydrocarbon feed 105 may comprise, consist of, or consist essentially of a topped crude oil having greater than or equal to 95%, greater than or equal to 98%, or even greater than or equal to 99% of its components having a boiling temperature greater than or equal to 160° C. or greater than or equal to 180° C., depending on the cut point temperature of the topping unit.

[0047] Fractional distillation

[0048] Fractionating 110 the hydrocarbon feed 105 to produce a light stream 115, an intermediate stream 120, a heavy stream 125, and a residual stream 130 can be performed in any separator. For example, the fractionating 110 step can include, but is not limited to, a distillation column, a fractionator, a flash tank, a knockout drum, a knockout drum, a centrifuge, a filter unit, a collector, a scrubber, an expansion unit, a membrane, a solvent extraction unit, a high pressure separator, a low pressure separator, or a combination of these.

[0049] Light Flow

[0050] Fractionating 110 the hydrocarbon feed 105 can produce a light stream 115. The light stream 115 can include hydrocarbons that boil below the boiling point of the light stream. For example, the boiling point of the light stream can be less than 200° C., such as less than 195° C., between 15° C. and 200° C., between 20° C. and 200° C., between 25° C. and 200° C., between 30° C. and 200° C., or any subset thereof. Based on the total weight of the light stream 115, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 99%, or even at least 99.9% by weight of the hydrocarbons in the light stream 115 can boil at a boiling point less than or equal to the boiling point of the light stream.

[0051] The light stream 115 may comprise at least 50 wt% of all hydrocarbons initially in the hydrocarbon feed 105 having a boiling point of less than or equal to 200° C. For example, the light stream 115 may comprise at least 75 wt%, at least 80 wt%, at least 90 wt%, at least 95 wt%, or at least 99 wt% of all hydrocarbons initially in the hydrocarbon feed 105 having a boiling point of less than or equal to 200° C., based on the total weight of the hydrocarbon feed 105. In some embodiments, the light stream 115 may comprise at least 75 wt%, at least 80 wt%, at least 90 wt%, at least 95 wt%, or at least 99 wt% of all hydrocarbons initially in the hydrocarbon feed 105 having a boiling point of from 25° C. to 200° C., from 35° C. to 200° C., or from 45° C. to 200° C.

[0052] The light stream 115 may comprise less than 5 wt% sulfur based on the total weight of the light stream 115. For example, the light stream 115 may comprise less than 2.5 wt%, less than 1 wt%, less than 0.5 wt%, less than 0.1 wt%, or even less than 0.01 wt% sulfur based on the total weight of the light stream 115.

[0053] Light stream 115 may contain less than 50 ppm nitrogen. For example, light stream 115 may contain less than 25 ppm, less than 15 ppm, less than 10 ppm, or even less than 5 ppm nitrogen.

[0054] The light stream 115 may contain less than 5 ppm nickel. For example, the light stream 115 may contain less than 2.5 ppm, less than 2 ppm, less than 1 ppm, or even less than 0.1 ppm nickel.

[0055] The light stream 115 may contain less than 5 ppm of vanadium. For example, the light stream 115 may contain less than 2.5 ppm, less than 2 ppm, less than 1 ppm, or even less than 0.1 ppm of vanadium.

[0056] The lights stream 115 may comprise from 50 wt% to 99 wt% paraffins based on the total weight of the lights stream 115. For example, the lights stream 115 may comprise from 60 wt% to 90 wt%, from 60 wt% to 80 wt%, from 65 wt% to 75 wt%, from 70 wt% to 75 wt%, or any subset thereof, based on the total weight of the lights stream 115.

[0057] The lights stream 115 may comprise from 1 wt% to 30 wt% cycloalkanes based on the total weight of the lights stream 115. For example, the lights stream 115 may comprise from 5 wt% to 25 wt%, from 10 wt% to 20 wt%, from 12.5 wt% to 17.5 wt%, or any subset thereof, based on the total weight of the lights stream 115.

[0058] The light stream 115 may comprise from 1 wt% to 25 wt% aromatics based on the total weight of the light stream 115. For example, the light stream 115 may comprise from 5 wt% to 20 wt%, from 10 wt% to 15 wt%, or any subset thereof, based on the total weight of the light stream 115.

[0059] Intermediate Stream

[0060] Fractionating 110 the hydrocarbon feed 105 may produce an intermediate stream 120. The intermediate stream 120 may include hydrocarbons boiling at a temperature between 200° C. and 371° C. For example, based on the total weight of the intermediate stream 120, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 99%, or even at least 99.9% by weight of the intermediate stream 120 may include hydrocarbons boiling at a temperature between 200° C. and 371° C.

[0061] Intermediate stream 120 may comprise at least 50 wt%, at least 75 wt%, at least 90 wt%, at least 95 wt%, at least 99 wt%, or even at least 99.9 wt% of all hydrocarbons initially boiling at 200°C to 371°C in hydrocarbon feed 105.

[0062] The intermediate stream 120 may comprise less than 5 wt% sulfur based on the total weight of the intermediate stream 120. For example, the intermediate stream 120 may comprise less than 2.5 wt%, less than 2 wt%, less than 1.5 wt%, less than 1 wt%, less than 0.5 wt%, less than 0.1 wt%, or even less than 0.01 wt% sulfur based on the total weight of the intermediate stream 120.

[0063] Intermediate stream 120 may contain less than 500 ppm nitrogen. For example, intermediate stream 120 may contain less than 250 ppm, less than 200 ppm, less than 150 ppm, less than 100 ppm, less than 50 ppm, less than 40 ppm, or less than 30 ppm nitrogen.

[0064] Intermediate stream 120 may contain less than 50 ppm nickel. For example, intermediate stream 120 may contain less than 25 ppm, less than 20 ppm, less than 15 ppm, less than 10 ppm, less than 5 ppm, less than 2.5 ppm, less than 1 ppm, or even less than 0.1 ppm nickel.

[0065] Intermediate stream 120 may contain less than 50 ppm vanadium. For example, intermediate stream 120 may contain less than 25 ppm, less than 20 ppm, less than 15 ppm, less than 10 ppm, less than 5 ppm, less than 2.5 ppm, less than 1 ppm, or even less than 0.1 ppm vanadium.

[0066] The intermediate stream 120 may comprise from 20 wt% to 60 wt% paraffins, based on the total weight of the intermediate stream 120. For example, the intermediate stream 120 may comprise from 25 wt% to 55 wt%, from 30 wt% to 50 wt%, from 35 wt% to 50 wt%, from 40 wt% to 45 wt%, or any subset thereof, based on the total weight of the intermediate stream 120.

[0067] The intermediate stream 120 may comprise from 20 wt% to 60 wt% cycloalkanes, based on the total weight of the intermediate stream 120. For example, the intermediate stream 120 may comprise from 25 wt% to 55 wt%, from 30 wt% to 50 wt%, from 35 wt% to 50 wt%, from 40 wt% to 45 wt%, or any subset thereof, based on the total weight of the intermediate stream 120.

[0068] Intermediate stream 120 may comprise from 1 wt% to 30 wt% aromatics, based on the total weight of intermediate stream 120. For example, intermediate stream 120 may comprise from 5 wt% to 25 wt%, from 10 wt% to 20 wt%, from 12.5 wt% to 17.5 wt%, or any subset thereof, based on the total weight of intermediate stream 120.

[0069] Heavy Flow

[0070] Fractionating 110 the hydrocarbon feed 105 may produce a heavy stream 125. The heavy stream 125 may include hydrocarbons boiling at a temperature between 371° C. and 540° C. For example, based on the total weight of the heavy stream 125, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 99%, or even at least 99.9% by weight of the heavy stream 125 may include hydrocarbons boiling at a temperature between 371° C. and 540° C.

[0071] Heavies stream 125 may comprise at least 50 wt%, at least 75 wt%, at least 90 wt%, at least 95 wt%, at least 99 wt%, or even at least 99.9 wt% of all hydrocarbons initially boiling at 371°C to 540°C in hydrocarbon feed 105 .

[0072] The heavy stream 125 may comprise less than 10 wt% sulfur based on the total weight of the heavy stream 125. For example, the heavy stream 125 may comprise less than 7.5 wt%, less than 5 wt%, less than 4 wt%, less than 3 wt%, less than 2.9 wt%, less than 2.8 wt%, less than 2.7 wt%, less than 2.6 wt%, less than 2.5 wt%, between 0.1 wt% and 10 wt%, between 0.5 wt% and 10 wt%, between 1 wt% and 10 wt%, between 2 wt% and 10 wt%, between 2 wt% and 5 wt%, between 2 wt% and 3 wt%, or any subset thereof, based on the total weight of the heavy stream 125.

[0073] The heavy stream 125 may contain less than 7500 ppm nitrogen. For example, the heavy stream 125 may contain less than 5000 ppm, less than 2500 ppm, less than 1500 ppm, less than 1000 ppm, less than 750 ppm, or less than 600 ppm nitrogen.

[0074] The heavy stream 125 may contain less than 500 ppm nickel. For example, the heavy stream 125 may contain less than 250 ppm, less than 10 ppm, less than 50 ppm, less than 25 ppm, less than 20 ppm, less than 15 ppm, less than 10 ppm, less than 5 ppm, less than 2.5 ppm, less than 1 ppm, or even less than 0.1 ppm nickel.

[0075] The heavy stream 125 may contain less than 500 ppm of vanadium. For example, the heavy stream 125 may contain less than 250 ppm, less than 10 ppm, less than 50 ppm, less than 25 ppm, less than 20 ppm, less than 15 ppm, less than 10 ppm, less than 5 ppm, less than 2.5 ppm, less than 1 ppm, or even less than 0.1 ppm of vanadium.

[0076] The heavy stream 125 may comprise from 15 wt% to 50 wt% paraffins, based on the total weight of the heavy stream 125. For example, the heavy stream 125 may comprise from 20 wt% to 45 wt%, from 25 wt% to 40 wt%, from 30 wt% to 35 wt%, or any subset thereof, based on the total weight of the heavy stream 125.

[0077] The heavy stream 125 may comprise from 5 wt% to 35 wt% cycloalkanes, based on the total weight of the heavy stream 125. For example, the heavy stream 125 may comprise from 10 wt% to 30 wt%, from 15 wt% to 25 wt%, from 17.5 wt% to 22.5 wt%, or any subset thereof, based on the total weight of the heavy stream 125.

[0078] The heavy stream 125 may comprise from 30 wt% to 65 wt% aromatics, based on the total weight of the heavy stream 125. For example, the heavy stream 125 may comprise from 35 wt% to 60 wt%, from 40 wt% to 55 wt%, from 45 wt% to 50 wt%, or any subset thereof, based on the total weight of the heavy stream 125.

[0079] Residual flow

[0080] Fractionating 110 the hydrocarbon feed 105 may produce a residue stream 130. The residue stream 130 may include hydrocarbons that boil at a temperature greater than 540° C. For example, based on the total weight of the residue stream 130, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 99%, or at least 99.9% by weight of the residue stream 130 may include hydrocarbons that boil at a temperature greater than 540° C.

[0081] Without being limited by theory, the fractionation point of the residue stream 130 is selected to cluster metal contaminants (such as Ni and V) and poly-aromatics in the residue stream 130 that is undergoing hydroprocessing.

[0082] Based on the total weight of hydrocarbon feed 105, residue stream 130 may comprise at least 50 wt%, at least 75 wt%, at least 90 wt%, at least 95 wt%, at least 99 wt%, or even at least 99.9 wt% of all hydrocarbons initially boiling at a temperature of at least 540°C in hydrocarbon feed 105.

[0083] The residue stream 130 may comprise less than 15 wt% sulfur based on the total weight of the residue stream 130. For example, the residue stream 130 may comprise less than 12.5 wt%, less than 10 wt%, less than 7.5 wt%, or less than 5 wt%, from 1 wt% to 15 wt%, from 1 wt% to 10 wt%, from 1 wt% to 5 wt%, or any subset thereof, based on the total weight of the residue stream 130.

[0084] The residue stream 130 may contain less than 2500 ppm nitrogen, such as less than 2000 ppm, less than 1500 ppm, less than 1000 ppm, less than 1750 ppm, less than 1600 ppm nitrogen. The residue stream 130 may contain at least 1000 ppm nitrogen, such as at least 1250 ppm, at least 1500 ppm, from 1000 ppm to 2500 ppm, from 1000 ppm to 2000 ppm, from 1250 ppm to 1750 ppm, from 1500 ppm to 1750 ppm, or any subset thereof.

[0085] The residue stream 130 may contain less than 1000 ppm nickel. For example, the residue stream 130 may contain less than 750 ppm, less than 500 ppm, less than 250 ppm, less than 100 ppm, less than 75 ppm, less than 50 ppm, less than 25 ppm, 20 ppm to 1000 ppm, 20 ppm to 100 ppm, or any subset thereof.

[0086] The residue stream 130 may contain less than 1000 ppm of vanadium. For example, the residue stream 130 may contain less than 750 ppm, less than 500 ppm, less than 250 ppm, less than 100 ppm, less than 75 ppm, 50 ppm to 100 ppm, 20 ppm to 1000 ppm, 20 ppm to 100 ppm, or any subset thereof.

[0087] The residue stream 130 may comprise from 40 wt% to 75 wt% cycloalkanes and aromatics, based on the total weight of the residue stream 130. For example, the residue stream 130 may comprise from 45 wt% to 70 wt%, from 50 wt% to 65 wt%, from 55 wt% to 60 wt%, or any subset thereof, based on the total weight of the residue stream 130.

[0088] Residue stream 130 may comprise from 15 wt% to 55 wt% polar aromatic hydrocarbons, based on the total weight of residue stream 130. For example, residue stream 130 may comprise from 20 wt% to 50 wt%, from 25 wt% to 45 wt%, from 30 wt% to 40 wt%, from 32.5 wt% to 37.5 wt%, or any subset thereof, based on the total weight of residue stream 130.

[0089] The residue stream 130 may comprise from 1 wt% to 12 wt% saturated hydrocarbons, based on the total weight of the residue stream 130. For example, the residue stream 130 may comprise from 2 wt% to 10 wt%, from 4 wt% to 9 wt%, from 6 wt% to 8 wt%, or any subset thereof, based on the total weight of the residue stream 130.

[0090] Hydrotreating unit

[0091] The residue stream 130 may then be hydrotreated 135. Hydrotreating 135 the residue stream 130 may include contacting the residue stream 130 with one or more hydrotreating catalysts in a hydrotreating system. The hydrotreating system may be a single reactor or a series of directly connected reactors. The residue stream 130 may be introduced directly into a hydrotreating unit after fractionation 110.

[0092] The residue stream 130 can be hydrotreated in one or more stages, such as in a three-stage hydrotreater. The multiple stages of the hydrotreater can contain different catalysts in different reaction zones. For example, the catalysts can be arranged in different beds, placed in separate reactors, or mixed in a single reactor. The residue stream 130 can contact one or more hydrotreating catalysts in a downflow pattern.

[0093] Hydroprocessing 135 the residue stream 130 may include exposing the residue stream 130 to one or more hydroprocessing catalysts, such as a hydrodemetallization (also known as "HDM") catalyst, a hydrodesulfurization (also known as "HDS") catalyst, and a hydrodearomatization (also known as "HDA") catalyst. In some embodiments, the one or more hydroprocessing catalysts may include a hydrodenitrogenation catalyst, a hydrodeoxygenation catalyst, or both.

[0094] The one or more hydroprocessing stages can be arranged in any order. For example, the one or more hydroprocessing catalysts can be arranged such that the residue stream 130 first contacts the HDM catalyst, then the HDS catalyst, and then the HDA catalyst. Alternatively, the one or more hydroprocessing stages can be arranged such that the residue stream 130 contacts the HDM catalyst, then the HDA catalyst, and then the HDS catalyst; or contacts the HDS, HDA, and HDM catalysts; or contacts the HDS catalyst, then the HDM catalyst, and then the HDA catalyst; or contacts the HDA catalyst, then the HDS catalyst, and then the HDM catalyst; or contacts the HDA catalyst, then the HDM catalyst, and then the HDS catalyst. Without being limited by theory, it is believed that contacting the residue stream 130 with the HDM and HDS catalysts before contacting the HDA catalyst can prevent or minimize deactivation of the HDA catalyst.

[0095] In alternative embodiments, only one or two of the one or more hydroprocessing stages and catalysts may be present. The one or more hydroprocessing catalysts may be arranged such that the crude oil contacts the HDM catalyst and then the HDA catalyst; or contacts the HDA catalyst and then the HDM catalyst; or contacts the HDS catalyst and then the HDA catalyst; or contacts the HDA catalyst and then the HDS catalyst; or contacts the HDM catalyst and then the HDS catalyst; or contacts the HDS catalyst and then the HDM catalyst.

[0096] In embodiments where the one or more hydroprocessing catalysts form a mixed bed, the residue stream 130 may contact the one or more hydroprocessing catalysts in a random or synchronous manner.

[0097] The HDM catalyst may include any catalyst suitable for hydrodemetallization. For example, the HDM catalyst may include one or more metals from Groups 5, 6, or 8-10 of the IUPAC periodic table. In some embodiments, the HDM catalyst may include platinum. The HDM catalyst may further include a support material, and the metal may be disposed on the support material. The support material may be gamma-alumina or silica / alumina extrudates, spheres, cylinders, beads, pellets, and combinations thereof. In some embodiments, the HDM catalyst may include a gamma-alumina support having a surface area of ​​100 square meters per gram (m2). 2 / g) to 160m 2 / g, for example 100m 2 / g to 130m 2 / g, or 130m 2 / g to 160m 2 / g. In one embodiment, the HDM catalyst may comprise a molybdenum metal catalyst supported on an alumina support (sometimes referred to as a "Mo / Al2O3 catalyst"). It should be understood throughout this disclosure that the metals contained in any disclosed catalyst may exist as sulfides or oxides or even other compounds.

[0098] In some embodiments, the HDM catalyst may comprise: 0.5 wt% to 12 wt% molybdenum oxide or sulfide, such as 2 wt% to 10 wt% or 3 wt% to 7 wt% molybdenum oxide or sulfide; and 88 wt% to 99.5 wt% alumina, such as 90 wt% to 98 wt% or 93 wt% to 97 wt% alumina.

[0099] The HDM catalyst may have a relatively large pore volume, such as at least 0.8 cubic centimeters per gram (cm3). 3 / g) (e.g., at least 0.9 cm 3 / g or even at least 1.0 cm 3 / g). The pore size of the HDM catalyst can be predominantly macroporous (i.e., having a pore size greater than 50 nanometers (nm)). Without being limited by theory, it is believed that this pore structure and volume can provide a large capacity for the adsorption of metals and optional dopants on the surface of the HDM catalyst. In one embodiment, the HDM catalyst may include a dopant comprising one or more compounds including an element selected from the group consisting of boron, silicon, halogens, phosphorus, and combinations thereof.

[0100] An exemplary HDM catalyst may include KFR-22 from Albemarle Corporation.

[0101] The HDS catalyst may comprise one or more metals from Groups 5, 6, or 8-10 of the IUPAC Periodic Table. The HDS catalyst may comprise one or more metals from Group 6 of the IUPAC Periodic Table and one metal from Groups 8-10 of the IUPAC Periodic Table. Examples of Group 6 metals include molybdenum and tungsten, and examples of Group 8-10 metals include nickel and cobalt. The HDS catalyst may further comprise a support material, and the metals may be disposed on the support material. In some embodiments, the HDS catalyst may comprise Mo and Ni supported on an alumina support (sometimes referred to as a "Mo-Ni / Al2O3 catalyst"). The HDS catalyst may also contain a dopant selected from the group consisting of boron, phosphorus, halogens, silicon, and combinations thereof. In one or more embodiments, the HDS catalyst may comprise: 10 wt% to 18 wt% molybdenum oxide or sulfide, such as 11 wt% to 17 wt% or 12 wt% to 16 wt% molybdenum oxide or sulfide; 1 wt% to 7 wt% nickel oxide or sulfide, such as 2 wt% to 6 wt% or 3 wt% to 5 wt% nickel oxide or sulfide; and 75 wt% to 89 wt% alumina, such as 77 wt% to 87 wt% or 79 wt% to 85 wt% alumina.

[0102] HDS catalyst can have 140m 2 / g to 200m 2 / g of surface area, such as 140m 2 / g to 170m 2 / g, or 170m 2 / g to 200m 2 / g. HDS catalyst may have 0.5cm 3 / g to 0.7cm 3 / g of the median pore volume, such as 0.6 cm 3 / g. The HDS catalyst may generally comprise a mesoporous structure having a pore size ranging from 12 nm to 50 nm.

[0103] An exemplary HDS catalyst may include KFR-33 from Albemarle Corporation.

[0104] The HDA catalyst may comprise one or more metals from Groups 5, 6, 8, 9, or 10 of the IUPAC Periodic Table. In some embodiments, the HDA catalyst may comprise one or more metals from Groups 5 or 6 of the IUPAC Periodic Table and one or more metals from Groups 8, 9, or 10 of the IUPAC Periodic Table. In some embodiments, the HDA catalyst may comprise molybdenum or tungsten from Group 6 and nickel or cobalt from Groups 8, 9, or 10. The HDA catalyst may further comprise a support material, such as a zeolite, and the metals may be disposed on the support material. In one embodiment, the HDA catalyst may comprise a tungsten and nickel metal catalyst supported on a mesoporous zeolite support (sometimes referred to as a "W-Ni / mesoporous zeolite catalyst"). In another embodiment, the HDA catalyst may comprise a molybdenum and nickel metal catalyst supported on a mesoporous zeolite support (sometimes referred to as a "Mo-Ni / mesoporous zeolite catalyst"). The zeolite support material may not be limited to any particular type of zeolite. However, it is contemplated that zeolites such as Y, beta, AWLZ-15, LZ-45, Y-82, Y-84, LZ-210, LZ-25, silicalite, or mordenite framework zeolites may be suitable for use in the presently described HDA catalysts.

[0105] The support material of the HDA catalyst (such as a mesoporous zeolite) can be characterized as mesoporous by having an average pore size of 2 nm to 50 nm. Without being bound by theory, it is believed that the relatively large pore size (i.e., mesopore) allows larger molecules to diffuse within the zeolite, which is believed to improve the reactivity and selectivity of the catalyst. Because the pore size is increased, aromatic molecules can more easily diffuse into the catalyst and can increase aromatic cracking. For example, in some conventional embodiments, the feedstock converted by the hydrotreating catalyst can be: vacuum gas oil; light cycle oil from, for example, a fluid catalytic cracking reactor; or coker gas oil from, for example, a coking unit. Compared to the molecular size of heavy oils (such as crude oil and atmospheric residue) that can be feedstocks for the present methods and systems, the molecular size in these oils is relatively small. Heavy oils are generally unable to diffuse within conventional zeolites and be converted at active sites located within the zeolite. Therefore, zeolites with larger pore sizes (i.e., mesoporous zeolites) can allow larger molecules of the heavy oil to overcome diffusion limitations and can promote the reaction and conversion of larger molecules of the heavy oil.

[0106] In one or more embodiments, the HDA catalyst may comprise: 18 wt% to 28 wt% tungsten sulfide or oxide, such as 20 wt% to 27 wt% or 22 wt% to 26 wt% tungsten or tungsten sulfide or oxide; 2 wt% to 8 wt% nickel oxide or sulfide, such as 3 wt% to 7 wt% or 4 wt% to 6 wt% nickel oxide or sulfide; and 5 wt% to 40 wt% medium pore zeolite, such as 10 wt% to 35 wt% or 10 wt% to 30 wt% zeolite. In another embodiment, the HDA catalyst may comprise: 12 wt% to 18 wt% molybdenum oxide or sulfide, such as 13 wt% to 17 wt% or 14 wt% to 16 wt% molybdenum oxide or sulfide; 2 wt% to 8 wt% nickel oxide or sulfide, such as 3 wt% to 7 wt% or 4 wt% to 6 wt% nickel oxide or sulfide; and 5 wt% to 40 wt% medium pore zeolite, such as 10 wt% to 35 wt% or 10 wt% to 30 wt% medium pore zeolite.

[0107] It should be understood that some embodiments of the presently described methods and systems may utilize HDA catalysts comprising mesoporous zeolites (i.e., having an average pore size of 2 nm to 50 nm). However, in other embodiments, the average pore size of the zeolite may be less than 2 nm (i.e., microporous).

[0108] An exemplary HDA catalyst may include KFR-70 from Albemarle Corporation.

[0109] The residue stream 130 may contact one or more hydroprocessing catalysts at a temperature of at least 300° C., at least 325° C., at least 350° C., at least 375° C., or at least 400° C. The residue stream 130 may contact one or more hydroprocessing catalysts at a temperature of less than 1000° C., less than 800° C., less than 600° C., less than 500° C., or less than 450° C.

[0110] The residue stream 130 may contact one or more hydroprocessing catalysts in the presence of hydrogen. For example, the atmosphere in which the residue stream 130 contacts the one or more hydroprocessing catalysts may be at least 10 mol% hydrogen, at least 25 mol% hydrogen, at least 50 mol% hydrogen, at least 75 mol% hydrogen, at least 90 mol% hydrogen, or even at least 99 mol% hydrogen.

[0111] The residue stream 130 can contact the one or more hydroprocessing catalysts at a pressure of at least 75 bar, at least 100 bar, at least 125 bar, or at least 150 bar. For example, the residue stream 130 can contact the one or more hydroprocessing catalysts at a hydrogen partial pressure of at least 10 bar, at least 20 bar, at least 30 bar, at least 50 bar, at least 75 bar, at least 100 bar, at least 125 bar, or at least 150 bar.

[0112] The residue stream 130 may contact the one or more hydroprocessing catalysts at a hydrogen / oil ratio of at least 600. For example, the residue stream 130 may contact the one or more hydroprocessing catalysts at a hydrogen / oil ratio of at least 800, at least 1000, at least 1200, from 600 to 1500, from 800 to 1400, from 1100 to 1300, or any subset thereof.

[0113] The residual stream 130 can be greater than 0.1h -1 , more than 0.2h -1 , greater than 0.25h -1 , greater than 0.28h -1 , less than 0.5h -1 , less than 0.4h -1 , less than 0.35h -1 , less than 0.32h -1 , 0.1h -1 to 0.5h -1 , 0.2h -1 to 0.4h -1 , 0.25h -1 to 0.35h -1 , 0.28h -1 to 0.32h -1 or any subset thereof.

[0114] Hydroprocessing residual stream

[0115] Hydroprocessing 135 the residue stream 130 may form a hydroprocessed residue stream 140 .

[0116] Based on the total weight of the hydrotreated residue stream 140, at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, at least 90 wt%, or even at least 99 wt% of the hydrotreated residue stream 140 may have a boiling point temperature of at least 500°C, such as at least 510°C, at least 520°C, at least 530°C, or at least 540°C.

[0117] The hydrotreated residue stream 140 may comprise less than 10 wt% sulfur, based on the total weight of the hydrotreated residue stream 140. For example, the hydrotreated residue stream 140 may comprise less than 8 wt%, less than 6 wt%, less than 4 wt%, less than 2 wt%, less than 1 wt%, less than 0.5 wt%, less than 0.25 wt%, or even less than 0.1 wt% sulfur, based on the total weight of the hydrotreated residue stream 140.

[0118] The sulfur content of hydrotreated residue stream 140 may be less than 20%, less than 15%, less than 10%, less than 5%, less than 4%, or less than 3%, less than 2%, or even less than 1% of the sulfur content of residue stream 130. Sulfur content may be measured according to standard test method ASTM D-4924.

[0119] The hydrotreated residue stream 140 may contain less than 5000 ppm nitrogen. For example, the hydrotreated residue stream 140 may contain less than 2500 ppm, less than 2000 ppm, less than 1500 ppm, less than 1000 ppm, less than 500 ppm, less than 250 ppm, less than 125 ppm, less than 75 ppm, less than 50 ppm, less than 25 ppm, less than 10 ppm, or even less than 1 ppm nitrogen.

[0120] The nitrogen content of hydrotreated residue stream 140 may be less than 30%, less than 25%, less than 20%, less than 15%, less than 10%, less than 5%, or even less than 1% of the nitrogen content of residue stream 130. Nitrogen content may be measured according to standard test method ASTM D-4629.

[0121] The hydrotreated residue stream 140 may contain less than 100 ppm nickel. For example, the hydrotreated residue stream 140 may contain less than 75 ppm, less than 50 ppm, less than 25 ppm, less than 15 ppm, less than 10 ppm, less than 5 ppm, or even less than 1 ppm nickel.

[0122] The nickel content of hydrotreated residue stream 140 may be less than 30%, less than 25%, less than 20%, less than 15%, less than 10%, less than 5%, or even less than 1% of the nickel content of residue stream 130 .

[0123] The hydrotreated residue stream 140 may contain less than 100 ppm vanadium. For example, the hydrotreated residue stream 140 may contain less than 75 ppm, less than 50 ppm, less than 25 ppm, less than 15 ppm, less than 10 ppm, less than 5 ppm, or even less than 1 ppm vanadium.

[0124] The vanadium content of the hydrotreated residue stream 140 may be less than 30%, less than 25%, less than 20%, less than 15%, less than 10%, less than 5%, or even less than 1% of the vanadium content of the residue stream 130 .

[0125] The aromatics content of hydrotreated residue stream 140 may be less than 30%, less than 25%, less than 20%, less than 15%, less than 10%, less than 5%, or even less than 1% of the aromatics content of residue stream 130 .

[0126] The hydrotreated residue stream 140 may have a naphthenic and aromatics concentration of 20 wt% to 55 wt%, based on the total weight of the hydrotreated residue stream 140. For example, the hydrotreated residue stream 140 may have a naphthenic and aromatics concentration of 25 wt% to 50 wt%, 30 wt% to 45 wt%, 35 wt% to 40 wt%, or any subset thereof, based on the total weight of the hydrotreated residue stream 140.

[0127] The hydrotreated residue stream 140 may have a polar aromatic compound concentration of 1 wt.% to 6 wt.%, based on the total weight of the hydrotreated residue stream 140. For example, the hydrotreated residue stream 140 may have a polar aromatic compound concentration of 2 wt.% to 5 wt.%, 3 wt.% to 4 wt.%, or any subset thereof, based on the total weight of the hydrotreated residue stream 140.

[0128] The hydrotreated residue stream 140 may comprise from 40 wt% to 75 wt% saturated hydrocarbons, based on the total weight of the hydrotreated residue stream 140. For example, the hydrotreated residue stream 140 may comprise from 45 wt% to 70 wt%, from 50 wt% to 65 wt%, from 55 wt% to 60 wt%, or any subset thereof, based on the total weight of the hydrotreated residue stream 140.

[0129] Spatial Effects of FCC

[0130] The method 100 for processing a hydrocarbon feed 105 may include introducing a light stream 115, an intermediate stream 120, a heavy stream 125, and a hydrotreated residual stream 140 into a single fluid catalytic cracking (FCC) reaction zone to produce a product stream comprising light olefins. The light stream 115, the intermediate stream 120, the heavy stream 125, and the hydrotreated residual stream 140 may be introduced directly into the FCC reaction zone.

[0131] The light stream 115 and the hydrotreated residue stream 140 may be exposed to more severe FCC cracking conditions than the intermediate stream 120 , and the intermediate stream 120 may be exposed to more severe FCC cracking conditions than the heavy stream 125 .

[0132] Exposing one stream to more severe FCC cracking conditions than another stream can include introducing the stream subjected to the more severe FCC cracking conditions into the FCC reaction zone upstream of the stream subjected to the less severe FCC cracking conditions. For example, the light stream 115 and the hydrotreated residual stream 140 can be introduced into the FCC reaction zone upstream of the intermediate stream 120, while the intermediate stream 120 can be introduced into the FCC reaction zone upstream of the heavy stream 125. Introducing a first stream upstream of a second stream can mean that the first stream is introduced vertically above the second stream. Without being limited by theory, it is believed that the closer the introduced stream is to the inlet of the FCC (such as a downflow FCC), the more severe the FCC cracking conditions become.

[0133] The light stream 115 and the hydrotreated residue stream 140 can be exposed to FCC cracking with the same severity as each other. Specifically, the light stream 115 and the hydrotreated residue stream 140 can have the same residence time and peak temperature in the FCC as each other. This can be achieved by combining the light stream 115 and the hydrotreated residue stream 140 before introducing them into the FCC.

[0134] The light stream 115 and the hydrotreated residue stream 140 may each have a longer residence time in the FCC than the intermediate stream 120 and the heavy stream 125. For example, the residence time of the light stream 115 and the hydrotreated residue stream 140 in the FCC may each be at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 75%, at least 100%, at least 125%, at least 150%, at least 175%, or at least 200% longer than the residence time of the intermediate stream 120 in the FCC. Specifically, the light stream 115 and the hydrotreated residue stream 140 may each have a residence time in the FCC of at least 0.5 seconds, at least 1 second, at least 2 seconds, from 1 second to 2 seconds, from 1 second to 3 seconds, or from 2 seconds to 3 seconds.

[0135] The light stream 115 and the hydrotreated residue stream 140 may each be exposed to a higher peak temperature in the FCC than the intermediate stream 120 and the heavy stream 125. For example, the peak temperature of the light stream 115 and the hydrotreated residue stream 140 in the FCC may be at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 5°C, at least 10°C, at least 15°C, at least 20°C, at least 25°C, at least 30°C, from 5°C to 50°C, from 10°C to 45°C, from 15°C to 40°C, from 25°C to 35°C, or any subset thereof, higher than the peak temperature of the intermediate stream 120 in the FCC. Specifically, the light stream 115 and the hydrotreated residue stream can each have a peak temperature in the FCC of 650°C to 720°C, such as 650°C to 710°C, 650°C to 700°C, 655°C to 710°C, 655°C to 695°C, 660°C to 690°C, 665°C to 685°C, 670°C to 680°C, 660°C to 700°C, 670°C to 700°C, or any subset thereof.

[0136] The intermediate stream 120 may be exposed to more severe FCC cracking conditions than the heavy stream 125. Specifically, the intermediate stream may have a longer residence time in the FCC than the heavy stream 125 and / or experience higher peak temperatures.

[0137] The intermediate stream 120 may have a longer residence time in the FCC than the heavy stream 125. For example, the residence time of the intermediate stream 120 in the FCC may be at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 75%, at least 100%, at least 125%, at least 150%, at least 175%, or at least 200% longer than the residence time of the heavy stream 125 in the FCC. Specifically, the intermediate stream 120 may have a residence time in the FCC of at least 0.5 seconds, at least 1 second, at least 1.5 seconds, at least 2 seconds, from 0.5 seconds to 1 second, from 0.5 seconds to 1.5 seconds, from 1 second to 1.5 seconds, from 1 second to 2 seconds, from 1.5 seconds to 2 seconds, from 1.5 seconds to 2.5 seconds, from 1 second to 3 seconds, from 1.5 seconds to 3 seconds, from 2 seconds to 3 seconds, or any subset thereof.

[0138] The intermediate stream 120 may be exposed to a higher peak temperature in the FCC than the intermediate stream 120. For example, the peak temperature of the intermediate stream 120 in the FCC may be at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 5°C, at least 10°C, at least 15°C, at least 20°C, at least 25°C, at least 30°C, from 5°C to 50°C, from 10°C to 45°C, from 15°C to 40°C, from 25°C to 35°C, or any subset thereof, higher than the peak temperature of the heavy stream 125 in the FCC. Specifically, the intermediate stream 120 may have a peak temperature in the FCC of at least 600°C, at least 625°C, at least 650°C, from 640°C to 680°C, from 650°C to 670°C, from 655°C to 665°C, or any subset thereof.

[0139] The heavy stream 125 may have a residence time in the FCC of less than 2 seconds. For example, the heavy stream 125 may have a residence time in the FCC of less than 1.5 seconds, less than 1 second, 0.1 to 2 seconds, 0.1 to 1.5 seconds, 0.1 to 1 second, 0.1 to 0.5 seconds, 0.25 to 2 seconds, 0.25 to 1.5 seconds, 0.25 to 1 second, 0.25 to 0.75 seconds, 0.25 to 0.5 seconds, 0.5 to 2 seconds, 0.5 to 1.5 seconds, 0.5 to 1 second, or any subset thereof.

[0140] The heavy stream 125 may be exposed to a peak temperature in the FCC of 625° C. to 665° C. For example, the heavy stream 125 may be exposed to a peak temperature in the FCC of 630° C. to 660° C., 635° C. to 655° C., 640° C. to 650° C., or any subset thereof.

[0141] FCC operating conditions

[0142] In some embodiments, the FCC reaction zone can be operated in a downflow manner. Without being limited by theory, it is believed that because the reactants and catalyst move together down the reaction zone in a downflow FCC, the spatial variation in severity, residence time, and temperature is greater than in an upflow or FCC.

[0143] A downflow FCC reactor, or "downflow reactor," refers to a reactor in which reactants flow downward from a catalyst / feed mixing zone through a cracking reaction zone to a separation zone. Hydrocarbons react in the cracking reaction zone upon contact with the FCC catalyst composition, causing at least a portion of the hydrocarbons to undergo one or more cracking reactions to form one or more cracking reaction products, such as light olefins. The catalyst temperature can be equal to or greater than the reaction temperature of the cracking reaction zone, transferring heat to the hydrocarbons and promoting the endothermic cracking reaction.

[0144] Steam can be introduced into the top of the cracking reaction zone to provide additional heating to the hydrocarbon and catalyst mixture. Steam can also serve as a diluent, reducing the hydrocarbon partial pressure in the FCC reactor. Steam can also prevent secondary reactions and help improve the selectivity of the cracking reaction.

[0145] After leaving the FCC reactor, the catalyst can be separated from the hydrocarbons to separate the spent catalyst. The spent catalyst can then be sent to a regenerator. The regenerated catalyst can have a greater activity than the spent catalyst.

[0146] The FCC reaction zone can operate under high severity conditions, also known as HS-FCC. The FCC reaction zone can operate at a peak temperature greater than or equal to 580°C, a weight ratio of FCC catalyst composition to crude oil of 2:1 to 10:1, and a residence time of 0.1 to 60 seconds.

[0147] The FCC reaction zone may operate at a peak temperature greater than or equal to 580° C. For example, the FCC system may operate at a peak temperature greater than 600° C., greater than 620° C., greater than 640° C., greater than 645° C., greater than 660° C., greater than 670° C., 600° C. to 700° C., 600° C. to 690° C., 600° C. to 680° C., 650° C. to 700° C., 650° C. to 690° C., 650° C. to 680° C., 670° C. to 700° C., 670° C. to 680° C., or any subset thereof. When the reaction temperature is above, for example, 750° C., 725° C., 700° C., 690° C., or 680° C., the hydrocarbons may experience increased thermal cracking and decreased catalytic cracking compared to embodiments where the reaction temperature is below 750° C., 725° C., 700° C., 690° C., or 680° C. Without being limited by theory, it is believed that thermal cracking of the hydrotreated effluent can increase the yield of ethylene and reduce the yield of other products.Catalytic cracking of hydrocarbons in the FCC reaction zone can produce greater quantities of desired products, such as light olefins and aromatics.

[0148] In the FCC reaction zone, the weight ratio of the FCC catalyst composition to hydrocarbons may be from 2: 1 to 10: 1, such as from 2: 1 to 8: 1, from 2: 1 to 6: 1, from 2: 1 to 4: 1, from 4: 1 to 10: 1, from 6: 1 to 10: 1, or from 8: 1 to 10: 1. It should be understood that "hydrocarbons," as used in this paragraph, refer to the combined hydrocarbons of light stream 115, intermediate stream 120, heavy stream 125, and hydrotreated residue stream 140.

[0149] The fluid catalytic cracking system can be operated with a catalyst to oil (CTO) weight ratio of 2: 1 to 10: 1, wherein the catalyst to oil weight ratio is the weight ratio of the FCC catalyst composition to the weight of hydrocarbons in the reaction mixture per unit volume comprising the light stream 115, the intermediate stream 120, the heavy stream 125, the hydrotreated residual stream 140, and the FCC catalyst composition. For example, the fluid catalytic cracking system can be operated with a catalyst to oil weight ratio of 2: 1 to 3: 1, 2: 1 to 5: 1, 2: 1 to 10: 1, 3: 1 to 5: 1, or 5: 1 to 10: 1. Without being bound by theory, it is believed that a catalyst to oil weight ratio of less than 2: 1 may not provide a sufficient amount of catalyst to catalytically crack hydrocarbons economically and productively. It is believed that a catalyst to oil weight ratio greater than 10: 1 may not be economically practical in large-scale commercial applications.

[0150] The hydrocarbons may contact the FCC catalyst composition with a residence time of from 0.1 seconds to 60 seconds. For example, the hydrocarbons may contact the FCC catalyst composition with a residence time of from 5 seconds to 60 seconds, from 10 seconds to 60 seconds, from 20 seconds to 60 seconds, from 30 seconds to 60 seconds, from 40 seconds to 60 seconds, from 50 seconds to 60 seconds, from 0.1 seconds to 50 seconds, from 0.1 seconds to 40 seconds, from 0.1 seconds to 30 seconds, from 0.1 seconds to 20 seconds, from 0.1 seconds to 10 seconds, from 10 seconds to 50 seconds, from 20 seconds to 40 seconds, or any subset thereof. Without being bound by any particular theory, it is believed that a residence time of less than 0.1 seconds may not provide sufficient time for the hydrocarbons to be adequately cracked by the FCC catalyst composition.

[0151] The hydrocarbon can contact the FCC catalyst composition in the presence of steam. For example, the ratio of hydrocarbon to FCC catalyst composition can be steam to hydrocarbon can be 0:1 to 1:1, such as 0:1 to 0.75:1, 0:1 to 0.5:1, 0:1 to 0.25:1, 0:1 to 0.1:1, 0:1 to 0.01:1, or any subset thereof.

[0152] The FCC catalyst composition may include one or more of various fluid catalytic cracking catalysts, which may be suitable for use in FCC reaction zones operating under high severity conditions. Examples of fluid catalytic cracking catalysts suitable for use as FCC catalyst compositions may include, but are not limited to, zeolites, silica-alumina catalysts, carbon monoxide combustion promoter additives, bottom oil 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 FCC catalyst composition for cracking may include, but are not limited to, Y zeolite, REY zeolite, USY zeolite, RE-USY zeolite, or a combination of these zeolites. The FCC catalyst composition 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 improve the octane number of FCC gasoline. In one or more embodiments, the FCC catalyst composition may include a mixture of ZSM-5 zeolite crystals and cracking catalyst zeolites and a matrix structure of a conventional FCC cracking catalyst. In one or more embodiments, the FCC catalyst composition may be a mixture of Y zeolite and ZSM-5 zeolite catalyst embedded with clay, alumina, and a binder.

[0153] In one or more embodiments, at least a portion of the FCC catalyst composition may 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 may increase olefin yields. Transition metals may include "elements whose atoms have partially filled d subshells or which produce cations having incomplete d subshells" [IUPAC, Compendium of Chemical Terminology, 2nd Edition ("Gold Book") (1997). Online revision: (2006) "Transition Elements"]. One or more transition metals or metal oxides may also be impregnated on the catalyst. The metal or metal oxide may include one or more metals from Groups 6-10 of the IUPAC periodic table. The metal or metal oxide may include one or more of molybdenum, rhenium, tungsten, or any combination of these. At least a portion of the FCC catalyst composition may be impregnated with tungsten oxide.

[0154] The FCC catalyst composition can be formed by various methods. According to one embodiment, the matrix material can be mixed with a fluid (such as water) to form a slurry, and the zeolite can be mixed with a fluid (such as water) alone to form a slurry. The matrix material slurry and the zeolite slurry can be combined under stirring. Separately, another slurry can be formed by combining a binder material with a fluid (such as water). The binder slurry can then be combined with a slurry containing the zeolite 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 microparticles of the cracking catalyst.

[0155] The FCC catalyst composition can be in the form of shaped particles, such as microspheres. As used in this disclosure, "particles" refer to particles with an average particle size of 0.1 microns to 100 microns. The size of a particle refers to the maximum length of the particle from one side to the other measured along the longest distance of the particle. For example, a spherical particle has a size equal to its diameter, or a rectangular prism-shaped particle has a maximum length equal to the hypotenuse extending from the opposite corner. In an embodiment, each zeolite component of the FCC catalyst composition can be included in each catalyst particle. However, in other embodiments, particles can be mixed, wherein the particles only comprise a portion of the FCC catalyst composition. For example, a mixture of two types of particles can be included in the FCC catalyst composition, wherein one type of particle only comprises ZSM-5 and the other type of particle only comprises USY zeolite.

[0156] The FCC catalyst composition may be contacted with steam prior to use in an FCC system. The purpose of the steam treatment may be to accelerate the hydrothermal aging of the FCC catalyst composition that occurs during operation of the FCC system to obtain an equilibrium catalyst. Without being bound by any particular theory, it is believed that the steam treatment may result in the removal of aluminum from the framework, thereby reducing the number of sites where framework hydrolysis may occur under hydrothermal and thermal conditions. This removal of aluminum results in an increase in the thermal and hydrothermal stability of the dealuminated zeolite. As smaller SiO4 tetrahedra replace larger AlO4 - tetrahedral, so dealumination can result in a reduction in unit cell size. Dealumination can also affect the acidity of the zeolite by removing framework aluminum and forming additional framework aluminum species. Dealumination can affect the acidity of the zeolite by reducing the total acidity and increasing the acid strength of the zeolite. The total acidity can be reduced due to the removal of framework aluminum that acts as Bronsted acid sites. The acid strength of the zeolite can be increased because paired acid sites are removed or the second coordinated, next neighboring aluminum is removed. The increase in acid strength can be attributed to the fact that the charge density on the protons of the OH groups is highest when there is no framework aluminum in the second coordination sphere. In an embodiment, the FCC catalyst composition can be contacted with steam at a temperature greater than or equal to 800°C for a period of 6 hours or longer before contacting the hydrocarbons with the FCC catalyst composition.

[0157] In an embodiment, one or more supplemental feed streams may be combined with the hydrocarbons prior to introducing the hydrocarbons to the FCC catalyst. The one or more supplemental feed streams may be added so that they contact the FCC catalyst simultaneously with the hydrocarbons of the light stream, the intermediate stream, the heavy stream, and the hydrotreated residual stream. The supplemental feed stream may include one or more of a vacuum residue, tar sands, asphalt, atmospheric residue, vacuum gas oil, demetallized oil, a naphtha stream, or a combination of these.

[0158] Product Flow

[0159] Fluid catalytic cracking 150 of light stream 115, intermediate stream 120, heavy stream 125, and hydrotreated residual stream 140 can produce a product stream 155 comprising light olefins. "Light olefins" refers to olefins containing two to four carbon atoms. For example, the cracked effluent can contain at least 15 weight percent, at least 20 weight percent, at least 25 weight percent, at least 30 weight percent, at least 35 weight percent, at least 40 weight percent, or at least 45 weight percent light olefins.

[0160] Product stream 155 may comprise at least 2 wt% C2 olefins, such as ethylene. For example, based on the total weight of product stream 155, product stream 155 may comprise at least 4 wt%, at least 6 wt%, at least 8 wt%, at least 10 wt%, from 8 wt% to 15 wt%, or any subset thereof, of C2 olefins.

[0161] Product stream 155 may contain at least 2 wt% C3 olefins, such as butenes. For example, based on the total weight of product stream 155, product stream 155 may contain at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 17 wt%, or at least 20 wt% C3 olefins.

[0162] Product stream 155 may contain at least 2 wt% C4 olefins, such as butenes. For example, based on the total weight of product stream 155, product stream 155 may contain at least 5 wt%, at least 10 wt%, at least 12 wt% C4 olefins.

[0163] Product stream 155 can comprise at least 5 wt% gasoline-series products. For example, based on the total weight of product stream 155, product stream 155 can comprise at least 10 wt%, at least 20 wt%, at least 25 wt%, or at least 30 wt% gasoline-series products.

[0164] Fluid catalytic cracking 150 of the light stream 115, the intermediate stream 120, the heavy stream 125, and the hydrotreated residue stream 140 can convert the hydrocarbons originally found in the hydrocarbon feed 105 into other products. For example, fluid catalytic cracking 150 can convert at least 50 weight percent, at least 60 weight percent, at least 70 weight percent, at least 80 weight percent, at least 90 weight percent, at least 95 weight percent, or even at least 99 weight percent of the hydrocarbons originally in the hydrocarbon feed 105 into other products, such as light olefins.

[0165] Fluid catalytic cracking 150 of the light stream 115, the intermediate stream 120, the heavy stream 125, and the hydrotreated residual stream 140 can convert a portion of the hydrocarbons originally found in the hydrocarbon feed 105 into coke. Coke is a solid residue produced when oil undergoes severe oxidation and thermal decomposition. Coke can be deposited on the catalyst, the reactor surface, or both. At any location, the coke may contaminate the surface and hinder the reaction. Contacting the above streams with the catalyst can convert less than 10 weight percent, less than 8 weight percent, less than 7 weight percent, less than 6 weight percent, less than 5 weight percent, or less than 4 weight percent of the hydrocarbons originally in the hydrocarbon feed into coke.

[0166] Example

[0167] Various aspects of the present disclosure will be further illustrated by the following examples. These examples are illustrative in nature and should not be construed as limiting the subject matter of the present disclosure.

[0168] Example 1

[0169] According to some embodiments of the present disclosure, Arabian light crude oil having an API gravity of 33.0 and a sulfur content of 1.6 wt% is fractionated in a distillation column to form a light stream, a middle stream, a heavy stream, and a residual stream. The properties of the feed crude oil stream and the resulting fractions (based on the total weight of the crude oil) are given in Table 1 below.

[0170] Table 1

[0171]

[0172] Example 2

[0173] The residual stream from Example 1 was hydrotreated in a three-stage hydrotreater. The reaction conditions were: weighted average bed temperature of 400°C, pressure of 150 bar, liquid hourly space velocity (LHSV) of 0.5 h -1 , the H2 / oil ratio is 1200:1 (v / v), the oil flow rate is 300 ml / h, and the H2 flow rate is 360 L / h.

[0174] The first section of the hydrotreater uses a KFR-22 catalyst from Albemarle to perform hydrodemetallization (HDM). The second section of the hydrotreater uses a KFR-33 catalyst from Albemarle to perform hydrodesulfurization (HDS). The third section of the hydrotreater uses a KFR-70 catalyst from Albemarle to perform hydrodearomatization (HDA). The first, second, and third sections are discrete beds stacked one on top of the other in a single reaction zone. The residue stream flows down to the first section, then to the second section, and then to the third section. The properties of the hydrotreated residue stream are shown in Table 2 below.

[0175] Table 2

[0176] Kinematic viscosity at 100°C <![CDATA[67.6mm 2 / s]]> Density at 60℃ <![CDATA[0.9g / cm 3 ]]> Sulfur (weight %) 0.36 Ni(ppm) 1 V(ppm) 3 Fe (ppm) ＜1 Na (ppm) ＜10

[0177] Example 3

[0178] Various fractions of Arabian light crude oil were cracked under the conditions shown in the following Table 4. Catalysts having the compositions shown in the following Table 3 were used in all reactions.

[0179] Table 3

[0180] Components weight% Notes ZSM-5 20 <![CDATA[Phosphorus is impregnated on zeolite with 7.5 wt% of P2O5]]> USY 21 <![CDATA[Lanthanum is impregnated on zeolite with 2.5 wt% La2O3]]> Alumina 8 Pural SB from Sasol clay 49 Kaolin Silicon dioxide 2 Ludox TM-40 added as colloidal silica

[0181] An Advanced Cracking Evaluation (ACE) unit was used to simulate a downflow FCC reaction zone with multiple entry points. The ACE unit simulates a commercial FCC process.

[0182] Before each experiment, the catalyst was loaded into the reactor and heated to the desired reaction temperature. N2 gas was fed from the bottom through a feed injector to keep the catalyst particles fluidized. Once the catalyst bed temperature reached within ±2°C of the reaction temperature, the reaction could begin. The feed was then injected at a predetermined time (on-time (TOS)). The desired catalyst to feed ratio was obtained by controlling the feed pump. The gaseous product was transported to a liquid receiver where C 5+ The hydrocarbons were condensed, and the remaining gas was sent to a gas receiver. After the catalyst stripping was complete, the reactor was heated to 700°C, and the nitrogen atmosphere was replaced with air to regenerate the catalyst. During the regeneration process, the released gas was sent to a CO2 analyzer. The coke yield was calculated from the flue gas flow rate and CO2 concentration. The above process was repeated for each of Examples 3(A) to 3(C).

[0183] Example 3(A)

[0184] The light stream from Example 1 and the hydrotreated residual stream from Example 2 were blended and fed to a fluidized bed reactor. To simulate the most severe cracking conditions as the first feed introduced into the FCC, a time on stream (TOS) of 75 seconds and a temperature of 675°C were used. The new catalyst was steam-deactivated at 810°C for 6 hours to simulate the equilibrium catalyst in the actual process. The steam-deactivated catalyst was used for this reaction. It should be understood that the TOS is directly proportional to the residence time.

[0185] Example 3(B)

[0186] The intermediate stream from Example 1 was then cracked in the same reactor. To simulate medium severity, 660° C. and a stream time TOS of 60 seconds were used. To simulate FCC, the catalyst from Example 3(A) was used without regeneration.

[0187] Example 3(C)

[0188] The heavy stream from Example 1 was then cracked in the same reactor using the spent catalyst. To simulate minimum severity, 645°C and a TOS of 45 seconds were used. To simulate FCC, the catalyst from Example 3(B) was used without regeneration.

[0189] Example 3 (merged)

[0190] The streams of Examples 3(A)-(C) were combined to form a single stream. The single stream simulated the output of processing whole crude oil according to the methods of the present disclosure.

[0191] Example 3 (combined) is the weighted average of Examples 3(A)-(C). Example 3(A) represents 43% by weight of the crude oil feed of Example 1. Example 3(B) represents 30% by weight of the crude oil feed of Example 1. Example 3(C) represents 24% by weight of the crude oil feed of Example 1.

[0192] Comparative Example 1 (CE-1)

[0193] The same Arabian light crude oil used in Example 3 was directly cracked in the same cracking reactor and under the same conditions as used in Example 3(A), using the most severe cracking conditions. Specifically, the temperature was 675°C and the TOS was 75 seconds.

[0194] Table 4

[0195]

[0196]

[0197] As can be seen in Table 4, the combined yield of total light olefins for the present process is significantly higher than that for the comparative process. In addition, each of Examples 3(A)-3(C) and Example 3 (Combined) exhibited significantly lower coke formation than Comparative Example CE-1.

[0198] aspect

[0199] According to a first aspect of the present disclosure, a method for treating a hydrocarbon feed comprises: fractionating the hydrocarbon feed into a light stream, an intermediate stream, a heavy stream, and a residual stream; hydrotreating the residual stream to form a hydrotreated residual stream; and feeding the light stream, the intermediate stream, the heavy stream, and the hydrotreated residual stream to a single fluid catalytic cracking (FCC) reaction zone to produce a product stream comprising light olefins. The light stream comprises hydrocarbons boiling below 200°C, the intermediate stream comprises hydrocarbons boiling between 200°C and 371°C, the heavy stream comprises hydrocarbons boiling between 371°C and 540°C, and the residual stream comprises hydrocarbons boiling above 540°C. The light stream and the hydrotreated residual stream are exposed to FCC cracking conditions that are more severe than the intermediate stream, and the intermediate stream is exposed to FCC cracking conditions that are more severe than the heavy stream. The FCC reaction zone operates in a downflow configuration, and the FCC operates under high severity conditions.

[0200] According to a second aspect of the present disclosure, in combination with the first aspect, the FCC system operates at a temperature greater than or equal to 580°C, a weight ratio of FCC catalyst composition to crude oil of 2:1 to 10:1, and a residence time of 0.1 to 60 seconds.

[0201] According to a third aspect of the present disclosure, in combination with any one of the first or second aspects, the light stream and the hydrotreated residue stream are combined before entering the FCC.

[0202] According to a fourth aspect of the present disclosure, in combination with any one of the first to third aspects, the light stream and the hydrotreated residue stream have the same residence time and peak temperature as each other in the FCC.

[0203] According to a fifth aspect of the present disclosure, in combination with any one of the first to fourth aspects, the light stream and the hydrotreated residual stream have a longer residence time in the FCC than the intermediate stream and the heavy stream.

[0204] According to a sixth aspect of the present disclosure, in combination with any one of the first to fifth aspects, the light stream and the hydrotreated residual stream are exposed to a higher peak temperature in the FCC than the intermediate stream and the heavy stream.

[0205] According to a seventh aspect of the present disclosure, in combination with any one of the first to sixth aspects, the intermediate stream has a longer residence time in the FCC than the heavy stream.

[0206] According to an eighth aspect of the present disclosure, in combination with any one of the first to seventh aspects, the intermediate stream is exposed to a higher peak temperature in the FCC than the heavy stream.

[0207] According to a ninth aspect of the present disclosure, in combination with any one of the first to eighth aspects, the heavy stream has a shorter residence time in the FCC than the intermediate stream.

[0208] According to a tenth aspect of the present disclosure, in combination with any one of the first to ninth aspects, the heavy stream is exposed to a lower peak temperature in the FCC than the intermediate stream.

[0209] According to an eleventh aspect of the present disclosure, in combination with any one of the first to tenth aspects, the residual stream is hydrotreated in a three-stage hydrotreatment unit.

[0210] According to a twelfth aspect of the present disclosure, in combination with any one of the first to eleventh aspects, hydroprocessing the residue stream includes exposing the residue stream to a hydrodemetallization catalyst, a hydrodesulfurization catalyst, and a hydrodearomatization catalyst.

[0211] According to a thirteenth aspect of the present disclosure, in combination with any one of the first to twelfth aspects, the light stream comprises at least 80 wt% of hydrocarbons boiling below 200°C.

[0212] According to a fourteenth aspect of the present disclosure, in combination with any one of the first to thirteenth aspects, the light stream comprises less than 1 wt% sulfur.

[0213] According to a fifteenth aspect of the present disclosure, in combination with any one of the first to fourteenth aspects, the intermediate stream comprises at least 80 wt% of hydrocarbons boiling at 200°C to 371°C.

[0214] According to a sixteenth aspect of the present disclosure, in combination with any one of the first to fifteenth aspects, the intermediate stream comprises less than 1 wt% sulfur.

[0215] According to a seventeenth aspect of the present disclosure, in combination with any one of the first to sixteenth aspects, the heavy stream comprises at least 80 wt% of hydrocarbons boiling at 371°C to 540°C.

[0216] According to an eighteenth aspect of the present disclosure, in combination with any one of the first to seventeenth aspects, the heavy stream comprises less than 3 wt% sulfur.

[0217] According to a nineteenth aspect of the present disclosure, in combination with any one of the first to eighteenth aspects, the residue stream comprises at least 80 wt% of hydrocarbons boiling above 540°C.

[0218] According to a twentieth aspect of the present disclosure, in combination with any one of the first to nineteenth aspects, the residue stream comprises at least 2 wt% sulfur.

[0219] According to a twenty-first aspect of the present disclosure, in combination with any one of the first to twentieth aspects, the feed stream is Arabian heavy crude oil, Arabian medium crude oil, Arabian light crude oil, or Arabian ultra-light crude oil.

[0220] According to a twenty-second aspect of the present disclosure, in combination with any one of the first to twenty-first aspects, the product stream comprising light olefins comprises at least 35 wt% of light olefins.

[0221] According to a twenty-third aspect of the present disclosure, in combination with any one of the first to twenty-second aspects, the product stream comprising light olefins comprises at least 25 wt% of gasoline series products.

[0222] According to a twenty-fourth aspect of the present disclosure, in combination with any one of the first to twenty-third aspects, the feed stream is whole crude oil.

[0223] According to a twenty-fifth aspect of the present disclosure, in combination with any one of the first to twenty-fourth aspects, the feed stream has an API gravity of 25 to 35.

[0224] According to a twenty-sixth aspect of the present disclosure, in combination with any one of aspects one to twenty-fifth, the feed stream is whole crude oil; the light stream comprises at least 80 weight % of hydrocarbons boiling below 200°C; the light stream accounts for at least 80 weight % of the hydrocarbons initially boiling below 200°C in the hydrocarbon feed; the intermediate stream comprises at least 80 weight % of hydrocarbons boiling at 200°C to 371°C; the intermediate stream accounts for at least 80 weight % of the hydrocarbons initially boiling at 371°C to 540°C in the hydrocarbon feed; the heavy stream comprises at least 80 weight % of hydrocarbons boiling at 371°C to 540°C; the heavy stream accounts for at least 80 weight % of the hydrocarbons initially boiling at 371°C to 540°C in the hydrocarbon feed; the residual stream comprises at least 80 weight % of the hydrocarbons initially boiling at 371°C to 540°C hydrocarbons boiling above 540°C; the residue stream comprises at least 80 weight percent of the hydrocarbons initially in the hydrocarbon feed boiling above 540°C; hydrotreating the residue stream comprises exposing the residue stream to a hydrodemetallization catalyst, a hydrodesulfurization catalyst, and a hydrodearomatization catalyst; the light stream and the hydrotreated residue stream have the same residence time and peak temperature in the FCC as each other; the light stream and the hydrotreated residue stream have a longer residence time in the FCC than the intermediate stream and the heavy stream; the light stream and the hydrotreated residue stream are exposed to a higher peak temperature in the FCC than the intermediate stream and the heavy stream; the intermediate stream has a longer residence time in the FCC than the heavy stream; and the intermediate stream is exposed to a higher peak temperature in the FCC than the heavy stream.

[0225] It should be noted that any two quantitative values ​​assigned to a property may constitute a range for that property, and that all combinations of ranges formed by all of the stated quantitative values ​​for a given property are contemplated in this disclosure.

[0226] It should be noted that one or more of the appended claims utilize the term "wherein" as a transitional phrase. For purposes of defining the present technology, it should be noted that this term is introduced in the claims as an open transitional phrase to introduce a list of features of the structure and should be interpreted in a manner similar to the more commonly used open-ended term "comprising."

[0227] Having described the subject matter of the present disclosure in detail with reference to specific aspects, it should be noted that the various details of these aspects should not be construed as implying that these details are essential components of these aspects. Rather, the claims appended hereto should be construed as the sole indicator of the breadth of the present disclosure and the respective scope of the various aspects described herein. Furthermore, it will be apparent that modifications and variations may be made without departing from the scope of the appended claims.

Claims

1. A method for treating a hydrocarbon feed, comprising: fractionating the hydrocarbon feed into a light stream, a middle stream, a heavy stream, and a residual stream; hydrotreating the residue stream to form a hydrotreated residue stream; as well as feeding the light stream, the intermediate stream, the heavy stream, and the hydrotreated residual stream to a single fluid catalytic cracking (FCC) reaction zone to produce a product stream comprising light olefins; wherein, The light stream comprises hydrocarbons boiling below 200°C, the intermediate stream comprises hydrocarbons boiling between 200°C and 371°C, the heavy stream comprises hydrocarbons boiling between 371°C and 540°C, and the residual stream comprises hydrocarbons boiling above 540°C; The light stream and the hydrotreated residual stream are exposed to more severe FCC cracking conditions than the intermediate stream; and The intermediate stream is exposed to more severe FCC cracking conditions than the heavy stream; The FCC reaction zone is operated in a downflow configuration; and The FCC operates under high severity conditions.

2. The method according to claim 1, wherein The FCC system operates at a temperature greater than or equal to 580° C., a weight ratio of the FCC catalyst composition to crude oil of 2:1 to 10:1, and a residence time of 0.1 to 60 seconds.

3. The method according to any one of claims 1 to 2, wherein The lights stream and the hydrotreated residue stream have the same residence time and peak temperature as each other in the FCC.

4. The method according to any one of claims 1 to 3, wherein The light stream and the hydrotreated residual stream have a longer residence time in the FCC than the intermediate stream and the heavy stream.

5. The method according to any one of claims 1 to 4, wherein The light stream and the hydrotreated residual stream are exposed to higher peak temperatures in the FCC than the intermediate stream and the heavy stream.

6. The method according to any one of claims 1 to 5, wherein The intermediate stream has a longer residence time in the FCC than the heavy stream.

7. The method according to any one of claims 1 to 6, wherein The intermediate stream is exposed to higher peak temperatures in the FCC than the heavy stream.

8. The method according to any one of claims 1 to 7, wherein The residual stream is hydrotreated in a three-stage hydrotreater.

9. The method according to any one of claims 1 to 8, wherein Hydrotreating the residue stream includes exposing the residue stream to a hydrodemetallization catalyst, a hydrodesulfurization catalyst, and a hydrodearomatization catalyst.

10. The method according to any one of claims 1 to 9, wherein The feed stream is whole crude oil having an API gravity of 25 to 35.

11. The method according to any one of claims 1 to 10, wherein: The light stream comprises at least 80% by weight of hydrocarbons boiling below 200°C; The intermediate stream comprises at least 80 wt% hydrocarbons boiling at 200°C to 371°C; The heavy stream comprises at least 80 wt% hydrocarbons boiling at 371°C to 540°C; and The residual stream comprises at least 80% by weight of hydrocarbons boiling above 540°C.

12. The method according to any one of claims 1 to 11, wherein: The heavy stream comprises less than 3% by weight sulfur; The residual stream comprises at least 2 wt% sulfur; or Both.

13. The method according to any one of claims 1 to 12, wherein The residual stream contains at least 1000 ppm nitrogen.

14. The method according to any one of claims 1 to 13, wherein The product stream comprising light olefins comprises at least 30 wt% light olefins.

15. The method according to any one of claims 1 to 14, wherein: The feed stream is whole crude oil; The light stream comprises at least 80% by weight of hydrocarbons boiling below 200°C; said light stream comprising at least 80 wt. % of the hydrocarbons initially boiling below 200° C. in said hydrocarbon feed; The intermediate stream comprises at least 80 wt% hydrocarbons boiling at 200°C to 371°C; The intermediate stream comprises at least 80 weight percent of the hydrocarbons initially boiling at 371° C. to 540° C. in the hydrocarbon feed; The heavy stream comprises at least 80 wt% hydrocarbons boiling at 371°C to 540°C; The heavy stream comprises at least 80 weight percent of the hydrocarbons initially boiling at 371° C. to 540° C. in the hydrocarbon feed; The residual stream comprises at least 80% by weight of hydrocarbons boiling above 540°C; The residual stream comprises at least 80% by weight of the hydrocarbons initially boiling above 540° C. in the hydrocarbon feed; hydrotreating the residue stream comprising exposing the residue stream to a hydrodemetallization catalyst, a hydrodesulfurization catalyst, and a hydrodearomatization catalyst; The light stream and the hydrotreated residual stream have the same residence time and peak temperature as each other in the FCC; The light stream and the hydrotreated residual stream have a longer residence time in the FCC than the intermediate stream and the heavy stream; The light stream and the hydrotreated residual stream are exposed to higher peak temperatures in the FCC than the intermediate stream and the heavy stream; The intermediate stream has a longer residence time in the FCC than the heavy stream; as well as The intermediate stream is exposed to higher peak temperatures in the FCC than the heavy stream.

Images